WorldWideScience

Sample records for surface chemistry bulk

  1. Roles of Bulk and Surface Chemistry in the Oxygen Exchange Kinetics and Related Properties of Mixed Conducting Perovskite Oxide Electrodes

    Directory of Open Access Journals (Sweden)

    Nicola H. Perry

    2016-10-01

    Full Text Available Mixed conducting perovskite oxides and related structures serving as electrodes for electrochemical oxygen incorporation and evolution in solid oxide fuel and electrolysis cells, respectively, play a significant role in determining the cell efficiency and lifetime. Desired improvements in catalytic activity for rapid surface oxygen exchange, fast bulk transport (electronic and ionic, and thermo-chemo-mechanical stability of oxygen electrodes will require increased understanding of the impact of both bulk and surface chemistry on these properties. This review highlights selected work at the International Institute for Carbon-Neutral Energy Research (I2CNER, Kyushu University, set in the context of work in the broader community, aiming to characterize and understand relationships between bulk and surface composition and oxygen electrode performance. Insights into aspects of bulk point defect chemistry, electronic structure, crystal structure, and cation choice that impact carrier concentrations and mobilities, surface exchange kinetics, and chemical expansion coefficients are emerging. At the same time, an understanding of the relationship between bulk and surface chemistry is being developed that may assist design of electrodes with more robust surface chemistries, e.g., impurity tolerance or limited surface segregation. Ion scattering techniques (e.g., secondary ion mass spectrometry, SIMS, or low energy ion scattering spectroscopy, LEIS with high surface sensitivity and increasing lateral resolution are proving useful for measuring surface exchange kinetics, diffusivity, and corresponding outer monolayer chemistry of electrodes exposed to typical operating conditions. Beyond consideration of chemical composition, the use of strain and/or a high density of active interfaces also show promise for enhancing performance.

  2. Coupling aerosol surface and bulk chemistry with a kinetic double layer model (K2-SUB: oxidation of oleic acid by ozone

    Directory of Open Access Journals (Sweden)

    C. Pfrang

    2010-05-01

    Full Text Available We present a kinetic double layer model coupling aerosol surface and bulk chemistry (K2-SUB based on the PRA framework of gas-particle interactions (Pöschl-Rudich-Ammann, 2007. K2-SUB is applied to a popular model system of atmospheric heterogeneous chemistry: the interaction of ozone with oleic acid. We show that our modelling approach allows de-convoluting surface and bulk processes, which has been a controversial topic and remains an important challenge for the understanding and description of atmospheric aerosol transformation. In particular, we demonstrate how a detailed treatment of adsorption and reaction at the surface can be coupled to a description of bulk reaction and transport that is consistent with traditional resistor model formulations.

    From literature data we have derived a consistent set of kinetic parameters that characterise mass transport and chemical reaction of ozone at the surface and in the bulk of oleic acid droplets. Due to the wide range of rate coefficients reported from different experimental studies, the exact proportions between surface and bulk reaction rates remain uncertain. Nevertheless, the model results suggest an important role of chemical reaction in the bulk and an approximate upper limit of ~10−11 cm2 s−1 for the surface reaction rate coefficient. Sensitivity studies show that the surface accommodation coefficient of the gas-phase reactant has a strong non-linear influence on both surface and bulk chemical reactions. We suggest that K2-SUB may be used to design, interpret and analyse future experiments for better discrimination between surface and bulk processes in the oleic acid-ozone system as well as in other heterogeneous reaction systems of atmospheric relevance.

