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Sample records for saprc-07 chemical mechanism

  1. Photochemical modeling in California with two chemical mechanisms: model intercomparison and response to emission reductions.

    Science.gov (United States)

    Cai, Chenxia; Kelly, James T; Avise, Jeremy C; Kaduwela, Ajith P; Stockwell, William R

    2011-05-01

    An updated version of the Statewide Air Pollution Research Center (SAPRC) chemical mechanism (SAPRC07C) was implemented into the Community Multiscale Air Quality (CMAQ) version 4.6. CMAQ simulations using SAPRC07C and the previously released version, SAPRC99, were performed and compared for an episode during July-August, 2000. Ozone (O3) predictions of the SAPRC07C simulation are generally lower than those of the SAPRC99 simulation in the key areas of central and southern California, especially in areas where modeled concentrations are greater than the federal 8-hr O3 standard of 75 parts per billion (ppb) and/or when the volatile organic compound (VOC)/nitrogen oxides (NOx) ratio is less than 13. The relative changes of ozone production efficiency (OPE) against the VOC/NOx ratio at 46 sites indicate that the OPE is reduced in SAPRC07C compared with SAPRC99 at most sites by as much as approximately 22%. The SAPRC99 and SAPRC07C mechanisms respond similarly to 20% reductions in anthropogenic VOC emissions. The response of the mechanisms to 20% NOx emissions reductions can be grouped into three cases. In case 1, in which both mechanisms show a decrease in daily maximum 8-hr O3 concentration with decreasing NOx emissions, the O3 decrease in SAPRC07C is smaller. In case 2, in which both mechanisms show an increase in O3 with decreasing NOx emissions, the O3 increase is larger in SAPRC07C. In case 3, SAPRC07C simulates an increase in O3 in response to reduced NOx emissions whereas SAPRC99 simulates a decrease in O3 for the same region. As a result, the areas where NOx controls would be disbeneficial are spatially expanded in SAPRC07C. Although the results presented here are valuable for understanding differences in predictions and model response for SAPRC99 and SAPRC07C, the study did not evaluate the impact of mechanism differences in the context of the U.S. Environmental Protection Agency's guidance for using numerical models in demonstrating air quality attainment

  2. Chemical kinetics and reaction mechanism

    International Nuclear Information System (INIS)

    Jung, Ou Sik; Park, Youn Yeol

    1996-12-01

    This book is about chemical kinetics and reaction mechanism. It consists of eleven chapters, which deal with reaction and reaction speed on reaction mechanism, simple reaction by rate expression, reversible reaction and simultaneous reaction, successive reaction, complicated reaction mechanism, assumption for reaction mechanism, transition state theory, successive reaction and oscillating reaction, reaction by solution, research method high except kinetics on reaction mechanism, high reaction of kinetics like pulsed radiolysis.

  3. Mechanical properties of chemically modified portuguese pinewood

    OpenAIRE

    Lopes, Duarte B; Mai, Carsten; Militz, Holger

    2014-01-01

    To turn wood into a construction material with enhanced properties, many methods of chemical modification have been developed in the last few decades. In this work, mechanical properties of pine wood were chemically modified, compared and evaluated. Maritime pine wood (Pinus pinaster) was modified with four chemical processes: 1,3-dimethylol-4,5- dihydroxyethyleneurea, N-methylol melamine formaldehyde, tetra-alkoxysilane and wax. The following mechanical properties were assessed experiment...

  4. Quantum mechanical tunneling in chemical physics

    CERN Document Server

    Nakamura, Hiroki

    2016-01-01

    Quantum mechanical tunneling plays important roles in a wide range of natural sciences, from nuclear and solid-state physics to proton transfer and chemical reactions in chemistry and biology. Responding to the need for further understanding of multidimensional tunneling, the authors have recently developed practical methods that can be applied to multidimensional systems. Quantum Mechanical Tunneling in Chemical Physics presents basic theories, as well as original ones developed by the authors. It also provides methodologies and numerical applications to real molecular systems. The book offers information so readers can understand the basic concepts and dynamics of multidimensional tunneling phenomena and use the described methods for various molecular spectroscopy and chemical dynamics problems. The text focuses on three tunneling phenomena: (1) energy splitting, or tunneling splitting, in symmetric double well potential, (2) decay of metastable state through tunneling, and (3) tunneling effects in chemical...

  5. Reduced chemical kinetic mechanisms for hydrocarbon fuels

    International Nuclear Information System (INIS)

    Montgomery, C.J.; Cremer, M.A.; Heap, M.P.; Chen, J-Y.; Westbrook, C.K.; Maurice, L.Q.

    1999-01-01

    Using CARM (Computer Aided Reduction Method), a computer program that automates the mechanism reduction process, a variety of different reduced chemical kinetic mechanisms for ethylene and n-heptane have been generated. The reduced mechanisms have been compared to detailed chemistry calculations in simple homogeneous reactors and experiments. Reduced mechanisms for combustion of ethylene having as few as 10 species were found to give reasonable agreement with detailed chemistry over a range of stoichiometries and showed significant improvement over currently used global mechanisms. The performance of reduced mechanisms derived from a large detailed mechanism for n-heptane was compared to results from a reduced mechanism derived from a smaller semi-empirical mechanism. The semi-empirical mechanism was advantageous as a starting point for reduction for ignition delay, but not for PSR calculations. Reduced mechanisms with as few as 12 species gave excellent results for n-heptane/air PSR calculations but 16-25 or more species are needed to simulate n-heptane ignition delay

  6. Mechanical and chemical decontamination of surfaces

    International Nuclear Information System (INIS)

    Kienhoefer, M.

    1982-01-01

    Decontamination does not mean more than a special technique of cleaning surfaces by methods well known in the industry. The main difference consists in the facts that more than just the visible dirt is to be removed and that radioactive contamination cannot be seen. Especially, intensive mechanical and chemical carry-off methods are applied to attack the surfaces. In order to minimize damages caused to the surfaces, the decontamination method is to adapt to the material and the required degree of decontamination. The various methods, their advantages and disadvantages are described, and the best known chemical solutions are shown. (orig./RW)

  7. Quantum mechanical facets of chemical bonds

    International Nuclear Information System (INIS)

    Daudel, R.

    1976-01-01

    To define the concept of bond is both a central problem of quantum chemistry and a difficult one. The concept of bond appeared little by little in the mind of chemists from empirical observations. From the wave-mechanical viewpoint it is not an observable. Therefore there is no precise operator associated with that concept. As a consequence there is not a unique approach to the idea of chemical bond. This is why it is preferred to present various quantum mechanical facets, e.g. the energetic facet, the density facet, the partitioning facet and the functional facet, of that important concept. (Auth.)

  8. Quantum mechanical calculations to chemical accuracy

    Science.gov (United States)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.

    1991-01-01

    The accuracy of current molecular-structure calculations is illustrated with examples of quantum mechanical solutions for chemical problems. Two approaches are considered: (1) the coupled-cluster singles and doubles (CCSD) with a perturbational estimate of the contribution of connected triple excitations, or CCDS(T); and (2) the multireference configuration-interaction (MRCI) approach to the correlation problem. The MRCI approach gains greater applicability by means of size-extensive modifications such as the averaged-coupled pair functional approach. The examples of solutions to chemical problems include those for C-H bond energies, the vibrational frequencies of O3, identifying the ground state of Al2 and Si2, and the Lewis-Rayleigh afterglow and the Hermann IR system of N2. Accurate molecular-wave functions can be derived from a combination of basis-set saturation studies and full configuration-interaction calculations.

  9. Mechanical and Chemical Signaling in Angiogenesis

    CERN Document Server

    2013-01-01

    This volume of Studies in Mechanobiology, Tissue Engineering and Biomaterials describes the most recent advances in angiogenesis research at all biological length scales: molecular, cellular and tissue, in both in vivo and in vitro settings.  Angiogenesis experts from diverse fields including engineering, cell and developmental biology, and chemistry have contributed chapters which focus on the mechanical and chemical signals which affect and promote blood vessel growth. Specific emphasis is given to novel methodologies and biomaterials that have been developed and applied to angiogenesis research. 

  10. Reaction Mechanism Generator: Automatic construction of chemical kinetic mechanisms

    Science.gov (United States)

    Gao, Connie W.; Allen, Joshua W.; Green, William H.; West, Richard H.

    2016-06-01

    Reaction Mechanism Generator (RMG) constructs kinetic models composed of elementary chemical reaction steps using a general understanding of how molecules react. Species thermochemistry is estimated through Benson group additivity and reaction rate coefficients are estimated using a database of known rate rules and reaction templates. At its core, RMG relies on two fundamental data structures: graphs and trees. Graphs are used to represent chemical structures, and trees are used to represent thermodynamic and kinetic data. Models are generated using a rate-based algorithm which excludes species from the model based on reaction fluxes. RMG can generate reaction mechanisms for species involving carbon, hydrogen, oxygen, sulfur, and nitrogen. It also has capabilities for estimating transport and solvation properties, and it automatically computes pressure-dependent rate coefficients and identifies chemically-activated reaction paths. RMG is an object-oriented program written in Python, which provides a stable, robust programming architecture for developing an extensible and modular code base with a large suite of unit tests. Computationally intensive functions are cythonized for speed improvements.

  11. Reduced Chemical Kinetic Mechanisms for JP-8 Combustion

    National Research Council Canada - National Science Library

    Montgomery, Christopher J; Cannon, S. M; Mawid, M. A; Sekar, B

    2002-01-01

    Using CARM (Computer Aided Reduction Method), a computer program that automates the mechanism reduction process, six different reduced chemical kinetic mechanisms for JP-8 combustion have been generated...

  12. Thermodynamic chemical energy transfer mechanisms of non-equilibrium, quasi-equilibrium, and equilibrium chemical reactions

    International Nuclear Information System (INIS)

    Roh, Heui-Seol

    2015-01-01

    Chemical energy transfer mechanisms at finite temperature are explored by a chemical energy transfer theory which is capable of investigating various chemical mechanisms of non-equilibrium, quasi-equilibrium, and equilibrium. Gibbs energy fluxes are obtained as a function of chemical potential, time, and displacement. Diffusion, convection, internal convection, and internal equilibrium chemical energy fluxes are demonstrated. The theory reveals that there are chemical energy flux gaps and broken discrete symmetries at the activation chemical potential, time, and displacement. The statistical, thermodynamic theory is the unification of diffusion and internal convection chemical reactions which reduces to the non-equilibrium generalization beyond the quasi-equilibrium theories of migration and diffusion processes. The relationship between kinetic theories of chemical and electrochemical reactions is also explored. The theory is applied to explore non-equilibrium chemical reactions as an illustration. Three variable separation constants indicate particle number constants and play key roles in describing the distinct chemical reaction mechanisms. The kinetics of chemical energy transfer accounts for the four control mechanisms of chemical reactions such as activation, concentration, transition, and film chemical reactions. - Highlights: • Chemical energy transfer theory is proposed for non-, quasi-, and equilibrium. • Gibbs energy fluxes are expressed by chemical potential, time, and displacement. • Relationship between chemical and electrochemical reactions is discussed. • Theory is applied to explore nonequilibrium energy transfer in chemical reactions. • Kinetics of non-equilibrium chemical reactions shows the four control mechanisms

  13. Chemical Mechanism Solvers in Air Quality Models

    Directory of Open Access Journals (Sweden)

    John C. Linford

    2011-09-01

    Full Text Available The solution of chemical kinetics is one of the most computationally intensivetasks in atmospheric chemical transport simulations. Due to the stiff nature of the system,implicit time stepping algorithms which repeatedly solve linear systems of equations arenecessary. This paper reviews the issues and challenges associated with the construction ofefficient chemical solvers, discusses several families of algorithms, presents strategies forincreasing computational efficiency, and gives insight into implementing chemical solverson accelerated computer architectures.

  14. Learning the mechanisms of chemical disequilibria

    Energy Technology Data Exchange (ETDEWEB)

    Nicholson, Schuyler B.; Alaghemandi, Mohammad [Department of Chemistry, University of Massachusetts Boston, Boston, Massachusetts 02125 (United States); Green, Jason R., E-mail: jason.green@umb.edu [Department of Chemistry, University of Massachusetts Boston, Boston, Massachusetts 02125 (United States); Department of Physics, University of Massachusetts Boston, Boston, Massachusetts 02125 (United States); Center for Quantum and Nonequilibrium Systems, University of Massachusetts Boston, Boston, Massachusetts 02125 (United States)

    2016-08-28

    When at equilibrium, large-scale systems obey thermodynamics because they have microscopic configurations that are typical. “Typical” states are a fraction of those possible with the majority of the probability. A more precise definition of typical states underlies the transmission, coding, and compression of information. However, this definition does not apply to natural systems that are transiently away from equilibrium. Here, we introduce a variational measure of typicality and apply it to atomistic simulations of a model for hydrogen oxidation. While a gaseous mixture of hydrogen and oxygen combusts, reactant molecules transform through a variety of ephemeral species en route to the product, water. Out of the exponentially growing number of possible sequences of chemical species, we find that greater than 95% of the probability concentrates in less than 1% of the possible sequences. Overall, these results extend the notion of typicality across the nonequilibrium regime and suggest that typical sequences are a route to learning mechanisms from experimental measurements. They also open up the possibility of constructing ensembles for computing the macroscopic observables of systems out of equilibrium.

  15. Learning the mechanisms of chemical disequilibria

    International Nuclear Information System (INIS)

    Nicholson, Schuyler B.; Alaghemandi, Mohammad; Green, Jason R.

    2016-01-01

    When at equilibrium, large-scale systems obey thermodynamics because they have microscopic configurations that are typical. “Typical” states are a fraction of those possible with the majority of the probability. A more precise definition of typical states underlies the transmission, coding, and compression of information. However, this definition does not apply to natural systems that are transiently away from equilibrium. Here, we introduce a variational measure of typicality and apply it to atomistic simulations of a model for hydrogen oxidation. While a gaseous mixture of hydrogen and oxygen combusts, reactant molecules transform through a variety of ephemeral species en route to the product, water. Out of the exponentially growing number of possible sequences of chemical species, we find that greater than 95% of the probability concentrates in less than 1% of the possible sequences. Overall, these results extend the notion of typicality across the nonequilibrium regime and suggest that typical sequences are a route to learning mechanisms from experimental measurements. They also open up the possibility of constructing ensembles for computing the macroscopic observables of systems out of equilibrium.

  16. Physical Chemistry Chemical Kinetics and Reaction Mechanism

    CERN Document Server

    Trimm, Harold H

    2011-01-01

    Physical chemistry covers diverse topics, from biochemistry to materials properties to the development of quantum computers. Physical chemistry applies physics and math to problems that interest chemists, biologists, and engineers. Physical chemists use theoretical constructs and mathematical computations to understand chemical properties and describe the behavior of molecular and condensed matter. Their work involves manipulations of data as well as materials. Physical chemistry entails extensive work with sophisticated instrumentation and equipment as well as state-of-the-art computers. This

  17. Mechanical properties of moso bamboo treated with chemical agents

    Science.gov (United States)

    Benhua Fei; Zhijia Liu; Zehui Jiang; Zhiyong Cai

    2013-01-01

    Bamboo is a type of biomass material and has great potential as a bioenergy resource for the future in China. Surface chemical and thermal–mechanical behavior play an important role in the manufacturing process of bamboo composites and pellets. In this study, moso bamboo was treated by sodium hydrate solution and acetic acid solution. Surface chemical and dynamic...

  18. A model for chemically-induced mechanical loading on MEMS

    DEFF Research Database (Denmark)

    Amiot, Fabien

    2007-01-01

    The development of full displacement field measurements as an alternative to the optical lever technique to measure the mechanical response for microelectro-mechanical systems components in their environment calls for a modeling of chemically-induced mechanical fields (stress, strain, and displac......The development of full displacement field measurements as an alternative to the optical lever technique to measure the mechanical response for microelectro-mechanical systems components in their environment calls for a modeling of chemically-induced mechanical fields (stress, strain...... of the system free energy and its dependence on the surface amount. It is solved in the cantilever case thanks to an asymptotic analysis, and an approached closed-form solution is obtained for the interfacial stress field. Finally, some conclusions regarding the transducer efficiency of cantilevers are drawn...

  19. Chemical and mechanical efficiencies of molecular motors and implications for motor mechanisms

    International Nuclear Information System (INIS)

    Wang Hongyun

    2005-01-01

    Molecular motors operate in an environment dominated by viscous friction and thermal fluctuations. The chemical reaction in a motor may produce an active force at the reaction site to directly move the motor forward. Alternatively a molecular motor may generate a unidirectional motion by rectifying thermal fluctuations using free energy barriers established in the chemical reaction. The reaction cycle has many occupancy states, each having a different effect on the motor motion. The average effect of the chemical reaction on the motor motion can be characterized by the motor potential profile. The biggest advantage of studying the motor potential profile is that it can be reconstructed from the time series of motor positions measured in single-molecule experiments. In this paper, we use the motor potential profile to express the Stokes efficiency as the product of the chemical efficiency and the mechanical efficiency. We show that both the chemical and mechanical efficiencies are bounded by 100% and, thus, are properly defined efficiencies. We discuss implications of high efficiencies for motor mechanisms: a mechanical efficiency close to 100% implies that the motor potential profile is close to a constant slope; a chemical efficiency close to 100% implies that (i) the chemical transitions are not slower than the mechanical motion and (ii) the equilibrium constant of each chemical transition is close to one

  20. Lincosamides: Chemical structure, biosynthesis, mechanism of action, resistance, and applications

    Czech Academy of Sciences Publication Activity Database

    Spížek, Jaroslav; Řezanka, Tomáš

    2017-01-01

    Roč. 133, June 1 SI (2017), s. 20-28 ISSN 0006-2952 Institutional support: RVO:61388971 Keywords : Lincosamides * Chemical structure * Biosynthesis and mechanism of action Subject RIV: EE - Microbiology, Virology OBOR OECD: Microbiology Impact factor: 4.581, year: 2016

  1. Chemical Mechanical Polishing Optimization for 4H-SiC

    National Research Council Canada - National Science Library

    Neslen, Craig

    2000-01-01

    .... Preliminary chemical mechanical polishing (CMP) studies of 1 3/8" 4H-SiC wafers were performed in an attempt to identify the polishing parameter values that result in a maximum material removal rate and thus reduce substrate polishing time...

  2. Quantum chemical investigation of mechanisms of silane oxidation

    DEFF Research Database (Denmark)

    Mader, Mary M.; Norrby, Per-Ola

    2001-01-01

    Several mechanisms for the peroxide oxidation of organosilanes to alcohols are compared by quantum chemical calculations, including solvation with the PCM method. Without doubt, the reaction proceeds via anionic, pentacoordinate silicate species, but a profound difference is found between in vacuo...

  3. Surface qualities after chemical-mechanical polishing on thin films

    International Nuclear Information System (INIS)

    Fu, Wei-En; Lin, Tzeng-Yow; Chen, Meng-Ke; Chen, Chao-Chang A.

    2009-01-01

    Demands for substrate and film surface planarizations significantly increase as the feature sizes of Integrated Circuit (IC) components continue to shrink. Chemical Mechanical Polishing (CMP), incorporating chemical and mechanical interactions to planarize chemically modified surface layers, has been one of the major manufacturing processes to provide global and local surface planarizations in IC fabrications. Not only is the material removal rate a concern, the qualities of the CMP produced surface are critical as well, such as surface finish, defects and surface stresses. This paper is to examine the CMP produced surface roughness on tungsten or W thin films based on the CMP process conditions. The W thin films with thickness below 1000 nm on silicon wafer were chemical-mechanical polished at different down pressures and platen speeds to produce different surface roughness. The surface roughness measurements were performed by an atomic force microscope (DI D3100). Results show that the quality of surface finish (R a value) is determined by the combined effects of down pressures and platen speeds. An optimal polishing condition is, then, possible for selecting the down pressures and platen speeds.

  4. Technology of combined chemical-mechanical fabrication of durable coatings

    Science.gov (United States)

    Smolentsev, V. P.; Ivanov, V. V.; Portnykh, A. I.

    2018-03-01

    The article presents the scientific fundamentals of methodology for calculating the modes and structuring the technological processes of combined chemical-mechanical fabrication of durable coatings. It is shown that they are based on classical patterns, describing the processes of simultaneous chemical and mechanical impact. The paper demonstrates the possibility of structuring a technological process, taking into account the systematic approach to impact management and strengthening the reciprocal positive influence of each impact upon the combined process. The combined processes have been planned for fabricating the model types of chemical-mechanical coatings of durable products in machine construction. The planning methodology is underpinned by a scientific hypothesis of a single source of impact management through energy potential of process components themselves, or by means of external energy supply through mechanical impact. The control of it is fairly thoroughly studied in the case of pulsed external strikes of hard pellets, similar to processes of vibroimpact hardening, thoroughly studied and mastered in many scientific schools of Russia.

  5. Chemical dynamics in the gas phase: Time-dependent quantum mechanics of chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Gray, S.K. [Argonne National Laboratory, IL (United States)

    1993-12-01

    A major goal of this research is to obtain an understanding of the molecular reaction dynamics of three and four atom chemical reactions using numerically accurate quantum dynamics. This work involves: (i) the development and/or improvement of accurate quantum mechanical methods for the calculation and analysis of the properties of chemical reactions (e.g., rate constants and product distributions), and (ii) the determination of accurate dynamical results for selected chemical systems, which allow one to compare directly with experiment, determine the reliability of the underlying potential energy surfaces, and test the validity of approximate theories. This research emphasizes the use of recently developed time-dependent quantum mechanical methods, i.e. wave packet methods.

  6. Influence of oxygen on the chemical stage of radiobiological mechanism

    International Nuclear Information System (INIS)

    Barilla, Jiří; Lokajíček, Miloš V.; Pisaková, Hana; Simr, Pavel

    2016-01-01

    The simulation of the chemical stage of radiobiological mechanism may be very helpful in studying the radiobiological effect of ionizing radiation when the water radical clusters formed by the densely ionizing ends of primary or secondary charged particle may form DSBs damaging DNA molecules in living cells. It is possible to study not only the efficiency of individual radicals but also the influence of other species or radiomodifiers (mainly oxygen) being present in water medium during irradiation. The mathematical model based on Continuous Petri nets (proposed by us recently) will be described. It makes it possible to analyze two main processes running at the same time: chemical radical reactions and the diffusion of radical clusters formed during energy transfer. One may study the time change of radical concentrations due to the chemical reactions running during diffusion process. Some orientation results concerning the efficiency of individual radicals in DSB formation (in the case of Co60 radiation) will be presented; the influence of oxygen present in water medium during irradiation will be shown, too. - Highlights: • Creation of the mathematical model. • Realization of the model with the help of Continuous Petri nets. • Obtain the time dependence of changes in the concentration of radicals. • Influence of oxygen on the chemical stage of radiobiological mechanism.

  7. Mechanical and chemical spinodal instabilities in finite quantum systems

    International Nuclear Information System (INIS)

    Colonna, M.; Chomaz, Ph.; Ayik, S.

    2001-01-01

    Self consistent quantum approaches are used to study the instabilities of finite nuclear systems. The frequencies of multipole density fluctuations are determined as a function of dilution and temperature, for several isotopes. The spinodal region of the phase diagrams is determined and it appears reduced by finite size effects. The role of surface and volume instabilities is discussed. Important chemical effects are associated with mechanical disruption and may lead to isospin fractionation. (authors)

  8. Coupling between chemical degradation and mechanical behaviour of leached concrete

    International Nuclear Information System (INIS)

    Nguyen, V.H.

    2005-10-01

    This work is in the context of the long term behavior of concrete employed in radioactive waste disposal. The objective is to study the coupled chemo-mechanical modelling of concrete. In the first part of this contribution, experimental investigations are described where the effects of the calcium leaching process of concrete on its mechanical properties are highlighted. An accelerated method has been chosen to perform this leaching process by using an ammonium nitrate solution. In the second part, we present a coupled phenomenological chemo-mechanical model that represents the degradation of concrete materials. On one hand, the chemical behavior is described by the simplified calcium leaching approach of cement paste and mortar. Then a homogenization approach using the asymptotic development is presented to take into account the influence of the presence of aggregates in concrete. And on the other hand, the mechanical part of the modelling is given. Here continuum damage mechanics is used to describe the mechanical degradation of concrete. The growth of inelastic strains observed during the mechanical tests is describes by means of a plastic like model. The model is established on the basis of the thermodynamics of irreversible processes framework. The coupled nonlinear problem at hand is addressed within the context of the finite element method. Finally, numerical simulations are compared with the experimental results for validation. (author)

  9. Mechanical and chemical recycling of solid plastic waste.

    Science.gov (United States)

    Ragaert, Kim; Delva, Laurens; Van Geem, Kevin

    2017-11-01

    This review presents a comprehensive description of the current pathways for recycling of polymers, via both mechanical and chemical recycling. The principles of these recycling pathways are framed against current-day industrial reality, by discussing predominant industrial technologies, design strategies and recycling examples of specific waste streams. Starting with an overview on types of solid plastic waste (SPW) and their origins, the manuscript continues with a discussion on the different valorisation options for SPW. The section on mechanical recycling contains an overview of current sorting technologies, specific challenges for mechanical recycling such as thermo-mechanical or lifetime degradation and the immiscibility of polymer blends. It also includes some industrial examples such as polyethylene terephthalate (PET) recycling, and SPW from post-consumer packaging, end-of-life vehicles or electr(on)ic devices. A separate section is dedicated to the relationship between design and recycling, emphasizing the role of concepts such as Design from Recycling. The section on chemical recycling collects a state-of-the-art on techniques such as chemolysis, pyrolysis, fluid catalytic cracking, hydrogen techniques and gasification. Additionally, this review discusses the main challenges (and some potential remedies) to these recycling strategies and ground them in the relevant polymer science, thus providing an academic angle as well as an applied one. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Temperature buffer test. Hydro-mechanical and chemical/ mineralogical characterizations

    International Nuclear Information System (INIS)

    Aakesson, Mattias; Olsson, Siv; Dueck, Ann; Nilsson, Ulf; Karnland, Ola; Kiviranta, Leena; Kumpulainen, Sirpa; Linden, Johan

    2012-01-01

    The Temperature Buffer Test (TBT) is a joint project between SKB/ANDRA and supported by ENRESA (modeling) and DBE (instrumentation), which aims at improving the understanding and to model the thermo-hydro-mechanical behavior of buffers made of swelling clay submitted to high temperatures (over 100 deg C) during the water saturation process. The test has been carried out in a KBS-3 deposition hole at Aspo HRL. It was installed during the spring of 2003. Two steel heaters (3 m long, 0.6 m diameter) and two buffer arrangements have been investigated: the lower heater was surrounded by rings of compacted Wyoming bentonite only, whereas the upper heater was surrounded by a composite barrier, with a sand shield between the heater and the bentonite. The test was dismantled and sampled during the winter of 2009/2010. This report presents the hydro-mechanical and chemical/mineralogical characterization program which was launched subsequent to the dismantling operation. The main goal has been to investigate if any significant differences could be observed between material from the field experiment and the reference material. The field samples were mainly taken from Ring 4 (located at the mid-section around the lower heater), in which the temperature in the innermost part reached 155 deg C. The following hydro-mechanical properties have been determined for the material (test technique within brackets): hydraulic conductivity (swelling pressure device), swelling pressure (swelling pressure device), unconfined compression strength (mechanical press), shear strength (triaxial cell) and retention properties (jar method). The following chemical/mineralogical properties (methods within brackets) were determined: anion analysis of water leachates (IC), chemical composition (ICP/AES+MS, EGA), cation exchange capacity (CEC, Cu-trien method) and exchangeable cations (exchange with NH4, ICPAES), mineralogical composition (XRD and FTIR), element distribution and microstructure (SEM and

  11. MULTIDISCIPLINARY PROJECTS FOR SECOND YEAR CHEMICAL AND MECHANICAL ENGINEERING STUDENTS

    Directory of Open Access Journals (Sweden)

    MARWAN M. SHAMEL

    2013-04-01

    Full Text Available In the second semester of the second year of a Mechanical Engineering course, students are supposed to take a Module Outside the Main Discipline (MOMD. This module is chosen to be “Product Design Exercise” a module that is offered to Chemical Engineering students at the same stage. The aim was to expose students from both disciplines to an environment in which they are encouraged to interact with and engage team members with a relatively different background. The students were divided into eight groups all comprised of Chemical and Mechanical Engineering students, and they were offered different open-ended projects that were selected to exploit the knowledge developed by the students thus far and they were slightly skewed towards Chemical Engineering. The students demonstrated a high level of cooperation and motivation throughout the period of the project. Effective communication and closing of knowledge gaps were prevalent. At the end of the project period, students produced a journal paper in lieu of the project report.

  12. Mechanisms of fuel-cladding chemical interaction: US interpretation

    International Nuclear Information System (INIS)

    Adamson, M.G.

    1977-01-01

    Proposed mechanisms of fuel-cladding chemical interaction (FCCI) in LMFBR fuel pins are reviewed and examined in terms of in-pile and out-of-pile data. From this examination several factors are identified which may govern the occurrence of localized deep intergranular penetrations of Type-316SS cladding. Using a plausible mechanistic hypothesis for FCCI, first steps have been taken towards developing a quantitative, physically-meaningful, mathematical method of predicting cladding wastage in operating fuel pins. Both kinetic and thermodynamic aspects of FCCI are considered in the development of this prediction method, together with a fuel chemistry model that describes the evolution of thermochemical conditions at the fuel-cladding gap. On the basis of results from recent fuel pin and laboratory tests a thermal transport mechanism has been proposed to explain the thermal gradient-induced migration of Fe, Cr, and Ni from cladding into the fuel. This mechanism involves chemical transport of the metallic cladding components (as tellurides) in liquid Cs-Te. (author)

  13. Mechanisms of fuel-cladding chemical interaction: US interpretation

    Energy Technology Data Exchange (ETDEWEB)

    Adamson, M G [General Electric Company, Vallecitos Nuclear Center, Pleasanton, CA (United States)

    1977-04-01

    Proposed mechanisms of fuel-cladding chemical interaction (FCCI) in LMFBR fuel pins are reviewed and examined in terms of in-pile and out-of-pile data. From this examination several factors are identified which may govern the occurrence of localized deep intergranular penetrations of Type-316SS cladding. Using a plausible mechanistic hypothesis for FCCI, first steps have been taken towards developing a quantitative, physically-meaningful, mathematical method of predicting cladding wastage in operating fuel pins. Both kinetic and thermodynamic aspects of FCCI are considered in the development of this prediction method, together with a fuel chemistry model that describes the evolution of thermochemical conditions at the fuel-cladding gap. On the basis of results from recent fuel pin and laboratory tests a thermal transport mechanism has been proposed to explain the thermal gradient-induced migration of Fe, Cr, and Ni from cladding into the fuel. This mechanism involves chemical transport of the metallic cladding components (as tellurides) in liquid Cs-Te. (author)

  14. Computational thermal, chemical, fluid, and solid mechanics for geosystems management.

    Energy Technology Data Exchange (ETDEWEB)

    Davison, Scott; Alger, Nicholas; Turner, Daniel Zack; Subia, Samuel Ramirez; Carnes, Brian; Martinez, Mario J.; Notz, Patrick K.; Klise, Katherine A.; Stone, Charles Michael; Field, Richard V., Jr.; Newell, Pania; Jove-Colon, Carlos F.; Red-Horse, John Robert; Bishop, Joseph E.; Dewers, Thomas A.; Hopkins, Polly L.; Mesh, Mikhail; Bean, James E.; Moffat, Harry K.; Yoon, Hongkyu

    2011-09-01

    This document summarizes research performed under the SNL LDRD entitled - Computational Mechanics for Geosystems Management to Support the Energy and Natural Resources Mission. The main accomplishment was development of a foundational SNL capability for computational thermal, chemical, fluid, and solid mechanics analysis of geosystems. The code was developed within the SNL Sierra software system. This report summarizes the capabilities of the simulation code and the supporting research and development conducted under this LDRD. The main goal of this project was the development of a foundational capability for coupled thermal, hydrological, mechanical, chemical (THMC) simulation of heterogeneous geosystems utilizing massively parallel processing. To solve these complex issues, this project integrated research in numerical mathematics and algorithms for chemically reactive multiphase systems with computer science research in adaptive coupled solution control and framework architecture. This report summarizes and demonstrates the capabilities that were developed together with the supporting research underlying the models. Key accomplishments are: (1) General capability for modeling nonisothermal, multiphase, multicomponent flow in heterogeneous porous geologic materials; (2) General capability to model multiphase reactive transport of species in heterogeneous porous media; (3) Constitutive models for describing real, general geomaterials under multiphase conditions utilizing laboratory data; (4) General capability to couple nonisothermal reactive flow with geomechanics (THMC); (5) Phase behavior thermodynamics for the CO2-H2O-NaCl system. General implementation enables modeling of other fluid mixtures. Adaptive look-up tables enable thermodynamic capability to other simulators; (6) Capability for statistical modeling of heterogeneity in geologic materials; and (7) Simulator utilizes unstructured grids on parallel processing computers.

  15. Chemical and mechanical decontamination processes to minimize secondary waste decommissioning

    International Nuclear Information System (INIS)

    Enda, M.; Ichikawa, N.; Yaita, Y.; Kanasaki, T.; Sakai, H.

    2008-01-01

    In the decommissioning of commercial nuclear reactors in Japan, prior to the dismantling of the nuclear power plants, there are plans to use chemical techniques to decontaminate reactor pressure vessels (RPVs), internal parts, primary loop recirculation systems (PLRs), reactor water clean up systems (RWCUs), etc., so as to minimize radiation sources in the materials to be disposed of. After dismantling the nuclear power plants, chemical and mechanical decontamination techniques will then be used to reduce the amounts of radioactive metallic waste. Toshiba Corporation has developed pre-dismantling and post-dismantling decontamination systems. In order to minimize the amounts of secondary waste, the T-OZON process was chosen for decontamination prior to the dismantling of nuclear power plants. Dismantling a nuclear power plant results in large amounts of metallic waste requiring decontamination; for example, about 20,000 tons of such waste is expected to result from the dismantling of a 110 MWe Boiling Water Reactor (BWR). Various decontamination methods have been used on metallic wastes in preparation for disposal in consideration of the complexity of the shapes of the parts and the type of material. The materials in such nuclear power plants are primarily stainless steel and carbon steel. For stainless steel parts having simple shapes, such as plates and pipes, major sources of radioactivity can be removed from the surface of the parts by bipolar electrolysis (electrolyte: H 2 SO 4 ). For stainless steel parts having complicated shapes, such as valves and pumps, major sources of radioactivity can be removed from the surfaces by redox chemical decontamination treatments (chemical agent: Ce(IV)). For carbon steel parts having simple shapes, decontamination by blasting with zirconia grit is effective in removing major sources of radioactivity at the surface, whereas for carbon steel parts having complicated shapes, major sources of radioactivity can be removed from

  16. [Formation mechanism and chemical safety of nonintentional chemical substances present in chlorinated drinking water and wastewater].

    Science.gov (United States)

    Onodera, Sukeo

    2010-09-01

    This paper reviews the formation mechanism and chemical safety of nonintentional chemical substances (NICS) present in chlorine-treated water containing organic contaminants. Undesirable compounds, i.e., NICS, may be formed under certain conditions when chlorine reacts with organic matter. The rate and extent of chlorine consumption with organics are strongly dependent on their chemical structures, particularly whether double bonds or sulfur and nitrogen atoms occur in the molecules. Organothiophosphorus pesticides (P=S type) are easily oxidized to their phosphorus compounds (P=O type) in chlorinated water containing HOCl as little as 0.5 mg/l, resulting in an increase in cholinesterase-inhibitory activity. Chlorination of phenols in water also produces a series of highly chlorinated compounds, including chlorophenols, chloroquinones, chlorinated carboxylic acids, and polychlorinated phenoxyphenols (PCPPs). In some of these chloroquinones, 2,6-dichloroalkylsemiquinones exhibit a strong mutagenic response as do positive controls used in the Ames test. 2-phenoxyphenols in these PCPPs are particularly interesting, as they are present in the chlorine-treated phenol solution and they are also precursors (predioxins) of the highly toxic chlorinated dioxins. Polynuclear aromatic hydrocarbons (PAHs) were found to undergo chemical changes due to hypochlorite reactions to give chloro-substituted PAHs, oxygenated (quinones) and hydroxylated (phenols) compounds, but they exhibit a lower mutagenic response. In addition, field work was performed in river water and drinking water to obtain information on chemical distribution and their safety, and the results are compared with those obtained in the model chlorination experiments.

  17. Characterization of chemical interactions during chemical mechanical polishing (CMP) of copper

    Science.gov (United States)

    Lee, Seung-Mahn

    2003-10-01

    Chemical mechanical polishing (CMP) has received much attention as an unique technique to provide a wafer level planarization in semiconductor manufacturing. However, despite the extensive use of CMP, it still remains one of the least understood areas in semiconductor processing. The lack of the fundamental understanding is a significant barrier to further advancements in CMP technology. One critical aspect of metal CMP is the formation of a thin surface layer on the metal surface. The formation and removal of this layer controls all the aspects of the CMP process, including removal rate, surface finish, etc. In this dissertation, we focus on the characterization of the formation and removal of the thin surface layer on the copper surface. The formation dynamics was investigated using static and dynamic electrochemical techniques, including potentiodynamic scans and chronoamperometry. The results were validated using XPS measurements. The mechanical properties of the surface layer were investigated using nanoindentation measurements. The electrochemical investigation showed that the thickness of the surface layer is controlled by the chemicals such as an oxidizer (hydrogen peroxide), a corrosion inhibitor (benzotriazole), a complexing agent (citric acid), and their concentrations. The dynamic electrochemical measurements indicated that the initial layer formation kinetics is unaffected by the corrosion inhibitors. The passivation due to the corrosion inhibitor becomes important only on large time scales (>200 millisecond). The porosity and the density of the chemically modified surface layer can be affected by additives of other chemicals such as citric acid. An optimum density of the surface layer is required for high polishing rate while at the same time maintaining a high degree of surface finish. Nanoindentation measurements indicated that the mechanical properties of the surface layer are strongly dependent on the chemical additives in the slurry. The CMP

  18. Development of a hybrid chemical/mechanical heat pump

    Science.gov (United States)

    Grzyll, Lawrence R.; Silvestri, John J.; Scaringe, Robert P.

    1991-01-01

    The authors present the current development status of a hybrid chemical/mechanical heat pump for low-lift applications. The heat pump provides electronics cooling by evaporating a pure refrigerant from an absorbent/refrigerant mixture in a generator/cold plate. The current development focused on evaluation of absorbent/refrigerant pairs, corrosion testing, pump and compressor design, and electronic cold plate design. Two cycle configurations were considered. The first configuration utilized a standard mechanical compressor and pump. The second cycle configuration investigated pumps and compressors with non-moving parts. An innovative generator/cold plate design is also presented. The development to date shows that this cycle has about the same performance as standard vapor compression heat pumps with standard refrigerants but may have some performance and reliability advantages over vapor compression heat pumps.

  19. Destructive electronics from electrochemical-mechanically triggered chemical dissolution

    International Nuclear Information System (INIS)

    Sim, Kyoseung; Wang, Xu; Yu, Cunjiang; Li, Yuhang; Linghu, Changhong; Song, Jizhou; Gao, Yang

    2017-01-01

    The considerable need to enhance data and hardware security suggest one possible future for electronics where it is possible to destroy them and even make them disappear physically. This paper reports a type of destructive electronics which features fast transience from chemical dissolution on-demand triggered in an electrochemical-mechanical manner. The detailed materials, mechanics, and device construction of the destructive electronics are presented. Experiment and analysis of the triggered releasing and transience study of electronic materials, resistors and metal-oxide-semiconductor field effect transistors illustrate the key aspects of the destructive electronics. The reported destructive electronics is useful in a wide range of areas from security and defense, to medical applications (paper)

  20. Exploring chemical reaction mechanisms through harmonic Fourier beads path optimization.

    Science.gov (United States)

    Khavrutskii, Ilja V; Smith, Jason B; Wallqvist, Anders

    2013-10-28

    Here, we apply the harmonic Fourier beads (HFB) path optimization method to study chemical reactions involving covalent bond breaking and forming on quantum mechanical (QM) and hybrid QM∕molecular mechanical (QM∕MM) potential energy surfaces. To improve efficiency of the path optimization on such computationally demanding potentials, we combined HFB with conjugate gradient (CG) optimization. The combined CG-HFB method was used to study two biologically relevant reactions, namely, L- to D-alanine amino acid inversion and alcohol acylation by amides. The optimized paths revealed several unexpected reaction steps in the gas phase. For example, on the B3LYP∕6-31G(d,p) potential, we found that alanine inversion proceeded via previously unknown intermediates, 2-iminopropane-1,1-diol and 3-amino-3-methyloxiran-2-ol. The CG-HFB method accurately located transition states, aiding in the interpretation of complex reaction mechanisms. Thus, on the B3LYP∕6-31G(d,p) potential, the gas phase activation barriers for the inversion and acylation reactions were 50.5 and 39.9 kcal∕mol, respectively. These barriers determine the spontaneous loss of amino acid chirality and cleavage of peptide bonds in proteins. We conclude that the combined CG-HFB method further advances QM and QM∕MM studies of reaction mechanisms.

  1. Mechanistic, kinetic, and processing aspects of tungsten chemical mechanical polishing

    Science.gov (United States)

    Stein, David

    This dissertation presents an investigation into tungsten chemical mechanical polishing (CMP). CMP is the industrially predominant unit operation that removes excess tungsten after non-selective chemical vapor deposition (CVD) during sub-micron integrated circuit (IC) manufacture. This work explores the CMP process from process engineering and fundamental mechanistic perspectives. The process engineering study optimized an existing CMP process to address issues of polish pad and wafer carrier life. Polish rates, post-CMP metrology of patterned wafers, electrical test data, and synergy with a thermal endpoint technique were used to determine the optimal process. The oxidation rate of tungsten during CMP is significantly lower than the removal rate under identical conditions. Tungsten polished without inhibition during cathodic potentiostatic control. Hertzian indenter model calculations preclude colloids of the size used in tungsten CMP slurries from indenting the tungsten surface. AFM surface topography maps and TEM images of post-CMP tungsten do not show evidence of plow marks or intergranular fracture. Polish rate is dependent on potassium iodate concentration; process temperature is not. The colloid species significantly affects the polish rate and process temperature. Process temperature is not a predictor of polish rate. A process energy balance indicates that the process temperature is predominantly due to shaft work, and that any heat of reaction evolved during the CMP process is negligible. Friction and adhesion between alumina and tungsten were studied using modified AFM techniques. Friction was constant with potassium iodate concentration, but varied with applied pressure. This corroborates the results from the energy balance. Adhesion between the alumina and the tungsten was proportional to the potassium iodate concentration. A heuristic mechanism, which captures the relationship between polish rate, pressure, velocity, and slurry chemistry, is presented

  2. Chemical Modification Effect on the Mechanical Properties of Coir Fiber

    Directory of Open Access Journals (Sweden)

    Samia Sultana Mir

    2012-04-01

    Full Text Available Natural fiber has a vital role as a reinforcing agent due to its renewable, low cost, biodegradable, less abrasive and eco-friendly nature. Whereas synthetic fibers like glass, boron, carbon, metallic, ceramic and inorganic fibers are expensive and not eco-friendly. Coir is one of the natural fibers easily available in Bangladesh and cheap. It is derived from the husk of the coconut (Cocos nucifera. Coir has one of the highest concentrations of lignin, which makes it stronger. In recent years, wide range of research has been carried out on fiber reinforced polymer composites [4-13].The aim of the present research is to characterize brown single coir fiber for manufacturing polymer composites reinforced with characterized fibers. Adhesion between the fiber and polymer is one of factors affecting the strength of manufactured composites. In order to increase the adhesion, the coir fiber was chemically treated separately in single stage (with Cr2(SO43•12(H2O and double stages (with CrSO4 and NaHCO3. Both the raw and treated fibers were characterized by tensile testing, Fourier transform infrared (FTIR spectroscopic analysis, scanning electron microscopic analysis. The result showed that the Young’s modulus increased, while tensile strength and strain to failure decreased with increase in span length. Tensile properties of chemically treated coir fiber was found higher than raw coir fiber, while the double stage treated coir fiber had better mechanical properties compared to the single stage treated coir fiber. Scanning electron micrographs showed rougher surface in case of the raw coir fiber. The surface was found clean and smooth in case of the treated coir fiber. Thus the performance of coir fiber composites in industrial application can be improved by chemical treatment.

  3. Development of clean chemical mechanical polishing systems; Clean CMP system

    Energy Technology Data Exchange (ETDEWEB)

    Tsujimura, M.; Hosokawa, M. [Ebara Corp., Tokyo (Japan)

    1998-10-20

    Described herein are clean chemical mechanical polishing (CMP) systems developed by Ebara. A CMP system needs advanced peripheral techniques, in addition to those for grinding adopted by the conventional system, in order to fully exhibit its inherent functions. An integrated design concept is essential for the CMP steps, including slurry supplying, polishing, washing, process controlling and waste fluid treatment. The Ebara has adopted a standard concept `Clean CMP, dry-in and dry-out of wafers,` and provided world`s highest grades of techniques for inter-layer insulating film, shallow trench isolation, plug and wiring. The head for the polishing module is specially designed by FEM, to improve homogeneity of wafers from the center to edges. The dresser is also specially designed, to improve pad surface topolody after dressing. A slurry dipsersing method is developed to reduce slurry consumption. Various washing modules, designed to have the same external shape, can be allocated to various functions. 10 figs.

  4. Chemical degradation mechanisms of membranes for alkaline membrane fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Choe, Yoong-Kee [National Institute of Advanced Industrial Science and Technology, Umezono 1-1-1, Tsukuba (Japan); Henson, Neil J.; Kim, Yu Seung [Los Alamos National Laboratory, Los Alamos, NM (United States)

    2015-12-31

    Chemical degradation mechanisms of membranes for alkaline membrane fuel cells have been investigated using density functional theory (DFT). We have elucidated that the aryl-ether moiety of membranes is one of the weakest site against attack of hydroxide ions. The results of DFT calculations for hydroxide initiated aryl-ether cleavage indicated that the aryl-ether cleavage occurred prior to degradation of cationic functional group. Such a weak nature of the aryl-ether group arises from the electron deficiency of the aryl group as well as the low bond dissociation energy. The DFT results suggests that removal of the aryl-ether group in the membrane should enhance the stability of membranes under alkaline conditions. In fact, an ether fee poly(phenylene) membrane exhibits excellent stability against the attack from hydroxide ions.

  5. Response of mechanical properties of glasses to their chemical, thermal and mechanical histories

    DEFF Research Database (Denmark)

    Yue, Yuanzheng

    , surface, thermal history or excess entropy of the final glass state. Here I review recent progresses in understanding of the responses of mechanical properties of oxide glasses to the compositional variation, thermal history and mechanical deformation. The tensile strength, elastic modulus and hardness...... of glass fibers are dependent on the thermal history (measured as fictive temperature), tension, chemical composition and redox state. However, the fictive temperature affects the hardness of bulk glass in a complicated manner, i.e., the effect does not exhibit a clear regularity in the range...... and micro-cracks occurring during indentation of a glass is discussed briefly. Finally I describe the future perspectives and challenges in understanding responses of mechanical properties of oxide glasses to compositional variation, thermal history and mechanical deformation....

  6. Mechanism of Interaction between Ionizing Radiation and Chemicals

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jin Kyu; Lee, B H; Shin, H S [and others

    2008-03-15

    This research project has been carried out jointly with INP (Poland) to develop technologies for 'Mechanism of Interaction between ionizing radiation and chemicals{sup .} Several biological end-points were assessed in experimental organisms such as higher plants, rats, cell lines and yeast cells to establish proper bioassay techniques. The Tradescantia somatic cell mutation assay was carried out, and immunohistochemistry and hormone assays were done in Fisher 344 rats and cell lines to analyse the combined effect of ionizing radiation with mercury chloride. Using the common regularities of combined actions of two factors, a theoretical model was established, and applied to the thermo radiation action and synergism between two chemicals, as well. The model approach made it possible to predict the condition under which the maximum synergism could be attained. The research results were published in high standard journals and presented in the scientific conferences to verify KAERI's current technology level. The experience of collaboration can be used as a fundamental tool for multinational collaboration, and make the role of improving relationship between Korea and Poland.

  7. Mechanism of Interaction between Ionizing Radiation and Chemicals

    International Nuclear Information System (INIS)

    Kim, Jin Kyu; Lee, B. H.; Shin, H. S.

    2008-03-01

    This research project has been carried out jointly with INP (Poland) to develop technologies for 'Mechanism of Interaction between ionizing radiation and chemicals . Several biological end-points were assessed in experimental organisms such as higher plants, rats, cell lines and yeast cells to establish proper bioassay techniques. The Tradescantia somatic cell mutation assay was carried out, and immunohistochemistry and hormone assays were done in Fisher 344 rats and cell lines to analyse the combined effect of ionizing radiation with mercury chloride. Using the common regularities of combined actions of two factors, a theoretical model was established, and applied to the thermo radiation action and synergism between two chemicals, as well. The model approach made it possible to predict the condition under which the maximum synergism could be attained. The research results were published in high standard journals and presented in the scientific conferences to verify KAERI's current technology level. The experience of collaboration can be used as a fundamental tool for multinational collaboration, and make the role of improving relationship between Korea and Poland

  8. Mechanism of Interaction between Ionizing Radiation and Chemicals

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jin Kyu; Lee, B. H.; Shin, H. S. (and others)

    2008-03-15

    This research project has been carried out jointly with INP (Poland) to develop technologies for 'Mechanism of Interaction between ionizing radiation and chemicals{sup .} Several biological end-points were assessed in experimental organisms such as higher plants, rats, cell lines and yeast cells to establish proper bioassay techniques. The Tradescantia somatic cell mutation assay was carried out, and immunohistochemistry and hormone assays were done in Fisher 344 rats and cell lines to analyse the combined effect of ionizing radiation with mercury chloride. Using the common regularities of combined actions of two factors, a theoretical model was established, and applied to the thermo radiation action and synergism between two chemicals, as well. The model approach made it possible to predict the condition under which the maximum synergism could be attained. The research results were published in high standard journals and presented in the scientific conferences to verify KAERI's current technology level. The experience of collaboration can be used as a fundamental tool for multinational collaboration, and make the role of improving relationship between Korea and Poland.

  9. Temperature buffer test. Hydro-mechanical and chemical/ mineralogical characterizations

    Energy Technology Data Exchange (ETDEWEB)

    Aakesson, Mattias; Olsson, Siv; Dueck, Ann; Nilsson, Ulf; Karnland, Ola [Clay Technology AB, Lund (Sweden); Kiviranta, Leena; Kumpulainen, Sirpa [BandTech Oy, Helsinki (Finland); Linden, Johan [Aabo Akademi, Aabo (Finland)

    2012-01-15

    The Temperature Buffer Test (TBT) is a joint project between SKB/ANDRA and supported by ENRESA (modeling) and DBE (instrumentation), which aims at improving the understanding and to model the thermo-hydro-mechanical behavior of buffers made of swelling clay submitted to high temperatures (over 100 deg C) during the water saturation process. The test has been carried out in a KBS-3 deposition hole at Aspo HRL. It was installed during the spring of 2003. Two steel heaters (3 m long, 0.6 m diameter) and two buffer arrangements have been investigated: the lower heater was surrounded by rings of compacted Wyoming bentonite only, whereas the upper heater was surrounded by a composite barrier, with a sand shield between the heater and the bentonite. The test was dismantled and sampled during the winter of 2009/2010. This report presents the hydro-mechanical and chemical/mineralogical characterization program which was launched subsequent to the dismantling operation. The main goal has been to investigate if any significant differences could be observed between material from the field experiment and the reference material. The field samples were mainly taken from Ring 4 (located at the mid-section around the lower heater), in which the temperature in the innermost part reached 155 deg C. The following hydro-mechanical properties have been determined for the material (test technique within brackets): hydraulic conductivity (swelling pressure device), swelling pressure (swelling pressure device), unconfined compression strength (mechanical press), shear strength (triaxial cell) and retention properties (jar method). The following chemical/mineralogical properties (methods within brackets) were determined: anion analysis of water leachates (IC), chemical composition (ICP/AES+MS, EGA), cation exchange capacity (CEC, Cu-trien method) and exchangeable cations (exchange with NH4, ICPAES), mineralogical composition (XRD and FTIR), element distribution and microstructure (SEM and

  10. Physical-chemical mechanisms of pattern formation during gastrulation

    Science.gov (United States)

    Bozorgui, Behnaz; Kolomeisky, Anatoly B.; Teimouri, Hamid

    2018-03-01

    Gastrulation is a fundamental phase during the biological development of most animals when a single layer of identical embryo cells is transformed into a three-layer structure, from which the organs start to develop. Despite a remarkable progress in quantifying the gastrulation processes, molecular mechanisms of these processes remain not well understood. Here we theoretically investigate early spatial patterning in a geometrically confined colony of embryonic stem cells. Using a reaction-diffusion model, a role of Bone-Morphogenetic Protein 4 (BMP4) signaling pathway in gastrulation is specifically analyzed. Our results show that for slow diffusion rates of BMP4 molecules, a new length scale appears, which is independent of the size of the system. This length scale separates the central region of the colony with uniform low concentrations of BMP molecules from the region near the colony edge where the concentration of signaling molecules is elevated. The roles of different components of the signaling pathway are also explained. Theoretical results are consistent with recent in vitro experiments, providing microscopic explanations for some features of early embryonic spatial patterning. Physical-chemical mechanisms of these processes are discussed.

  11. Spontaneous grafting of diazonium salts: chemical mechanism on metallic surfaces.

    Science.gov (United States)

    Mesnage, Alice; Lefèvre, Xavier; Jégou, Pascale; Deniau, Guy; Palacin, Serge

    2012-08-14

    The spontaneous reaction of diazonium salts on various substrates has been widely employed since it consists of a simple immersion of the substrate in the diazonium salt solution. As electrochemical processes involving the same diazonium salts, the spontaneous grafting is assumed to give covalently poly(phenylene)-like bonded films. Resistance to solvents and to ultrasonication is commonly accepted as indirect proof of the existence of a covalent bond. However, the most relevant attempts to demonstrate a metal-C interface bond have been obtained by an XPS investigation of spontaneously grafted films on copper. Similarly, our experiments give evidence of such a bond in spontaneously grafted films on nickel substrates in acetonitrile. In the case of gold substrates, the formation of a spontaneous film was unexpected but reported in the literature in parallel to our observations. Even if no interfacial bond was observed, formation of the films was explained by grafting of aryl cations or radicals on the surface arising from dediazoniation, the film growing later by azo coupling, radical addition, or cationic addition on the grafted phenyl layer. Nevertheless, none of these mechanisms fits our experimental results showing the presence of an Au-N bond. In this work, we present a fine spectroscopic analysis of the coatings obtained on gold and nickel substrates that allow us to propose a chemical structure of such films, in particular, their interface with the substrates. After testing the most probable mechanisms, we have concluded in favor of the involvement of two complementary mechanisms which are the direct reaction of diazonium salts with the gold surface that accounts for the observed Au-N interfacial bonds as well as the formation of aryl cations able to graft on the substrate through Au-C linkages.

  12. Development and Validation of Chemical Kinetic Mechanism Reduction Scheme for Large-Scale Mechanisms

    DEFF Research Database (Denmark)

    Poon, Hiew Mun; Ng, Hoon Kiat; Gan, Suyin

    2014-01-01

    This work is an extension to a previously reported work on chemical kinetic mechanism reduction scheme for large-scale mechanisms. Here, Perfectly Stirred Reactor (PSR) was added as a criterion of data source for mechanism reduction instead of using only auto-ignition condition. As a result......) simulations were performed to study the spray combustion phenomena within a constant volume bomb. Both non-reacting and reacting conditions were applied in this study. Liquid and vapor penetration lengths were replicated for non-reacting diesel spray. For reacting diesel spray, both ignition delay and lift......-off length were simulated. The simulation results were then compared to the experimental data of Sandia National Laboratories and No. 2 Diesel Fuel (D2) was designated as the reference fuel. Both liquid and vapor penetrations for non-reacting condition were well-matched, while ignition delay was advanced...

  13. Chemical, mechanical and biological properties of contemporary composite surface sealers.

    Science.gov (United States)

    Anagnostou, Maria; Mountouris, George; Silikas, Nick; Kletsas, Dimitris; Eliades, George

    2015-12-01

    To evaluate the chemical, mechanical, and biological properties of modern composite surface sealers (CSS) having different compositions. The CSS products tested were Biscover LV (BC), Durafinish (DF), G-Coat Plus (GC), and Permaseal (PS). The tests performed were: (A): degree of conversion (DC%) by ATR-FTIR spectroscopy; (B): thickness of O2-inhibition layer by transmission optical microscopy; (C): surface hardness, 10 min after irradiation and following 1 week water storage, employing a Vickers indenter (VHN); (D): color (ΔE*) and gloss changes (ΔGU) after toothbrush abrasion, using L*a*b* colorimetry and glossimetry; (E): accelerated wear (GC,PS only) by an OHSU wear simulator plus 3D profilometric analysis, and (F): cytotoxicity testing of aqueous CSS eluents on human gingival fibroblast cultures employing the methyl-(3)H thymidine DNA labeling method. Statistical analyses included 1-way (A, B, ΔE*, ΔGU) and 2-way (C, F) ANOVAs, plus Tukey post hoc tests. Student's t-test was used to evaluate the results of the accelerated wear test (α=0.05 for all). The rankings of the statistical significant differences were: (A) PS (64.9)>DF,BC,GC (56.1-53.9) DC%; (B) DF,PS (12.3,9.8)>GC,BC (5.2,4.8) μm; (C): GC (37.6)>BC,DF (32.6,31.1)>PS (26.6) VHN (10 min/dry) and BC,DF (29.3,28.7)>GC(26.5)>PS(21.6) VHN (1w/water), with no significant material/storage condition interaction; (D): no differences were found among GC,DF,BC,PS (0.67-1.11) ΔE*, with all values within the visually acceptable range and PS,BC (32.8,29.4)>GC,DF (19.4,12.9) ΔGU; (E): no differences were found between GC and PS in volume loss (0.10,0.11 mm(3)), maximum (113.9,130.5 μm) and mean wear depths (30.3,27.5 μm); (F): at 1% v/v concentration, DF showed toxicity (23% vital cells vs 95-102% for others). However, at 5% v/v concentration DF (0%) and BC (9%) were the most toxic, whereas GC (58%) and PS (56%) showed moderate toxicity. Important chemical, mechanical, and biological properties exist among

  14. Performance of a hybrid chemical/mechanical heat pump

    Science.gov (United States)

    Silvestri, John J.; Scaringe, Robert P.; Grzyll, Lawrence R.

    1990-01-01

    The authors present the design and preliminary results of the performance of a hybrid chemical/mechanical, low-lift (20 C) heat pump. Studies have indicated that this heat pump has several advantages over the traditional single fluid vapor compression (reverse Rankine) heat pump. Included in these benefits are: 1) increased COPc due to the approximation of the cycle to the Lorenz cycle and due to the availability of the heat of solution, along with the heat of vaporization, to provide cooling; and 2) ease of variation in system cooling capacity by changing the fluid composition. The system performance is predicted for a variety of refrigerant-absorbent pairs. Cooling capacity is determined for systems operating with ammonia as the refrigerant and lithium nitrate and sodium thiocyanate as the absorbents and also with water as the refrigerant and magnesium chloride, potassium hydroxide, lithium bromide, sodium hydroxide, and sulfuric acid as the absorbents. Early indications have shown that the systems operating with water as the refrigerant operate at 2-4 times the capacity of the ammonia-refrigerant-based systems. Using existing working fluids in the proposed innovative design, a coefficient-of-performance improvement of 21 percent is possible when compared to the best vapor compression systems analyzed.

  15. Endocrine-disrupting chemicals: associated disorders and mechanisms of action.

    Science.gov (United States)

    De Coster, Sam; van Larebeke, Nicolas

    2012-01-01

    The incidence and/or prevalence of health problems associated with endocrine-disruption have increased. Many chemicals have endocrine-disrupting properties, including bisphenol A, some organochlorines, polybrominated flame retardants, perfluorinated substances, alkylphenols, phthalates, pesticides, polycyclic aromatic hydrocarbons, alkylphenols, solvents, and some household products including some cleaning products, air fresheners, hair dyes, cosmetics, and sunscreens. Even some metals were shown to have endocrine-disrupting properties. Many observations suggesting that endocrine disruptors do contribute to cancer, diabetes, obesity, the metabolic syndrome, and infertility are listed in this paper. An overview is presented of mechanisms contributing to endocrine disruption. Endocrine disruptors can act through classical nuclear receptors, but also through estrogen-related receptors, membrane-bound estrogen-receptors, and interaction with targets in the cytosol resulting in activation of the Src/Ras/Erk pathway or modulation of nitric oxide. In addition, changes in metabolism of endogenous hormones, cross-talk between genomic and nongenomic pathways, cross talk with estrogen receptors after binding on other receptors, interference with feedback regulation and neuroendocrine cells, changes in DNA methylation or histone modifications, and genomic instability by interference with the spindle figure can play a role. Also it was found that effects of receptor activation can differ in function of the ligand.

  16. Endocrine-Disrupting Chemicals: Associated Disorders and Mechanisms of Action

    Directory of Open Access Journals (Sweden)

    Sam De Coster

    2012-01-01

    Full Text Available The incidence and/or prevalence of health problems associated with endocrine-disruption have increased. Many chemicals have endocrine-disrupting properties, including bisphenol A, some organochlorines, polybrominated flame retardants, perfluorinated substances, alkylphenols, phthalates, pesticides, polycyclic aromatic hydrocarbons, alkylphenols, solvents, and some household products including some cleaning products, air fresheners, hair dyes, cosmetics, and sunscreens. Even some metals were shown to have endocrine-disrupting properties. Many observations suggesting that endocrine disruptors do contribute to cancer, diabetes, obesity, the metabolic syndrome, and infertility are listed in this paper. An overview is presented of mechanisms contributing to endocrine disruption. Endocrine disruptors can act through classical nuclear receptors, but also through estrogen-related receptors, membrane-bound estrogen-receptors, and interaction with targets in the cytosol resulting in activation of the Src/Ras/Erk pathway or modulation of nitric oxide. In addition, changes in metabolism of endogenous hormones, cross-talk between genomic and nongenomic pathways, cross talk with estrogen receptors after binding on other receptors, interference with feedback regulation and neuroendocrine cells, changes in DNA methylation or histone modifications, and genomic instability by interference with the spindle figure can play a role. Also it was found that effects of receptor activation can differ in function of the ligand.

  17. Novel ceria-polymer microcomposites for chemical mechanical polishing

    International Nuclear Information System (INIS)

    Coutinho, Cecil A.; Mudhivarthi, Subrahmanya R.; Kumar, Ashok; Gupta, Vinay K.

    2008-01-01

    Abrasive particles are key components in slurries for chemical mechanical polishing (CMP). Since the particle characteristics determine surface quality of wafers during polishing, in this research, novel abrasive composite particles have been developed. These composite particles contain nanoparticles of ceria dispersed within cross-linked, polymeric microspheres such that the average mass fraction of ceria is approximately 50% in the particles. The microspheres are formed by co-polymerization of N-isopropylacrylamide (NIPAM) with 3-(trimethoxysilyl)propyl methacrylate (MPS) and contain interpenetrating (IP) chains of poly(acrylic acid) (PAAc). Infrared spectroscopy, dynamic light scattering, and transmission electron microscopy are employed to characterize the composite particles. Planarization of silicon dioxide wafers is studied on a bench-top CMP tester and the polished surfaces are characterized by ellipsometry, atomic force and optical microscopy. Slurries formed from the composite ceria-polymer particles lead to lower topographical variations and surface roughness than slurries of only ceria nanoparticles even though both slurries achieve similar removal rates of ∼100 nm/min for similar ceria content. Polishing with the novel composite particles gives surfaces devoid of scratches and particle deposition, which makes these particles suitable for the next generation slurries in CMP

  18. Novel ceria-polymer microcomposites for chemical mechanical polishing

    Energy Technology Data Exchange (ETDEWEB)

    Coutinho, Cecil A. [Department of Chemical and Biomedical Engineering, University of South Florida (United States); Mudhivarthi, Subrahmanya R.; Kumar, Ashok [Nanomaterials and Nanomanufacturing Research Center, University of South Florida (United States); Department of Mechanical Engineering, University of South Florida (United States); Gupta, Vinay K. [Department of Chemical and Biomedical Engineering, University of South Florida (United States)], E-mail: vkgupta@eng.usf.edu

    2008-12-30

    Abrasive particles are key components in slurries for chemical mechanical polishing (CMP). Since the particle characteristics determine surface quality of wafers during polishing, in this research, novel abrasive composite particles have been developed. These composite particles contain nanoparticles of ceria dispersed within cross-linked, polymeric microspheres such that the average mass fraction of ceria is approximately 50% in the particles. The microspheres are formed by co-polymerization of N-isopropylacrylamide (NIPAM) with 3-(trimethoxysilyl)propyl methacrylate (MPS) and contain interpenetrating (IP) chains of poly(acrylic acid) (PAAc). Infrared spectroscopy, dynamic light scattering, and transmission electron microscopy are employed to characterize the composite particles. Planarization of silicon dioxide wafers is studied on a bench-top CMP tester and the polished surfaces are characterized by ellipsometry, atomic force and optical microscopy. Slurries formed from the composite ceria-polymer particles lead to lower topographical variations and surface roughness than slurries of only ceria nanoparticles even though both slurries achieve similar removal rates of {approx}100 nm/min for similar ceria content. Polishing with the novel composite particles gives surfaces devoid of scratches and particle deposition, which makes these particles suitable for the next generation slurries in CMP.

  19. Mechano-chemical synthesis of strontium britholites: Reaction mechanism

    International Nuclear Information System (INIS)

    Gmati, N.; Boughzala, K.; Bouzouita, K.; Abdellaoui, M.

    2011-01-01

    The britholites have gained a great interest thanks to their potential applications as matrices for the confinement of the byproducts in the nuclear industry such as minor actinides and long-lived fission products. However, the preparation of britholites requires high temperatures, above 1200 C. In this work, we strive to prepare these kinds of compounds by a mechano-chemical synthesis at room temperature from the starting materials SrF 2 , SrCO 3 , Sr 2 P 2 O 7 , La 2 O 3 and SiO 2 using a planetary ball mill. The obtained results showed that the prepared products were carbonated apatites and the corresponding powders contained some unreacted silica and lanthana. To obtain pure britholites, a heat-treatment at 1100 C was required. The mechanism involved in the different steps of the reaction is discussed in this paper. The obtained results suggest that the use of raw materials containing no carbonate is expected to directly lead to pure britholites by appropriate milling at room temperature. (authors)

  20. Mechanical properties of uniaxial natural fabric Grewia tilifolia reinforced epoxy based composites: Effects of chemical treatment

    CSIR Research Space (South Africa)

    Jayaramudu, J

    2014-07-01

    Full Text Available The effects of chemical treatment on the mechanical, morphological, and chemical resistance properties of uniaxial natural fabrics, Grewia tilifolia/epoxy composites, were studied. In order to enhance the interfacial bonding between the epoxy matrix...

  1. Analysis of mechanism of complex chemical reaction taking radiation chemical purification of gases from impurities as an example

    International Nuclear Information System (INIS)

    Gerasimov, G.Ya.; Makarov, V.N.

    1997-01-01

    Algorithm of selecting optimal mechanism of complex chemical reaction, enabling to reduce the number of its stages, is suggested. Main steps of constructing the kinetic model of the medium are considered, taking the radiation chemical purification (using fast electron radiation) of gases (N 2 , CO 2 , O 2 and others) from impurities as an example. 17 refs., 3 figs., 2 tabs

  2. Chemical stability of insulin. 4. Mechanisms and kinetics of chemical transformations in pharmaceutical formulation.

    Science.gov (United States)

    Brange, J

    1992-01-01

    Insulin decomposes by a multitude of chemical reactions [1-3]. It deamidates at two different residues by entirely different mechanisms. In acid, deamidation at AsnA21 is intramolecularly catalyzed by the protonated C-terminal, whereas above pH 6 an intermediate imide formation at residue AsnB3 leads to isoAsp and Asp derivatives. The imide formation requires a large rotation around the alpha-carbon/peptide carbonyl carbon bond at B3, corresponding to a 10 A movement of the B-chain N-terminal. The main determinant for the rate of B3 deamidation, as well as for the ratio between the two products formed, is the local conformational structure, which is highly influenced by various excipients and the physical state of the insulin. An amazing thermolysin-like, autoproteolytic cleavage of the A-chain takes place in rhombohedral insulin crystals, mediated by a concerted catalytic action by several, inter-hexameric functional groups and Zn2+. Intermolecular, covalent cross-linking of insulin molecules occurs via several mechanisms. The most prominent type of mechanism is aminolysis by the N-terminals, leading to isopeptide linkages with the A-chain side-chain amides of residues GlnA15, AsnA18 and AsnA21. The same type of reaction also leads to covalent cross-linking of the N-terminal in protamine with insulin. Disulfide exchange reactions, initiated by lysis of the A7-B7 disulfide bridge, lead mainly to formation of covalent oligo- and polymers. Activation energy (Ea) for the neutral deamidation and the aminolysis reactions was found to be 80 and 119 KJ/mol, respectively.

  3. Chemical Mechanical Polishing of Ruthenium, Cobalt, and Black Diamond Films

    Science.gov (United States)

    Peethala, Brown Cornelius

    Ta/TaN bilayer serves as the diffusion barrier as well as the adhesion promoter between Cu and the dielectric in 32 nm technology devices. A key concern of future technology devices (layer (vs. a bilayer of Ta/TaN) to act as a barrier. During patterning, they need to be planarized using conventional chemical mechanical polishing (CMP) to achieve a planar surface. However, CMP of these new barrier materials requires novel slurry compositions that provide adequate selectivity towards Cu and dielectric films, and minimize galvanic corrosion. Apart from the application as a barrier, Ru also has been proposed as a lower electrode material in metal-insulator-metal capacitors where high (> 50 nm/min) Ru removal rates (RRs) are required and as a stop layer in magnetic recording head fabrication where low (hydroxide (KOH). It was also determined that increased the ionic strength is not responsible for the observed increase in Ru removal rate. Benzotirazole (BTA) and ascorbic acid were added to the slurry to reduce the open circuit potential (Eoc) difference between Cu and Ru to ˜20 mV from about 550 mV in the absence of additives. A removal mechanism with KIO4 as the oxidizing agent is proposed based on the formation of several ruthenium oxides, some of which formed residues on the polishing pad below a pH of ˜7. Next, a colloidal silica-based slurry with hydrogen peroxide (H 2O2) as the oxidizer (1 wt%), and arginine (0.5 wt%) as the complexing agent was developed to polish Co at pH 10. The Eoc between Cu and Co at the above conditions was reduced to ˜20 mV compared to ˜250 mV in the absence of additives, suggestive of reduced galvanic corrosion during the Co polishing. The slurry also has the advantages of good post-polish surface quality at pH 10, and no dissolution rate. BTA at a concentration of 5mM in this slurry inhibited Cu dissolution rates and yielded a Cu/Co RR ratio of ˜0.8:1 while the open potential difference between Cu and Co was further reduced to ˜10

  4. Some chemical and physico-mechanical properties of pear cultivars

    African Journals Online (AJOL)

    STORAGESEVER

    2009-02-18

    Feb 18, 2009 ... carried out at the Biological Material Laboratory in Agricultural. Machinery Department and Fruit Science Laboratory in Horticulture. Department of Ataturk University, Erzurum, Turkey. Chemical analysis. All chemical properties of the pear cultivars were investigated on randomly selected fifty fruit samples.

  5. A proposed chemical mechanism for biological phosphate removal ...

    African Journals Online (AJOL)

    DRINIE

    2003-04-02

    Apr 2, 2003 ... Water Utilisation Division, Department of Chemical Engineering, University of ... wastewater reacts with orthophosphate under anaerobic conditions to make ... role of acetates and other short-chain carbon compounds in bio-.

  6. Enhanced understanding of the relationship between chemical modification and mechanical properties of wood

    Science.gov (United States)

    Charles R. Frihart; Daniel J. Yelle; John Ralph; Robert J. Moon; Donald S. Stone; Joseph E. Jakes

    2008-01-01

    Chemical additions to wood often change its bulk properties, which can be determined using conventional macroscopic mechanical tests. However, the controlling interactions between chemicals and wood take place at and below the scale of individual cells and cell walls. To better understand the effects of chemical additions to wood, we have adapted and extended two...

  7. Use of near infared spectroscopy to measure the chemical and mechanical properties of solid wood

    Science.gov (United States)

    Stephen S. Kelley; Timothy G. Rials; Rebecca Snell; Leslie H. Groom; Amie Sluiter

    2004-01-01

    Near infrared (NIR) spectroscopy (500 nm-2400 nm), coupled with multivariate analytic (MVA) statistical techniques, have been used to predict the chemical and mechanical properties of solid loblolly pine wood. The samples were selected from different radial locations and heights of three loblolly pine trees grown in Arkansas. The chemical composition and mechanical...

  8. Use of near infrared spectroscopy to measure the chemical and mechanical properties of solid wood

    Science.gov (United States)

    Stephen S. Kelley; Timothy G. Rials; Rebecca Snell; Leslie H. Groom; Amie Sluiter

    2004-01-01

    Near infrared (NIR) spectroscopy (500 nm-2400 nm), coupled with multivariate analytic (MVA) statistical techniques, have been used to predict the chemical and mechanical properties of solid loblolly pine wood. The samples were selected from different radial locations and heights of three loblolly pine trees grown in Arkansas. The chemical composition and mechanical...

  9. Quantum chemical approaches: semiempirical molecular orbital and hybrid quantum mechanical/molecular mechanical techniques.

    Science.gov (United States)

    Bryce, Richard A; Hillier, Ian H

    2014-01-01

    The use of computational quantum chemical methods to aid drug discovery is surveyed. An overview of the various computational models spanning ab initio, density function theory, semiempirical molecular orbital (MO), and hybrid quantum mechanical (QM)/molecular mechanical (MM) methods is given and their strengths and weaknesses are highlighted, focussing on the challenge of obtaining the accuracy essential for them to make a meaningful contribution to drug discovery. Particular attention is given to hybrid QM/MM and semiempirical MO methods which have the potential to yield the necessary accurate predictions of macromolecular structure and reactivity. These methods are shown to have advanced the study of many aspects of substrate-ligand interactions relevant to drug discovery. Thus, the successful parametrization of semiempirical MO methods and QM/MM methods can be used to model noncovalent substrate-protein interactions, and to lead to improved scoring functions. QM/MM methods can be used in crystal structure refinement and are particularly valuable for modelling covalent protein-ligand interactions and can thus aid the design of transition state analogues. An extensive collection of examples from the areas of metalloenzyme structure, enzyme inhibition, and ligand binding affinities and scoring functions are used to illustrate the power of these techniques.