  3. A UNIFIED MONTE CARLO TREATMENT OF GAS-GRAIN CHEMISTRY FOR LARGE REACTION NETWORKS. II. A MULTIPHASE GAS-SURFACE-LAYERED BULK MODEL

    International Nuclear Information System (INIS)

    Vasyunin, A. I.; Herbst, Eric

    2013-01-01

    The observed gas-phase molecular inventory of hot cores is believed to be significantly impacted by the products of chemistry in interstellar ices. In this study, we report the construction of a full macroscopic Monte Carlo model of both the gas-phase chemistry and the chemistry occurring in the icy mantles of interstellar grains. Our model treats icy grain mantles in a layer-by-layer manner, which incorporates laboratory data on ice desorption correctly. The ice treatment includes a distinction between a reactive ice surface and an inert bulk. The treatment also distinguishes between zeroth- and first-order desorption, and includes the entrapment of volatile species in more refractory ice mantles. We apply the model to the investigation of the chemistry in hot cores, in which a thick ice mantle built up during the previous cold phase of protostellar evolution undergoes surface reactions and is eventually evaporated. For the first time, the impact of a detailed multilayer approach to grain mantle formation on the warm-up chemistry is explored. The use of a multilayer ice structure has a mixed impact on the abundances of organic species formed during the warm-up phase. For example, the abundance of gaseous HCOOCH 3 is lower in the multilayer model than in previous grain models that do not distinguish between layers (so-called two phase models). Other gaseous organic species formed in the warm-up phase are affected slightly. Finally, we find that the entrapment of volatile species in water ice can explain the two-jump behavior of H 2 CO previously found in observations of protostars.

  4. Surface Chemistry in Nanoscale Materials

    Science.gov (United States)

    Biener, Jürgen; Wittstock, Arne; Baumann, Theodore F.; Weissmüller, Jörg; Bäumer, Marcus; Hamza, Alex V.

    2009-01-01

    Although surfaces or, more precisely, the surface atomic and electronic structure, determine the way materials interact with their environment, the influence of surface chemistry on the bulk of the material is generally considered to be small. However, in the case of high surface area materials such as nanoporous solids, surface properties can start to dominate the overall material behavior. This allows one to create new materials with physical and chemical properties that are no longer determined by the bulk material, but by their nanoscale architectures. Here, we discuss several examples, ranging from nanoporous gold to surface engineered carbon aerogels that demonstrate the tuneability of nanoporous solids for sustainable energy applications.

  5. Surface Chemistry in Nanoscale Materials

    Directory of Open Access Journals (Sweden)

    Alex V. Hamza

    2009-12-01

    Full Text Available Although surfaces or, more precisely, the surface atomic and electronic structure, determine the way materials interact with their environment, the influence of surface chemistry on the bulk of the material is generally considered to be small. However, in the case of high surface area materials such as nanoporous solids, surface properties can start to dominate the overall material behavior. This allows one to create new materials with physical and chemical properties that are no longer determined by the bulk material, but by their nanoscale architectures. Here, we discuss several examples, ranging from nanoporous gold to surface engineered carbon aerogels that demonstrate the tuneability of nanoporous solids for sustainable energy applications.

  6. Surface chemistry essentials

    CERN Document Server

    Birdi, K S

    2013-01-01

    Surface chemistry plays an important role in everyday life, as the basis for many phenomena as well as technological applications. Common examples range from soap bubbles, foam, and raindrops to cosmetics, paint, adhesives, and pharmaceuticals. Additional areas that rely on surface chemistry include modern nanotechnology, medical diagnostics, and drug delivery. There is extensive literature on this subject, but most chemistry books only devote one or two chapters to it. Surface Chemistry Essentials fills a need for a reference that brings together the fundamental aspects of surface chemistry w

  7. On-surface synthesis on a bulk insulator surface

    Science.gov (United States)

    Richter, Antje; Floris, Andrea; Bechstein, Ralf; Kantorovich, Lev; Kühnle, Angelika