  10. Protein Structure Validation and Refinement Using Chemical Shifts Derived from Quantum Mechanics

    DEFF Research Database (Denmark)

    Bratholm, Lars Andersen

    to within 3 A. Furthermore, a fast quantum mechanics based chemical shift predictor was developed together with methodology for using chemical shifts in structure simulations. The developed predictor was used for renement of several protein structures and for reducing the computational cost of quantum...... mechanics / molecular mechanics (QM/MM) computations of chemical shieldings. Several improvements to the predictor is ongoing, where among other things, kernel based machine learning techniques have successfully been used to improve the quantum mechanical level of theory used in the predictions....

  11. A proposed chemical mechanism for biological phosphate removal ...

    African Journals Online (AJOL)

    This paper presents an alternative for the ";all biological"; phosphate removal model. It is postulated that a chemical substance in wastewater reacts with orthophosphate under anaerobic conditions to make the so-called luxury uptake of phosphorus possible in biological nutrient removal (BNR) activated sludge plants.

  12. Study on chemical mechanical polishing of silicon wafer with megasonic vibration assisted.

    Science.gov (United States)

    Zhai, Ke; He, Qing; Li, Liang; Ren, Yi

    2017-09-01

    Chemical mechanical polishing (CMP) is the primary method to realize the global planarization of silicon wafer. In order to improve this process, a novel method which combined megasonic vibration to assist chemical mechanical polishing (MA-CMP) is developed in this paper. A matching layer structure of polishing head was calculated and designed. Silicon wafers are polished by megasonic assisted chemical mechanical polishing and traditional chemical mechanical polishing respectively, both coarse polishing and precision polishing experiments were carried out. With the use of megasonic vibration, the surface roughness values Ra reduced from 22.260nm to 17.835nm in coarse polishing, and the material removal rate increased by approximately 15-25% for megasonic assisted chemical mechanical polishing relative to traditional chemical mechanical polishing. Average Surface roughness values Ra reduced from 0.509nm to 0.387nm in precision polishing. The results show that megasonic assisted chemical mechanical polishing is a feasible method to improve polishing efficiency and surface quality. The material removal and finishing mechanisms of megasonic vibration assisted polishing are investigated too. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Lignin chemical degradation using redistribution mechanism and its biomass applications

    OpenAIRE

    Nanayakkara, Sepa Yasandrika

    2017-01-01

    Lignin is one of the most abundant renewable raw materials available on earth and it has the potential to yield valuable low molecular weight aromatic compounds if it can be depolymerized selectively. Despite its unique characteristics as a natural product with multiple chemical and biophysical functionalities, it is largely under-exploited, because of the lack of available methods that effect depolymerization in a selective manner. One of the dominant linkages in lignin has a similar ary...

  14. Chemical mechanism of the fluoride-inhibition of fermentation

    Energy Technology Data Exchange (ETDEWEB)

    Warburg, O; Christian, W

    1941-08-01

    Among the fluoride-sensitive fermentation elements, enolase is the most sensitive. An investigation was made, quantitatively, of fluoride inhibition for chemically pure magnesium-enolase using an optical enolase test. Data show that the effective compound for fluoride inhibition is a complex magnesium-fluoro-phosphate and that the magnesium-fluoro-phosphate inhibits fermentation by combining proportionally to its concentration with the ferment-protein in a dissociating manner.

  15. Insights into the mechanisms on chemical reactions: reaction paths for chemical reactions

    International Nuclear Information System (INIS)

    Dunning, T.H. Jr.; Rosen, E.; Eades, R.A.

    1987-01-01

    We report reaction paths for two prototypical chemical reactions: Li + HF, an electron transfer reaction, and OH + H 2 , an abstraction reaction. In the first reaction we consider the connection between the energetic terms in the reaction path Hamiltonian and the electronic changes which occur upon reaction. In the second reaction we consider the treatment of vibrational effects in chemical reactions in the reaction path formalism. 30 refs., 9 figs

  16. Chemical mechanical glass polishing with cerium oxide: Effect of selected physico-chemical characteristics on polishing efficiency

    Czech Academy of Sciences Publication Activity Database

    Janoš, P.; Ederer, J.; Pilařová, V.; Henych, Jiří; Tolasz, Jakub; Milde, D.; Opletal, T.

    2016-01-01

    Roč. 362, SEP (2016), s. 114-120 ISSN 0043-1648 R&D Projects: GA MŠk(CZ) LM2015073 Institutional support: RVO:61388980 Keywords : Chemical mechanical polishing * Ceria-based polishing powders * Polishing efficienc Subject RIV: CA - Inorganic Chemistry Impact factor: 2.531, year: 2016

  17. The Molecular Mechanism of Alternative P450-Catalyzed Metabolism of Environmental Phenolic Endocrine-Disrupting Chemicals

    DEFF Research Database (Denmark)

    Ji, Li; Ji, Shujing; Wang, Chenchen

    2018-01-01

    Understanding the bioactivation mechanisms to predict toxic metabolites is critical for risk assessment of phenolic endocrine-disrupting chemicals (EDCs). One mechanism involves ipso-substitution, which may contribute to the total turnover of phenolic EDCs, yet the detailed mechanism and its rela...

  18. Quantum chemical aided prediction of the thermal decomposition mechanisms and temperatures of ionic liquids

    International Nuclear Information System (INIS)

    Kroon, Maaike C.; Buijs, Wim; Peters, Cor J.; Witkamp, Geert-Jan

    2007-01-01

    The long-term thermal stability of ionic liquids is of utmost importance for their industrial application. Although the thermal decomposition temperatures of various ionic liquids have been measured previously, experimental data on the thermal decomposition mechanisms and kinetics are scarce. It is desirable to develop quantitative chemical tools that can predict thermal decomposition mechanisms and temperatures (kinetics) of ionic liquids. In this work ab initio quantum chemical calculations (DFT-B3LYP) have been used to predict thermal decomposition mechanisms, temperatures and the activation energies of the thermal breakdown reactions. These quantum chemical calculations proved to be an excellent method to predict the thermal stability of various ionic liquids

  19. Protein structure refinement using a quantum mechanics-based chemical shielding predictor

    DEFF Research Database (Denmark)

    Bratholm, Lars Andersen; Jensen, Jan Halborg

    2017-01-01

    The accurate prediction of protein chemical shifts using a quantum mechanics (QM)-based method has been the subject of intense research for more than 20 years but so far empirical methods for chemical shift prediction have proven more accurate. In this paper we show that a QM-based predictor...... of a protein backbone and CB chemical shifts (ProCS15, PeerJ, 2016, 3, e1344) is of comparable accuracy to empirical chemical shift predictors after chemical shift-based structural refinement that removes small structural errors. We present a method by which quantum chemistry based predictions of isotropic...

  20. Quantum chemical study of the mechanisms of oxidation of ethylene ...

    Indian Academy of Sciences (India)

    lanl2tz basis set.32–36. Spartan uses a graphical model builder for input preparation. Molecules were constructed and mini- mized interactively using an appropriate molecular mechanics force field. All structural optimizations were done without symmetry restrictions. Normal mode analysis was performed to verify the nature ...

  1. Mechanical Characteristics of Chemically Degraded Surface Layers of Wood

    Czech Academy of Sciences Publication Activity Database

    Frankl, Jiří; Kloiber, Michal; Drdácký, Miloš; Tippner, J.; Bryscejn, Jan

    2012-01-01

    Roč. 2, č. 11 (2012), s. 694-700 ISSN 2159-5275 R&D Projects: GA ČR(CZ) GPP105/11/P628 Institutional support: RVO:68378297 Keywords : wood * corrosion * defibering * mechanical properties Subject RIV: JN - Civil Engineering http://www.davidpublishing.com

  2. Mechanisms in endogenous leukemia virus induction by radiation and chemicals

    International Nuclear Information System (INIS)

    Tennant, R.W.; Rascati, R.J.; Lavelle, G.C.

    1976-01-01

    A model of endogenous leukemia virus induction in AKR strain mouse cells based on two distinct types of alterations in cellular or proviral DNA is presented. The first type are non-repairable alterations, such as those caused by the incorporation of halogenated pyrimidines; the second type are repairable lesions, such as those caused by irradiation or certain other chemicals. The production of non-repairable lesions leads to the formation of a stable, proviral state which is dependent upon cell division for complete virus expression. A stable provirus intermediate state is not demonstrable in cells induced by treatments which cause repairable lesions, since replication of damaged or altered DNA must occur before the lesions are removed by repair synthesis. Experimental support for this model is presented

  3. Mechanical behavior of chemically treated Jute/Polymer composites

    Directory of Open Access Journals (Sweden)

    Murali B

    2014-03-01

    Full Text Available Fiber which serves as a reinforcement in reinforced plastics may be synthetic or natural past studies show that only artificial fibers such as glass, carbon etc., have been used in fiber reinforced plastics. Although glass and other synthetic fiber reinforced plastics possess high specific strength, their fields of application are very limited because of their inherent higher cost of production. In this connection, an investigation has been carried out to make use of jute , a natural fiber abundantly available in India. Natural fibers are not only strong and lightweight but also relatively very cheap. In the present work, jute composites are developed and their mechanical properties are evaluated. Mechanical properties of jute/polymer and compared with glass fiber/epoxy. These results indicate that jute can be used as a potential reinforcing material for making low load bearing thermoplastic composites.

  4. Change of mechanical properties of molybdenum after chemical heat treatment

    International Nuclear Information System (INIS)

    Skuratov, L.P.; Yatsimirskij, V.K.; Kirillova, N.V.

    1987-01-01

    Gaseous media (argon, ammonia, nitrogen-hydrogen-ammonia mixture) are studied for their effect on mechanical characteristics of molybdenum at temperatures up to 1000 deg C. It is established that the highest hardening occurs when molybdenum is esposed in the nitrogen-hydrogen medium, while the highest lost of strength takes place in the ammonia medium. An increase of the ammonia concentration in nitrogen-hydrogen-ammonia mixture promotes regular increasing of the deformation rate. With ammonia concentration of 33.3% the gaseous mixture acts the same as pure ammonia. Change of physical-and-mechanical properties of molybdenum under the action of nitrogen-containing gaseous media is associated with formation of molybdenum compounds with nitrogen. During nitriding in ammonia an internal (volume) nitriding proceeds while in the medium of nitrogen-hydrogen mixture surface nitride layers form

  5. Control of Maillard Reactions in Foods: Strategies and Chemical Mechanisms.

    Science.gov (United States)

    Lund, Marianne N; Ray, Colin A

    2017-06-14

    Maillard reactions lead to changes in food color, organoleptic properties, protein functionality, and protein digestibility. Numerous different strategies for controlling Maillard reactions in foods have been attempted during the past decades. In this paper, recent advances in strategies for controlling the Maillard reaction and subsequent downstream reaction products in food systems are critically reviewed. The underlying mechanisms at play are presented, strengths and weaknesses of each strategy are discussed, and reasonable reaction mechanisms are proposed to reinforce the evaluations. The review includes strategies involving addition of functional ingredients, such as plant polyphenols and vitamins, as well as enzymes. The resulting trapping or modification of Maillard targets, reactive intermediates, and advanced glycation endproducts (AGEs) are presented with their potential unwanted side effects. Finally, recent advances in processing for control of Maillard reactions are discussed.

  6. CH4/air homogeneous autoignition: A comparison of two chemical kinetics mechanisms

    KAUST Repository

    Tingas, Efstathios Al.; Manias, Dimitris M.; Sarathy, Mani; Goussis, Dimitris A.

    2018-01-01

    Reactions contributing to the generation of the explosive time scale that characterise autoignition of homogeneous stoichiometric CH4/air mixture are identified using two different chemical kinetics models; the well known GRI-3.0 mechanism (53

  7. Efficacy and mechanisms of non-antibacterial, chemical plaque control by dentifrices - An in vitro study

    NARCIS (Netherlands)

    Busscher, Henk J.; White, Don J.; Atema-Smit, Jelly; van der Mei, Henny C.

    Objectives: The provision of antiplaque benefits to dentifrices assists patients in improving hygiene and reducing susceptibility to gingivitis and caries. Chemical plaque control involves different mechanisms and is mostly associated with antibacterial effects, but also includes effects on pellicle

  8. Neutralization of Aerosolized Bio-Agents by Filled Nanocomposite Materials through Thermal and Chemical Inactivation Mechanisms

    Science.gov (United States)

    2016-06-01

    Bio -agents by Filled Nanocomposite Materials through Thermal and Chemical Inactivation Mechanisms Distribution Statement A. Approved for public...of Cincinnati Project Title: Neutralization of Aerosolized Bio -agents by Filled Nanocomposite Materials through Thermal and Chemical Inactivation...fire ball, where they will not effectively interact with any viable bio -aerosol. 1.1.4. Conclusions Cryo-milling is necessary to achieve a

  9. Chemical and mechanical control of corrosion product transport

    Energy Technology Data Exchange (ETDEWEB)

    Hede Larsen, O; Blum, R [I/S Fynsvaerket, Faelleskemikerne, Odense (Denmark); Daucik, K [I/S Skaerbaekvaerket, Faelleskemikerne, Fredericia (Denmark)

    1996-12-01

    The corrosion products formed in the condensate and feedwater system of once-through boilers are precipitated and deposited inside the evaporator tubes mainly in the burner zone at the highest heat flux. Depositions lead to increased oxidation rate and increased metal temperature of the evaporator tubes, hereby decreasing tube lifetime. This effect is more important in the new high efficiency USC boilers due to increased feedwater temperature and hence higher thermal load on the evaporator tubes. The only way to reduce the load on the evaporator tubes is to minimise corrosion product transport to the boiler. Two general methods for minimising corrosion product transport to the boiler have been evaluated through measurement campaigns for Fe in the water/steam cycle in supercritical boilers within the ELSAM area. One method is to reduce corrosion in the low temperature condensate system by changing conditioning mode from alkaline volatile treatment (AVT) to oxygenated treatment (OT). The other method is to filtrate part of the condensate with a mechanical filter at the deaerator. The results show, that both methods are effective at minimising Fe-transport to the boiler, but changing to OT has the highest effect and should always be used, whenever high purity condensate is maintained. Whether mechanical filtration also is required, depends on the boiler, specifically the load on the evaporator. A simplified calculation model for lifetime evaluation of evaporator tubes has been developed. This model has been used for evaluating the effect of corrosion product transport to the boiler on evaporator tube lifetime. Conventional supercritical boilers generally can achieve sufficient lifetime by AVT and even better by OT, whereas all measures to reduce Fe-content of feedwater, including OT and mechanical filtration, should be taken, to ensure sufficient lifetime for the new boilers with advanced steam data - 290 bar/580 deg. C and above. (au)

  10. Corrosion problems of materials for mechanical, power and chemical engineering

    International Nuclear Information System (INIS)

    Bouska, P.; Cihal, V.; Malik, K.; Vyklicky, M.; Stefec, R.

    1988-01-01

    The proceedings contain 47 contributions, out of which 8 have been inputted in INIS. These are concerned with various corrosion problems of WWER primary circuit components and their testing. The factors affecting the corrosion resistance are analyzed, the simultaneous corrosion action of decontamination of steels is assessed, and the corrosion cracking of special steels is dealt with. The effects of deformation on the corrosion characteristics are examined for steel to be used in fast reactors. The corrosion potentials were measured for various steels. A testing facility for corrosion-mechanical tests is briefly described. (M.D.). 5 figs., 5 tabs., 25 refs

  11. Comparison of different chemical kinetic mechanisms of methane combustion in an internal combustion engine configuration

    OpenAIRE

    Ennetta Ridha; Hamdi Mohamed; Said Rachid

    2008-01-01

    Three chemical kinetic mechanisms of methane combustion were tested and compared using the internal combustion engine model of Chemkin 4.02 [1]: one-step global reaction mechanism, four-step mechanism, and the standard detailed scheme GRIMECH 3.0. This study shows good concordances, especially between the four-step and the detailed mechanisms in the prediction of temperature and main species profiles. But reduced schemes were incapables to predict pollutant emissions in an internal combustion...

  12. Endocrine-disrupting Chemicals: Review of Toxicological Mechanisms Using Molecular Pathway Analysis

    Science.gov (United States)

    Yang, Oneyeol; Kim, Hye Lim; Weon, Jong-Il; Seo, Young Rok

    2015-01-01

    Endocrine disruptors are known to cause harmful effects to human through various exposure routes. These chemicals mainly appear to interfere with the endocrine or hormone systems. As importantly, numerous studies have demonstrated that the accumulation of endocrine disruptors can induce fatal disorders including obesity and cancer. Using diverse biological tools, the potential molecular mechanisms related with these diseases by exposure of endocrine disruptors. Recently, pathway analysis, a bioinformatics tool, is being widely used to predict the potential mechanism or biological network of certain chemicals. In this review, we initially summarize the major molecular mechanisms involved in the induction of the above mentioned diseases by endocrine disruptors. Additionally, we provide the potential markers and signaling mechanisms discovered via pathway analysis under exposure to representative endocrine disruptors, bisphenol, diethylhexylphthalate, and nonylphenol. The review emphasizes the importance of pathway analysis using bioinformatics to finding the specific mechanisms of toxic chemicals, including endocrine disruptors. PMID:25853100

  13. 79Se: geochemical and crystallo-chemical retardation mechanisms

    International Nuclear Information System (INIS)

    Chen, F.; Ewing, R.C.

    1999-01-01

    79 Se is a long-lived (1.1 x 10 6 yrs) fission product which is chemically and radiologically toxic. Under Eh-pH conditions typical of oxidative alteration of spent nuclear fuel, selenite, SeO 3 2- or HSeO 3 - or selenate, SeO 4 2- , are the dominant aqueous species of selenium. Because of the high solubility of metal-selenites and metal-selenates and the low adsorption of selenite and selenate aqueous species by geological materials under alkaline conditions, selenium may be highly mobile. However, 79 Se released from altered fuel may become immobilized by incorporation into secondary uranyl phases as low concentration impurities, and this may significantly reduce the mobility of selenium. Analysis and comparison of the known structures of uranyl phases indicate that (SeO 3 ) may substitute for (SiO 3 OH) in structures of α-uranophane and boltwoodite that are expected to be the dominant alteration products of UO 2 in Si-rich groundwater. The substitutions (SeO 3 ) (SiO 3 OH) in sklodowskite, Mg[(UO 2 )(SiO 3 OH)] 2 (H 2 O) 6 and (SeO 3 ) (PO 4 ) in phurcalite, Ca 2 [(UO 2 ) 3 (PO 4 ) 2 O 2 ](H 2 O) 7 , may occur with the eliminated apical anion being substituted for by an H 2 O group, but experimental investigation is required. The close similarity between the sheets in the structures of rutherfordine, [(UO 2 )(CO 3 )] and [(UO 2 )(SeO 3 )] implies that the substitution (SeO 3 ) (CO 3 ) can occur in rutherfordine, and possibly other uranyl carbonates. However, the substitutions: (SeO 3 ) (SiO 4 ) in soddyite and (SeO 3 ) (PO 4 ) in phosphuranylite may disrupt their structural connectivity and are, therefore, unlikely. (orig.)

  14. Mechanisms of environmental chemicals that enable the cancer hallmark of evasion of growth suppression.

    Science.gov (United States)

    Nahta, Rita; Al-Mulla, Fahd; Al-Temaimi, Rabeah; Amedei, Amedeo; Andrade-Vieira, Rafaela; Bay, Sarah N; Brown, Dustin G; Calaf, Gloria M; Castellino, Robert C; Cohen-Solal, Karine A; Colacci, Annamaria; Cruickshanks, Nichola; Dent, Paul; Di Fiore, Riccardo; Forte, Stefano; Goldberg, Gary S; Hamid, Roslida A; Krishnan, Harini; Laird, Dale W; Lasfar, Ahmed; Marignani, Paola A; Memeo, Lorenzo; Mondello, Chiara; Naus, Christian C; Ponce-Cusi, Richard; Raju, Jayadev; Roy, Debasish; Roy, Rabindra; Ryan, Elizabeth P; Salem, Hosni K; Scovassi, A Ivana; Singh, Neetu; Vaccari, Monica; Vento, Renza; Vondráček, Jan; Wade, Mark; Woodrick, Jordan; Bisson, William H

    2015-06-01

    As part of the Halifax Project, this review brings attention to the potential effects of environmental chemicals on important molecular and cellular regulators of the cancer hallmark of evading growth suppression. Specifically, we review the mechanisms by which cancer cells escape the growth-inhibitory signals of p53, retinoblastoma protein, transforming growth factor-beta, gap junctions and contact inhibition. We discuss the effects of selected environmental chemicals on these mechanisms of growth inhibition and cross-reference the effects of these chemicals in other classical cancer hallmarks. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  15. Report of National Cancer Institute symposium: comparison of mechanisms of carcinogenesis by radiation and chemical agents. I. Common molecular mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Borg, D.C.

    1984-01-01

    Some aspects of molecular mechanisms common to radiation and chemical carcinogenesis are discussed, particularly the DNA damage done by these agents. Emphasis is placed on epidemiological considerations and on dose-response models used in risk assessment to extrapolate from experimental data obtained at high doses to the effects from long-term, low-level exposures. 3 references, 6 figures. (ACR)

  16. Report of National Cancer Institute symposium: comparison of mechanisms of carcinogenesis by radiation and chemical agents. I. Common molecular mechanisms

    International Nuclear Information System (INIS)

    Borg, D.C.

    1984-01-01

    Some aspects of molecular mechanisms common to radiation and chemical carcinogenesis are discussed, particularly the DNA damage done by these agents. Emphasis is placed on epidemiological considerations and on dose-response models used in risk assessment to extrapolate from experimental data obtained at high doses to the effects from long-term, low-level exposures. 3 references, 6 figures

  17. Influence of mechanical and chemical degradation on surface gloss of resin composite materials

    NARCIS (Netherlands)

    Ardu, S.; Braut, V.; Uhac, I.; Benbachir, N.; Feilzer, A.J.; Krejci, I.

    2009-01-01

    Purpose: To determine the changes in surface gloss of different composite materials after simulation of mechanical and chemical aging mechanisms. Methods: 36 specimens were fabricated for each material and polished with 120-, 220-, 500-, 1200-, 2400- and 4000- grit SiC abrasive paper, respectively.

  18. Reduced chemical kinetic mechanisms for NOx emission prediction in biomass combustion

    DEFF Research Database (Denmark)

    Houshfar, Ehsan; Skreiberg, Øyvind; Glarborg, Peter

    2012-01-01

    Because of the complex composition of biomass, the chemical mechanism contains many different species and therefore a large number of reactions. Although biomass gas‐phase combustion is fairly well researched and understood, the proposed mechanisms are still complex and need very long computational...... time and powerful hardware resources. A reduction of the mechanism for biomass volatile oxidation has therefore been performed to avoid these difficulties. The selected detailed mechanism in this study contains 81 species and 703 elementary reactions. Necessity analysis is used to determine which...... reactions and chemical species, that is, 35 species and 198 reactions, corresponding to 72% reduction in the number of reactions and, therefore, improving the computational time considerably. Yet, the model based on the reduced mechanism predicts correctly concentrations of NOx and CO that are essentially...

  19. Organic chemical aging mechanisms: An annotated bibliography. Waste Tank Safety Program

    Energy Technology Data Exchange (ETDEWEB)

    Samuels, W.D.; Camaioni, D.M.; Nelson, D.A.

    1993-09-01

    An annotated bibliography has been compiled of the potential chemical and radiological aging mechanisms of the organic constituents (non-ferrocyanide) that would likely be found in the UST at Hanford. The majority of the work that has been conducted on the aging of organic chemicals used for extraction and processing of nuclear materials has been in conjunction with the acid or PUREX type processes. At Hanford the waste being stored in the UST has been stabilized with caustic. The aging factors that were used in this work were radiolysis, hydrolysis and nitrite/nitrate oxidation. The purpose of this work was two-fold: to determine whether or not research had been or is currently being conducted on the species associated with the Hanford UST waste, either as a mixture or as individual chemicals or chemical functionalities, and to determine what areas of chemical aging need to be addressed by further research.

  20. Theoretical study of coupling mechanisms between oxygen diffusion, chemical reaction, mechanical stresses in a solid-gas reactive system

    International Nuclear Information System (INIS)

    Creton, N.; Optasanu, V.; Montesin, T.; Garruchet, S.

    2008-01-01

    This paper offers a study of oxygen dissolution into a solid, and its consequences on the mechanical behaviour of the material. In fact, mechanical strains strongly influence the oxidation processes and may be, in some materials, responsible for cracking. To realize this study, mechanical considerations are introduced into the classical diffusion laws. Simulations were made for the particular case of uranium dioxide, which undergoes the chemical fragmentation. According to our simulations, the hypothesis of a compression stress field into the oxidised UO 2 compound near the internal interface is consistent with some oxidation mechanisms of oxidation experimentally observed. More generally, this work will be extended to the simulation to an oxide layer growth on a metallic substrate. (authors)

  1. Development of a Procedure to Apply Detailed Chemical Kinetic Mechanisms to CFD Simulations as Post Processing

    DEFF Research Database (Denmark)

    Skjøth-Rasmussen, Martin Skov; Glarborg, Peter; Jensen, Anker

    2003-01-01

    mechanism. It involves post-processing of data extracted from computational fluid dynamics simulations. Application of this approach successfully describes combustion chemistry in a standard swirl burner, the so-called Harwell furnace. Nevertheless, it needs validation against more complex combustion models......It is desired to make detailed chemical kinetic mechanisms applicable to the complex geometries of practical combustion devices simulated with computational fluid dynamics tools. This work presents a novel general approach to combining computational fluid dynamics and a detailed chemical kinetic...

  2. Evidence from pharmacology and pathophysiology suggests that chemicals with dissimilar mechanisms of action could be of bigger concern in the toxicological risk assessment of chemical mixtures than chemicals with a similar mechanism of action.

    Science.gov (United States)

    Hadrup, Niels

    2014-08-01

    Mathematical models have been developed for the toxicological risk assessment of chemical mixtures. However, exposure data as well as single chemical toxicological data are required for these models. When addressing this data need, it could be attractive to focus on chemicals with similar mechanisms of action, similar modes of action or with common target organs. In the European Union, efforts are currently being made to subgroup chemicals according to this need. However, it remains to be determined whether this is the best strategy to obtain data for risk assessment. In conditions such as cancer or HIV, it is generally recognised that pharmacological combination therapy targeting different mechanisms of action is more effective than a strategy where only one mechanism is targeted. Moreover, in diseases such as acute myocardial infarction and congestive heart failure, several organ systems concomitantly contribute to the pathophysiology, suggesting that a grouping based on common target organs may also be inefficient. A better option may be to prioritise chemicals on the basis of potency and risk of exposure. In conclusion, there are arguments to suggest that we should concomitantly consider all targets that a chemical can affect in the human body and not merely a subset. Copyright © 2014 Elsevier Inc. All rights reserved.

  3. New mechanical chemical equilibrium in the copper-zinc alloys obtained by mechanical alloying

    International Nuclear Information System (INIS)

    Dianez, M.J; Criado, J.M; Donoso, E; Diaz, G

    2006-01-01

    A series of copper zinc alloys have been synthesized in the entire composition range Cu10Zn to Cu70Zn respectively, by mechanical alloying at room temperature in a planetary high-energy mill. A mechanism is proposed for the mechanical alloying reaction of the copper and zinc. It is made clear that the mechanical treatment considerably extends the range of composition of the α phase up to a content of 41% zinc, instead of the 36% accepted by the conventional phase diagrams. Exact determinations of the phase α reticular parameter were carried out as a function of its composition which can be used to determine the zinc content of the brass α. The results show that a brass phase α may be obtained containing 49% zinc in samples that include a mixture of phases α and β' after reaching stationary state as a function of the milling time. The stability field of phases β' and γ also displace noticeably higher values than those expected from the conventional binary Cu-Zn diagram. This behavior has been explained as a function of the nanometric texture generated by the milling (CW)

  4. Mechanisms of gas phase decomposition of C-nitro compounds from quantum chemical data

    International Nuclear Information System (INIS)

    Khrapkovskii, Grigorii M; Shamov, Alexander G; Nikolaeva, E V; Chachkov, D V

    2009-01-01

    Data on the mechanisms of gas-phase monomolecular decomposition of nitroalkanes, nitroalkenes and nitroarenes obtained using modern quantum chemical methods are described systematically. The attention is focused on the discussion of multistage decomposition of nitro compounds to elementary experimentally observed products. Characteristic features of competition of different mechanisms and the effect of molecular structure on the change in the Arrhenius parameters of the primary reaction step are considered.

  5. Mechanisms of gas phase decomposition of C-nitro compounds from quantum chemical data

    Energy Technology Data Exchange (ETDEWEB)

    Khrapkovskii, Grigorii M; Shamov, Alexander G; Nikolaeva, E V; Chachkov, D V [Kazan State Technological University, Kazan (Russian Federation)

    2009-10-31

    Data on the mechanisms of gas-phase monomolecular decomposition of nitroalkanes, nitroalkenes and nitroarenes obtained using modern quantum chemical methods are described systematically. The attention is focused on the discussion of multistage decomposition of nitro compounds to elementary experimentally observed products. Characteristic features of competition of different mechanisms and the effect of molecular structure on the change in the Arrhenius parameters of the primary reaction step are considered.

  6. Coupling effects of chemical stresses and external mechanical stresses on diffusion

    International Nuclear Information System (INIS)

    Xuan Fuzhen; Shao Shanshan; Wang Zhengdong; Tu Shantung

    2009-01-01

    Interaction between diffusion and stress fields has been investigated extensively in the past. However, most of the previous investigations were focused on the effect of chemical stress on diffusion due to the unbalanced mass transport. In this work, the coupling effects of external mechanical stress and chemical stress on diffusion are studied. A self-consistent diffusion equation including the chemical stress and external mechanical stress gradient is developed under the framework of the thermodynamic theory and Fick's law. For a thin plate subjected to unidirectional tensile stress fields, the external stress coupled diffusion equation is solved numerically with the help of the finite difference method for one-side and both-side charging processes. Results show that, for such two types of charging processes, the external stress gradient will accelerate the diffusion process and thus increase the value of concentration while reducing the magnitude of chemical stress when the direction of diffusion is identical to that of the stress gradient. In contrast, when the direction of diffusion is opposite to that of the stress gradient, the external stress gradient will obstruct the process of solute penetration by decreasing the value of concentration and increasing the magnitude of chemical stress. For both-side charging process, compared with that without the coupling effect of external stress, an asymmetric distribution of concentration is produced due to the asymmetric mechanical stress field feedback to diffusion.

  7. CSP-based chemical kinetics mechanisms simplification strategy for non-premixed combustion: An application to hybrid rocket propulsion

    KAUST Repository

    Ciottoli, Pietro P.; Malpica Galassi, Riccardo; Lapenna, Pasquale E.; Leccese, G.; Bianchi, D.; Nasuti, F.; Creta, F.; Valorani, M.

    2017-01-01

    A set of simplified chemical kinetics mechanisms for hybrid rocket applications using gaseous oxygen (GOX) and hydroxyl-terminated polybutadiene (HTPB) is proposed. The starting point is a 561-species, 2538-reactions, detailed chemical kinetics

  8. Protein structure refinement using a quantum mechanics-based chemical shielding predictor.

    Science.gov (United States)

    Bratholm, Lars A; Jensen, Jan H

    2017-03-01

    The accurate prediction of protein chemical shifts using a quantum mechanics (QM)-based method has been the subject of intense research for more than 20 years but so far empirical methods for chemical shift prediction have proven more accurate. In this paper we show that a QM-based predictor of a protein backbone and CB chemical shifts (ProCS15, PeerJ , 2016, 3, e1344) is of comparable accuracy to empirical chemical shift predictors after chemical shift-based structural refinement that removes small structural errors. We present a method by which quantum chemistry based predictions of isotropic chemical shielding values (ProCS15) can be used to refine protein structures using Markov Chain Monte Carlo (MCMC) simulations, relating the chemical shielding values to the experimental chemical shifts probabilistically. Two kinds of MCMC structural refinement simulations were performed using force field geometry optimized X-ray structures as starting points: simulated annealing of the starting structure and constant temperature MCMC simulation followed by simulated annealing of a representative ensemble structure. Annealing of the CHARMM structure changes the CA-RMSD by an average of 0.4 Å but lowers the chemical shift RMSD by 1.0 and 0.7 ppm for CA and N. Conformational averaging has a relatively small effect (0.1-0.2 ppm) on the overall agreement with carbon chemical shifts but lowers the error for nitrogen chemical shifts by 0.4 ppm. If an amino acid specific offset is included the ProCS15 predicted chemical shifts have RMSD values relative to experiments that are comparable to popular empirical chemical shift predictors. The annealed representative ensemble structures differ in CA-RMSD relative to the initial structures by an average of 2.0 Å, with >2.0 Å difference for six proteins. In four of the cases, the largest structural differences arise in structurally flexible regions of the protein as determined by NMR, and in the remaining two cases, the large structural

  9. Development of a Mechanical Analysis System Considering Chemical Transitions of Barrier Materials

    International Nuclear Information System (INIS)

    Sahara, F.; Murakami, T.; Ito, H.; Kobayashi, I.; Yokozeki, K.

    2006-01-01

    An analysis system for the long-term mechanical behavior of barrier materials (MACBECE: Mechanical Analysis system considering Chemical transitions of Bentonite-based and Cement-based materials) was developed in order to improve the reliability of the evaluation of the hydraulic field that is one of the important environmental conditions in the safety assessment of the TRU waste disposal in Japan. The MACBECE is a system that calculates the deformation of barrier materials using their chemical property changes as inputs, and subsequently their hydraulic conductivity taking both their chemical property changes and deformation into consideration. This paper provides a general description of MACBECE and the results of experimental analysis carried out using MACBECE. (authors)

  10. A computational environment for creating and testing reduced chemical kinetic mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Montgomery, C.J.; Swensen, D.A.; Harding, T.V.; Cremer, M.A.; Bockelie, M.J. [Reaction Engineering International, Salt Lake City, UT (USA)

    2002-02-01

    This paper describes software called computer assisted reduced mechanism problem solving environment (CARM-PSE) that gives the engineer the ability to rapidly set up, run and examine large numbers of problems comparing detailed and reduced (approximate) chemistry. CARM-PSE integrates the automatic chemical mechanism reduction code CARM and the codes that simulate perfectly stirred reactors and plug flow reactors into a user-friendly computational environment. CARM-PSE gives the combustion engineer the ability to easily test chemical approximations over many hundreds of combinations of inputs in a multidimensional parameter space. The demonstration problems compare detailed and reduced chemical kinetic calculations for methane-air combustion, including nitrogen oxide formation, in a stirred reactor and selective non-catalytic reduction of NOx, in coal combustion flue gas.

  11. Establishment of the carbon label mechanism of coal chemical products based oncarbon footprint

    Directory of Open Access Journals (Sweden)

    Wu Bishan

    Full Text Available ABSTRACT After redefining the carbon footprint and carbon label, the paper analyzesthe significance of the carbon labels under the background of the low carbon economy development, and establishes the concept of model of the carbon labels mechanism to chemical products. At the same time, the paper quantitatively studies carbon label data sourceof three kinds of coal chemical industry power products, which are fromhaving not CCS technologies of supercritical boiler of coal, using CCS technologies of supercritical boiler of coal and adopting CCS and IGCC technologies to power generation in CCI. Based on the three kinds of differences, the paper puts forward of establishing the carbon labels mechanism of chemical products under the low carbon consumption.

  12. Protein structure validation and refinement using amide proton chemical shifts derived from quantum mechanics

    DEFF Research Database (Denmark)

    Christensen, Anders Steen; Linnet, Troels Emtekær; Borg, Mikael

    2013-01-01

    We present the ProCS method for the rapid and accurate prediction of protein backbone amide proton chemical shifts - sensitive probes of the geometry of key hydrogen bonds that determine protein structure. ProCS is parameterized against quantum mechanical (QM) calculations and reproduces high level...

  13. Use of Chemical Mixtures to Differentiate Mechanisms of Endocrine Action in a Small Fish Model

    Science.gov (United States)

    Various assays with adult fish have been developed to identify potential endocrine-disrupting chemicals (EDCs) which may cause toxicity via alterations in the hypothalamic-pituitary-gonadal (HPG) axis via different mechanisms/modes of action (MOA). These assays can be sensitive ...

  14. Mechanical properties and chemical stability of pivalolactone-based poly(ether ester)s

    NARCIS (Netherlands)

    Tijsma, E.J.; Tijsma, E.J.; van der Does, L.; Bantjes, A.; Bantjes, A.; Vulic, I.

    1994-01-01

    The processing, mechanical and chemical properties of poly(ether ester)s, prepared from pivalolactone (PVL), 1,4-butanediol (4G) and dimethyl terephthalate (DMT), were studied. The poly(ether ester)s could easily be processed by injection moulding, owing to their favourable rheological and thermal

  15. Lifetimes of organic photovoltaics: Combining chemical and physical characterisation techniques to study degradation mechanisms

    DEFF Research Database (Denmark)

    Norrman, K.; Larsen, N.B.; Krebs, Frederik C

    2006-01-01

    Degradation mechanisms of a photovoltaic device with an Al/C-60/C-12-PSV/PEDOT:PSS/ITO/glass geometry was studied using a combination of in-plane physical and chemical analysis techniques: TOF-SIMS, AFM, SEM, interference microscopy and fluorescence microscopy. A comparison was made between...

  16. Plant management in natural areas: balancing chemical, mechanical, and cultural control methods

    Science.gov (United States)

    Steven Manning; James. Miller

    2011-01-01

    After determining the best course of action for control of an invasive plant population, it is important to understand the variety of methods available to the integrated pest management professional. A variety of methods are now widely used in managing invasive plants in natural areas, including chemical, mechanical, and cultural control methods. Once the preferred...

  17. A MODELING AND SIMULATION LANGUAGE FOR BIOLOGICAL CELLS WITH COUPLED MECHANICAL AND CHEMICAL PROCESSES.

    Science.gov (United States)

    Somogyi, Endre; Glazier, James A

    2017-04-01

    Biological cells are the prototypical example of active matter. Cells sense and respond to mechanical, chemical and electrical environmental stimuli with a range of behaviors, including dynamic changes in morphology and mechanical properties, chemical uptake and secretion, cell differentiation, proliferation, death, and migration. Modeling and simulation of such dynamic phenomena poses a number of computational challenges. A modeling language describing cellular dynamics must naturally represent complex intra and extra-cellular spatial structures and coupled mechanical, chemical and electrical processes. Domain experts will find a modeling language most useful when it is based on concepts, terms and principles native to the problem domain. A compiler must then be able to generate an executable model from this physically motivated description. Finally, an executable model must efficiently calculate the time evolution of such dynamic and inhomogeneous phenomena. We present a spatial hybrid systems modeling language, compiler and mesh-free Lagrangian based simulation engine which will enable domain experts to define models using natural, biologically motivated constructs and to simulate time evolution of coupled cellular, mechanical and chemical processes acting on a time varying number of cells and their environment.

  18. A reconsideration for forming mechanism of optic fiber probe fabricated by static chemical etching

    Science.gov (United States)

    Chen, Yiru; Shen, Ruiqi

    2016-07-01

    The studies on the mechanism of static chemical etching are supplemented in this paper. Surface tension and diffusion effect are both taken into account. Theoretical analysis and data fitting show that the slant angle of the liquid-liquid interface leads to the maximum liquid rising, when diffusion effect is negligible.

  19. Mechanical, chemical and radiological characterization of the graphite of the UNGG reactors type

    International Nuclear Information System (INIS)

    Bresard, I.; Bonal, J.P.

    2000-01-01

    In the framework of UNGG reactors type dismantling procedures, the characterization of the graphite, used as moderator, has to be realized. This paper presents the mechanical, chemical and radiological characterizations, the properties measured and gives some results in the case of the Bugey 1 reactor. (A.L.B.)

  20. Structure-mechanism-based engineering of chemical regulators targeting distinct pathological factors in Alzheimer's disease.

    Science.gov (United States)

    Beck, Michael W; Derrick, Jeffrey S; Kerr, Richard A; Oh, Shin Bi; Cho, Woo Jong; Lee, Shin Jung C; Ji, Yonghwan; Han, Jiyeon; Tehrani, Zahra Aliakbar; Suh, Nayoung; Kim, Sujeong; Larsen, Scott D; Kim, Kwang S; Lee, Joo-Yong; Ruotolo, Brandon T; Lim, Mi Hee

    2016-10-13

    The absence of effective therapeutics against Alzheimer's disease (AD) is a result of the limited understanding of its multifaceted aetiology. Because of the lack of chemical tools to identify pathological factors, investigations into AD pathogenesis have also been insubstantial. Here we report chemical regulators that demonstrate distinct specificity towards targets linked to AD pathology, including metals, amyloid-β (Aβ), metal-Aβ, reactive oxygen species, and free organic radicals. We obtained these chemical regulators through a rational structure-mechanism-based design strategy. We performed structural variations of small molecules for fine-tuning their electronic properties, such as ionization potentials and mechanistic pathways for reactivity towards different targets. We established in vitro and/or in vivo efficacies of the regulators for modulating their targets' reactivities, ameliorating toxicity, reducing amyloid pathology, and improving cognitive deficits. Our chemical tools show promise for deciphering AD pathogenesis and discovering effective drugs.

  1. Mechanical and chemical compaction in fine-grained shallow-water limestones.

    Science.gov (United States)

    Shinn, E.A.; Robbin, D.M.

    1983-01-01

    Significant mechanical compaction resulted from pressures simulating less than 305 m of burial. Increasing loads to an equivalent of more than 3400 m did not significantly increase compaction or reduce sediment core length. Chemical compaction (pressure dissolution) was detected only in sediment cores compacted to pressures greater than 3400 m of burial. These short-term experiments suggest that chemical compaction would begin at much shallower depths given geologic time. Compaction experiments that caused chemical compaction lend support to the well-established hypothesis; that cement required to produce a low-porosity/low-permeability fine-grained limestone is derived internally. Dissolution, ion diffusion, and reprecipitation are considered the most likely processes for creating significant thicknesses of dense limestone in the geologic record. Continuation of chemical compaction after significant porosity reduction necessitates expulsion of connate fluids, possibly including hydrocarbons. -from Authors

  2. Intercomparison of chemical mechanisms for air quality policy formulation and assessment under North American conditions.

    Science.gov (United States)

    Derwent, Richard

    2017-07-01

    The intercomparison of seven chemical mechanisms for their suitability for air quality policy formulation and assessment is described. Box modeling techniques were employed using 44 sets of background environmental conditions covering North America to constrain the chemical development of the longer lived species. The selected mechanisms were modified to enable an unbiased assessment of the adequacy of the parameterizations of photochemical ozone production from volatile organic compound (VOC) oxidation in the presence of NO x . Photochemical ozone production rates responded differently to 30% NO x and VOC reductions with the different mechanisms, despite the striking similarities between the base-case ozone production rates. The 30% reductions in NO x and VOCs also produced changes in OH. The responses in OH to 30% reductions in NO x and VOCs appeared to be more sensitive to mechanism choice, compared with the responses in the photochemical ozone production rates. Although 30% NO x reductions generally led to decreases in OH, 30% reductions in VOCs led to increases in OH, irrespective of mechanism choice and background environmental conditions. The different mechanisms therefore gave different OH responses to NO x and VOC reductions and so would give different responses in terms of changes in the fate and behavior of air toxics, acidification and eutrophication, and fine particle formation compared with others, in response to ozone control strategies. Policymakers need to understand that there are likely to be inherent differences in the responses to ozone control strategies between different mechanisms, depending on background environmental conditions and the extents of NO x and VOC reductions under consideration. The purpose of this paper is to compare predicted ozone responses to NO x and VOC reductions with seven chemical mechanisms under North American conditions. The good agreement found between the tested mechanisms should provide some support for their

  3. Chemical reaction of hexagonal boron nitride and graphite nanoclusters in mechanical milling systems

    Energy Technology Data Exchange (ETDEWEB)

    Muramatsu, Y.; Grush, M.; Callcott, T.A. [Univ. of Tennessee, Knoxville, TN (United States)] [and others

    1997-04-01

    Synthesis of boron-carbon-nitride (BCN) hybrid alloys has been attempted extensively by many researchers because the BCN alloys are considered an extremely hard material called {open_quotes}super diamond,{close_quotes} and the industrial application for wear-resistant materials is promising. A mechanical alloying (MA) method of hexagonal boron nitride (h-BN) with graphite has recently been studied to explore the industrial synthesis of the BCN alloys. To develop the MA method for the BCN alloy synthesis, it is necessary to confirm the chemical reaction processes in the mechanical milling systems and to identify the reaction products. Therefore, the authors have attempted to confirm the chemical reaction process of the h-BN and graphite in mechanical milling systems using x-ray absorption near edge structure (XANES) methods.

  4. Chemical reaction of hexagonal boron nitride and graphite nanoclusters in mechanical milling systems

    International Nuclear Information System (INIS)

    Muramatsu, Y.; Grush, M.; Callcott, T.A.

    1997-01-01

    Synthesis of boron-carbon-nitride (BCN) hybrid alloys has been attempted extensively by many researchers because the BCN alloys are considered an extremely hard material called open-quotes super diamond,close quotes and the industrial application for wear-resistant materials is promising. A mechanical alloying (MA) method of hexagonal boron nitride (h-BN) with graphite has recently been studied to explore the industrial synthesis of the BCN alloys. To develop the MA method for the BCN alloy synthesis, it is necessary to confirm the chemical reaction processes in the mechanical milling systems and to identify the reaction products. Therefore, the authors have attempted to confirm the chemical reaction process of the h-BN and graphite in mechanical milling systems using x-ray absorption near edge structure (XANES) methods

  5. A coupled mechanical and chemical damage model for concrete affected by alkali–silica reaction

    Energy Technology Data Exchange (ETDEWEB)

    Pignatelli, Rossella, E-mail: rossellapignatelli@gmail.com [Department of Civil and Environmental Engineering, Politecnico di Milano, Piazza L. da Vinci 32, 20133 Milano (Italy); Lombardi Ingegneria S.r.l., Via Giotto 36, 20145 Milano (Italy); Comi, Claudia, E-mail: comi@stru.polimi.it [Department of Civil and Environmental Engineering, Politecnico di Milano, Piazza L. da Vinci 32, 20133 Milano (Italy); Monteiro, Paulo J.M., E-mail: monteiro@ce.berkeley.edu [Department of Civil and Environmental Engineering, University of California, Berkeley, CA 94720 (United States)

    2013-11-15

    To model the complex degradation phenomena occurring in concrete affected by alkali–silica reaction (ASR), we formulate a poro-mechanical model with two isotropic internal variables: the chemical and the mechanical damage. The chemical damage, related to the evolution of the reaction, is caused by the pressure generated by the expanding ASR gel on the solid concrete skeleton. The mechanical damage describes the strength and stiffness degradation induced by the external loads. As suggested by experimental results, degradation due to ASR is considered to be localized around reactive sites. The effect of the degree of saturation and of the temperature on the reaction development is also modeled. The chemical damage evolution is calibrated using the value of the gel pressure estimated by applying the electrical diffuse double-layer theory to experimental values of the surface charge density in ASR gel specimens reported in the literature. The chemo-damage model is first validated by simulating expansion tests on reactive specimens and beams; the coupled chemo-mechanical damage model is then employed to simulate compression and flexure tests results also taken from the literature. -- Highlights: •Concrete degradation due to ASR in variable environmental conditions is modeled. •Two isotropic internal variables – chemical and mechanical damage – are introduced. •The value of the swelling pressure is estimated by the diffuse double layer theory. •A simplified scheme is proposed to relate macro- and microscopic properties. •The chemo-mechanical damage model is validated by simulating tests in literature.

  6. Chemical compounds from anthropogenic environment and immune evasion mechanisms: potential interactions

    Science.gov (United States)

    Kravchenko, Julia; Corsini, Emanuela; Williams, Marc A.; Decker, William; Manjili, Masoud H.; Otsuki, Takemi; Singh, Neetu; Al-Mulla, Faha; Al-Temaimi, Rabeah; Amedei, Amedeo; Colacci, Anna Maria; Vaccari, Monica; Mondello, Chiara; Scovassi, A. Ivana; Raju, Jayadev; Hamid, Roslida A.; Memeo, Lorenzo; Forte, Stefano; Roy, Rabindra; Woodrick, Jordan; Salem, Hosni K.; Ryan, Elizabeth P.; Brown, Dustin G.; Lowe, Leroy; Lyerly, H.Kim

    2015-01-01

    An increasing number of studies suggest an important role of host immunity as a barrier to tumor formation and progression. Complex mechanisms and multiple pathways are involved in evading innate and adaptive immune responses, with a broad spectrum of chemicals displaying the potential to adversely influence immunosurveillance. The evaluation of the cumulative effects of low-dose exposures from the occupational and natural environment, especially if multiple chemicals target the same gene(s) or pathway(s), is a challenge. We reviewed common environmental chemicals and discussed their potential effects on immunosurveillance. Our overarching objective was to review related signaling pathways influencing immune surveillance such as the pathways involving PI3K/Akt, chemokines, TGF-β, FAK, IGF-1, HIF-1α, IL-6, IL-1α, CTLA-4 and PD-1/PDL-1 could individually or collectively impact immunosurveillance. A number of chemicals that are common in the anthropogenic environment such as fungicides (maneb, fluoxastrobin and pyroclostrobin), herbicides (atrazine), insecticides (pyridaben and azamethiphos), the components of personal care products (triclosan and bisphenol A) and diethylhexylphthalate with pathways critical to tumor immunosurveillance. At this time, these chemicals are not recognized as human carcinogens; however, it is known that they these chemicalscan simultaneously persist in the environment and appear to have some potential interfere with the host immune response, therefore potentially contributing to promotion interacting with of immune evasion mechanisms, and promoting subsequent tumor growth and progression. PMID:26002081

  7. Surface-modified polymeric pads for enhanced performance during chemical mechanical planarization

    International Nuclear Information System (INIS)

    Deshpande, S.; Dakshinamurthy, S.; Kuiry, S.C.; Vaidyanathan, R.; Obeng, Y.S.; Seal, S.

    2005-01-01

    The chemical mechanical planarization (CMP) process occurs at an atomic level at the slurry/wafer interface and hence slurries and polishing pads play a critical role in their successful implementation. Polyurethane is a commonly used polymer in the manufacturing of CMP pads. These pads are incompatible with some chemicals present in the CMP slurries, such as hydrogen peroxide. To overcome these problems, Psiloquest has developed new Application Specific Pads (ASP). Surface of such pads has been modified by depositing a thin film of tetraethyl orthosilicate using plasma-enhanced chemical vapor deposition (PECVD) process. In the present study, mechanical properties of such coated pads have been investigated using nanoindentation. The surface morphology and the chemistry of the ASP were studied using scanning electron microcopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy techniques. It was observed that mechanical and chemical properties of the pad top surface are a function of the PECVD coating time. Such PECVD-treated pads are found to be hydrophilic and do not require storage in aqueous media during the not-in-use period. The metal removal rate using such surface-modified polishing pads was found to increase linearly with the PECVD coating time

  8. Evaluation and Development of Chemical Kinetic Mechanism Reduction Scheme for Biodiesel and Diesel Fuel Surrogates

    DEFF Research Database (Denmark)

    Poon, Hiew Mun; Ng, Hoon Kiat; Gan, Suyin

    2013-01-01

    The aim of this study is to evaluate the existing chemical kinetic mechanism reduction techniques. From here, an appropriate reduction scheme was developed to create compact yet comprehensive surrogate models for both diesel and biodiesel fuels for diesel engine applications. The reduction...... techniques applied here were Directed Relation Graph (DRG), DRG with Error Propagation, DRG-aided Sensitivity Analysis, and DRG with Error Propagation and Sensitivity Analysis. Nonetheless, the reduced mechanisms generated via these techniques were not sufficiently small for application in multi......-dimensional computational fluid dynamics (CFD) study. A new reduction scheme was therefore formulated. A 68-species mechanism for biodiesel surrogate and a 49-species mechanism for diesel surrogate were successfully derived from the respective detailed mechanisms. An overall 97% reduction in species number...

  9. Comparison of physico-chemical properties of various lignites treated by mechanical thermal expression

    Energy Technology Data Exchange (ETDEWEB)

    Janine Hulston; Alan L. Chaffee; Christian Bergins; Karl Strauss [Monash University, Vic. (Australia). School of Chemistry and CRC for Clean Power from Lignite

    2005-12-01

    This study investigates how the Mechanical Thermal Expression (MTE) process affects the physico-chemical properties of low rank lignites sourced from Australia, Greece, and Germany. The MTE process was effective in reducing the moisture content of all three coals and resulted in significant Na reductions in both the Australian and German coals. However, the organic composition of the coals investigated remained relatively unaffected. Upon oven drying, all wet MTE products underwent significant shrinkage, the degree of which was dependent upon the temperature and pressure used during the MTE process. Upon rehydration, the oven-dried MTE products underwent significant swelling, which is most likely related to the chemical composition of the coals.

  10. Effects of chemical contamination on HDPE - thermo-mechanical and characterisation properties

    International Nuclear Information System (INIS)

    Ashraf, G.

    2002-01-01

    Studying the effects of chemical contamination on HDPE is an important precursor in recycling of plastic packaging and polymer reprocessing. This research involves and discusses the results of an in-depth investigation into the effects of chemically contaminating, using various acids, commercial grade high density polyethylene (HDPE) used commonly in packaging applications. An extensive formulation study was conducted and it became obvious that in some cases degradation had occurred to HDPE when chemically contaminated with particular functional group types. The functional groups in contaminated HDPE were successfully identified. A variety of analytical techniques such as Fourier transform Infra-red spectroscopy, X-ray Florescence, x-ray photo electron spectroscopy could identify compounds such as HCl acid, HNO/sub 3/ acid and other related contaminants. Some chemical additives had effects on the mechanical and thermal properties when added in the most appropriate concentration. The results have shown lower tensile modulus and strength tensile elongation, lower modular weight, melt flow index and crystallinity. The amount of contaminant concentration, the type of chemical functional groups used and the type of test selected to affect degradation are important factors in proving the effects of chemical contamination on HDPE in the melt state. (author)

  11. Utilizing toxicogenomic data to understand chemical mechanism of action in risk assessment

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, Vickie S., E-mail: wilson.vickie@epa.gov [National Health and Environmental Effects Research Laboratory, Office of Research and Development, U.S. Environmental Protection Agency, Research Triangle Park, NC 27711 (United States); Keshava, Nagalakshmi [National Center for Environmental Assessment, Office of Research and Development, U.S. Environmental Protection Agency, 1200 Pennsylvania Ave., NW, Washington, DC 20460 (United States); Hester, Susan [National Health and Environmental Effects Research Laboratory, Office of Research and Development, U.S. Environmental Protection Agency, Research Triangle Park, NC 27711 (United States); Segal, Deborah; Chiu, Weihsueh [National Center for Environmental Assessment, Office of Research and Development, U.S. Environmental Protection Agency, 1200 Pennsylvania Ave., NW, Washington, DC 20460 (United States); Thompson, Chad M. [ToxStrategies, Inc., 23501 Cinco Ranch Blvd., Suite G265, Katy, TX 77494 (United States); Euling, Susan Y. [National Center for Environmental Assessment, Office of Research and Development, U.S. Environmental Protection Agency, 1200 Pennsylvania Ave., NW, Washington, DC 20460 (United States)

    2013-09-15

    The predominant role of toxicogenomic data in risk assessment, thus far, has been one of augmentation of more traditional in vitro and in vivo toxicology data. This article focuses on the current available examples of instances where toxicogenomic data has been evaluated in human health risk assessment (e.g., acetochlor and arsenicals) which have been limited to the application of toxicogenomic data to inform mechanism of action. This article reviews the regulatory policy backdrop and highlights important efforts to ultimately achieve regulatory acceptance. A number of research efforts on specific chemicals that were designed for risk assessment purposes have employed mechanism or mode of action hypothesis testing and generating strategies. The strides made by large scale efforts to utilize toxicogenomic data in screening, testing, and risk assessment are also discussed. These efforts include both the refinement of methodologies for performing toxicogenomics studies and analysis of the resultant data sets. The current issues limiting the application of toxicogenomics to define mode or mechanism of action in risk assessment are discussed together with interrelated research needs. In summary, as chemical risk assessment moves away from a single mechanism of action approach toward a toxicity pathway-based paradigm, we envision that toxicogenomic data from multiple technologies (e.g., proteomics, metabolomics, transcriptomics, supportive RT-PCR studies) can be used in conjunction with one another to understand the complexities of multiple, and possibly interacting, pathways affected by chemicals which will impact human health risk assessment.

  12. Utilizing toxicogenomic data to understand chemical mechanism of action in risk assessment

    International Nuclear Information System (INIS)

    Wilson, Vickie S.; Keshava, Nagalakshmi; Hester, Susan; Segal, Deborah; Chiu, Weihsueh; Thompson, Chad M.; Euling, Susan Y.

    2013-01-01

    The predominant role of toxicogenomic data in risk assessment, thus far, has been one of augmentation of more traditional in vitro and in vivo toxicology data. This article focuses on the current available examples of instances where toxicogenomic data has been evaluated in human health risk assessment (e.g., acetochlor and arsenicals) which have been limited to the application of toxicogenomic data to inform mechanism of action. This article reviews the regulatory policy backdrop and highlights important efforts to ultimately achieve regulatory acceptance. A number of research efforts on specific chemicals that were designed for risk assessment purposes have employed mechanism or mode of action hypothesis testing and generating strategies. The strides made by large scale efforts to utilize toxicogenomic data in screening, testing, and risk assessment are also discussed. These efforts include both the refinement of methodologies for performing toxicogenomics studies and analysis of the resultant data sets. The current issues limiting the application of toxicogenomics to define mode or mechanism of action in risk assessment are discussed together with interrelated research needs. In summary, as chemical risk assessment moves away from a single mechanism of action approach toward a toxicity pathway-based paradigm, we envision that toxicogenomic data from multiple technologies (e.g., proteomics, metabolomics, transcriptomics, supportive RT-PCR studies) can be used in conjunction with one another to understand the complexities of multiple, and possibly interacting, pathways affected by chemicals which will impact human health risk assessment

  13. A comparison of chemical mechanisms using tagged ozone production potential (TOPP analysis

    Directory of Open Access Journals (Sweden)

    J. Coates

    2015-08-01

    Full Text Available Ground-level ozone is a secondary pollutant produced photochemically from reactions of NOx with peroxy radicals produced during volatile organic compound (VOC degradation. Chemical transport models use simplified representations of this complex gas-phase chemistry to predict O3 levels and inform emission control strategies. Accurate representation of O3 production chemistry is vital for effective prediction. In this study, VOC degradation chemistry in simplified mechanisms is compared to that in the near-explicit Master Chemical Mechanism (MCM using a box model and by "tagging" all organic degradation products over multi-day runs, thus calculating the tagged ozone production potential (TOPP for a selection of VOCs representative of urban air masses. Simplified mechanisms that aggregate VOC degradation products instead of aggregating emitted VOCs produce comparable amounts of O3 from VOC degradation to the MCM. First-day TOPP values are similar across mechanisms for most VOCs, with larger discrepancies arising over the course of the model run. Aromatic and unsaturated aliphatic VOCs have the largest inter-mechanism differences on the first day, while alkanes show largest differences on the second day. Simplified mechanisms break VOCs down into smaller-sized degradation products on the first day faster than the MCM, impacting the total amount of O3 produced on subsequent days due to secondary chemistry.

  14. CH4/air homogeneous autoignition: A comparison of two chemical kinetics mechanisms

    KAUST Repository

    Tingas, Efstathios Al.

    2018-03-11

    Reactions contributing to the generation of the explosive time scale that characterise autoignition of homogeneous stoichiometric CH4/air mixture are identified using two different chemical kinetics models; the well known GRI-3.0 mechanism (53/325 species/reactions with N-chemistry) and the AramcoMech mechanism from NUI Galway (113/710 species/reactions without N-chemistry; Combustion and Flame 162:315-330, 2015). Although the two mechanisms provide qualitatively similar results (regarding ignition delay and profiles of temperature, of mass fractions and of explosive time scale), the 113/710 mechanism was shown to reproduce the experimental data with higher accuracy than the 53/325 mechanism. The present analysis explores the origin of the improved accuracy provided by the more complex kinetics mechanism. It is shown that the reactions responsible for the generation of the explosive time scale differ significantly. This is reflected to differences in the length of the chemical and thermal runaways and in the set of the most influential species.

  15. Research Update: Mechanical properties of metal-organic frameworks – Influence of structure and chemical bonding

    Directory of Open Access Journals (Sweden)

    Wei Li

    2014-12-01

    Full Text Available Metal-organic frameworks (MOFs, a young family of functional materials, have been attracting considerable attention from the chemistry, materials science, and physics communities. In the light of their potential applications in industry and technology, the fundamental mechanical properties of MOFs, which are of critical importance for manufacturing, processing, and performance, need to be addressed and understood. It has been widely accepted that the framework topology, which describes the overall connectivity pattern of the MOF building units, is of vital importance for the mechanical properties. However, recent advances in the area of MOF mechanics reveal that chemistry plays a major role as well. From the viewpoint of materials science, a deep understanding of the influence of chemical effects on MOF mechanics is not only highly desirable for the development of novel functional materials with targeted mechanical response, but also for a better understanding of important properties such as structural flexibility and framework breathing. The present work discusses the intrinsic connection between chemical effects and the mechanical behavior of MOFs through a number of prototypical examples.

  16. Research Update: Mechanical properties of metal-organic frameworks - Influence of structure and chemical bonding

    Science.gov (United States)

    Li, Wei; Henke, Sebastian; Cheetham, Anthony K.

    2014-12-01

    Metal-organic frameworks (MOFs), a young family of functional materials, have been attracting considerable attention from the chemistry, materials science, and physics communities. In the light of their potential applications in industry and technology, the fundamental mechanical properties of MOFs, which are of critical importance for manufacturing, processing, and performance, need to be addressed and understood. It has been widely accepted that the framework topology, which describes the overall connectivity pattern of the MOF building units, is of vital importance for the mechanical properties. However, recent advances in the area of MOF mechanics reveal that chemistry plays a major role as well. From the viewpoint of materials science, a deep understanding of the influence of chemical effects on MOF mechanics is not only highly desirable for the development of novel functional materials with targeted mechanical response, but also for a better understanding of important properties such as structural flexibility and framework breathing. The present work discusses the intrinsic connection between chemical effects and the mechanical behavior of MOFs through a number of prototypical examples.

  17. Correlation between electrical, mechanical and chemical properties of fresh and used aircraft engine oils

    Science.gov (United States)

    Gajewski, Juliusz B.; Głogowski, Marek J.; Paszkowski, Maciej; Czarnik-Matusewicz, Bogusława

    2011-06-01

    In this paper the results are presented of measurements of electrical, mechanical and chemical properties of fresh and used aircraft engine oils. Oils were used in a four-stroke aircraft engine and their samples were taken after the 50-hour work of the engine. The resistivity, permittivity and viscosity of oils were measured as a function of temperature. Additionally, some measurements of the absorbance spectra and size of particles contained in the oils were carried out. The significant reduction in the resistivity of the used Total oil was observed. The relative permittivity of both used oils was slightly increased. The oil's relative viscosity depends on temperature of oil and given time that elapsed from the very first moment when the shear force was applied in a rheometer. The results obtained allowed one to identify more precisely the chemical and physico-chemical interactions occurring in the tested samples, as compared with a typical infrared spectroscopy.

  18. Effect of mechanical activation on structure changes and reactivity in further chemical modification of lignin.

    Science.gov (United States)

    Zhao, Xiaohong; Zhang, Yanjuan; Hu, Huayu; Huang, Zuqiang; Yang, Mei; Chen, Dong; Huang, Kai; Huang, Aimin; Qin, Xingzhen; Feng, Zhenfei

    2016-10-01

    Lignin was treated by mechanical activation (MA) in a customized stirring ball mill, and the structure and reactivity in further esterification were studied. The chemical structure and morphology of MA-treated lignin and the esterified products were analyzed by chemical analysis combined with UV/vis spectrometer, FTIR,NMR, SEM and particle size analyzer. The results showed that MA contributed to the increase of aliphatic hydroxyl, phenolic hydroxyl, carbonyl and carboxyl groups but the decrease of methoxyl groups. Moreover, MA led to the decrease of particle size and the increase of specific surface area and roughness of surface in lignin. The reactivity of lignin was enhanced significantly for the increase of hydroxyl content and the improvement of mass transfer in chemical reaction caused by the changes of molecular structure and morphological structure. The process of MA is green and simple, and is an effective method for enhancing the reactivity of lignin. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Correlation between electrical, mechanical and chemical properties of fresh and used aircraft engine oils

    International Nuclear Information System (INIS)

    Gajewski, Juliusz B; Glogowski, Marek J; Paszkowski, Maciej; Czarnik-Matusewicz, Boguslawa

    2011-01-01

    In this paper the results are presented of measurements of electrical, mechanical and chemical properties of fresh and used aircraft engine oils. Oils were used in a four-stroke aircraft engine and their samples were taken after the 50-hour work of the engine. The resistivity, permittivity and viscosity of oils were measured as a function of temperature. Additionally, some measurements of the absorbance spectra and size of particles contained in the oils were carried out. The significant reduction in the resistivity of the used Total oil was observed. The relative permittivity of both used oils was slightly increased. The oil's relative viscosity depends on temperature of oil and given time that elapsed from the very first moment when the shear force was applied in a rheometer. The results obtained allowed one to identify more precisely the chemical and physico-chemical interactions occurring in the tested samples, as compared with a typical infrared spectroscopy.

  20. Physico-chemical mechanism for the vapors sensitivity of photoluminescent InP quantum dots

    Science.gov (United States)

    Prosposito, P.; De Angelis, R.; De Matteis, F.; Hatami, F.; Masselink, W. T.; Zhang, H.; Casalboni, M.

    2016-03-01

    InP/InGaP surface quantum dots are interesting materials for optical chemical sensors since they present an intense emission at room temperature, whose intensity changes rapidly and reversibly depending on the composition of the environmental atmosphere. We present here their emission properties by time resolved photoluminescence spectroscopy investigation and we discuss the physico-chemical mechanism behind their sensitivity to the surrounding atmosphere. Photoluminescence transients in inert atmosphere (N2) and in solvent vapours of methanol, clorophorm, acetone and water were measured. The presence of vapors of clorophorm, acetone and water showed a very weak effect on the transient times, while an increase of up to 15% of the decay time was observed for methanol vapour exposure. On the basis of the vapor molecule nature (polarity, proticity, steric hindrance, etc.) and of the interaction of the vapor molecules with the quantum dots surface a sensing mechanism involving quantum dots non-radiative surface states is proposed.

  1. Physico-chemical mechanism for the vapors sensitivity of photoluminescent InP quantum dots

    International Nuclear Information System (INIS)

    Prosposito, P.; De Angelis, R.; De Matteis, F.; Casalboni, M.; Hatami, F.; Masselink, W.T.; Zhang, H.

    2016-01-01

    InP/InGaP surface quantum dots are interesting materials for optical chemical sensors since they present an intense emission at room temperature, whose intensity changes rapidly and reversibly depending on the composition of the environmental atmosphere. We present here their emission properties by time resolved photoluminescence spectroscopy investigation and we discuss the physico-chemical mechanism behind their sensitivity to the surrounding atmosphere. Photoluminescence transients in inert atmosphere (N 2 ) and in solvent vapours of methanol, chloroform, acetone and water were measured. The presence of vapors of chloroform, acetone and water showed a very weak effect on the transient times, while an increase of up to 15% of the decay time was observed for methanol vapour exposure. On the basis of the vapor molecule nature (polarity, proticity, steric hindrance, etc.) and of the interaction of the vapor molecules with the quantum dots surface a sensing mechanism involving quantum dots non-radiative surface states is proposed. (paper)

  2. Comparison of interaction mechanisms of copper phthalocyanine and nickel phthalocyanine thin films with chemical vapours

    Science.gov (United States)

    Ridhi, R.; Singh, Sukhdeep; Saini, G. S. S.; Tripathi, S. K.

    2018-04-01

    The present study deals with comparing interaction mechanisms of copper phthalocyanine and nickel phthalocyanine with versatile chemical vapours: reducing, stable aromatic and oxidizing vapours namely; diethylamine, benzene and bromine. The variation in electrical current of phthalocyanines with exposure of chemical vapours is used as the detection parameter for studying interaction behaviour. Nickel phthalocyanine is found to exhibit anomalous behaviour after exposure of reducing vapour diethylamine due to alteration in its spectroscopic transitions and magnetic states. The observed sensitivities of copper phthalocyanine and nickel phthalcyanine films are different in spite of their similar bond numbers, indicating significant role of central metal atom in interaction mechanism. The variations in electronic transition levels after vapours exposure, studied using UV-Visible spectroscopy confirmed our electrical sensing results. Bromine exposure leads to significant changes in vibrational bands of metal phthalocyanines as compared to other vapours.

  3. Promise of combined hydrothermal/chemical and mechanical refining for pretreatment of woody and herbaceous biomass.

    Science.gov (United States)

    Kim, Sun Min; Dien, Bruce S; Singh, Vijay

    2016-01-01

    Production of advanced biofuels from woody and herbaceous feedstocks is moving into commercialization. Biomass needs to be pretreated to overcome the physicochemical properties of biomass that hinder enzyme accessibility, impeding the conversion of the plant cell walls to fermentable sugars. Pretreatment also remains one of the most costly unit operations in the process and among the most critical because it is the source of chemicals that inhibit enzymes and microorganisms and largely determines enzyme loading and sugar yields. Pretreatments are categorized into hydrothermal (aqueous)/chemical, physical, and biological pretreatments, and the mechanistic details of which are briefly outlined in this review. To leverage the synergistic effects of different pretreatment methods, conducting two or more pretreatments consecutively has gained attention. Especially, combining hydrothermal/chemical pretreatment and mechanical refining, a type of physical pretreatment, has the potential to be applied to an industrial plant. Here, the effects of the combined pretreatment (combined hydrothermal/chemical pretreatment and mechanical refining) on energy consumption, physical structure, sugar yields, and enzyme dosage are summarized.

  4. Chemical weathering as a mechanism for the climatic control of bedrock river incision

    Science.gov (United States)

    Murphy, Brendan P.; Johnson, Joel P. L.; Gasparini, Nicole M.; Sklar, Leonard S.

    2016-04-01

    Feedbacks between climate, erosion and tectonics influence the rates of chemical weathering reactions, which can consume atmospheric CO2 and modulate global climate. However, quantitative predictions for the coupling of these feedbacks are limited because the specific mechanisms by which climate controls erosion are poorly understood. Here we show that climate-dependent chemical weathering controls the erodibility of bedrock-floored rivers across a rainfall gradient on the Big Island of Hawai‘i. Field data demonstrate that the physical strength of bedrock in streambeds varies with the degree of chemical weathering, which increases systematically with local rainfall rate. We find that incorporating the quantified relationships between local rainfall and erodibility into a commonly used river incision model is necessary to predict the rates and patterns of downcutting of these rivers. In contrast to using only precipitation-dependent river discharge to explain the climatic control of bedrock river incision, the mechanism of chemical weathering can explain strong coupling between local climate and river incision.

  5. Performance test of multicomponent quantum mechanical calculation with polarizable continuum model for proton chemical shift.

    Science.gov (United States)

    Kanematsu, Yusuke; Tachikawa, Masanori

    2015-05-21

    Multicomponent quantum mechanical (MC_QM) calculations with polarizable continuum model (PCM) have been tested against liquid (1)H NMR chemical shifts for a test set of 80 molecules. Improvement from conventional quantum mechanical calculations was achieved for MC_QM calculations. The advantage of the multicomponent scheme could be attributed to the geometrical change from the equilibrium geometry by the incorporation of the hydrogen nuclear quantum effect, while that of PCM can be attributed to the change of the electronic structure according to the polarization by solvent effects.

  6. Analysis of mechanical and chemical pellet-clad interaction during power ramps

    International Nuclear Information System (INIS)

    Vogl, W.; Hering, W.; Peehs; Lavake, J.

    1979-01-01

    A research and development program is being conducted by KWU and C-E to investigate Pellet/Clad Interaction (PCI) in LWR fuel rods during power ramping. Out-of-pile iodine stress corrosion cracking studies, in-pile ramp experiments and hot cell chemical and metallographical post-irradiation examinations are being performed to study and evaluate both the power limitations and the basic mechanisms of PCI as well as practical methods to improve ramping performance. (orig.)

  7. Electronic and Mechanical Properties of GrapheneGermanium Interfaces Grown by Chemical Vapor Deposition

    Science.gov (United States)

    2015-10-27

    that graphene acts as a diffusion barrier to ambient contaminants, as similarly prepared bare Ge exposed to ambient conditions possesses a much...in-plane order underneath the graphene (Figure 1b,f). The stabilization of Ge terraces with half-step heights indicates that the graphene modifies the...Electronic and Mechanical Properties of Graphene −Germanium Interfaces Grown by Chemical Vapor Deposition Brian Kiraly,†,‡ Robert M. Jacobberger

  8. Postharvest Chemical, Sensorial and Physical-Mechanical Properties of Wild Apricot (Prunus armeniaca L.)

    OpenAIRE

    Evica MRATINIĆ; Bojan POPOVSKI; Tomo MILOŠEVIĆ; Melpomena POPOVSKA

    2011-01-01

    Some chemical, sensorial and physical-mechanical properties of 19 apricot genotypes and Hungarian Best (control) such as moisture content, soluble solids content, titratable acidity ratio and their ratio, fruit and stone mass, flesh/stone ratio, fruit dimensions (length, width, thickness), arithmetic and geometric mean diameter, sphericity, surface area and aspect ratio were determined. Their application is also discussed. The highest moisture content and stone mass observed in X-1/1/04 and X...