    2018-04-01

    On-surface synthesis has rapidly emerged as a most promising approach to prepare functional molecular structures directly on a support surface. Compared to solution synthesis, performing chemical reactions on a surface offers several exciting new options: due to the absence of a solvent, reactions can be envisioned that are otherwise not feasible due to the insolubility of the reaction product. Perhaps even more important, the confinement to a two-dimensional surface might enable reaction pathways that are not accessible otherwise. Consequently, on-surface synthesis has attracted great attention in the last decade, with an impressive number of classical reactions transferred to a surface as well as new reactions demonstrated that have no classical analogue. So far, the majority of the work has been carried out on conducting surfaces. However, when aiming for electronic decoupling of the resulting structures, e.g. for the use in future molecular electronic devices, non-conducting surfaces are highly desired. Here, we review the current status of on-surface reactions demonstrated on the (10.4) surface of the bulk insulator calcite. Besides thermally induced C-C coupling of halogen-substituted aryls, photochemically induced [2  +  2] cycloaddition has been proven possible on this surface. Moreover, experimental evidence exists for coupling of terminal alkynes as well as diacetylene polymerization. While imaging of the resulting structures with dynamic atomic force microscopy provides a direct means of reaction verification, the detailed reaction pathway often remains unclear. Especially in cases where the presence of metal atoms is known to catalyze the corresponding solution chemistry reaction (e.g. in the case of the Ullmann reaction), disclosing the precise reaction pathway is of importance to understand and generalize on-surface reactivity on a bulk insulator surface. To this end, density-functional theory calculations have proven to provide atomic

  8. Water at surfaces with tunable surface chemistries

    Science.gov (United States)

    Sanders, Stephanie E.; Vanselous, Heather; Petersen, Poul B.

    2018-03-01

    Aqueous interfaces are ubiquitous in natural environments, spanning atmospheric, geological, oceanographic, and biological systems, as well as in technical applications, such as fuel cells and membrane filtration. Where liquid water terminates at a surface, an interfacial region is formed, which exhibits distinct properties from the bulk aqueous phase. The unique properties of water are governed by the hydrogen-bonded network. The chemical and physical properties of the surface dictate the boundary conditions of the bulk hydrogen-bonded network and thus the interfacial properties of the water and any molecules in that region. Understanding the properties of interfacial water requires systematically characterizing the structure and dynamics of interfacial water as a function of the surface chemistry. In this review, we focus on the use of experimental surface-specific spectroscopic methods to understand the properties of interfacial water as a function of surface chemistry. Investigations of the air-water interface, as well as efforts in tuning the properties of the air-water interface by adding solutes or surfactants, are briefly discussed. Buried aqueous interfaces can be accessed with careful selection of spectroscopic technique and sample configuration, further expanding the range of chemical environments that can be probed, including solid inorganic materials, polymers, and water immiscible liquids. Solid substrates can be finely tuned by functionalization with self-assembled monolayers, polymers, or biomolecules. These variables provide a platform for systematically tuning the chemical nature of the interface and examining the resulting water structure. Finally, time-resolved methods to probe the dynamics of interfacial water are briefly summarized before discussing the current status and future directions in studying the structure and dynamics of interfacial water.

  9. Organometallic chemistry of metal surfaces

    International Nuclear Information System (INIS)

    Muetterties, E.L.

    1981-06-01

    The organometallic chemistry of metal surfaces is defined as a function of surface crystallography and of surface composition for a set of cyclic hydrocarbons that include benzene, toluene, cyclohexadienes, cyclohexene, cyclohexane, cyclooctatetraene, cyclooctadienes, cyclooctadiene, cycloheptatriene and cyclobutane. 12 figures

  10. Transformation kinetics for surface and bulk nucleation

    Energy Technology Data Exchange (ETDEWEB)

    Villa, Elena, E-mail: elena.villa@unimi.it [University of Milan, Department of Mathematics, via Saldini 50, 20133 Milano (Italy); Rios, Paulo R., E-mail: prrios@metal.eeimvr.uff.br [Universidade Federal Fluminense, Escola de Engenharia Industrial Metalurgica de Volta Redonda, Av. dos Trabalhadores 420, 27255-125 Volta Redonda, RJ (Brazil)] [RWTH Aachen University, Institut fuer Metallkunde und Metallphysik, D-52056 Aachen (Germany)

    2010-04-15

    A rigorous mathematical approach based on the causal cone and stochastic geometry concepts is used to derive new exact expressions for transformation kinetics theory. General expressions for the mean volume density and the volume fraction are derived for both surface and bulk nucleation in a general Borel subset of R{sup 3}. In practice, probably any specimen shape of engineering interest is going to be a Borel set. An expression is also derived for the important case of polyhedral shape, in which surface nucleation may take place on the faces, edges and vertices of the polyhedron as well as within the bulk. Moreover, explicit expressions are given for surface and bulk nucleation for three specific shapes of engineering relevance: two parallel planes, an infinitely long cylinder and a sphere. Superposition is explained in detail and it permits the treatment of situations in which surface and bulk nucleation take place simultaneously. The new exact expressions presented here result in a significant increase in the number of exactly solvable cases available to formal kinetics.