  9. Combined Ultrasonic Elliptical Vibration and Chemical Mechanical Polishing of Monocrystalline Silicon

    Directory of Open Access Journals (Sweden)

    Liu Defu

    2016-01-01

    Full Text Available An ultrasonic elliptical vibration assisted chemical mechanical polishing(UEV-CMP is employed to achieve high material removal rate and high surface quality in the finishing of hard and brittle materials such as monocrystalline silicon, which combines the functions of conventional CMP and ultrasonic machining. In theultrasonic elliptical vibration aided chemical mechanical polishingexperimental setup developed by ourselves, the workpiece attached at the end of horn can vibrate simultaneously in both horizontal and vertical directions. Polishing experiments are carried out involving monocrystalline silicon to confirm the performance of the proposed UEV-CMP. The experimental results reveal that the ultrasonic elliptical vibration can increase significantly the material removal rate and reduce dramatically the surface roughness of monocrystalline silicon. It is found that the removal rate of monocrystalline silicon polished by UEV-CMP is increased by approximately 110% relative to that of conventional CMP because a passive layer on the monocrystalline silicon surface, formed by the chemical action of the polishing slurry, will be removed not only by the mechanical action of CMP but also by ultrasonic vibration action. It indicates that the high efficiency and high quality CMP of monocrystalline silicon can be performed with the proposed UEV-CMP technique.

  10. Benchmarking quantum mechanical calculations with experimental NMR chemical shifts of 2-HADNT

    Science.gov (United States)

    Liu, Yuemin; Junk, Thomas; Liu, Yucheng; Tzeng, Nianfeng; Perkins, Richard

    2015-04-01

    In this study, both GIAO-DFT and GIAO-MP2 calculations of nuclear magnetic resonance (NMR) spectra were benchmarked with experimental chemical shifts. The experimental chemical shifts were determined experimentally for carbon-13 (C-13) of seven carbon atoms for the TNT degradation product 2-hydroxylamino-4,6-dinitrotoluene (2-HADNT). Quantum mechanics GIAO calculations were implemented using Becke-3-Lee-Yang-Parr (B3LYP) and other six hybrid DFT methods (Becke-1-Lee-Yang-Parr (B1LYP), Becke-half-and-half-Lee-Yang-Parr (BH and HLYP), Cohen-Handy-3-Lee-Yang-Parr (O3LYP), Coulomb-attenuating-B3LYP (CAM-B3LYP), modified-Perdew-Wang-91-Lee-Yang-Parr (mPW1LYP), and Xu-3-Lee-Yang-Parr (X3LYP)) which use the same correlation functional LYP. Calculation results showed that the GIAO-MP2 method gives the most accurate chemical shift values, and O3LYP method provides the best prediction of chemical shifts among the B3LYP and other five DFT methods. Three types of atomic partial charges, Mulliken (MK), electrostatic potential (ESP), and natural bond orbital (NBO), were also calculated using MP2/aug-cc-pVDZ method. A reasonable correlation was discovered between NBO partial charges and experimental chemical shifts of carbon-13 (C-13).

  11. The TOMCAT global chemical transport model v1.6: description of chemical mechanism and model evaluation

    Directory of Open Access Journals (Sweden)

    S. A. Monks

    2017-08-01

    Full Text Available This paper documents the tropospheric chemical mechanism scheme used in the TOMCAT 3-D chemical transport model. The current scheme includes a more detailed representation of hydrocarbon chemistry than previously included in the model, with the inclusion of the emission and oxidation of ethene, propene, butane, toluene and monoterpenes. The model is evaluated against a range of surface, balloon, aircraft and satellite measurements. The model is generally able to capture the main spatial and seasonal features of high and low concentrations of carbon monoxide (CO, ozone (O3, volatile organic compounds (VOCs and reactive nitrogen. However, model biases are found in some species, some of which are common to chemistry models and some that are specific to TOMCAT and warrant further investigation. The most notable of these biases are (1 a negative bias in Northern Hemisphere (NH winter and spring CO and a positive bias in Southern Hemisphere (SH CO throughout the year, (2 a positive bias in NH O3 in summer and a negative bias at high latitudes during SH winter and (3 a negative bias in NH winter C2 and C3 alkanes and alkenes. TOMCAT global mean tropospheric hydroxyl radical (OH concentrations are higher than estimates inferred from observations of methyl chloroform but similar to, or lower than, multi-model mean concentrations reported in recent model intercomparison studies. TOMCAT shows peak OH concentrations in the tropical lower troposphere, unlike other models which show peak concentrations in the tropical upper troposphere. This is likely to affect the lifetime and transport of important trace gases and warrants further investigation.

  12. Identifying the causes of differences in ozone production from the CB05 and CBMIV chemical mechanisms

    Directory of Open Access Journals (Sweden)

    R. D. Saylor

    2012-02-01

    Full Text Available An investigation was conducted to identify the mechanistic differences between two versions of the carbon bond gas-phase chemical mechanism (CB05 and CBMIV which consistently lead to larger ground-level ozone concentrations being produced in the CB05 version of the National Air Quality Forecasting Capability (NAQFC modeling system even though the two parallel forecast systems utilize the same meteorology and base emissions and similar initial and boundary conditions. Box models of each of the mechanisms as they are implemented in the NAQFC were created and a set of 12 sensitivity simulations was designed. The sensitivity simulations independently probed the conceptual mechanistic differences between CB05 and CBMIV and were exercised over a 45-scenario simulation suite designed to emulate the wide range of chemical regimes encountered in a continental-scale atmospheric chemistry model. Results of the sensitivity simulations indicate that two sets of reactions that were included in the CB05 mechanism, but which were absent from the CBMIV mechanism, are the primary causes of the greater ozone production in the CB05 version of the NAQFC. One set of reactions recycles the higher organic peroxide species of CB05 (ROOH, resulting in additional photochemically reactive products that act to produce additional ozone in some chemical regimes. The other set of reactions recycles reactive nitrogen from less reactive forms back to NO2, increasing the effective NOx concentration of the system. In particular, the organic nitrate species (NTR, which was a terminal product for reactive nitrogen in the CBMIV mechanism, acts as a reservoir species in CB05 to redistribute NOx from major source areas to potentially NOx-sensitive areas where additional ozone may be produced in areas remote from direct NOx sources.

  13. Comparison of Moringa Oleifera seeds oil characterization produced chemically and mechanically

    Science.gov (United States)

    Eman, N. A.; Muhamad, K. N. S.

    2016-06-01

    It is established that virtually every part of the Moringa oleifera tree (leaves, stem, bark, root, flowers, seeds, and seeds oil) are beneficial in some way with great benefits to human being. The tree is rich in proteins, vitamins, minerals. All Moringa oleifera food products have a very high nutritional value. They are eaten directly as food, as supplements, and as seasonings as well as fodder for animals. The purpose of this research is to investigate the effect of seeds particle size on oil extraction using chemical method (solvent extraction). Also, to compare Moringa oleifera seeds oil properties which are produced chemically (solvent extraction) and mechanically (mechanical press). The Moringa oleifera seeds were grinded, sieved, and the oil was extracted using soxhlet extraction technique with n-Hexane using three different size of sample (2mm, 1mm, and 500μm). The average oil yield was 36.1%, 40.80%, and 41.5% for 2mm, 1mm, and 500μm particle size, respectively. The properties of Moringa oleifera seeds oil were: density of 873 kg/m3, and 880 kg/m3, kinematic viscosity of 42.2mm2/s and 9.12mm2/s for the mechanical and chemical method, respectively. pH, cloud point and pour point were same for oil produced with both methods which is 6, 18°C and 12°C, respectively. For the fatty acids, the oleic acid is present with high percentage of 75.39%, and 73.60% from chemical and mechanical method, respectively. Other fatty acids are present as well in both samples which are (Gadoleic acid, Behenic acid, Palmitic acid) which are with lower percentage of 2.54%, 5.83%, and 5.73%, respectively in chemical method oil, while they present as 2.40%, 6.73%, and 6.04%, respectively in mechanical method oil. In conclusion, the results showed that both methods can produce oil with high quality. Moringa oleifera seeds oil appear to be an acceptable good source for oil rich in oleic acid which is equal to olive oil quality, that can be consumed in Malaysia where the olive oil

  14. Chemical compounds from anthropogenic environment and immune evasion mechanisms: potential interactions.

    Science.gov (United States)

    Kravchenko, Julia; Corsini, Emanuela; Williams, Marc A; Decker, William; Manjili, Masoud H; Otsuki, Takemi; Singh, Neetu; Al-Mulla, Faha; Al-Temaimi, Rabeah; Amedei, Amedeo; Colacci, Anna Maria; Vaccari, Monica; Mondello, Chiara; Scovassi, A Ivana; Raju, Jayadev; Hamid, Roslida A; Memeo, Lorenzo; Forte, Stefano; Roy, Rabindra; Woodrick, Jordan; Salem, Hosni K; Ryan, Elizabeth P; Brown, Dustin G; Bisson, William H; Lowe, Leroy; Lyerly, H Kim

    2015-06-01

    An increasing number of studies suggest an important role of host immunity as a barrier to tumor formation and progression. Complex mechanisms and multiple pathways are involved in evading innate and adaptive immune responses, with a broad spectrum of chemicals displaying the potential to adversely influence immunosurveillance. The evaluation of the cumulative effects of low-dose exposures from the occupational and natural environment, especially if multiple chemicals target the same gene(s) or pathway(s), is a challenge. We reviewed common environmental chemicals and discussed their potential effects on immunosurveillance. Our overarching objective was to review related signaling pathways influencing immune surveillance such as the pathways involving PI3K/Akt, chemokines, TGF-β, FAK, IGF-1, HIF-1α, IL-6, IL-1α, CTLA-4 and PD-1/PDL-1 could individually or collectively impact immunosurveillance. A number of chemicals that are common in the anthropogenic environment such as fungicides (maneb, fluoxastrobin and pyroclostrobin), herbicides (atrazine), insecticides (pyridaben and azamethiphos), the components of personal care products (triclosan and bisphenol A) and diethylhexylphthalate with pathways critical to tumor immunosurveillance. At this time, these chemicals are not recognized as human carcinogens; however, it is known that they these chemicalscan simultaneously persist in the environment and appear to have some potential interfere with the host immune response, therefore potentially contributing to promotion interacting with of immune evasion mechanisms, and promoting subsequent tumor growth and progression. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  15. The Radical Pair Mechanism and the Avian Chemical Compass: Quantum Coherence and Entanglement

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yiteng [Purdue Univ., West Lafayette, IN (United States); Kais, Sabre [Purdue Univ., West Lafayette, IN (United States); Berman, Gennady Petrovich [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2015-02-02

    We review the spin radical pair mechanism which is a promising explanation of avian navigation. This mechanism is based on the dependence of product yields on 1) the hyperfine interaction involving electron spins and neighboring nuclear spins and 2) the intensity and orientation of the geomagnetic field. One surprising result is that even at ambient conditions quantum entanglement of electron spins can play an important role in avian magnetoreception. This review describes the general scheme of chemical reactions involving radical pairs generated from singlet and triplet precursors; the spin dynamics of the radical pairs; and the magnetic field dependence of product yields caused by the radical pair mechanism. The main part of the review includes a description of the chemical compass in birds. We review: the general properties of the avian compass; the basic scheme of the radical pair mechanism; the reaction kinetics in cryptochrome; quantum coherence and entanglement in the avian compass; and the effects of noise. We believe that the quantum avian compass can play an important role in avian navigation and can also provide the foundation for a new generation of sensitive and selective magnetic-sensing nano-devices.

  16. Relationships between chemical structure, mechanical properties and materials processing in nanopatterned organosilicate fins

    Directory of Open Access Journals (Sweden)

    Gheorghe Stan

    2017-04-01

    Full Text Available The exploitation of nanoscale size effects to create new nanostructured materials necessitates the development of an understanding of relationships between molecular structure, physical properties and material processing at the nanoscale. Numerous metrologies capable of thermal, mechanical, and electrical characterization at the nanoscale have been demonstrated over the past two decades. However, the ability to perform nanoscale molecular/chemical structure characterization has only been recently demonstrated with the advent of atomic-force-microscopy-based infrared spectroscopy (AFM-IR and related techniques. Therefore, we have combined measurements of chemical structures with AFM-IR and of mechanical properties with contact resonance AFM (CR-AFM to investigate the fabrication of 20–500 nm wide fin structures in a nanoporous organosilicate material. We show that by combining these two techniques, one can clearly observe variations of chemical structure and mechanical properties that correlate with the fabrication process and the feature size of the organosilicate fins. Specifically, we have observed an inverse correlation between the concentration of terminal organic groups and the stiffness of nanopatterned organosilicate fins. The selective removal of the organic component during etching results in a stiffness increase and reinsertion via chemical silylation results in a stiffness decrease. Examination of this effect as a function of fin width indicates that the loss of terminal organic groups and stiffness increase occur primarily at the exposed surfaces of the fins over a length scale of 10–20 nm. While the observed structure–property relationships are specific to organosilicates, we believe the combined demonstration of AFM-IR with CR-AFM should pave the way for a similar nanoscale characterization of other materials where the understanding of such relationships is essential.

  17. Effect of chemical disinfectant on the transverse strength of heat-polymerized acrylic resins subjected to mechanical and chemical polishing: an in vitro study.

    Science.gov (United States)

    Sharan, Smitha; Kavitha, H R; Konde, Harish; Kalahasti, Deepthi

    2012-05-01

    To evaluate the effect of chemical disinfectant on the transverse strength of heat-polymerized acrylic resins subjected to mechanical and chemical polishing. A total of 256 rectangular specimens (65 * 10 * 3 mm) 128 per resin (Lucitone-199 and Acralyn-H) were fabricated. One side of each specimen was not polished and the other was either mechanically (n = 96) or chemically (n = 96) polished and immersed for 10, 30 and 60 minutes in 2% alkaline glutaraldehyde. Mechanically polished (n = 32) and chemically polished (n = 32) control specimens were immersed only in distilled water. The transverse strength (N/mm(2)) was tested for failure in a universal testing machine, at a crosshead speed of 5 mm/min. Data were statistically analyzed using 2-way ANOVA and Student t-test. chemical polishing resulted in significantly lower transverse strength values than mechanical polishing. Lucitone- 199 resin demonstrated the highest overall transverse strength for the materials tested. Heat-polymerized acrylic resins either mechanically or chemically polished, did not demonstrate significant changes in transverse strength during immersion in the disinfecting solution tested, regardless of time of immersion. Lucitone-199 resin demonstrated the highest overall transverse strength for the materials tested and significantly stronger than Acralyn-H with either type of polishing following immersion in 2% alkaline glutaraldehyde. There is a concern that immersion in chemical solutions often used for cleansing and disinfection of prostheses may undermine the strength and structure of denture base resins. In this study it was observed that, the transverse strength of samples of Lucitone-199 was higher than that of the samples of Acralyn-H. The chances of fracture of the denture made of Lucitone-199 are less than that of dentures made of Acralyn-H. The chemically polished dentures may be more prone to fracture than mechanically polished dentures.

  18. Effects of bioleaching on the mechanical and chemical properties of waste rocks

    Science.gov (United States)

    Yin, Sheng-Hua; Wu, Ai-Xiang; Wang, Shao-Yong; Ai, Chun-Ming

    2012-01-01

    Bioleaching processes cause dramatic changes in the mechanical and chemical properties of waste rocks, and play an important role in metal recovery and dump stability. This study focused on the characteristics of waste rocks subjected to bioleaching. A series of experiments were conducted to investigate the evolution of rock properties during the bioleaching process. Mechanical behaviors of the leached waste rocks, such as failure patterns, normal stress, shear strength, and cohesion were determined through mechanical tests. The results of SEM imaging show considerable differences in the surface morphology of leached rocks located at different parts of the dump. The mineralogical content of the leached rocks reflects the extent of dissolution and precipitation during bioleaching. The dump porosity and rock size change under the effect of dissolution, precipitation, and clay transportation. The particle size of the leached rocks decreased due to the loss of rock integrity and the conversion of dry precipitation into fine particles.

  19. Mechanism of alkalinity lowering and chemical equilibrium model of high fly ash silica fume cement

    International Nuclear Information System (INIS)

    Hoshino, Seiichi; Honda, Akira; Negishi, Kumi

    2014-01-01

    The mechanism of alkalinity lowering of a High Fly ash Silica fume Cement (HFSC) under liquid/solid ratio conditions where the pH is largely controlled by the soluble alkali components (Region I) has been studied. This mechanism was incorporated in the chemical equilibrium model of HFSC. As a result, it is suggested that the dissolution and precipitation behavior of SO 4 2- partially contributes to alkalinity lowering of HFSC in Region I. A chemical equilibrium model of HFSC incorporating alkali (Na, K) adsorption, which was presumed as another contributing factor of the alkalinity lowering effect, was also developed, and an HFSC immersion experiment was analyzed using the model. The results of the developed model showed good agreement with the experiment results. From the above results, it was concluded that the alkalinity lowering of HFSC in Region I was attributed to both the dissolution and precipitation behavior of SO 4 2- and alkali adsorption, in addition to the absence of Ca(OH) 2 . A chemical equilibrium model of HFSC incorporating alkali and SO 4 2- adsorption was also proposed. (author)

  20. Integration of large chemical kinetic mechanisms via exponential methods with Krylov approximations to Jacobian matrix functions

    KAUST Repository

    Bisetti, Fabrizio

    2012-06-01

    Recent trends in hydrocarbon fuel research indicate that the number of species and reactions in chemical kinetic mechanisms is rapidly increasing in an effort to provide predictive capabilities for fuels of practical interest. In order to cope with the computational cost associated with the time integration of stiff, large chemical systems, a novel approach is proposed. The approach combines an exponential integrator and Krylov subspace approximations to the exponential function of the Jacobian matrix. The components of the approach are described in detail and applied to the ignition of stoichiometric methane-air and iso-octane-air mixtures, here described by two widely adopted chemical kinetic mechanisms. The approach is found to be robust even at relatively large time steps and the global error displays a nominal third-order convergence. The performance of the approach is improved by utilising an adaptive algorithm for the selection of the Krylov subspace size, which guarantees an approximation to the matrix exponential within user-defined error tolerance. The Krylov projection of the Jacobian matrix onto a low-dimensional space is interpreted as a local model reduction with a well-defined error control strategy. Finally, the performance of the approach is discussed with regard to the optimal selection of the parameters governing the accuracy of its individual components. © 2012 Copyright Taylor and Francis Group, LLC.

  1. Contributions of chemical and mechanical surface properties and temperature effect on the adhesion at the nanoscale

    International Nuclear Information System (INIS)

    Awada, Houssein; Noel, Olivier; Hamieh, Tayssir; Kazzi, Yolla; Brogly, Maurice

    2011-01-01

    The atomic force microscope (AFM) is a powerful tool to investigate surface properties of model systems at the nanoscale. However, to get semi-quantitative and reproducible data with the AFM, it is necessary to establish a rigorous experimental procedure. In particular, a systematic calibration procedure of AFM measurements is necessary before producing reliable semi-quantitative data. In this paper, we study the contributions of the chemical and mechanical surface properties or the temperature influence on the adhesion energy at a local scale. To reach this objective, two types of model systems were considered. The first one is composed of rigid substrates (silicon wafers or AFM tips covered with gold) which were chemically modified by molecular self-assembling monolayers to display different surface properties (methyl and hydroxyl functional groups). The second one consists of model polymer networks (cross-linked polydimethylsiloxane) of variable mechanical properties. The comparison of the force curves obtained from the two model systems shows that the viscoelastic contributions dominate for the adhesion with polymer substrates, whereas, chemical contributions dominate for the rigid substrates. The temperature effect on the adhesion energy is also reported. Finally, we propose a relation for the adhesion energy at the nanoscale. This relation relates the energy measured during the separation of the contact to the three parameters: the surface properties of the polymer, the energy dissipated within the contact zone and the temperature.

  2. The testing of thermal-mechanical-hydrological-chemical processes using a large block

    International Nuclear Information System (INIS)

    Lin, W.; Wilder, D.G.; Blink, J.A.; Blair, S.C.; Buscheck, T.A.; Chesnut, D.A.; Glassley, W.E.; Lee, K.; Roberts, J.J.

    1994-01-01

    The radioactive decay heat from nuclear waste packages may, depending on the thermal load, create coupled thermal-mechanical-hydrological-chemical (TMHC) processes in the near-field environment of a repository. A group of tests on a large block (LBT) are planned to provide a timely opportunity to test and calibrate some of the TMHC model concepts. The LBT is advantageous for testing and verifying model concepts because the boundary conditions are controlled, and the block can be characterized before and after the experiment. A block of Topopah Spring tuff of about 3 x 3 x 4.5 m will be sawed and isolated at Fran Ridge, Nevada Test Site. Small blocks of the rock adjacent to the large block will be collected for laboratory testing of some individual thermal-mechanical, hydrological, and chemical processes. A constant load of about 4 MPa will be applied to the top and sides of the large block. The sides will be sealed with moisture and thermal barriers. The large block will be heated with one heater in each borehole and guard heaters on the sides so that a dry-out zone and a condensate zone will exist simultaneously. Temperature, moisture content, pore pressure, chemical composition, stress and displacement will be measured throughout the block during the heating and cool-down phases. The results from the experiments on small blocks and the tests on the large block will provide a better understanding of some concepts of the coupled TMHC processes

  3. Effect of chemical treatment of Kevlar fibers on mechanical interfacial properties of composites.

    Science.gov (United States)

    Park, Soo-Jin; Seo, Min-Kang; Ma, Tae-Jun; Lee, Douk-Rae

    2002-08-01

    In this work, the effects of chemical treatment on Kevlar 29 fibers have been studied in a composite system. The surface characteristics of Kevlar 29 fibers were characterized by pH, acid-base value, X-ray photoelectron spectroscopy (XPS), and FT-IR. The mechanical interfacial properties of the final composites were studied by interlaminar shear strength (ILSS), critical stress intensity factor (K(IC)), and specific fracture energy (G(IC)). Also, impact properties of the composites were investigated in the context of differentiating between initiation and propagation energies and ductile index (DI) along with maximum force and total energy. As a result, it was found that chemical treatment with phosphoric acid solution significantly affected the degree of adhesion at interfaces between fibers and resin matrix, resulting in improved mechanical interfacial strength in the composites. This was probably due to the presence of chemical polar groups on Kevlar surfaces, leading to an increment of interfacial binding force between fibers and matrix in a composite system.

  4. Effect of Chemical Treatment on Physical, Mechanical and Thermal Properties of Ladies Finger Natural Fiber

    Directory of Open Access Journals (Sweden)

    S. I. Hossain

    2013-01-01

    Full Text Available In present research, natural fiber obtained from ladies finger plant was chemically treated separately using alkali (2% NaOH, chromium sulfate (4% , and chromium sulfate and sodium bicarbonate (4% . Both raw and chemically treated fibers were subsequently characterized using mechanical (tensile, structural (Fourier transform infrared spectroscopy and scanning electron microscopy, and thermal (thermogravimetric analysis. Fourier analysis showed the presence of (−OH group in the ladies plant fiber. Scanning electron micrographs revealed rougher surface in case of alkali treated fiber, while thin coating layer was formed on the fiber surface during other two treatments. Tensile test on ladies finger single fiber was carried out by varying span length. The tensile strength and Young's modulus values were found to be increased after chemical treatment. For both raw and chemically treated fibers, Young's modulus increased and tensile strength decreased with increase in span length. Thermogravimetric analysis indicated the same level of thermal stability for both raw and treated ladies finger fibers.

  5. Benefits of integrating chemical and mechanical cleaning processes for steam generator sludge removal

    International Nuclear Information System (INIS)

    Varrin, R.D.; Ferriter, A.M.; Oliver, T.W.; Le Surf, J.E.

    1992-01-01

    This paper discusses the benefits of performing in-bundle tubesheet lancing in conjunction with chemical cleaning of PWR and PHWR steam generators in which a hard sludge pile is known to exist. The primary benefits of in-bundle lancing are to: (1) increase the exposed area of the sludge pile by cutting furrows in the surface thereby enhancing dissolution of sludge, (2) reduce the volume of solvents required since material removed by lancing does not have to be dissolved chemically, (3) improve rinsing and removal of residual solvent between iron and copper dissolution steps, and (4) allow for verification of process effectiveness by providing high quality in-bundle visual inspection. The reduction in solvent volumes can lead to a significant reduction in solvent costs and waste processing. A case study which includes an economic evaluation for a combined chemical and mechanical cleaning shows a potential cost saving of up to US$ 300,000 over use of chemical cleaning alone. 14 refs., 2 tabs., 2 figs

  6. Enhancing the Chemical and Mechanical Durability of Polymer Electrolyte Membranes for Fuel Cell Applications

    Science.gov (United States)

    Baker, Andrew M.

    Polymer electrolyte membrane (PEM) fuel cells are energy conversion devices which generate electricity from the electrochemical reaction of hydrogen and oxygen. Currently, widespread adoption of PEM fuel cell technology is hindered by low component durability and high costs. In this work, strategies were investigated to improve the mechanical and chemical durability of the ion conducting polymer, or ionomer, which comprises the PEM, in order to directly address these limitations. Owing to their exceptional mechanical properties, carbon nanotubes (CNTs) were investigated for mechanical reinforcement of the PEM. Because of their electronic conductivity, which diminishes cell performance, two strategies were developed to enable the use of CNTs as PEM reinforcement. These systems result in enhanced mechanical properties without sacrificing performance of the PEM during operation. Further, when coated with ceria (CeO2), which scavenges radicals that are generated during operation and cause PEM chemical degradation by attacking vulnerable chemical groups in the ionomer, MWCNTs further improved PEM chemical durability. During cell fabrication, conditioning, and discharge, Ce rapidly migrates between the PEM and catalyst layers (CLs), which reduces catalyst efficiency and leaves areas of the cell defenseless against radical attacks. Therefore, in order to stabilize Ce and localize it to areas of highest radical generation, it is critical to understand and identify the relative influences of different migration mechanisms. Using a novel elemental analysis technique, Ce migration was characterized due to potential and concentration gradients, water flux, and degradation of Ce-exchanged sulfonic acid groups within the PEM. Additionally, Zr-doped ceria was employed to resist migration due to ionomer degradation which improved cell durability, without reducing performance, resulting in PEM Ce stabilization near its initial concentrations after > 1,400 hours of testing. Ce was

  7. Chemical, mechanical, and tribological properties of pulsed-laser-deposited titanium carbide and vanadium carbide

    International Nuclear Information System (INIS)

    Krzanowski, J.E.; Leuchtner, R.E.

    1997-01-01

    The chemical, mechanical, and tribological properties of pulsed-laser-deposited TiC and VC films are reported in this paper. Films were deposited by ablating carbide targets using a KrF (λ = 248 nm) laser. Chemical analysis of the films by XPS revealed oxygen was the major impurity; the lowest oxygen concentration obtained in a film was 5 atom%. Oxygen was located primarily on the carbon sublattice of the TiC structure. The films were always substoichiometric, as expected, and the carbon in the films was identified primarily as carbidic carbon. Nanoindentation hardness tests gave values of 39 GPa for TiC and 26 GPa for VC. The friction coefficient for the TiC films was 0.22, while the VC film exhibited rapid material transfer from the steel ball to the substrate resulting in steel-on-steel tribological behavior

  8. Evaluation of environmental impacts during chemical mechanical polishing (CMP) for sustainable manufacturing

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Hyun Seop; Park, Sun Joon; Jeong, Hae Do [Pusan National University, Busan (Korea, Republic of)

    2013-02-15

    Reducing energy consumption has become a critical issue in manufacturing. The semiconductor industry in particular is confronted with environmental regulations on pollution associated with electric energy, chemical, and ultrapure water (UPW) consumptions. This paper presents the results of an evaluation of the environmental impacts during chemical mechanical polishing (CMP), a key process for planarization of dielectrics and metal films in ultra-large-scale integrated circuits. The steps in the CMP process are idling, conditioning, wetting, wafer loading/unloading, head dropping, polishing, and rinsing. The electric energy, CMP slurry, and UPW consumptions associated with the process and their impacts on global warming are evaluated from an environmental standpoint. The estimates of electric energy, slurry, and UPW consumptions as well as the associated greenhouse gas emissions presented in this paper will provide a technical aid for reducing the environmental burden associated with electricity consumption during the CMP process.

  9. Thermal chemical-mechanical reactive flow model of shock initiation in solid explosives

    International Nuclear Information System (INIS)

    Nicholls, A.L. III; Tarver, C.M.

    1998-01-01

    The three dimensional Arbitrary Lagrange Eulerian hydrodynamic computer code ALE3D with fully coupled thermal-chemical-mechanical material models provides the framework for the development of a physically realistic model of shock initiation and detonation of solid explosives. The processes of hot spot formation during shock compression, subsequent ignition of reaction or failure to react, growth of reaction in individual hot spots, and coalescence of reacting hot spots during the transition to detonation can now be modeled using Arrhenius chemical kinetic rate laws and heat transfer to propagate the reactive flow. This paper discusses the growth rates of reacting hot spots in HMX and TATB and their coalescence during shock to detonation transition. Hot spot deflagration rates are found to be fast enough to consume explosive particles less than 10 mm in diameter during typical shock duration times, but larger particles must fragment and create more reactive surface area in order to be rapidly consumed

  10. The Electronic Flux in Chemical Reactions. Insights on the Mechanism of the Maillard Reaction

    Science.gov (United States)

    Flores, Patricio; Gutiérrez-Oliva, Soledad; Herrera, Bárbara; Silva, Eduardo; Toro-Labbé, Alejandro

    2007-11-01

    The electronic transfer that occurs during a chemical process is analysed in term of a new concept, the electronic flux, that allows characterizing the regions along the reaction coordinate where electron transfer is actually taking place. The electron flux is quantified through the variation of the electronic chemical potential with respect to the reaction coordinate and is used, together with the reaction force, to shed light on reaction mechanism of the Schiff base formation in the Maillard reaction. By partitioning the reaction coordinate in regions in which different process might be taking place, electronic reordering associated to polarization and transfer has been identified and found to be localized at specific transition state regions where most bond forming and breaking occur.

  11. Evolution of mechanical properties of silicate glasses: Impact of the chemical composition and effects of irradiation

    International Nuclear Information System (INIS)

    Barlet, Marina

    2014-01-01

    This thesis examines: (1) how the chemical composition changes the hardness, toughness, and stress corrosion cracking behavior in model pristine and (2) how external irradiation impact these properties. It is to be incorporated in the context of the storage of nuclear waste in borosilicate glass matrix, the structural integrity of which should be assessed. Eight simplified borosilicate glasses made of 3 oxides with modulated proportions (SiO 2 -B 2 O 3 -Na 2 O (SBN) have been selected and their hardness, toughness, and stress corrosion cracking behavior have been characterized prior and after irradiation. The comparative study of the non-irradiated SBN glasses provides the role played by the chemical composition. The sodium content is found to be the key parameter: As it increases, the glass plasticity increases, leading to changes in the mechanical response to strain. Hardness (Hv) and toughness (Kc) decrease since the flow under indenter increases. The analysis of the stress corrosion behavior evidences a clear shift of the SCC curves linked also to the glass plasticity. Four of the 8 simplified SBN glass systems highlight the influence of electron, light and heavy ions irradiations on the mechanical properties. Once again, the sodium content is a key parameter. It is found to inhibit the glass modification: Glasses with high sodium content are more stable. Ions irradiations highlight the predominant role of nuclear interaction in changing the glass properties. Finally, electronic interaction induced by helium and electron irradiation does not lead to the same structural/mechanical glasses variations. (author) [fr

  12. Chemical influence on the hydro-mechanical behaviour of high-density bentonite

    Energy Technology Data Exchange (ETDEWEB)

    Castellanos, E.; Romero, E.; Lioret, A. [Technical Univ. of Catalonia UPC, Barcelona (Spain); Musso, G. [Politecnico di Torino, Torino (Italy)

    2005-07-01

    In radioactive waste disposal schemes, during the operational period of clay barriers, solute transport an d thermal gradients may alter the solute concentration of pore water. These induced changes have important consequences on hydro-mechanical properties and microstructural alterations (mineral composition and pore size distribution changes) of the clay barrier. Chemically induced changes originated by different imbibition fluids and soil mineral compositions have been a subject with a long research tradition. These researches have been mainly focused on the behaviour of reconstituted soils starting from slurry and saturated wit h saline solutions at elevated concentrations, where hydro-mechanical changes (soil compressibility and water permeability changes) are clearly detected. In contrast, available information concerning the response of high-density clays subjected to chemically induced actions with a wide range of pore solution concentrations is very limited in spite of its practical relevance to environmental geotechnics. This situation has been caused, at least in part, by the difficulties in detecting important hydro-mechanical changes when clays with low water storage capacity have been used. Nevertheless, this paper will demonstrate that even in the case of high-density fabrics, considerable changes can be observed when high-activity clays (bentonites) are imbibed with different pore fluid compositions. (authors)

  13. Effect of additives for higher removal rate in lithium niobate chemical mechanical planarization

    International Nuclear Information System (INIS)

    Jeong, Sukhoon; Lee, Hyunseop; Cho, Hanchul; Lee, Sangjik; Kim, Hyoungjae; Kim, Sungryul; Park, Jaehong; Jeong, Haedo

    2010-01-01

    High roughness and a greater number of defects were created by lithium niobate (LN; LiNbO 3 ) processes such as traditional grinding and mechanical polishing (MP), should be decreased for manufacturing LN device. Therefore, an alternative process for gaining defect-free and smooth surface is needed. Chemical mechanical planarization (CMP) is suitable method in the LN process because it uses a combination approach consisting of chemical and mechanical effects. First of all, we investigated the LN CMP process using commercial slurry by changing various process conditions such as down pressure and relative velocity. However, the LN CMP process time using commercial slurry was long to gain a smooth surface because of lower material removal rate (MRR). So, to improve the material removal rate (MRR), the effects of additives such as oxidizer (hydrogen peroxide; H 2 O 2 ) and complexing agent (citric acid; C 6 H 8 O 7 ) in a potassium hydroxide (KOH) based slurry, were investigated. The manufactured slurry consisting of H 2 O 2 -citric acid in the KOH based slurry shows that the MRR of the H 2 O 2 at 2 wt% and the citric acid at 0.06 M was higher than the MRR for other conditions.

  14. Postharvest Chemical, Sensorial and Physical-Mechanical Properties of Wild Apricot (Prunus armeniaca L.

    Directory of Open Access Journals (Sweden)

    Evica MRATINIĆ

    2011-11-01

    Full Text Available Some chemical, sensorial and physical-mechanical properties of 19 apricot genotypes and Hungarian Best (control such as moisture content, soluble solids content, titratable acidity ratio and their ratio, fruit and stone mass, flesh/stone ratio, fruit dimensions (length, width, thickness, arithmetic and geometric mean diameter, sphericity, surface area and aspect ratio were determined. Their application is also discussed. The highest moisture content and stone mass observed in X-1/1/04 and X-1/2/04, soluble solids content in ZO-1/03, titratable acidity in ZL-2/03, SS/TA ratio in ZL-1/03, and fruit mass and flesh/stone ratio in DL-1/1/04 genotype. The most number of genotypes have orange and deep orange skin and flesh colour, respectively, whereas sweet kernel taste was predominant in most genotypes. Regarding physical-mechanical properties, the superior fruit dimensions (length, width, thickness, arithmetic and geometric mean diameter and surface area observed in DL-1/1/04 genotype, whereas the highest sphericity and surface area observed in X-1/1/04 and X-1/2/04 genotypes. Also, the series of genotypes evaluated have better chemical, sensorial and physical-mechanical properties than Hungarian Best (control. Finally, information about these properties is very important for understanding the behaviour of the product during the postharvest operations.

  15. Synthetically chemical-electrical mechanism for controlling large scale reversible deformation of liquid metal objects

    Science.gov (United States)

    Zhang, Jie; Sheng, Lei; Liu, Jing

    2014-11-01

    Reversible deformation of a machine holds enormous promise across many scientific areas ranging from mechanical engineering to applied physics. So far, such capabilities are still hard to achieve through conventional rigid materials or depending mainly on elastomeric materials, which however own rather limited performances and require complicated manipulations. Here, we show a basic strategy which is fundamentally different from the existing ones to realize large scale reversible deformation through controlling the working materials via the synthetically chemical-electrical mechanism (SCHEME). Such activity incorporates an object of liquid metal gallium whose surface area could spread up to five times of its original size and vice versa under low energy consumption. Particularly, the alterable surface tension based on combination of chemical dissolution and electrochemical oxidation is ascribed to the reversible shape transformation, which works much more flexible than many former deformation principles through converting electrical energy into mechanical movement. A series of very unusual phenomena regarding the reversible configurational shifts are disclosed with dominant factors clarified. This study opens a generalized way to combine the liquid metal serving as shape-variable element with the SCHEME to compose functional soft machines, which implies huge potential for developing future smart robots to fulfill various complicated tasks.

  16. Viscoelasticity of biofilms and their recalcitrance to mechanical and chemical challenges

    Science.gov (United States)

    Peterson, Brandon W.; He, Yan; Ren, Yijin; Zerdoum, Aidan; Libera, Matthew R.; Sharma, Prashant K.; van Winkelhoff, Arie-Jan; Neut, Danielle; Stoodley, Paul; van der Mei, Henny C.; Busscher, Henk J.

    2015-01-01

    We summarize different studies describing mechanisms through which bacteria in a biofilm mode of growth resist mechanical and chemical challenges. Acknowledging previous microscopic work describing voids and channels in biofilms that govern a biofilms response to such challenges, we advocate a more quantitative approach that builds on the relation between structure and composition of materials with their viscoelastic properties. Biofilms possess features of both viscoelastic solids and liquids, like skin or blood, and stress relaxation of biofilms has been found to be a corollary of their structure and composition, including the EPS matrix and bacterial interactions. Review of the literature on viscoelastic properties of biofilms in ancient and modern environments as well as of infectious biofilms reveals that the viscoelastic properties of a biofilm relate with antimicrobial penetration in a biofilm. In addition, also the removal of biofilm from surfaces appears governed by the viscoelasticity of a biofilm. Herewith, it is established that the viscoelasticity of biofilms, as a corollary of structure and composition, performs a role in their protection against mechanical and chemical challenges. Pathways are discussed to make biofilms more susceptible to antimicrobials by intervening with their viscoelasticity, as a quantifiable expression of their structure and composition. PMID:25725015

  17. Structural, mechanical and chemical evaluation of molar-incisor hypomineralization-affected enamel: A systematic review.

    Science.gov (United States)

    Elhennawy, Karim; Manton, David John; Crombie, Felicity; Zaslansky, Paul; Radlanski, Ralf J; Jost-Brinkmann, Paul-Georg; Schwendicke, Falk

    2017-11-01

    To systematically assess and contrast reported differences in microstructure, mineral density, mechanical and chemical properties between molar-incisor-hypomineralization-affected (MIH) enamel and unaffected enamel. Studies on extracted human teeth, clinically diagnosed with MIH, reporting on the microstructure, mechanical properties or the chemical composition and comparing them to unaffected enamel were reviewed. Electronic databases (PubMed, Embase and Google Scholar) were screened; hand searches and cross-referencing were also performed. Twenty-two studies were included. Fifteen studies on a total of 201 teeth investigated the structural properties, including ten (141 teeth) on microstructure and seven (60 teeth) on mineral density; six (29 teeth) investigated the mechanical properties and eleven (87 teeth) investigated the chemical properties of MIH-affected enamel and compared them to unaffected enamel. Studies unambiguously found a reduction in mineral quantity and quality (reduced Ca and P content), reduction of hardness and modulus of elasticity (also in the clinically sound-appearing enamel bordering the MIH-lesion), an increase in porosity, carbon/carbonate concentrations and protein content compared to unaffected enamel. were ambiguous with regard to the extent of the lesion through the enamel to the enamel-dentin junction, the Ca/P ratio and the association between clinical appearance and defect severity. There is an understanding of the changes related to MIH-affected enamel. The association of these changes with the clinical appearance and resulting implications for clinical management are unclear. MIH-affected enamel is greatly different from unaffected enamel. This has implications for management strategies. The possibility of correlating the clinical appearance of MIH-affected enamel with the severity of enamel changes and deducing clinical concepts (risk stratification etc.) is limited. Crown Copyright © 2017. Published by Elsevier Ltd. All

  18. Chemical and mechanical performance properties for various final waste forms -- PSPI scoping study

    International Nuclear Information System (INIS)

    Farnsworth, R.K.; Larsen, E.D.; Sears, J.W.; Eddy, T.L.; Anderson, G.L.

    1996-09-01

    The US DOE is obtaining data on the performance properties of the various final waste forms that may be chosen as primary treatment products for the alpha-contaminated low-level and transuranic waste at the INEL's Transuranic Storage Area. This report collects and compares selected properties that are key indicators of mechanical and chemical durability for Portland cement concrete, concrete formed under elevated temperature and pressure, sulfur polymer cement, borosilicate glass, and various forms of alumino-silicate glass, including in situ vitrification glass and various compositions of iron-enriched basalt (IEB) and iron-enriched basalt IV (IEB4). Compressive strength and impact resistance properties were used as performance indicators in comparative evaluation of the mechanical durability of each waste form, while various leachability data were used in comparative evaluation of each waste form's chemical durability. The vitrified waste forms were generally more durable than the non-vitrified waste forms, with the iron-enriched alumino-silicate glasses and glass/ceramics exhibiting the most favorable chemical and mechanical durabilities. It appears that the addition of zirconia and titania to IEB (forming IEB4) increases the leach resistance of the lanthanides. The large compositional ranges for IEB and IEB4 more easily accommodate the compositions of the waste stored at the INEL than does the composition of borosilicate glass. It appears, however, that the large potential variation in IEB and IEB4 compositions resulting from differing waste feed compositions can impact waste form durability. Further work is needed to determine the range of waste stream feed compositions and rates of waste form cooling that will result in acceptable and optimized IEB or IEB4 waste form performance. 43 refs

  19. Recolonization of the oral cavity by Streptococcus mutans after a combined mechanical/chemical antisepsis protocol.

    Science.gov (United States)

    Farina, R; Squarzoni, M A; Calura, G; Trombelli, L

    2009-06-01

    The bacterial colonization of teeth by Streptococcus mutans (StrepM) represents a major risk factor for the development of dental caries. At present, no clinical studies have explored the effect of a combined mechanical-chemical antisepsis protocol in a periodontally-healthy population and the pattern of recolonization of StrepM in subjects whose StrepM infection was successfully eradicated. The present study was designed in order to 1) determine the salivary and plaque changes in StrepM content after a combined mechanical/chemical antisepsis protocol; and 2) evaluate the pattern of recolonization when StrepM was successfully eradicated from saliva and plaque. Thirty-five periodontally-healthy and caries-susceptible subjects successfully entered and concluded the study. At baseline, non-surgical periodontal therapy was performed according to the principles of full mouth disinfection. Adjunctive home-based rinsing with a 0.2% chlorhexidine mouthrinse was requested for the following week. StrepM concentration was assessed in saliva and plaque at the initial contact appointment, at baseline, and 1-week, 1-month, 3-month and 6-month follow-up. A significant effect of ''time'' on StrepM concentration in saliva and plaque was observed (P<0.000). In subjects with successful eradication of StrepM at 1 week (N=17 plaque samples), StrepM infection recurrence occurred within 3-6 months. The results of the present study demonstrated that 1) the application of the investigated mechanical/chemical antisepsis protocol can effectively reduce StrepM colonies in saliva and plaque of periodontally healthy subjects; and 2) in plaque samples, StrepM infection recurrence tends to occur within 3-6 months.

  20. Physico-mechanical properties of coir fiber/LDPE composites: Effect of chemical treatment and compatibilizer

    Energy Technology Data Exchange (ETDEWEB)

    Prasad, Nirupama; Agarwal, Vijay Kumar; Sihha, Shishir [Indian Institute of Technology Roorkee, Uttrakhand (India)

    2015-12-15

    Coir fiber/low density polyethylene (LDPE) composites were fabricated with different fiber loading (10- 30 wt%) using compression molding technique. A fiber loading of 20 wt% was found optimum, with maximum mechanical properties. Further, the effect of fiber treatment (alkali and acrylic acid) and compatibilizer (MA-g-LDPE) incorporation on the mechanical and water absorption properties of the LDPE composites were studied and compared. The results showed that MA-g-LDPE incorporation into untreated and treated fiber composites led to improved mechanical properties and water resistance compared with the same composite formulation without MA-g-LDPE. However, treated fiber composites with MA-g-LDPE showed lower mechanical properties than untreated fiber without MA-g- LDPE, due to the removal of hydroxyl groups from the hemicellulose and lignin region of the fiber and degradation of fibers by chemical attack. From SEM studies on the tensile fractured composite samples, a good relationship has been observed between the morphological and mechanical properties.

  1. Physico-chemical and hydraulic mechanisms of radionuclide mobilization in aquatic systems

    International Nuclear Information System (INIS)

    Konoplev, A.V.; Bulgakov, A.A.; Comans, R.N.J.; Hilton, J.; Smith, J.; Madruga, M.J.; Voitsekhovich, O.V.; Sansone, U.; Kudelsky, A.V.

    1996-01-01

    This paper presents main results of joint studies carried out in frame of EC-coordinated ECP-3 Project 'Modelling and study of the mechanisms of the transfer of radioactive material from the terrestrial ecosystem to and in water bodies around Chernobyl' in part of geochemical pathways. Physico-chemical models of specific migration processes are developed and recommended for application as sub models for inclusion in the decision support system (JSP-1). Main parameters, determining the behaviour of radionuclides in aquatic ecosystems are identified and methods for their estimation in |emergency situations are proposed

  2. Computational organic chemistry: bridging theory and experiment in establishing the mechanisms of chemical reactions.

    Science.gov (United States)

    Cheng, Gui-Juan; Zhang, Xinhao; Chung, Lung Wa; Xu, Liping; Wu, Yun-Dong

    2015-02-11

    Understanding the mechanisms of chemical reactions, especially catalysis, has been an important and active area of computational organic chemistry, and close collaborations between experimentalists and theorists represent a growing trend. This Perspective provides examples of such productive collaborations. The understanding of various reaction mechanisms and the insight gained from these studies are emphasized. The applications of various experimental techniques in elucidation of reaction details as well as the development of various computational techniques to meet the demand of emerging synthetic methods, e.g., C-H activation, organocatalysis, and single electron transfer, are presented along with some conventional developments of mechanistic aspects. Examples of applications are selected to demonstrate the advantages and limitations of these techniques. Some challenges in the mechanistic studies and predictions of reactions are also analyzed.

  3. Changes in mechanical and chemical wood properties by electron beam irradiation

    International Nuclear Information System (INIS)

    Schnabel, Thomas; Huber, Hermann; Grünewald, Tilman A.; Petutschnigg, Alexander

    2015-01-01

    Highlights: • Changes in wood due to electron beam irradiations (EBI) were evaluated. • Wood components undergo different altering mechanisms due to the irradiation. • Chemical reactions in wood lead to better surface hardness of low irradiated wood. - Abstract: This study deals with the influence of various electron beam irradiation (EBI) dosages on the Brinell hardness of Norway spruce. The results of the hardness measurements and the FT-IR spectroscopic analysis show different effects of the EBI at dosages of 25, 50, 100 and 200 kGy. It was assumed that the lignin and carbohydrates undergo different altering mechanisms due to the EBI treatment. New cleavage products and condensation reactions of lignin and carbohydrates lead to better surface hardness of low irradiated wood samples. These results provide a useful basis for further investigations on the changes in wood chemistry and material properties due to electron beam irradiations

  4. Changes in mechanical and chemical wood properties by electron beam irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Schnabel, Thomas, E-mail: thomas.schnabel@fh-salzburg.ac.at [Salzburg University of Applied Sciences, Department of Forest Products Technology and Wood Constructions, Marktstraße 136a, 5431 Kuchl (Austria); Huber, Hermann [Salzburg University of Applied Sciences, Department of Forest Products Technology and Wood Constructions, Marktstraße 136a, 5431 Kuchl (Austria); Grünewald, Tilman A. [BOKU University of Natural Resources and Life Sciences, Institute of Physics and Materials Science, Peter Jordan Straße 82, 1190 Vienna (Austria); Petutschnigg, Alexander [Salzburg University of Applied Sciences, Department of Forest Products Technology and Wood Constructions, Marktstraße 136a, 5431 Kuchl (Austria); BOKU University of Natural Resources and Life Sciences, Konrad Lorenzstraße 24, 3430 Tulln (Austria)

    2015-03-30

    Highlights: • Changes in wood due to electron beam irradiations (EBI) were evaluated. • Wood components undergo different altering mechanisms due to the irradiation. • Chemical reactions in wood lead to better surface hardness of low irradiated wood. - Abstract: This study deals with the influence of various electron beam irradiation (EBI) dosages on the Brinell hardness of Norway spruce. The results of the hardness measurements and the FT-IR spectroscopic analysis show different effects of the EBI at dosages of 25, 50, 100 and 200 kGy. It was assumed that the lignin and carbohydrates undergo different altering mechanisms due to the EBI treatment. New cleavage products and condensation reactions of lignin and carbohydrates lead to better surface hardness of low irradiated wood samples. These results provide a useful basis for further investigations on the changes in wood chemistry and material properties due to electron beam irradiations.

  5. Studies on physico-chemical and mechanical properties of the irradiated latex modified mortar

    International Nuclear Information System (INIS)

    Yassene, A.A.M.A.

    2009-01-01

    This thesis contains three chapter; chapter(I): Introduction and literature review on:- Introduction to polymer. - Mechanism of polymer-cement co-matrix formation.-Sulphate attack. - Solidification /stabilization of heavy metal in cement mortar. chapter(II): Materials and experimental techniques that include: 1- Preparation of latex polymer films from different polymer latices of styrene butadine rubber latex (SBR), poly (styrene-acrylic ester) latex (SAE) and vinylacetate /versatic -ester copolymer latex (C2A). The effect of γ-irradiation dose on the physico - chemical and mechanical properties of different latex polymer films was studied.2- Preparation of latex polymer-modified cement mortar with different ratios of cement: latex polymer and different curing method.3- Solidification /stabilization (S/S) of electroplating heavy metal precipitate in latex polymer- modified mortar with different cement /electroplating heavy metal sludge ratio. chapter(III) results and discussion

  6. The I2 dissociation mechanisms in the chemical oxygen-iodine laser revisited.

    Science.gov (United States)

    Waichman, K; Barmashenko, B D; Rosenwaks, S

    2012-06-28

    The recently suggested mechanism of I(2) dissociation in the chemical oxygen-iodine laser (COIL) [K. Waichman, B. D. Barmashenko, and S. Rosenwaks, J. Appl. Phys. 106, 063108 (2009); and J. Chem. Phys. 133, 084301 (2010)] was largely based on the suggestion of V. N. Azyazov, S. Yu. Pichugin, and M. C. Heaven [J. Chem. Phys. 130, 104306 (2009)] that the vibrational population of O(2)(a) produced in the chemical generator is high enough to play an essential role in the dissociation. The results of model calculations based on this mechanism agreed very well with measurements of the small signal gain g, I(2) dissociation fraction F, and temperature T in the COIL. This mechanism is here revisited, following the recent experiments of M. V. Zagidullin [Quantum Electron. 40, 794 (2010)] where the observed low population of O(2)(b, v = 1) led to the conclusion that the vibrational population of O(2)(a) at the outlet of the generator is close to thermal equilibrium value. This value corresponds to a very small probability, ∼0.05, of O(2)(a) energy pooling to the states O(2)(X,a,b, v > 0). We show that the dissociation mechanism can reproduce the experimentally observed values of g, F, and T in the COIL only if most of the energy released in the processes of O(2)(a) energy pooling and O(2)(b) quenching by H(2)O ends up as vibrational energy of the products, O(2)(X,a,b), where the vibrational states v = 2 and 3 are significantly populated. We discuss possible reasons for the differences in the suggested vibrational population and explain how these differences can be reconciled.

  7. CHEMICALS

    CERN Multimedia

    Medical Service

    2002-01-01

    It is reminded that all persons who use chemicals must inform CERN's Chemistry Service (TIS-GS-GC) and the CERN Medical Service (TIS-ME). Information concerning their toxicity or other hazards as well as the necessary individual and collective protection measures will be provided by these two services. Users must be in possession of a material safety data sheet (MSDS) for each chemical used. These can be obtained by one of several means : the manufacturer of the chemical (legally obliged to supply an MSDS for each chemical delivered) ; CERN's Chemistry Service of the General Safety Group of TIS ; for chemicals and gases available in the CERN Stores the MSDS has been made available via EDH either in pdf format or else via a link to the supplier's web site. Training courses in chemical safety are available for registration via HR-TD. CERN Medical Service : TIS-ME :73186 or service.medical@cern.ch Chemistry Service : TIS-GS-GC : 78546

  8. An optimized chemical kinetic mechanism for HCCI combustion of PRFs using multi-zone model and genetic algorithm

    International Nuclear Information System (INIS)

    Neshat, Elaheh; Saray, Rahim Khoshbakhti

    2015-01-01

    Highlights: • A new chemical kinetic mechanism for PRFs HCCI combustion is developed. • New mechanism optimization is performed using genetic algorithm and multi-zone model. • Engine-related combustion and performance parameters are predicted accurately. • Engine unburned HC and CO emissions are predicted by the model properly. - Abstract: Development of comprehensive chemical kinetic mechanisms is required for HCCI combustion and emissions prediction to be used in engine development. The main purpose of this study is development of a new chemical kinetic mechanism for primary reference fuels (PRFs) HCCI combustion, which can be applied to combustion models to predict in-cylinder pressure and exhaust CO and UHC emissions, accurately. Hence, a multi-zone model is developed for HCCI engine simulation. Two semi-detailed chemical kinetic mechanisms those are suitable for premixed combustion are used for n-heptane and iso-octane HCCI combustion simulation. The iso-octane mechanism contains 84 species and 484 reactions and the n-heptane mechanism contains 57 species and 296 reactions. A simple interaction between iso-octane and n-heptane is considered in new mechanism. The multi-zone model is validated using experimental data for pure n-heptane and iso-octane. A new mechanism is prepared by combination of these two mechanisms for n-heptane and iso-octane blended fuel, which includes 101 species and 594 reactions. New mechanism optimization is performed using genetic algorithm and multi-zone model. Mechanism contains low temperature heat release region, which decreases with increasing octane number. The results showed that the optimized chemical kinetic mechanism is capable of predicting engine-related combustion and performance parameters. Also after implementing the optimized mechanism, engine unburned HC and CO emissions predicted by the model are in good agreement with the corresponding experimental data

  9. Passivation of mechanically polished, chemically etched and anodized zirconium in various aqueous solutions: Impedance measurements

    International Nuclear Information System (INIS)

    Abo-Elenien, G.M.; Abdel-Salam, O.E.

    1987-01-01

    Zirconium and its alloys are finding increasing applications especially in water-cooled nuclear reactors. Because of the fact that zirconium is electronegative (E 0 = -1.529V) its corrosion resistance in aqueous solutions is largely determined by the existence of a thin oxide film on its surface. The structure and properties of this film depend in the first place on the method of surface pre-treatment. This paper presents an experimental study of the nature of the oxide film on mechanically polished, chemically etched and anodized zirconium. Ac impedance measurements carried out in various acidic, neutral and alkaline solutions show that the film thickness depends on the method of surface pre-treatment and the type of electrolyte solution. The variation of the potential and impedance during anodization of zirconium at low current density indicates that the initial stages of polarization consist of oxide build-up at a rate dependent on the nature of the electrode surface and the electrolyte. Oxygen evolution commences at a stage where oxide thickening starts to decline. The effect of frequency on the measured impedance indicates that the surface reactivity, and hence the corrosion rate, decreases in the following order: mechanically polished > chemically etched > anodized

  10. Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds

    KAUST Repository

    Wang, Zhandong

    2017-11-28

    Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability of liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500–600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound’s molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. Finally, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels.

  11. Effects of fatigue on the chemical and mechanical degradation of model stent sub-units.

    Science.gov (United States)

    Dreher, Maureen L; Nagaraja, Srinidhi; Batchelor, Benjamin

    2016-06-01

    Understanding the fatigue and durability performance of implantable cardiovascular stents is critical for assessing their performance. When the stent is manufactured from an absorbable material, however, this durability assessment is complicated by the transient nature of the device. Methodologies for evaluating the fatigue performance of absorbable stents while accurately simulating the degradation are limited and little is known about the interaction between fatigue and degradation. In this study, we investigated the fatigue behavior and effect of fatigue on the degradation rate for a model absorbable cardiovascular stent. Custom v-shaped stent sub-units manufactured from poly(L-lactide), i.e., PLLA, were subjected to a simultaneous fatigue and degradation study with cycle counts representative of one year of expected in vivo use. Fatigue loading was carried out such that the polymer degraded at a rate that was aligned with a modest degree of fatigue acceleration. Control, un-loaded specimens were also degraded under static immersion conditions representative of simulated degradation without fatigue. The study identified that fatigue loading during degradation significantly increased specimen stiffness and lowered the force at break. Fatigue loading also significantly increased the degree of molecular weight decline highlighting an interaction between mechanical loading and chemical degradation. This study demonstrates that fatigue loading during degradation can affect both the mechanical properties and the chemical degradation rate. The results are important for defining appropriate in vitro degradation conditions for absorbable stent preclinical evaluation. Published by Elsevier Ltd.

  12. Benzotriazole as a passivating agent during chemical mechanical planarization of Ni–P alloy substrates

    International Nuclear Information System (INIS)

    Mu, Yan; Zhong, Mingjie; Rushing, Kenneth J.; Li, Yuzhuo; Shipp, Devon A.

    2014-01-01

    Highlights: • Benzotriazole (BTA) is used to passivate the Chemical Mechanical Planarization of Ni-P alloys. • BTA significantly decreases the average R a of the polished surfaces at low concentrations. • XPS, AFM and electrochemical studies are used to probe passivation effects of BTA on Ni–P surfaces. • Findings potentially impact hard disk drive manufacturing processes. - Abstract: With the rapid increase of data storage density on computer hard disk drives (HDDs), the operation distance between read/write head and disk surface has fallen to just a few nanometers. Chemical mechanical planarization (CMP) has been selected as the best process to produce high quality surface finish during the manufacturing of Ni–P alloy substrates for HDD applications. Herein we report, for the first time, the use of benzotriazole (BTA) as a passivating agent in CMP slurries to decrease the surface roughness (R a ). Results show that the average R a of the polished surfaces is decreased to 0.2 nm in a 5 μm × 5 μm scan area with the adding of 2 mM BTA. X-ray photoelectron spectroscopy (XPS) and electrochemical studies results further prove the interaction between BTA and Ni–P surface and the formation of an effective passivating layer on Cu in CMP slurries containing BTA

  13. Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds

    KAUST Repository

    Wang, Zhandong; Popolan-Vaida, Denisia M.; Chen, Bingjie; Moshammer, Kai; Mohamed, Samah; Wang, Heng; Sioud, Salim; Raji, Misjudeen; Kohse-Hö inghaus, Katharina; Hansen, Nils; Dagaut, Philippe; Leone, Stephen R.; Sarathy, Mani

    2017-01-01

    Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability of liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500–600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound’s molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. Finally, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels.

  14. A path flux analysis method for the reduction of detailed chemical kinetic mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Wenting; Ju, Yiguang [Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ 08544 (United States); Chen, Zheng [State Key Laboratory for Turbulence and Complex Systems, College of Engineering, Peking University, Beijing 100871 (China); Gou, Xiaolong [School of Power Engineering, Chongqing University, Chongqing 400044 (China)

    2010-07-15

    A direct path flux analysis (PFA) method for kinetic mechanism reduction is proposed and validated by using high temperature ignition, perfect stirred reactors, and steady and unsteady flame propagations of n-heptane and n-decane/air mixtures. The formation and consumption fluxes of each species at multiple reaction path generations are analyzed and used to identify the important reaction pathways and the associated species. The formation and consumption path fluxes used in this method retain flux conservation information and are used to define the path indexes for the first and the second generation reaction paths related to a targeted species. Based on the indexes of each reaction path for the first and second generations, different sized reduced chemical mechanisms which contain different number of species are generated. The reduced mechanisms of n-heptane and n-decane obtained by using the present method are compared to those generated by the direct relation graph (DRG) method. The reaction path analysis for n-decane is conducted to demonstrate the validity of the present method. The comparisons of the ignition delay times, flame propagation speeds, flame structures, and unsteady spherical flame propagation processes showed that with either the same or significantly less number of species, the reduced mechanisms generated by the present PFA are more accurate than that of DRG in a broad range of initial pressures and temperatures. The method is also integrated with the dynamic multi-timescale method and a further increase of computation efficiency is achieved. (author)

  15. Operating mechanisms of electrolytes in magnesium ion batteries: chemical equilibrium, magnesium deposition, and electrolyte oxidation.

    Science.gov (United States)

    Kim, Dong Young; Lim, Younhee; Roy, Basab; Ryu, Young-Gyoon; Lee, Seok-Soo

    2014-12-21

    Since the early nineties there have been a number of reports on the experimental development of Mg electrolytes based on organo/amide-magnesium chlorides and their transmetalations. However, there are no theoretical papers describing the underlying operating mechanisms of Mg electrolytes, and there is no clear understanding of these mechanisms. We have therefore attempted to clarify the operating mechanisms of Mg electrolytes by studying the characteristics of Mg complexes, solvation, chemical equilibrium, Mg-deposition processes, electrolyte-oxidation processes, and oxidative degradation mechanism of RMgCl-based electrolytes, using ab initio calculations. The formation and solvation energies of Mg complexes highly depend on the characteristics of R groups. Thus, changes in R groups of RMgCl lead to changes in the equilibrium position and the electrochemical reduction and oxidation pathways and energies. We first provide a methodological scheme for calculating Mg reduction potential values in non-aqueous electrolytes and electrochemical windows. We also describe a strategy for designing Mg electrolytes to maximize the electrochemical windows and oxidative stabilities. These results will be useful not only for designing improved Mg electrolytes, but also for developing new electrolytes in the future.

  16. Influence of Chemical, Mechanical, and Transport Processes on Wellbore Leakage from Geologic CO2 Storage Reservoirs.

    Science.gov (United States)

    Carroll, Susan A; Iyer, Jaisree; Walsh, Stuart D C

    2017-08-15

    Wells are considered to be high-risk pathways for fluid leakage from geologic CO 2 storage reservoirs, because breaches in this engineered system have the potential to connect the reservoir to groundwater resources and the atmosphere. Given these concerns, a few studies have assessed leakage risk by evaluating regulatory records, often self-reported, documenting leakage in gas fields. Leakage is thought to be governed largely by initial well-construction quality and the method of well abandonment. The geologic carbon storage community has raised further concerns because acidic fluids in the CO 2 storage reservoir, alkaline cement meant to isolate the reservoir fluids from the overlying strata, and steel casings in wells are inherently reactive systems. This is of particular concern for storage of CO 2 in depleted oil and gas reservoirs with numerous legacy wells engineered to variable standards. Research suggests that leakage risks are not as great as initially perceived because chemical and mechanical alteration of cement has the capacity to seal damaged zones. Our work centers on defining the coupled chemical and mechanical processes governing flow in damaged zones in wells. We have developed process-based models, constrained by experiments, to better understand and forecast leakage risk. Leakage pathways can be sealed by precipitation of carbonate minerals in the fractures and deformation of the reacted cement. High reactivity of cement hydroxides releases excess calcium that can precipitate as carbonate solids in the fracture network under low brine flow rates. If the flow is fast, then the brine remains undersaturated with respect to the solubility of calcium carbonate minerals, and zones depleted in calcium hydroxides, enriched in calcium carbonate precipitates, and made of amorphous silicates leached of original cement minerals are formed. Under confining pressure, the reacted cement is compressed, which reduces permeability and lowers leakage risks. The

  17. Effects of chemical alteration on fracture mechanical properties in hydrothermal systems

    Science.gov (United States)

    Callahan, O. A.; Eichhubl, P.; Olson, J. E.

    2015-12-01

    Fault and fracture networks often control the distribution of fluids and heat in hydrothermal and epithermal systems, and in related geothermal and mineral resources. Additional chemical influences on conduit evolution are well documented, with dissolution and precipitation of mineral species potentially changing the permeability of fault-facture networks. Less well understood are the impacts of chemical alteration on the mechanical properties governing fracture growth and fracture network geometry. We use double-torsion (DT) load relaxation tests under ambient air conditions to measure the mode-I fracture toughness (KIC) and subcritical fracture growth index (SCI) of variably altered rock samples obtained from outcrop in Dixie Valley, NV. Samples from southern Dixie Valley include 1) weakly altered granite, characterized by minor sericite in plagioclase, albitization and vacuolization of feldspars, and incomplete replacement of biotite with chlorite, and 2) granite from an area of locally intense propylitic alteration with chlorite-calcite-hematite-epidote assemblages. We also evaluated samples of completely silicified gabbro obtained from the Dixie Comstock epithermal gold deposit. In the weakly altered granite KIC and SCI are 1.3 ±0.2 MPam1/2 (n=8) and 59 ±25 (n=29), respectively. In the propylitic assemblage KIC is reduced to 0.6 ±0.1 MPam1/2 (n=11), and the SCI increased to 75 ±36 (n = 33). In both cases, the altered materials have lower fracture toughness and higher SCI than is reported for common geomechanical standards such as Westerly Granite (KIC ~1.7 MPam1/2; SCI ~48). Preliminary analysis of the silicified gabbro shows a significant increase in fracture toughness, 3.6 ±0.4 MPam1/2 (n=2), and SCI, 102 ±45 (n=19), compared to published values for gabbro (2.9 MPam1/2 and SCI = 32). These results suggest that mineralogical and textural changes associated with different alteration assemblages may result in spatially variable rates of fracture

  18. Effects of Nanofillers on the Thermo-Mechanical Properties and Chemical Resistivity of Epoxy Nanocomposites.

    Science.gov (United States)

    Atchudan, Raji; Pandurangan, Arumugam; Joo, Jin

    2015-06-01

    MWCNTs was synthesized using Ni-Cr/MgO by CVD method and were purified. The purified MWCNT was used as a filler material for the fabrication of epoxy nanocomposites. The epoxy nanocomposites with different amount (wt% = 0.5, 1.0, 2.0, 3.0, 4.0 and 5.0) of nanofillers (CB, SiO2 and MWCNTs) were prepared by casting method. The effects of nanofillers on the properties of neat epoxy matrix were well studied. The thermal properties of nanocomposites were studied using DSC, TGA and flame retardant, and also the mechanical properties such as tensile strength, flexural strength, compressive strength, impact strength, determination of hardness and chemical resistance were studied extensively. Based on the experiment's results, 2 wt% MWCNTs loading in epoxy resin showed the highest improvement in tensile strength, as compared to neat epoxy and to other epoxy systems (CB/epoxy, SiO2/epoxy). Improvements in tensile strength, glass transition temperature and decomposition temperature were observed by the addition of MWCNTs. The mechanical properties of the epoxy nanocomposites were improved due to the interfacial bonding between the MWCNTs and epoxy resin. Strain hardening behavior was higher for MWCNT/epoxy nanocomposites compared with CB/epoxy and SiO2/epoxy nanocomposites. The investigation of thermal and mechanical properties reveals that the incorporation of MWCNTs into the epoxy nanocomposites increases its thermal stability to a great extent. Discrete increase of glass transition temperature of nanocomposites is linearly dependent on MWCNTs content. Due to strong interfacial bonding between MWCNTs and epoxy resin, the chemical resistivity of MWCNT/epoxy nanocomposites is superior to neat epoxy and other epoxy systems.

  19. Electromagnetic interference shielding properties and mechanisms of chemically reduced graphene aerogels

    International Nuclear Information System (INIS)

    Bi, Shuguang; Zhang, Liying; Mu, Chenzhong; Liu, Ming; Hu, Xiao

    2017-01-01

    Graphical abstract: The electromagnetic interference shielding behavior and proposed mechanisms of ultralight free-standing 3D graphene aerogels. - Highlights: • The electromagnetic interference (EMI) shielding properties and mechanisms of ultralight 3D graphene aerogels (GAs) were systematically studied with respect to both the unique porous network and the intrinsic properties of the graphene sheets. • Thickness of the shielding material played a critical role on EMI SE. • By compressing the porous GAs into compact film didnt increase the EMI SE despite the increased electrical conductivity and connectivity. EMI SE is highly dependent on the effective amounts of the materials response to the EM waves. - Abstract: Graphene was recently demonstrated to exhibit excellent electromagnetic interference (EMI) shielding performance. In this work, ultralight (∼5.5 mg/cm"3) graphene aerogels (GAs) were fabricated through assembling graphene oxide (GO) using freeze-drying followed by a chemical reduction method. The EMI shielding properties and mechanisms of GAs were systematically studied with respect to the intrinsic properties of the reduced graphene oxide (rGO) sheets and the unique porous network. The EMI shielding effectiveness (SE) of GAs was increased from 20.4 to 27.6 dB when the GO was reduced by high concentration of hydrazine vapor. The presence of more sp"2 graphitic lattice and free electrons from nitrogen atoms resulted in the enhanced EMI SE. Absorption was the dominant shielding mechanism of GAs. Compressing the highly porous GAs into compact thin films did not change the EMI SE, but shifted the dominant shielding mechanism from absorption to reflection.

  20. Electromagnetic interference shielding properties and mechanisms of chemically reduced graphene aerogels

    Energy Technology Data Exchange (ETDEWEB)

    Bi, Shuguang [Temasek Laboratories, Nanyang Technological University, 50 Nanyang Drive, 637553 (Singapore); Zhang, Liying, E-mail: LY.Zhang@ntu.edu.sg [Temasek Laboratories, Nanyang Technological University, 50 Nanyang Drive, 637553 (Singapore); Mu, Chenzhong [School of Material Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798 (Singapore); Liu, Ming, E-mail: LIUMING@ntu.edu.sg [Temasek Laboratories, Nanyang Technological University, 50 Nanyang Drive, 637553 (Singapore); Hu, Xiao [Temasek Laboratories, Nanyang Technological University, 50 Nanyang Drive, 637553 (Singapore); School of Material Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798 (Singapore)

    2017-08-01

    Graphical abstract: The electromagnetic interference shielding behavior and proposed mechanisms of ultralight free-standing 3D graphene aerogels. - Highlights: • The electromagnetic interference (EMI) shielding properties and mechanisms of ultralight 3D graphene aerogels (GAs) were systematically studied with respect to both the unique porous network and the intrinsic properties of the graphene sheets. • Thickness of the shielding material played a critical role on EMI SE. • By compressing the porous GAs into compact film didnt increase the EMI SE despite the increased electrical conductivity and connectivity. EMI SE is highly dependent on the effective amounts of the materials response to the EM waves. - Abstract: Graphene was recently demonstrated to exhibit excellent electromagnetic interference (EMI) shielding performance. In this work, ultralight (∼5.5 mg/cm{sup 3}) graphene aerogels (GAs) were fabricated through assembling graphene oxide (GO) using freeze-drying followed by a chemical reduction method. The EMI shielding properties and mechanisms of GAs were systematically studied with respect to the intrinsic properties of the reduced graphene oxide (rGO) sheets and the unique porous network. The EMI shielding effectiveness (SE) of GAs was increased from 20.4 to 27.6 dB when the GO was reduced by high concentration of hydrazine vapor. The presence of more sp{sup 2} graphitic lattice and free electrons from nitrogen atoms resulted in the enhanced EMI SE. Absorption was the dominant shielding mechanism of GAs. Compressing the highly porous GAs into compact thin films did not change the EMI SE, but shifted the dominant shielding mechanism from absorption to reflection.

  1. Role of crystal orientation on chemical mechanical polishing of single crystal copper

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Aibin, E-mail: abzhu@mail.xjtu.edu.cn; He, Dayong; Luo, Wencheng; Liu, Yangyang

    2016-11-15

    Highlights: • The role of crystal orientation in cooper CMP by quasi-continuum was studied. • The atom displacement diagrams were obtained and analyzed. • The stress distribution diagrams and load-displacement curves were analyzed. • This research is helpful to revealing the material removal mechanism of CMP. - Abstract: The material removal mechanism of single crystal copper in chemical mechanical polishing (CMP) has not been intensively investigated. And the role of crystal orientation in CMP of single crystal cooper is not quite clear yet. Quasi-continuum method was adopted in this paper to simulate the process of nano-particles grinding on single crystal copper in CMP process. Three different crystal orientations, i.e. x[100]y[001], x[001]y[110] and x[–211]y[111], were chosen for analysis. The atom displacement diagrams, stress distribution diagrams and load-displacement curves were obtained. After analyzing the deformation mechanism, residual stress of the work piece material and cutting force, results showed that, the crystal orientation of work piece has great influence on the deformation characteristics and surface quality of work piece during polishing. In the A(001)[100] orientation, the residual stress distribution after polishing is deeper, and the stress is larger than that in the B(110)[001] and C(111)[–211] orientations. And the average tangential cutting force in the A(001)[100] orientation is much larger than those in the other two crystal orientation. This research is helpful to revealing the material removal mechanism of CMP process.

  2. Tribochemical interaction between nanoparticles and surfaces of selective layer during chemical mechanical polishing

    International Nuclear Information System (INIS)

    Ilie, Filip

    2013-01-01

    Nanoparticles have been widely used in polish slurries such as those in the chemical mechanical polishing (CMP) process. For understanding the mechanisms of CMP, an atomic force microscope (AFM) is used to characterize polished surfaces of selective layers, after a set of polishing experiments. To optimize the CMP polishing process, one needs to get information on the interaction between the nano-abrasive slurry nanoparticles and the surface of selective layer being polished. The slurry used in CMP process of the solid surfaces is slurry with large nanoparticle size colloidal silica sol nano-abrasives. Silica sol nano-abrasives with large nanoparticle are prepared and characterized by transmission electron microscopy, particles colloidal size, and Zeta potential in this paper. The movement of nanoparticles in liquid and the interaction between nanoparticles and solid surfaces coating with selective layer are very important to obtain an atomic alloy smooth surface in the CMP process. We investigate the nanoparticle adhesion and removal processes during CMP and post-CMP cleaning. The mechanical interaction between nanoparticles and the wafer surface was studied using a microcontact wear model. This model considers the nanoparticle effects between the polishing interfaces during load balancing. Experimental results on polishing and cleaning are compared with numerical analysis. This paper suggests that during post-CMP cleaning, a combined effort in chemical and mechanical interaction (tribochemical interactions) would be effective in removal of small nanoparticles during cleaning. For large nanoparticles, more mechanical forces would be more effective. CMP results show that the removal rate has been improved to 367 nm/min and root mean square (RMS) of roughness has been reduced from 4.4 to 0.80 nm. Also, the results show that the silica sol nano-abrasives about 100 nm are of higher stability (Zeta potential is −65 mV) and narrow distribution of nanoparticle

  3. Thermal-mechanical-hydrological-chemical responses in the single heater test at the ESF

    International Nuclear Information System (INIS)

    Lin, W.; Blair, S.; Buettner, M

    1997-01-01

    The Single Heater Test (SHT) is conducted in the Exploratory Studies Facility (ESF) to study the thermal-mechanical responses of the rock mass. A set of boreholes were drilled in the test region for conducting a scoping test of the coupled thermal-mechanical- hydrological-chemical (TMHC) processes. The holes for the TMHC tests include electrical resistivity tomography (ERT), neutron logging/temperature, hydrological, and optical multiple point borehole extensometers. A 4-kW heater was installed in the heater hole, and was energized on August 26, 1996. Some observed movements of the water around the heater are associated with a possible dry-out region near the heater. The water that has been moved is more dilute than the in situ ground water, except for the concentration of Ca. This indicates that fractures are the major water pathways, and the displaced water may have reached an equilibrium with carbonate minerals on the fracture surfaces. No mechanical-hydrological coupling has been observed. The tests are on-going, and more data will be collected and analyzed

  4. Mechanical properties of chemical vapor deposited coatings for fusion reactor application

    International Nuclear Information System (INIS)

    Mullendore, A.W.; Whitley, J.B.; Pierson, H.O.; Mattox, D.M.