  11. Surface chemistry theory and applications

    CERN Document Server

    Bikerman, J J

    2013-01-01

    Surface Chemistry Theory and Applications focuses on liquid-gas, liquid-liquid, solid-gas, solid-liquid, and solid-solid surfaces. The book first offers information on liquid-gas surfaces, including surface tension, measurement of surface tension, rate of capillarity rise, capillary attraction, bubble pressure and pore size, and surface tension and temperature. The text then ponders on liquid-liquid and solid-gas surfaces. Discussions focus on surface energy of solids, surface roughness and cleanness, adsorption of gases and vapors, adsorption hysteresis, interfacial tension, and interfacial t

  12. Surface Chemistry of Gold Nanorods.

    Science.gov (United States)

    Burrows, Nathan D; Lin, Wayne; Hinman, Joshua G; Dennison, Jordan M; Vartanian, Ariane M; Abadeer, Nardine S; Grzincic, Elissa M; Jacob, Lisa M; Li, Ji; Murphy, Catherine J

    2016-10-04

    Gold nanorods have garnered a great deal of scientific interest because of their unique optical properties, and they have the potential to greatly impact many areas of science and technology. Understanding the structure and chemical makeup of their surfaces as well as how to tailor them is of paramount importance in the development of their successful applications. This Feature Article reviews the current understanding of the surface chemistry of as-synthesized gold nanorods, methods of tailoring the surface chemistry of gold nanorods with various inorganic and organic coatings/ligands, and the techniques employed to characterize ligands on the surface of gold nanorods as well as the associated measurement challenges. Specifically, we address the challenges of determining how thick the ligand shell is, how many ligands per nanorod are present on the surface, and where the ligands are located in regiospecific and mixed-ligand systems. We conclude with an outlook on the development of the surface chemistry of gold nanorods leading to the development of a synthetic nanoparticle surface chemistry toolbox analogous to that of synthetic organic chemistry and natural product synthesis.

  13. Surface chemistry in three dimensions

    DEFF Research Database (Denmark)

    Bollinger, Mikkel; Jacobsen, Karsten Wedel; Nørskov, Jens Kehlet

    2000-01-01

    the usual single surface ('2D') process because indirect adsorbate-adsorbate interactions in the transition state are absent in the '3D' case. The prospects for STM-induced single molecule chemistry and for '3D' catalysts are discussed. (C) 2000 Elsevier Science B.V. All rights reserved.......Based on self-consistent density functional calculations it is shown that a new dissociation process for CO adsorbed on a Ru(0001) surface is made possible when the distance to a second Ru(0001) surface placed just above it is below some critical value. This '3D' process is more facile than...

  14. Enhancement of surface magnetism due to bulk bond dilution

    International Nuclear Information System (INIS)

    Tsallis, C.; Sarmento, E.F.; Albuquerque, E.L. de

    1985-01-01

    Within a renormalization group scheme, the phase diagram of a semi-infinite simple cubic Ising ferromagnet is discussed, with arbitrary surface and bulk coupling constants, and including possible dilution of the bulk bonds. It is obtained that dilution makes easier the appearance of surface magnetism in the absence of bulk magnetism. (Author) [pt

  15. Bulk water freezing dynamics on superhydrophobic surfaces

    Science.gov (United States)

    Chavan, S.; Carpenter, J.; Nallapaneni, M.; Chen, J. Y.; Miljkovic, N.

    2017-01-01

    In this study, we elucidate the mechanisms governing the heat-transfer mediated, non-thermodynamic limited, freezing delay on non-wetting surfaces for a variety of characteristic length scales, Lc (volume/surface area, 3 mm commercial superhydrophobic spray coatings, showing a monotonic increase in freezing time with coating thickness. The added thermal resistance of thicker coatings was much larger than that of the nanoscale superhydrophobic features, which reduced the droplet heat transfer and increased the total freezing time. Transient finite element method heat transfer simulations of the water slab freezing process were performed to calculate the overall heat transfer coefficient at the substrate-water/ice interface during freezing, and shown to be in the range of 1-2.5 kW/m2K for these experiments. The results shown here suggest that in order to exploit the heat-transfer mediated freezing delay, thicker superhydrophobic coatings must be deposited on the surface, where the coating resistance is comparable to the bulk water/ice conduction resistance.

  16. Photoelectron spectroscopy bulk and surface electronic structures

    CERN Document Server

    Suga, Shigemasa

    2014-01-01

    Photoelectron spectroscopy is now becoming more and more required to investigate electronic structures of various solid materials in the bulk, on surfaces as well as at buried interfaces. The energy resolution was much improved in the last decade down to 1 meV in the low photon energy region. Now this technique is available from a few eV up to 10 keV by use of lasers, electron cyclotron resonance lamps in addition to synchrotron radiation and X-ray tubes. High resolution angle resolved photoelectron spectroscopy (ARPES) is now widely applied to band mapping of materials. It attracts a wide attention from both fundamental science and material engineering. Studies of the dynamics of excited states are feasible by time of flight spectroscopy with fully utilizing the pulse structures of synchrotron radiation as well as lasers including the free electron lasers (FEL). Spin resolved studies also made dramatic progress by using higher efficiency spin detectors and two dimensional spin detectors. Polarization depend...

  17. Liquid flow along a solid surface reversibly alters interfacial chemistry.

    Science.gov (United States)

    Lis, Dan; Backus, Ellen H G; Hunger, Johannes; Parekh, Sapun H; Bonn, Mischa

    2014-06-06

    In nature, aqueous solutions often move collectively along solid surfaces (for example, raindrops falling on the ground and rivers flowing through riverbeds). However, the influence of such motion on water-surface interfacial chemistry is unclear. In this work, we combine surface-specific sum frequency generation spectroscopy and microfluidics to show that at immersed calcium fluoride and fused silica surfaces, flow leads to a reversible modification of the surface charge and subsequent realignment of the interfacial water molecules. Obtaining equivalent effects under static conditions requires a substantial change in bulk solution pH (up to 2 pH units), demonstrating the coupling between flow and chemistry. These marked flow-induced variations in interfacial chemistry should substantially affect our understanding and modeling of chemical processes at immersed surfaces. Copyright © 2014, American Association for the Advancement of Science.

  18. Optimizing chemistry of bulk metallic glasses for improved thermal stability

    International Nuclear Information System (INIS)

    Dulikravich, G S; Egorov, I N; Colaco, M J

    2008-01-01

    Thermo-mechanical-physical properties of bulk metallic glasses (BMGs) depend strongly on the concentrations of each of the chemical elements in a given alloy. The proposed methodology for simultaneously optimizing these multiple properties by accurately determining proper concentrations of each of the alloying elements is based on the use of computational algorithms rather than on traditional experimentation, expert experience and intuition. Specifically, the proposed BMG design method combines an advanced stochastic multi-objective evolutionary optimization algorithm based on self-adapting response surface methodology and an existing database of experimentally evaluated BMG properties. During the iterative computational design procedure, a relatively small number of new BMGs need to be manufactured and experimentally evaluated for their properties in order to continuously verify the accuracy of the entire design methodology. Concentrations of the most important alloying elements can be predicted so that new BMGs have multiple properties optimized in a Pareto sense. This design concept was verified for superalloys using strictly experimental data. Thus, the key innovation here lies in arriving at the BMG compositions which will have the highest glass forming ability by utilizing an advanced multi-objective optimization algorithm while requiring a minimum number of BMGs to be manufactured and tested in order to verify the predicted performance of the predicted BMG compositions

  19. Bulk-mediated surface transport in the presence of bias

    Science.gov (United States)

    Berezhkovskii, Alexander M.; Dagdug, Leonardo; Bezrukov, Sergey M.