    1980-01-01

    Chemical vapor deposited coatings of TiB 2 , TiC and boron on graphite substrates are being developed for application as limiter materials in magnetic confinement fusion reactors. In this application severe thermal shock conditions exist and to do effective thermo-mechanical modelling of the material response it is necessary to acquire elastic moduli, fracture strength and strain to fracture data for the coatings. Four point flexure tests have been conducted from room temperature to 2000 0 C on TiB 2 and boron coated graphite with coatings in tension and compression and the mechanical properties extracted from the load-deflection data. In addition, stress relaxation tests from 500 to 1150 0 C were performed on TiB 2 and TiC coated graphite beams to assess the low levels of plastic deformation which occur in these coatings. Significant differences have been observed between the effective mechanical properties of the coatings and literature values of the bulk properties

  5. Kandelia obovata (S., L.) Yong tolerance mechanisms to Cadmium: Subcellular distribution, chemical forms and thiol pools

    International Nuclear Information System (INIS)

    Weng Bosen; Xie Xiangyu; Weiss, Dominik J.; Liu Jingchun; Lu Haoliang; Yan Chongling

    2012-01-01

    Highlights: ► Cadmium tolerance mechanisms of Kandelia obovata was investigated systematacially. ► Thiol pool can play roles in cadmium detoxification mechanisms. ► Increasing cadmium treatment strength caused proportional increase of cadmium uptake. ► More than half of cadmium was localized in cell walls, and lowest in membranes. ► Sodium chloride and acetic acid extractable fractions were dominant. - Abstract: In order to explore the detoxification mechanisms adopted by mangrove under cadmium (Cd) stress, we investigated the subcellular distribution and chemical forms of Cd, in addition to the change of the thiol pools in Kandelia obovata (S., L.) Yong, which were cultivated in sandy culture medium treated with sequential Cd solution. We found that Cd addition caused a proportional increase of Cd in the organs of K. obovata. The investigation of subcellular distribution verified that most of the Cd was localized in the cell wall, and the lowest was in the membrane. Results showed sodium chloride and acetic acid extractable Cd fractions were dominant. The contents of non-protein thiol compounds, Glutathione and phytochelatins in K. obovata were enhanced by the increasing strength of Cd treatment. Therefore, K. obovata can be defined as Cd tolerant plant, which base on cell wall compartmentalization, as well as protein and organic acids combination.

  6. Kinetic calorimetry in the study of the mechanism of low-temperature chemical reactions

    Science.gov (United States)

    Barkalov, I. M.; Kiryukhin, D. P.

    Chemical reactions are always followed by a change in the reacting system enthalpy, hence, calorimetry as a method of enthalpy and heat capacity measuring is a universal and, sometimes, even the only possible way of studying chemical reaction kinetics. Throughout its long history, the calorimeter, having preserved the positions of the main method of thermodynamic studies, has conquered a new field of application: that of kinetic study of chemical reactions. The advantages and disadvantages of the kinetic calorimeter are now obvious. First, the advantages are: (1) the possibility of measuring the rate of a chemical reaction without any special requirements being imposed on the reaction medium (solid, viscous, multicomponent systems); (2) the high efficiency: a large volume of kinetic information in one experiment and a non-destructive character of changes; (3) the possibility of measuring directly in the field of ionizing radiation (γ-radiation, accelerated electrons) and light; and (4) recording of the chemical conversion directly at the time of its occurrence. The disadvantages of this method are: (1) the high inertia of standard calorimeter systems (τC⋍102-103S), which restricts the possibilities of studying fast processes; and (2) the complexity of the correct organization of the calorimeter experiment when the parameters of the process are changed (overheating in the sample, conversion of the process to explosive and auto wave regimens). One of the oldest and most universal methods of studying the mechanism of chemical reactions, calorimetry, is now passing through a period of turbulent development due to the advances in electronics and computerization. The wide variety of types of calorimeter set-ups and the large assortment of measurement schemes in the currently described methods complicate the experimental selection of the necessary instrument rather than facilitate it. The basic principles of the method, the types of calorimeters, and the measuring

  7. Effect of conditioner load on the polishing pad surface during chemical mechanical planarization process

    Energy Technology Data Exchange (ETDEWEB)

    Shin, Cheol Min; Qin, Hong Yi; Hong, Seok Jun; Jeon, Sang Hyuk; Kulkarni, Atul; Kim, Tae Sun [Sungkyunkwan University, Suwon (Korea, Republic of)

    2016-12-15

    During the Chemical mechanical planarization (CMP), the pad conditioning process can affect the pad surface characteristics. Among many CMP process parameters, the improper applied load on the conditioner arm may have adverse effects on the polyurethane pad. In this work, we evaluated the pad surface properties under the various conditioner arm applied during pad conditioning process. The conditioning pads were evaluated for surface topography, surface roughness parameters such as Rt and Rvk and Material removal rate (MRR) and within-wafer non-uniformity after wafer polishing. We observed that, the pad asperities were collapsed in the direction of conditioner rotation and blocks the pad pores applied conditioner load. The Rvk value and MRR were founded to be in relation with 4 > 1 > 7 kgF conditioner load. Hence, this study shows that, 4 kgF applied load by conditioner is most suitable for the pad conditioning during CMP.

  8. Kinematic analysis of in situ measurement during chemical mechanical planarization process

    Energy Technology Data Exchange (ETDEWEB)

    Li, Hongkai; Wang, Tongqing; Zhao, Qian; Meng, Yonggang; Lu, Xinchun, E-mail: xclu@tsinghua.edu.cn [State Key Laboratory of Tribology, Tsinghua University, Beijing 100084 (China)

    2015-10-15

    Chemical mechanical planarization (CMP) is the most widely used planarization technique in semiconductor manufacturing presently. With the aid of in situ measurement technology, CMP tools can achieve good performance and stable productivity. However, the in situ measurement has remained unexplored from a kinematic standpoint. The available related resources for the kinematic analysis are very limited due to the complexity and technical secret. In this paper, a comprehensive kinematic analysis of in situ measurement is provided, including the analysis model, the measurement trajectory, and the measurement time of each zone of wafer surface during the practical CMP process. In addition, a lot of numerical calculations are performed to study the influences of main parameters on the measurement trajectory and the measurement velocity variation of the probe during the measurement process. All the efforts are expected to improve the in situ measurement system and promote the advancement in CMP control system.

  9. A physicochemical mechanism of chemical gas sensors using an AC analysis.

    Science.gov (United States)

    Moon, Jaehyun; Park, Jin-Ah; Lee, Su-Jae; Lee, Jeong-Ik; Zyung, Taehyong; Shin, Eui-Chol; Lee, Jong-Sook

    2013-06-21

    Electrical modeling of the chemical gas sensors was successfully applied to TiO2 nanofiber gas sensors by developing an equivalent circuit model where the junction capacitance as well as the resistance can be separated from the comparable stray capacitance. The Schottky junction impedance exhibited a characteristic skewed arc described by a Cole-Davidson function, and the variation of the fit and derived parameters with temperature, bias, and NO2 gas concentration indicated definitely a physicochemical sensing mechanism based on the Pt|TiO2 Schottky junctions against the conventional supposition of the enhanced sensitivity in nanostructured gas sensors with high grain boundary/surface area. Analysis on a model Pt|TiO2|Pt structure also confirmed the characteristic impedance response of TiO2 nanofiber sensors.

  10. Optical system to study temperature influenced chemical and mechanical changes to the PCD structure

    CSIR Research Space (South Africa)

    Masina, B

    2010-09-01

    Full Text Available .csir.co.za An optical system to study temperature influenced chemical and mechanical changes to the PCD structure Bathusile Masina and Andrew Forbes SAIP 2010: Applied and Industrial Physics 1 October 2010 © CSIR 2010 Slide 2 It is acknowledged that temperature... re (K el vi n) Minutes © CSIR 2010 Slide 15 -0.008 -0.006 -0.004 -0.002 0.000 0.002 0.004 0.006 0.008 0.4 0.5 0.6 0.7 0.8 0.9 1.0 N or m al iz ed T em pe ra tu re r (m) At steady state we predict a gradient temperature...

  11. Chemical-Free Cotton Defoliation by; Mechanical, Flame and Laser Girdling

    Directory of Open Access Journals (Sweden)

    Mathew G. Pelletier

    2017-01-01

    Full Text Available A novel new way to achieve chemical-free defoliation of cotton is discussed. The research found that by severing the phloem tissue on the main stalk, via a girdling operation, the operation stimulated the cotton plant to alter its growth into an early senescence pathway that resulted in the plant shedding its leaves and opening up all its bolls, leaving the plant in the perfect state for machine harvesting. Even with follow-up rains, zero regrowth occurred in the treated plants, unlike the untreated control plots where significant regrowth did occur. This report compares the results of greenhouse and field trials where the girdling operation was performed by hand, flame, mechanical and via a CO2 laser to achieve phloem tissue severance. Design parameters for a prototype laser girdling system are also provided. Results suggest that for deficit irrigated cotton, girdling can provide an alternative means to defoliate cotton.

  12. Effects of chemical complexity on the autoxidation mechanisms of endocyclic alkene ozonolysis products

    DEFF Research Database (Denmark)

    Rissanen, Matti P.; Kurtén, Theo; Sipilä, Mikko

    2015-01-01

    (NO3-) based ionization scheme. The experiments were performed in borosilicate glass flow tube reactors at room temperature (T = 293 ± 3 K) and at ambient pressure. An ensemble of oxidized monomer and dimer products was detected, with elemental compositions obtained from the high......Formation of highly oxidized, multifunctional products in the ozonolysis of three endocyclic alkenes, 1- methylcyclohexene, 4-methylcyclohexene, and α-pinene, was investigated using a chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer with a nitrate ion......-resolution mass spectra. The monomer product distributions have O/C ratios from 0.8 to 1.6 and can be explained with an autocatalytic oxidation mechanism (=autoxidation) where the oxygen-centered peroxy radical (RO2) intermediates internally rearrange by intramolecular hydrogen shift reactions...

  13. Quantum chemical modeling of the inhibition mechanism of monoamine oxidase by oxazolidinone and analogous heterocyclic compounds.

    Science.gov (United States)

    Erdem, Safiye Sağ; Özpınar, Gül Altınbaş; Boz, Ümüt

    2014-02-01

    Monoamine oxidase (MAO, EC 1.4.3.4) is responsible from the oxidation of a variety of amine neurotransmitters. MAO inhibitors are used for the treatment of depression or Parkinson's disease. They also inhibit the catabolism of dietary amines. According to one hypothesis, inactivation results from the formation of a covalent adduct to a cysteine residue in the enzyme. If the adduct is stable enough, the enzyme is inhibited for a long time. After a while, enzyme can turn to its active form as a result of adduct breakdown by β-elimination. In this study, the proposed inactivation mechanism was modeled and tested by quantum chemical calculations. Eight heterocyclic methylthioamine derivatives were selected to represent the proposed covalent adducts. Activation energies related to their β-elimination reactions were calculated using ab initio and density functional theory methods. Calculated activation energies were in good agreement with the relative stabilities of the hypothetical adducts predicted in the literature by enzyme inactivation measurements.

  14. Mechanism and degree of chemical elements effect on atmosphere corrosion resistance of steels

    International Nuclear Information System (INIS)

    Vu Din' Vuj

    1991-01-01

    It follows from the proposed regression equations that falourable effect of chemical elements on steel resistance to atmospheric corrosion is determined by their ability to increase interatom bond stability in iron crystal lattice and form corrosion products with high protection properties. Element positive influence on steel corrosion resistance decreases in the following order: S, P, Si, Mn, Cu, Cr, Ni, C in semiurban tropical atmosphere and S, Mn, Sr, Cu, Ni, Cr in coastal atmosphere. In the latter case C increases corrosion in a greater degree as compared to P. Small ammounts of Mo decrease steel resistance in semiurban atmosphere and almost do not influence it in the coastal one. Possible mechanisms of individual element influence on steel corrosion resistance are considered

  15. The coordination between mechanical and chemical subsystems initiates locomotion of Physarum plasmodial fragments

    Science.gov (United States)

    Zhang, Shun; Guy, Robert; Del Alamo, Juan Carlos

    2017-11-01

    Physarum polycephalum is a multinucleated slime mold whose endoplasm flows periodically driven by the contraction of its ectoplasm, a dense shell of F-actin cross-linked by myosin molecular motors and attached to the cell membrane. We find that physarum fragments smaller than 100 microns remain round and stay in place. However, larger fragments break symmetry leading to sustained forward locomotion, in process that is reminiscent of an interfacial instability that seems to settle around two different limit cycles (traveling waves and standing waves). We use both theory and experiments to study how coordination emerges between the different mechanical and chemical subsystems of the fragment to initiate locomotion. The role of many involved factors, such as fragment size, substratum adhesiveness, rheological properties, actin polymerization and traction stresses are investigated, and we find they agree well with our predictive model.

  16. Reactive Ion Etching as Cleaning Method Post Chemical Mechanical Polishing for Phase Change Memory Device

    International Nuclear Information System (INIS)

    Min, Zhong; Zhi-Tang, Song; Bo, Liu; Song-Lin, Feng; Bomy, Chen

    2008-01-01

    In order to improve nano-scale phase change memory performance, a super-clean interface should be obtained after chemical mechanical polishing (CMP) of Ge 2 Sb 2 Te 5 phase change films. We use reactive ion etching (RIE) as the cleaning method. The cleaning effect is analysed by scanning electron microscopy and an energy dispersive spectrometer. The results show that particle residue on the surface has been removed. Meanwhile, Ge 2 Sb 2 Te 5 material stoichiometric content ratios are unchanged. After the top electrode is deposited, current-voltage characteristics test demonstrates that the set threshold voltage is reduced from 13 V to 2.7V and the threshold current from 0.1mA to 0.025mA. Furthermore, we analyse the RIE cleaning principle and compare it with the ultrasonic method

  17. Effects of He-Ne laser beam on mechanical, heat, chemical and superficial wounds

    International Nuclear Information System (INIS)

    Kakai, S.F.K.; Albarwari, S.E.; Alsenawi, T.A.

    1988-02-01

    This study summarizes the effects of low-doses of He-Ne laser radiation (λ = 6328 A), on healing of four types of wounds, including mechanical, heat, chemical and superficial wounds. The results revealed that variations between complete wound-closure in irradiated samples and that of control groups were statistically significant. Moreover, the results suggest that the stimulative action of laser is an accumulative phenomenon, that affects factors involved in the course of wound healing. The results also indicate that the skin epithelium is a highly responsive tissue towards this sort of radiation, which suggests that the stimulative action of He-Ne laser could be assayed easily by using such tissues as a test target. (author). 11 refs, 2 tabs

  18. Panel report on coupled thermo-mechanical-hydro-chemical processes associated with a nuclear waste repository

    International Nuclear Information System (INIS)

    Tsang, C.F.; Mangold, D.C.

    1984-07-01

    Four basic physical processes, thermal, hydrological, mechanical and chemical, are likely to occur in 11 different types of coupling during the service life of an underground nuclear waste repository. A great number of coupled processes with various degrees of importance for geological repositories were identified and arranged into these 11 types. A qualitative description of these processes and a tentative evaluation of their significance and the degree of uncertainty in prediction is given. Suggestions for methods of investigation generally include, besides theoretical work, laboratory and large scale field testing. Great efforts of a multidisciplinary nature are needed to elucidate details of several coupled processes under different temperature conditions in different geological formations. It was suggested that by limiting the maximum temperature to 100 0 C in the backfill and in the host rock during the whole service life of the repository the uncertainties in prediction of long-term repository behavior might be considerably reduced

  19. Panel report on coupled thermo-mechanical-hydro-chemical processes associated with a nuclear waste repository

    Energy Technology Data Exchange (ETDEWEB)

    Tsang, C.F.; Mangold, D.C. (eds.)

    1984-07-01

    Four basic physical processes, thermal, hydrological, mechanical and chemical, are likely to occur in 11 different types of coupling during the service life of an underground nuclear waste repository. A great number of coupled processes with various degrees of importance for geological repositories were identified and arranged into these 11 types. A qualitative description of these processes and a tentative evaluation of their significance and the degree of uncertainty in prediction is given. Suggestions for methods of investigation generally include, besides theoretical work, laboratory and large scale field testing. Great efforts of a multidisciplinary nature are needed to elucidate details of several coupled processes under different temperature conditions in different geological formations. It was suggested that by limiting the maximum temperature to 100{sup 0}C in the backfill and in the host rock during the whole service life of the repository the uncertainties in prediction of long-term repository behavior might be considerably reduced.

  20. Chemical mechanical planarization of amorphous Ge2Sb2Te5 with a soft pad

    International Nuclear Information System (INIS)

    He Aodong; Liu Bo; Song Zhitang; Lü Yegang; Li Juntao; Liu Weili; Feng Songlin; Wu Guanping

    2013-01-01

    Chemical mechanical planarization (CMP) of amorphous Ge 2 Sb 2 Te 5 (a-GST) is investigated using two typical soft pads (politex REG and AT) in acidic slurry. After CMP, it is found that the removal rate (RR) of a-GST increases with an increase of runs number for both pads. However, it achieves the higher RR and better surface quality of a-GST for an AT pad. The in-situ sheet resistance (R s ) measure shows the higher R s of a-GST polishing can be gained after CMP using both pads and the high R s is beneficial to lower the reset current for the PCM cells. In order to find the root cause of the different RR of a-GST polishing with different pads, the surface morphology and characteristics of both new and used pads are analyzed, it shows that the AT pad has smaller porosity size and more pore counts than that of the REG pad, and thus the AT pad can transport more fresh slurry to the reaction interface between the pad and a-GST, which results in the high RR of a-GST due to enhanced chemical reaction. (semiconductor technology)

  1. Chemical mechanical polishing characteristics of ITO thin film prepared by RF magnetron sputtering

    International Nuclear Information System (INIS)

    Lee, Kang-Yeon; Choi, Gwon-Woo; Kim, Yong-Jae; Choi, Youn-Ok; Kim, Nam-Oh

    2012-01-01

    Indium-tin-oxide (ITO) thin films have attracted intensive interest because of their unique properties of good conductivity, high optical transmittance over the visible region and easy patterning ability. ITO thin films have found many applications in anti-static coatings, thermal heaters, solar cells, flat panel displays (FPDs), liquid crystal displays (LCDs), electroluminescent devices, sensors and organic light-emitting diodes (OLEDs). ITO thin films are generally fabricated by using various methods, such as spraying, chemical vapor deposition (CVD), evaporation, electron gun deposition, direct current electroplating, high frequency sputtering, and reactive sputtering. In this research, ITO films were grown on glass substrates by using a radio-frequency (RF) magnetron sputtering method. In order to achieve a high transmittance and a low resistivity, we examined the various film deposition conditions, such as substrate temperature, working pressure, annealing temperature, and deposition time. Next, in order to improve the surface quality of the ITO thin films, we performed a chemical mechanical polishing (CMP) with different process parameters and compared the electrical and the optical properties of the polished ITO thin films. The best CMP conditions with a high removal rate, low nonuniformity, low resistivity and high transmittance were as follows: platen speed, head speed, polishing time, and slurry flow rate of 30 rpm, 30 rpm, 60 sec, and 60 ml/min, respectively.

  2. Chemically induced aneuploidy in mammalian cells: mechanisms and biological significance in cancer

    Energy Technology Data Exchange (ETDEWEB)

    Oshimura, M.; Barrett, J.C.

    1986-01-01

    A literature review with over 200 references examines the growing body of evidence from human and animal cancer cytogenetics that aneuploidy is an important chromosome change in carcinogenesis. Evidence from in vitro cell transformation studies supports the idea that aneuploidy has a direct effect on the conversion of a normal cell to a preneoplastic or malignant cell. Induction of an aneuploid state in a preneoplastic or neoplastic cell could have any of the following four biological effects: a change in gene dosage, a change in gene balance, expression of a recessive mutation, or a change in genetic instability (which could secondarily lead to neoplasia). There are a number of possible mechanisms by which chemicals might induce aneuploidy, including effects on microtubules, damage to essential elements for chromosome function reduction in chromosome condensation or pairing, induction of chromosome interchanges, unresolved recombination structures, increased chromosome stickiness, damage to centrioles, impairment of chromosome alignment ionic alterations during mitosis, damage to the nuclear membrane, and a physical disruption of chromosome segregation. Therefore, a number of different targets exist for chemically induced aneuploidy.

  3. Effects of catalyst concentration and ultraviolet intensity on chemical mechanical polishing of GaN

    Science.gov (United States)

    Wang, Jie; Wang, Tongqing; Pan, Guoshun; Lu, Xinchun

    2016-08-01

    Effects of catalyst concentration and ultraviolet intensity on chemical mechanical polishing (CMP) of GaN were deeply investigated in this paper. Working as an ideal homogeneous substrate material in LED industry, GaN ought to be equipped with a smooth and flat surface. Taking the strong chemical stability of GaN into account, photocatalytic oxidation technology was adopted in GaN CMP process to realize efficient removal. It was found that, because of the improved reaction rate of photocatalytic oxidation, GaN material removal rate (MRR) increases by a certain extent with catalyst concentration increasing. Cross single line analysis on the surface after polishing by Phase Shift MicroXAM-3D was carried out to prove the better removal effect with higher catalyst concentration. Ultraviolet intensity field in H2O2-SiO2-based polishing system was established and simulated, revealing the variation trend of ultraviolet intensity around the outlet of the slurry. It could be concluded that, owing to the higher planarization efficiency and lower energy damage, the UV lamp of 125 W is the most appropriate lamp in this system. Based on the analysis, defects removal model of this work was proposed to describe the effects of higher catalyst concentration and higher power of UV lamp.

  4. Mechanism of waste biomass pyrolysis: Effect of physical and chemical pre-treatments

    International Nuclear Information System (INIS)

    Das, Oisik; Sarmah, Ajit K.

    2015-01-01

    To impart usability in waste based biomass through thermo-chemical reactions, several physical and chemical pre-treatments were conducted to gain an insight on their mode of action, effect on the chemistry and the change in thermal degradation profiles. Two different waste biomasses (Douglas fir, a softwood and hybrid poplar, a hardwood) were subjected to four different pre-treatments, namely, hot water pre-treatment, torrefaction, acid (sulphuric acid) and salt (ammonium phosphate) doping. Post pre-treatments, the changes in the biomass structure, chemistry, and thermal makeup were studied through electron microscopy, atomic absorption/ultra violet spectroscopy, ion exchange chromatography, and thermogravimetry. The pre-treatments significantly reduced the amounts of inorganic ash, extractives, metals, and hemicellulose from both the biomass samples. Furthermore, hot water and torrefaction pre-treatment caused mechanical disruption in biomass fibres leading to smaller particle sizes. Torrefaction of Douglas fir wood yielded more solid product than hybrid poplar. Finally, the salt pre-treatment increased the activation energies of the biomass samples (especially Douglas fir) to a great extent. Thus, salt pre-treatment was found to bestow thermal stability in the biomass. - Highlights: • Pre-treatments reduce ash, extractives, alkalines and hemicellulose from biomass. • Torrefaction of Douglas fir yields more solid product than hybrid poplar. • Salt pretreatment significantly increases the activation energy of biomass. • Acid and salt pretreatment bestows thermal stability in biomass.

  5. Evaluation of the Chemical and Mechanical Properties of Hardening High-Calcium Fly Ash Blended Concrete.

    Science.gov (United States)

    Fan, Wei-Jie; Wang, Xiao-Yong; Park, Ki-Bong

    2015-09-07

    High-calcium fly ash (FH) is the combustion residue from electric power plants burning lignite or sub-bituminous coal. As a mineral admixture, FH can be used to produce high-strength concrete and high-performance concrete. The development of chemical and mechanical properties is a crucial factor for appropriately using FH in the concrete industry. To achieve sustainable development in the concrete industry, this paper presents a theoretical model to systematically evaluate the property developments of FH blended concrete. The proposed model analyzes the cement hydration, the reaction of free CaO in FH, and the reaction of phases in FH other than free CaO. The mutual interactions among cement hydration, the reaction of free CaO in FH, and the reaction of other phases in FH are also considered through the calcium hydroxide contents and the capillary water contents. Using the hydration degree of cement, the reaction degree of free CaO in FH, and the reaction degree of other phases in FH, the proposed model evaluates the calcium hydroxide contents, the reaction degree of FH, chemically bound water, porosity, and the compressive strength of hardening concrete with different water to binder ratios and FH replacement ratios. The evaluated results are compared to experimental results, and good consistencies are found.

  6. Cell adhesion over two distinct surfaces varied with chemical and mechanical properties

    International Nuclear Information System (INIS)

    Huang, Chih-Ling; Liao, Jiunn-Der; Yang, Chia-Fen; Chang, Chia-Wei; Ju, Ming-Shaung; Lin, Chou-Ching K.

    2009-01-01

    Chitosan is widely recognized as a natural and proper scaffold material; however, as a base substrate, it shows little promotion effect for the growth of cultured fibroblast cells. In this study, chitosan in a film form was prepared and used as a cell-culturing matrix, followed by patterning the evaporated Au upon it. Micro-scale Au clusters of ∼ 150 μm in diameter and ∼ 20 nm in thickness were then patterned and adhered upon the chitosan matrix. Physical and chemical properties of Au/chitosan were characterized. In particular, nano-indentation with dynamic contact module was applied to measure the nano-hardness of the tailored surfaces on Au/chitosan. Fibroblast cells were thereafter cultured on Au/chitosan. Experimental results demonstrated that as compared with the chitosan matrix, Au clusters and their boundary area exhibited favorable to promote cell adhesion, spreading, and growth. As well, nano-hardness on the boundary area of Au/chitosan significantly enhanced, while the cultured fibroblast cells aggregated upon Au clusters and the boundary area. In combination with the possible chemical and mechanical changes resulted by the evaporation of Au clusters upon the chitosan matrix, a selectively-enhanced Au/chitosan to promote fibroblast cells proliferation was created. Such design is anticipated for enabling a surface for scaffold materials with the cell-guidable function.

  7. Mechanical Properties and Chemical Resistance of New Composites for Oil Pump Impellers

    Directory of Open Access Journals (Sweden)

    Dilyus I. Chukov

    2018-05-01

    Full Text Available In this paper, a new class of high-performance composites and a method of their production based on the carbonization of an elastomeric matrix are proposed. The use of elastomeric matrix makes it possible to manufacture products with complex shapes, while the subsequent carbonization can significantly improve their properties by changing the chemical nature of the elastomeric matrix. Such an approach can reduce the products’ machining cost, especially for composites reinforced with super hard fillers such as silicon carbide at high filling degrees. Low-temperature carbonization makes it possible to obtain composites with mechanical behavior similar to that of ceramics. In contrast to classical elastomeric materials, the nitrile butadiene rubber (NBR-based compounds were highly filled (300 parts per hundred rubber-PHR with different carbon fillers and silicon carbide; then cured and carbonized at low-temperature 360 °C with the carbonization cycle of 12 h. The feasibility of the production method was validated through the manufacturing of products with complex shapes—impellers for electric centrifugal pumps. It was found that the carbonized composites have good chemical resistance and low water absorption. The composites have high Shore D hardnesses (93–96, ultimate tensile strengths (62–85 MPa, Young’s moduli (17–24 GPa, and compressive strengths (155–181 MPa.

  8. Chemical Mechanisms and Their Applications in the Goddard Earth Observing System (GEOS) Earth System Model.

    Science.gov (United States)

    Nielsen, J Eric; Pawson, Steven; Molod, Andrea; Auer, Benjamin; da Silva, Arlindo M; Douglass, Anne R; Duncan, Bryan; Liang, Qing; Manyin, Michael; Oman, Luke D; Putman, William; Strahan, Susan E; Wargan, Krzysztof

    2017-12-01

    NASA's Goddard Earth Observing System (GEOS) Earth System Model (ESM) is a modular, general circulation model (GCM), and data assimilation system (DAS) that is used to simulate and study the coupled dynamics, physics, chemistry, and biology of our planet. GEOS is developed by the Global Modeling and Assimilation Office (GMAO) at NASA Goddard Space Flight Center. It generates near-real-time analyzed data products, reanalyses, and weather and seasonal forecasts to support research targeted to understanding interactions among Earth System processes. For chemistry, our efforts are focused on ozone and its influence on the state of the atmosphere and oceans, and on trace gas data assimilation and global forecasting at mesoscale discretization. Several chemistry and aerosol modules are coupled to the GCM, which enables GEOS to address topics pertinent to NASA's Earth Science Mission. This paper describes the atmospheric chemistry components of GEOS and provides an overview of its Earth System Modeling Framework (ESMF)-based software infrastructure, which promotes a rich spectrum of feedbacks that influence circulation and climate, and impact human and ecosystem health. We detail how GEOS allows model users to select chemical mechanisms and emission scenarios at run time, establish the extent to which the aerosol and chemical components communicate, and decide whether either or both influence the radiative transfer calculations. A variety of resolutions facilitates research on spatial and temporal scales relevant to problems ranging from hourly changes in air quality to trace gas trends in a changing climate. Samples of recent GEOS chemistry applications are provided.

  9. Adsorption treatment of oxide chemical mechanical polishing wastewater from a semiconductor manufacturing plant by electrocoagulation

    Energy Technology Data Exchange (ETDEWEB)

    Chou, Wei-Lung, E-mail: wlchou@sunrise.hk.edu.tw [Department of Safety, Health and Environmental Engineering, Hungkuang University, No. 34, Chung-Chie Road, Sha-Lu, Taichung 433, Taiwan (China); Wang, Chih-Ta [Department of Safety Health and Environmental Engineering, Chung Hwa University of Medical Technology, Tainan Hsien 717, Taiwan (China); Chang, Wen-Chun; Chang, Shih-Yu [Department of Safety, Health and Environmental Engineering, Hungkuang University, No. 34, Chung-Chie Road, Sha-Lu, Taichung 433, Taiwan (China)

    2010-08-15

    In this study, metal hydroxides generated during electrocoagulation (EC) were used to remove the chemical oxygen demand (COD) of oxide chemical mechanical polishing (oxide-CMP) wastewater from a semiconductor manufacturing plant by EC. Adsorption studies were conducted in a batch system for various current densities and temperatures. The COD concentration in the oxide-CMP wastewater was effectively removed and decreased by more than 90%, resulting in a final wastewater COD concentration that was below the Taiwan discharge standard (100 mg L{sup -1}). Since the processed wastewater quality exceeded the direct discharge standard, the effluent could be considered for reuse. The adsorption kinetic studies showed that the EC process was best described using the pseudo-second-order kinetic model at the various current densities and temperatures. The experimental data were also tested against different adsorption isotherm models to describe the EC process. The Freundlich adsorption isotherm model predictions matched satisfactorily with the experimental observations. Thermodynamic parameters, including the Gibbs free energy, enthalpy, and entropy, indicated that the COD adsorption of oxide-CMP wastewater on metal hydroxides was feasible, spontaneous and endothermic in the temperature range of 288-318 K.

  10. Adsorption treatment of oxide chemical mechanical polishing wastewater from a semiconductor manufacturing plant by electrocoagulation

    International Nuclear Information System (INIS)

    Chou, Wei-Lung; Wang, Chih-Ta; Chang, Wen-Chun; Chang, Shih-Yu

    2010-01-01

    In this study, metal hydroxides generated during electrocoagulation (EC) were used to remove the chemical oxygen demand (COD) of oxide chemical mechanical polishing (oxide-CMP) wastewater from a semiconductor manufacturing plant by EC. Adsorption studies were conducted in a batch system for various current densities and temperatures. The COD concentration in the oxide-CMP wastewater was effectively removed and decreased by more than 90%, resulting in a final wastewater COD concentration that was below the Taiwan discharge standard (100 mg L -1 ). Since the processed wastewater quality exceeded the direct discharge standard, the effluent could be considered for reuse. The adsorption kinetic studies showed that the EC process was best described using the pseudo-second-order kinetic model at the various current densities and temperatures. The experimental data were also tested against different adsorption isotherm models to describe the EC process. The Freundlich adsorption isotherm model predictions matched satisfactorily with the experimental observations. Thermodynamic parameters, including the Gibbs free energy, enthalpy, and entropy, indicated that the COD adsorption of oxide-CMP wastewater on metal hydroxides was feasible, spontaneous and endothermic in the temperature range of 288-318 K.

  11. Investigation of microstructure and mechanical properties of phosphocalcic bone substitute using the chemical wet method

    Science.gov (United States)

    Alimi, Latifa; Bahloul, Lynda; Azzi, Afef; Guerfi, Souad; Ismail, Fadhel; Chaoui, Kamel

    2018-05-01

    Selection of calcium phosphate base materials in reconstructive bone surgery is justified by the surprising similarities in chemical compositions with human bones. The closest to natural apatite material is the hydroxyapatite (HAp) which has a chemical composition based on calcium and phosphate (Ca10(PO4)6(OH)2). In this study, HAp is synthesized using the wet precipitation method from hydrated calcium chloride (CaCl2,12H2O) and di-sodium hydrogen phosphate di-hydrate (HNa2PO4,2H2O). The powder is calcinated at 900°C and 1200°C in order to compare with sintered condition at 1150°C. Vickers microhardness tests and X-ray diffraction analyzes are used for the characterization of the crystalline material. Mechanical properties (Hv, σe, σr, and KC) and the degree of crystallinity (Xc) are discussed according to heat treatment temperatures. Results indicate that heat treating the powder at 1200°C increased crystallinity up to 72%. At the same time, microhardness increased with temperature and even outmatched the sintered case at 1150°C. Fracture toughness is ameliorated with increasing heat treatment temperature by more than two folds.

  12. Chemical compounds and mechanisms involved in the formation and stabilization of foam in sparkling wines.

    Science.gov (United States)

    Kemp, Belinda; Condé, Bruna; Jégou, Sandrine; Howell, Kate; Vasserot, Yann; Marchal, Richard

    2018-02-08

    The visual properties of sparkling wine including foam and bubbles are an indicator of sparkling wine quality. Foam properties, particularly foam height (FH) and foam stability (TS), are significantly influenced by the chemical composition of the wine. This review investigates our current knowledge of specific chemical compounds and, the mechanisms by which they influence the foam properties of sparkling wines. Grape and yeast proteins, amino acids, polysaccharides, phenolic compounds, organic acids, fatty acids, ethanol and sugar are examined with respect to their contribution to foam characteristics in sparkling wines made with the Traditional, Transfer, and Charmat and carbonation methods. Contradictory results have been identified that appear to be due to the analytical methods used to measure and quantify compounds and foam. Biopolymer complexes are discussed and absent knowledge with regards to thaumatin-like proteins (TLPs), polysaccharides, amino acids, oak-derived phenolic compounds and organic acids are identified. Future research is also likely to concentrate on visual analysis of sparkling wines by in-depth imaging analysis and specific sensory analysis techniques.

  13. Adsorption treatment of oxide chemical mechanical polishing wastewater from a semiconductor manufacturing plant by electrocoagulation.

    Science.gov (United States)

    Chou, Wei-Lung; Wang, Chih-Ta; Chang, Wen-Chun; Chang, Shih-Yu

    2010-08-15

    In this study, metal hydroxides generated during electrocoagulation (EC) were used to remove the chemical oxygen demand (COD) of oxide chemical mechanical polishing (oxide-CMP) wastewater from a semiconductor manufacturing plant by EC. Adsorption studies were conducted in a batch system for various current densities and temperatures. The COD concentration in the oxide-CMP wastewater was effectively removed and decreased by more than 90%, resulting in a final wastewater COD concentration that was below the Taiwan discharge standard (100 mg L(-1)). Since the processed wastewater quality exceeded the direct discharge standard, the effluent could be considered for reuse. The adsorption kinetic studies showed that the EC process was best described using the pseudo-second-order kinetic model at the various current densities and temperatures. The experimental data were also tested against different adsorption isotherm models to describe the EC process. The Freundlich adsorption isotherm model predictions matched satisfactorily with the experimental observations. Thermodynamic parameters, including the Gibbs free energy, enthalpy, and entropy, indicated that the COD adsorption of oxide-CMP wastewater on metal hydroxides was feasible, spontaneous and endothermic in the temperature range of 288-318 K. Copyright 2010 Elsevier B.V. All rights reserved.

  14. Mechanism of waste biomass pyrolysis: Effect of physical and chemical pre-treatments

    Energy Technology Data Exchange (ETDEWEB)

    Das, Oisik [Department of Biological Systems Engineering, Washington State University, Pullman 99164-6120, WA (United States); Department of Civil and Environmental Engineering, University of Auckland, Auckland 1142 (New Zealand); Sarmah, Ajit K., E-mail: a.sarmah@auckland.ac.nz [Department of Civil and Environmental Engineering, University of Auckland, Auckland 1142 (New Zealand)

    2015-12-15

    To impart usability in waste based biomass through thermo-chemical reactions, several physical and chemical pre-treatments were conducted to gain an insight on their mode of action, effect on the chemistry and the change in thermal degradation profiles. Two different waste biomasses (Douglas fir, a softwood and hybrid poplar, a hardwood) were subjected to four different pre-treatments, namely, hot water pre-treatment, torrefaction, acid (sulphuric acid) and salt (ammonium phosphate) doping. Post pre-treatments, the changes in the biomass structure, chemistry, and thermal makeup were studied through electron microscopy, atomic absorption/ultra violet spectroscopy, ion exchange chromatography, and thermogravimetry. The pre-treatments significantly reduced the amounts of inorganic ash, extractives, metals, and hemicellulose from both the biomass samples. Furthermore, hot water and torrefaction pre-treatment caused mechanical disruption in biomass fibres leading to smaller particle sizes. Torrefaction of Douglas fir wood yielded more solid product than hybrid poplar. Finally, the salt pre-treatment increased the activation energies of the biomass samples (especially Douglas fir) to a great extent. Thus, salt pre-treatment was found to bestow thermal stability in the biomass. - Highlights: • Pre-treatments reduce ash, extractives, alkalines and hemicellulose from biomass. • Torrefaction of Douglas fir yields more solid product than hybrid poplar. • Salt pretreatment significantly increases the activation energy of biomass. • Acid and salt pretreatment bestows thermal stability in biomass.

  15. Photofunctionalization of Titanium: An Alternative Explanation of Its Chemical-Physical Mechanism.

    Directory of Open Access Journals (Sweden)

    Marco Roy

    Full Text Available To demonstrate that titanium implant surfaces as little as 4 weeks from production are contaminated by atmospheric hydrocarbons. This phenomenon, also known as biological ageing can be reversed by UVC irradiation technically known as photofunctionalization. To propose a new model from our experimental evidence to explain how the changes in chemical structure of the surface will affect the adsorption of amino acids on the titanium surface enhancing osteointegration.In our study XPS and AES were used to analyze the effects of UVC irradiation (photofunctionalization in reversing biological ageing of titanium. SEM was used to analyze any possible effects on the topography of the surface.UVC irradiation was able to reverse biological ageing of titanium by greatly reducing the amount of carbon contamination present on the implant surface by up to 4 times, while the topography of the surface was not affected. UVC photon energy reduces surface H2O and increases TiOH with many -OH groups being produced. These groups explain the super-hydrophilic effect from photofunctionalization when these groups come into contact with water.Photofunctionalization has proven to be a valid method to reduce the amount of hydrocarbon contamination on titanium dental implants and improve biological results. The chemisorption mechanisms of amino acids, in our study, are dictated by the chemical structure and electric state present on the surface, but only in the presence of an also favourable geometrical composition at the atomical level.

  16. Disruptive environmental chemicals and cellular mechanisms that confer resistance to cell death.

    Science.gov (United States)

    Narayanan, Kannan Badri; Ali, Manaf; Barclay, Barry J; Cheng, Qiang Shawn; D'Abronzo, Leandro; Dornetshuber-Fleiss, Rita; Ghosh, Paramita M; Gonzalez Guzman, Michael J; Lee, Tae-Jin; Leung, Po Sing; Li, Lin; Luanpitpong, Suidjit; Ratovitski, Edward; Rojanasakul, Yon; Romano, Maria Fiammetta; Romano, Simona; Sinha, Ranjeet K; Yedjou, Clement; Al-Mulla, Fahd; Al-Temaimi, Rabeah; Amedei, Amedeo; Brown, Dustin G; Ryan, Elizabeth P; Colacci, Annamaria; Hamid, Roslida A; Mondello, Chiara; Raju, Jayadev; Salem, Hosni K; Woodrick, Jordan; Scovassi, A Ivana; Singh, Neetu; Vaccari, Monica; Roy, Rabindra; Forte, Stefano; Memeo, Lorenzo; Kim, Seo Yun; Bisson, William H; Lowe, Leroy; Park, Hyun Ho

    2015-06-01

    Cell death is a process of dying within biological cells that are ceasing to function. This process is essential in regulating organism development, tissue homeostasis, and to eliminate cells in the body that are irreparably damaged. In general, dysfunction in normal cellular death is tightly linked to cancer progression. Specifically, the up-regulation of pro-survival factors, including oncogenic factors and antiapoptotic signaling pathways, and the down-regulation of pro-apoptotic factors, including tumor suppressive factors, confers resistance to cell death in tumor cells, which supports the emergence of a fully immortalized cellular phenotype. This review considers the potential relevance of ubiquitous environmental chemical exposures that have been shown to disrupt key pathways and mechanisms associated with this sort of dysfunction. Specifically, bisphenol A, chlorothalonil, dibutyl phthalate, dichlorvos, lindane, linuron, methoxychlor and oxyfluorfen are discussed as prototypical chemical disruptors; as their effects relate to resistance to cell death, as constituents within environmental mixtures and as potential contributors to environmental carcinogenesis. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  17. Application of chemical methods to assess the mechanism of alkali activation in low calcium fly ash

    Energy Technology Data Exchange (ETDEWEB)

    Arjunan, P.; Silsbee, M.R.; Roy, D.M. [Pennsylvania State Univ., PA (United States). Materials Research Lab.

    1999-11-01

    A better understanding of the amount of fly ash unreacted remaining after alkali activation of low calcium fly ash is necessary for elucidating the underlying alkali activation mechanism. An approach to this determination is reported in this study which utilizes an ethylenediamine tetraacetic acid/triethanolamine/NaOH mixture to determine the unreacted fly ash particles present in an OPC-low calcium fly ash mixture, with and without alkali activation. This study also uses another chemical technique called orthophosphoric acid dissolution method to assess the amount of unreacted crystalline phases present in hydrated OPC-ash mixtures at different ages of hydration. The information obtained from these two chemical techniques was used to identify the nature of unreacted fly ash particles present in the hydrated samples. The amount of unreacted fly ash and the compressive strength data were correlated to assess the extent of influence of alkali activation on the reactivity of the amorphous and crystalline phase content of the low calcium fly ash.

  18. The way to zeros: The future of semiconductor device and chemical mechanical polishing technologies

    Science.gov (United States)

    Tsujimura, Manabu

    2016-06-01

    For the last 60 years, the development of cutting-edge semiconductor devices has strongly emphasized scaling; the effort to scale down current CMOS devices may well achieve the target of 5 nm nodes by 2020. Planarization by chemical mechanical polishing (CMP), is one technology essential for supporting scaling. This paper summarizes the history of CMP transitions in the planarization process as well as the changing degree of planarity required, and, finally, introduces innovative technologies to meet the requirements. The use of CMP was triggered by the replacement of local oxidation of silicon (LOCOS) as the element isolation technology by shallow trench isolation (STI) in the 1980s. Then, CMP’s use expanded to improving embedability of aluminum wiring, tungsten (W) contacts, Cu wiring, and, more recently, to its adoption in high-k metal gate (HKMG) and FinFET (FF) processes. Initially, the required degree of planarity was 50 nm, but now 0 nm is required. Further, zero defects on a post-CMP wafer is now the goal, and it is possible that zero psi CMP loading pressure will be required going forward. Soon, it seems, everything will have to be “zero” and perfect. Although the process is also chemical in nature, the CMP process is actually mechanical with a load added using slurry particles several tens of nm in diameter. Zero load in the loading process, zero nm planarity with no trace of processing, and zero residual foreign material, including the very slurry particles used in the process, are all required. This article will provide an overview of how to achieve these new requirements and what technologies should be employed.

  19. Fabrication of ruthenium thin film and characterization of its chemical mechanical polishing process

    International Nuclear Information System (INIS)

    Chou, Yi-Sin; Yen, Shi-Chern; Jeng, King-Tsai

    2015-01-01

    The fabrication of Ru thin film is conducted on titanium (Ti)-based rotating disk electrodes (RDE) by electrodeposition and characteristics of its chemical mechanical polishing (CMP) are investigated to be employed for copper diffusion layer applications in various semiconductor-device interconnects. The electrodeposits obtained under different electrodeposition conditions are characterized using atomic force microscope (AFM) and field emission scanning electron microscope (FESEM). Experimental results indicate that the Ru electrodeposition exhibits a Tafel behavior with a 2e metal ion reduction process. Both exchange current density and cathodic transfer coefficient are determined. A quasi Koutecky–Levich analysis is proposed to analyze the electrodeposition processes under different applied current density conditions and the activation overpotentials together with electrodeposition rate constants are obtained. For Ru CMP operations, slurries containing metal-free 2wt% ammonium persulfate and 2wt% silica abrasive at various pH values are employed. Potentiodynamic polarization studies indicate that the corrosion current density varies in the presence of ammonia while the static etch rate remains low. Both chemical and mechanical effects are investigated and analyzed, and the CMP efficacy factors are obtained. - Highlights: • Ru electrodeposition is a 2e metal ion reduction process with Tafel behavior. • Ru electrodeposition on Ti RDE fits a quasi Koutecky–Levich equation. • Metal-free slurry is employed for CMP operation to avoid contamination. • The Ru CMP process is affected by the surface condition and the pH of slurry. • The CMP efficacy factor should be high in order to obtain a smooth surface

  20. Fabrication of ruthenium thin film and characterization of its chemical mechanical polishing process

    Energy Technology Data Exchange (ETDEWEB)

    Chou, Yi-Sin [Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan (China); Yen, Shi-Chern, E-mail: scyen@ntu.edu.tw [Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan (China); Jeng, King-Tsai [Research Division I, TIER, 7F, No. 16-8, Dehuei St., Taipei 10461, Taiwan (China)

    2015-07-15

    The fabrication of Ru thin film is conducted on titanium (Ti)-based rotating disk electrodes (RDE) by electrodeposition and characteristics of its chemical mechanical polishing (CMP) are investigated to be employed for copper diffusion layer applications in various semiconductor-device interconnects. The electrodeposits obtained under different electrodeposition conditions are characterized using atomic force microscope (AFM) and field emission scanning electron microscope (FESEM). Experimental results indicate that the Ru electrodeposition exhibits a Tafel behavior with a 2e metal ion reduction process. Both exchange current density and cathodic transfer coefficient are determined. A quasi Koutecky–Levich analysis is proposed to analyze the electrodeposition processes under different applied current density conditions and the activation overpotentials together with electrodeposition rate constants are obtained. For Ru CMP operations, slurries containing metal-free 2wt% ammonium persulfate and 2wt% silica abrasive at various pH values are employed. Potentiodynamic polarization studies indicate that the corrosion current density varies in the presence of ammonia while the static etch rate remains low. Both chemical and mechanical effects are investigated and analyzed, and the CMP efficacy factors are obtained. - Highlights: • Ru electrodeposition is a 2e metal ion reduction process with Tafel behavior. • Ru electrodeposition on Ti RDE fits a quasi Koutecky–Levich equation. • Metal-free slurry is employed for CMP operation to avoid contamination. • The Ru CMP process is affected by the surface condition and the pH of slurry. • The CMP efficacy factor should be high in order to obtain a smooth surface.

  1. Implicit coupling of turbulent diffusion with chemical reaction mechanisms for prognostic atmospheric dispersion models

    Energy Technology Data Exchange (ETDEWEB)

    Berlowitz, D.R.

    1996-11-01

    In the last few decades the negative impact by humans on the thin atmospheric layer enveloping the earth, the basis for life on this planet, has increased steadily. In order to halt, or at least slow down this development, the knowledge and study of these anthropogenic influence has to be increased and possible remedies have to be suggested. An important tool for these studies are computer models. With their help the atmospheric system can be approximated and the various processes, which have led to the current situation can be quantified. They also serve as an instrument to assess short or medium term strategies to reduce this human impact. However, to assure efficiency as well as accuracy, a careful analysis of the numerous processes involved in the dispersion of pollutants in the atmosphere is called for. This should help to concentrate on the essentials and also prevent excessive usage of sometimes scarce computing resources. The basis of the presented work is the EUMAC Zooming Model (ETM), and particularly the component calculating the dispersion of pollutants in the atmosphere, the model MARS. The model has two main parts: an explicit solver, where the advection and the horizontal diffusion of pollutants are calculated, and an implicit solution mechanism, allowing the joint computation of the change of concentration due to chemical reactions, coupled with the respective influence of the vertical diffusion of the species. The aim of this thesis is to determine particularly the influence of the horizontal components of the turbulent diffusion on the existing implicit solver of the model. Suggestions for a more comprehensive inclusion of the full three dimensional diffusion operator in the implicit solver are made. This is achieved by an appropriate operator splitting. A selection of numerical approaches to tighten the coupling of the diffusion processes with the calculation of the applied chemical reaction mechanisms are examined. (author) figs., tabs., refs.

  2. Physico-mechanical and chemical screening of packaging plastics and laminates for food irradiation

    International Nuclear Information System (INIS)

    Cabalar, Patrick Jay E.; Laurio, Christian D.

    2014-03-01

    Evaluation of selected commercially-available packaging plastics and laminated plastics i.e., PET12/PE50, PET12/CPS40, Laminaed PET/PE, VMPET12/PE70, Nylon/PE, Nylon15/PE50, PET/Foil/PE, PlainPET/FOIL7/PE100, and OPP20/Foil6.5/PE40, are conducted by employing methods for determining physico-mechanical properties and performing chemical analyses to assess the suitability for food irradiation at 10kGy. Isotope Ratio Mass Spectrometry (IR-MS0 is also performed to measure isotopic ratio changes of 18 O/ 16 O and 2 H/ 1 H to determine raqdiolysis on water in contact with the packaging materials. IR-MS suggests that PET/FOIL PE and OPP 20/Foil 6.5/PE40 in δ 18 O%o after irradiation has significantly increased. Tensile strength and Young's modulus are obtained to assess physical changes between irradiated samples. Data showed that PET12/CPS40 have the highet tensile strength 60.2 MPa and Young's modulus (141.80GPa) value, after irradiation and has no significant difference to their non irradiated samples. Other packaging materials with the same result are OPP20/FOIL6.5/PE40, PET12/PE50 and NYLON50/PE. Residual test gives information on the extent of leaching or radiolytic byproduct evolved upon irradiation. Based on the result, all packaging plastics and laminates passess the overall migration test since residues did not significanty migrated. Chemical screening includes GPC and GC-MS analyses in determining the possible radiolytic by-products that liberate upon rdiation of the samples s well as determining the components that is already present prior to irradiation. Based on the comparison of the chromatograms ofGPC for both samples of VMPET12/PE70 and OPP20/Foil6.5/PE40, radiation has small effect on the yield of radiolytic leachates aside from increasing the abundance of the componenet that is already present prior to irradiation. GC-MS results suggest that PET/FOIL/PE produced volatile compounds before and after irradiation namely 3,3-Dimethylheptane (8

  3. Computer modelling system of the chemical composition and treatment parameters influence on mechanical properties of structural steels

    OpenAIRE

    L.A. Dobrzański; R. Honysz

    2009-01-01

    Purpose: This paper presents Neuro-Lab. It is an authorship programme, which use algorithms of artificial intelligence for structural steels mechanical properties estimation.Design/methodology/approach: On the basis of chemical composition, parameters of heat and mechanical treatment and elements of geometrical shape and size this programme has the ability to calculate the mechanical properties of examined steel and introduce them as raw numeric data or in graphic as influence charts. Possibl...

  4. Effect of mechanical and chemical clay removals by hydrocyclone and dispersants on coal flotation

    Energy Technology Data Exchange (ETDEWEB)

    Oats, W.J.; Ozdemir, O.; Nguyen, A.V. [University of Queensland, Brisbane, Qld. (Australia). School of Chemical Engineering

    2010-04-15

    Fine minerals, mostly clays, are known to have a detrimental effect on coal flotation. This paper focuses on the effect of mechanical and chemical removals of fine minerals by hydrocyclone and dispersants on coal flotation. The experimental results showed that the flotation recovery slightly increased from medium acidic to medium alkaline ranges. The flotation experiments carried out with dispersants at different dosages showed that the dispersants did not enhance the flotation recovery significantly. However, the removal of the fine fraction from the feed using a hydrocyclone significantly increased the flotation recovery. The bubble-particle attachment tests also indicated that the attachment time between an air bubble and the coal particles increased in the presence of clay particles. These attachment time results clearly showed that the clay particles adversely affected the flotation of coal particles by covering the coal surfaces which reduced the efficiency of bubble-coal attachment. An analysis based on the colloid stability theory showed that the clay coating was governed by the van der Waals attraction and that the double-layer interaction played a secondary role. It was also concluded that the best way to increase the flotation recovery in the presence of clays was to remove these fine minerals by mechanical means such as hydrocylones.

  5. Investigation research on the evaluation of a coupled thermo-hydro-mechanical-chemical phenomena. 4

    International Nuclear Information System (INIS)

    Ishihara, Yoshinao; Sagawa, Hiroshi; Matsuoka, Fushiki; Chijimatsu, Masakazu; Amemiya, Kiyoshi

    2005-02-01

    In order to realize a coupling analysis in the near field of the geological disposal system, the coupling analysis code 'COUPLYS (Coupling analysis system)' on the Thermo-Hydro-Mechanical-Chemical (THMC) phenomena by THAMES, Dtransu-3D·EL and PHREEQC, those are existing analysis code, is developed in this study. (1) We have introduced 8 nodes element for THAMES code in order to solve the coupled thermal, hydraulic and mechanical phenomena. Furthermore, in order to obtain the reliable resolution, each phenomenon is solved separately instead of full coupling. (2) In order to upgrade Dtransu-3D·EL model, we have introduced gas diffusion independent on aqueous element. (3) We have adopted surface site density for the bentonite depend on water content and CSH solid phase based on the ratio of C/S for cementitious material in the geochemistry module, and studied on the methodology of time mesh for kinetic model and separate method for pore water chemistry in the bentonite. (4) In order to develop THMC code, we have modified Multi p hreeqc to keep efficiency distributed processing for geochemical calculation and modified COUPLYS to calculate continuous treatment, and studied on the coupling module. After THAMES, Dtransu, PHREEQC and the hydraulic conductivity module were installed in COUPLYS, verification study was carried out to check basic function. (5) In order to ensure efficiency of analysis processor, we have developed supporting tool for graphic processor for THMC code and supporting tool of interpretation for geochemistry results. (author)

  6. Mechanisms of chemical modification of neoplastic cell transformation by ionizing radiation

    International Nuclear Information System (INIS)

    Yang, T.C.; Tobias, C.A.

    1985-01-01

    During space travel, astronauts will be continuously exposed to ionizing radiation; therefore, it is necessary to minimize the radiation damage by all possible means. The authors' studies show that DMSO (when present during irradiation) can protect cells from being killed and transformed by X rays and that low concentration of DMSO can reduce the transformation frequency significantly when it is applied to cells, even many days after irradiation. The process of neoplastic cell transformation is a complicated one and includes at least two different stages: induction and expression. DMSO apparently can modify the radiation damage during both stages. There are several possible mechanisms for the DMSO effect: (1) changing the cell membrane structure and properties; (2) inducing cell differentiation by acting on DNA; and (3) scavanging free radicals in the cell. Recent studies with various chemical agents, e.g., 5-azacytidine, dexamethane, rhodamin-123, etc., indicate that the induction of cell differentiation by acting on DNA may be an important mechanism for the suppression of expression of neoplastic cell transformation by DMSO

  7. Mechanical and chemical responses of low-velocity impacted RDX and HMX explosive powders

    Science.gov (United States)

    Wu, Yanqing; Guo, Hongfu; Huang, Fenglei; Bao, Xiaowei; Explosion; damage Team

    2017-06-01

    The experimental analyses of mechanical and chemical responses of RDX and HMX particles were performed based on the optimized drop-weight experimental system equipped with the High-Speed Camera (HSC). It has been found that Jetting phenomenon observed by HSC is the result of the energy released by gaseous products, which push the pulverized or melted explosives to splash radially. Jetting is the only and the most obvious difference between reactive and inert particles prior to combustion so that jetting can be regarded as the sign of ignition. Area expansion velocity, jetting velocity, and flame propagation velocity have been estimated via image processing, making it possible to characterize mechanical deformation and violence of reaction of each stage. Hot-spots coalescence promotes flame propagation whose velocity reflects the violence of deflagration reaction. Jetting appearance time can be used to determine time-to-ignition more accurately than other ways. For RDX, molten phase plays an important role to the formation of the hot-spots. Multiple particles experienced more severe burning reactions than an individual particle. China National Nature Science Foundation (11572045), ``Science Challenging Program'' (JCKY2016212A501),opening fund from Safety ammunition research and Development Center (RMC2015B03).

  8. Properties, synthesis, and growth mechanisms of carbon nanotubes with special focus on thermal chemical vapor deposition.

    Science.gov (United States)

    Nessim, Gilbert D

    2010-08-01

    Carbon nanotubes (CNTs) have been extensively investigated in the last decade because their superior properties could benefit many applications. However, CNTs have not yet made a major leap into industry, especially for electronic devices, because of fabrication challenges. This review provides an overview of state-of-the-art of CNT synthesis techniques and illustrates their major technical difficulties. It also charts possible in situ analyses and new reactor designs that might enable commercialization. After a brief description of the CNT properties and of the various techniques used to synthesize substrate-free CNTs, the bulk of this review analyzes chemical vapor deposition (CVD). This technique receives special attention since it allows CNTs to be grown in predefined locations, provides a certain degree of control of the types of CNTs grown, and may have the highest chance to succeed commercially. Understanding the primary growth mechanisms at play during CVD is critical for controlling the properties of the CNTs grown and remains the major hurdle to overcome. Various factors that influence CNT growth receive a special focus: choice of catalyst and substrate materials, source gases, and process parameters. This review illustrates important considerations for in situ characterization and new reactor designs that may enable researchers to better understand the physical growth mechanisms and to optimize the synthesis of CNTs, thus contributing to make carbon nanotubes a manufacturing reality.

  9. Sex-Specific Effects of Combined Exposure to Chemical and Non-chemical Stressors on Neuroendocrine Development: a Review of Recent Findings and Putative Mechanisms.

    Science.gov (United States)

    Cowell, Whitney J; Wright, Rosalind J

    2017-12-01

    Environmental toxicants and psychosocial stressors share many biological substrates and influence overlapping physiological pathways. Increasing evidence indicates stress-induced changes to the maternal milieu may prime rapidly developing physiological systems for disruption by concurrent or subsequent exposure to environmental chemicals. In this review, we highlight putative mechanisms underlying sex-specific susceptibility of the developing neuroendocrine system to the joint effects of stress or stress correlates and environmental toxicants (bisphenol A, alcohol, phthalates, lead, chlorpyrifos, and traffic-related air pollution). We provide evidence indicating that concurrent or tandem exposure to chemical and non-chemical stressors during windows of rapid development is associated with sex-specific synergistic, potentiated and reversed effects on several neuroendocrine endpoints related to hypothalamic-pituitary-adrenal axis function, sex steroid levels, neurotransmitter circuits, and innate immune function. We additionally identify gaps, such as the role that the endocrine-active placenta plays, in our understanding of these complex interactions. Finally, we discuss future research needs, including the investigation of non-hormonal biomarkers of stress. We demonstrate multiple physiologic systems are impacted by joint exposure to chemical and non-chemical stressors differentially among males and females. Collectively, the results highlight the importance of evaluating sex-specific endpoints when investigating the neuroendocrine system and underscore the need to examine exposure to chemical toxicants within the context of the social environment.

  10. Multiple stressor effects in Chlamydomonas reinhardtii – Toward understanding mechanisms of interaction between effects of ultraviolet radiation and chemical pollutants

    Energy Technology Data Exchange (ETDEWEB)

    Korkaric, Muris [Eawag, Swiss Federal Institute of Aquatic Science and Technology, Department of Environmental Toxicology, 8600, Duebendorf (Switzerland); ETH Zürich, Institute of Biogeochemistry and Pollutant Dynamics, 8092 Zürich (Switzerland); Behra, Renata; Fischer, Beat B. [Eawag, Swiss Federal Institute of Aquatic Science and Technology, Department of Environmental Toxicology, 8600, Duebendorf (Switzerland); Junghans, Marion [Swiss Center for Applied Ecotoxicology Eawag-EPFL, 8600, Duebendorf (Switzerland); Eggen, Rik I.L., E-mail: rik.eggen@eawag.ch [Eawag, Swiss Federal Institute of Aquatic Science and Technology, Department of Environmental Toxicology, 8600, Duebendorf (Switzerland); ETH Zürich, Institute of Biogeochemistry and Pollutant Dynamics, 8092 Zürich (Switzerland)

    2015-05-15

    Highlights: • Systematic study of multiple stressor effects of UVR and chemicals in C. reinhardtii. • UVR and chemicals did not act independently on algal photosynthesis and reproduction. • Multiple stressor effects of UVR and chemicals depended on chemical MOA. • Synergistic effect interactions not limited to oxidative stress inducing chemicals. • Multiple MOAs of UVR may limit applicability of current prediction models. - Abstract: The effects of chemical pollutants and environmental stressors, such as ultraviolet radiation (UVR), can interact when organisms are simultaneously exposed, resulting in higher (synergistic) or lower (antagonistic) multiple stressor effects than expected based on the effects of single stressors. Current understanding of interactive effects is limited due to a lack of mechanism-based multiple stressor studies. It has been hypothesized that effect interactions may generally occur if chemical and non-chemical stressors cause similar physiological effects in the organism. To test this hypothesis, we exposed the model green alga Chlamydomonas reinhardtii to combinations of UVR and single chemicals displaying modes of action (MOA) similar or dissimilar to the impact of UVR on photosynthesis. Stressor interactions were analyzed based on the independent action model. Effect interactions were found to depend on the MOA of the chemicals, and also on their concentrations, the exposure time and the measured endpoint. Indeed, only chemicals assumed to cause effects on photosynthesis similar to UVR showed interactions with UVR on photosynthetic yield: synergistic in case of Cd(II) and paraquat and antagonistic in case of diuron. No interaction on photosynthesis was observed for S-metolachlor, which acts dissimilarly to UVR. However, combined effects of S-metolachlor and UVR on algal reproduction were synergistic, highlighting the importance of considering additional MOA of UVR. Possible mechanisms of stressor effect interactions are

  11. Multiple stressor effects in Chlamydomonas reinhardtii – Toward understanding mechanisms of interaction between effects of ultraviolet radiation and chemical pollutants

    International Nuclear Information System (INIS)

    Korkaric, Muris; Behra, Renata; Fischer, Beat B.; Junghans, Marion; Eggen, Rik I.L.

    2015-01-01

    Highlights: • Systematic study of multiple stressor effects of UVR and chemicals in C. reinhardtii. • UVR and chemicals did not act independently on algal photosynthesis and reproduction. • Multiple stressor effects of UVR and chemicals depended on chemical MOA. • Synergistic effect interactions not limited to oxidative stress inducing chemicals. • Multiple MOAs of UVR may limit applicability of current prediction models. - Abstract: The effects of chemical pollutants and environmental stressors, such as ultraviolet radiation (UVR), can interact when organisms are simultaneously exposed, resulting in higher (synergistic) or lower (antagonistic) multiple stressor effects than expected based on the effects of single stressors. Current understanding of interactive effects is limited due to a lack of mechanism-based multiple stressor studies. It has been hypothesized that effect interactions may generally occur if chemical and non-chemical stressors cause similar physiological effects in the organism. To test this hypothesis, we exposed the model green alga Chlamydomonas reinhardtii to combinations of UVR and single chemicals displaying modes of action (MOA) similar or dissimilar to the impact of UVR on photosynthesis. Stressor interactions were analyzed based on the independent action model. Effect interactions were found to depend on the MOA of the chemicals, and also on their concentrations, the exposure time and the measured endpoint. Indeed, only chemicals assumed to cause effects on photosynthesis similar to UVR showed interactions with UVR on photosynthetic yield: synergistic in case of Cd(II) and paraquat and antagonistic in case of diuron. No interaction on photosynthesis was observed for S-metolachlor, which acts dissimilarly to UVR. However, combined effects of S-metolachlor and UVR on algal reproduction were synergistic, highlighting the importance of considering additional MOA of UVR. Possible mechanisms of stressor effect interactions are

  12. Activation of chemical biological defense mechanisms and remission of vital oxidative injury by low dose radiation

    International Nuclear Information System (INIS)

    Yamaoka, K.; Nomura, T.; Kojima, S.

    2000-01-01

    Excessive active oxygen produced in vivo by various causes is toxic. Accumulation of oxidation injuries due to excessive active causes cell and tissue injuries, inducing various pathologic conditions such as aging and carcinogenesis. On the other hand, there are chemical defense mechanisms in the body that eliminate active oxygen or repair damaged molecules, defending against resultant injury. It is interesting reports that appropriate oxidation stress activate the chemical biological defense mechanisms. In this study, to elucidate these phenomena and its mechanism by low dose radiation, we studied on the below subjects. Activation of chemical biological defense mechanisms by low dose radiation: (1) The effects radiation on lipid peroxide (LPO) levels in the organs, membrane fluidity and the superoxide dismutase (SOD) activity were examined in rats and rabbits. Rats were irradiated with low dose X-ray over their entire bodies, and rabbits inhaled vaporized radon spring water, which primarily emitted α-ray. The following results were obtained. Unlike high dose X-ray, low dose X-ray and radon inhalation both reduced LPO levels and made the state of the SH-group on membrane-bound proteins closer to that of juvenile animals, although the sensitivity to radioactivity varied depending on the age of the animals and among different organs and tissues. The SOD activity was elevated, suggesting that low dose X-ray and radon both activate the host defensive function. Those changes were particularly marked in the organs related to immune functions of the animals which received low dose X-ray, while they were particularly marked in the brain after radon inhalation. It was also found that those changes continued for longer periods after low dose X-irradiation. (2) Since SOD is an enzyme that mediates the dismutation of O 2 - to H 2 O 2 , the question as to whether the resultant H 2 O 2 is further detoxicated into H 2 O and O 2 or not must still be evaluated. Hence, we studied

  13. Chemical Shifts of the Carbohydrate Binding Domain of Galectin-3 from Magic Angle Spinning NMR and Hybrid Quantum Mechanics/Molecular Mechanics Calculations.

    Science.gov (United States)

    Kraus, Jodi; Gupta, Rupal; Yehl, Jenna; Lu, Manman; Case, David A; Gronenborn, Angela M; Akke, Mikael; Polenova, Tatyana

    2018-03-22

    Magic angle spinning NMR spectroscopy is uniquely suited to probe the structure and dynamics of insoluble proteins and protein assemblies at atomic resolution, with NMR chemical shifts containing rich information about biomolecular structure. Access to this information, however, is problematic, since accurate quantum mechanical calculation of chemical shifts in proteins remains challenging, particularly for 15 N H . Here we report on isotropic chemical shift predictions for the carbohydrate recognition domain of microcrystalline galectin-3, obtained from using hybrid quantum mechanics/molecular mechanics (QM/MM) calculations, implemented using an automated fragmentation approach, and using very high resolution (0.86 Å lactose-bound and 1.25 Å apo form) X-ray crystal structures. The resolution of the X-ray crystal structure used as an input into the AF-NMR program did not affect the accuracy of the chemical shift calculations to any significant extent. Excellent agreement between experimental and computed shifts is obtained for 13 C α , while larger scatter is observed for 15 N H chemical shifts, which are influenced to a greater extent by electrostatic interactions, hydrogen bonding, and solvation.

  14. Selenium and vitamin E inhibit radiogenic and chemically induced transformation in vitro via different mechanisms

    International Nuclear Information System (INIS)

    Borek, C.; Ong, A.; Mason, H.; Donahue, L.; Biaglow, J.E.

    1986-01-01

    Results from in vivo and in vitro studies showing that antioxidants may act as anticarcinogens support the role of active oxygen in carcinogenesis and provide impetus for exploring the functions of dietary antioxidants in cancer prevention by using in vitro models. The authors examined the single and combined effects of selenium, a component of glutathione peroxidase, and vitamin E, a known antioxidant, on cell transformation induced in C3H/10T-1/2 cells by x-rays, benzo[a]pyrene, or tryptophan pyrolysate and on the levels of cellular scavenging systems peroxide destruction. Incubation of C3H/10T-1/2 cells with 2.5 μM Na 2 SeO 3 (selenium) or with 7 μM α-tocopherol succinate (vitamin E) 24 hr prior to exposure to x-rays or the chemical carcinogens resulted in an inhibition of transformation by each of the antioxidants with an additive-inhibitory action when the two nutrients were combined. Cellular pretreatment with selenium resulted in increased levels of cellular glutathione peroxidase, catalase, and nonprotein thiols (glutathione) and in an enhanced destruction of peroxide. The results support our earlier studies showing that free radical-mediated events play a role in radiation and chemically induced transformation. They indicate that selenium and vitamin E act alone and in additive fashion as radioprotecting and chemopreventing agents. The results further suggest that selenium confers protection in part by inducing or activating cellular free-radical scavenging systems and by enhancing peroxide breakdown while vitamin E appears to confer its protection by and alternate complementary mechanism

  15. Models of nanoparticles movement, collision, and friction in chemical mechanical polishing (CMP)

    Energy Technology Data Exchange (ETDEWEB)

    Ilie, Filip, E-mail: filip@meca.omtr.pub.ro [Polytechnic University of Bucharest, Department of Machine Elements and Tribology (Romania)

    2012-03-15

    Nanoparticles have been widely used in polishing slurry such as chemical mechanical polishing (CMP) process. The movement of nanoparticles in polishing slurry and the interaction between nanoparticles and solid surface are very important to obtain an atomic smooth surface in CMP process. Polishing slurry contains abrasive nanoparticles (with the size range of about 10-100 nm) and chemical reagents. Abrasive nanoparticles and hydrodynamic pressure are considered to cause the polishing effect. Nanoparticles behavior in the slurry with power-law viscosity shows great effect on the wafer surface in polishing process. CMP is now a standard process of integrated circuit manufacturing at nanoscale. Various models can dynamically predict the evolution of surface topography for any time point during CMP. To research, using a combination of individual nanoscale friction measurements for CMP of SiO{sub 2}, in an analytical model, to sum these effects, and the results scale CMP experiments, can guide the research and validate the model. CMP endpoint measurements, such as those from motor current traces, enable verification of model predictions, relating to friction and wear in CMP and surface topography evolution for different types of CMP processes and patterned chips. In this article, we explore models of the microscopic frictional force based on the surface topography and present both experimental and theoretical studies on the movement of nanoparticles in polishing slurry and collision between nanoparticles, as well as between the particles and solid surfaces in time of process CMP. Experimental results have proved that the nanoparticle size and slurry properties have great effects on the polishing results. The effects of the nanoparticle size and the slurry film thickness are also discussed.

  16. Effect of chemical and mechanical weed control on cassava yield, soil quality and erosion under cassava cropping system

    Science.gov (United States)

    Islami, Titiek; Wisnubroto, Erwin; Utomo, Wani

    2016-04-01

    Three years field experiments were conducted to study the effect of chemical and mechanical weed control on soil quality and erosion under cassava cropping system. The experiment were conducted at University Brawijaya field experimental station, Jatikerto, Malang, Indonesia. The experiments were carried out from 2011 - 2014. The treatments consist of three cropping system (cassava mono culture; cassava + maize intercropping and cassava + peanut intercropping), and two weed control method (chemical and mechanical methods). The experimental result showed that the yield of cassava first year and second year did not influenced by weed control method and cropping system. However, the third year yield of cassava was influence by weed control method and cropping system. The cassava yield planted in cassava + maize intercropping system with chemical weed control methods was only 24 t/ha, which lower compared to other treatments, even with that of the same cropping system used mechanical weed control. The highest cassava yield in third year was obtained by cassava + peanuts cropping system with mechanical weed control method. After three years experiment, the soil of cassava monoculture system with chemical weed control method possessed the lowest soil organic matter, and soil aggregate stability. During three years of cropping soil erosion in chemical weed control method, especially on cassava monoculture, was higher compared to mechanical weed control method. The soil loss from chemical control method were 40 t/ha, 44 t/ha and 54 t/ha for the first, second and third year crop. The soil loss from mechanical weed control method for the same years was: 36 t/ha, 36 t/ha and 38 t/ha. Key words: herbicide, intercropping, soil organic matter, aggregate stability.

  17. A reliable control system for measurement on film thickness in copper chemical mechanical planarization system

    Energy Technology Data Exchange (ETDEWEB)

    Li, Hongkai; Qu, Zilian; Zhao, Qian; Tian, Fangxin; Zhao, Dewen; Meng, Yonggang; Lu, Xinchun [State Key Laboratory of Tribology, Tsinghua University, Beijing 100084 (China)

    2013-12-15

    In recent years, a variety of film thickness measurement techniques for copper chemical mechanical planarization (CMP) are subsequently proposed. In this paper, the eddy-current technique is used. In the control system of the CMP tool developed in the State Key Laboratory of Tribology, there are in situ module and off-line module for measurement subsystem. The in situ module can get the thickness of copper film on wafer surface in real time, and accurately judge when the CMP process should stop. This is called end-point detection. The off-line module is used for multi-points measurement after CMP process, in order to know the thickness of remained copper film. The whole control system is structured with two levels, and the physical connection between the upper and the lower is achieved by the industrial Ethernet. The process flow includes calibration and measurement, and there are different algorithms for two modules. In the process of software development, C++ is chosen as the programming language, in combination with Qt OpenSource to design two modules’ GUI and OPC technology to implement the communication between the two levels. In addition, the drawing function is developed relying on Matlab, enriching the software functions of the off-line module. The result shows that the control system is running stably after repeated tests and practical operations for a long time.

  18. Chemical and mechanical instabilities in high energy heavy-ion collisions

    International Nuclear Information System (INIS)

    Gervino, G; Lavagno, A; Pigato, D

    2015-01-01

    We investigate the possible thermodynamic instability in a warm and dense nuclear medium where a phase transition from nucleonic matter to resonance-dominated Δ-matter can take place. Such a phase transition is characterized by both mechanical instability (fluctuations on the baryon density) and by chemical-diffusive instability (fluctuations on the isospin concentration) in asymmetric nuclear matter. Similarly to the liquid-gas phase transition, the nucleonic and the Δ-matter phase have a different isospin density in the mixed phase. In the liquid-gas phase transition, the process of producing a larger neutron excess in the gas phase is referred to as isospin fractionation. A similar effects can occur in the nucleon-Δ matter phase transition due essentially to a Δ − excess in the Δ-matter phase in asymmetric nuclear matter. In this context, we study the hadronic equation of state by means of an effective quantum relativistic mean field model with the inclusion of the full octet of baryons, the Δ-isobar degrees of freedom, and the lightest pseudoscalar and vector mesons. Finally, we will investigate the presence of thermodynamic instabilities in a hot and dense nuclear medium where phases with different values of antibaryon-baryon ratios and strangeness content may coexist. Such a physical regime could be in principle investigated in the future high-energy compressed nuclear matter experiments where will make it possible to create compressed baryonic matter with a high net baryon density. (paper)

  19. Design of an ultraprecision computerized numerical control chemical mechanical polishing machine and its implementation

    Science.gov (United States)

    Zhang, Chupeng; Zhao, Huiying; Zhu, Xueliang; Zhao, Shijie; Jiang, Chunye

    2018-01-01

    The chemical mechanical polishing (CMP) is a key process during the machining route of plane optics. To improve the polishing efficiency and accuracy, a CMP model and machine tool were developed. Based on the Preston equation and the axial run-out error measurement results of the m circles on the tin plate, a CMP model that could simulate the material removal at any point on the workpiece was presented. An analysis of the model indicated that lower axial run-out error led to lower material removal but better polishing efficiency and accuracy. Based on this conclusion, the CMP machine was designed, and the ultraprecision gas hydrostatic guideway and rotary table as well as the Siemens 840Dsl numerical control system were incorporated in the CMP machine. To verify the design principles of machine, a series of detection and machining experiments were conducted. The LK-G5000 laser sensor was employed for detecting the straightness error of the gas hydrostatic guideway and the axial run-out error of the gas hydrostatic rotary table. A 300-mm-diameter optic was chosen for the surface profile machining experiments performed to determine the CMP efficiency and accuracy.

  20. Relaxation of the chemical bond skin chemisorption size matter ZTP mechanics H2O myths

    CERN Document Server

    Sun, Chang Q

    2014-01-01

    The aim of this book is to explore the detectable properties of a material to the parameters of bond and non-bond involved and to clarify the interdependence of various properties. This book is composed of four parts; Part I deals with the formation and relaxation dynamics of bond and non-bond during chemisorptions with uncovering of the correlation among the chemical bond, energy band, and surface potential barrier (3B) during reactions; Part II is focused on the relaxation of bonds between atoms with fewer neighbors than the ideal in bulk with unraveling of the bond order-length-strength (BOLS) correlation mechanism, which clarifies the nature difference between nanostructures and bulk of the same substance; Part III deals with the relaxation dynamics of bond under heating and compressing with revealing of rules on the temperature-resolved elastic and plastic properties of low-dimensional materials; Part IV is focused on the asymmetric relaxation dynamics of the hydrogen bond (O:H-O) and the anomalous behav...

  1. Manipulating mammalian cell morphologies using chemical-mechanical polished integrated circuit chips

    Science.gov (United States)

    Moussa, Hassan I.; Logan, Megan; Siow, Geoffrey C.; Phann, Darron L.; Rao, Zheng; Aucoin, Marc G.; Tsui, Ting Y.

    2017-12-01

    Tungsten chemical-mechanical polished integrated circuits were used to study the alignment and immobilization of mammalian (Vero) cells. These devices consist of blanket silicon oxide thin films embedded with micro- and nano-meter scale tungsten metal line structures on the surface. The final surfaces are extremely flat and smooth across the entire substrate, with a roughness in the order of nanometers. Vero cells were deposited on the surface and allowed to adhere. Microscopy examinations revealed that cells have a strong preference to adhere to tungsten over silicon oxide surfaces with up to 99% of cells adhering to the tungsten portion of the surface. Cells self-aligned and elongated into long threads to maximize contact with isolated tungsten lines as thin as 180 nm. The orientation of the Vero cells showed sensitivity to the tungsten line geometric parameters, such as line width and spacing. Up to 93% of cells on 10 μm wide comb structures were aligned within ± 20° of the metal line axis. In contrast, only 22% of cells incubated on 0.18 μm comb patterned tungsten lines were oriented within the same angular interval. This phenomenon is explained using a simple model describing cellular geometry as a function of pattern width and spacing, which showed that cells will rearrange their morphology to maximize their contact to the embedded tungsten. Finally, it was discovered that the materials could be reused after cleaning the surfaces, while maintaining cell alignment capability.

  2. Teaching-Learning-Based Optimization with Learning Enthusiasm Mechanism and Its Application in Chemical Engineering

    Directory of Open Access Journals (Sweden)

    Xu Chen

    2018-01-01

    Full Text Available Teaching-learning-based optimization (TLBO is a population-based metaheuristic search algorithm inspired by the teaching and learning process in a classroom. It has been successfully applied to many scientific and engineering applications in the past few years. In the basic TLBO and most of its variants, all the learners have the same probability of getting knowledge from others. However, in the real world, learners are different, and each learner’s learning enthusiasm is not the same, resulting in different probabilities of acquiring knowledge. Motivated by this phenomenon, this study introduces a learning enthusiasm mechanism into the basic TLBO and proposes a learning enthusiasm based TLBO (LebTLBO. In the LebTLBO, learners with good grades have high learning enthusiasm, and they have large probabilities of acquiring knowledge from others; by contrast, learners with bad grades have low learning enthusiasm, and they have relative small probabilities of acquiring knowledge from others. In addition, a poor student tutoring phase is introduced to improve the quality of the poor learners. The proposed method is evaluated on the CEC2014 benchmark functions, and the computational results demonstrate that it offers promising results compared with other efficient TLBO and non-TLBO algorithms. Finally, LebTLBO is applied to solve three optimal control problems in chemical engineering, and the competitive results show its potential for real-world problems.

  3. Influence of silane content and filler distribution on chemical-mechanical properties of resin composites

    Directory of Open Access Journals (Sweden)

    Tathy Aparecida XAVIER

    2015-01-01

    Full Text Available This study investigated the influence of silane concentration and filler size distribution on the chemical-mechanical properties of experimental composites. Experimental composites with silane contents of 0%, 1% and 3% (in relation to filler mass and composites with mixtures of barium glass particles (median size = 0.4, 1 and 2 μm and nanometric silica were prepared for silane and filler analyses, respectively. The degree of conversion (DC was analyzed by FTIR. Biaxial flexural strength (BFS was tested after 24-h or 90-d storage in water, and fracture toughness, after 24 h. The data were subjected to ANOVA and Tukey’s test (p = 0.05. The DC was not significantly affected by the silane content or filler distribution. The 0% silane group had the lowest immediate BFS, and the 90-d storage time reduced the strength of the 0% and 3% groups. BFS was not affected by filler distribution, and aging decreased the BFS of all the groups. Silanization increased the fracture toughness of both the 1% and 3% groups, similarly. Significantly higher fracture toughness was observed for mixtures with 2 μm glass particles. Based on the results, 3% silane content boosted the initial strength, but was more prone to degradation after water storage. Variations in the filler distribution did not affect BFS, but fracture toughness was significantly improved by increasing the filler size.

  4. Fabrication and growth mechanism of carbon nanospheres by chemical vapor deposition

    International Nuclear Information System (INIS)

    Tian, F.; He, C.N.

    2010-01-01

    The synthesis of carbon nanospheres (CNSs) by chemical vapor deposition (CVD) of methane on catalyst of Ni-Al composite powders was reported. The influence factors on the growth morphology of CNSs, such as reaction temperature, reaction time and different carrier gases concerning hydrogen, nitrogen as well as no carrier gas were investigated using transmission electron microscope. The results showed that the reaction temperature had great effect on the structure of CNSs, higher temperature led to high-crystallized CNSs with high purity. The reaction time brought no significant influence to the structure of CNSs, but the average diameter of the CNSs was obviously increased with prolonging the reaction time. Relatively pure CNSs could be obtained with hydrogen as the carrier gas but with poor product rate compared with the CNSs with no carrier gas. Proper amount of CNSs with pure characteristic could be obtained with nitrogen as the carrier gas. Finally, a growth mechanism of dissolution-precipitation-diffusion is proposed for elucidating the growth process of general CNSs.

  5. Thulium oxide fuel characterization study: Part 2, Environmental behavior and mechanical, thermal and chemical stability enhancement

    International Nuclear Information System (INIS)

    Nelson, C.A.

    1970-12-01

    A study was performed of the correlation between fuel form stability and exposure environment of (temperature and atmosphere). 100% Tm 2 O 3 , 80% Tm 2 O 3 /20% Yb 2 O 3 and 100% Yb 2 O 3 wafers were subjected to air, dynamic vacuum and static vacuum at temperatures to 2000 0 C for times to 100 hours. Results showed the Tm 2 O 3 /Yb 2 O 3 cubic structure to be unaffected by elemental levels of iron, aluminum, magnesium and silicon and unaffected by the environmental conditions imposed on the wafers. A second task emphasized the optimization of the thermal, mechanical and chemical stability of Tm 2 O 3 fuel forms. Enhancement was sought through process variable optimization and the addition of metal oxides to Tm 2 O 3 . CaO, TiO 2 and Al 2 O 3 were added to form a grain boundary precipitate to control fines generation. The presence of 1% additive was inadequate to depress the melting point of Tm 2 O 3 or to change the cubic crystalline structure of Tm 2 O 3 /Yb 2 O 3 . Tm 2 O 3 /Yb 2 O 3 wafers containing CaO developed a grain boundary phase that improved the resistance to fines generation. The presence of Yb 2 O 3 did not appear to measurably influence behavior

  6. Influence of Mechanical and Chemical Degradation in the Surface Roughness, Gloss, and Color of Microhybrid Composites.

    Science.gov (United States)

    Lemos, Cleidiel Aa; Mauro, Silvio J; Dos Santos, Paulo H; Briso, Andre Lf; Fagundes, Ticiane C

    2017-04-01

    The aim of this study was to investigate the association of different degradations on the roughness, gloss, and color changes of microhybrid composites. Ten specimens were prepared for Charisma, Amelogen Plus, Point 4, and Opallis resins. Surfaces were polished and baseline measurements of roughness, gloss, and color were recorded. Specimens were then submitted to chemical and mechanical challenges, and the specimens were reevaluated. Roughness and gloss were analyzed by Kruskal -Wallis and Dunn's test (p one-way analysis of variance and Tukey's tests (p gloss (p gloss, there was no difference between composites before challenges. However, all composites showed a significant increase of roughness after challenges, with highest values for Charisma. The gloss was influenced by challenges, evidencing the best gloss for Point 4. Charisma showed the highest value of color change. There was no correlation between surface roughness and gloss for the initial analysis, and after the challenges. Composites were influenced by association of challenges, and Charisma showed the highest changes for roughness, gloss, and color. The type of composite resin influenced the properties of materials, which are surface roughness, gloss, and color change. The dentist should be aware of the performance of different brands, to choose the correct required composite resin for each type of patient or region to be restored.

  7. A Detailed Chemical Kinetic Reaction Mechanism for Oxidation of Four Small Alkyl Esters in Laminar Premixed Flames

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C K; Pitz, W J; Westmoreland, P R; Dryer, F L; Chaos, M; Osswald, P; Kohse-Hoinghaus, K; Cool, T A; Wang, J; Yang, B; Hansen, N; Kasper, T

    2008-02-08

    A detailed chemical kinetic reaction mechanism has been developed for a group of four small alkyl ester fuels, consisting of methyl formate, methyl acetate, ethyl formate and ethyl acetate. This mechanism is validated by comparisons between computed results and recently measured intermediate species mole fractions in fuel-rich, low pressure, premixed laminar flames. The model development employs a principle of similarity of functional groups in constraining the H atom abstraction and unimolecular decomposition reactions in each of these fuels. As a result, the reaction mechanism and formalism for mechanism development are suitable for extension to larger oxygenated hydrocarbon fuels, together with an improved kinetic understanding of the structure and chemical kinetics of alkyl ester fuels that can be extended to biodiesel fuels. Variations in concentrations of intermediate species levels in these flames are traced to differences in the molecular structure of the fuel molecules.

  8. Physico-chemical and mechanical properties of microencapsulated phase change material

    International Nuclear Information System (INIS)

    Giro-Paloma, Jessica; Oncins, Gerard; Barreneche, Camila; Martínez, Mònica; Fernández, A. Inés; Cabeza, Luisa F.

    2013-01-01

    Highlights: ► Microencapsulated phase change material MPCM (Micronal∗ DS 5001) was evaluated in this study. ► Due to the reported microcapsules breakage, physical and mechanical properties were analysed. ► Mechanical response was evaluated by AFM with indentation mode under different temperatures. ► The main result is that stiffness of MPCM depends on the temperature assay and particle size. - Abstract: Microencapsulated phase change materials (MPCM) are well known in advanced technologies for the utilization in active and passive systems, which have the capacity to absorb and slowly release the latent heat involved in a phase change process. Microcapsules consist of little containers, which are made of polymer on the outside, and paraffin wax as PCM in the inside. The use of microencapsulated PCM has many advantages as microcapsules can handle phase change materials as core allowing the preparation of slurries. However there are some concerns about cycling of MPCM slurries because of the breakage of microcapsules during charging/discharging and the subsequent loss of effectiveness. This phenomenon motivates the study of the mechanical response when a force is applied to the microcapsule. The maximum force that Micronal® DS 5001 can afford before breaking was determined by Atomic Force Microscopy (AFM). To simulate real conditions in service, assays were done at different temperatures: with the PCM in solid state at 25 °C, and with the PCM melted at 45 °C and 80 °C. To better understand the behavior of these materials, Micronal® DS 5001 microcapsules were characterized using different physic-chemical techniques. Microcapsules Fourier Transform Infrared Spectroscopy (FT-IR) results showed the main vibrations corresponding to acrylic groups of the outside polymer. Thermal stability was studied by Thermogravimetrical Analysis (TGA), and X-ray Fluorescence (XRF) was used to characterize the resulting inorganic residue. The thermal properties were

  9. A coupled model between mechanical deformation and chemical diffusion: An explanation for the preservation of chemical zonation in plagioclase at high temperatures

    Science.gov (United States)

    Zhong, Xin; Vrijmoed, Johannes; Moulas, Evangelos; Tajcmanová, Lucie

    2016-04-01

    Compositional zoning in metamorphic minerals have been generally recognized as an important geological feature to decipher the metamorphic history of rocks. The observed chemical zoning of, e.g. garnet, is commonly interpreted as disequilibrium between the fractionated inner core and the surrounding matrix. However, chemically zoned minerals were also observed in high grade rocks (T>800 degree C) where the duration of metamorphic processes was independently dated to take several Ma. This implies that temperature may not be the only factor that controls diffusion timescales, and grain scale pressure variation was proposed to be a complementary factor that may significantly contribute to the formation and preservation of chemical zoning in high temperature metamorphic minerals [Tajcmanová 2013, 2015]. Here, a coupled model is developed to simulate viscous deformation and chemical diffusion. The numerical approach considers the conservation of mass, momentum, and a constitutive relation developed from equilibrium thermodynamics. A compressible viscoelastic rheology is applied, which associates the volumetric change triggered by deformation and diffusion to a change of pressure. The numerical model is applied to the chemically zoned plagioclase rim described by [Tajcmanová 2014]. The diffusion process operating during the plagioclase rim formation can lead to a development of a pressure gradient. Such a pressure gradient, if maintained during ongoing viscous relaxation, can lead to the preservation of the observed chemical zonation in minerals. An important dimensionless number, the Deborah number, is defined as the ratio between the Maxwell viscoelastic relaxation time and the characteristic diffusion time. It characterizes the relative influence between the maintenance of grain scale pressure variation and chemical diffusion. Two extreme regimes are shown: the mechanically-controlled regime (high Deborah number) and diffusion-controlled regime (low Deborah number

  10. Multiple stressor effects in Chlamydomonas reinhardtii--toward understanding mechanisms of interaction between effects of ultraviolet radiation and chemical pollutants.

    Science.gov (United States)

    Korkaric, Muris; Behra, Renata; Fischer, Beat B; Junghans, Marion; Eggen, Rik I L

    2015-05-01

    The effects of chemical pollutants and environmental stressors, such as ultraviolet radiation (UVR), can interact when organisms are simultaneously exposed, resulting in higher (synergistic) or lower (antagonistic) multiple stressor effects than expected based on the effects of single stressors. Current understanding of interactive effects is limited due to a lack of mechanism-based multiple stressor studies. It has been hypothesized that effect interactions may generally occur if chemical and non-chemical stressors cause similar physiological effects in the organism. To test this hypothesis, we exposed the model green alga Chlamydomonas reinhardtii to combinations of UVR and single chemicals displaying modes of action (MOA) similar or dissimilar to the impact of UVR on photosynthesis. Stressor interactions were analyzed based on the independent action model. Effect interactions were found to depend on the MOA of the chemicals, and also on their concentrations, the exposure time and the measured endpoint. Indeed, only chemicals assumed to cause effects on photosynthesis similar to UVR showed interactions with UVR on photosynthetic yield: synergistic in case of Cd(II) and paraquat and antagonistic in case of diuron. No interaction on photosynthesis was observed for S-metolachlor, which acts dissimilarly to UVR. However, combined effects of S-metolachlor and UVR on algal reproduction were synergistic, highlighting the importance of considering additional MOA of UVR. Possible mechanisms of stressor effect interactions are discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

  11. Review on effect of chemical, thermal, additive treatment on mechanical properties of basalt fiber and their composites

    Science.gov (United States)

    Jain, Naman; Singh, Vinay Kumar; Chauhan, Sakshi

    2017-12-01

    Basalt fiber is emerging out the new reinforcing material for composites. To overcome some of the disadvantages of fibers such as poor bonding to polymers, low thermal stability and high moisture absorption fiber characteristics are modified with chemical, thermal and additive treatments. Chemical treatment corrosive resistance to alkali and acid were investigated which were used to clean and modify the surface of fiber for higher bonding with resins. To improve the thermal stability and reduce moisture uptake thermal treatment such as plasma and non thermal plasma were used which increased the surface roughness and change the chemical composition of surface of basalt fiber. Additive treatment is used to improve the mechanical properties of fibers, in basalt fiber additive treatment was done with SiO2 additive because of its chemical composition which contains major content of SiO2. In present investigation review on the effect of different treatment such as chemical, thermal and additive were studied. Effect of these treatment on chemical composition of the surface of basalt fiber and corrosion to acidic and alkali solution were studied with their effect on mechanical properties of basalt fiber and their composite.

  12. A review of the chemical and physical mechanisms of the storage stability of fast pyrolysis bio-oils

    Energy Technology Data Exchange (ETDEWEB)

    Diebold, J.P.

    1999-01-27

    Understanding the fundamental chemical and physical aging mechanisms is necessary to learn how to produce a bio-oil that is more stable during shipping and storage. This review provides a basis for this understanding and identifies possible future research paths to produce bio-oils with better storage stability.

  13. Pine growth and plant community response to chemical vs. mechanical site preparation for establishing loblolly and slash pine

    Science.gov (United States)

    James H. Miller; Zhijuan Qiu

    1995-01-01

    Chemical and mechanical site preparation methods were studied for establishing loblolly (Pinus taeda L) and slash (P. elliottii var. elliottii Engelm.) pine following both integrated fuelwood-pulpwood harvesting and conventional whole-tree harvesting of pines and hardwoods in southem Alabama's Middle Coastal...

  14. Long-term degradation of chemical structures and mechanical properties in polyethylene induced by ion-beam irradiation

    International Nuclear Information System (INIS)

    Oka, T.; Hama, Y.

    2004-01-01

    The long-term degradation in polyethylene irradiated with ion beams was studied. We found the changes of the chemical structures and the mechanical properties with time storage. S-PE has a good resistance to ion-beam irradiation because the crystallinity and density were very low. (author)

  15. Accelerated detection of brown-rot decay : comparison of soil block test, chemical analysis, mechanical properties, and immunodetection

    Science.gov (United States)

    C. A. Clausen; S. N. Kartal

    2003-01-01

    Early detection of wood decay is critical because decay fungi can cause rapid structural failure. The objective of this study was to compare the sensitivity of different methods purported to detect brown-rot decay in the early stages of development. The immunodiagnostic wood decay (IWD)test, soil block test/cake pan test, mechanical property tests, and chemical...

  16. Plasma-enhanced chemical vapor deposited silicon oxynitride films for optical waveguide bridges for use in mechanical sensors

    DEFF Research Database (Denmark)

    Storgaard-Larsen, Torben; Leistiko, Otto

    1997-01-01

    In this paper the influence of RF power, ammonia flow, annealing temperature, and annealing time on the optical and mechanical properties of plasma-enhanced chemically vapor deposited silicon oxynitride films, is presented. A low refractive index (1.47 to 1.48) film having tensile stress has been...

  17. CHEMICAL OIL SPILL DISPERSANTS: UPDATE STATE-OF-THE- ART ON MECHANISM OF ACTION AND LABORATORY TESTING FOR PERFORMANCE

    Science.gov (United States)

    Chemical dispersants are formulations designed to facilitate dispersion of an oil slick into small droplets that disperse to non-problematic concentrations in an underlying water column. This project had two primary objectives: (1) update information on mechanisms of action of ...

  18. Evidence from pharmacology and pathophysiology suggests that chemicals with dissimilar mechanisms of action could be of bigger concern in the toxicological risk assessment of chemical mixtures than chemicals with a similar mechanism of action

    DEFF Research Database (Denmark)

    Hadrup, Niels

    2014-01-01

    Mathematical models have been developed for the toxicological risk assessment of chemical mixtures. However, exposure data as well as single chemical toxicological data are required for these models. When addressing this data need, it could be attractive to focus on chemicals with similar...... concomitantly contribute to the pathophysiology, suggesting that a grouping based on common target organs may also be inefficient. A better option may be to prioritise chemicals on the basis of potency and risk of exposure. In conclusion, there are arguments to suggest that we should concomitantly consider all...... targets that a chemical can affect in the human body and not merely a subset....

  19. Coupled Thermo-Hydro-Mechanical-Chemical Modeling of Water Leak-Off Process during Hydraulic Fracturing in Shale Gas Reservoirs

    Directory of Open Access Journals (Sweden)

    Fei Wang

    2017-11-01

    Full Text Available The water leak-off during hydraulic fracturing in shale gas reservoirs is a complicated transport behavior involving thermal (T, hydrodynamic (H, mechanical (M and chemical (C processes. Although many leak-off models have been published, none of the models fully coupled the transient fluid flow modeling with heat transfer, chemical-potential equilibrium and natural-fracture dilation phenomena. In this paper, a coupled thermo-hydro-mechanical-chemical (THMC model based on non-equilibrium thermodynamics, hydrodynamics, thermo-poroelastic rock mechanics, and non-isothermal chemical-potential equations is presented to simulate the water leak-off process in shale gas reservoirs. The THMC model takes into account a triple-porosity medium, which includes hydraulic fractures, natural fractures and shale matrix. The leak-off simulation with the THMC model involves all the important processes in this triple-porosity medium, including: (1 water transport driven by hydraulic, capillary, chemical and thermal osmotic convections; (2 gas transport induced by both hydraulic pressure driven convection and adsorption; (3 heat transport driven by thermal convection and conduction; and (4 natural-fracture dilation considered as a thermo-poroelastic rock deformation. The fluid and heat transport, coupled with rock deformation, are described by a set of partial differential equations resulting from the conservation of mass, momentum, and energy. The semi-implicit finite-difference algorithm is proposed to solve these equations. The evolution of pressure, temperature, saturation and salinity profiles of hydraulic fractures, natural fractures and matrix is calculated, revealing the multi-field coupled water leak-off process in shale gas reservoirs. The influences of hydraulic pressure, natural-fracture dilation, chemical osmosis and thermal osmosis on water leak-off are investigated. Results from this study are expected to provide a better understanding of the

  20. Effectiveness of aged graffiti cleaning on granite by chemical and mechanical procedures

    Science.gov (United States)

    Gomes, Vera; Dionísio, Amélia; Santiago Pozo-Antonio, José

    2017-04-01

    Granite is one of the most common building stones in the European Cultural Heritage mainly in Northwest Iberian Peninsula. Nowadays, graffiti when a result of an act of vandalism is one of the most important threat, involving a serious risk to heritage sustainability. The cleaning is expensive and in most of the cases, the complete removal is not achieved. Many cities worldwide spend huge amounts of money in cleaning campaigns and European Commission started to create urban environment policies to prevent and eliminate graffiti and also finance projects to develop new cleaning procedures and antigraffiti coatings1,2. However, in many cases graffiti is applied in monuments and façades without antigraffiti and in real practice, they are only cleaned after being long exposure to the atmosphere, reaction with the environment (rain and atmospheric pollutants) and also with the substrate, leading changes in their physical and chemical properties. However, no scientific studies focused on graffiti aging were found and also on the influence of the aging on the cleaning effectiveness, which is always evaluated with fresh graffiti. Therefore, the need to optimize the cleaning of aged graffiti is urgent. This paper aims to study the influence of the exposition of graffiti paintings to one of the most important urban contaminant SO2 on the cleaning effectiveness of graffiti on the valuable ornamental granite Rosa Porriño. Two different chemical products and two different mechanical procedures based on low pressure projection (wet and dry) were evaluated. Four different colour graffiti paintings (red, black, blue and silver) with different compositions were tested. The criteria for assessing the global cleaning effectiveness was considering the graffiti extraction and also the damage induced on the substrate through changes in the chromatic parameters, static contact angle and surface roughness of the stones, identification of deleterious products and modification of the

  1. Electro-Analytical Study of Material Interfaces Relevant for Chemical Mechanical Planarization and Lithium Ion Batteries

    Science.gov (United States)

    Turk, Michael C.

    This dissertation work involves two areas of experimental research, focusing specifically on the applications of electro-analytical techniques for interfacial material characterization. The first area of the work is centered on the evaluation and characterization of material components used for chemical mechanical planarization (CMP) in the fabrication of semiconductor devices. This part also represents the bulk of the projects undertaken for the present dissertation. The other area of research included here involves exploratory electrochemical studies of certain electrolyte and electrode materials for applications in the development of advanced lithium ion secondary batteries. The common element between the two areas of investigation is the technical approach that combines a broad variety of electro-analytical characterization techniques to examine application specific functions of the associated materials and devices. The CMP related projects concentrate on designing and evaluating materials for CMP slurries that would be useful in the processing of copper interconnects for the sub-22 nm technology node. Specifically, ruthenium and cobalt are nontraditional barrier materials currently considered for the new interconnects. The CMP schemes used to process the structures based on these metals involve complex surface chemistries of Ru, Co and Cu (used for wiring lines). The strict requirement of defect-control while maintaining material removal by precisely regulated tribo-corrosion complicates the designs of the CMP slurries needed to process these systems. Since Ru is electrochemically more noble than Cu, the surface regions of Cu assembled in contact with Ru tend to generate defects due to galvanic corrosion in the CMP environment. At the same time, Co is strongly reactive in the typical slurry environment and is prone to developing galvanic corrosion induced by Cu. The present work explores a selected class of alkaline slurry formulations aimed at reducing these

  2. Elucidation of Mechanisms and Selectivities of Metal-Catalyzed Reactions using Quantum Chemical Methodology.

    Science.gov (United States)

    Santoro, Stefano; Kalek, Marcin; Huang, Genping; Himo, Fahmi

    2016-05-17

    Quantum chemical techniques today are indispensable for the detailed mechanistic understanding of catalytic reactions. The development of modern density functional theory approaches combined with the enormous growth in computer power have made it possible to treat quite large systems at a reasonable level of accuracy. Accordingly, quantum chemistry has been applied extensively to a wide variety of catalytic systems. A huge number of problems have been solved successfully, and vast amounts of chemical insights have been gained. In this Account, we summarize some of our recent work in this field. A number of examples concerned with transition metal-catalyzed reactions are selected, with emphasis on reactions with various kinds of selectivities. The discussed cases are (1) copper-catalyzed C-H bond amidation of indoles, (2) iridium-catalyzed C(sp(3))-H borylation of chlorosilanes, (3) vanadium-catalyzed Meyer-Schuster rearrangement and its combination with aldol- and Mannich-type additions, (4) palladium-catalyzed propargylic substitution with phosphorus nucleophiles, (5) rhodium-catalyzed 1:2 coupling of aldehydes and allenes, and finally (6) copper-catalyzed coupling of nitrones and alkynes to produce β-lactams (Kinugasa reaction). First, the methodology adopted in these studies is presented briefly. The electronic structure method in the great majority of these kinds of mechanistic investigations has for the last two decades been based on density functional theory. In the cases discussed here, mainly the B3LYP functional has been employed in conjunction with Grimme's empirical dispersion correction, which has been shown to improve the calculated energies significantly. The effect of the surrounding solvent is described by implicit solvation techniques, and the thermochemical corrections are included using the rigid-rotor harmonic oscillator approximation. The reviewed examples are chosen to illustrate the usefulness and versatility of the adopted methodology in

  3. Effect of Molecular Structure on Modulation of Passivation Films on Copper Chemical Mechanical Planarization

    Science.gov (United States)

    Mlynarski, Amy

    In order to optimize the chemical mechanical planarization (CMP) process, there is a need to further understand the synergistic relationship between chemical and mechanical parameters to enhance the polishing process. CMP chemistry is very complex, as it contains complexing agents, oxidizing agents, passivating agents, and abrasive particles. This variety of components ensues chaos within the system, which complicates the understanding of the direct impact each component has on the CMP process. In order for there to be efficiency in the polishing process, specifically for copper (Cu) polishing, the chemistry must create a softened passivation layer on the Cu surface that is able to be readily removed by applied mechanical abrasion. Focusing on Cu CMP, the oxidation of Cu to Cu2+ needs to be thoroughly understood in order to probe the formation of creating this ideal passivated layer, which protects recessed Cu regions. The type of film that is formed, the strength of the film, and even the efficiency of film removal will be altered depending on the chemistry of interaction at the Cu surface. This thesis focuses on understanding the working mechanism of the film formation on Cu, depending on the passivating agent added to the system. The different passivating agents used, more specifically benzotriazole (BTA), triazole (TAZ), salicylhydroxamic acid (SHA), and benzimidazole (BIA), have all been known to create a light coat of protection on the recessed metal, providing corrosion resistance. In order to study the differences in these films, many different techniques can be utilized to characterize the films, such as electrochemical scans, referred to as Tafel plots, which will be performed to compare the differences of the films. By altering the temperature within the system, the activation energy for each system can also be determined as another way to characterize the density of the passive film formed. Furthermore, the generation of *OH will be monitored since the

  4. Chemical characterization and ecotoxicity of three soil foaming agents used in mechanized tunneling.

    Science.gov (United States)

    Baderna, Diego; Lomazzi, Eleonora; Passoni, Alice; Pogliaghi, Alberto; Petoumenou, Maria Ifigeneia; Bagnati, Renzo; Lodi, Marco; Viarengo, Aldo; Sforzini, Susanna; Benfenati, Emilio; Fanelli, Roberto

    2015-10-15

    The construction of tunnels and rocks with mechanized drills produces several tons of rocky debris that are today recycled as construction material or as soil replacement for covering rocky areas. The lack of accurate information about the environmental impact of these excavated rocks and foaming agents added during the excavation process has aroused increasing concern for ecosystems and human health. The present study proposes an integrated approach to the assessment of the potential environmental impact of three foaming agents containing different anionic surfactants and other polymers currently on the market and used in tunnel boring machines. The strategy includes chemical characterization with high resolution mass spectrometry techniques to identify the components of each product, the use of in silico tools to perform a similarity comparison among these compounds and some pollutants already listed in regulatory frameworks to identify possible threshold concentrations of contamination, and the application of a battery of ecotoxicological assays to investigate the impact of each foaming mixture on model organisms of soil (higher plants and Eisenia andrei) and water communities (Daphnia magna). The study identified eleven compounds not listed on the material safety data sheets for which we have identified possible concentrations of contamination based on existing regulatory references. The bioassays allowed us to determine the no effect concentrations (NOAECs) of the three mixtures, which were subsequently used as threshold concentration for the product in its entirety. The technical mixtures used in this study have a different degree of toxicity and the predicted environmental concentrations based on the conditions of use are lower than the NOAEC for soils but higher than the NOAEC for water, posing a potential risk to the waters due to the levels of foaming agents in the muck. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Chemical characterization and ecotoxicity of three soil foaming agents used in mechanized tunneling

    Energy Technology Data Exchange (ETDEWEB)

    Baderna, Diego, E-mail: diego.baderna@marionegri.it [Laboratory of Environmental Chemistry and Toxicology, IRCCS – Istituto di Ricerche Farmacologiche Mario Negri, Via Giuseppe La Masa 19, 20156 Milan (Italy); Lomazzi, Eleonora [Laboratory of Environmental Chemistry and Toxicology, IRCCS – Istituto di Ricerche Farmacologiche Mario Negri, Via Giuseppe La Masa 19, 20156 Milan (Italy); Passoni, Alice [Unit of Analytical Instrumentation, IRCCS – Istituto di Ricerche Farmacologiche Mario Negri, Via Giuseppe La Masa 19, 20156 Milan (Italy); Pogliaghi, Alberto; Petoumenou, Maria Ifigeneia [Laboratory of Environmental Chemistry and Toxicology, IRCCS – Istituto di Ricerche Farmacologiche Mario Negri, Via Giuseppe La Masa 19, 20156 Milan (Italy); Bagnati, Renzo [Unit of Analytical Instrumentation, IRCCS – Istituto di Ricerche Farmacologiche Mario Negri, Via Giuseppe La Masa 19, 20156 Milan (Italy); Lodi, Marco [Laboratory of Environmental Chemistry and Toxicology, IRCCS – Istituto di Ricerche Farmacologiche Mario Negri, Via Giuseppe La Masa 19, 20156 Milan (Italy); Viarengo, Aldo; Sforzini, Susanna [Department of Sciences and Technological Innovation (DiSIT), University of Piemonte Orientale “A. Avogadro”, 15121 Alessandria (Italy); Benfenati, Emilio [Laboratory of Environmental Chemistry and Toxicology, IRCCS – Istituto di Ricerche Farmacologiche Mario Negri, Via Giuseppe La Masa 19, 20156 Milan (Italy); Fanelli, Roberto [Department of Environmental Health Sciences, IRCCS – Istituto di Ricerche Farmacologiche Mario Negri, Via Giuseppe La Masa 19, 20156 Milan (Italy)

    2015-10-15

    Highlights: • An integrated approach was applied to study three foaming agents. • Several compounds not reported on the safety data sheets were identified by HRMS. • Environmental impacts were investigated with a battery of biological assays. • An ecotoxicological ranking of the products was obtained. - Abstract: The construction of tunnels and rocks with mechanized drills produces several tons of rocky debris that are today recycled as construction material or as soil replacement for covering rocky areas. The lack of accurate information about the environmental impact of these excavated rocks and foaming agents added during the excavation process has aroused increasing concern for ecosystems and human health. The present study proposes an integrated approach to the assessment of the potential environmental impact of three foaming agents containing different anionic surfactants and other polymers currently on the market and used in tunnel boring machines. The strategy includes chemical characterization with high resolution mass spectrometry techniques to identify the components of each product, the use of in silico tools to perform a similarity comparison among these compounds and some pollutants already listed in regulatory frameworks to identify possible threshold concentrations of contamination, and the application of a battery of ecotoxicological assays to investigate the impact of each foaming mixture on model organisms of soil (higher plants and Eisenia andrei) and water communities (Daphnia magna). The study identified eleven compounds not listed on the material safety data sheets for which we have identified possible concentrations of contamination based on existing regulatory references. The bioassays allowed us to determine the no effect concentrations (NOAECs) of the three mixtures, which were subsequently used as threshold concentration for the product in its entirety. The technical mixtures used in this study have a different degree of toxicity

  6. Chemical and mechanical changes during leaf expansion of four woody species of dry Restinga woodland.

    Science.gov (United States)

    Schlindwein, C C D; Fett-Neto, A G; Dillenburg, L R

    2006-07-01

    Young leaves are preferential targets for herbivores, and plants have developed different strategies to protect them. This study aimed to evaluate different leaf attributes of presumed relevance in protection against herbivory in four woody species (Erythroxylum argentinum, Lithrea brasiliensis, Myrciaria cuspidata, and Myrsine umbellata), growing in a dry restinga woodland in southern Brazil. Evaluation of leaf parameters was made through single-point sampling of leaves (leaf mass per area and leaf contents of nitrogen, carbon, and pigments) at three developmental stages and through time-course sampling of expanding leaves (area and strength). Leaves of M. umbellata showed the highest leaf mass per area (LMA), the largest area, and the longest expansion period. On the other extreme, Myrc. cuspidata had the smallest LMA and leaf size, and the shortest expansion period. Similarly to L. brasiliensis, it displayed red young leaves. None of the species showed delayed-greening, which might be related to the high-irradiance growth conditions. Nitrogen contents reduced with leaf maturity and reached the highest values in the young leaves of E. argentinum and Myrc. cuspidata and the lowest in M. umbellata. Each species seems to present a different set of protective attributes during leaf expansion. Myrciaria cuspidata appears to rely mostly on chemical defences to protect its soft leaves, and anthocyanins might play this role at leaf youth, while M. umbellata seems to invest more on mechanical defences, even at early stages of leaf growth, as well as on a low allocation of nitrogen to the leaves. The other species display intermediate characteristics.

  7. Chemical characterization and ecotoxicity of three soil foaming agents used in mechanized tunneling

    International Nuclear Information System (INIS)

    Baderna, Diego; Lomazzi, Eleonora; Passoni, Alice; Pogliaghi, Alberto; Petoumenou, Maria Ifigeneia; Bagnati, Renzo; Lodi, Marco; Viarengo, Aldo; Sforzini, Susanna; Benfenati, Emilio; Fanelli, Roberto

    2015-01-01

    Highlights: • An integrated approach was applied to study three foaming agents. • Several compounds not reported on the safety data sheets were identified by HRMS. • Environmental impacts were investigated with a battery of biological assays. • An ecotoxicological ranking of the products was obtained. - Abstract: The construction of tunnels and rocks with mechanized drills produces several tons of rocky debris that are today recycled as construction material or as soil replacement for covering rocky areas. The lack of accurate information about the environmental impact of these excavated rocks and foaming agents added during the excavation process has aroused increasing concern for ecosystems and human health. The present study proposes an integrated approach to the assessment of the potential environmental impact of three foaming agents containing different anionic surfactants and other polymers currently on the market and used in tunnel boring machines. The strategy includes chemical characterization with high resolution mass spectrometry techniques to identify the components of each product, the use of in silico tools to perform a similarity comparison among these compounds and some pollutants already listed in regulatory frameworks to identify possible threshold concentrations of contamination, and the application of a battery of ecotoxicological assays to investigate the impact of each foaming mixture on model organisms of soil (higher plants and Eisenia andrei) and water communities (Daphnia magna). The study identified eleven compounds not listed on the material safety data sheets for which we have identified possible concentrations of contamination based on existing regulatory references. The bioassays allowed us to determine the no effect concentrations (NOAECs) of the three mixtures, which were subsequently used as threshold concentration for the product in its entirety. The technical mixtures used in this study have a different degree of toxicity

  8. CSP-based chemical kinetics mechanisms simplification strategy for non-premixed combustion: An application to hybrid rocket propulsion

    KAUST Repository

    Ciottoli, Pietro P.

    2017-08-14

    A set of simplified chemical kinetics mechanisms for hybrid rocket applications using gaseous oxygen (GOX) and hydroxyl-terminated polybutadiene (HTPB) is proposed. The starting point is a 561-species, 2538-reactions, detailed chemical kinetics mechanism for hydrocarbon combustion. This mechanism is used for predictions of the oxidation of butadiene, the primary HTPB pyrolysis product. A Computational Singular Perturbation (CSP) based simplification strategy for non-premixed combustion is proposed. The simplification algorithm is fed with the steady-solutions of classical flamelet equations, these being representative of the non-premixed nature of the combustion processes characterizing a hybrid rocket combustion chamber. The adopted flamelet steady-state solutions are obtained employing pure butadiene and gaseous oxygen as fuel and oxidizer boundary conditions, respectively, for a range of imposed values of strain rate and background pressure. Three simplified chemical mechanisms, each comprising less than 20 species, are obtained for three different pressure values, 3, 17, and 36 bar, selected in accordance with an experimental test campaign of lab-scale hybrid rocket static firings. Finally, a comprehensive strategy is shown to provide simplified mechanisms capable of reproducing the main flame features in the whole pressure range considered.

  9. Modeling the effects of cohesive energy for single particle on the material removal in chemical mechanical polishing at atomic scale

    International Nuclear Information System (INIS)

    Wang Yongguang; Zhao Yongwu; An Wei; Wang Jun

    2007-01-01

    This paper proposes a novel mathematical model for chemical mechanical polishing (CMP) based on interface solid physical and chemical theory in addition to energy equilibrium knowledge. And the effects of oxidation concentration and particle size on the material removal in CMP are investigated. It is shown that the mechanical energy and removal cohesive energy couple with the particle size, and being a cause of the non-linear size-removal rate relation. Furthermore, it also shows a nonlinear dependence of removal rate on removal cohesive energy. The model predictions are in good qualitative agreement with the published experimental data. The current study provides an important starting point for delineating the micro-removal mechanism in the CMP process at atomic scale

  10. Phenomenological description of selected elementary chemical reaction mechanisms: An information-theoretic study

    International Nuclear Information System (INIS)

    Esquivel, R.O.; Flores-Gallegos, N.; Iuga, C.; Carrera, E.M.; Angulo, J.C.; Antolin, J.

    2010-01-01

    The information-theoretic description of the course of two elementary chemical reactions allows a phenomenological description of the chemical course of the hydrogenic abstraction and the S N 2 identity reactions by use of Shannon entropic measures in position and momentum spaces. The analyses reveal their synchronous/asynchronous mechanistic behavior.

  11. Analysis of the mechanical behavior of single wall carbon nanotubes by a modified molecular structural mechanics model incorporating an advanced chemical force field

    Science.gov (United States)

    Eberhardt, Oliver; Wallmersperger, Thomas

    2018-03-01

    The outstanding properties of carbon nanotubes (CNTs) keep attracting the attention of researchers from different fields. CNTs are promising candidates for applications e.g. in lightweight construction but also in electronics, medicine and many more. The basis for the realization of the manifold applications is a detailed knowledge of the material properties of the carbon nanotubes. In particular for applications in lightweight constructions or in composites, the knowledge of the mechanical behavior of the CNTs is of vital interest. Hence, a lot of effort is put into the experimental and theoretical determination of the mechanical material properties of CNTs. Due to their small size, special techniques have to be applied. In this research, a modified molecular structural mechanics model for the numerical determination of the mechanical behavior of carbon nanotubes is presented. It uses an advanced approach for the geometrical representation of the CNT structure while the covalent bonds in the CNTs are represented by beam elements. Furthermore, the model is specifically designed to overcome major drawbacks in existing molecular structural mechanics models. This includes energetic consistency with the underlying chemical force field. The model is developed further to enable the application of a more advanced chemical force field representation. The developed model is able to predict, inter alia, the lateral and radial stiffness properties of the CNTs. The results for the lateral stiffness are given and discussed in order to emphasize the progress made with the presented approach.

  12. A coupled mechanical-chemical model for reflecting the influence of stress on oxidation reactions in thermal barrier coating

    Science.gov (United States)

    Chen, Lin; Yueming, Li

    2018-06-01

    In this paper, a coupled mechanical-chemical model is established based on the thermodynamic framework, in which the contribution of chemical expansion to free energy is introduced. The stress-dependent chemical potential equilibrium at the gas-solid interface and the stress gradient-dependent diffusion equation as well as a so-called generalized force which is conjugate to the oxidation rate are derived from the proposed model, which could reflect the influence of stresses on the oxidation reaction. Based on the proposed coupled mechanical-chemical model, a user element subroutine is developed in ABAQUS. The numerical simulation of the high temperature oxidation in the thermal barrier coating is carried out to verify the accuracy of the proposed model, and then the influence of stresses on the oxidation reaction is investigated. In thermally grown oxide, the considerable stresses would be induced by permanent volumetric swelling during the oxidation. The stresses play an important role in the chemical potential equilibrium at the gas-solid interface and strongly affect the oxidation reaction. The gradient of the stresses, however, only occurs in the extremely thin oxidation front layer, which plays a very limited role in the oxidation reaction. The generalized force could be divided into the stress-dependent and the stress-independent parts. Comparing with the stress-independent part, the stress-dependent part is smaller, which has little influence on oxidation reaction.

  13. Investigation research on the evaluation of a coupled thermo-hydro-mechanical-chemical phenomena. 2. Result report

    International Nuclear Information System (INIS)

    Ishihara, Yoshinao; Ito Takaya; Chijimatsu, Masakazu; Amemiya, Kiyoshi; Shiozaki, Isao; Neyama, Atsushi; Tanaka, Yumiko

    2003-02-01

    In order to realize a coupling analysis in the near field of the geological disposal system, the coupling analysis code on the thermo-hydro-mechanical-chemical phenomena by THAMES, Dtransu and phreeqe60, which are existing analysis code, is developed in this study. And we carried out the case analysis on the thermo-hydro-mechanical-chemical phenomena by this code. (1) We have developed coupling analysis system to manage coupling analysis and to control coupling process automatically for THAMES (thermo-hydro-mechanical analysis code), Dtransu (mass transport analysis code) and phreeqe60 (geochemical analysis code). (2) Some supporting module, which includes transfer of dissolution concentration and total concentration (dissolution + precipitation concentration), was prepared as a functional expansion. And in order to treat multi-chemical elements, we have codified mass transport analysis code. (3) We have prepared hydraulic conductivity module of buffer material depending on change of dry density due to chemical equilibrium (dissolution and precipitation of minerals), and change of concentration of NaCl solutions. After THAMES, Dtransu, phreeqe60 and hydraulic conductivity module were installed in the COUPLYS, sensitivity analysis was carried out to check basic operation. (4) In order to confirm the applicability of the developed THMC analysis code, we have carried out case analysis on 1-dimensional and 3-dimensional model which including vitrified waste, over-pack, buffer material and rock in the HLW near-field. (author)

  14. Effect of Single and Double Stage Chemically Treated Kenaf Fibers on Mechanical Properties of Polyvinyl Alcohol Film

    Directory of Open Access Journals (Sweden)

    Md Ershad Ali

    2014-12-01

    Full Text Available The physico-mechanical properties of lignocellulosic kenaf fiber reinforced polyvinyl alcohol (PVA biocomposite films were investigated. To improve the properties of the biocomposite, kenaf fibers were chemically treated separately in a single stage (with Cr2(SO4312(H2O and double stages (with CrSO4 and NaHCO3 to improve the adhesion and compatibility between the kenaf fiber and PVA matrix. PVA was reinforced with various compositions of chemically treated kenaf fiber by using a solution casting technique. Microstructural analyses and mechanical tests were subsequently conducted. Scanning electron microscopic analysis indicated that chemical treatment improved the uniformity distribution of kenaf fiber within the PVA matrix. FTIR and XRD analyses confirmed the presence of chromium on the fiber surface. The tensile strength of PVA reinforced with chemical treated kenaf fiber was found to be higher than those reinforced with untreated kenaf. The Young’s modulus, flexural strength, and flexural modulus increased with fiber loading for both untreated and treated kenaf fiber reinforced PVA films. The double stage treated kenaf fiber showed better mechanical properties and lower moisture uptake than the single stage treated kenaf fiber.

  15. Changes in mechanical, chemical, and thermal sensitivity of the cornea after topical application of nonsteroidal anti-inflammatory drugs.

    Science.gov (United States)

    Acosta, M Carmen; Berenguer-Ruiz, Leticia; García-Gálvez, Alberto; Perea-Tortosa, David; Gallar, Juana; Belmonte, Carlos

    2005-01-01

    In addition to their well-known anti-inflammatory actions, some of the nonsteroidal anti-inflammatory drugs (NSAIDs) appear to have an analgesic effect. In human subjects, the changes in threshold and intensity of sensations evoked by mechanical, chemical, and thermal stimulation of the cornea induced by topical administration of two commercial NSAIDs, diclofenac sodium (Voltaren; Novartis, Basel, Switzerland) and flurbiprofen (Ocuflur; Allergan, Irvine, CA), were studied. Corneal sensitivity was measured in 10 young, healthy subjects with a gas esthesiometer. Chemical (10%-70% CO2 in air), mechanical (0-264 mL/min), and thermal (corneal temperature changes between -4.5 degrees C and +3 degrees C around the normal value) stimuli were applied to the center of the cornea. The intensity and perceived magnitude of the psychophysical attributes of the evoked sensation were scored at the end of the pulse in a 10-cm, continuous visual analog scale (VAS). The threshold was expressed as the stimulus intensity that evoked a VAS score >0.5. Sensitivity was measured in both eyes of each subject on two separate days, one without treatment and the other 30 minutes after topical application of 0.03% flurbiprofen (seven subjects) or 0.1% diclofenac sodium (six subjects). Diclofenac attenuated significantly all the sensation parameters evoked by high-intensity mechanical, chemical, and thermal stimuli. Flurbiprofen produced a slight reduction of the sensations evoked by mechanical and chemical stimulation that became significant only for the irritation caused by chemical stimuli of maximum intensity (70% CO2). None of the drugs modified significantly the detection threshold of the different stimuli. Flurbiprofen had a very limited effect on sensations evoked by corneal stimulation, whereas diclofenac reduced the intensity of sensations evoked by stimuli of different modality, suggesting a mild local anesthetic effect of this drug on all types of corneal sensory fibers. Such

  16. Chemical-mechanical polishing of metal and dielectric films for microelectronic applications

    Science.gov (United States)

    Hegde, Sharath

    The demand for smaller, faster devices has led the integrated circuit (IC) industry to continually increase the device density on a chip while simultaneously reducing feature dimensions. Copper interconnects and multilevel metallization (MLM) schemes were introduced to meet some of these challenges. With the employment of MLM in the ultra-large-scale-integrated (ULSI) circuit fabrication technology, repeated planarization of different surface layers with tolerance of a few nanometers is required. Presently, chemical-mechanical planarization (CMP) is the only technique that can meet this requirement. Damascene and shallow trench isolation processes are currently used in conjunction with CMP in the fabrication of multilevel copper interconnects and isolation of devices, respectively, for advanced logic and memory devices. These processes, at some stage, require simultaneous polishing of two different materials using a single slurry that offers high polish rates, high polish selectivity to one material over the other and good post-polish surface finish. Slurries containing one kind of abrasive particles do not meet most of these demands due mainly to the unique physical and chemical properties of each abrasive. However, if a composite particle is formed that takes the advantages of different abrasives while mitigating their disadvantages, the CMP performance of resulting abrasives would be compelling. It is demonstrated that electrostatic interactions between ceria and silica particles at pH 4 can be used to produce composite particles with enhanced functionality. Zeta potential measurement and TEM images used for particle characterization show the presence of such composite particles with smaller shell particles attached onto larger core particles. Slurries containing ceria (core)/silica (shell) and silica (core)/ceria (shell) composite particles when used to polish metal and dielectric films, respectively, yield both enhanced metal and dielectric film removal rates

  17. Coupled Thermo-Mechanical and Photo-Chemical Degradation Mechanisms that determine the Reliability and Operational Lifetimes for CPV Technologies

    Energy Technology Data Exchange (ETDEWEB)

    Dauskardt, Reinhold H. [Stanford Univ., CA (United States)

    2017-04-30

    This project sought to identify and characterize the coupled intrinsic photo-chemo-mechanical degradation mechanisms that determine the reliability and operational lifetimes for CPV technologies. Over a three year period, we have completed a highly successful program which has developed quantitative metrologies and detailed physics-based degradation models, providing new insight into the fundamental reliability physics necessary for improving materials, creating accelerated testing protocols, and producing more accurate lifetime predictions. The tasks for the program were separated into two focus areas shown in the figure below. Focus Area 1, led by Reinhold Dauskardt and Warren Cai with a primary collaboration with David Miller of NREL, studied the degradation mechanisms present in encapsulant materials. Focus Area 2, led by Reinhold Dauskardt and Ryan Brock with a primary collaboration with James Ermer and Peter Hebert of Spectrolab, studied stress development and degradation within internal CPV device interfaces. Each focus area was productive, leading to several publications, including findings on the degradation of silicone encapsulant under terrestrial UV, a model for photodegradation of silicone encapsulant adhesion, quantification and process tuning of antireflective layers on CPV, and discovery of a thermal cycling degradation mechanism present in metal gridline structures.

  18. Redirecting adenovirus tropism by genetic, chemical, and mechanical modification of the adenovirus surface for cancer gene therapy.

    Science.gov (United States)

    Yoon, A-Rum; Hong, Jinwoo; Kim, Sung Wan; Yun, Chae-Ok

    2016-06-01

    Despite remarkable advancements, clinical evaluations of adenovirus (Ad)-mediated cancer gene therapies have highlighted the need for improved delivery and targeting. Genetic modification of Ad capsid proteins has been extensively attempted. Although genetic modification enhances the therapeutic potential of Ad, it is difficult to successfully incorporate extraneous moieties into the capsid and the engineering process is laborious. Recently, chemical modification of the Ad surface with nanomaterials and targeting moieties has been found to enhance Ad internalization into the target by both passive and active mechanisms. Alternatively, external stimulus-mediated targeting can result in selective accumulation of Ad in the tumor and prevent dissemination of Ad into surrounding nontarget tissues. In the present review, we discuss various genetic, chemical, and mechanical engineering strategies for overcoming the challenges that hinder the therapeutic efficacy of Ad-based approaches. Surface modification of Ad by genetic, chemical, or mechanical engineering strategies enables Ad to overcome the shortcomings of conventional Ad and enhances delivery efficiency through distinct and unique mechanisms that unmodified Ad cannot mimic. However, although the therapeutic potential of Ad-mediated gene therapy has been enhanced by various surface modification strategies, each strategy still possesses innate limitations that must be addressed, requiring innovative ideas and designs.

  19. Effect of layering sequence and chemical treatment on the mechanical properties of woven kenaf–aramid hybrid laminated composites

    International Nuclear Information System (INIS)

    Yahaya, R.; Sapuan, S.M.; Jawaid, M.; Leman, Z.; Zainudin, E.S.

    2015-01-01

    Highlights: • The mechanical properties of woven kenaf/Kevlar hybrid composites were analysed. • The layering sequences affect the mechanical properties of hybrid composites. • Treated kenaf improves the mechanical properties of hybrid composites. - Abstract: This work aims to evaluate the effect of layering sequence and chemical treatment on mechanical properties of woven kenaf–Kevlar composites. Woven kenaf–aramid hybrid laminated composites fabricated through hand lay-up techniques by arranging woven kenaf and Kevlar fabrics in different layering sequences and by using treated kenaf mat. To evaluate the effect of chemical treatment on hybrid composites, the woven kenaf mat was treated with 6% sodium hydroxide (NaOH) diluted solution and compared mechanical properties with untreated kenaf hybrid composites. Results shows that the tensile properties of hybrid composites improved in 3-layer composites compared to 4-layer composites. Hybrid composite with Kevlar as outer layers display a better mechanical properties as compared to other hybrid composites. Tensile and flexural properties of treated hybrid composites are better than non-treated hybrid composites. The fractured surface of hybrid composites was investigated by scanning electron microscopy. This study is a part of exploration of potential application of the hybrid composite in high velocity impact application

  20. Consumable Process Development for Chemical Mechanical Planarization of Bit Patterned Media for Magnetic Storage Fabrication

    Science.gov (United States)

    Bonivel, Joseph T., Jr.

    2010-09-01

    As the superparamagnetic limit is reached, the magnetic storage industry looks to circumvent the barrier by implementing patterned media (PM) as a viable means to store and access data. Chemical mechanical polishing (CMP) is a semiconductor fabrication technique used to planarize surfaces and is investigated as a method to ensure that the PM is polished to surface roughness parameters that allow the magnetic read/write head to move seamlessly across the PM. Results from this research have implications in feasibility studies of utilizing CMP as the main planarization technique for PM fabrication. Benchmark data on the output parameters of the CMP process, for bit patterned media (BPM), based on the machine process parameters, pad properties, and slurry characteristics are optimized. The research was conducted in a systematic manner in which the optimized parameters for each phase are utilized in future phases. The optimum results from each of the phases provide an overall optimum characterization for BPM CMP. Results on the CMP machine input parameters indicate that for optimal surface roughness and material removal, low polish pressures and high velocities should be used on the BPM. Pad characteristics were monitored by non destructive technique and results indicate much faster deterioration of all padcharacteristics versus polish time of BPM when compared to IC CMP. The optimum pad for PM polishing was the IC 1400 dual layer Suba V pad with a shore hardness of 57, and a k-groove pattern. The final phase of polishing evaluated the slurry polishing properties and novel nanodiamond (ND) slurry was created and benchmarked on BPM. The resulting CMP output parameters were monitored and neither the ND slurry nor the thermally responsive polymer slurry performed better than the commercially available Cabot iCue slurry for MRR or surface roughness. Research results indicate CMP is a feasible planarization technique for PM fabrication, but successful implementation of CMP

  1. Surface-treated commercially pure titanium for biomedical applications: Electrochemical, structural, mechanical and chemical characterizations

    International Nuclear Information System (INIS)

    Ogawa, Erika S.; Matos, Adaias O.; Beline, Thamara; Marques, Isabella S.V.; Sukotjo, Cortino; Mathew, Mathew T.; Rangel, Elidiane C.; Cruz, Nilson C.; Mesquita, Marcelo F.; Consani, Rafael X.

    2016-01-01

    Modified surfaces have improved the biological performance and biomechanical fixation of dental implants compared to machined (polished) surfaces. However, there is a lack of knowledge about the surface properties of titanium (Ti) as a function of different surface treatment. This study investigated the role of surface treatments on the electrochemical, structural, mechanical and chemical properties of commercial pure titanium (cp-Ti) under different electrolytes. Cp-Ti discs were divided into 6 groups (n = 5): machined (M—control); etched with HCl + H_2O_2 (Cl), H_2SO_4 + H_2O_2 (S); sandblasted with Al_2O_3 (Sb), Al_2O_3 followed by HCl + H_2O_2 (SbCl), and Al_2O_3 followed by H_2SO_4 + H_2O_2 (SbS). Electrochemical tests were conducted in artificial saliva (pHs 3; 6.5 and 9) and simulated body fluid (SBF—pH 7.4). All surfaces were characterized before and after corrosion tests using atomic force microscopy, scanning electron microscopy, energy dispersive microscopy, X-ray diffraction, surface roughness, Vickers microhardness and surface free energy. The results indicated that Cl group exhibited the highest polarization resistance (R_p) and the lowest capacitance (Q) and corrosion current density (I_c_o_r_r) values. Reduced corrosion stability was noted for the sandblasted groups. Acidic artificial saliva decreased the R_p values of cp-Ti surfaces and produced the highest I_c_o_r_r values. Also, the surface treatment and corrosion process influenced the surface roughness, Vickers microhardness and surface free energy. Based on these results, it can be concluded that acid-etching treatment improved the electrochemical stability of cp-Ti and all treated surfaces behaved negatively in acidic artificial saliva. - Highlights: • Characterization of surface treatment for biomedical implants was investigated. • Sandblasting reduced the corrosion stability of cp-Ti. • Acid etching is a promising dental implants surface treatment.

  2. Mechanism of Methane Chemical Looping Combustion with Hematite Promoted with CeO 2

    Energy Technology Data Exchange (ETDEWEB)

    Miller, Duane D.; Siriwardane, Ranjani

    2013-08-15

    Chemical looping combustion (CLC) is a promising technology for fossil fuel combustion that produces sequestration-ready CO{sub 2} stream, reducing the energy penalty of CO{sub 2} separation from flue gases. An effective oxygen carrier for CLC will readily react with the fuel gas and will be reoxidized upon contact with oxygen. This study investigated the development of a CeO{sub 2}-promoted Fe{sub 2}O{sub 3}-hematite oxygen carrier suitable for the methane CLC process. Composition of CeO{sub 2} is between 5 and 25 wt % and is lower than what is generally used for supports in Fe{sub 2}O{sub 3} carrier preparations. The incorporation of CeO{sub 2} to the natural ore hematite strongly modifies the reduction behavior in comparison to that of CeO{sub 2} and hematite alone. Temperature-programmed reaction studies revealed that the addition of even 5 wt % CeO{sub 2} enhances the reaction capacity of the Fe{sub 2}O{sub 3} oxygen carrier by promoting the decomposition and partial oxidation of methane. Fixed-bed reactor data showed that the 5 wt % cerium oxides with 95 wt % iron oxide produce 2 times as much carbon dioxide in comparison to the sum of carbon dioxide produced when the oxides were tested separately. This effect is likely due to the reaction of CeO{sub 2} with methane forming intermediates, which are reactive for extracting oxygen from Fe{sub 2}O{sub 3} at a considerably faster rate than the rate of the direct reaction of Fe{sub 2}O{sub 3} with methane. These studies reveal that 5 wt % CeO{sub 2}/Fe{sub 2}O{sub 3} gives stable conversions over 15 reduction/oxidation cycles. Lab-scale reactor studies (pulsed mode) suggest the methane reacts initially with CeO{sub 2} lattice oxygen to form partial oxidation products (CO + H{sub 2}), which continue to react with oxygen from neighboring Fe{sub 2}O{sub 3}, leading to its complete oxidation to form CO{sub 2}. The reduced cerium oxide promotes the methane decomposition reaction to form C + H{sub 2}, which continue to

  3. Surface-treated commercially pure titanium for biomedical applications: Electrochemical, structural, mechanical and chemical characterizations

    Energy Technology Data Exchange (ETDEWEB)

    Ogawa, Erika S.; Matos, Adaias O.; Beline, Thamara [Department of Prosthodontics and Periodontology, Piracicaba Dental School, University of Campinas (UNICAMP), Av Limeira, 901, Piracicaba, São Paulo 13414-903 (Brazil); IBTN/Br—Institute of Biomaterials, Tribocorrosion and Nanomedicine—Brazilian Branch (Brazil); Marques, Isabella S.V. [Department of Prosthodontics and Periodontology, Piracicaba Dental School, University of Campinas (UNICAMP), Av Limeira, 901, Piracicaba, São Paulo 13414-903 (Brazil); Sukotjo, Cortino [Department of Restorative Dentistry, University of Illinois at Chicago, College of Dentistry, 801 S Paulina, Chicago, IL, USA, 60612 (United States); IBTN—Institute of Biomaterials, Tribocorrosion and Nanomedicine (United States); Mathew, Mathew T. [IBTN—Institute of Biomaterials, Tribocorrosion and Nanomedicine (United States); Department of Biomedical Sciences, University of Illinois, College of Medicine at Rockford, 1601 Parkview Avenue, Rockford, IL, USA, 61107 (United States); Rangel, Elidiane C.; Cruz, Nilson C. [IBTN/Br—Institute of Biomaterials, Tribocorrosion and Nanomedicine—Brazilian Branch (Brazil); Laboratory of Technological Plasmas, Engineering College, Univ Estadual Paulista (UNESP), Av Três de Março, 511, Sorocaba, São Paulo 18087-180 (Brazil); Mesquita, Marcelo F.; Consani, Rafael X. [Department of Prosthodontics and Periodontology, Piracicaba Dental School, University of Campinas (UNICAMP), Av Limeira, 901, Piracicaba, São Paulo 13414-903 (Brazil); and others

    2016-08-01

    Modified surfaces have improved the biological performance and biomechanical fixation of dental implants compared to machined (polished) surfaces. However, there is a lack of knowledge about the surface properties of titanium (Ti) as a function of different surface treatment. This study investigated the role of surface treatments on the electrochemical, structural, mechanical and chemical properties of commercial pure titanium (cp-Ti) under different electrolytes. Cp-Ti discs were divided into 6 groups (n = 5): machined (M—control); etched with HCl + H{sub 2}O{sub 2} (Cl), H{sub 2}SO{sub 4} + H{sub 2}O{sub 2} (S); sandblasted with Al{sub 2}O{sub 3} (Sb), Al{sub 2}O{sub 3} followed by HCl + H{sub 2}O{sub 2} (SbCl), and Al{sub 2}O{sub 3} followed by H{sub 2}SO{sub 4} + H{sub 2}O{sub 2} (SbS). Electrochemical tests were conducted in artificial saliva (pHs 3; 6.5 and 9) and simulated body fluid (SBF—pH 7.4). All surfaces were characterized before and after corrosion tests using atomic force microscopy, scanning electron microscopy, energy dispersive microscopy, X-ray diffraction, surface roughness, Vickers microhardness and surface free energy. The results indicated that Cl group exhibited the highest polarization resistance (R{sub p}) and the lowest capacitance (Q) and corrosion current density (I{sub corr}) values. Reduced corrosion stability was noted for the sandblasted groups. Acidic artificial saliva decreased the R{sub p} values of cp-Ti surfaces and produced the highest I{sub corr} values. Also, the surface treatment and corrosion process influenced the surface roughness, Vickers microhardness and surface free energy. Based on these results, it can be concluded that acid-etching treatment improved the electrochemical stability of cp-Ti and all treated surfaces behaved negatively in acidic artificial saliva. - Highlights: • Characterization of surface treatment for biomedical implants was investigated. • Sandblasting reduced the corrosion stability of cp

  4. Influence of trace aromatics on the chemical growth mechanisms of Titan aerosol analogues

    Science.gov (United States)

    Gautier, Thomas; Sebree, Joshua A.; Li, Xiang; Pinnick, Veronica T.; Grubisic, Andrej; Loeffler, Mark J.; Getty, Stephanie A.; Trainer, Melissa G.; Brinckerhoff, William B.

    2017-06-01

    The chemical structure and formation pathways of Titan aerosols remain largely unknown. In this work, we studied the effect of trace aromatics on the chemical composition and formation pathways of laboratory analogues of Titan's organic aerosols. The aerosol analogues were produced using four different trace aromatic molecules, comprised of one or two aromatic rings, each with or without a nitrogen heteroatom. Samples were then analyzed by laser desorption/ionization Mass Spectrometry (LDMS), revealing a high variability in the sample composition depending on the trace aromatic used. Our work reveals that the final chemical structure of the aerosols depends strongly on the number of aromatic rings in the trace molecule, leading either to a polymeric or to a random co-polymeric growth of the sample. These different chemical structures can affect the physical properties of the aerosol. Future analysis of Titan's aerosols using better resolution could potentially determine whether either of the growth hypotheses are preferred.

  5. Integration of large chemical kinetic mechanisms via exponential methods with Krylov approximations to Jacobian matrix functions

    KAUST Repository

    Bisetti, Fabrizio

    2012-01-01

    with the computational cost associated with the time integration of stiff, large chemical systems, a novel approach is proposed. The approach combines an exponential integrator and Krylov subspace approximations to the exponential function of the Jacobian matrix

  6. Endocrine disrupting chemicals in fish: developing exposure indicators and predictive models of effects based on mechanism of action.

    Science.gov (United States)

    Ankley, Gerald T; Bencic, David C; Breen, Michael S; Collette, Timothy W; Conolly, Rory B; Denslow, Nancy D; Edwards, Stephen W; Ekman, Drew R; Garcia-Reyero, Natalia; Jensen, Kathleen M; Lazorchak, James M; Martinović, Dalma; Miller, David H; Perkins, Edward J; Orlando, Edward F; Villeneuve, Daniel L; Wang, Rong-Lin; Watanabe, Karen H

    2009-05-05

    Knowledge of possible toxic mechanisms (or modes) of action (MOA) of chemicals can provide valuable insights as to appropriate methods for assessing exposure and effects, thereby reducing uncertainties related to extrapolation across species, endpoints and chemical structure. However, MOA-based testing seldom has been used for assessing the ecological risk of chemicals. This is in part because past regulatory mandates have focused more on adverse effects of chemicals (reductions in survival, growth or reproduction) than the pathways through which these effects are elicited. A recent departure from this involves endocrine-disrupting chemicals (EDCs), where there is a need to understand both MOA and adverse outcomes. To achieve this understanding, advances in predictive approaches are required whereby mechanistic changes caused by chemicals at the molecular level can be translated into apical responses meaningful to ecological risk assessment. In this paper we provide an overview and illustrative results from a large, integrated project that assesses the effects of EDCs on two small fish models, the fathead minnow (Pimephales promelas) and zebrafish (Danio rerio). For this work a systems-based approach is being used to delineate toxicity pathways for 12 model EDCs with different known or hypothesized toxic MOA. The studies employ a combination of state-of-the-art genomic (transcriptomic, proteomic, metabolomic), bioinformatic and modeling approaches, in conjunction with whole animal testing, to develop response linkages across biological levels of organization. This understanding forms the basis for predictive approaches for species, endpoint and chemical extrapolation. Although our project is focused specifically on EDCs in fish, we believe that the basic conceptual approach has utility for systematically assessing exposure and effects of chemicals with other MOA across a variety of biological systems.

  7. Mechanisms controlling temperature dependent mechanical and electrical behavior of SiH4 reduced chemically vapor deposited W

    International Nuclear Information System (INIS)

    Joshi, R.V.; Prasad, V.; Krusin-Elbaum, L.; Yu, M.; Norcott, M.

    1990-01-01

    The effects of deposition temperature on growth, composition, structure, adhesion properties, stress, and resistivity of chemically vapor deposited W deposited purely by SiH 4 reduction of WF 6 are discussed. At lower deposition temperatures, due to incomplete Si reduction reaction, a small amount of Si is incorporated in the film. This elemental Si in W is responsible for the observed high stresses and high resistivities over a wide temperature range. With the increase in the deposition temperature, the conversion of incorporated Si as well as the initial Si reduction are taking place, stimulating increased grain growth and thereby relieving stress and reducing resistivity. The optimum values for stress and resistivity are achieved around 500 degree C, as Si content is at its minimum. At higher temperatures the reaction between residual Si and W, is the prime cause of resistivity increase

  8. Enhancing both the mechanical and chemical properties of paper sheet by graft co-polymerization with acrylonitrile/methyl methacrylate

    Directory of Open Access Journals (Sweden)

    H.M. Abd El Salam

    2014-09-01

    Full Text Available The chemical graft copolymerization reaction of acrylonitrile (AN and methyl methacrylate (MMA binary mixture onto paper sheet was performed. The effect of initiator concentration, monomer concentration and temperature on the reaction rate was studied. The reaction rate equation of the graft copolymerization reaction is found to be RP = K2 [Initiator]0.795[Monomer]2.007. The apparent activation energy (Ea of the copolymerization reaction is found to be 75.01 kJ/mol. The infrared characteristic absorption bands for cellulosic paper structure and the paper gr-AN-MMA are investigated. Tensile break load, porosity and burst strength were measured for the grafted and pure paper sheet. It was found that the mechanical properties are improved by grafting copolymerization. The chemical resistance of the graft product against a strong acid a strong alkali, polar and nonpolar solvents was investigated. It was found that the resistance to these chemicals is enhanced by grafting.

  9. Report on NCI symposium: comparison of mechanisms of carcinogenesis by radiation and chemical agents. II. Cellular and animal models

    International Nuclear Information System (INIS)

    Fry, R.J.M.

    1984-01-01

    The point at which the common final pathway for induction of cancer by chemical carcinogens and ionizing radiation has not been identified. Although common molecular targets are suggested by recent findings about the role of oncogenes, the mechanism by which the deposition of radiation energy and the formation of adducts or other DNA lesions induced by chemicals affects the changes in the relevant targets may be quite different. The damage to DNA that plays no part in the transformation events, but that influences the stability of the genome, and therefore, the probability of subsequent changes that influence tumorigenesis may be more readily induced by some agents than others. Similarly, the degree of cytotoxic effects that disrupt tissue integrity and increase the probability of expression of initiated cells may be dependent on the type of carcinogen. Also, evidence was presented that repair of the initial lesions could be demonstrated after exposure to low-LET radiation but not after exposure to chemical carcinogens

  10. Report on NCI symposium: comparison of mechanisms of carcinogenesis by radiation and chemical agents. II. Cellular and animal models

    Energy Technology Data Exchange (ETDEWEB)

    Fry, R.J.M.

    1984-01-01

    The point at which the common final pathway for induction of cancer by chemical carcinogens and ionizing radiation has not been identified. Although common molecular targets are suggested by recent findings about the role of oncogenes, the mechanism by which the deposition of radiation energy and the formation of adducts or other DNA lesions induced by chemicals affects the changes in the relevant targets may be quite different. The damage to DNA that plays no part in the transformation events, but that influences the stability of the genome, and therefore, the probability of subsequent changes that influence tumorigenesis may be more readily induced by some agents than others. Similarly, the degree of cytotoxic effects that disrupt tissue integrity and increase the probability of expression of initiated cells may be dependent on the type of carcinogen. Also, evidence was presented that repair of the initial lesions could be demonstrated after exposure to low-LET radiation but not after exposure to chemical carcinogens.

  11. Quantum chemical study of the mechanism of action of vitamin K epoxide reductase (VKOR)

    Science.gov (United States)

    Deerfield, David, II; Davis, Charles H.; Wymore, Troy; Stafford, Darrel W.; Pedersen, Lee G.