    2017-07-01

    Surface transport, when the particle is allowed to leave the surface, travel in the bulk for some time, and then return to the surface, is referred to as bulk-mediated surface transport. Recently, we proposed a formalism that significantly simplifies analysis of bulk-mediated surface diffusion [A. M. Berezhkovskii, L. Dagdug, and S. M. Bezrukov, J. Chem. Phys. 143, 084103 (2015)]. Here this formalism is extended to bulk-mediated surface transport in the presence of bias, i.e., when the particle has arbitrary drift velocities on the surface and in the bulk. A key advantage of our approach is that the transport problem reduces to that of a two-state problem of the particle transitions between the surface and the bulk. The latter can be solved with relative ease. The formalism is used to find the Laplace transforms of the first two moments of the particle displacement over the surface in time t at arbitrary values of the particle drift velocities and diffusivities on the surface and in the bulk. This allows us to analyze in detail the time dependence of the effective drift velocity of the particle on the surface, which can be highly nontrivial.

  20. Magmatic and fragmentation controls on volcanic ash surface chemistry

    Science.gov (United States)

    Ayris, Paul M.; Diplas, Spyros; Damby, David E.; Hornby, Adrian J.; Cimarelli, Corrado; Delmelle, Pierre; Scheu, Bettina; Dingwell, Donald B.

    2016-04-01

    The chemical effects of silicate ash ejected by explosive volcanic eruptions on environmental systems are fundamentally mediated by ash particle surfaces. Ash surfaces are a composite product of magmatic properties and fragmentation mechanisms, as well as in-plume and atmospheric alteration processes acting upon those surfaces during and after the eruption. Recent attention has focused on the capacity of alteration processes to shape ash surfaces; most notably, several studies have utilised X-ray photoelectron spectroscopy (XPS), a technique probing the elemental composition and coordination state of atoms within the top 10 nm of ash surfaces, to identify patterns of elemental depletions and enrichments relative to bulk ash chemical composition. Under the presumption of surface and bulk equivalence, any disparities have been previously attributed to surface alteration processes, but the ubiquity of some depletions (e.g., Ca, Fe) across multiple ash studies, irrespective of eruptive origin, could suggest these to be features of the surface produced at the instant of magma fragmentation. To investigate this possibility further, we conducted rapid decompression experiments at different pressure conditions and at ambient and magmatic temperature on porous andesitic rocks. These experiments produced fragmented ash material untouched by secondary alteration, which were compared to particles produced by crushing of large clasts from the same experiments. We investigated a restricted size fraction (63-90 μm) from both fragmented and crushed materials, determining bulk chemistry and mineralogy via XRF, SEM-BSE and EPMA, and investigated the chemical composition of the ash surface by XPS. Analyses suggest that fragmentation under experimental conditions partitioned a greater fraction of plagioclase-rich particles into the selected size fraction, relative to particles produced by crushing. Trends in surface chemical composition in fragmented and crushed particles mirror that

  1. Recent advances in quantum dot surface chemistry.

    Science.gov (United States)

    Hines, Douglas A; Kamat, Prashant V

    2014-03-12

    Quantum dot (QD) surface chemistry is an emerging field in semiconductor nanocrystal related research. Along with size manipulation, the careful control of QD surface chemistry allows modulation of the optical properties of a QD suspension. Even a single molecule bound to the surface can introduce new functionalities. Herein, we summarize the recent advances in QD surface chemistry and the resulting effects on optical and electronic properties. Specifically, this review addresses three main issues: (i) how surface chemistry affects the optical properties of QDs, (ii) how it influences the excited state dynamics, and (iii) how one can manipulate surface chemistry to control the interactions between QDs and metal oxides, metal nanoparticles, and in self-assembled QD monolayers.