    Possible model, but simplistic, mechanisms for the action of vitamin K epoxide reductase (VKOR) are investigated with quantum mechanical methods (B3LYP/6-311G**). The geometries of proposed model intermediates in the mechanisms are energy optimized. Finally, the energetics of the proposed (pseudo-enzymatic) pathways are compared. We find that the several pathways are all energetically feasible. These results will be useful for designing quantum mechanical/molecular mechanical method (QM/MM) studies of the enzymatic pathway once three-dimensional structural data are determined and available for VKOR.

  12. Fracture Toughness, Mechanical Property, And Chemical Characterization Of A Critical Modification To The NASA SLS Solid Booster Internal Material System

    Science.gov (United States)

    Pancoast, Justin; Garrett, William; Moe, Gulia

    2015-01-01

    A modified propellant-liner-insulation (PLI) bondline in the Space Launch System (SLS) solid rocket booster required characterization for flight certification. The chemical changes to the PLI bondline and the required additional processing have been correlated to mechanical responses of the materials across the bondline. Mechanical properties testing and analyses included fracture toughness, tensile, and shear tests. Chemical properties testing and analyses included Fourier transform infrared (FTIR) spectroscopy, cross-link density, high-performance liquid chromatography (HPLC), gas chromatography (GC), gel permeation chromatography (GPC), and wave dispersion X-ray fluorescence (WDXRF). The testing identified the presence of the expected new materials and found the functional bondline performance of the new PLI system was not significantly changed from the old system.

  13. Application of TCF bleaching in mixtures of chemical and mechanics fibers recycled: alternative for the paper industry

    International Nuclear Information System (INIS)

    Fuentes L, Jhonattan; Uribe R, Gabriel H

    2009-01-01

    In this paper we study the technical feasibility of using mixtures composed by mechanical and chemical fibers recycled in the production of tissue paper, using TCF bleaching sequences that improve the optical properties of this raw material. At present, chemical fibers recycled are used, but their limited availability and high cost,stimulate the search for raw materials which replace them partially. Bleaching stages were carried out at atmospheric pressure, with the oxidative process made with hydrogen peroxide at 80 celsius degrade in 1.5 hours and the reductive stage with FAS, VBrite, Thiourea Dioxide in situ or Chromaclear at 60 celsius degrade for 1 hour. The obtained results allow to deduce that the addition of mechanical recycled fiber significantly affects the optical properties of mixtures. However, some of the bleaching sequences applied manage to compensate, at least partly, the effect of adding this raw material of lower quality and cost.

  14. Effects of mechanical and chemical processes on the degradation of plastic beach debris on the island of Kauai, Hawaii

    International Nuclear Information System (INIS)

    Cooper, David A; Corcoran, Patricia L

    2010-01-01

    Plastic debris is accumulating on the beaches of Kauai at an alarming rate, averaging 484 pieces/day in one locality. Particles sampled were analyzed to determine the effects of mechanical and chemical processes on the breakdown of polymers in a subtropical setting. Scanning electron microscopy (SEM) indicates that plastic surfaces contain fractures, horizontal notches, flakes, pits, grooves, and vermiculate textures. The mechanically produced textures provide ideal loci for chemical weathering to occur which further weakens the polymer surface leading to embrittlement. Fourier transform infrared spectroscopy (FTIR) results show that some particles have highly oxidized surfaces as indicated by intense peaks in the lower wavenumber region of the spectra. Our textural analyses suggest that polyethylene has the potential to degrade more readily than polypropylene. Further evaluation of plastic degradation in the natural environment may lead to a shift away from the production and use of plastic materials with longer residence times.

  15. Elucidating mechanisms of toxic action of dissolved organic chemicals in oil sands process-affected water (OSPW).

    Science.gov (United States)

    Morandi, Garrett D; Wiseman, Steve B; Guan, Miao; Zhang, Xiaowei W; Martin, Jonathan W; Giesy, John P

    2017-11-01

    Oil sands process-affected water (OSPW) is generated during extraction of bitumen in the surface-mining oil sands industry in Alberta, Canada, and is acutely and chronically toxic to aquatic organisms. It is known that dissolved organic compounds in OSPW are responsible for most toxic effects, but knowledge of the specific mechanism(s) of toxicity, is limited. Using bioassay-based effects-directed analysis, the dissolved organic fraction of OSPW has previously been fractionated, ultimately producing refined samples of dissolved organic chemicals in OSPW, each with distinct chemical profiles. Using the Escherichia coli K-12 strain MG1655 gene reporter live cell array, the present study investigated relationships between toxic potencies of each fraction, expression of genes and characterization of chemicals in each of five acutely toxic and one non-toxic extract of OSPW derived by use of effects-directed analysis. Effects on expressions of genes related to response to oxidative stress, protein stress and DNA damage were indicative of exposure to acutely toxic extracts of OSPW. Additionally, six genes were uniquely responsive to acutely toxic extracts of OSPW. Evidence presented supports a role for sulphur- and nitrogen-containing chemical classes in the toxicity of extracts of OSPW. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Development and validation of a generic reduced chemical kinetic mechanism for CFD spray combustion modelling of biodiesel fuels

    DEFF Research Database (Denmark)

    Cheng, Xinwei; Ng, Hoon Kiat; Ho, Jee Hou

    2015-01-01

    In this reported work, a generic reduced biodiesel chemical kinetic mechanism, with components of methyl decanoate (C11H22O2, MD), methyl-9-decenoate (C11H20O2, MD9D) and n-heptane (C7H16) was built to represent the methyl esters of coconut, palm, rapeseed and soybean. The reduced biodiesel...... and detailed mechanism predictions, for each zero-dimensional (0D) auto-ignition and extinction process using CHEMKIN-PRO. Maximum percentage errors of less than 40.0% were recorded when the predicted ignition delay (ID) periods for coconut, palm, rapeseed and soybean methyl esters were compared to those...

  17. Biological and Chemical Removal of Primary Cilia Affects Mechanical Activation of Chondrogenesis Markers in Chondroprogenitors and Hypertrophic Chondrocytes.

    Science.gov (United States)

    Deren, Matthew E; Yang, Xu; Guan, Yingjie; Chen, Qian

    2016-02-04

    Chondroprogenitors and hypertrophic chondrocytes, which are the first and last stages of the chondrocyte differentiation process, respectively, are sensitive to mechanical signals. We hypothesize that the mechanical sensitivity of these cells depends on the cell surface primary cilia. To test this hypothesis, we removed the primary cilia by biological means with transfection with intraflagellar transport protein 88 (IFT88) siRNA or by chemical means with chloral hydrate treatment. Transfection of IFT88 siRNA significantly reduced the percentage of ciliated cells in both chondroprogenitor ATDC5 cells as well as primary hypertrophic chondrocytes. Cyclic loading (1 Hz, 10% matrix deformation) of ATDC5 cells in three-dimensional (3D) culture stimulates the mRNA levels of chondrogenesis marker Type II collagen (Col II), hypertrophic chondrocyte marker Type X collagen (Col X), and a molecular regulator of chondrogenesis and chondrocyte hypertrophy bone morphogenetic protein 2 (BMP-2). The reduction of ciliated chondroprogenitors abolishes mechanical stimulation of Col II, Col X, and BMP-2. In contrast, cyclic loading stimulates Col X mRNA levels in hypertrophic chondrocytes, but not those of Col II and BMP-2. Both biological and chemical reduction of ciliated hypertrophic chondrocytes reduced but failed to abolish mechanical stimulation of Col X mRNA levels. Thus, primary cilia play a major role in mechanical stimulation of chondrogenesis and chondrocyte hypertrophy in chondroprogenitor cells and at least a partial role in hypertrophic chondrocytes.

  18. Biological and Chemical Removal of Primary Cilia Affects Mechanical Activation of Chondrogenesis Markers in Chondroprogenitors and Hypertrophic Chondrocytes

    Directory of Open Access Journals (Sweden)

    Matthew E. Deren

    2016-02-01

    Full Text Available Chondroprogenitors and hypertrophic chondrocytes, which are the first and last stages of the chondrocyte differentiation process, respectively, are sensitive to mechanical signals. We hypothesize that the mechanical sensitivity of these cells depends on the cell surface primary cilia. To test this hypothesis, we removed the primary cilia by biological means with transfection with intraflagellar transport protein 88 (IFT88 siRNA or by chemical means with chloral hydrate treatment. Transfection of IFT88 siRNA significantly reduced the percentage of ciliated cells in both chondroprogenitor ATDC5 cells as well as primary hypertrophic chondrocytes. Cyclic loading (1 Hz, 10% matrix deformation of ATDC5 cells in three-dimensional (3D culture stimulates the mRNA levels of chondrogenesis marker Type II collagen (Col II, hypertrophic chondrocyte marker Type X collagen (Col X, and a molecular regulator of chondrogenesis and chondrocyte hypertrophy bone morphogenetic protein 2 (BMP-2. The reduction of ciliated chondroprogenitors abolishes mechanical stimulation of Col II, Col X, and BMP-2. In contrast, cyclic loading stimulates Col X mRNA levels in hypertrophic chondrocytes, but not those of Col II and BMP-2. Both biological and chemical reduction of ciliated hypertrophic chondrocytes reduced but failed to abolish mechanical stimulation of Col X mRNA levels. Thus, primary cilia play a major role in mechanical stimulation of chondrogenesis and chondrocyte hypertrophy in chondroprogenitor cells and at least a partial role in hypertrophic chondrocytes.

  19. Systematic reduction of complex tropospheric chemical mechanisms, Part II: Lumping using a time-scale based approach

    Directory of Open Access Journals (Sweden)

    L. E. Whitehouse

    2004-01-01

    Full Text Available This paper presents a formal method of species lumping that can be applied automatically to intermediate compounds within detailed and complex tropospheric chemical reaction schemes. The method is based on grouping species with reference to their chemical lifetimes and reactivity structures. A method for determining the forward and reverse transformations between individual and lumped compounds is developed. Preliminary application to the Leeds Master Chemical Mechanism (MCMv2.0 has led to the removal of 734 species and 1777 reactions from the scheme, with minimal degradation of accuracy across a wide range of test trajectories relevant to polluted tropospheric conditions. The lumped groups are seen to relate to groups of peroxy acyl nitrates, nitrates, carbonates, oxepins, substituted phenols, oxeacids and peracids with similar lifetimes and reaction rates with OH. In combination with other reduction techniques, such as sensitivity analysis and the application of the quasi-steady state approximation (QSSA, a reduced mechanism has been developed that contains 35% of the number of species and 40% of the number of reactions compared to the full mechanism. This has led to a speed up of a factor of 8 in terms of computer calculation time within box model simulations.

  20. Chemical, Mechanical, and Durability Properties of Concrete with Local Mineral Admixtures under Sulfate Environment in Northwest China.

    Science.gov (United States)

    Nie, Qingke; Zhou, Changjun; Shu, Xiang; He, Qiang; Huang, Baoshan

    2014-05-13

    Over the vast Northwest China, arid desert contains high concentrations of sulfate, chloride, and other chemicals in the ground water, which poses serious challenges to infrastructure construction that routinely utilizes portland cement concrete. Rapid industrialization in the region has been generating huge amounts of mineral admixtures, such as fly ash and slags from energy and metallurgical industries. These industrial by-products would turn into waste materials if not utilized in time. The present study evaluated the suitability of utilizing local mineral admixtures in significant quantities for producing quality concrete mixtures that can withstand the harsh chemical environment without compromising the essential mechanical properties. Comprehensive chemical, mechanical, and durability tests were conducted in the laboratory to characterize the properties of the local cementitious mineral admixtures, cement mortar and portland cement concrete mixtures containing these admixtures. The results from this study indicated that the sulfate resistance of concrete was effectively improved by adding local class F fly ash and slag, or by applying sulfate resistance cement to the mixtures. It is noteworthy that concrete containing local mineral admixtures exhibited much lower permeability (in terms of chloride ion penetration) than ordinary portland cement concrete while retaining the same mechanical properties; whereas concrete mixtures made with sulfate resistance cement had significantly reduced strength and much increased chloride penetration comparing to the other mixtures. Hence, the use of local mineral admixtures in Northwest China in concrete mixtures would be beneficial to the performance of concrete, as well as to the protection of environment.

  1. Mechanical properties of chemically bonded sand core materials dipped in sol-gel coating impregnated with filter

    DEFF Research Database (Denmark)

    Nwaogu, Ugochukwu Chibuzoh; Tiedje, Niels Skat

    2012-01-01

    A novel sol-gel coating impregnated with filter dust was applied on chemically bonded sand core materials by dipping. After curing, the strengths of the core materials were measured under uniaxial loading using a new strength testing machine (STM). The STM presents the loading history as a force-...... of the chemically bonded sand core materials, a combination of flexural and compression tests is suggested for improving the casting quality. © 2012 W. S. Maney & Son Ltd.......A novel sol-gel coating impregnated with filter dust was applied on chemically bonded sand core materials by dipping. After curing, the strengths of the core materials were measured under uniaxial loading using a new strength testing machine (STM). The STM presents the loading history as a force...... the strengths were increased under compression. The mode of fracture of the chemically bonded sand core materials was observed to be intergranular through the binder. The stiffness of the chemically bonded sand core materials was determined. For better understanding of the mechanical properties...

  2. Family matters: effect of host plant variation in chemical and mechanical defenses on a sequestering specialist herbivore.

    Science.gov (United States)

    Dimarco, Romina D; Nice, Chris C; Fordyce, James A

    2012-11-01

    Insect herbivores contend with various plant traits that are presumed to function as feeding deterrents. Paradoxically, some specialist insect herbivores might benefit from some of these plant traits, for example by sequestering plant chemical defenses that herbivores then use as their own defense against natural enemies. Larvae of the butterfly species Battus philenor (L.) (Papilionidae) sequester toxic alkaloids (aristolochic acids) from their Aristolochia host plants, rendering larvae and adults unpalatable to a broad range of predators. We studied the importance of two putative defensive traits in Aristolochia erecta: leaf toughness and aristolochic acid content, and we examined the effect of intra- and interplant chemical variation on the chemical phenotype of B. philenor larvae. It has been proposed that genetic variation for sequestration ability is "invisible to natural selection" because intra- and interindividual variation in host-plant chemistry will largely eliminate a role for herbivore genetic variation in determining an herbivore's chemical phenotype. We found substantial intra- and interplant variation in leaf toughness and in the aristolochic acid chemistry in A. erecta. Based on field observations and laboratory experiments, we showed that first-instar larvae preferentially fed on less tough, younger leaves and avoided tougher, older leaves, and we found no evidence that aristolochic acid content influenced first-instar larval foraging. We found that the majority of variation in the amount of aristolochic acid sequestered by larvae was explained by larval family, not by host-plant aristolochic acid content. Heritable variation for sequestration is the predominant determinant of larval, and likely adult, chemical phenotype. This study shows that for these highly specialized herbivores that sequester chemical defenses, traits that offer mechanical resistance, such as leaf toughness, might be more important determinants of early-instar larval

  3. Defence biochemical mechanisms of the organisms against chemical pollution and ionizing radiations

    International Nuclear Information System (INIS)

    Olinescu, Radu

    2001-01-01

    Acute exposure to high concentrations / doses of chemical pollutants and ionizing radiation usually kills giving no chance for survival, if not immediately, than later followed by specific diseases. Fortunately, this acute exposure is accidental, but chronic, low level exposure is also damaging. The involvement of pollution, especially of chemically produced, one in the etiology of several diseases is still under intensive research. Compared to other kinds of pollution (radioactive, microbiological), the chemical one seldom kills suddenly; it acts slowly, silently, by accumulation into the tissues, eventually inducing a failure of certain organ. The body is continuously adapting to low level concentrations of chemicals from environment until a certain threshold. All organisms, including humans, have a limited capacity of resisting the effects of various types of pollutants. Extensive laboratory research, demonstrated that most of damaging organic pollutants cause the formation of free radicals when they penetrate into the body and are metabolized. Free radicals are very reactive and are known to damage tissues with potentially fatal results. Substantial experimental evidence in recent years has demonstrated that all organisms are endowed with versatile, efficient antioxidant systems, that provide protection against the formation or effects of free radicals. However, the antioxidant systems are limited and when their capacity of protection is exceeded, injury resulting in illness or death occurs. In most cases, the harmful effects of chemicals on organisms depend on the biotransformation step, where free radicals are produced as byproducts of the metabolic reactions. The damaging effects of chemical pollutants are mostly restricted to an important organ depending on the way of penetration, nature of the compound and concentration. The organisms possess specific and nonspecific defense systems, which act from the exposure step, with attempt to block the entry of

  4. The underlying toxicological mechanism of chemical mixtures: A case study on mixture toxicity of cyanogenic toxicants and aldehydes to Photobacterium phosphoreum

    Energy Technology Data Exchange (ETDEWEB)

    Tian, Dayong [State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092 (China); Department of Chemical and Environmental Engineering, Anyang Institute of Technology, Anyang 455000 (China); Lin, Zhifen, E-mail: lzhifen@tongji.edu.cn [State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092 (China); Zhou, Xianghong [Department of Public Management, Tongji University, Shanghai 200092 (China); Yin, Daqiang [Key Laboratory of Yangtze River Water Environment, Ministry of Education, College of Environmental Science and Engineering, Tongji University, Shanghai 200092 (China)

    2013-10-15

    Intracellular chemical reaction of chemical mixtures is one of the main reasons that cause synergistic or antagonistic effects. However, it still remains unclear what the influencing factors on the intracellular chemical reaction are, and how they influence on the toxicological mechanism of chemical mixtures. To reveal this underlying toxicological mechanism of chemical mixtures, a case study on mixture toxicity of cyanogenic toxicants and aldehydes to Photobacterium phosphoreum was employed, and both their joint effects and mixture toxicity were observed. Then series of two-step linear regressions were performed to describe the relationships between joint effects, the expected additive toxicities and descriptors of individual chemicals (including concentrations, binding affinity to receptors, octanol/water partition coefficients). Based on the quantitative relationships, the underlying joint toxicological mechanisms were revealed. The result shows that, for mixtures with their joint effects resulting from intracellular chemical reaction, their underlying toxicological mechanism depends on not only their interaction with target proteins, but also their transmembrane actions and their concentrations. In addition, two generic points of toxicological mechanism were proposed including the influencing factors on intracellular chemical reaction and the difference of the toxicological mechanism between single reactive chemicals and their mixtures. This study provided an insight into the understanding of the underlying toxicological mechanism for chemical mixtures with intracellular chemical reaction. - Highlights: • Joint effects of nitriles and aldehydes at non-equitoxic ratios were determined. • A novel descriptor, ligand–receptor interaction energy (E{sub binding}), was employed. • Quantitative relationships for mixtures were developed based on a novel descriptor. • The underlying toxic mechanism was revealed based on quantitative relationships. • Two

  5. The underlying toxicological mechanism of chemical mixtures: A case study on mixture toxicity of cyanogenic toxicants and aldehydes to Photobacterium phosphoreum

    International Nuclear Information System (INIS)

    Tian, Dayong; Lin, Zhifen; Zhou, Xianghong; Yin, Daqiang

    2013-01-01

    Intracellular chemical reaction of chemical mixtures is one of the main reasons that cause synergistic or antagonistic effects. However, it still remains unclear what the influencing factors on the intracellular chemical reaction are, and how they influence on the toxicological mechanism of chemical mixtures. To reveal this underlying toxicological mechanism of chemical mixtures, a case study on mixture toxicity of cyanogenic toxicants and aldehydes to Photobacterium phosphoreum was employed, and both their joint effects and mixture toxicity were observed. Then series of two-step linear regressions were performed to describe the relationships between joint effects, the expected additive toxicities and descriptors of individual chemicals (including concentrations, binding affinity to receptors, octanol/water partition coefficients). Based on the quantitative relationships, the underlying joint toxicological mechanisms were revealed. The result shows that, for mixtures with their joint effects resulting from intracellular chemical reaction, their underlying toxicological mechanism depends on not only their interaction with target proteins, but also their transmembrane actions and their concentrations. In addition, two generic points of toxicological mechanism were proposed including the influencing factors on intracellular chemical reaction and the difference of the toxicological mechanism between single reactive chemicals and their mixtures. This study provided an insight into the understanding of the underlying toxicological mechanism for chemical mixtures with intracellular chemical reaction. - Highlights: • Joint effects of nitriles and aldehydes at non-equitoxic ratios were determined. • A novel descriptor, ligand–receptor interaction energy (E binding ), was employed. • Quantitative relationships for mixtures were developed based on a novel descriptor. • The underlying toxic mechanism was revealed based on quantitative relationships. • Two generic

  6. Cation solvation with quantum chemical effects modeled by a size-consistent multi-partitioning quantum mechanics/molecular mechanics method.

    Science.gov (United States)

    Watanabe, Hiroshi C; Kubillus, Maximilian; Kubař, Tomáš; Stach, Robert; Mizaikoff, Boris; Ishikita, Hiroshi

    2017-07-21

    In the condensed phase, quantum chemical properties such as many-body effects and intermolecular charge fluctuations are critical determinants of the solvation structure and dynamics. Thus, a quantum mechanical (QM) molecular description is required for both solute and solvent to incorporate these properties. However, it is challenging to conduct molecular dynamics (MD) simulations for condensed systems of sufficient scale when adapting QM potentials. To overcome this problem, we recently developed the size-consistent multi-partitioning (SCMP) quantum mechanics/molecular mechanics (QM/MM) method and realized stable and accurate MD simulations, using the QM potential to a benchmark system. In the present study, as the first application of the SCMP method, we have investigated the structures and dynamics of Na + , K + , and Ca 2+ solutions based on nanosecond-scale sampling, a sampling 100-times longer than that of conventional QM-based samplings. Furthermore, we have evaluated two dynamic properties, the diffusion coefficient and difference spectra, with high statistical certainty. Furthermore the calculation of these properties has not previously been possible within the conventional QM/MM framework. Based on our analysis, we have quantitatively evaluated the quantum chemical solvation effects, which show distinct differences between the cations.

  7. Evaluation of reduced chemical kinetic mechanisms used for modeling mild combustion for natural gas

    Directory of Open Access Journals (Sweden)

    Hamdi Mohamed

    2009-01-01

    Full Text Available A numerical and parametric study was performed to evaluate the potential of reduced chemistry mechanisms to model natural gas chemistry including NOx chemistry under mild combustion mode. Two reduced mechanisms, 5-step and 9-step, were tested against the GRI-Mech3.0 by comparing key species, such as NOx, CO2 and CO, and gas temperature predictions in idealized reactors codes under mild combustion conditions. It is thus concluded that the 9-step mechanism appears to be a promising reduced mechanism that can be used in multi-dimensional codes for modeling mild combustion of natural gas.

  8. Mechanical and chemical analyses across dental porcelain fused to CP titanium or Ti6Al4V

    International Nuclear Information System (INIS)

    Souza, Júlio C.M.; Henriques, Bruno; Ariza, Edith; Martinelli, Antonio E.; Nascimento, Rubens M.; Silva, Filipe S.; Rocha, Luís A.; Celis, Jean-Pierre

    2014-01-01

    The aim of this study was to evaluate the evolution of mechanical properties and chemical variation across veneering dental porcelain fused to different titanium-based substrates. Test samples were synthesized by fusing dental feldspar-based porcelain onto commercially pure titanium grade II or Ti6Al4V alloy. Samples were cross-sectioned at angles of 10 and 90° to the interface plane. Afterwards, nanoindentation tests and Scanning Electron Microscopy (SEM) imaging coupled to an Energy Dispersive Spectroscopy (EDS) system were carried out across interfaces extending from the metal towards the porcelain area. Elemental diffusion profiles across the porcelain-to-metal interfaces were also obtained by EDS analysis. The mismatch in mechanical properties found in porcelain-to-Ti6Al4V interfaces was lower than that of porcelain-to-CP titanium. Cracking was noticed at low-thickness veneering dental porcelain regions after the nanoindentation tests of samples cross-sectioned at low angles to the interface plane. A wide reaction zone between titanium and porcelain as well as higher incidence of defects was noticed at the porcelain-to-CP titanium interfaces. This study confirmed Ti6Al4V as an improved alternative to CP-titanium as it showed to establish a better interface with the veneering dental porcelain considering the slight chemical interaction and the lower mechanical properties mismatch. The elastic modulus of porcelain-to-Ti6Al4V samples showed to be less sensitive to porcelain thickness variations. - Highlights: • This study reveals mechanical and chemical behaviors across porcelain/titanium interfaces. • Cracks were noticed after nanoindentation on thin porcelain layers. • Ti6Al4V/porcelain showed a better mechanical behavior than that at CP-Ti/porcelain

  9. The action of chemical and mechanical stresses on single and dual species biofilm removal of drinking water bacteria.

    Science.gov (United States)

    Gomes, I B; Lemos, M; Mathieu, L; Simões, M; Simões, L C

    2018-08-01

    The presence of biofilms in drinking water distribution systems (DWDS) is a global public health concern as they can harbor pathogenic microorganisms. Sodium hypochlorite (NaOCl) is the most commonly used disinfectant for microbial growth control in DWDS. However, its effect on biofilm removal is still unclear. This work aims to evaluate the effects of the combination of chemical (NaOCl) and mechanical stresses on the removal of single and dual species biofilms of two bacteria isolated from DWDS and considered opportunistic, Acinectobacter calcoaceticus and Stenotrophomonas maltophilia. A rotating cylinder reactor was successfully used for the first time in drinking water biofilm studies with polyvinyl chloride as substratum. The single and dual species biofilms presented different characteristics in terms of metabolic activity, mass, density, thickness and content of proteins and polysaccharides. Their complete removal was not achieved even when a high NaOCl concentrations and an increasing series of shear stresses (from 2 to 23Pa) were applied. In general, NaOCl pre-treatment did not improve the impact of mechanical stress on biofilm removal. Dual species biofilms were colonized mostly by S. maltophilia and were more susceptible to chemical and mechanical stresses than these single species. The most efficient treatment (93% biofilm removal) was the combination of NaOCl at 175mg·l -1 with mechanical stress against dual species biofilms. Of concern was the high tolerance of S. maltophilia to chemical and mechanical stresses in both single and dual species biofilms. The overall results demonstrate the inefficacy of NaOCl on biofilm removal even when combined with high shear stresses. Copyright © 2018 Elsevier B.V. All rights reserved.

  10. XPS, UV–vis spectroscopy and AFM studies on removal mechanisms of Si-face SiC wafer chemical mechanical polishing (CMP)

    International Nuclear Information System (INIS)

    Zhou, Yan; Pan, Guoshun; Shi, Xiaolei; Xu, Li; Zou, Chunli; Gong, Hua; Luo, Guihai

    2014-01-01

    Highlights: • CMP removal mechanism of Si-face SiC wafer is investigated through XPS analysis. • UV–vis spectroscopy is used to study CMP removal mechanisms. • CMP removal model of Si-face SiC wafer is proposed. • The variations of atomic step morphology on ultra-smooth surface via AFM is studied. - Abstract: Chemical mechanical polishing (CMP) removal mechanisms of on-axis Si-face SiC wafer have been investigated through X-ray photoelectron spectroscopy (XPS), UV–visible (UV–vis) spectroscopy and atomic force microscopy (AFM). XPS results indicate that silicon oxide is formed on Si-face surface polished by the slurry including oxidant H 2 O 2 , but not that after immersing in H 2 O 2 solution. UV–vis spectroscopy curves prove that • OH hydroxyl radical could be generated only under CMP polishing by the slurry including H 2 O 2 and abrasive, so as to promote oxidation of Si-face to realize the effective removal; meanwhile, alkali KOH during CMP could induce the production of more radicals to improve the removal. On the other side, ultra-smooth polished surface with atomic step structure morphology and extremely low Ra of about 0.06 nm (through AFM) is obtained using the developed slurry with silica nanoparticle abrasive. Through investigating the variations of the atomic step morphology on the surface polished by different slurries, it's reveals that CMP removal mechanism involves a simultaneous process of surface chemical reaction and nanoparticle atomic scale abrasion

  11. Coupling between chemical degradation and mechanical behaviour of leached concrete; Couplage degradation chimique - comportement en compression du beton

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, V H

    2005-10-15

    This work is in the context of the long term behavior of concrete employed in radioactive waste disposal. The objective is to study the coupled chemo-mechanical modelling of concrete. In the first part of this contribution, experimental investigations are described where the effects of the calcium leaching process of concrete on its mechanical properties are highlighted. An accelerated method has been chosen to perform this leaching process by using an ammonium nitrate solution. In the second part, we present a coupled phenomenological chemo-mechanical model that represents the degradation of concrete materials. On one hand, the chemical behavior is described by the simplified calcium leaching approach of cement paste and mortar. Then a homogenization approach using the asymptotic development is presented to take into account the influence of the presence of aggregates in concrete. And on the other hand, the mechanical part of the modelling is given. Here continuum damage mechanics is used to describe the mechanical degradation of concrete. The growth of inelastic strains observed during the mechanical tests is describes by means of a plastic like model. The model is established on the basis of the thermodynamics of irreversible processes framework. The coupled nonlinear problem at hand is addressed within the context of the finite element method. Finally, numerical simulations are compared with the experimental results for validation. (author)

  12. Chemical grafting of the superhydrophobic surface on copper with hierarchical microstructure and its formation mechanism

    Science.gov (United States)

    Cai, Junyan; Wang, Shuhui; Zhang, Junhong; Liu, Yang; Hang, Tao; Ling, Huiqin; Li, Ming

    2018-04-01

    In this paper, a superhydrophobic surface with hierarchical structure was fabricated by chemical deposition of Cu micro-cones array, followed by chemical grafting of poly(methyl methacrylate) (PMMA). Water contact measurements give contact angle of 131.0° on these surfaces after PMMA grafting of 2 min and 165.2° after 6 min. The superhydrophobicity results from two factors: (1) the hierarchical structure due to Cu micro-cones array and the second level structure caused by intergranular corrosion during grafting of PMMA (confirmed by the scanning electron microscopy) and (2) the chemical modification of a low surface energy PMMA layer (confirmed by Fourier transform infrared spectrometer and X-ray photoelectron spectroscopy). In the chemical grafting process, the spontaneous reduction of nitrobenzene diazonium (NBD) tetrafluoroborate not only causes the corrosion of the Cu surface that leads to a hierarchical structure, but also initiates the polymerization of methyl methacrylate (MMA) monomers and thus the low free energy surface. Such a robust approach to fabricate the hierarchical structured surface with superhydrophobicity is expected to have practical application in anti-corrosion industry.

  13. Environmental chemicals and their effects on female reproductive health: Searching for molecular mechanisms and effect biomarkers

    DEFF Research Database (Denmark)

    Johansson, Hanna Katarina Lilith

    Incorrect developmental programming of the female reproductive tract can lead to compromised reproductive fitness later in life. It has been suggested that exposure to endocrine disrupting chemicals (EDCs) in utero can disrupt ovarian programming in humans, which is supported by several animal st...

  14. Mechanisms governing the physico-chemical processes of transfer in NPP circuits

    International Nuclear Information System (INIS)

    Brusakov, V.P.; Sedov, V.M.; Khitrov, Yu.A.; Rybalchenko, I.L.

    1983-01-01

    The paper deals with the theoretical physico-chemical processes of corrosion products and their radionuclide transport in NPS circuits by thermoelectromotive and electromotive forces of microgalvanic couples. The laboratory and rig test results as well as the NPP operating experience data confirm the developed theoretical concept validity

  15. Enhancement of mechanical properties and interfacial adhesion by chemical odification of natural fibre reinforced polypropylene composites

    CSIR Research Space (South Africa)

    Erasmus, E

    2008-11-01

    Full Text Available with the polymer matrix. Therefore, the constituents need to be chemically modified to enhancing adhesion between fibre and polymer matrix. The aim of this work is to improve the interfacial adhesion between the polypropylene matrix and the natural fibre...

  16. Hazard characterisation of chemicals in food and diet : dose response, mechanisms and extrapolation issues

    NARCIS (Netherlands)

    Dybing, E.; Doe, J.; Groten, J.; Kleiner, J.; O'Brien, J.; Renwick, A.G.; Schlatter, J.; Steinberg, P.; Tritscher, A.; Walker, R.; Younes, M.

    2002-01-01

    Hazard characterisation of low molecular weight chemicals in food and diet generally use a no-observed-adverse-effect level (NOAEL) or a benchmark dose as the starting point. For hazards that are considered not to have thresholds for their mode of action, low-dose extrapolation and other modelling

  17. Impact of supersonic and subsonic aircraft on ozone: Including heterogeneous chemical reaction mechanisms

    International Nuclear Information System (INIS)

    Kinnison, D.E.; Wuebbles, D.J.

    1992-01-01

    Preliminary calculations suggest that heterogeneous reactions are important in calculating the impact on ozone from emissions of trace gases from aircraft fleets. In this study, three heterogeneous chemical processes that occur on background sulfuric acid aerosols are included and their effects on O 3 , NO x , Cl x , HCl, N 2 O 5 , ClONO 2 are calculated

  18. Mechanisms of chemical generation of volatile hydrides for trace element determination (IUPAC Technical Report)

    Czech Academy of Sciences Publication Activity Database

    D'Ulivo, A.; Dědina, Jiří; Mester, Z.; Sturgeon, R. E.; Wang, Q.; Welz, B.

    2011-01-01

    Roč. 83, č. 6 (2011), s. 1283-1340 ISSN 0033-4545 Institutional research plan: CEZ:AV0Z40310501 Keywords : borane complexes * chemical generation of volatile hydrides (CHG) * volatile hydrides Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 2.789, year: 2011

  19. EFFECT OF REMOVING OLEORESIN WITH VARIOUS CHEMICAL COMPOUNDS ON PHYSICAL AND MECHANICAL PROPERTIES OF KERUING WOOD (DIPTEROCARPUS SPP.

    Directory of Open Access Journals (Sweden)

    Bambang Wiyono

    2007-03-01

    Full Text Available Keruing  (Dipterocarpus spp.  was  the  second  important  wood  export of   Indonesia. Unfortunately, this wood contains oleoresin that hinders its utilization. Currently, the method used to remove oleoresin from keruing is by soaking it into bollied sodium salt solution. Result of  this method is unsatisfactory because the residual heavy oleoresin might still appear on the wood surface. The study was conducted to determine suitable chemical compounds for removing oleoresin from keruing, and the effects on physical and mechanical properties of the wood. Four types of chemical compounds were tested, i.e. sodium chloride, oxalic acid, sulfuric acid, and nitric acid, each at the concentrations of  0.5 percent, 1.0 percent, and 1.5 percent. Wood samples were soaked in the boiling solution at different concentration level for seven hours. When the solution cooled down, the oleoresin exudated out of  the wood samples was separated. The oleoresin was weighed for recovery determination after air dried, and the wood samples were cut into smaller-sized specimens for the physical and mechanical testing (MOE, MOR, compression parallel to grain, hardness and density. Results showed that sulfuric acid was the best chemical compound for removing oleoresin, and the higher the concentration the greater the oleoresin recovery. The second best chemical compound was nitric acid at an optimum concentration of one percent. The soaking of keruing in sulfuric acid and oxalic acid solution resulted in paler wood color compare with the untreated wood sample. Nitric acid solutions caused the color of the wood surface to turn into yellow brownish. The physical and mechanical properties (MOE, MOR, compression parallel to grain, hardness and density of the oleoresin-removed keruing were slightly lower than the untreated (control samples.

  20. Magnetic isotope effect and theory of atomic orbital hybridization to predict a mechanism of chemical exchange reactions.

    Science.gov (United States)

    Epov, Vladimir N

    2011-08-07

    A novel approach is suggested to investigate the mechanisms of chemical complexation reactions based on the results of Fujii with co-workers; they have experimentally observed that several metals and metalloids demonstrate mass-independent isotope fractionation during the reactions with the DC18C6 crown ether using solvent-solvent extraction. In this manuscript, the isotope fractionation caused by the magnetic isotope effect is used to understand the mechanisms of chemical exchange reactions. Due to the rule that reactions are allowed for certain electron spin states, and forbidden for others, magnetic isotopes show chemical anomalies during these reactions. Mass-independent fractionation is suggested to take place due to the hyperfine interaction of the nuclear spin with the electron spin of the intermediate product. Moreover, the sign of the mass-independent fractionation is found to be dependent on the element and its species, which is also explained by the magnetic isotope effect. For example, highly negative mass-independent isotope fractionation of magnetic isotopes was observed for reactions of DC18C6 with SnCl(2) species and with several Ru(III) chloro-species, and highly positive for reactions of this ether with TeCl(6)(2-), and with several Cd(II) and Pd(II) species. The atomic radius of an element is also a critical parameter for the reaction with crown ether, particularly the element ions with [Kr]4d(n)5s(m) electron shell fits the best with the DC18C6 crown ring. It is demonstrated that the magnetic isotope effect in combination with the theory of orbital hybridization can help to understand the mechanism of complexation reactions. The suggested approach is also applied to explain previously published mass-independent fractionation of Hg isotopes in other types of chemical exchange reactions. This journal is © the Owner Societies 2011

  1. Synthesis and growth mechanism of Fe-catalyzed carbon nanotubes by plasma-enhanced chemical vapor deposition

    International Nuclear Information System (INIS)

    Jiang Jun; Feng Tao; Cheng Xinhong; Dai Lijuan; Cao Gongbai; Jiang Bingyao; Wang Xi; Liu Xianghuai; Zou Shichang

    2006-01-01

    Plasma-enhanced chemical vapor deposition (PECVD) was used to grow Fe-catalyzed carbon nanotubes (CNTs). The nanotubes had a uniform diameter in the range of about 10-20 nm. A base growth mode was responsible for the CNTs growth using a mixture of H 2 (60 sccm) and C 2 H 2 (15 sccm). For a mixture of H 2 (100 sccm) and C 2 H 2 (25 sccm), a complicated growth mechanism took place involving both the base growth and the tip growth. X-ray photoelectron spectroscopy measurements revealed that the grown CNTs contained C-H covalent bonds and Fe-C bonds located at the interface between them and the substrates. The factors determining the growth mechanism of CNTs are discussed and their growth mechanisms with the different gas ratios are suggested

  2. The Neurobiological Mechanism of Chemical Aversion (Emetic Therapy for Alcohol Use Disorder: An fMRI Study

    Directory of Open Access Journals (Sweden)

    Ralph L. Elkins

    2017-09-01

    Full Text Available A recent NIH epidemiology study found the lifetime prevalence of alcohol use disorder in the United States to be 29%. Alcohol drinking behavior is strongly “learned” via pleasure center activation/reinforcement. Alcohol craving is a powerful desire to drink alcoholic beverages. Craving was added as one of the defining criteria for alcohol use disorder in DSM5, and craving reduction is becoming an increasingly important treatment goal. In the current study, patients with alcohol use disorder received 10 days of inpatient multi-modal treatments at Schick Shadel Hospital (SSH of Seattle. The treatments included five chemical aversion conditioning sessions that associated alcohol cues (and alcohol with nausea and emesis. All patients met DSM4 criteria for alcohol use disorder, were heavy drinkers, and reported craving alcohol pre-treatment. Craving reduction was one of the primary treatment goals. This is the first fMRI study to measure the effects of chemical aversion therapy on alcohol craving-related brain activity. Patients were recruited as subjects for the University of Washington (UW brain scan study following SSH admission but before treatment onset. Prior to treatment, patients reported craving/desire for alcohol. After treatment (after four SSH chemical aversion treatments, again after five SSH chemical treatments, 30 and 90-days post-discharge, these same patients reported avoidance/aversion to alcohol. Most of the participants (69% reported being still sober 12 months post-treatment. Consistent with a craving reduction mechanism of how chemical aversion therapy facilitates sobriety, results of the UW fMRI brain scans showed significant pre- to post-treatment reductions in craving-related brain activity in the occipital cortex. Additional fMRI brain scan studies are needed to further explore the neurobiological mechanism of chemical aversion therapy treatment for alcohol use disorder, and other substance use disorders for which

  3. Chemical Kinetics for Bridging Molecular Mechanisms and Macroscopic Measurements of Amyloid Fibril Formation.

    Science.gov (United States)

    Michaels, Thomas C T; Šarić, Anđela; Habchi, Johnny; Chia, Sean; Meisl, Georg; Vendruscolo, Michele; Dobson, Christopher M; Knowles, Tuomas P J

    2018-04-20

    Understanding how normally soluble peptides and proteins aggregate to form amyloid fibrils is central to many areas of modern biomolecular science, ranging from the development of functional biomaterials to the design of rational therapeutic strategies against increasingly prevalent medical conditions such as Alzheimer's and Parkinson's diseases. As such, there is a great need to develop models to mechanistically describe how amyloid fibrils are formed from precursor peptides and proteins. Here we review and discuss how ideas and concepts from chemical reaction kinetics can help to achieve this objective. In particular, we show how a combination of theory, experiments, and computer simulations, based on chemical kinetics, provides a general formalism for uncovering, at the molecular level, the mechanistic steps that underlie the phenomenon of amyloid fibril formation.

  4. Chemical Kinetics for Bridging Molecular Mechanisms and Macroscopic Measurements of Amyloid Fibril Formation

    Science.gov (United States)

    Michaels, Thomas C. T.; Šarić, Anđela; Habchi, Johnny; Chia, Sean; Meisl, Georg; Vendruscolo, Michele; Dobson, Christopher M.; Knowles, Tuomas P. J.

    2018-04-01

    Understanding how normally soluble peptides and proteins aggregate to form amyloid fibrils is central to many areas of modern biomolecular science, ranging from the development of functional biomaterials to the design of rational therapeutic strategies against increasingly prevalent medical conditions such as Alzheimer's and Parkinson's diseases. As such, there is a great need to develop models to mechanistically describe how amyloid fibrils are formed from precursor peptides and proteins. Here we review and discuss how ideas and concepts from chemical reaction kinetics can help to achieve this objective. In particular, we show how a combination of theory, experiments, and computer simulations, based on chemical kinetics, provides a general formalism for uncovering, at the molecular level, the mechanistic steps that underlie the phenomenon of amyloid fibril formation.

  5. Study of kinetics and mechanism of diazo compound reactions using nuclear chemical polarization

    International Nuclear Information System (INIS)

    Gragerov, I.P.; Levit, A.F.; Kiprianova, L.A.; Buchachenko, A.L.; Sterleva, T.G.

    1975-01-01

    It has been established that at the rate-determining steps of the radical reactions in which aniline interacts with isoamyl nitrite and substituted diazo salts interact with sodium methylate, tertiary fatty amines, or phosphinic acid, no transfer of a single electron occurs. The processes of single electron transfer do not seem to play a decisive role in the kinetics of most transformations of diazo compounds. Chemical nuclear polarization is shown to be suitable for kinetic studies of fast radical processes

  6. Combined Biological and Chemical Mechanisms for Degradation of Insensitive Munitions in the Presence of Alternate Explosives

    Science.gov (United States)

    2017-06-21

    substrate for respiration or fermentation , a process called endogenous respiration and endogenous fermentation respectively. In most treatments with...commercial product, process , or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement...showed that DNAN can be readily reduced by chemical and biological processes at pH 7 within 24 hours, and at pH 8 and 9 in

  7. Reduced chemical mechanisms for ammonia/methane co-firing for gas turbine applications

    OpenAIRE

    Xiao, Hua; Howard, M.S.; Valera Medina, Agustin; Dooley, S.; Bowen, Philip John

    2017-01-01

    Energy storage is one of the major challenges facing the world towards its challenging 2050 climate-change targets. A potential enabler of a low-carbon economy is the energy vector hydrogen. However, issues associated with hydrogen have led to consider other molecules such as ammonia as a potential candidate for chemical storage. Apart from its relatively high stability under atmospheric temperature, ammonia has the added attraction that it can also be sold on international markets or be used...

  8. Theoretical studies of surface enhanced hyper-Raman spectroscopy: The chemical enhancement mechanism

    Science.gov (United States)

    Valley, Nicholas; Jensen, Lasse; Autschbach, Jochen; Schatz, George C.

    2010-08-01

    Hyper-Raman spectra for pyridine and pyridine on the surface of a tetrahedral 20 silver atom cluster are calculated using static hyperpolarizability derivatives obtained from time dependent density functional theory. The stability of the results with respect to choice of exchange-correlation functional and basis set is verified by comparison with experiment and with Raman spectra calculated for the same systems using the same methods. Calculated Raman spectra were found to match well with experiment and previous theoretical calculations. The calculated normal and surface enhanced hyper-Raman spectra closely match experimental results. The chemical enhancement factors for hyper-Raman are generally larger than for Raman (102-104 versus 101-102). Integrated hyper-Raman chemical enhancement factors are presented for a set of substituted pyridines. A two-state model is developed to predict these chemical enhancement factors and this was found to work well for the majority of the molecules considered, providing a rationalization for the difference between hyper-Raman and Raman enhancement factors.

  9. Study of the mechanism of radiation-chemical transformations in rubber-resinous materials

    International Nuclear Information System (INIS)

    Sharova, L.B.; Astakhova, L.G. Trufanova, N.D.; Persinen, A.A.; Vasil'ev, I.A.

    1993-01-01

    Materials based on butadiene-nitrile rubbers reinforced by phenol-formaldehyde resins presently find wide application as reliable heat-insulating coatings for various metallic constructions and are utilized under exposure to ionizing radiation. In this connection, when estimating the assured lifetime of heat-insulating coatings, it is necessary to take into account the character and degree of their radiation-chemical transformations. The aim of the present work was to study the radiation-chemical transformations of materials based on a composite of butadiene-nitrile rubber and phenol-formaldehyde resin. The investigations were carried out on model materials S-O, S-25, S-100, S-130, and S-150 based on the SKN-40M rubber with a varied content of SF-010A brand phenol-formaldehyde resin, the content of which in parts by weight per 100 parts by weight of rubber is indicated in the specifications of the materials. The possible directions of the radiation-chemical transformations in the rubber-resinous vulcanizates were studied by the method of disrupted total internal reflection (MDTIR) IR spectroscopy

  10. Quantum mechanical model for the anticarcinogenic effect of extremely-low-frequency electromagnetic fields on early chemical hepatocarcinogenesis

    Science.gov (United States)

    Godina-Nava, Juan José; Torres-Vega, Gabino; López-Riquelme, Germán Octavio; López-Sandoval, Eduardo; Samana, Arturo Rodolfo; García Velasco, Fermín; Hernández-Aguilar, Claudia; Domínguez-Pacheco, Arturo

    2017-02-01

    Using the conventional Haberkorn approach, it is evaluated the recombination of the radical pair (RP) singlet spin state to study theoretically the cytoprotective effect of an extremely-low-frequency electromagnetic field (ELF-EMF) on early stages of hepatic cancer chemically induced in rats. The proposal is that ELF-EMF modulates the interconversion rate of singlet and triplet spin states of the RP populations modifying the products from the metabolization of carcinogens. Previously, we found that the daily treatment with ELF-EMF 120 Hz inhibited the number and area of preneoplastic lesions in chemical carcinogenesis. The singlet spin population is evaluated diagonalizing the spin density matrix through the Lanczos method in a radical pair mechanism (RPM). Using four values of the interchange energy, we have studied the variations over the singlet population. The low magnetic field effect as a test of the influence over the enzymatic chemical reaction is evaluated calculating the quantum yield. Through a bootstrap technique the range is found for the singlet decay rate for the process. Applying the quantum measurements concept, we addressed the impact toward hepatic cells. The result contributes to improving our understanding of the chemical carcinogenesis process affected by charged particles that damage the DNA.

  11. Impact of chemical treatments on the mechanical and water absorption properties of coconut fibre (Cocos nucifera reinforced polypropylene composites

    Directory of Open Access Journals (Sweden)

    Isiaka O. OLADELE

    2016-07-01

    Full Text Available In this work, chemically treated coconut fibres were used to reinforce Homopolymer Polypropylene in order to ascertain the effect of the treatments on the mechanical and water absorption properties of the composites produced. Coconut fibre was first extracted from its husk by soaking it in water and was dried before it was cut into 10 mm lengths. It was then chemically treated in alkali solution of sodium hydroxide (NaOH and potassium hydroxide (KOH in a shaker water bath. The treated coconut fibres were used as reinforcements in polypropylene matrix to produce composites of varied fibre weight contents; 2, 4, 6, 8 and 10 wt.%. Tensile and flexural properties were investigated using universal testing machine while water absorption test was carried out on the samples for 7 days. It was observed from the results that, NaOH treated samples gave the best tensile properties while KOH treated samples gave the best flexural and water repellent properties.

  12. On the mechanism of effective chemical reactions with turbulent mixing of reactants and finite rate of molecular reactions

    Energy Technology Data Exchange (ETDEWEB)

    Vorotilin, V. P., E-mail: VPVorotilin@yandex.ru [Russian Academy of Sciences, Institute of Applied Mechanics (Russian Federation)

    2017-01-15

    A generalization of the theory of chemical transformation processes under turbulent mixing of reactants and arbitrary values of the rate of molecular reactions is presented that was previously developed for the variant of an instantaneous reaction [13]. The use of the features of instantaneous reactions when considering the general case, namely, the introduction of the concept of effective reaction for the reactant volumes and writing a closing conservation equation for these volumes, became possible due to the partition of the whole amount of reactants into “active” and “passive” classes; the reactants of the first class are not mixed and react by the mechanism of instantaneous reactions, while the reactants of the second class approach each other only through molecular diffusion, and therefore their contribution to the reaction process can be neglected. The physical mechanism of reaction for the limit regime of an ideal mixing reactor (IMR) is revealed and described. Although formally the reaction rate in this regime depends on the concentration of passive fractions of the reactants, according to the theory presented, the true (hidden) mechanism of the reaction is associated only with the reaction of the active fractions of the reactants with vanishingly small concentration in the volume of the reactor. It is shown that the rate constant of fast chemical reactions can be evaluated when the mixing intensity of reactants is much less than that needed to reach the mixing conditions in an IMR.

  13. Chemical composition, water vapor permeability, and mechanical properties of yuba film influenced by soymilk depth and concentration.

    Science.gov (United States)

    Zhang, Siran; Lee, Jaesang; Kim, Yookyung

    2018-03-01

    Yuba is a soy protein-lipid film formed during heating of soymilk. This study described yuba as an edible film by analyzing its chemical composition, water vapor permeability (WVP), and mechanical properties. Three yuba films were prepared by using different concentrations and depths of soymilk: HS (86 g kg -1 and 2.3 cm), LS (70 g kg -1 and 2.3 cm), and LD (70 g kg -1 and 3.0 cm). As yuba was successively skimmed, the protein, lipid, and SH content decreased, but carbohydrate and SS content increased. Though both the initial concentration and the depth of soymilk affect the properties of the films, the depth of soymilk influences WVP and tensile strength (TS) more. The WVP of the HS and LS changed the least (13-17 g mm kPa -1 m -2 day 1 ), while that of the LD changed the most (13-35 g mm kPa -1 m -2 day -1 ). There were no differences (P > 0.05) in the TS between the HS and LS. LD had the greatest decrease of TS and the lowest TS among the groups. The earlier the yuba films were collected, the greater the elongation of the films was: 129% (HS), 113% (LS), and 155% (LD). The initial concentration and the depth of soymilk changed the chemical composition and structure of the yuba films. The LS yuba produced more uniform edible films with good mechanical properties. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

  14. Effect of in vitro enzymatic degradation on 3D printed poly(ε-caprolactone) scaffolds: morphological, chemical and mechanical properties.

    Science.gov (United States)

    Ferreira, Joana; Gloria, Antonio; Cometa, Stefania; Coelho, Jorge F J; Domingos, Marco

    2017-07-27

    In recent years, the tissue engineering (TE) field has significantly benefited from advanced techniques such as additive manufacturing (AM), for the design of customized 3D scaffolds with the aim of guided tissue repair. Among the wide range of materials available to biomanufacture 3D scaffolds, poly(ε-caprolactone) (PCL) clearly arises as the synthetic polymer with the greatest potential, due to its unique properties - namely, biocompatibility, biodegradability, thermal and chemical stability and processability. This study aimed for the first time to investigate the effect of pore geometry on the in vitro enzymatic chain cleavage mechanism of PCL scaffolds manufactured by the AM extrusion process. Methods: Morphological properties of 3D printed PCL scaffolds before and after degradation were evaluated using Scanning Electron Microscopy (SEM) and micro-computed tomography (μ-CT). Differential Scanning Calorimetry (DSC) was employed to determine possible variations in the crystallinity of the scaffolds during the degradation period. The molecular weight was assessed using Size Exclusion Chromatography (SEC) while the mechanical properties were investigated under static compression conditions. Morphological results suggested a uniform reduction of filament diameter, while increasing the scaffolds' porosity. DSC analysis revealed and increment in the crystallinity degree while the molecular weight, evaluated through SEC, remained almost constant during the incubation period (25 days). Mechanical analysis highlighted a decrease in the compressive modulus and maximum stress over time, probably related to the significant weight loss of the scaffolds. All of these results suggest that PCL scaffolds undergo enzymatic degradation through a surface erosion mechanism, which leads to significant variations in mechanical, physical and chemical properties, but which has little influence on pore geometry.

  15. Effect of surface physical and chemical properties on interaction and annihilation mechanisms of positrons

    International Nuclear Information System (INIS)

    Gol'danskij, V.I.; Levin, B.M.; Shantarovich, V.P.

    1982-01-01

    The possibility of positron use is illustrated, to investigate physical and chemical properties of the surface, by a number of effects found by the authors while studying the interaction and annihilation of β + -decay positrons in highly-dispersed heterogeneous systems positronium formation and ortho-para conversion close to the surface of metal particles in a dielectric matrix, postronium oxidation by proton centers on the surface of an aluminosilicate catalyst). The ways, new in the main, are revealed to study the properties of the surface by the technique of monochromatic positron beams of low energy

  16. The structure and growth mechanism of Si nanoneedles prepared by plasma-enhanced chemical vapor deposition

    Czech Academy of Sciences Publication Activity Database

    Červenka, Jiří; Ledinský, Martin; Stuchlík, Jiří; Stuchlíková, The-Ha; Bakardjieva, Snejana; Hruška, Karel; Fejfar, Antonín; Kočka, Jan

    2010-01-01

    Roč. 21, č. 41 (2010), 415604/1-415604/7 ISSN 0957-4484 R&D Projects: GA MŠk(CZ) LC06040; GA AV ČR KAN400100701; GA MŠk LC510 EU Projects: European Commission(XE) 240826 - PolySiMode Institutional research plan: CEZ:AV0Z10100521; CEZ:AV0Z40320502 Keywords : nanoneedles * nanowires * silicon * plasma * chemical vapor deposition * crystal structure * growth * phonon * SEM * Raman Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.644, year: 2010

  17. ELECTROREDUCTION MECHANISM OF Ni(DMG)-2 COMPLEX STUDIED WITH QUANTUM CHEMICAL METHOD

    Institute of Scientific and Technical Information of China (English)

    倪亚明; 任镜清; 黎健; 王德民; 梁伟根; 朱芝仙; 高小霞

    1990-01-01

    The electronic structures of the species Ni(DMG)2, (Ni(DMG)2)- and (Ni(DMG)2)2- have been studied by INDO quantum chemical method. The results have clearly shown that in the first stage of the electroreduction of Ni(DMG)2, one electron interacts with the d orbitals on the nickel atom, while in the further stage the second electron interacts with the p orbitals on the nitrogen atoms. It conforms with our electrochemical experimental studies which showed that not only Ni(Ⅱ) is reduced but also DMG is catalytically reduced during the reduction of Ni(DMG)2.

  18. Development of a detailed chemical mechanism (MCMv3.1 for the atmospheric oxidation of aromatic hydrocarbons

    Directory of Open Access Journals (Sweden)

    C. Bloss

    2005-01-01

    Full Text Available The Master Chemical Mechanism has been updated from MCMv3 to MCMv3.1 in order to take into account recent improvements in the understanding of aromatic photo-oxidation. Newly available kinetic and product data from the literature have been incorporated into the mechanism. In particular, the degradation mechanisms for hydroxyarenes have been revised following the observation of high yields of ring-retained products, and product studies of aromatic oxidation under relatively low NOx conditions have provided new information on the branching ratios to first generation products. Experiments have been carried out at the European Photoreactor (EUPHORE to investigate key subsets of the toluene system. These results have been used to test our understanding of toluene oxidation, and, where possible, refine the degradation mechanisms. The evaluation of MCMv3 and MCMv3.1 using data on benzene, toluene, p-xylene and 1,3,5-trimethylbenzene photosmog systems is described in a companion paper, and significant model shortcomings are identified. Ideas for additional modifications to the mechanisms, and for future experiments to further our knowledge of the details of aromatic photo-oxidation are discussed.

  19. A Model to Couple Flow, Thermal and Reactive Chemical Transport, and Geo-mechanics in Variably Saturated Media

    Science.gov (United States)

    Yeh, G. T.; Tsai, C. H.

    2015-12-01

    This paper presents the development of a THMC (thermal-hydrology-mechanics-chemistry) process model in variably saturated media. The governing equations for variably saturated flow and reactive chemical transport are obtained based on the mass conservation principle of species transport supplemented with Darcy's law, constraint of species concentration, equation of states, and constitutive law of K-S-P (Conductivity-Degree of Saturation-Capillary Pressure). The thermal transport equation is obtained based on the conservation of energy. The geo-mechanic displacement is obtained based on the assumption of equilibrium. Conventionally, these equations have been implicitly coupled via the calculations of secondary variables based on primary variables. The mechanisms of coupling have not been obvious. In this paper, governing equations are explicitly coupled for all primary variables. The coupling is accomplished via the storage coefficients, transporting velocities, and conduction-dispersion-diffusion coefficient tensor; one set each for every primary variable. With this new system of equations, the coupling mechanisms become clear. Physical interpretations of every term in the coupled equations will be discussed. Examples will be employed to demonstrate the intuition and superiority of these explicit coupling approaches. Keywords: Variably Saturated Flow, Thermal Transport, Geo-mechanics, Reactive Transport.

  20. Chemical adhesion rather than mechanical retention enhances resin bond durability of a dental glass-ceramic with leucite crystallites

    International Nuclear Information System (INIS)

    Meng, X F; Yoshida, K; Gu, N

    2010-01-01

    This study aims to evaluate the effect of chemical adhesion by a silane coupler and mechanical retention by hydrofluoric acid (HFA) etching on the bond durability of resin to a dental glass ceramic with leucite crystallites. Half of the ceramic plates were etched with 4.8% HFA (HFA group) for 60 s, and the other half were not treated (NoHFA group). The scale of their surface roughness and rough area was measured by a 3D laser scanning microscope. These plates then received one of the following two bond procedures to form four bond test groups: HFA/cement, NoHFA/cement, HFA/silane/cement and NoHFA/silane/cement. The associated micro-shear bond strength and bond failure modes were tested after 0 and 30 000 thermal water bath cycles. Four different silane/cement systems (Monobond S/Variolink II, GC Ceramic Primer/Linkmax HV, Clearfil Ceramic Primer/Clearfil Esthetic Cement and Porcelain Liner M/SuperBond C and B) were used. The data for each silane/cement system were analyzed by three-way ANOVA. HFA treatment significantly increased the surface R a and R y values and the rough area of the ceramic plates compared with NoHFA treatment. After 30 000 thermal water bath cycles, the bond strength of all the test groups except the HFA/Linkmax HV group was significantly reduced, while the HFA/Linkmax HV group showed only adhesive interface failure. The other HFA/cement groups and all NoHFA/cement groups lost bond strength completely, and all NoHFA/silane/cement groups with chemical adhesion had significantly higher bond strength and more ceramic cohesive failures than the respective HFA/cement groups with mechanical retention. The result of the HFA/silane/cement groups with both chemical adhesion and mechanical retention revealed that HFA treatment could enhance the bond durability of resin/silanized glass ceramics, which might result from the increase of the chemical adhesion area on the ceramic rough surface and subsequently reduced degradation speed of the silane coupler

  1. Chemical adhesion rather than mechanical retention enhances resin bond durability of a dental glass-ceramic with leucite crystallites

    Energy Technology Data Exchange (ETDEWEB)

    Meng, X F [Department of Prosthodontics, The Stomatological Hospital Affiliated Medical School, Nanjing University, Nanjing 210008 (China); Yoshida, K [Division of Applied Prosthodontics, Graduate School of Biomedical Sciences, Nagasaki University, Nagasaki 852-8588 (Japan); Gu, N, E-mail: mengsoar@nju.edu.c [Jiangsu Key Laboratory for Biomaterials and Devices, School of Biological Science and Medical Engineering, Southeast University, Nanjing 210096 (China)

    2010-08-01

    This study aims to evaluate the effect of chemical adhesion by a silane coupler and mechanical retention by hydrofluoric acid (HFA) etching on the bond durability of resin to a dental glass ceramic with leucite crystallites. Half of the ceramic plates were etched with 4.8% HFA (HFA group) for 60 s, and the other half were not treated (NoHFA group). The scale of their surface roughness and rough area was measured by a 3D laser scanning microscope. These plates then received one of the following two bond procedures to form four bond test groups: HFA/cement, NoHFA/cement, HFA/silane/cement and NoHFA/silane/cement. The associated micro-shear bond strength and bond failure modes were tested after 0 and 30 000 thermal water bath cycles. Four different silane/cement systems (Monobond S/Variolink II, GC Ceramic Primer/Linkmax HV, Clearfil Ceramic Primer/Clearfil Esthetic Cement and Porcelain Liner M/SuperBond C and B) were used. The data for each silane/cement system were analyzed by three-way ANOVA. HFA treatment significantly increased the surface R{sub a} and R{sub y} values and the rough area of the ceramic plates compared with NoHFA treatment. After 30 000 thermal water bath cycles, the bond strength of all the test groups except the HFA/Linkmax HV group was significantly reduced, while the HFA/Linkmax HV group showed only adhesive interface failure. The other HFA/cement groups and all NoHFA/cement groups lost bond strength completely, and all NoHFA/silane/cement groups with chemical adhesion had significantly higher bond strength and more ceramic cohesive failures than the respective HFA/cement groups with mechanical retention. The result of the HFA/silane/cement groups with both chemical adhesion and mechanical retention revealed that HFA treatment could enhance the bond durability of resin/silanized glass ceramics, which might result from the increase of the chemical adhesion area on the ceramic rough surface and subsequently reduced degradation speed of the silane

  2. Review on mechanism of directly fabricating wafer-scale graphene on dielectric substrates by chemical vapor deposition

    Science.gov (United States)

    Ning, Jing; Wang, Dong; Chai, Yang; Feng, Xin; Mu, Meishan; Guo, Lixin; Zhang, Jincheng; Hao, Yue

    2017-07-01

    To date, chemical vapor deposition on transition metal catalysts is a potential way to achieve low cost, high quality and uniform wafer-scale graphene. However, the removal and transfer process of the annoying catalytic metals underneath can bring large amounts of uncertain factors causing the performance deterioration of graphene, such as the pollution of surface polymeric residues, unmentioned doping and structural damages. Thus, to develop a technique of directly fabricating graphene on dielectric substrates is quite meaningful. In this review, we will present specific methods of catalyst- or transfer-free techniques for graphene growth and discuss the diversity of growth mechanisms.

  3. Nonlinear Hamiltonian mechanics applied to molecular dynamics theory and computational methods for understanding molecular spectroscopy and chemical reactions

    CERN Document Server

    Farantos, Stavros C

    2014-01-01

    This brief presents numerical methods for describing and calculating invariant phase space structures, as well as solving the classical and quantum equations of motion for polyatomic molecules. Examples covered include simple model systems to realistic cases of molecules spectroscopically studied. Vibrationally excited and reacting molecules are nonlinear dynamical systems, and thus, nonlinear mechanics is the proper theory to elucidate molecular dynamics by investigating invariant structures in phase space. Intramolecular energy transfer, and the breaking and forming of a chemical bond have now found a rigorous explanation by studying phase space structures.

  4. Study of the Chemical Mechanism Involved in the Formation of Tungstite in Benzyl Alcohol by the Advanced QEXAFS Technique

    DEFF Research Database (Denmark)

    Olliges‐Stadler, Inga; Stötzel, Jan; Koziej, Dorota

    2012-01-01

    Insight into the complex chemical mechanism for the formation of tungstite nanoparticles obtained by the reaction of tungsten hexachloride with benzyl alcohol is presented herein. The organic and inorganic species involved in the formation of the nanoparticles were studied by time‐dependent gas......‐scanning extended X‐ray absorption fine structure spectroscopy enabled the time‐dependent evolution of the starting compound, the intermediates and the product to be monitored over the full reaction period. The reaction starts with fast chlorine substitution and partial reduction during the dissolution...

  5. Endocrine-disrupting chemicals-Mechanisms of action on male reproductive system.

    Science.gov (United States)

    Sidorkiewicz, Iwona; Zaręba, Kamil; Wołczyński, Sławomir; Czerniecki, Jan

    2017-07-01

    Endocrine-disrupting chemicals (EDCs) are exogenous compounds that can cause disturbances in the endocrine system and have multiple harmful effects on health by targeting different organs and systems in the human body. Mass industrial production and widespread use of EDCs have resulted in worldwide contamination. Accumulating evidence suggest that human exposure to EDCs is related to the impairment of male reproductive function and can interrupt other hormonally regulated metabolic processes, particularly if exposure occurs during early development. Investigation of studies absent in previous reviews and meta-analysis of adverse effects of EDCs on functioning of the male reproductive system is the core of this work. Four main modes of action of EDCs on male fertility have been summarized in this review. First, studies describing estrogen- pathway disturbing chemicals are investigated. Second, androgen-signaling pathway alterations and influence on androgen sensitive tissues are examined. Third, evaluation of steroidogenesis dysfunction is discussed by focusing on the steroid hormone biosynthesis pathway, which is targeted by EDCs. Last, the reportedly destructive role of reactive oxygen species (ROS) on sperm function is discussed. Spermatogenesis is a remarkably complex process, hence multiple studies point out various dysfunctions depending on the development state at which the exposure occurred. Collected data show the need to account for critical windows of exposure such as fetal, perinatal and pubertal periods as well as effects of mixtures of several compounds in future research.

  6. Investigation of the chemical mechanisms involved in the electropulsation of membranes at the molecular level.

    Science.gov (United States)

    Breton, Marie; Mir, Lluis M

    2018-02-01

    The chemical consequences of electropulsation on giant unilamellar vesicles (GUVs), in particular the possible oxidation of unsaturated phospholipids, have been investigated by mass spectrometry, flow cytometry and absorbance methods. Pulse application induced oxidation of the GUV phospholipids and the oxidation level depended on the duration of the pulse. Light and O 2 increased the level of pulse-induced lipid peroxidation whereas the presence of antioxidants either in the membrane or in the solution completely suppressed peroxidation. Importantly, pulse application did not create additional reactive oxygen species (ROS) in GUV-free solution. Lipid peroxidation seems to result from a facilitation of the lipid peroxidation by the ROS already present in the solution before pulsing, not from a direct pulse-induced peroxidation. The pulse would facilitate the entrance of ROS in the core of the membrane, allowing the contact between ROS and lipid chains and provoking the oxidation. Our findings demonstrate that the application of electric pulses on cells could induce the oxidation of the membrane phospholipids since cell membranes contain unsaturated lipids. The chemical consequences of electropulsation will therefore have to be taken into account in future biomedical applications of electropulsation since oxidized phospholipids play a key role in many signaling pathways and diseases. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Chemical functionalization of ceramic tile surfaces by silane coupling agents: polymer modified mortar adhesion mechanism implications

    Directory of Open Access Journals (Sweden)

    Alexandra Ancelmo Piscitelli Mansur

    2008-09-01

    Full Text Available Adhesion between tiles and mortars are crucial to the stability of ceramic tile systems. From the chemical point of view, weak forces such as van der Waals forces and hydrophilic interactions are expected to be developed preferably at the tiles and polymer modified Portland cement mortar interface. The main goal of this paper was to use organosilanes as primers to modify ceramic tile hydrophilic properties to improve adhesion between ceramic tiles and polymer modified mortars. Glass tile surfaces were treated with several silane derivatives bearing specific functionalities. Contact angle measurements and Fourier Transform Infrared Spectroscopy (FTIR were used for evaluating the chemical changes on the tile surface. In addition, pull-off tests were conducted to assess the effect on adhesion properties between tile and poly(ethylene-co-vinyl acetate, EVA, modified mortar. The bond strength results have clearly shown the improvement of adherence at the tile-polymer modified mortar interface, reflecting the overall balance of silane, cement and polymer interactions.

  8. Reduction and Uncertainty Analysis of Chemical Mechanisms Based on Local and Global Sensitivities

    Science.gov (United States)

    Esposito, Gaetano

    Numerical simulations of critical reacting flow phenomena in hypersonic propulsion devices require accurate representation of finite-rate chemical kinetics. The chemical kinetic models available for hydrocarbon fuel combustion are rather large, involving hundreds of species and thousands of reactions. As a consequence, they cannot be used in multi-dimensional computational fluid dynamic calculations in the foreseeable future due to the prohibitive computational cost. In addition to the computational difficulties, it is also known that some fundamental chemical kinetic parameters of detailed models have significant level of uncertainty due to limited experimental data available and to poor understanding of interactions among kinetic parameters. In the present investigation, local and global sensitivity analysis techniques are employed to develop a systematic approach of reducing and analyzing detailed chemical kinetic models. Unlike previous studies in which skeletal model reduction was based on the separate analysis of simple cases, in this work a novel strategy based on Principal Component Analysis of local sensitivity values is presented. This new approach is capable of simultaneously taking into account all the relevant canonical combustion configurations over different composition, temperature and pressure conditions. Moreover, the procedure developed in this work represents the first documented inclusion of non-premixed extinction phenomena, which is of great relevance in hypersonic combustors, in an automated reduction algorithm. The application of the skeletal reduction to a detailed kinetic model consisting of 111 species in 784 reactions is demonstrated. The resulting reduced skeletal model of 37--38 species showed that the global ignition/propagation/extinction phenomena of ethylene-air mixtures can be predicted within an accuracy of 2% of the full detailed model. The problems of both understanding non-linear interactions between kinetic parameters and

  9. Ionization mechanisms in capillary supercritical fluid chromatography-chemical ionization mass spectrometry

    NARCIS (Netherlands)

    Houben, R.J.; Leclercq, P.A.; Cramers, C.A.M.G.

    1991-01-01

    Ionization mechanisms have been studied for supercritical fluid chromatography (SFC) with mass spectrometric (MS) detection. One of the problems associated with SFC-MS is the interference of mobile phase constituents in the ionization process, which complicates the interpretation of the resulting

  10. Simulations of the dispersion of reactive pollutants in a street canyon, considering different chemical mechanisms and micromixing

    Science.gov (United States)

    Garmory, A.; Kim, I. S.; Britter, R. E.; Mastorakos, E.

    The Stochastic Fields (SF) or Field Monte Carlo method has been used to model the dispersion of reactive scalars in a street canyon, using a simple chemistry and the CBM-IV mechanism. SF is a Probability Density Function (PDF) method which allows both means and variances of the scalars to be calculated as well as considering the effect of segregation on reaction rates. It was found that the variance of reactive scalars such as NO 2 was very high in the mixing region at roof-top level with rms values of the order of the mean values. The effect of segregation on major species such as O 3 was found to be very small using either mechanism, however, some radical species in CBM-IV showed a significant difference. These were found to be the seven species with the fastest chemical timescales. The calculated photostationary state defect was also found to be in error when segregation is neglected.

  11. Kinetic mechanism of molecular energy transfer and chemical reactions in low-temperature air-fuel plasmas.

    Science.gov (United States)

    Adamovich, Igor V; Li, Ting; Lempert, Walter R

    2015-08-13

    This work describes the kinetic mechanism of coupled molecular energy transfer and chemical reactions in low-temperature air, H2-air and hydrocarbon-air plasmas sustained by nanosecond pulse discharges (single-pulse or repetitive pulse burst). The model incorporates electron impact processes, state-specific N(2) vibrational energy transfer, reactions of excited electronic species of N(2), O(2), N and O, and 'conventional' chemical reactions (Konnov mechanism). Effects of diffusion and conduction heat transfer, energy coupled to the cathode layer and gasdynamic compression/expansion are incorporated as quasi-zero-dimensional corrections. The model is exercised using a combination of freeware (Bolsig+) and commercial software (ChemKin-Pro). The model predictions are validated using time-resolved measurements of temperature and N(2) vibrational level populations in nanosecond pulse discharges in air in plane-to-plane and sphere-to-sphere geometry; temperature and OH number density after nanosecond pulse burst discharges in lean H(2)-air, CH(4)-air and C(2)H(4)-air mixtures; and temperature after the nanosecond pulse discharge burst during plasma-assisted ignition of lean H2-mixtures, showing good agreement with the data. The model predictions for OH number density in lean C(3)H(8)-air mixtures differ from the experimental results, over-predicting its absolute value and failing to predict transient OH rise and decay after the discharge burst. The agreement with the data for C(3)H(8)-air is improved considerably if a different conventional hydrocarbon chemistry reaction set (LLNL methane-n-butane flame mechanism) is used. The results of mechanism validation demonstrate its applicability for analysis of plasma chemical oxidation and ignition of low-temperature H(2)-air, CH(4)-air and C(2)H(4)-air mixtures using nanosecond pulse discharges. Kinetic modelling of low-temperature plasma excited propane-air mixtures demonstrates the need for development of a more accurate

  12. 3-D simulation of soot formation in a direct-injection diesel engine based on a comprehensive chemical mechanism and method of moments

    Science.gov (United States)

    Zhong, Bei-Jing; Dang, Shuai; Song, Ya-Na; Gong, Jing-Song

    2012-02-01

    Here, we propose both a comprehensive chemical mechanism and a reduced mechanism for a three-dimensional combustion simulation, describing the formation of polycyclic aromatic hydrocarbons (PAHs), in a direct-injection diesel engine. A soot model based on the reduced mechanism and a method of moments is also presented. The turbulent diffusion flame and PAH formation in the diesel engine were modelled using the reduced mechanism based on the detailed mechanism using a fixed wall temperature as a boundary condition. The spatial distribution of PAH concentrations and the characteristic parameters for soot formation in the engine cylinder were obtained by coupling a detailed chemical kinetic model with the three-dimensional computational fluid dynamic (CFD) model. Comparison of the simulated results with limited experimental data shows that the chemical mechanisms and soot model are realistic and correctly describe the basic physics of diesel combustion but require further development to improve their accuracy.

  13. In-Situ Ion Source Cleaning: Review of Chemical Mechanisms and Evaluation Data at Production Fabs

    International Nuclear Information System (INIS)

    Kaim, R.; Bishop, S.; Byl, O.; Eldridge, D.; Marganski, P.; Mayer, J.; Sweeney, J.; Yedave, S.; Fuchs, D.; Spreitzer, S.; Vogel, J.; Dunn, J.; Lundquist, P.; Rolland, J.; Romig, T.; Newman, D.; Mitchell, M.; Ditzler, K.