  2. Bulk and surface characterization of novel photoresponsive polymeric systems

    Science.gov (United States)

    Venkataramani, Shivshankar

    This dissertation presents a detailed characterization of two important classes of photoresponsive polymers-polydiacetylenes (PDAs) and azopolymers. Bulk and surface characterization techniques were used to evaluate the structure-property relationships of the PDAs and surface characterization, in particular-atomic force microscopy (AFM) was used to characterize the azopolymers. PDAs from bis-alkylurethanes of 5,7 dodecadiyn 1,12-diol (viz.,) ETCD, IPUDO and PUDO are of particular interest in view of reports of reversible thermochromic and photochromic phase transitions in these materials. Thermochromism in the above PDAs is associated with a first order phase transition involving expansion of the crystallographic unit cell, the preservation of the urethane hydrogen bonding and possibly some relief of mechanical strain upon heating. Insights into thermochromism obtained from studies of nonthermochromic forms of PDA-ETCD are discussed. Some of the bulk characterization experiments reported In the literature are repeated. The motivation to investigate the surface morphology of the PDA single crystals using AFM was derived from Raman spectroscopy studies of various PDAs in which dispersion of the Raman spectrum indicating surface heterogeneity was observed. Micron scale as well as molecularly resolved images were obtained The micron scale images indicated a variable surface of the crystals. The molecularly resolved images showed a well defined 2-D lattice and are interpreted in terms of known crystallographic data. The surface parameters obtained from AFM measurements are similar to those determined from X-ray diffraction. During an attempt of AFM imaging of IPUDO crystals exposed to 254 nm ultraviolet light, it was observed that these crystals undergo a "macroscopic shattering". In the interest of rigorously defining conditions for photochromism, this research has undertaken a combined study of the surface morphology of the above mentioned PDA crystals by AFM and the

  3. Surface, interface and bulk materials characterization using Indus synchrotron sources

    International Nuclear Information System (INIS)

    Phase, Deodatta M.

    2014-01-01

    Synchrotron radiation sources, providing intense, polarized and stable beams of ultra violet, soft and hard x-ray photons, are having great impact on physics, chemistry, biology, materials science and other areas research. In particular synchrotron radiation has revolutionized materials characterization techniques by enhancing its capabilities for investigating the structural, electronic and magnetic properties of solids. The availability of synchrotron sources and necessary instrumentation has led to considerable improvements in spectral resolution and intensities. As a result, application scope of different materials characterization techniques has tremendously increased particularly in the analysis of solid surfaces, interfaces and bulk materials. The Indian synchrotron storage ring, Indus-1 and Indus-2 are in operation at RRCAT, Indore. The UGC-DAE CSR with the help of university scientist had designed and developed an angle integrated photoelectron spectroscopy (AlPES) beam line on Indus-1 storage ring of 450 MeV and polarized light beam line for soft x-ray absorption spectroscopy (SXAS) on Indus-2 storage ring of 2.5 GeV. (author)

  4. Surface Coordination Chemistry of Metal Nanomaterials.

    Science.gov (United States)

    Liu, Pengxin; Qin, Ruixuan; Fu, Gang; Zheng, Nanfeng

    2017-02-15

    Surface coordination chemistry of nanomaterials deals with the chemistry on how ligands are coordinated on their surface metal atoms and influence their properties at the molecular level. This Perspective demonstrates that there is a strong link between surface coordination chemistry and the shape-controlled synthesis, and many intriguing surface properties of metal nanomaterials. While small adsorbates introduced in the synthesis can control the shapes of metal nanocrystals by minimizing their surface energy via preferential coordination on specific facets, surface ligands properly coordinated on metal nanoparticles readily promote their catalysis via steric interactions and electronic modifications. The difficulty in the research of surface coordination chemistry of nanomaterials mainly lies in the lack of effective tools to characterize their molecular surface coordination structures. Also highlighted are several model material systems that facilitate the characterizations of surface coordination structures, including ultrathin nanostructures, atomically precise metal nanoclusters, and atomically dispersed metal catalysts. With the understanding of surface coordination chemistry, the molecular mechanisms behind various important effects (e.g., promotional effect of surface ligands on catalysis, support effect in supported metal nanocatalysts) of metal nanomaterials are disclosed.