    2008-01-01

    Since the concept of chemical in-situ ion implanter cleaning was introduced at IIT2006 [1], evaluations of the XeF 2 cleaning technology have taken place or are ongoing at more than 40 production fabs worldwide. Testing has been focused on assessing effects of cleaning in the source arc chamber and extraction regions. In this paper we describe use of the cleaning technology in a production environment and summarize evaluation data showing advantages of the technology for improving ion source life, reducing glitching, improving beam auto-tuning and avoiding species cross-contamination. More details of the evaluations are given in several separate papers submitted to this Conference. We have supplemented the fab production data with laboratory experiments designed to investigate the reactivity of XeF 2 and fundamental aspects of the source deposition and cleaning processes. These experiments are summarized here, and more details can be found in separate papers submitted to this Conference

  14. Discovery of chemical oscillatory layering in adarce from Rehai, Tengchong, Yunnan and its genetic mechanism

    International Nuclear Information System (INIS)

    Wang Jianghai; Dong Jinquan

    1994-01-01

    Based on characteristics of mineral assemblages and compositions of sinter in several typical region, Western Yunnan, it is recognized that rhythmic compositional layering is widespread in sinter. According to self-organization theory and fluid dynamic experiments completed by predecessors, the authors have studied dynamic features of fluids in thermo-chamber; and concluded that in which double-diffusive convection layering would imperatively take place on the basis of estimation of dynamic parameters and determination of differences between RT and R0. Finally, a two-stage genetic model has been put forward for explaining the rhythmic layering in sinter, i.e. :1) double-diffusive convection of fluid in chambers was induced by the gradients of temperature and concentration; and 2) the rising of layered fluids and the precipitation of the chemical material occurred. Obviously, rhythmic layering in sinter is a typical self-organizational phenomenon

  15. Stress hysteresis and mechanical properties of plasma-enhanced chemical vapor deposited dielectric films

    Science.gov (United States)

    Thurn, Jeremy; Cook, Robert F.; Kamarajugadda, Mallika; Bozeman, Steven P.; Stearns, Laura C.

    2004-02-01

    A comprehensive survey is described of the responses of three plasma-enhanced chemical vapor deposited dielectric film systems to thermal cycling and indentation contact. All three films—silicon oxide, silicon nitride, and silicon oxy-nitride—exhibited significant nonequilibrium permanent changes in film stress on thermal cycling or annealing. The linear relationship between stress and temperature changed after the films were annealed at 300 °C, representing a structural alteration in the film reflecting a change in coefficient of thermal expansion or biaxial modulus. A double-substrate method was used to deduce both thermoelastic properties before and after the anneal of selected films and the results were compared with the modulus deconvoluted from small-scale depth-sensing indentation experiments (nanoindentation). Rutherford backscattering spectrometry and hydrogen forward scattering were used to deduce the composition of the films and it was found that all the films contained significant amounts of hydrogen.

  16. Thermal and chemical treatment of polymer optical fiber Bragg grating sensors for enhanced mechanical sensitivity

    DEFF Research Database (Denmark)

    Pospori, Andreas; Marques, C. A. F.; Saez-Rodriguez, D.

    2017-01-01

    An investigation of the thermal annealing effects on the strain, stress, and force sensitivities of polymer optical fiber Bragg grating sensors is performed. We demonstrate for the first time that the fiber annealing can enhance both stress and force sensitivities of Bragg grating sensors......, with the possible cause being the molecular relaxation of the polymer when fiber is raised above the β-transition temperature. A simple, cost-effective, but well controlled method for fiber annealing is also presented in this work. In addition, the effects of chemical etching on the strain, stress, and force...... sensitivities have been investigated. Results show that fiber etching too can increase the force sensitivity, and it can also affect the strain and stress sensitivities of the Bragg grating sensors....

  17. Thermal and chemical treatment of polymer optical fiber Bragg grating sensors for enhanced mechanical sensitivity

    Science.gov (United States)

    Pospori, A.; Marques, C. A. F.; Sáez-Rodríguez, D.; Nielsen, K.; Bang, O.; Webb, D. J.

    2017-07-01

    An investigation of the thermal annealing effects on the strain, stress, and force sensitivities of polymer optical fiber Bragg grating sensors is performed. We demonstrate for the first time that the fiber annealing can enhance both stress and force sensitivities of Bragg grating sensors, with the possible cause being the molecular relaxation of the polymer when fiber is raised above the β -transition temperature. A simple, cost-effective, but well controlled method for fiber annealing is also presented in this work. In addition, the effects of chemical etching on the strain, stress, and force sensitivities have been investigated. Results show that fiber etching too can increase the force sensitivity, and it can also affect the strain and stress sensitivities of the Bragg grating sensors.

  18. Thermal and mechanical behaviour of oxygen carrier materials for chemical looping combustion in a packed bed reactor

    International Nuclear Information System (INIS)

    Jacobs, M.; Van Noyen, J.; Larring, Y.; Mccann, M.; Pishahang, M.; Amini, S.; Ortiz, M.; Galluci, F.; Sint-Annaland, M.V.; Tournigant, D.; Louradour, E.; Snijkers, F.

    2015-01-01

    Highlights: • Ilmenite-based oxygen carriers were developed for packed-bed chemical looping. • Addition of Mn_2O_3 increased mechanical strength and microstructure of the carriers. • Oxygen carriers were able to withstand creep and thermal cycling up to 1200 °C. • Ilmenite-based granules are a promising shape for packed-bed reactor conditions. - Abstract: Chemical looping combustion (CLC) is a promising carbon capture technology where cyclic reduction and oxidation of a metallic oxide, which acts as a solid oxygen carrier, takes place. With this system, direct contact between air and fuel can be avoided, and so, a concentrated CO_2 stream is generated after condensation of the water in the exit gas stream. An interesting reactor system for CLC is a packed bed reactor as it can have a higher efficiency compared to a fluidized bed concept, but it requires other types of oxygen carrier particles. The particles must be larger to avoid a large pressure drop in the reactor and they must be mechanically strong to withstand the severe reactor conditions. Therefore, oxygen carriers in the shape of granules and based on the mineral ilmenite were subjected to thermal cycling and creep tests. The mechanical strength of the granules before and after testing was investigated by crush tests. In addition, the microstructure of these oxygen particles was studied to understand the relationship between the physical properties and the mechanical performance. It was found that the granules are a promising shape for a packed bed reactor as no severe degradation in strength was noticed upon thermal cycling and creep testing. Especially, the addition of Mn_2O_3 to the ilmenite, which leads to the formation of an iron–manganese oxide, seems to results in stronger granules than the other ilmenite-based granules.

  19. Optimization and analysis of large chemical kinetic mechanisms using the solution mapping method - Combustion of methane

    Science.gov (United States)

    Frenklach, Michael; Wang, Hai; Rabinowitz, Martin J.

    1992-01-01

    A method of systematic optimization, solution mapping, as applied to a large-scale dynamic model is presented. The basis of the technique is parameterization of model responses in terms of model parameters by simple algebraic expressions. These expressions are obtained by computer experiments arranged in a factorial design. The developed parameterized responses are then used in a joint multiparameter multidata-set optimization. A brief review of the mathematical background of the technique is given. The concept of active parameters is discussed. The technique is applied to determine an optimum set of parameters for a methane combustion mechanism. Five independent responses - comprising ignition delay times, pre-ignition methyl radical concentration profiles, and laminar premixed flame velocities - were optimized with respect to thirteen reaction rate parameters. The numerical predictions of the optimized model are compared to those computed with several recent literature mechanisms. The utility of the solution mapping technique in situations where the optimum is not unique is also demonstrated.

  20. Thermal-chemical-mechanical feedback during fluid-rock interactions: Implications for chemical transport and scales of equilibria in the crust

    International Nuclear Information System (INIS)

    Dutrow, Barbara

    2008-01-01

    Our research evaluates the hypothesis that feedback amongst thermal-chemical-mechanical processes operative in fluid-rock systems alters the fluid flow dynamics of the system which, in turn, affects chemical transport and temporal and spatial scales of equilibria, thus impacting the resultant mineral textural development of rocks. Our methods include computational experimentation and detailed analyses of fluid-infiltrated rocks from well-characterized terranes. This work focuses on metamorphic rocks and hydrothermal systems where minerals and their textures are utilized to evaluate pressure (P), temperature (T), and time (t) paths in the evolution of mountain belts and ore deposits, and to interpret tectonic events and the timing of these events. Our work on coupled processes also extends to other areas where subsurface flow and transport in porous media have consequences such as oil and gas movement, geothermal system development, transport of contaminants, nuclear waste disposal, and other systems rich in fluid-rock reactions. Fluid-rock systems are widespread in the geologic record. Correctly deciphering the products resulting from such systems is important to interpreting a number of geologic phenomena. These systems are characterized by complex interactions involving time-dependent, non-linear processes in heterogeneous materials. While many of these interactions have been studied in isolation, they are more appropriately analyzed in the context of a system with feedback. When one process impacts another process, time and space scales as well as the overall outcome of the interaction can be dramatically altered. Our goals to test this hypothesis are: to develop and incorporate algorithms into our 3D heat and mass transport code to allow the effects of feedback to be investigated numerically, to analyze fluid infiltrated rocks from a variety of terranes at differing P-T conditions, to identify subtle features of the infiltration of fluids and/or feedback, and

  1. Chemical structure, network topology, and porosity effects on the mechanical properties of Zeolitic Imidazolate Frameworks

    OpenAIRE

    Tan, J. C.; Bennett, T. D.; Cheetham, A. K.

    2010-01-01

    The mechanical properties of seven zeolitic imidazolate frameworks (ZIFs) based on five unique network topologies have been systematically characterized by single-crystal nanoindentation studies. We demonstrate that the elastic properties of ZIF crystal structures are strongly correlated to the framework density and the underlying porosity. For the systems considered here, the elastic modulus was found to range from 3 to 10 GPa, whereas the hardness property lies between 300 MPa and 1.1 GPa. ...

  2. Investigation research on the evaluation of a coupled thermo-hydro-mechanical-chemical phenomena. Outline report

    International Nuclear Information System (INIS)

    Chijimatsu, Masakazu; Amemiya, Kiyoshi; Neyama, Atsushi; Iwata, Hiroshi; Nakagawa, Koichi; Ishihara, Yoshinao; Shiozaki, Isao; Sagawa, Hiroshi

    2002-02-01

    In order to realize a coupling analysis in the near field of the geological disposal system, this study has been studied on the addition of the mass transport model to the coupled thermo-hydro-mechanical analysis code (THAMES) and preliminary coupling analysis by using development environmental tool (Diffpack) for numerical analysis. (1) In order to prepare the strategy on the addition of the mass transport model to the coupled thermo-hydro-mechanical analysis code (THAMES), we have studied on the requirement of THAMES-Transport and methodology of coupling analysis. After that we set out modification plan by the Eulerian-Lagrangian (EL) method. (2) Based on the document of modification plan, we have done addition of the mass transport model to the coupled thermo-hydro-mechanical analysis code (THAMES) and carried out verification analysis in order to confirm on the accuracy of THAMES-Transport. (3) In order to understand on the behavior of NaCl in the porewater under the coupled thermo-hydro-mechanical phenomena in the HLW engineered barrier system, we have calculated coupling phenomenon by using THAMES-Transport. Transportation and concentration phenomena of NaCl are calculated but precipitation of NaCl is not occurred under the analysis conditions in this report. (4) In order to confirm about feasibility of coupling analysis under the development environmental tool (Diffpack) for numerical analysis, we have carried out on the design work and writing program of the preliminary coupling system. In this study, we have adopted existing transport model (HYDROGEOCHEM) and geochemical model (phreeqe60) for preliminary coupling system. (5) In order to confirm program correctness of preliminary coupling system, we have carried out benchmarking analysis by using existing reactive-transport analysis code (HYDROGEOCHEM). (6) We have been prepared short-range development plan based on through the modification study of THAMES and writing program of the preliminary coupling

  3. Explodator: A new skeleton mechanism for the halate driven chemical oscillators

    Science.gov (United States)

    Noszticzius, Z.; Farkas, H.; Schelly, Z. A.

    1984-06-01

    In the first part of this work, some shortcomings in the present theories of the Belousov-Zhabotinskii oscillating reaction are discussed. In the second part, a new oscillatory scheme, the limited Explodator, is proposed as an alternative skeleton mechanism. This model contains an always unstable three-variable Lotka-Volterra core (the ``Explodator'') and a stabilizing limiting reaction. The new scheme exhibits Hopf bifurcation and limit cycle oscillations. Finally, some possibilities and problems of a generalization are mentioned.

  4. Using optical tweezers to relate the chemical and mechanical cross-bridge cycles.

    OpenAIRE

    Steffen, Walter; Sleep, John

    2004-01-01

    In most current models of muscle contraction there are two translational steps, the working stroke, whereby an attached myosin cross-bridge moves relative to the actin filament, and the repriming step, in which the cross-bridge returns to its original orientation. The development of single molecule methods has allowed a more detailed investigation of the relationship of these mechanical steps to the underlying biochemistry. In the normal adenosine triphosphate cycle, myosin.adenosine diphosph...

  5. Investigation research on the evaluation of a coupled thermo-hydro-mechanical-chemical phenomena. Result report

    International Nuclear Information System (INIS)

    Chijimatsu, Masakazu; Amemiya, Kiyoshi; Shiozaki, Isao; Neyama, Atsushi; Iwata, Hiroshi; Nakagawa, Koichi; Ishihara, Yoshinao; Sagawa, Hiroshi

    2002-02-01

    In order to realize a coupling analysis in the near field of the geological disposal system, this study has been studied on the addition of the mass transport model to the coupled thermo-hydro-mechanical analysis code (THAMES) and preliminary coupling analysis by using development environmental tool (Diffpack) for numerical analysis. (1) In order to prepare the strategy on the addition of the mass transport model to the coupled thermo-hydro-mechanical analysis code (THAMES), we have studied on the requirement of THAMES-Transport and methodology of coupling analysis. After that we set out modification plan by the Eulerian-Lagrangian (EL) method. (2) Based on the document of modification plan, we have done addition of the mass transport model to the coupled thermo-hydro-mechanical analysis code (THAMES) and carried out verification analysis in order to confirm on the accuracy of THAMES-Transport. (3) In order to understand on the behavior of NaCl in the porewater under the coupled thermo-hydro-mechanical phenomena in the HLW engineered barrier system, we have calculated coupling phenomenon by using THAMES-Transport. Transportation and concentration phenomena of NaCl are calculated but precipitation of NaCl is not occurred under the analysis conditions in this report. (4) In order to confirm about feasibility of coupling analysis under the development environmental tool (Diffpack) for numerical analysis, we have carried out on the design work and writing program of the preliminary coupling system. In this study, we have adopted existing transport model (HYDROGEOCHEM) and geochemical model (phreeqe 60) for preliminary coupling system. (5) In order to confirm program correctness of preliminary coupling system, we have carried out benchmarking analysis by using existing reactive-transport analysis code (HYDROGEOCHEM). (6) We have been prepared short-range development plan based on through the modification study of THAMES and writing program of the preliminary coupling

  6. The bell that rings light a primer in quantum mechanics and chemical bonding

    CERN Document Server

    Wallace, Dorothy

    2006-01-01

    This book is an introduction to quantum mechanics and mathematics that leads to the solution of the Schrodinger equation. It can be read and understood by undergraduates without sacrificing the mathematical details necessary for a complete solution giving the shapes of molecular orbitals seen in every chemistry text. Readers are introduced to many mathematical topics new to the undergraduate curriculum, such as basic representation theory, Schur's lemma, and the Legendre polynomials.

  7. New approaches to chemical reaction mechanisms by means of radiation chemistry

    International Nuclear Information System (INIS)

    Fujitsuka, Mamoru; Majima, Tetsuro

    2009-01-01

    Since active species generated during radiolysis can be used as oxidative or reductive regents of various organic and inorganic compounds, radiation chemistry has been applied to wide range of research fields. We have studied charge-delocalization process in molecular systems, properties of intermediates in the excited states, mechanism of light emitting device, photo-catalyst for degradation of toxic compounds and so on by means of radiation chemistry. In the present paper, we summarize our recent research results. (author)

  8. Effect of chemical composition and microstructure on the mechanical behavior of fish scales from Megalops Atlanticus.

    Science.gov (United States)

    Gil-Duran, S; Arola, D; Ossa, E A

    2016-03-01

    This paper presents an experimental study of the composition, microstructure and mechanical behavior of scales from the Megalops Atlanticus (Atlantic tarpon). The microstructure and composition were evaluated by Scanning Electron Microscopy (SEM) and RAMAN spectroscopy, respectively. The mechanical properties were evaluated in uniaxial tension as a function of position along the length of the fish (head, mid-length and tail). Results showed that the scales are composed of collagen and hydroxyapatite, and these constituents are distributed within three well-defined layers from the bottom to the top of the scale. The proportion of these layers with respect to the total scale thickness varies radially. The collagen fibers are arranged in plies with different orientations and with preferred orientation in the longitudinal direction of the fish. Results from the tensile tests showed that scales from Megalops Atlanticus exhibit variations in the elastic modulus as a function of body position. Additional testing performed with and without the highly mineralized top layers of the scale revealed that the mechanical behavior is anisotropic and that the highest strength was exhibited along the fish length. Furthermore, removing the top mineralized layers resulted in an increase in the tensile strength of the scale. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. Physical, chemical and mechanical properties of pehuen cellulosic husk and its pehuen-starch based composites.

    Science.gov (United States)

    Castaño, J; Rodríguez-Llamazares, S; Carrasco, C; Bouza, R

    2012-11-06

    Pehuen cellulosic husk was characterized and employed as reinforcement for composite materials. In this research, thermoplastic pehuen starch (TPS) and TPS/poly(lactic acid) (PLA)/polyvinyl alcohol (PVA) composites, reinforced with 5 and 10% of pehuen husk, were prepared by melt-blending. Comparative samples of pehuen TPS and TPS/PLA/PVA blend were also studied. Physical, thermal, structural and mechanical properties of composites were evaluated. Pehuen husk mainly consists of cellulose (50 wt%), hemicellulose (30 wt%) and lignin (14 wt%). In respect to lipids, this husk has only a 0.6 wt%. Its surface is smooth and damage-free and it is decomposed above 325 °C. The incorporation of pehuen husk improved considerably the thermal stability and mechanical properties of the studied composites, mainly in TPS composites. Their thermal stability enhances since biofiber hinders the "out-diffusion" of volatile molecules from the polymer matrix, while mechanical properties could raise due to the natural affinity between husk and starch in the pehuen seed. Copyright © 2012 Elsevier Ltd. All rights reserved.

  10. Thermal-mechanical-chemical responses of polymer-bonded explosives using a mesoscopic reactive model under impact loading.

    Science.gov (United States)

    Wang, XinJie; Wu, YanQing; Huang, FengLei

    2017-01-05

    A mesoscopic framework is developed to quantify the thermal-mechanical-chemical responses of polymer-bonded explosive (PBX) samples under impact loading. A mesoscopic reactive model is developed for the cyclotetramethylenetetranitramine (HMX) crystal, which incorporates nonlinear elasticity, crystal plasticity, and temperature-dependent chemical reaction. The proposed model was implemented in the finite element code ABAQUS by the user subroutine VUMAT. A series of three-dimensional mesoscale models were constructed and calculated under low-strength impact loading scenarios from 100m/s to 600m/s where only the first wave transit is studied. Crystal anisotropy and microstructural heterogeneity are responsible for the nonuniform stress field and fluctuations of the stress wave front. At a critical impact velocity (≥300m/s), a chemical reaction is triggered because the temperature contributed by the volumetric and plastic works is sufficiently high. Physical quantities, including stress, temperature, and extent of reaction, are homogenized from those across the microstructure at the mesoscale to compare with macroscale measurements, which will advance the continuum-level models. The framework presented in this study has important implications in understanding hot spot ignition processes and improving predictive capabilities in energetic materials. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. The influence of the “cage effect” on the mechanism of reversible bimolecular multistage chemical reactions in solutions

    International Nuclear Information System (INIS)

    Doktorov, Alexander B.

    2015-01-01

    Manifestations of the “cage effect” at the encounters of reactants are theoretically treated by the example of multistage reactions in liquid solutions including bimolecular exchange reactions as elementary stages. It is shown that consistent consideration of quasi-stationary kinetics of multistage reactions (possible only in the framework of the encounter theory) for reactions proceeding near reactants contact can be made on the basis of the concepts of a “cage complex.” Though mathematically such a consideration is more complicated, it is more clear from the standpoint of chemical notions. It is established that the presence of the “cage effect” leads to some important effects not inherent in reactions in gases or those in solutions proceeding in the kinetic regime, such as the appearance of new transition channels of reactant transformation that cannot be caused by elementary event of chemical conversion for the given mechanism of reaction. This results in that, for example, rate constant values of multistage reaction defined by standard kinetic equations of formal chemical kinetics from experimentally measured kinetics can differ essentially from real values of these constants

  12. The influence of the "cage effect" on the mechanism of reversible bimolecular multistage chemical reactions in solutions.

    Science.gov (United States)

    Doktorov, Alexander B

    2015-08-21

    Manifestations of the "cage effect" at the encounters of reactants are theoretically treated by the example of multistage reactions in liquid solutions including bimolecular exchange reactions as elementary stages. It is shown that consistent consideration of quasi-stationary kinetics of multistage reactions (possible only in the framework of the encounter theory) for reactions proceeding near reactants contact can be made on the basis of the concepts of a "cage complex." Though mathematically such a consideration is more complicated, it is more clear from the standpoint of chemical notions. It is established that the presence of the "cage effect" leads to some important effects not inherent in reactions in gases or those in solutions proceeding in the kinetic regime, such as the appearance of new transition channels of reactant transformation that cannot be caused by elementary event of chemical conversion for the given mechanism of reaction. This results in that, for example, rate constant values of multistage reaction defined by standard kinetic equations of formal chemical kinetics from experimentally measured kinetics can differ essentially from real values of these constants.

  13. The influence of the “cage effect” on the mechanism of reversible bimolecular multistage chemical reactions in solutions

    Energy Technology Data Exchange (ETDEWEB)

    Doktorov, Alexander B., E-mail: doktorov@kinetics.nsc.ru [Voevodsky Institute of Chemical Kinetics & Combustion, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russia and Novosibirsk State University, Novosibirsk 630090 (Russian Federation)

    2015-08-21

    Manifestations of the “cage effect” at the encounters of reactants are theoretically treated by the example of multistage reactions in liquid solutions including bimolecular exchange reactions as elementary stages. It is shown that consistent consideration of quasi-stationary kinetics of multistage reactions (possible only in the framework of the encounter theory) for reactions proceeding near reactants contact can be made on the basis of the concepts of a “cage complex.” Though mathematically such a consideration is more complicated, it is more clear from the standpoint of chemical notions. It is established that the presence of the “cage effect” leads to some important effects not inherent in reactions in gases or those in solutions proceeding in the kinetic regime, such as the appearance of new transition channels of reactant transformation that cannot be caused by elementary event of chemical conversion for the given mechanism of reaction. This results in that, for example, rate constant values of multistage reaction defined by standard kinetic equations of formal chemical kinetics from experimentally measured kinetics can differ essentially from real values of these constants.

  14. Effects of Graphene Oxide and Chemically-Reduced Graphene Oxide on the Dynamic Mechanical Properties of Epoxy Amine Composites

    Directory of Open Access Journals (Sweden)

    Cristina Monteserín

    2017-09-01

    Full Text Available Composites based on epoxy/graphene oxide (GO and epoxy/reduced graphene oxide (rGO were investigated for thermal-mechanical performance focusing on the effects of the chemical groups present on nanoadditive-enhanced surfaces. GO and rGO obtained in the present study have been characterized by Fourier transform infrared spectroscopy (FTIR, X-ray photoelectron spectroscopy (XPS, and X-ray powder diffraction (XRD demonstrating that materials with different oxidation degrees have been obtained. Thereafter, GO/epoxy and rGO/epoxy nanocomposites were successfully prepared and thoroughly characterized by dynamic mechanical thermal analysis (DMTA and transmission electron microscopy (TEM. A significant increase in the glass transition temperature was found in comparison with the neat epoxy. The presence of functional groups on the graphene surface leads to chemical interactions between these functional groups on GO and rGO surfaces with the epoxy, contributing to the possible formation of covalent bonds between GO and rGO with the matrix. The presence of oxidation groups on GO also contributes to an improved exfoliation, intercalation, and distribution of the GO sheets in the composites with respect to the rGO based composites.

  15. A comparative study on thermal, mechanical and dielectric characteristics of low density polyethylene crosslinked by radiation and chemical methods

    International Nuclear Information System (INIS)

    Kim, B.H.; Ling, D.Y.; Kim, J.S.

    1976-01-01

    A comparative study on thermal, static mechanical and dielectric characteristics were made over a temperature range of ca. 20 0 C to 320 0 C and a frequency range of KHZ band on low density polyethylene specimens crosslinked, respectively, by radiation and chemical method. The thermal property of both specimens shows that softening point appears to unchange by crosslinking however, melting and liquidizing temperatures attain rapid increase at the imitation of crosslinking. Mechanical properties show little difference to both specimens crosslinked by different method, further the behaviors were discussed in connection with the relaxation of molecular segments in amorphous phase. Dose dependent dielectric characteristics observed at ambient temperature under several fixed frequencies exhibit extremities at ca. 20 Mrad and the behaviors also were interpreted qualitatively by taking into consideration of dipole concentration change in amorphous phase together with the role of specimen geometry to the depth of oxidative layer. Observing frequency dependent dielectric characteristics, it was also proved that ionic conduction loss is appreciably greater in the specimen prepared by chemical method than that by radiation. (author)

  16. Effect of Formononetin on Mechanical Properties and Chemical Composition of Bones in Rats with Ovariectomy-Induced Osteoporosis

    Directory of Open Access Journals (Sweden)

    Ilona Kaczmarczyk-Sedlak

    2013-01-01

    Full Text Available Formononetin is a naturally occurring isoflavone, which can be found in low concentrations in many dietary products, but the greatest sources of this substance are Astragalus membranaceus, Trifolium pratense, Glycyrrhiza glabra, and Pueraria lobata, which all belong to Fabaceae family. Due to its structural similarity to 17β-estradiol, it can mimic estradiol’s effect and therefore is considered as a “phytoestrogen.” The aim of this study was to examine the effect of formononetin on mechanical properties and chemical composition of bones in rats with ovariectomy-induced osteoporosis. 12-week-old female rats were divided into 4 groups: sham-operated, ovariectomized, ovariectomized treated with estradiol (0.2 mg/kg and ovariectomized treated with formononetin (10 mg/kg. Analyzed substances were administered orally for 4 weeks. Ovariectomy caused osteoporotic changes, which can be observed in bone biomechanical features (decrease of maximum load and fracture load and increase of displacements for maximum and fracture loads and bone chemical composition (increase of water and organic fraction content, while a decrease of minerals takes place. Supplementation with formononetin resulted in slightly enhanced bone mechanical properties and bone chemistry improvement (significantly lower water content and insignificantly higher mineral fraction content. To summarize, administration of formononetin to ovariectomized rats shows beneficial effect on bone biomechanical features and chemistry; thus, it can prevent osteoporosis development.

  17. Exact results in nonequilibrium statistical mechanics: Formalism and applications in chemical kinetics and single-molecule free energy estimation

    Science.gov (United States)

    Adib, Artur B.

    In the last two decades or so, a collection of results in nonequilibrium statistical mechanics that departs from the traditional near-equilibrium framework introduced by Lars Onsager in 1931 has been derived, yielding new fundamental insights into far-from-equilibrium processes in general. Apart from offering a more quantitative statement of the second law of thermodynamics, some of these results---typified by the so-called "Jarzynski equality"---have also offered novel means of estimating equilibrium quantities from nonequilibrium processes, such as free energy differences from single-molecule "pulling" experiments. This thesis contributes to such efforts by offering three novel results in nonequilibrium statistical mechanics: (a) The entropic analog of the Jarzynski equality; (b) A methodology for estimating free energies from "clamp-and-release" nonequilibrium processes; and (c) A directly measurable symmetry relation in chemical kinetics similar to (but more general than) chemical detailed balance. These results share in common the feature of remaining valid outside Onsager's near-equilibrium regime, and bear direct applicability in protein folding kinetics as well as in single-molecule free energy estimation.

  18. Mechanical, electronic, chemical bonding and optical properties of cubic BaHfO3: First-principles calculations

    International Nuclear Information System (INIS)

    Liu Qijun; Liu Zhengtang; Feng Liping; Tian Hao

    2010-01-01

    We have performed ab-initio total energy calculations using the plane-wave ultrasoft pseudopotential technique based on the first-principles density-functional theory (DFT) to study structural parameters, mechanical, electronic, chemical bonding and optical properties of cubic BaHfO 3 . The calculated lattice parameter and independent elastic constants are in good agreement with previous theoretical and experimental work. The bulk, shear and Young's modulus, Poisson coefficient, compressibility and Lame constants are obtained using Voigt-Reuss-Hill method and the Debye temperature is estimated using Debye-Grueneisen model, which are consistent with previous results. Electronic and chemical bonding properties have been studied from the calculations of band structure, density of states and charge densities. Furthermore, in order to clarify the mechanism of optical transitions of cubic BaHfO 3 , the complex dielectric function, refractive index, extinction coefficient, reflectivity, absorption efficient, loss function and complex conductivity function are calculated. Then, we have explained the origins of spectral peaks on the basis of the theory of crystal-field and molecular-orbital bonding.

  19. Chemical and Mechanical Weed Control Methods and Their Effects on Photosynthetic Pigments and Grain Yield of Kidney Bean

    Directory of Open Access Journals (Sweden)

    A.S Ghatari

    2015-11-01

    Full Text Available To evaluate the integrated management of weeds in red kidney bean, a split-plot experiment using randomized complete block design with three replications was conducted in 2013 in the Damavand County. In this experiment, the mechanical control treatments consisted of two levels (no cultivation and one cultivation asseigned to main plots and controlling chemical treatments consisted of six levels (non-application of herbicides, pre-emergence herbicide application of Pursuit with full dose of 1 liter per hectare, pre-emergence herbicide application of Pursuit a dose decreased 0.5 liters per hectare, post-emergence herbicide application of Pursuit dose reduced to 0.3 liters per hectare + 2 thousand citogate, post-emergence herbicide application of Pursuit with a reduced dose of 0.5 liters per hectare + 2 thousand citogate, post-emergence herbicide application of Pursuit full dose of 1 liter per hectar + 2 thousand citogate to subplots. The results showed that the effects of interaction between herbicide application and cultivation for traits of carotenoids, chlorophyll a, chlorophyll b and total chlorophyll contents, density of weeds and their dry weights were significant at 1 %, and grain yield at the 5% probability levels. The highest bean seed yield with an average of 5461.6 kg.ha-1 and lowest weed dry weight with an average of 345.9 kg.ha-1 were related to pre-emergence herbicide and cultivation with a dose of 1 liter per hectare treatment. The difference between full and reduced doses of chemical weed control was non-significant. It could be concluded that integrated mechanical and chemical weed control not only may increase seed yield but also reduce, environmental hazards.

  20. Combined comparative and chemical proteomics on the mechanisms of levo-tetrahydropalmatine-induced antinociception in the formalin test.

    Science.gov (United States)

    Wang, Chen; Zhou, Jiangrui; Wang, Shuowen; Ye, Mingliang; Jiang, Chunlei; Fan, Guorong; Zou, Hanfa

    2010-06-04

    This study investigated the mechanisms involved in the antinociceptive action induced by levo-tetrahydropalmatine (l-THP) in the formalin test by combined comparative and chemical proteomics. Rats were pretreated with l-THP by the oral route (40 mg/kg) 1 h before formalin injection. The antinociceptive effect of l-THP was shown in the first and second phases of the formalin test. To address the mechanisms by which l-THP inhibits formalin-induced nociception in rats, the combined comparative and chemical proteomics were applied. A novel high-throughput comparative proteomic approach based on 2D-nano-LC-MS/MS was applied to simultaneously evaluate the deregulated proteins involved in the response of l-THP treatment in formalin-induced pain rats. Thousands of proteins were identified, among which 17 proteins survived the stringent filter criteria and were further included for functional discussion. Two proteins (Neurabin-1 and Calcium-dependent secretion activator 1) were randomly selected, and their expression levels were further confirmed by Western Blots. The results matched well with those of proteomics. In the present study, we also described the development and application of l-THP immobilized beads to bind the targets. Following incubation with cellular lysates, the proteome interacting with the fixed l-THP was identified. The results of comparative and chemical proteomics were quite complementary. Although the precise roles of these identified moleculars in l-THP-induced antinociception need further study, the combined results indicated that proteins associated with signal transduction, vesicular trafficking and neurotransmitter release, energy metabolism, and ion transport play important roles in l-THP-induced antinociception in the formalin test.

  1. Mechanism of pulse discharge production of iodine atoms from CF3I molecules for a chemical oxygen-iodine laser

    International Nuclear Information System (INIS)

    Kochetov, I V; Napartovich, A P; Vagin, N P; Yuryshev, N N

    2009-01-01

    The pulsed chemical oxygen-iodine laser (COIL) development is aimed at many new applications. Pulsed electric discharge is most effective in turning COIL operation into the pulse mode by instant production of iodine atoms. A numerical model is developed for simulations of the pulsed COIL initiated by an electric discharge. The model comprises a system of kinetic equations for neutral and charged species, electric circuit equation, gas thermal balance equation and the photon balance equation. Reaction rate coefficients for processes involving electrons are found by solving the electron Boltzmann equation, which is re-calculated in a course of computations when plasma parameters changed. The processes accounted for in the Boltzmann equation include excitation and ionization of atoms and molecules, dissociation of molecules, electron attachment processes, electron-ion recombination, electron-electron collisions, second-kind collisions and stepwise excitation of molecules. The last processes are particularly important because of a high singlet oxygen concentration in gas flow from the singlet oxygen chemical generator. Results of numerical simulations are compared with experimental laser pulse waveforms. It is concluded that there is satisfactory agreement between theory and the experiment. The prevailing mechanism of iodine atom formation from the CF 3 I donor in a very complex kinetic system of the COIL medium under pulse discharge conditions, based on their detailed numerical modelling and by comparing these results both with experimental results of other authors and their own experiments, is established. The dominant iodine atom production mechanism for conditions under study is the electron-impact dissociation of CF 3 I molecules. It was proved that in the conditions of the experiment the secondary chemical reactions with O atoms play an insignificant role.

  2. Electrochemical studies of Copper, Tantalum and Tantalum Nitride surfaces in aqueous solutions for applications in chemical-mechanical and electrochemical-mechanical planarization

    Science.gov (United States)

    Sulyma, Christopher Michael

    This report will investigate fundamental properties of materials involved in integrated circuit (IC) manufacturing. Individual materials (one at a time) are studied in different electrochemical environmental solutions to better understand the kinetics associated with the polishing process. Each system tries to simulate a real CMP environment in order to compare our findings with what is currently used in industry. To accomplish this, a variety of techniques are used. The voltage pulse modulation technique is useful for electrochemical processing of metal and alloy surfaces by utilizing faradaic reactions like electrodeposition and electrodissolution. A theoretical framework is presented in chapter 4 to facilitate quantitative analysis of experimental data (current transients) obtained in this approach. A typical application of this analysis is demonstrated for an experimental system involving electrochemical removal of copper surface layers, a relatively new process for abrasive-free electrochemical mechanical planarization of copper lines used in the fabrication of integrated circuits. Voltage pulse modulated electrodissolution of Cu in the absence of mechanical polishing is activated in an acidic solution of oxalic acid and hydrogen peroxide. The current generated by each applied voltage step shows a sharp spike, followed by a double-exponential decay, and eventually attains the rectangular shape of the potential pulses. For the second system in chapter 5, open-circuit potential measurements, cyclic voltammetry and Fourier transform impedance spectroscopy have been used to study pH dependent surface reactions of Cu and Ta rotating disc electrodes (RDEs) in aqueous solutions of succinic acid (SA, a complexing agent), hydrogen peroxide (an oxidizer), and ammonium dodecyl sulfate (ADS, a corrosion inhibitor for Cu). The surface chemistries of these systems are relevant for the development of a single-slurry approach to chemical mechanical planarization (CMP) of Cu

  3. Microstructure, mechanical properties and chemical degradation of brazed AISI 316 stainless steel/alumina systems

    International Nuclear Information System (INIS)

    Paiva, O.C.; Barbosa, M.A.

    2008-01-01

    The main aims of the present study are simultaneously to relate the brazing parameters with: (i) the correspondent interfacial microstructure, (ii) the resultant mechanical properties and (iii) the electrochemical degradation behaviour of AISI 316 stainless steel/alumina brazed joints. Filler metals on such as Ag-26.5Cu-3Ti and Ag-34.5Cu-1.5Ti were used to produce the joints. Three different brazing temperatures (850, 900 and 950 deg. C), keeping a constant holding time of 20 min, were tested. The objective was to understand the influence of the brazing temperature on the final microstructure and properties of the joints. The mechanical properties of the metal/ceramic (M/C) joints were assessed from bond strength tests carried out using a shear solicitation loading scheme. The fracture surfaces were studied both morphologically and structurally using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction analysis (XRD). The degradation behaviour of the M/C joints was assessed by means of electrochemical techniques. It was found that using a Ag-26.5Cu-3Ti brazing alloy and a brazing temperature of 850 deg. C, produces the best results in terms of bond strength, 234 ± 18 MPa. The mechanical properties obtained could be explained on the basis of the different compounds identified on the fracture surfaces by XRD. On the other hand, the use of the Ag-34.5Cu-1.5Ti brazing alloy and a brazing temperature of 850 deg. C produces the best results in terms of corrosion rates (lower corrosion current density), 0.76 ± 0.21 μA cm -2 . Nevertheless, the joints produced at 850 deg. C using a Ag-26.5Cu-3Ti brazing alloy present the best compromise between mechanical properties and degradation behaviour, 234 ± 18 MPa and 1.26 ± 0.58 μA cm -2 , respectively. The role of Ti diffusion is fundamental in terms of the final value achieved for the M/C bond strength. On the contrary, the Ag and Cu distribution along the brazed interface seem to

  4. Chemical durability and degradation mechanisms of HT9 based alloy waste forms with variable Zr content

    Energy Technology Data Exchange (ETDEWEB)

    Olson, L. N. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2015-10-30

    In Corrosion studies were undertaken on alloy waste forms that can result from advanced electrometallurgical processing techniques to better classify their durability and degradation mechanisms. The waste forms were based on the RAW3-(URe) composition, consisting primarily of HT9 steel and other elemental additions to simulate nuclear fuel reprocessing byproducts. The solution conditions of the corrosion studies were taken from an electrochemical testing protocol, and meant to simulate conditions in a repository. The alloys durability was examined in alkaline and acidic brines.

  5. Chemical and mechanical bioerosion of boring sponges from Mexican Pacific coral reefs.

    Science.gov (United States)

    Nava, Héctor; Carballo, José Luis

    2008-09-01

    Species richness (S) and frequency of invasion (IF) by boring sponges on living colonies of Pocillopora spp. from National Park Isla Isabel (México, East Pacific Ocean) are presented. Twelve species belonging to the genera Aka, Cliona, Pione, Thoosa and Spheciospongia were found, and 56% of coral colonies were invaded by boring sponges, with Cliona vermifera Hancock 1867 being the most abundant species (30%). Carbonate dissolution rate and sediment production were quantified for C. vermifera and Cliona flavifodina Rützler 1974. Both species exhibited similar rates of calcium carbonate (CaCO3) dissolution (1.2+/-0.4 and 0.5+/-0.2 kg CaCO3 m(-2) year(-1), respectively, mean +/- s.e.m.), and sediment production (3.3+/-0.6 and 4.6+/-0.5 kg CaCO3 m(-2) year(-1)), resulting in mean bioerosion rates of 4.5+/-0.9 and 5.1+/-0.5 kg CaCO3 m(-2) year(-1), respectively. These bioerosion rates are close to previous records of coral calcification per unit of area, suggesting that sponge bioerosion alone can promote disequilibrium in the reef accretion/destruction ratio in localities that are heavily invaded by boring sponges. The proportion of dissolved material by C. vermifera and C. flavifodina (27 and 10.2%, respectively) confirms that chemical bioerosion plays an important role in sponge bioerosion and in the CaCO3 cycle in coral reefs.

  6. Dissociation mechanism of HNIW ions investigated by chemical ionization and electron impact mass spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Rongjie; Xiao, Hemiao [School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China)

    2006-04-15

    Chemical Ionization (CI) with Collision-Induced Dissociation (CID) spectroscopy and Electron Impacting (EI) with metastable Mass analyzed Ion Kinetic Energy (MIKE) spectroscopy have been applied to study ionic dissociations of Hexanitrohexaazaisowurtzitane (HNIW). Similarities and differences between EI/MIKE and CI/CID mass spectra of HNIW were analyzed. In EI mass spectra, the ions [HNIW-n NO{sub 2}]{sup +} (n=2-5), such as the ion at m/z 347, were less frequent (1-2% relative abundance), but in CI mass spectra, these ions were very abundant. For some ions of large molar mass from HNIW, their dissociations pathways from parent ions to daughter ions were built according to CID and MIKE spectra. Molecular ions of HNIW with a protonated nitro group at five-member ring seem more stable than at six-member ring. The HNIW ions losing five of six nitro groups are very stable based on CID spectra, which agrees with some research results for thermal decomposition of HNIW in literature. (Abstract Copyright [2006], Wiley Periodicals, Inc.)

  7. Quantum Chemical Study on the Antioxidation Mechanism of Piceatannol and Isorhapontigenin toward Hydroxyl and Hydroperoxyl Radicals.

    Directory of Open Access Journals (Sweden)

    Yang Lu

    Full Text Available A systematic study of the antioxidation mechanisms behind hydroxyl (•OH and hydroperoxyl (•OOH radical scavenging activity of piceatannol (PIC and isorhapontigenin (ISO was carried out using density functional theory (DFT method. Two reaction mechanisms, abstraction (ABS and radical adduct formation (RAF, were discussed. A total of 24 reaction pathways of scavenging •OH and •OOH with PIC and ISO were investigated in the gas phase and solution. The thermodynamic and kinetic properties of all pathways were calculated. Based on these results, we evaluated the antioxidant activity of every active site of PIC and ISO and compared the abilities of PIC and ISO to scavenge radicals. According to our results, PIC and ISO may act as effective •OH and •OOH scavengers in organism. A4-hydroxyl group is a very important active site for PIC and ISO to scavenge radicals. The introducing of -OH or -OCH3 group to the ortho-position of A4-hydroxyl group would increase its antioxidant activity. Meanwhile, the conformational effect was researched, the results suggest that the presence and pattern of intramolecular hydrogen bond (IHB are considerable in determining the antioxidant activity of PIC and ISO.

  8. Mechanisms involved in the chemical inhibition of the Eosin-sensitized photooxidation of trypsin

    Energy Technology Data Exchange (ETDEWEB)

    Rizzuto, F.; Spikes, J.D.

    1975-01-01

    A large series of compounds was screened for ability to protect trypsin from eosin-sensitized photodynamic inactivation. Eosin-sensitized photooxidation reactions of this type typically proceed via the triplet state of the dye and often involve singlet state oxygen as the oxidizing entity. In order to determine the mechanisms by which trypsin is protected from photoinactivation, a number of good protective agents (inhibitors) and some non-protective agents were selected for more detailed flash photolysis studies. Good inhibitors such as p-phenylenediamine, n-propyl gallate, serotonin creatinine sulfate and p-toluenediamine competed efficiently with oxygen and with trypsin for reaction with the triplet state of eosin. The inhibitors were shown to quench triplet eosin to the ground state and/or reduce triplet eosin to form the semireduced eosin radical and an oxidized form of the inhibitor. In the latter case, oxidized inhibitor could react by a reverse electron transfer reaction with the semireduced eosin radical to regenerate ground state eosin and the inhibitor. The good inhibitors also competed effectively with trypsin for oxidation by semioxidized eosin, thus giving another possible protective mechanism. Non-inhibitors such as halogen ions and the paramagnetic ions Co/sup + +/, Cu/sup + +/ and Mn/sup + +/ reacted only slowly with triplet and with semioxidized eosin. The primary pathway for the eosin-sensitized photooxidation of trypsin at pH 8.0 involved singlet oxygen, although semioxidized eosin may also participate.

  9. On the mechanisms associated with the chemical reactivity of Be in steam

    International Nuclear Information System (INIS)

    Petti, D.A.; Smolik, G.R.; Anderl, R.A.

    2000-01-01

    One safety concern surrounding beryllium as a plasma-facing material in a water-cooled Tokamak is steam interactions with hot beryllium and the production of significant quantities of hydrogen. We have tested several different product forms of Be with different densities and levels of porosity. Oxidation kinetics has been determined by measurements of hydrogen release with a mass spectrometer, volumetric measurements of the product gas and weight change of the sample. We discuss and compare with the literature the fundamental mechanisms and kinetics controlling the oxidation of Be in steam. Fully dense beryllium exhibits parabolic, linear and accelerating modes of oxidation as temperature increases from 450 deg. C to 1200 deg. C. The oxidation mechanisms and temperature trends are similar for other product forms. Oxidation rates are higher, however, when processing or annealing significantly increases the extent of interconnected porosity and consequently the effective surface area. The effective surface area as measured by BET surface analyses is a key parameter when comparing oxidation rates

  10. Functionalized magnetic nanowires for chemical and magneto-mechanical induction of cancer cell death

    KAUST Repository

    Martinez Banderas, Aldo Isaac

    2016-10-24

    Exploiting and combining different properties of nanomaterials is considered a potential route for next generation cancer therapies. Magnetic nanowires (NWs) have shown good biocompatibility and a high level of cellular internalization. We induced cancer cell death by combining the chemotherapeutic effect of doxorubicin (DOX)-functionalized iron NWs with the mechanical disturbance under a low frequency alternating magnetic field. (3-aminopropyl)triethoxysilane (APTES) and bovine serum albumin (BSA) were separately used for coating NWs allowing further functionalization with DOX. Internalization was assessed for both formulations by confocal reflection microscopy and inductively coupled plasma-mass spectrometry. From confocal analysis, BSA formulations demonstrated higher internalization and less agglomeration. The functionalized NWs generated a comparable cytotoxic effect in breast cancer cells in a DOX concentration-dependent manner, (~60% at the highest concentration tested) that was significantly different from the effect produced by free DOX and non-functionalized NWs formulations. A synergistic cytotoxic effect is obtained when a magnetic field (1 mT, 10 Hz) is applied to cells treated with DOX-functionalized BSA or APTES-coated NWs, (~70% at the highest concentration). In summary, a bimodal method for cancer cell destruction was developed by the conjugation of the magneto-mechanical properties of iron NWs with the effect of DOX producing better results than the individual effects.

  11. Functionalized magnetic nanowires for chemical and magneto-mechanical induction of cancer cell death

    KAUST Repository

    Martinez Banderas, Aldo; Aires, Antonio; Teran, Francisco J.; Perez, Jose E.; Cadenas, Jael F.; Alsharif, Nouf; Ravasi, Timothy; Cortajarena, Aitziber L.; Kosel, Jü rgen

    2016-01-01

    Exploiting and combining different properties of nanomaterials is considered a potential route for next generation cancer therapies. Magnetic nanowires (NWs) have shown good biocompatibility and a high level of cellular internalization. We induced cancer cell death by combining the chemotherapeutic effect of doxorubicin (DOX)-functionalized iron NWs with the mechanical disturbance under a low frequency alternating magnetic field. (3-aminopropyl)triethoxysilane (APTES) and bovine serum albumin (BSA) were separately used for coating NWs allowing further functionalization with DOX. Internalization was assessed for both formulations by confocal reflection microscopy and inductively coupled plasma-mass spectrometry. From confocal analysis, BSA formulations demonstrated higher internalization and less agglomeration. The functionalized NWs generated a comparable cytotoxic effect in breast cancer cells in a DOX concentration-dependent manner, (~60% at the highest concentration tested) that was significantly different from the effect produced by free DOX and non-functionalized NWs formulations. A synergistic cytotoxic effect is obtained when a magnetic field (1 mT, 10 Hz) is applied to cells treated with DOX-functionalized BSA or APTES-coated NWs, (~70% at the highest concentration). In summary, a bimodal method for cancer cell destruction was developed by the conjugation of the magneto-mechanical properties of iron NWs with the effect of DOX producing better results than the individual effects.

  12. Mechanical properties and chemical bonding of the Os–B system: A first-principles study

    International Nuclear Information System (INIS)

    Ji Zongwei; Hu Chaohao; Wang Dianhui; Zhong Yan; Yang Jiong; Zhang Wenqing; Zhou Huaiying

    2012-01-01

    The mechanical properties of Os–B compounds containing different boron contents have been investigated systemically by first-principles calculations. Two previously unreported crystal structures of Os 2 B 5 and OsB 3 , crystallizing in space groups R3m and P-6m2 respectively, are determined using the ab initio evolutionary structure prediction. The calculated elastic constants, bulk modulus, shear modulus, Young’s modulus, Poisson’s ratio, and hardness for Os–B compounds are in good agreement with the available experimental values. Our results show that the hardness of osmium borides increases with increasing boron content. Os 2 B 5 and OsB 3 , with hardnesses of 34.4 and 36.9 GPa respectively, can almost be considered as potential superhard materials. Further analyses on density of states, crystal orbital Hamilton population, and electron localization function demonstrate that the electronic structure of Os–B compounds is directly responsible for their particular mechanical properties. High hardness in Os 2 B 5 and OsB 3 is mainly attributed to the occurrence of strong B–B covalent bonds and the disappearance of some ductile Os–Os metallic bonds.

  13. Swelling, Mechanics, and Thermal/Chemical Stability of Hydrogels Containing Phenylboronic Acid Side Chains

    Directory of Open Access Journals (Sweden)

    Arum Kim

    2017-12-01

    Full Text Available We report here studies of swelling, mechanics, and thermal stability of hydrogels consisting of 20 mol % methacrylamidophenylboronic acid (MPBA and 80 mol % acrylamide (AAm, lightly crosslinked with methylenebisacrylamide (Bis. Swelling was measured in solutions of fixed ionic strength, but with varying pH values and fructose concentrations. Mechanics was studied by compression and hold. In the absence of sugar or in the presence of fructose, the modulus was mostly maintained during the hold period, while a significant stress relaxation was seen in the presence of glucose, consistent with reversible, dynamic crosslinks provided by glucose, but not fructose. Thermal stability was determined by incubating hydrogels at pH 7.4 at room temperature, and 37, 50, and 65 °C, and monitoring swelling. In PBS (phosphate buffered saline solutions containing 9 mM fructose, swelling remained essentially complete for 50 days at room temperature, but decreased substantially with time at the higher temperatures, with accelerated reduction of swelling with increasing temperature. Controls indicated that over long time periods, both the MPBA and AAm units were experiencing conversion to different species.

  14. Functionalized magnetic nanowires for chemical and magneto-mechanical induction of cancer cell death.

    Science.gov (United States)

    Martínez-Banderas, Aldo Isaac; Aires, Antonio; Teran, Francisco J; Perez, Jose Efrain; Cadenas, Jael F; Alsharif, Nouf; Ravasi, Timothy; Cortajarena, Aitziber L; Kosel, Jürgen

    2016-10-24

    Exploiting and combining different properties of nanomaterials is considered a potential route for next generation cancer therapies. Magnetic nanowires (NWs) have shown good biocompatibility and a high level of cellular internalization. We induced cancer cell death by combining the chemotherapeutic effect of doxorubicin (DOX)-functionalized iron NWs with the mechanical disturbance under a low frequency alternating magnetic field. (3-aminopropyl)triethoxysilane (APTES) and bovine serum albumin (BSA) were separately used for coating NWs allowing further functionalization with DOX. Internalization was assessed for both formulations by confocal reflection microscopy and inductively coupled plasma-mass spectrometry. From confocal analysis, BSA formulations demonstrated higher internalization and less agglomeration. The functionalized NWs generated a comparable cytotoxic effect in breast cancer cells in a DOX concentration-dependent manner, (~60% at the highest concentration tested) that was significantly different from the effect produced by free DOX and non-functionalized NWs formulations. A synergistic cytotoxic effect is obtained when a magnetic field (1 mT, 10 Hz) is applied to cells treated with DOX-functionalized BSA or APTES-coated NWs, (~70% at the highest concentration). In summary, a bimodal method for cancer cell destruction was developed by the conjugation of the magneto-mechanical properties of iron NWs with the effect of DOX producing better results than the individual effects.

  15. KDP Aqueous Solution-in-Oil Microemulsion for Ultra-Precision Chemical-Mechanical Polishing of KDP Crystal

    Directory of Open Access Journals (Sweden)

    Hui Dong

    2017-03-01

    Full Text Available A novel functional KH2PO4 (KDP aqueous solution-in-oil (KDP aq/O microemulsion system for KDP crystal ultra-precision chemical-mechanical polishing (CMP was prepared. The system, which consisted of decanol, Triton X-100, and KH2PO4 aqueous solution, was available at room temperature. The functional KDP aq/O microemulsion system was systematically studied and applied as polishing solution to KDP CMP technology. In this study, a controlled deliquescent mechanism was proposed for KDP polishing with the KDP aq/O microemulsion. KDP aqueous solution, the chemical etchant in the polishing process, was caged into the micelles in the microemulsion, leading to a limitation of the reaction between the KDP crystal and KDP aqueous solution only if the microemulsion was deformed under the effect of the external force. Based on the interface reaction dynamics, KDP aqueous solutions with different concentrations (cKDP were applied to replace water in the traditional water-in-oil (W/O microemulsion. The practicability of the controlled deliquescent mechanism was proved by the decreasing material removal rate (MRR with the increasing of the cKDP. As a result, the corrosion pits on the KDP surface were avoided to some degree. Moreover, the roughnesses of KDP with KDP aq/O microemulsion (cKDP was changed from 10 mM to 100 mM as polishing solutions were smaller than that with the W/O microemulsion. The smallest surface root-mean-square roughness of 1.5 nm was obtained at a 30 mmol/L KDP aq solution, because of the most appropriate deliquescent rate and MRR.

  16. Evaluation of phenyl-propanedione on yellowing and chemical-mechanical properties of experimental dental resin-based materials

    Directory of Open Access Journals (Sweden)

    Dayane Carvalho Ramos Salles de OLIVEIRA

    Full Text Available ABSTRACT Objective To evaluate the influence of phenyl-propanedione on yellowing and chemical-mechanical properties of experimental resin-based materials photoactivated using different light curing units (LCUs. Material and Methods Experimental resin-based materials with the same organic matrix (60:40 wt% BisGMA:TEGDMA were mechanically blended using a centrifugal mixing device. To this blend, different photoinitiator systems were added in equimolar concentrations with aliphatic amine doubled by wt%: 0.4 wt% CQ; 0.38 wt% PPD; or 0.2 wt% CQ and 0.19 wt% PPD. The degree of conversion (DC, flexural strength (FS, Young’s modulus (YM, Knoop hardness (KNH, crosslinking density (CLD, and yellowing (Y were evaluated (n=10. All samples were light cured with the following LCUs: a halogen lamp (XL 2500, a monowave LED (Radii, or a polywave LED (Valo with 16 J/cm2. The results were analysed by two-way ANOVA and Tukey’s test (α=0.05. Results No statistical differences were found between the different photoinitiator systems to KNH, CLS, FS, and YM properties (p≥0.05. PPD/CQ association showed the higher DC values compared with CQ and PPD isolated systems when photoactivated by a polywave LED (p≤0.05. Y values were highest for the CQ compared with the PPD systems (p≤0.05. Conclusion PPD isolated system promoted similar chemical and mechanical properties and less yellowing compared with the CQ isolated system, regardless of the LCU used.

  17. Rates and Mechanisms of Oil Shale Pyrolysis: A Chemical Structure Approach

    Energy Technology Data Exchange (ETDEWEB)

    Fletcher, Thomas; Pugmire, Ronald

    2015-01-01

    Three pristine Utah Green River oil shale samples were obtained and used for analysis by the combined research groups at the University of Utah and Brigham Young University. Oil shale samples were first demineralized and the separated kerogen and extracted bitumen samples were then studied by a host of techniques including high resolution liquid-state carbon-13 NMR, solid-state magic angle sample spinning 13C NMR, GC/MS, FTIR, and pyrolysis. Bitumen was extracted from the shale using methanol/dichloromethane and analyzed using high resolution 13C NMR liquid state spectroscopy, showing carbon aromaticities of 7 to 11%. The three parent shales and the demineralized kerogens were each analyzed with solid-state 13C NMR spectroscopy. Carbon aromaticity of the kerogen was 23-24%, with 10-12 aromatic carbons per cluster. Crushed samples of Green River oil shale and its kerogen extract were pyrolyzed at heating rates from 1 to 10 K/min at pressures of 1 and 40 bar and temperatures up to 1000°C. The transient pyrolysis data were fit with a first-order model and a Distributed Activation Energy Model (DAEM). The demineralized kerogen was pyrolyzed at 10 K/min in nitrogen at atmospheric pressure at temperatures up to 525°C, and the pyrolysis products (light gas, tar, and char) were analyzed using 13C NMR, GC/MS, and FTIR. Details of the kerogen pyrolysis have been modeled by a modified version of the chemical percolation devolatilization (CPD) model that has been widely used to model coal combustion/pyrolysis. This refined CPD model has been successful in predicting the char, tar, and gas yields of the three shale samples during pyrolysis. This set of experiments and associated modeling represents the most sophisticated and complete analysis available for a given set of oil shale samples.

  18. Mechanisms of radiation - chemical conversion of high-paraffinic crude oil

    International Nuclear Information System (INIS)

    Zaikin, Yu.A.; Zaikina, R.F.; Silverman, J.

    2002-01-01

    Complete text of publication follows. Regularities of radiation-thermal cracking (RTC) are studied in high-paraffinic oil. Irradiation of oil samples by 2 MeV electrons was performed using a special facility assembled at the electron accelerator ELU-4. The following characteristic RTC features were observed in oil with high contents of heavy paraffins: low level of isomerization in light RTC fractions; very high polymerization rate and low olefin contents in RTC products; relatively low yields of light fractions at low irradiation dose rates; increase in the molecular weight of the gasoline fraction as the irradiation dose rate grows. Similar intense polymerization of RTC products was observed in our experiments with such wastes of oil extraction as asphalt-pitch-paraffin sediments (APPS). Theoretically this feedstock contains great reserves of hydrogen, and, therefore, has high potential yields of light fractions. However, in this case RTC was accompanied by intense reactions of polymerization and chemical adsorption that limited the maximum yields of light RTC products to 40% in our experiments. A specific feature of APPS radiation-induced destruction is formation of the big amount of a reactive paraffinic residue. As a result of interaction with the polymerizing residue the light liquid fractions were completely absorbed and the heavy residue got denser and solidified after several days of exposure at room temperature. RTC regularities in heavy paraffinic oil differ from those observed both in highly viscous petroleum feedstock and light paraffin oils. We attribute these observations to the behavior of heavy alkyl radicals that initiate polymerization and isomerization in heavy paraffin fractions

  19. The quantum-chemical investigation of N-cyclization reaction mechanism for epichlorohydrin aminolysis products

    Directory of Open Access Journals (Sweden)

    Andrey V. Tokar

    2014-12-01

    Full Text Available The mechanism of intramolecular cyclization for products of epichlorohydrin aminolysis by secondary amines has been investigated at ab initio level of theory. By comparative analysis of energetic characteristics, which obtained in vacuo as well as in acetonitrile solution with the trace quantities of water as an «active» solvation partner of reaction, it has been shown a decisive role of solvent, which occurs mainly at the expense of the polarizable effects for nonspecific solvation. Indeed, the addition to the substrate of one water molecule have decreased corresponding EACT values only 24.1 kJ/mol, while the appearance of acetonitrile surroundings have the same influence ~42.0 kJ/mol. The results of calculations are in good agreement with that data, which have been obtained for such type modeling previously.

  20. Response to a temperature modulation as a signature of chemical mechanisms.

    Science.gov (United States)

    Berthoumieux, H; Jullien, L; Lemarchand, A

    2007-11-01

    We consider n reactive species involved in unimolecular reactions and submitted to a temperature modulation of small amplitude. We determine the conditions on the rate constants for which the deviations from the equilibrium concentrations of each species can be optimized and find the analytical expression of the frequency associated with an extremum of concentration shift in the case n=3. We prove that the frequency dependence of the displacement of equilibrium gives access to the number n of species involved in the mechanism. We apply the results to the case of the transformation of a reactant into a product through a possible reactive intermediate and find the order relation obeyed by the activation energies of the different barriers. The results typically apply to enzymatic catalysis with kinetics of Michaelis-Menten type.

  1. Fully mechanized welding of pipelines in the chemical industry and reactor construction

    International Nuclear Information System (INIS)

    Born, K.

    1984-01-01

    Pipes are increasingly being used as a construction element involving a growing demand for modern welding technology. The pulsed-arc welding procedures occupy an important position in mechanized pipe welding especially where flanged joints are to be made on turning pipes with a burner fixed in place. When the construction prohibits the turning of pipes, the orbital welding technique may be used. The paper discusses the question how the economic efficiency of TIG in inert-gas welding, which is the commonly used welding technique, could be enhanced and in how far other pulsed-arc welding methods, e.g. plasma keyhole or MIG/MAG pulsed-arc could be used in future. This could be done using the new possibilities offered by modern power sources and process technology. (orig.) [de

  2. Offgas Analysis and Pyrolysis Mechanism of Activated Carbon from Bamboo Sawdust by Chemical Activation With KOH

    Institute of Scientific and Technical Information of China (English)

    TIAN Yong; LIU Ping; WANG Xiufang; ZHONG Guoying; CHEN Guanke

    2011-01-01

    Bamboo sawdust was used as the precursor for the multipurpose use of waste.Offgases released during the activation process of bamboo by KOH were investigated quantitatively and qualitatively by a gas analyzer. TG/DTG curves during the pyrolysis process with different impregnation weight ratios (KOH to bamboo) were obtained by a thermogravimetric analyzer. Pyrolysis mechanism of bamboo was proposed. The results showed that the offgases were composed of CO, NO,SO2 and hydrocarbon with the concentration of 1 372, 37, 86, 215 mg/L, respectively. Thermogravimetric analysis indicated that the pyrolytic process mainly experienced two steps. The first was the low temperature activation step (lower than 300 ℃), which was the pre-activation and induction period.The second was the high temperature activation step(higher than 550 ℃), which was a radial activation followed by pore production. The second process was the key to control the pore distribution of the final product.

  3. Effect of chemical treatments on the mechanical properties of peanut shell and cement blends

    Directory of Open Access Journals (Sweden)

    Gatani, M.

    2010-06-01

    Full Text Available An abundance of agri-food waste in the area around Cordoba, Argentina, has driven the development of new construction materials. This study explored the applicability of peanut shells as additions in cement blends and the suitability of the properties of the resulting mixes for use in construction materials. The mechanical properties of the specimens were observed to improve when the shells were previously treated with quicklime (CaO or when sodium silicate and aluminium sulphate were added to the blend. While the resulting materials did not exhibit the same mechanical properties as traditional mortars and concretes, they do appear to be apt for use in lightweight and non-bearing structures.

    La abundante disponibilidad de residuos de la agroindustria local (Córdoba, Argentina, ha promovido el desarrollo de nuevos materiales para la construcción. Este trabajo de investigación se desarrolla a partir de la utilización de cáscara de maní como agregado en mezclas de cemento a fin de conocer las propiedades obtenidas en relación al tratamiento de dicho agregado, para la producción de materiales de construcción. Los ensayos demostraron mejoras en las propiedades mecánicas de las probetas realizadas con cemento y cáscaras previamente tratadas con cal viva (CaO, también en aquéllas aditivadas con silicato de sodio y sulfato de aluminio. Si bien los materiales resultantes no tienen las propiedades mecánicas de los morteros y hormigones tradicionales, parecen interesantes para ser aplicadas en componentes de construcción livianos y de uso no portante.

  4. A study of the chemical, mechanical, and surface properties of thin films of hydrogenated amorphous carbon

    Energy Technology Data Exchange (ETDEWEB)

    Vandentop, G.J.

    1990-07-01

    Amorphous hydrogenated carbon (a-C:H) films were studied with the objective of elucidating the nucleation and growth mechanisms, and the origin of their unique physical properties. The films were deposited onto Si(100) substrates both on the powered (negatively self-biased) and on the grounded electrodes from methane in an rf plasma (13.56 MHz) at 65 mTorr and 300 to 370 K. The films produced at the powered electrode exhibited superior mechanical properties, such as high hardness. A mass spectrometer was used to identify neutral species and positive ions incident on the electrodes from the plasma, and also to measure ion energies. The effect of varying ion energy flux on the properties of a-C:H films was investigated using a novel pulsed biasing technique. It was demonstrated that ions were not the dominant deposition species as the total ion flux measured was insufficient to account for the observed deposition rate. The interface between thin films of a-C:H and silicon substrates was investigated using angle resolved x-ray photoelectron spectroscopy. A silicon carbide layer was detected at the interface of a hard a-C:H film formed at the powered electrode. At the grounded electrode, where the kinetic energy is low, no interfacial carbide layer was observed. Scanning tunneling microscopy and high energy electron energy loss spectroscopy was used to investigate the initial stages of growth of a-C:H films. On graphite substrates, films formed at the powered electrode were observed to nucleate in clusters approximately 50 {Angstrom} in diameter, while at the grounded electrode no cluster formation was observed. 58 figs.

  5. Mechanisms of the hepatoprotective effects of tamoxifen against drug-induced and chemical-induced acute liver injuries

    Energy Technology Data Exchange (ETDEWEB)

    Yoshikawa, Yukitaka; Miyashita, Taishi; Higuchi, Satonori [Drug Metabolism and Toxicology, Faculty of Pharmaceutical Sciences, Kanazawa University, Kakuma-machi, Kanazawa 920‐1192 (Japan); Tsuneyama, Koichi [Department of Diagnostic Pathology, Graduate School of Medicine and Pharmaceutical Science for Research, University of Toyama, Sugitani, Toyama 930‐0194 (Japan); Endo, Shinya [Drug Metabolism and Toxicology, Faculty of Pharmaceutical Sciences, Kanazawa University, Kakuma-machi, Kanazawa 920‐1192 (Japan); Tsukui, Tohru [Research Center for Genomic Medicine, Saitama Medical University, Yamane, Hidaka 350‐1241 (Japan); Toyoda, Yasuyuki; Fukami, Tatsuki; Nakajima, Miki [Drug Metabolism and Toxicology, Faculty of Pharmaceutical Sciences, Kanazawa University, Kakuma-machi, Kanazawa 920‐1192 (Japan); Yokoi, Tsuyoshi, E-mail: tyokoi@p.kanazawa-u.ac.jp [Drug Metabolism and Toxicology, Faculty of Pharmaceutical Sciences, Kanazawa University, Kakuma-machi, Kanazawa 920‐1192 (Japan)

    2012-10-01

    Although estrogen receptor (ER)α agonists, such as estradiol and ethinylestradiol (EE2), cause cholestasis in mice, they also reduce the degree of liver injury caused by hepatotoxicants as well as ischemia–reperfusion. The functional mechanisms of ERα have yet to be elucidated in drug-induced or chemical-induced liver injury. The present study investigated the effects of an ERα agonist, selective ER modulators (SERMs) and an ER antagonist on drug-induced and chemical-induced liver injuries caused by acetaminophen, bromobenzene, diclofenac, and thioacetamide (TA). We observed hepatoprotective effects of EE2, tamoxifen (TAM) and raloxifene pretreatment in female mice that were exposed to a variety of hepatotoxic compounds. In contrast, the ER antagonist did not show any hepatoprotective effects. DNA microarray analyses suggested that monocyte to macrophage differentiation-associated 2 (Mmd2) protein, which has an unknown function, is commonly increased by TAM and RAL pretreatment, but not by pretreatment with the ER antagonist. In ERα-knockout mice, the hepatoprotective effects of TAM and the increased expression of Mmd2 mRNA were not observed in TA-induced liver injury. To investigate the function of Mmd2, the expression level of Mmd2 mRNA was significantly knocked down to approximately 30% in mice by injection of siRNA for Mmd2 (siMmd2). Mmd2 knockdown resulted in a reduction of the protective effects of TAM on TA-induced liver injury in mice. This is the first report of the involvement of ERα in drug-induced or chemical-induced liver injury. Upregulation of Mmd2 protein in the liver was suggested as the mechanism of the hepatoprotective effects of EE2 and SERMs. -- Highlights: ► Liver injury induced by drugs or chemicals was investigated in mice. ► Liver injury was suppressed by pretreatment with tamoxifen in female mice. ► Mmd2, whose function was unknown, could be a candidate gene for liver protection. ► Tamoxifen up-regulated Mmd2 mRNA expression

  6. Mechanisms of the hepatoprotective effects of tamoxifen against drug-induced and chemical-induced acute liver injuries

    International Nuclear Information System (INIS)

    Yoshikawa, Yukitaka; Miyashita, Taishi; Higuchi, Satonori; Tsuneyama, Koichi; Endo, Shinya; Tsukui, Tohru; Toyoda, Yasuyuki; Fukami, Tatsuki; Nakajima, Miki; Yokoi, Tsuyoshi

    2012-01-01

    Although estrogen receptor (ER)α agonists, such as estradiol and ethinylestradiol (EE2), cause cholestasis in mice, they also reduce the degree of liver injury caused by hepatotoxicants as well as ischemia–reperfusion. The functional mechanisms of ERα have yet to be elucidated in drug-induced or chemical-induced liver injury. The present study investigated the effects of an ERα agonist, selective ER modulators (SERMs) and an ER antagonist on drug-induced and chemical-induced liver injuries caused by acetaminophen, bromobenzene, diclofenac, and thioacetamide (TA). We observed hepatoprotective effects of EE2, tamoxifen (TAM) and raloxifene pretreatment in female mice that were exposed to a variety of hepatotoxic compounds. In contrast, the ER antagonist did not show any hepatoprotective effects. DNA microarray analyses suggested that monocyte to macrophage differentiation-associated 2 (Mmd2) protein, which has an unknown function, is commonly increased by TAM and RAL pretreatment, but not by pretreatment with the ER antagonist. In ERα-knockout mice, the hepatoprotective effects of TAM and the increased expression of Mmd2 mRNA were not observed in TA-induced liver injury. To investigate the function of Mmd2, the expression level of Mmd2 mRNA was significantly knocked down to approximately 30% in mice by injection of siRNA for Mmd2 (siMmd2). Mmd2 knockdown resulted in a reduction of the protective effects of TAM on TA-induced liver injury in mice. This is the first report of the involvement of ERα in drug-induced or chemical-induced liver injury. Upregulation of Mmd2 protein in the liver was suggested as the mechanism of the hepatoprotective effects of EE2 and SERMs. -- Highlights: ► Liver injury induced by drugs or chemicals was investigated in mice. ► Liver injury was suppressed by pretreatment with tamoxifen in female mice. ► Mmd2, whose function was unknown, could be a candidate gene for liver protection. ► Tamoxifen up-regulated Mmd2 mRNA expression

  7. The ion dependent change in the mechanism of charge storage of chemically preintercalated bilayered vanadium oxide electrodes

    Science.gov (United States)

    Clites, Mallory; Pomerantseva, Ekaterina

    2017-08-01

    Chemical pre-intercalation is a soft chemistry synthesis approach that allows for the insertion of inorganic ions into the interlayer space of layered battery electrode materials prior to electrochemical cycling. Previously, we have demonstrated that chemical pre-intercalation of Na+ ions into the structure of bilayered vanadium oxide (δ-V2O5) results in record high initial capacities above 350 mAh g-1 in Na-ion cells. This performance is attributed to the expanded interlayer spacing and predefined diffusion pathways achieved by the insertion of charge-carrying ions. However, the effect of chemical pre-intercalation of δ-V2O5 has not been studied for other ion-based systems beyond sodium. In this work, we report the effect of the chemically preintercalated alkali ion size on the mechanism of charge storage of δ- MxV2O5 (M = Li, Na, K) in Li-ion, Na-ion, and K-ion batteries, respectively. The interlayer spacing of the δ-MxV2O5 varied depending on inserted ion, with 11.1 Å achieved for Li-preintercalated δ-V2O5, 11.4 Å for Na-preintercalated δ- V2O5, and 9.6 Å for K-preintercalated δ-V2O5. Electrochemical performance of each material has been studied in its respective ion-based system (δ-LixV2O5 in Li-ion cells, δ-NaxV2O5 in Na-ion cells, and δ-KxV2O5 in K-ion cells). All materials demonstrated high initial capacities above 200 mAh g-1. However, the mechanism of charge storage differed depending on the charge-carrying ion, with Li-ion cells demonstrating predominantly pseudocapacitive behavior and Naion and K-ion cells demonstrating a significant portion of capacity from diffusion-limited intercalation processes. In this study, the combination of increased ionic radii of the charge-carrying ions and decreased synthesized interlayer spacing of the bilayered vanadium oxide phase correlates to an increase in the portion of capacity attributed diffusion-limited charge-storage processes.

  8. NMR chemical shift and J coupling parameterization and quantum mechanical reference spectrum simulation for selected nerve agent degradation products in aqueous conditions.

    Science.gov (United States)

    Koskela, Harri; Anđelković, Boban

    2017-10-01

    The spectral parameters of selected nerve agent degradation products relevant to the Chemical Weapons Convention, namely, ethyl methylphosphonate, isopropyl methylphosphonate, pinacolyl methylphosphonate and methylphosphonic acid, were studied in wide range of pH conditions and selected temperatures. The pH and temperature dependence of chemical shifts and J couplings was parameterized using Henderson-Hasselbalch-based functions. The obtained parameters allowed calculation of precise chemical shifts and J coupling constants in arbitrary pH conditions and typical measurement temperatures, thus facilitating quantum mechanical simulation of reference spectra in the chosen magnetic field strength for chemical verification. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  9. Evaluation of the influence of mechanical activation on physical and chemical properties of municipal solid waste incineration sludge.

    Science.gov (United States)

    Caprai, V; Florea, M V A; Brouwers, H J H

    2018-06-15

    Despite numerous studies concerning the application of by-products in the construction field, municipal solid waste incineration (MSWI) residues are not widely used as secondary building materials. In some European countries, washing treatment to the full bottom ash (BA) fraction (0-32 mm) is applied, isolating more contaminated particles, smaller than 0.063 mm. Therefore, a MWSI sludge is produced, having a high moisture content, and thus a limited presence of soluble species. In order to enhance its performance as building material, here, dry mechanical activation is applied on MSWI sludge. Thereafter, a reactivity comparison between reference BA and untreated and treated MSWI sludge is provided, evaluating their behaviour in the presence of cement and their pozzolanic activity. Moreover, the mechanical performances, as 25% substitution of Portland cement (PC) are assessed, based on the EN 450. Mechanical activation enhances MSWI sludge physically due to the improved particle morphology and packing. Chemically, the hydration degree of PC is enhanced by the MSWI sludge by ≈25%. The milling treatment proved to be beneficial to the residues performances in the presence of PC, providing 32% higher strength than untreated sample. Environmentally, the compliance with the unshaped material legislation is successfully verified, according to the Soil Quality Decree. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. The critical chemical and mechanical regulation of folic acid on neural engineering.

    Science.gov (United States)

    Kim, Gloria B; Chen, Yongjie; Kang, Weibo; Guo, Jinshan; Payne, Russell; Li, Hui; Wei, Qiong; Baker, Julianne; Dong, Cheng; Zhang, Sulin; Wong, Pak Kin; Rizk, Elias B; Yan, Jiazhi; Yang, Jian

    2018-04-03

    The mandate of folic acid supplementation in grained products has reduced the occurrence of neural tube defects by one third in the U.S since its introduction by the Food and Drug Administration in 1998. However, the advantages and possible mechanisms of action of using folic acid for peripheral nerve engineering and neurological diseases still remain largely elusive. Herein, folic acid is described as an inexpensive and multifunctional niche component that modulates behaviors in different cells in the nervous system. The multiple benefits of modulation include: 1) generating chemotactic responses on glial cells, 2) inducing neurotrophin release, and 3) stimulating neuronal differentiation of a PC-12 cell system. For the first time, folic acid is also shown to enhance cellular force generation and global methylation in the PC-12 cells, thereby enabling both biomechanical and biochemical pathways to regulate neuron differentiation. These findings are evaluated in vivo for clinical translation. Our results suggest that folic acid-nerve guidance conduits may offer significant benefits as a low-cost, off-the-shelf product for reaching the functional recovery seen with autografts in large sciatic nerve defects. Consequently, folic acid holds great potential as a critical and convenient therapeutic intervention for neural engineering, regenerative medicine, medical prosthetics, and drug delivery. Copyright © 2018 Elsevier Ltd. All rights reserved.

  11. An integrated chemical biology approach reveals the mechanism of action of HIV replication inhibitors.

    Science.gov (United States)

    Pagano, Nicholas; Teriete, Peter; Mattmann, Margrith E; Yang, Li; Snyder, Beth A; Cai, Zhaohui; Heil, Marintha L; Cosford, Nicholas D P

    2017-12-01

    Continuous flow (microfluidic) chemistry was employed to prepare a small focused library of dihydropyrimidinone (DHPM) derivatives. Compounds in this class have been reported to exhibit activity against the human immunodeficiency virus (HIV), but their molecular target had not been identified. We tested the initial set of DHPMs in phenotypic assays providing a hit (1i) that inhibited the replication of the human immunodeficiency virus HIV in cells. Flow chemistry-driven optimization of 1i led to the identification of HIV replication inhibitors such as 1l with cellular potency comparable with the clinical drug nevirapine (NVP). Mechanism of action (MOA) studies using cellular and biochemical assays coupled with 3D fingerprinting and in silico modeling demonstrated that these drug-like probe compounds exert their effects by inhibiting the viral reverse transcriptase polymerase (RT). This led to the design and synthesis of the novel DHPM 1at that inhibits the replication of drug resistant strains of HIV. Our work demonstrates that combining flow chemistry-driven analogue refinement with phenotypic assays, in silico modeling and MOA studies is a highly effective strategy for hit-to-lead optimization applicable to the discovery of future therapeutic agents. Copyright © 2017. Published by Elsevier Ltd.

  12. Using optical tweezers to relate the chemical and mechanical cross-bridge cycles.

    Science.gov (United States)

    Steffen, Walter; Sleep, John

    2004-12-29

    In most current models of muscle contraction there are two translational steps, the working stroke, whereby an attached myosin cross-bridge moves relative to the actin filament, and the repriming step, in which the cross-bridge returns to its original orientation. The development of single molecule methods has allowed a more detailed investigation of the relationship of these mechanical steps to the underlying biochemistry. In the normal adenosine triphosphate cycle, myosin.adenosine diphosphate.phosphate (M.ADP.Pi) binds to actin and moves it by ca. 5 nm on average before the formation of the end product, the rigor actomyosin state. All the other product-like intermediate states tested were found to give no net movement indicating that M.ADP.Pi alone binds in a pre-force state. Myosin states with bound, unhydrolysed nucleoside triphosphates also give no net movement, indicating that these must also bind in a post-force conformation and that the repriming, post- to pre-transition during the forward cycle must take place while the myosin is dissociated from actin. These observations fit in well with the structural model in which the working stroke is aligned to the opening of the switch 2 element of the ATPase site.

  13. Studies Related to Chemical Mechanisms of Gas Formation in Hanford High-Level Nuclear Wastes

    International Nuclear Information System (INIS)

    Barefield, E. Kent; Liotta, Charles L.; Neumann, Henry M.

    2002-01-01

    The objective of this work is to develop a more detailed mechanistic understanding of the thermal reactions that lead to gas production in certain high-level waste storage tanks at the Hanford, Washington site. Prediction of the combustion hazard for these wastes and engineering parameters for waste processing depend upon both a knowledge of the composition of stored wastes and the changes that they undergo as a result of thermal and radiolytic decomposition. Since 1980 when Delagard first demonstrated that gas production (H2and N2O initially, later N2 and NH3)in the affected tanks was related to oxidative degradation of metal complexants present in the waste, periodic attempts have been made to develop detailed mechanisms by which the gases were formed. These studies have resulted in the postulation of a series of reactions that account for many of the observed products, but which involve several reactions for which there is limited, or no, precedent. For example, Al(OH)4 has been postulated to function as a Lewis acid to catalyze the reaction of nitrite ion with the metal complexants, NO is proposed as an intermediate, and the ratios of gaseous products may be a result of the partitioning of NO between two or more reactions. These reactions and intermediates have been the focus of this project since its inception in 1996

  14. The Bioelectric Code: Reprogramming Cancer and Aging From the Interface of Mechanical and Chemical Microenvironments

    Directory of Open Access Journals (Sweden)

    Brian B. Silver

    2018-03-01

    Full Text Available Cancer is a complex, heterogeneous group of diseases that can develop through many routes. Broad treatments such as chemotherapy destroy healthy cells in addition to cancerous ones, but more refined strategies that target specific pathways are usually only effective for a limited number of cancer types. This is largely due to the multitude of physiological variables that differ between cells and their surroundings. It is therefore important to understand how nature coordinates these variables into concerted regulation of growth at the tissue scale. The cellular microenvironment might then be manipulated to drive cells toward a desired outcome at the tissue level. One unexpected parameter, cellular membrane voltage (Vm, has been documented to exert control over cellular behavior both in culture and in vivo. Manipulating this fundamental cellular property influences a remarkable array of organism-wide patterning events, producing striking outcomes in both tumorigenesis as well as regeneration. These studies suggest that Vm is not only a key intrinsic cellular property, but also an integral part of the microenvironment that acts in both space and time to guide cellular behavior. As a result, there is considerable interest in manipulating Vm both to treat cancer as well as to regenerate organs damaged or deteriorated during aging. However, such manipulations have produced conflicting outcomes experimentally, which poses a substantial barrier to understanding the fundamentals of bioelectrical reprogramming. Here, we summarize these inconsistencies and discuss how the mechanical microenvironment may impact bioelectric regulation.

  15. Mechanisms Controlling Hypoxia Data Atlas: High-resolution hydrographic and chemical observations from 2003-2014

    Science.gov (United States)

    Zimmerle, H.; DiMarco, S. F.

    2016-02-01

    The Mechanisms Controlling Hypoxia (MCH) project consisted of 31 cruises from 2003-2014 with an objective to investigate the physical and biogeochemical processes that control the hypoxic zone on the Texas-Louisiana shelf in the northern Gulf of Mexico. The known seasonal low oxygen conditions in this region are the result of river-derived nutrients, freshwater input, and wind. The MCH Data Atlas showcases in situ data and subsequent products produced during the duration of the project, focusing on oceanographic observations from 2010-2014. The Atlas features 230 high-resolution vertical sections from nine cruises using the Acrobat undulating towed vehicle that contained a CTD along with sensors measuring oxygen, fluorescence, and turbidity. Vertical profiles along the 20-meter isobaths section feature temperature, salinity, chlorophyll, and dissolved oxygen from the Acrobat towfish and CTD rosette as well as separate selected profiles from the CTD. Surface planview maps show the horizontal distribution of temperature, salinity, chlorophyll, beam transmission, and CDOM observed by the shipboard flow-through system. Bottom planview maps present the horizontal distribution of dissolved oxygen as well as temperature and salinity from the CTD rosette and Acrobat towfish along the shelf's seafloor. Informational basemaps display the GPS cruise track as well as individual CTD stations for each cruise. The shelf concentrations of CTD rosette bottle nutrients, including nitrate, nitrite, phosphate, ammonia, and silicate are displayed in select plots. Shipboard ADCP current velocity fields are also represented. MCH datasets and additional products are featured as an electronic version to compliment the published atlas. The MCH Data Atlas provides a showcase for the spatial and temporal variability of the environmental parameters associated with the annual hypoxic event and will be a useful tool in the continued monitoring and assessment of Gulf coastal hypoxia.

  16. Interaction mechanisms of radioactive, chemical and thermal releases from the nuclear industry: Methodology for considering co-operative effects

    International Nuclear Information System (INIS)

    Streffer, C.

    1975-01-01

    A number of chemicals are known which can modify radiation effects on cell killing, carcinogenesis and mutagenesis. In this paper data are reported for radiosensitizing agents. In order to discuss the interaction mechanisms of these synergistic effects, the action of radiation on DNA, on its biological functions and on its metabolism are explained briefly. Also it is indicated that part of the radiation effects in the DNA can be 'repaired' and that living cells can recover from radiation damage. One group of radiosensitizers interacts with cellular DNA or with the DNP-complex. These reactions change the configurational structure or metabolism of DNA and DNP. In this connection the action of antibiotics such as actinomycin D, and the action of SH-blocking agents such as iodoacetamide and NEM, as well as the action of alkylating agents, are discussed. A second group of radiosensitizers, especially with hypoxic cells, are the electron affinic chemicals like nitro-compounds, ketones and others. Data are also given on the modification of radiation effects by changes in temperature. Further, the problem of whether synergistic effects are to be expected arising from the chemicals and radiation originating in the nuclear industry is considered. Data show that repair and recovery processes especially are modified by radiosensitizers. The implications of this fact on sensitization at low radiation doses and at low dose rates, as well as the effect of high LET radiation, are considered. It is of interest that the dose modifying factor of some sensitizers can reach a magnitude of a factor of two to three. (author)

  17. Investigation of chemical and electrochemical reactions mechanisms in a direct carbon fuel cell using olive wood charcoal as sustainable fuel

    Science.gov (United States)

    Elleuch, Amal; Halouani, Kamel; Li, Yongdan

    2015-05-01

    Direct carbon fuel cell (DCFC) is a high temperature fuel cell using solid carbon as fuel. The use of environmentally friendly carbon material constitutes a promising option for the DCFC future. In this context, this paper focuses on the use of biomass-derived charcoal renewable fuel. A practical investigation of Tunisian olive wood charcoal (OW-C) in planar DCFCs is conducted and good power density (105 mW cm-2) and higher current density (550 mA cm-2) are obtained at 700 °C. Analytical and predictive techniques are performed to explore the relationships between fuel properties and DCFC chemical and electrochemical mechanisms. High carbon content, carbon-oxygen groups and disordered structure, are the key parameters allowing the achieved good performance. Relatively complex chain reactions are predicted to explain the gas evolution within the anode. CO, H2 and CH4 participation in the anodic reaction is proved.

  18. Bioaccumulation and subacute toxicity of mechanically and chemically dispersed heavy fuel oil in sea urchin (Glyptocidaris crenulari

    Directory of Open Access Journals (Sweden)

    Bailin Yang

    2015-12-01

    Full Text Available Oil spills have a disastrous ecological impact on ecosystems but few data are available for the effects of dispersed oil on benthic marine organisms. In order to provide information for assessment, we analysed the hydrocarbon compositions of the mechanically dispersed water accommodated fraction (MDWAF and the chemically dispersed water accommodated fraction (CDWAF of No. 120 fuel oil, their bioaccumulation, and DNA damage related to oil exposure, using the sea urchin as a sentinel organism. The results show that the concentration of polycyclic aromatic hydrocarbon in the tissues of sea urchin exposed to the CDWAF is higher than that of those exposed to the MDWAF. The single cell gel electrophoresis assay results also indicated higher DNA damage from exposure to the CDWAF of oil. Thus, dispersants should be applied with caution in oil spill accidents.

  19. Chemical mechanical polishing of hard disk substrate with {alpha}-alumina-g-polystyrene sulfonic acid composite abrasive

    Energy Technology Data Exchange (ETDEWEB)

    Lei Hong, E-mail: hong_lei2005@yahoo.com.c [Research Center of Nano-science and Nano-technology, Shanghai University, Shanghai 200444 (China); Bu Naijing; Chen Ruling; Hao Ping [Research Center of Nano-science and Nano-technology, Shanghai University, Shanghai 200444 (China); Neng Sima; Tu Xifu; Yuen Kwok [Shenzhen Kaifa Magnetic Recording Co., LTD, Shenzhen, 518035 (China)

    2010-05-03

    {alpha}-Alumina-g-polystyrene sulfonic acid ({alpha}-Al{sub 2}O{sub 3}-g-PSS) composite abrasive was prepared by surface activation, graft polymerization and sulfonation, successively. The composition, dispersibility and morphology of the product were characterized by Fourier transformed infrared spectroscopy, laser particle size analysis and scanning electron microscopy, respectively. The chemical mechanical polishing (CMP) performances of the composite abrasive on hard disk substrate with nickel-phosphorous plating were investigated. The microscopy images of the polished surfaces show that {alpha}-Al{sub 2}O{sub 3}-g-PSS composite abrasive results in improved CMP and post-CMP cleaning performances than pure {alpha}-alumina abrasive under the same testing conditions.

  20. Chemical mechanical polishing of BTO thin film for vertical sidewall patterning of high-density memory capacitor

    International Nuclear Information System (INIS)

    Kim, Nam-Hoon; Ko, Pil-Ju; Seo, Yong-Jin; Lee, Woo-Sun

    2006-01-01

    Most high-k materials cannot to be etched easily. Problems such as low etch rate, poor sidewall angle, plasma damage, and process complexity have emerged in high-density DRAM fabrication. Chemical mechanical polishing (CMP) by the damascene process has been used to pattern high-k materials for high-density capacitor. Barium titanate (BTO) thin film, a typical high-k material, was polished with three types of silica slurry having different pH values. Sufficient removal rate with adequate selectivity to realize the pattern mask of tetra-ethyl ortho-silicate (TEOS) film for the vertical sidewall angle was obtained. The changes of X-ray diffraction pattern and dielectric constant by CMP process were negligible. Planarization was also achieved for the subsequent multilevel processes. Our new CMP approach will provide a guideline for effective patterning of high-k materials by CMP

  1. Influence of wood-derived biochar on the physico-mechanical and chemical characteristics of agricultural soils

    Science.gov (United States)

    Ahmed, Ahmed S. F.; Raghavan, Vijaya

    2018-01-01

    Amendment of soil with biochar has been shown to enhance fertility and increase crop productivity, but the specific influence of biochar on soil workability remains unclear. Select physico-mechanical and chemical properties of clay loam and sandy loam soils were measured after amendment with wood-derived biochar of two particle size ranges (0.5-425 and 425-850 µm) at five dosages ranging from 0.5 to 10% dry weight. Whereas the clay loam soil workability decreased when the finer wood-derived biochar was applied at rates of 6 or 10%, soil fertility was not enhanced. The sandy loam soil, due to Proctor compaction, significantly decreased in bulk density with 6 and 10% wood-derived biochar amendments indicating higher soil resistance to compaction.

  2. Physical-chemical model for the mechanism of glass corrosion with particular consideration of simulated radioactive waste glasses

    International Nuclear Information System (INIS)

    Grambow, B.

    1985-01-01

    A physical-chemical model for the mechanism of glass corrosion is described. This model can be used for predicting, interpreting, and extrapolating experimental results. In static leaching tests the rate of corrosion generally decreases with time. Some authors assume that the surface layer, which grows during the course of the reaction, protects the underlying glass from further attack by the aqueous phase. Other authors assume that the saturation effects in solution are responsible for reducing the rate of the reaction. It is demonstrated within the scope of this work that examples can be found for both concepts; however, transport processes in the surface layer and/or in solution can be excluded as rate-determining processes within a majority of the examined cases. The location of the corrosion reaction is the boundary surface between the surface layer and the not yet attacked glass (transition zone)

  3. Influence of Wafer Edge Geometry on Removal Rate Profile in Chemical Mechanical Polishing: Wafer Edge Roll-Off and Notch

    Science.gov (United States)

    Fukuda, Akira; Fukuda, Tetsuo; Fukunaga, Akira; Tsujimura, Manabu

    2012-05-01

    In the chemical mechanical polishing (CMP) process, uniform polishing up to near the wafer edge is essential to reduce edge exclusion and improve yield. In this study, we examine the influences of inherent wafer edge geometries, i.e., wafer edge roll-off and notch, on the CMP removal rate profile. We clarify the areas in which the removal rate profile is affected by the wafer edge roll-off and the notch, as well as the intensity of their effects on the removal rate profile. In addition, we propose the use of a small notch to reduce the influence of the wafer notch and present the results of an examination by finite element method (FEM) analysis.

  4. Effect of harvest time and field retting duration on the chemical composition, morphology and mechanical properties of hemp fibers

    DEFF Research Database (Denmark)

    Liu, Ming; Fernando, Dinesh; Daniel, Geoffrey

    2015-01-01

    tThe large variability in the mechanical properties of hemp fibers is an issue in relation to their use inhigh-grade composites. The objective of the present study was to determine the optimal growth stage forharvesting hemp fibers for use in composites and to evaluate the effect of field retting......% at seed maturity.A highly significant reduction in cellulose deposition in fiber cell walls was reflected by reduced fiberwall thickness with plant maturity and was related to the development and ripening of hemp seeds.A statistically significant increase in lignin deposition and a slight decrease...... in pectins in hemp fibercell walls were also noted with stem maturity. Microscopy observations and histochemical analyzescorroborated the results from the chemical analyzes and revealed variations in morphological aspectsand spatial micro-distributions of carbohydrates and lignin within the cell structure...

  5. Mechanical and chemical properties of polyvinyl alcohol modified cement mortar with silica fume used as matrix including radioactive waste

    International Nuclear Information System (INIS)

    Dakroury, A. M.

    2007-01-01

    This paper discussed the mechanical and chemical properties of polyvinyl alcohol - modified cement mortar with silica fume to assess the safety for disposal of radioactive waste. The modified cement mortars containing polyvinyl alcohol (PVA) in the presence of 10 % silica fume (SF) .The chemical reaction between polymer and cement - hydrated product were investigated by the Infrared Spectral Technology, Differential Thermal Analysis and X-ray diffraction. The leaching of 137Cs from a waste composite into a surrounding fluid has been studied .The results shown that PVA increases the strength and decreases the porosity. The increase in strength duo to the interaction of PVA with cement , may be forming some new compound that fill the pores or improve the bond between the cement . The pozzolanic reaction of the SF increases the calcium silicate hydrates in the hardening matrix composites. There is distinct change in the refinement of the pore structure in cement composites giving fewer capillary pores and more of the finer gel pores

  6. Study on the Effects of Corrosion Inhibitor According to the Functional Groups for Cu Chemical Mechanical Polishing in Neutral Environment

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Sang Won; Kim, Jae Jeong [Institute of Chemical Process, Seoul National University, Seoul (Korea, Republic of)

    2015-08-15

    As the aluminum (Al) metallization process was replaced with copper (Cu), the damascene process was introduced, which required the planarization step to eliminate over-deposited Cu with Chemical Mechanical Polishing (CMP) process. In this study, the verification of the corrosion inhibitors, one of the Cu CMP slurry components, was conducted to find out the tendency regarding the carboxyl and amino functional group in neutral environment. Through the results of etch rate, removal rate, and chemical ability of corrosion inhibitors based on 1H-1,2,4-triazole as the base corrosion inhibitor, while the amine functional group presents high Cu etching ability, carboxyl functional group shows lower Cu etching ability than base-corrosion inhibitor which means that it increases passivation effect by making strong passivation layer. It implies that the corrosion inhibitor with amine functional group was proper to apply for 1st Cu CMP slurry owing to the high etch rate and with carboxyl functional group was favorable for the 2nd Cu CMP slurry due to the high Cu removal rate/dissolution rate ratio.

  7. Material Characterization in the Electro-Analytic Approach for Applications in Chemical Mechanical Planarization and Electrochemical Energy Systems

    Science.gov (United States)

    Rock, Simon E.

    The work presented in this thesis covers electro-analytical characterization for multiple applications in material science. Electrochemical techniques were used to investigate soluble film formation on metals used in chemical mechanical planarization in order to better understand the removal rate process by studying new chemicals proposed by groups in industry. Second, an ionic liquid was used as an electrolyte in a lithium ion cathode half cell to show the essential functionality of the IL and the temperature advantage over traditional electrolytes. Lastly, a comprehensive measurement for charge recombination in dye-sensitized solar cells was performed using both open-circuit voltage decay and impedance spectroscopy, which may be used to better understand the limiting factors that affect the cell's efficiently. Electrochemical techniques were applied to new methods and materials to extend the development of material manufacturing and advance the measurement process. The fabrication of interconnect structures for semiconductor devices requires low down-pressure chemical mechanical planarization (CMP) of Ta barrier layers. Guanidine carbonate (GC) serves as an effective surface-complexing agent for such CMP applications, where the rate of Ta removal can be chemically controlled through pH-tuned selectivity with respect to the removal of Cu lines. Electrochemical techniques are employed in this work to study the surface-modifying roles of GC that make this chemical an attractive complexing agent for Ta CMP. In addition, the effects of including H2O2 (an oxidizer) and dodecyl benzene sulfonic acid (DBSA, a dissolution inhibitor for Cu) in GC-based CMP solutions are investigated to examine the selective CMP mechanisms of Ta and Cu in these solutions. The results suggest that the removal of Ta is supported in part by structurally weak guanidinium-tantalic-acid surface complexes formed on Ta/Ta2O5. The bicarbonate/carbonate anions of GC also facilitate Ta removal through

  8. Mechanism of dark decomposition of iodine donor in the active medium of a pulsed chemical oxygen - iodine laser

    International Nuclear Information System (INIS)

    Andreeva, Tamara L; Kuznetsova, S V; Maslov, A I; Sorokin, Vadim N

    2002-01-01

    A scheme is proposed that describes the dark decomposition of iodide - the donor of iodine - and the relaxation of singlet oxygen in the chlorine-containing active medium of a pulsed chemical oxygen - iodine laser (COIL). For typical compositions of the active media of pulsed COILs utilising CH 3 I molecules as iodine donors, a branching chain reaction of the CH 3 I decomposition accompanied by the efficient dissipation of singlet oxygen is shown to develop even at the stage of filling the active volume. In the active media with CF 3 I as the donor, a similar chain reaction is retarded due to the decay of CF 3 radicals upon recombination with oxygen. The validity of this mechanism is confirmed by a rather good agreement between the results of calculations and the available experimental data. The chain decomposition of alkyliodides accompanied by an avalanche production of iodine atoms represents a new way of efficient chemical production of iodine for a COIL. (active media)

  9. Coupled effects of the precipitation of secondary species on the mechanical behaviour and chemical degradation of concretes

    International Nuclear Information System (INIS)

    Planel, D.

    2002-06-01

    Sulfate attack of cement-based materials remains an important problem for the durability assessment of containers and disposal engineering barriers dedicated to the long-term storage of radioactive wastes since underground water which may reach these elements contains small quantities of sulfates (7-31 mmol/1). This work contributes to the study of sulfate-induced damage mechanisms, to their understanding and modelling. The experimental phases of this study aimed at the understanding of the different physico-chemical phenomena involved during an external sulfate attack at following their evolution and their impact on the transport and mechanical properties of the material. Leaching experiments in pure water and in a solution of sodium sulfate (with a sulfate content of 15 mmol/1), have been performed simultaneously on OPC paste (w/c 0,4)in order to allow a comparison of test results. The frequent analysis of the leachant has shown a consumption of sulfate ions by the matrix, proportional to the square rate of time. The use of X-Ray Diffraction on powders, obtained by scraping the calcium-depleted part of the samples, led a precise view of the cement paste mineralogy, during sulfate attack. The use of Scanning Electron Microscopy (SEM) and Energy Dispersive Spectrometer (EDS) confirmed the correctness of XRD profiles and brought important informations concerning cracking distribution and localisation. In addition, a visual monitoring of crack appearance and evolution completed the previous observations. Based on these experimental results, a simplified model accounting for the chemical degradation of cement paste in sulfated water has been proposed. A geochemical code, coupling the chemistry in solution with the reactive transport in porous media has been used for this purpose. The model accounts for the evolution of transport properties (diffusivity) associated with the calcium-depleting of the cement matrix and the precipitation of secondary phases (gypsum

  10. Studies of some physical-mechanical and chemical property in organic waste to use for biogas production in Cuba

    International Nuclear Information System (INIS)

    Martinez Hernández, Carlos M.; Oechsner, Hans; Brulé, Mathieu; Marañon Maison, Elena

    2014-01-01

    The work approaches the study of some physical-mechanical and chemical properties of agricultural organic residuals which can be used in the biogas production in Cuba´s plants production, using their co-fermentation. It has also been necessary to collect agricultural biomass, canteen waste, influent and effluents of a biogas plant Nina Bonita) next to Santa Clara city, Cuba, for their later analysis. the investigated biomass samples (sorghum.49V-96, sorghum-132 R, sunflower JE-94, cassava, corn, sweet potato skin, bread, potatoes and peanut skin); as well as the influent and effluents of the investigated biogas plant were analyzed in some laboratories belonging to the Central University of Las Villas. Other analyses were done in the biogas lab at Hohenheim University. The maximum value of specifies methane yield achieved was with the sunflower JE-94 (0.393 m3/kg VS), while the minimum value was reached with the peanut shell (0.095 m3/Kg VS).The main objective of the work consists on determining some of the physical-mechanical and chemical properties like carbon nitrogen ratio (C/N), specific methane production (m3/kg VS), total solid (TS), organic total solid (oTS), alkalinity (pH) and volatile solid (VS) in agricultural organic residuals and canteen waste, which can be used for the production of biogas under co-fermentation with animal manure under Cuban conditions. In order to do this, we developed some experiments to syringes, small and real scale. (author)

  11. [Incidence and risk factors of venous thromboembolism in major spinal surgery with no chemical or mechanical prophylaxis].

    Science.gov (United States)

    Rojas-Tomba, F; Gormaz-Talavera, I; Menéndez-Quintanilla, I E; Moriel-Durán, J; García de Quevedo-Puerta, D; Villanueva-Pareja, F

    2016-01-01

    To evaluate the incidence of venous thromboembolism in spine surgery with no chemical and mechanical prophylaxis, and to determine the specific risk factors for this complication. A historical cohort was analysed. All patients subjected to major spinal surgery, between January 2010 and September 2014, were included. No chemical or mechanical prophylaxis was administered in any patient. Active mobilisation of lower limbs was indicated immediately after surgery, and early ambulation started in the first 24-48 hours after surgery. Clinically symptomatic cases were confirmed by Doppler ultrasound of the lower limbs or chest CT angiography. A sample of 1092 cases was studied. Thromboembolic events were observed in 6 cases (.54%); 3 cases (.27%) with deep venous thrombosis and 3 cases (.27%) with pulmonary thromboembolism. A lethal case was identified (.09%). There were no cases of major bleeding or epidural haematoma. The following risk factors were identified: a multilevel fusion at more than 4 levels, surgeries longer than 130 minutes, patients older than 70 years of age, hypertension, and degenerative scoliosis. There is little scientific evidence on the prevention of thromboembolic events in spinal surgery. In addition to the disparity of prophylactic methods indicated by different specialists, it is important to weigh the risk-benefit of intra- and post-operative bleeding, and even the appearance of an epidural haematoma. Prophylaxis should be assessed in elderly patients over 70 years old, who are subjected to surgeries longer than 130 minutes, when 4 or more levels are involved. Copyright © 2015 SECOT. Published by Elsevier Espana. All rights reserved.

  12. A progress report for the large block test of the coupled thermal-mechanical-hydrological-chemical processes

    International Nuclear Information System (INIS)

    Lin, W.; Wilder, D.G.; Blink, J.

    1994-10-01

    This is a progress report on the Large Block Test (LBT) project. The purpose of the LBT is to study some of the coupled thermal-mechanical-hydrological-chemical (TMHC) processes in the near field of a nuclear waste repository under controlled boundary conditions. To do so, a large block of Topopah Spring tuff will be heated from within for about 4 to 6 months, then cooled down for about the same duration. Instruments to measure temperature, moisture content, stress, displacement, and chemical changes will be installed in three directions in the block. Meanwhile, laboratory tests will be conducted on small blocks to investigate individual thermal-mechanical, thermal-hydrological, and thermal-chemical processes. The fractures in the large block will be characterized from five exposed surfaces. The minerals on fracture surfaces will be studied before and after the test. The results from the LBT will be useful for testing and building confidence in models that will be used to predict TMHC processes in a repository. The boundary conditions to be controlled on the block include zero moisture flux and zero heat flux on the sides, constant temperature on the top, and constant stress on the outside surfaces of the block. To control these boundary conditions, a load-retaining frame is required. A 3 x 3 x 4.5 m block of Topopah Spring tuff has been isolated on the outcrop at Fran Ridge, Nevada Test Site. Pre-test model calculations indicate that a permeability of at least 10 -15 m 2 is required so that a dryout zone can be created within a practical time frame when the block is heated from within. Neutron logging was conducted in some of the vertical holes to estimate the initial moisture content of the block. It was found that about 60 to 80% of the pore volume of the block is saturated with water. Cores from the vertical holes have been used to map the fractures and to determine the properties of the rock. A current schedule is included in the report

  13. Synthesis of polycarbonate urethane elastomers and effects of the chemical structures on their thermal, mechanical and biocompatibility properties.

    Science.gov (United States)

    Zhu, Rong; Wang, Yiyu; Zhang, Zongrui; Ma, Daiwei; Wang, Xinyu

    2016-06-01

    In this study, to obtain biomedical polyurethane elastomers with good mechanical properties and biocompatibility, a series of polycarbonate urethanes were synthesized via a two-step solution of polymerization method using the poly(1,6-hexanediol)carbonate diols (PCDL) as the soft segment, 4,4'-methylenebis(cyclohexyl isocyanate) (H12MDI), 1,6-hexamethylene diisocyanate (HDI) and 1,4-butanediol (BDO) as the hard segment with dibutyltin dilaurate as the catalyst. In this article, we illustrated the physical behaviors were obviously influenced by synthetic routes. And their chemical and physical structures were investigated by gel permeation chromatograph (GPC), differential scanning calorimeter (DSC), fourier transform infrared spectrography (FT-IR) and mechanical properties tests. The surface wettability were studied by contact angle measurement (CA). As a kind of short-term implant biomaterial, the results of the hemolysis and platelet adhesive tests were recorded by spectrophotometer and scanning electron microscopy (SEM), indicating the materials have a great potential for developments and applications in biomedical field.

  14. Synthesis of polycarbonate urethane elastomers and effects of the chemical structures on their thermal, mechanical and biocompatibility properties

    Directory of Open Access Journals (Sweden)

    Rong Zhu

    2016-06-01

    Full Text Available In this study, to obtain biomedical polyurethane elastomers with good mechanical properties and biocompatibility, a series of polycarbonate urethanes were synthesized via a two-step solution of polymerization method using the poly(1,6-hexanediolcarbonate diols (PCDL as the soft segment, 4,4′-methylenebis(cyclohexyl isocyanate (H12MDI, 1,6-hexamethylene diisocyanate (HDI and 1,4-butanediol (BDO as the hard segment with dibutyltin dilaurate as the catalyst. In this article, we illustrated the physical behaviors were obviously influenced by synthetic routes. And their chemical and physical structures were investigated by gel permeation chromatograph (GPC, differential scanning calorimeter (DSC, fourier transform infrared spectrography (FT-IR and mechanical properties tests. The surface wettability were studied by contact angle measurement (CA. As a kind of short-term implant biomaterial, the results of the hemolysis and platelet adhesive tests were recorded by spectrophotometer and scanning electron microscopy (SEM, indicating the materials have a great potential for developments and applications in biomedical field.

  15. Elucidating Direct Photolysis Mechanisms of Different Dissociation Species of Norfloxacin in Water and Mg2+ Effects by Quantum Chemical Calculations.

    Science.gov (United States)

    Wang, Se; Wang, Zhuang

    2017-11-11

    The study of pollution due to combined antibiotics and metals is urgently needed. Photochemical processes are an important transformation pathway for antibiotics in the environment. The mechanisms underlying the effects of metal-ion complexation on the aquatic photochemical transformation of antibiotics in different dissociation forms are crucial problems in science, and beg solutions. Herein, we investigated the mechanisms of direct photolysis of norfloxacin (NOR) in different dissociation forms in water and metal ion Mg 2+ effects using quantum chemical calculations. Results show that different dissociation forms of NOR had different maximum electronic absorbance wavelengths (NOR 2+ direct photolysis pathways were de-ethylation (N7-C8 bond cleavage) and decarboxylation (C2-C5 bond cleavage). Furthermore, the presence of Mg 2+ changed the order of the wavelength at maximum electronic absorbance (NOR⁺-Mg 2+ direct photolysis of NOR⁰, NOR⁺, and NOR 2+ . The calculated TS results indicated that the presence of Mg 2+ increased E a for most direct photolysis pathways of NOR, while it decreased E a for some direct photolysis pathways such as the loss of the piperazine ring and the damage of the piperazine ring of NOR⁰ and the defluorination of NOR⁺.

  16. Mechanical control of the plasmon coupling with Au nanoparticle arrays fixed on the elastomeric film via chemical bond

    Science.gov (United States)

    Bedogni, Elena; Kaneko, Satoshi; Fujii, Shintaro; Kiguchi, Manabu

    2017-03-01

    We have fabricated Au nanoparticle arrays on the flexible poly(dimethylsiloxane) (PDMS) film. The nanoparticles were bound to the film via a covalent bond by a ligand exchange reaction. Thanks to the strong chemical bonding, highly stable and uniformly dispersed Au nanoparticle arrays were fixed on the PDMS film. The Au nanoparticle arrays were characterized by the UV-vis, scanning electron microscope (SEM) and surface enhanced Raman scattering (SERS). The UV-vis and SEM measurements showed the uniformity of the surface-dispersed Au nanoparticles, and SERS measurement confirmed the chemistry of the PDMS film. Reflecting the high stability and the uniformity of the Au nanoparticle arrays, the plasmon wavelength of the Au nanoparticles reversely changed with modulation of the interparticle distance, which was induced by the stretching of the PDMS film. The plasmon wavelength linearly decreased from 664 to 591 nm by stretching of 60%. The plasmon wavelength shift can be explained by the change in the strength of the plasmon coupling which is mechanically controlled by the mechanical strain.

  17. Influence of Powder Outgassing Conditions on the Chemical, Microstructural, and Mechanical Properties of a 14 wt% Cr Ferritic ODS Steel

    Science.gov (United States)

    Sornin, D.; Giroux, P.-F.; Rigal, E.; Fabregue, D.; Soulas, R.; Hamon, D.

    2017-11-01

    Oxide dispersion-strengthened ferritic stainless steels are foreseen as fuel cladding tube materials for the new generation of sodium fast nuclear reactors. Those materials, which exhibit remarkable creep properties at high temperature, are reinforced by a dense precipitation of nanometric oxides. This precipitation is obtained by mechanical alloying of a powder and subsequent consolidation. Before consolidation, to obtain a fully dense material, the powder is vacuumed to outgas trapped gases and species adsorbed at the surface of the powder particles. This operation is commonly done at moderate to high temperature to evacuate as much as possible volatile species. This paper focuses on the influence of outgassing conditions on some properties of the further consolidated materials. Chemical composition and microstructural characterization of different materials obtained from various outgassing cycles are compared. Finally, impact toughness of those materials is evaluated by using Charpy testing. This study shows a significant influence of the outgassing conditions on the mechanical properties of the consolidated material. However, microstructure and oxygen contents seem poorly impacted by the various outgassing conditions.

  18. Mechanisms of chemical vapor generation by aqueous tetrahydridoborate. Recent developments toward the definition of a more general reaction model

    Science.gov (United States)

    D'Ulivo, Alessandro

    2016-05-01

    A reaction model describing the reactivity of metal and semimetal species with aqueous tetrahydridoborate (THB) has been drawn taking into account the mechanism of chemical vapor generation (CVG) of hydrides, recent evidences on the mechanism of interference and formation of byproducts in arsane generation, and other evidences in the field of the synthesis of nanoparticles and catalytic hydrolysis of THB by metal nanoparticles. The new "non-analytical" reaction model is of more general validity than the previously described "analytical" reaction model for CVG. The non-analytical model is valid for reaction of a single analyte with THB and for conditions approaching those typically encountered in the synthesis of nanoparticles and macroprecipitates. It reduces to the previously proposed analytical model under conditions typically employed in CVG for trace analysis (analyte below the μM level, borane/analyte ≫ 103 mol/mol, no interference). The non-analytical reaction model is not able to explain all the interference effects observed in CVG, which can be achieved only by assuming the interaction among the species of reaction pathways of different analytical substrates. The reunification of CVG, the synthesis of nanoparticles by aqueous THB and the catalytic hydrolysis of THB inside a common frame contribute to rationalization of the complex reactivity of aqueous THB with metal and semimetal species.

  19. Influence of PVA and silica on chemical, thermo-mechanical and electrical properties of Celluclast-treated nanofibrillated cellulose composites.

    Science.gov (United States)

    Poyraz, Bayram; Tozluoğlu, Ayhan; Candan, Zeki; Demir, Ahmet; Yavuz, Mustafa

    2017-11-01

    This study reports on the effects of organic polyvinyl alcohol (PVA) and inorganic silica polymer on properties of Celluclast-treated nanofibrillated cellulose composites. Nanofibrillated cellulose was isolated from Eucalyptus camaldulensis and prior to high-pressure homogenizing was pretreated with Celluclast enzyme in order to lower energy consumption. Three nanocomposite films were fabricated via the casting process: nanofibrillated cellulose (CNF), nanocellulose-PVA (CNF-P) and nanocellulose-silica (CNF-Si). Chemical characterization, crystallization and thermal stability were determined using FT-IR and TGA. Morphological alterations were monitored with SEM. The Young's and storage moduli of the nanocomposites were determined via a universal testing machine and DTMA. The real and imaginary parts of permittivity and electric modulus were evaluated using an impedance analyzer. The crystallinity values of the nanocomposites calculated from the FT-IR were in agreement with the TGA results, showing that the lowest crystallinity value was in the CNF-Si. The CNF-P displayed the highest tensile strength. At a high temperature interval, the storage modulus of the CNF-Si was greater than that of the CNF or CNF-P. The CNF-Si also exhibited a completed singular relaxation process, while the CNF and the CNF-P processes were uncompleted. Consequently, in terms of industrial applications, although the CNF-P composite had mechanical advantages, the CNF-Si composite displayed the best thermo-mechanical properties. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Two-component spin-coated Ag/CNT composite films based on a silver heterogeneous nucleation mechanism adhesion-enhanced by mechanical interlocking and chemical grafting

    Science.gov (United States)

    Zhang, Yang; Kang, Zhixin; Bessho, Takeshi

    2017-03-01

    In this paper, a new method for the synthesis of silver carbon nanotube (Ag/CNT) composite films as conductive connection units for flexible electronic devices is presented. This method is about a two-component solution process by spin coating with an after-treatment annealing process. In this method, multi-walled carbon nanotubes (MWCNTs) act as the core of silver heterogeneous nucleation, which can be observed and analyzed by a field-emission scanning electron microscope. With the effects of mechanical interlocking, chemical grafting, and annealing, the interfacial adhesive strength between films and PET sheets was enhanced to 12 N cm-1. The tensile strength of the Ag/CNT composite films was observed to increase by 38% by adding 5 g l-1 MWCNTs. In the four-probe method, the resistivity of Ag/CNT-5 declined by 78.2% compared with pristine Ag films. The anti-fatigue performance of the Ag/CNT composite films was monitored by cyclic bending deformation and the results revealed that the growth rate of electrical resistance during the deformation was obviously retarded. As for industrial application, this method provides an efficient low-cost way to prepare Ag/CNT composite films and can be further applied to other coating systems.

  1. Evaluation of the catalytic mechanism of AICAR transformylase by pH-dependent kinetics, mutagenesis, and quantum chemical calculations.

    Science.gov (United States)

    Shim, J H; Wall, M; Benkovic, S J; Díaz, N; Suárez, D; Merz, K M

    2001-05-23

    The catalytic mechanism of 5-aminoimidazole-4-carboxamide ribonucleotide transformylase (AICAR Tfase) is evaluated with pH dependent kinetics, site-directed mutagenesis, and quantum chemical calculations. The chemistry step, represented by the burst rates, was not pH-dependent, which is consistent with our proposed mechanism that the 4-carboxamide of AICAR assists proton shuttling. Quantum chemical calculations on a model system of 5-amino-4-carboxamide imidazole (AICA) and formamide using the B3LYP/6-31G level of theory confirmed that the 4-carboxamide participated in the proton-shuttling mechanism. The result also indicated that the amide-assisted mechanism is concerted such that the proton transfers from the 5-amino group to the formamide are simultaneous with nucleophilic attack by the 5-amino group. Because the process does not lead to a kinetically stable intermediate, the intramolecular proton transfer from the 5-amino group through the 4-carboxamide to the formamide proceeds in the same transition state. Interestingly, the calculations predicted that protonation of the N3 of the imidazole of AICA would reduce the energy barrier significantly. However, the pK(a) of the imidazole of AICAR was determined to be 3.23 +/- 0.01 by NMR titration, and AICAR is likely to bind to the enzyme with its imidazole in the free base form. An alternative pathway was suggested by modeling Lys266 to have a hydrogen-bonding interaction with the N3 of the imidazole of AICAR. Lys266 has been implicated in catalysis based on mutagenesis studies and the recent X-ray structure of AICAR Tfase. The quantum chemical calculations on a model system that contains AICA complexed with CH3NH3+ as a mimic of the Lys residue confirmed that such an interaction lowered the activation energy of the reaction and likewise implicated the 4-carboxamide. To experimentally verify this hypothesis, we prepared the K266R mutant and found that its kcat is reduced by 150-fold from that of the wild type

  2. Process Parameters for Successful Synthesis of Carbon Nanotubes by Chemical Vapor Deposition: Implications for Chemical Mechanisms and Life-cycle Assessment

    Science.gov (United States)

    Xue, Ke

    Manufacturing of carbon nanotubes (CNTs) via chemical vapor deposition (CVD) calls for thermal treatment associated with gas-phase rearrangement and catalyst deposition to achieve high cost efficiency and limited influence on environmental impact. Taking advantage of higher degree of structure control and economical efficiency, catalytic chemical vapor deposition (CCVD) has currently become the most prevailing synthesis approach for the synthesis of large-scale pure CNTs in past years. Because the synthesis process of CNTs dominates the potential ecotoxic impacts, materials consumption, energy consumption and greenhouse gas emissions should be further limited to efficiently reduce life cycle ecotoxicity of carbon naotubes. However, efforts to reduce energy and material requirements in synthesis of CNTs by CCVD are hindered by a lack of mechanistic understanding. In this thesis, the effect of operating parameters, especially the temperature, carbon source concentration, and residence time on the synthesis were studied to improve the production efficiency in a different angle. Thus, implications on the choice of operating parameters could be provided to help the synthesis of carbon nanotubes. Here, we investigated the typical operating parameters in conditions that have yielded successful CNT production in the published academic literature of over seventy articles. The data were filtered by quality of the resultant product and deemed either "successful" or "unsuccessful" according to the authors. Furthermore, growth rate data were tabulated and used as performance metric for the process whenever possible. The data provided us an opportunity to prompt possible and common methods for practioners in the synthesis of CNTs and motivate routes to achieve energy and material minimization. The statistical analysis revealed that methane and ethylene often rely on thermal conversion process to form direct carbon precursor; further, methane and ethylene could not be the direct

  3. Nanoscale chemical and mechanical characterization of thin films:sum frequency generation (SFG) vibrational spectroscopy at buriedinterfaces

    Energy Technology Data Exchange (ETDEWEB)

    Kweskin, Sasha Joseph [Univ. of California, Berkeley, CA (United States)

    2006-01-01

    Sum frequency generation (SFG) surface vibrational spectroscopy was used to characterize interfaces pertinent to current surface engineering applications, such as thin film polymers and novel catalysts. An array of advanced surface science techniques like scanning probe microscopy (SPM), x-ray photoelectron spectroscopy (XPS), gas chromatography (GC) and electron microscopy were used to obtain experimental measurements complementary to SFG data elucidating polymer and catalyst surface composition, surface structure, and surface mechanical behavior. Experiments reported in this dissertation concentrate on three fundamental questions: (1) How does the interfacial molecular structure differ from that of the bulk in real world applications? (2) How do differences in chemical environment affect interface composition or conformation? (3) How do these changes correlate to properties such as mechanical or catalytic performance? The density, surface energy and bonding at a solid interface dramatically alter the polymer configuration, physics and mechanical properties such as surface glass transition, adhesion and hardness. The enhanced sensitivity of SFG at the buried interface is applied to three systems: a series of acrylates under compression, the compositions and segregation behavior of binary polymer polyolefin blends, and the changes in surface structure of a hydrogel as a function of hydration. In addition, a catalytically active thin film of polymer coated nanoparticles is investigated to evaluate the efficacy of SFG to provide in situ information for catalytic reactions involving small mass adsorption and/or product development. Through the use of SFG, in situ total internal reflection (TIR) was used to increase the sensitivity of SFG and provide the necessary specificity to investigate interfaces of thin polymer films and nanostructures previously considered unfeasible. The dynamic nature of thin film surfaces is examined and it is found that the non

  4. The mechanism study of efficient degradation of hydrophobic nonylphenol in solution by a chemical-free technology of sonophotolysis

    Energy Technology Data Exchange (ETDEWEB)

    Xu, L.J.; Chu, W., E-mail: cewchu@polyu.edu.hk; Lee, Po-Heng; Wang, Jian

    2016-05-05

    Highlights: • pH influenced NP sonophotolysis by changing its existing form and light absorption. • NO{sub 3}{sup −} accelerated NP sonophotolysis while HCO{sub 3}{sup −} showed insignificant influence. • Both ortho- and meta-hydroxy-NP species can exist together thermodynamically. • Only the ortho-4-nonyl-benzoquinone is dominant thermodynamically. • The mechanism of ortho-hydroxy-NP formation was the addition of HO· and H· - Abstract: Nonylphenol is a hydrophobic endocrine disrupting compound, which can inhibit the growth of sewage bacteria in biological processes. This study investigated the degradation of 4-n-nonylphenol (NP) in water by a chemical-free technology of sonophotolysis with emphasis on the impacts of several important parameters, including light intensity, solution pH, two commonly seen inorganic ions (i.e. NO{sub 3}{sup −} and HCO{sub 3}{sup −}), and principally on the examination of degradation mechanisms. It was found that, solution pH could significantly influence both NP degradation efficiency and the synergistic effect of sonophotolytic process, where higher synergistic effect was obtained at more acidic condition. In addition, the presence of NO{sub 3}{sup −} accelerated NP degradation by both acting as a photosensitizer and providing NO{sub 2}· radicals, while HCO{sub 3}{sup −} had little effect on NP degradation. Identification of intermediates of NP degradation indicated that NP sonophotolysis was mainly initiated by the formation of hydroxy-NP, and a new intermediate di-hydroxy-NP was identified for the first time ever in this study. Through thermodynamic analysis, results indicated that both ortho- and meta-hydroxy-NP species can coexist in the solution but the ortho-4-NBZQ (4-nonyl-benzoquinone) is dominant. In addition, the mechanism of ortho-hydroxy-NP formation was suggested by the addition of HO· and H· radicals.

  5. Mechanical and Microstructure Study of Nickel-Based ODS Alloys Processed by Mechano-Chemical Bonding and Ball Milling

    Science.gov (United States)

    Amare, Belachew N.

    Due to the need to increase the efficiency of modern power plants, land-based gas turbines are designed to operate at high temperature creating harsh environments for structural materials. The elevated turbine inlet temperature directly affects the materials at the hottest sections, which includes combustion chamber, blades, and vanes. Therefore, the hottest sections should satisfy a number of material requirements such as high creep strength, ductility at low temperature, high temperature oxidation and corrosion resistance. Such requirements are nowadays satisfied by implementing superalloys coated by high temperature thermal barrier coating (TBC) systems to protect from high operating temperature required to obtain an increased efficiency. Oxide dispersive strengthened (ODS) alloys are being considered due to their high temperature creep strength, good oxidation and corrosion resistance for high temperature applications in advanced power plants. These alloys operating at high temperature are subjected to different loading systems such as thermal, mechanical, and thermo-mechanical combined loads at operation. Thus, it is critical to study the high temperature mechanical and microstructure properties of such alloys for their structural integrity. The primary objective of this research work is to investigate the mechanical and microstructure properties of nickel-based ODS alloys produced by combined mechano-chemical bonding (MCB) and ball milling subjected to high temperature oxidation, which are expected to be applied for high temperature turbine coating with micro-channel cooling system. Stiffness response and microstructure evaluation of such alloy systems was studied along with their oxidation mechanism and structural integrity through thermal cyclic exposure. Another objective is to analyze the heat transfer of ODS alloy coatings with micro-channel cooling system using finite element analysis (FEA) to determine their feasibility as a stand-alone structural

  6. Understanding the undelaying mechanism of HA-subtyping in the level of physic-chemical characteristics of protein.

    Directory of Open Access Journals (Sweden)

    Mansour Ebrahimi

    Full Text Available The evolution of the influenza A virus to increase its host range is a major concern worldwide. Molecular mechanisms of increasing host range are largely unknown. Influenza surface proteins play determining roles in reorganization of host-sialic acid receptors and host range. In an attempt to uncover the physic-chemical attributes which govern HA subtyping, we performed a large scale functional analysis of over 7000 sequences of 16 different HA subtypes. Large number (896 of physic-chemical protein characteristics were calculated for each HA sequence. Then, 10 different attribute weighting algorithms were used to find the key characteristics distinguishing HA subtypes. Furthermore, to discover machine leaning models which can predict HA subtypes, various Decision Tree, Support Vector Machine, Naïve Bayes, and Neural Network models were trained on calculated protein characteristics dataset as well as 10 trimmed datasets generated by attribute weighting algorithms. The prediction accuracies of the machine learning methods were evaluated by 10-fold cross validation. The results highlighted the frequency of Gln (selected by 80% of attribute weighting algorithms, percentage/frequency of Tyr, percentage of Cys, and frequencies of Try and Glu (selected by 70% of attribute weighting algorithms as the key features that are associated with HA subtyping. Random Forest tree induction algorithm and RBF kernel function of SVM (scaled by grid search showed high accuracy of 98% in clustering and predicting HA subtypes based on protein attributes. Decision tree models were successful in monitoring the short mutation/reassortment paths by which influenza virus can gain the key protein structure of another HA subtype and increase its host range in a short period of time with less energy consumption. Extracting and mining a large number of amino acid attributes of HA subtypes of influenza A virus through supervised algorithms represent a new avenue for

  7. Understanding the undelaying mechanism of HA-subtyping in the level of physic-chemical characteristics of protein.

    Science.gov (United States)

    Ebrahimi, Mansour; Aghagolzadeh, Parisa; Shamabadi, Narges; Tahmasebi, Ahmad; Alsharifi, Mohammed; Adelson, David L; Hemmatzadeh, Farhid; Ebrahimie, Esmaeil

    2014-01-01

    The evolution of the influenza A virus to increase its host range is a major concern worldwide. Molecular mechanisms of increasing host range are largely unknown. Influenza surface proteins play determining roles in reorganization of host-sialic acid receptors and host range. In an attempt to uncover the physic-chemical attributes which govern HA subtyping, we performed a large scale functional analysis of over 7000 sequences of 16 different HA subtypes. Large number (896) of physic-chemical protein characteristics were calculated for each HA sequence. Then, 10 different attribute weighting algorithms were used to find the key characteristics distinguishing HA subtypes. Furthermore, to discover machine leaning models which can predict HA subtypes, various Decision Tree, Support Vector Machine, Naïve Bayes, and Neural Network models were trained on calculated protein characteristics dataset as well as 10 trimmed datasets generated by attribute weighting algorithms. The prediction accuracies of the machine learning methods were evaluated by 10-fold cross validation. The results highlighted the frequency of Gln (selected by 80% of attribute weighting algorithms), percentage/frequency of Tyr, percentage of Cys, and frequencies of Try and Glu (selected by 70% of attribute weighting algorithms) as the key features that are associated with HA subtyping. Random Forest tree induction algorithm and RBF kernel function of SVM (scaled by grid search) showed high accuracy of 98% in clustering and predicting HA subtypes based on protein attributes. Decision tree models were successful in monitoring the short mutation/reassortment paths by which influenza virus can gain the key protein structure of another HA subtype and increase its host range in a short period of time with less energy consumption. Extracting and mining a large number of amino acid attributes of HA subtypes of influenza A virus through supervised algorithms represent a new avenue for understanding and

  8. Investigation research on the evaluation of a coupled thermo-hydro-mechanical-chemical phenomena. 3. Result Report

    International Nuclear Information System (INIS)

    Ishihara, Yoshinao; Ito, Takaya; Chijimatsu, Masakazu; Amemiya, Kiyoshi; Shiozaki, Isao

    2004-02-01

    In order to realize a coupling analysis in the near field of the geological disposal system, the coupling analysis code 'COUPLYS (Coupling analysis system)' on the Thermo-Hydro-Mechanical-Chemical (THMC) phenomena by THAMES, Dtransu and phreeqc, which are existing analysis code, is developed in this study. And some case analyses on THMC phenomena are carried out by this code. (1) Some supporting modules, which include the transfer of dissolution concentration and total concentration (dissolution + precipitation concentration), were prepared as a functional expansion. And in order to add on the function of treat de-gases and gases diffusion, accumulation and dilution phenomena, the mass transport analysis code was modified. (2) We have modified reactive transport module to treat ionic exchange, surface reaction and kinetic reaction in the each barrier. (3) We have prepared hydraulic conductivity module of buffer material depending on change of dry density due to chemical equilibrium (dissolution and precipitation of minerals), degradation of buffer material such as Ca-type bentonite and change of concentration of NaCl solutions. After THAMES, Dtransu, phreeqc and the hydraulic conductivity module were installed in COUPLYS (Coupling Analysis), verification study was carried out to check basic function. And we have modified COUPLYS to control coupling process. (4) In order to confirm the applicability of the developed THMC analysis code (existing analysis code and COUPLYS), we have carried out case analyses on 1-dimensional and 3-dimensional model which are including vitrified waste, over-pack, buffer material and rock in the HLW near-field. (author)

  9. The influence of hydrogen on the chemical, mechanical, optical/electronic, and electrical transport properties of amorphous hydrogenated boron carbide

    International Nuclear Information System (INIS)

    Nordell, Bradley J.; Karki, Sudarshan; Nguyen, Thuong D.; Rulis, Paul; Caruso, A. N.; Paquette, Michelle M.; Purohit, Sudhaunshu S.; Li, Han; King, Sean W.; Dutta, Dhanadeep; Gidley, David; Lanford, William A.

    2015-01-01

    Because of its high electrical resistivity, low dielectric constant (κ), high thermal neutron capture cross section, and robust chemical, thermal, and mechanical properties, amorphous hydrogenated boron carbide (a-B x C:H y ) has garnered interest as a material for low-κ dielectric and solid-state neutron detection applications. Herein, we investigate the relationships between chemical structure (atomic concentration B, C, H, and O), physical/mechanical properties (density, porosity, hardness, and Young's modulus), electronic structure [band gap, Urbach energy (E U ), and Tauc parameter (B 1/2 )], optical/dielectric properties (frequency-dependent dielectric constant), and electrical transport properties (resistivity and leakage current) through the analysis of a large series of a-B x C:H y thin films grown by plasma-enhanced chemical vapor deposition from ortho-carborane. The resulting films exhibit a wide range of properties including H concentration from 10% to 45%, density from 0.9 to 2.3 g/cm 3 , Young's modulus from 10 to 340 GPa, band gap from 1.7 to 3.8 eV, Urbach energy from 0.1 to 0.7 eV, dielectric constant from 3.1 to 7.6, and electrical resistivity from 10 10 to 10 15 Ω cm. Hydrogen concentration is found to correlate directly with thin-film density, and both are used to map and explain the other material properties. Hardness and Young's modulus exhibit a direct power law relationship with density above ∼1.3 g/cm 3 (or below ∼35% H), below which they plateau, providing evidence for a rigidity percolation threshold. An increase in band gap and decrease in dielectric constant with increasing H concentration are explained by a decrease in network connectivity as well as mass/electron density. An increase in disorder, as measured by the parameters E U and B 1/2 , with increasing H concentration is explained by the release of strain in the network and associated decrease in structural disorder. All of these correlations in a

  10. Mechanical, physico-chemical, and antimicrobial properties of gelatin-based film incorporated with catechin-lysozyme

    Directory of Open Access Journals (Sweden)

    Rawdkuen Saroat

    2012-11-01

    Full Text Available Abstract Background Microbial activity is a primary cause of deterioration in many foods and is often responsible for reduced quality and safety. Food-borne illnesses associated with E. coli O157:H7, S. aureus, S. enteritidis and L. monocytogenes are a major public health concern throughout the world. A number of methods have been employed to control or prevent the growth of these microorganisms in food. Antimicrobial packaging is one of the most promising active packaging systems for effectively retarding the growth of food spoilage and pathogenic microorganisms. The aim of this study was to determine the mechanical, physico-chemical properties and inhibitory effects of the fish gelatin films against selected food spoilage microorganisms when incorporated with catechin-lysozyme. Results The effect of the catechin-lysozyme combination addition (CLC: 0, 0.125, 0.25, and 0.5%, w/v on fish gelatin film properties was monitored. At the level of 0.5% addition, the CLC showed the greatest elongation at break (EAB at 143.17% with 0.039 mm thickness, and the lowest water vapor permeability (WVP at 6.5 x 10−8 g·mm·h-1·cm-2·Pa-1, whereas the control showed high tensile strength (TS and the highest WVP. Regarding color attributes, the gelatin film without CLC addition gave the highest lightness (L* 91.95 but lowest in redness (a*-1.29 and yellowness (b* 2.25 values. The light transmission of the film did not significantly decrease and nor did film transparency (p>0.05 with increased CLC. Incorporating CLC could not affect the film microstructure. The solubility of the gelatin based film incorporated with CLC was not affected, especially at a high level of addition (p>0.05. Inhibitory activity of the fish gelatin film against E.coli, S.aureus, L. innocua and S. cerevisiae was concentration dependent. Conclusions These findings suggested that CLC incorporation can improve mechanical, physico-chemical, and antimicrobial properties of the resulting films

  11. Relating mechanical properties and chemical bonding in an inorganic-organic framework material: a single-crystal nanoindentation study.

    Science.gov (United States)

    Tan, Jin Chong; Furman, Joshua D; Cheetham, Anthony K

    2009-10-14

    We report the application of nanoindentation and atomic force microscopy to establish the fundamental relationships between mechanical properties and chemical bonding in a dense inorganic-organic framework material: Ce(C(2)O(4))(HCO(2)), 1. Compound 1 is a mixed-ligand 3-D hybrid which crystallizes in an orthorhombic space group, in which its three basic building blocks, i.e. the inorganic metal-oxygen-metal (M-O-M) chains and the two organic bridging ligands, (oxalate and formate) are all oriented perpendicular to one another. This unique architecture enabled us to decouple the elastic and plastic mechanical responses along the three primary axes of a single crystal to understand the contribution associated with stiff vs compliant basic building blocks. The (001)-oriented facet that features rigid oxalate ligands down the c-axis exhibits the highest stiffness and hardness (E approximately 78 GPa and H approximately 4.6 GPa). In contrast, the (010)-oriented facet was found to be the most compliant and soft (E approximately 43 GPa and H approximately 3.9 GPa), since the formate ligand, which is the more compliant building block within this framework, constitutes the primary linkages down the b-axis. Notably, intermediate stiffness and hardness (E approximately 52 GPa and H approximately 4.1 GPa) were measured on the (100)-oriented planes. This can be attributed to the Ce-O-Ce chains that zigzag down the a-axis (Ce...Ce metal centers form an angle of approximately 132 degrees) and also the fact that the 9-coordinated CeO(9) polyhedra are expected to be geometrically more compliant. Our results present the first conclusive evidence that the crystal orientation dominated by inorganic chains is not necessarily more robust from the mechanical properties standpoint. Rigid organic bridging ligands (such as oxalate), on the other hand, can be used to produce greater stiffness and hardness properties in a chosen crystallographic orientation. This study demonstrates that

  12. Genomic mechanisms of stress tolerance for the industrial yeast Saccharomyces cerevisiae against major chemical classes of inhibitors

    Science.gov (United States)

    Numerous toxic chemical compounds liberated from lignocellulosic biomass pretreatment inhibit subsequent microbial fermentation that pose a significant challenge to a sustainable and renewable bio-based fermentation industry. Toxin removal procedures by physical or chemical means are essentially imp...

  13. Characterization of nociceptive response to chemical, mechanical, and thermal stimuli in adolescent rats with neonatal dopamine depletion.

    Science.gov (United States)

    Ogata, M; Noda, K; Akita, H; Ishibashi, H

    2015-03-19

    Rats with dopamine depletion caused by 6-hydroxydopamine (6-OHDA) treatment during adulthood and the neonatal period exhibit akinetic motor activity and spontaneous motor hyperactivity during adolescence, respectively, indicating that the behavioral effects of dopamine depletion depend on the period of lesion development. Dopamine depletion during adulthood induces hyperalgesic response to mechanical, thermal, and/or chemical stimuli, whereas the effects of neonatal dopamine depletion on nociceptive response in adolescent rats are yet to be examined. The latter aspect was addressed in this study, and behavioral responses were examined using von-Frey, tail flick, and formalin tests. The formalin test revealed that rats with neonatal dopamine depletion exhibited a significant increase in nociceptive response during interphase (6-15min post formalin injection) and phase 2 (16-75min post formalin injection). This increase in nociceptive response to the formalin injection was not reversed by pretreatment with methamphetamine, which ameliorates motor hyperactivity observed in adolescent rats with neonatal 6-OHDA treatment. The von-Frey filament and tail flick tests failed to reveal significant differences in withdrawal thresholds between neonatal 6-OHDA-treated and vehicle-treated rats. The spinal neuronal response to the formalin injection into the rat hind paw was also examined through immunohistochemical analysis of c-Fos protein. Significantly increased numbers of c-Fos-immunoreactive cells were observed in laminae I-II and V-VI of the ipsilateral spinal cord to the site of the formalin injection in rats with neonatal dopamine depletion compared with vehicle-treated rats. These results suggest that the dopaminergic neural system plays a crucial role in the development of a neural network for tonic pain, including the spinal neural circuit for nociceptive transmission, and that the mechanism underlying hyperalgesia to tonic pain is not always consistent with that of

  14. Report on hydro-mechanical and chemical-mineralogical analyses of the bentonite buffer in Canister Retrieval Test

    Energy Technology Data Exchange (ETDEWEB)

    Dueck, Ann; Johannesson, Lars-Erik; Kristensson, Ola; Olsson, Siv [Clay Technology AB (Sweden)

    2011-12-15

    The effect of five years of exposure to repository-like conditions on compacted Wyoming bentonite was determined by comparing the hydraulic, mechanical, and mineralogical properties of samples from the bentonite buffer of the Canister Retrieval Test (CRT) with those of reference material. The CRT, located at the Swedish Aspo Hard Rock Laboratory (HRL), was a full-scale field experiment simulating conditions relevant for the Swedish KBS-3 concept for disposal of high-level radioactive waste in crystalline host rock. The compacted bentonite, surrounding a copper canister equipped with heaters, had been subjected to heating at temperatures up to 95 deg C and hydration by natural Na-Ca-Cl type groundwater for almost five years at the time of retrieval. Under the thermal and hydration gradients that prevailed during the test, sulfate in the bentonite was redistributed and accumulated as anhydrite close to the canister. The major change in the exchangeable cation pool was a loss in Mg in the outer parts of the blocks, suggesting replacement of Mg mainly by Ca along with the hydration with groundwater. Close to the copper canister, small amounts of Cu were incorporated in the bentonite. A reduction of strain at failure was observed in the innermost part of the bentonite buffer, but no influence was seen on the shear strength. No change of the swelling pressure was observed, while a modest decrease in hydraulic conductivity was found for the samples with the highest densities. No coupling was found between these changes in the hydro-mechanical properties and the montmorillonite . the X-ray diffraction characteristics, the cation exchange properties, and the average crystal chemistry of the Na-converted < 1 {mu}m fractions provided no evidence of any chemical/structural changes in the montmorillonite after the 5-year hydrothermal test.

  15. Fabrication and mechanical behavior of bulk nanoporous Cu via chemical de-alloying of Cu–Al alloys

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Fei, E-mail: chenfei027@gmail.com [State Key Lab of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China); Chen, Xi; Zou, Lijie; Yao, Yao; Lin, Yaojun; Shen, Qiang [State Key Lab of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China); Lavernia, Enrique J. [Department of Chemical Engineering and Materials Science, University of California at Irvine, Irvine, CA 92697 (United States); Zhang, Lianmeng, E-mail: lmzhang@whut.edu.cn [State Key Lab of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China)

    2016-04-13

    We report on a study of the influence of microstructure on the mechanical behavior of bulk nanoporous Cu fabricated by chemical de-alloying of Cu{sub 50}Al{sub 50}, Cu{sub 40}Al{sub 60}, Cu{sub 33}Al{sub 67} and Cu{sub 30}Al{sub 70} (at%) alloys. The precursor Cu–Al alloys were fabricated using arc melting and bulk nanoporous Cu was obtained by subsequent de-alloying of Cu–Al alloys in 20 wt% NaOH aqueous solution at a temperature of 65 °C. We studied the microstructure of the precursor Cu–Al alloys, as well as that of the as de-alloyed bulk nanoporous Cu, using X-ray diffraction, scanning electron microscopy and energy dispersive spectrometry. Moreover, the compressive strength of bulk nanoporous Cu was measured and the relationship between microstructure and mechanical properties was studied. Our results show that the microstructure of bulk nanoporous Cu is characterized by bi-continuous interpenetrating ligament-channels with a ligament size of 130±20 nm (for Cu{sub 50}Al{sub 50}), 170±20 nm (for Cu{sub 40}Al{sub 60}) and 160±10 nm (for Cu{sub 33}Al{sub 67}). Interestingly the microstructure of de-alloyed Cu{sub 30}Al{sub 70} is bimodal with nanopores (100's nm) and interspersed featureless regions a few microns in size. The compressive strength increased with decreasing volume fraction of porosity; as porosity increased 56.3±2% to 73.9±2%, the compressive strength decreased from 17.18±1 MPa to 2.71±0.5 MPa.

  16. Kinetics of physico-chemical processes during intensive mechanical processing of ZnO-MnO{sub 2} powder mixture

    Energy Technology Data Exchange (ETDEWEB)

    Kakazey, M.; Vlasova, M.; Dominguez-Patino, M. [CIICAp-Universidad Autonoma del Estado de Morelos, Cuernavaca (Mexico); Juarez-Arellano, E.A., E-mail: eajuarez@unpa.edu.mx [Universidad del Papaloapan, Tuxtepec, Oaxaca (Mexico); Bykov, A. [Institute for Problems of Materials Science of NASU, Kyiv (Ukraine); Leon, I. [CIQ-Universidad Autonoma del Estado de Morelos, Cuernavaca (Mexico); Siqueiros-Diaz, A. [FCQI-Universidad Autonoma del Estado de Morelos, Cuernavaca (Mexico)

    2011-10-15

    Experimental results of electron paramagnetic resonance spectra, X-ray diffraction, scanning electron microscopy and infrared spectroscopy demonstrate that the kinetic of the physical and chemical processes that takes place during prolonged intensive mechanical processing (MP, 03120min) of powder mixtures of 50%wt ZnO+50%wt MnO{sub 2} can be described as a three stage process. (1) 030min, particles destruction, formation of superficial defects, fast increment of sample average temperature (from 290 to {approx}600K) and annealing of defects with the lowest energy of activation E{sub ac}. (2) 30390min, further particle destruction, slow increment of sample average temperature (from {approx}600 to {approx}700K), formation and growth of a very disordered layer of {beta}-MnO{sub 2} around ZnO particles, dehydration of MnO{sub 2}, formation of solid solution of Mn{sup 2+} ions in ZnO, formation of nano-quasiamorphous states in the ZnO-MnO{sub 2} mixture and onset of the formation of the ZnMnO{sub 3} phase. (3) 3903120min, the sample average temperature remains constant ({approx}700K), the reaction is completed and the spinel ZnMnO{sub 3} phase with a unit cell a=8.431(1) A and space group Fd3-barm is the only phase present in the sample. No ferromagnetism at room temperature was detected in this study. - Highlights: > The kinetics during mechanical processing of ZnO-MnO{sub 2} samples is a three stage process. > First stage, reduction of crystallites size and accumulation of defects. > Second stage, nano-quasiamorphous states formation and onset of the ZnMnO{sub 3} phase. > Third stage, complete reaction to the spinel ZnMnO{sub 3} phase.

  17. Kinetics of physico-chemical processes during intensive mechanical processing of ZnO-MnO2 powder mixture

    International Nuclear Information System (INIS)

    Kakazey, M.; Vlasova, M.; Dominguez-Patino, M.; Juarez-Arellano, E.A.; Bykov, A.; Leon, I.; Siqueiros-Diaz, A.

    2011-01-01

    Experimental results of electron paramagnetic resonance spectra, X-ray diffraction, scanning electron microscopy and infrared spectroscopy demonstrate that the kinetic of the physical and chemical processes that takes place during prolonged intensive mechanical processing (MP, 0 MP >3120min) of powder mixtures of 50%wt ZnO+50%wt MnO 2 can be described as a three stage process. (1) 0 MP >30min, particles destruction, formation of superficial defects, fast increment of sample average temperature (from 290 to ∼600K) and annealing of defects with the lowest energy of activation E ac . (2) 30 MP >390min, further particle destruction, slow increment of sample average temperature (from ∼600 to ∼700K), formation and growth of a very disordered layer of β-MnO 2 around ZnO particles, dehydration of MnO 2 , formation of solid solution of Mn 2+ ions in ZnO, formation of nano-quasiamorphous states in the ZnO-MnO 2 mixture and onset of the formation of the ZnMnO 3 phase. (3) 390 MP >3120min, the sample average temperature remains constant (∼700K), the reaction is completed and the spinel ZnMnO 3 phase with a unit cell a=8.431(1) A and space group Fd3-barm is the only phase present in the sample. No ferromagnetism at room temperature was detected in this study. - Highlights: → The kinetics during mechanical processing of ZnO-MnO 2 samples is a three stage process. → First stage, reduction of crystallites size and accumulation of defects. → Second stage, nano-quasiamorphous states formation and onset of the ZnMnO 3 phase. → Third stage, complete reaction to the spinel ZnMnO 3 phase.

  18. Quantification of Chemical and Mechanical Effects on the Formation of the G-Quadruplex and i-Motif in Duplex DNA.

    Science.gov (United States)

    Selvam, Sangeetha; Mandal, Shankar; Mao, Hanbin

    2017-09-05

    The formation of biologically significant tetraplex DNA species, such as G-quadruplexes and i-motifs, is affected by chemical (ions and pH) and mechanical [superhelicity (σ) and molecular crowding] factors. Because of the extremely challenging experimental conditions, the relative importance of these factors on tetraplex folding is unknown. In this work, we quantitatively evaluated the chemical and mechanical effects on the population dynamics of DNA tetraplexes in the insulin-linked polymorphic region using magneto-optical tweezers. By mechanically unfolding individual tetraplexes, we found that ions and pH have the largest effects on the formation of the G-quadruplex and i-motif, respectively. Interestingly, superhelicity has the second largest effect followed by molecular crowding conditions. While chemical effects are specific to tetraplex species, mechanical factors have generic influences. The predominant effect of chemical factors can be attributed to the fact that they directly change the stability of a specific tetraplex, whereas the mechanical factors, superhelicity in particular, reduce the stability of the competing species by changing the kinetics of the melting and annealing of the duplex DNA template in a nonspecific manner. The substantial dependence of tetraplexes on superhelicity provides strong support that DNA tetraplexes can serve as topological sensors to modulate fundamental cellular processes such as transcription.

  19. Technical basis and programmatic requirements for large block testing of coupled thermal-mechanical-hydrological-chemical processes

    International Nuclear Information System (INIS)

    Lin, Wunan.

    1993-09-01

    This document contains the technical basis and programmatic requirements for a scientific investigation plan that governs tests on a large block of tuff for understanding the coupled thermal- mechanical-hydrological-chemical processes. This study is part of the field testing described in Section 8.3.4.2.4.4.1 of the Site Characterization Plan (SCP) for the Yucca Mountain Project. The first, and most important objective is to understand the coupled TMHC processes in order to develop models that will predict the performance of a nuclear waste repository. The block and fracture properties (including hydrology and geochemistry) can be well characterized from at least five exposed surfaces, and the block can be dismantled for post-test examinations. The second objective is to provide preliminary data for development of models that will predict the quality and quantity of water in the near-field environment of a repository over the current 10,000 year regulatory period of radioactive decay. The third objective is to develop and evaluate the various measurement systems and techniques that will later be employed in the Engineered Barrier System Field Tests (EBSFT)

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