  5. Surface and bulk conductivity of vanadium dioxide

    Science.gov (United States)

    Tutov, E. A.; Manannikov, A. V.; Al-Khafaji, H. I.; Zlomanov, V. P.

    2017-03-01

    The dc and ac resistances of a TR-68 thermistor based on the vanadium dioxide film have been measured and the temperature dependence of the resistance in the semiconductor-metal transition region under adsorption has been studied. The energy band model has been proposed, which explains the anomalous response to adsorption of donor gases by the inversion of the conductivity type of vanadium dioxide surface layers.

  6. Self-referenced directional enhanced Raman scattering using plasmon waveguide resonance for surface and bulk sensing

    Science.gov (United States)

    Wan, Xiu-mei; Gao, Ran; Lu, Dan-feng; Qi, Zhi-mei

    2018-01-01

    Surface plasmon-coupled emission has been widely used in fluorescence imaging, biochemical sensing, and enhanced Raman spectroscopy. A self-referenced directional enhanced Raman scattering for simultaneous detection of surface and bulk effects by using plasmon waveguide resonance (PWR) based surface plasmon-coupled emission has been proposed and experimentally demonstrated. Raman scattering was captured on the prism side in Kretschmann-surface plasmon-coupled emission. The distinct penetration depths (δ) of the evanescent field for the transverse electric (TE) and transverse magnetic (TM) modes result in different detected distances of the Raman signal. The experimental results demonstrate that the self-referenced directional enhanced Raman scattering of the TE and TM modes based on the PWR can detect and distinguish the surface and bulk effects simultaneously, which appears to have potential applications in researches of chemistry, medicine, and biology.

  7. Switching surface chemistry with supramolecular machines.

    Energy Technology Data Exchange (ETDEWEB)

    Dunbar, Timothy D.; Kelly, Michael James; Jeppesen, Jan O. (University of California, Los Angeles, CA); Bunker, Bruce Conrad; Matzke, Carolyn M.; Stoddart, J. Fraser; Huber, Dale L.; Kushmerick, James G.; Flood, Amar H. (University of California, Los Angeles, CA); Perkins, Julie (University of California, Los Angeles, CA); Cao, Jianguo (University of California, Los Angeles, CA)

    2005-07-01

    Tethered supramolecular machines represent a new class of active self-assembled monolayers in which molecular configurations can be reversibly programmed using electrochemical stimuli. We are using these machines to address the chemistry of substrate surfaces for integrated microfluidic systems. Interactions between the tethered tetracationic cyclophane host cyclobis(paraquat-p-phenylene) and dissolved {pi}-electron-rich guest molecules, such as tetrathiafulvalene, have been reversibly switched by oxidative electrochemistry. The results demonstrate that surface-bound supramolecular machines can be programmed to adsorb or release appropriately designed solution species for manipulating surface chemistry.

  8. The Effect of Aqueous Alteration in Antarctic Carbonaceous Chondrites from Comparative ICP-MS Bulk Chemistry

    Science.gov (United States)

    Alonso-Azcarate, J.; Trigo-Rodriguez, J. M.; Moyano-Cambero, C. E.; Zolensky, M.

    2014-01-01

    Terrestrial ages of Antarctic carbonaceous chondrites (CC) indicate that these meteorites have been preserved in or on ice for, at least, tens of thousands of years. Due to the porous structure of these chondrites formed by the aggregation of silicate-rich chondrules, refractory inclusions, metal grains, and fine-grained matrix materials, the effect of pervasive terrestrial water is relevant. Our community defends that pristine CC matrices are representing samples of scarcely processed protoplanetary disk materials as they contain stellar grains, but they might also trace parent body processes. It is important to study the effects of terrestrial aqueous alteration in promoting bulk chemistry changes, and creating distinctive alteration minerals. Particularly because it is thought that aqueous alteration has particularly played a key role in some CC groups in modifying primordial bulk chemistry, and homogenizing the isotopic content of fine-grained matrix materials. Fortunately, the mineralogy produced by parent-body and terrestrial aqueous alteration processes is distinctive. With the goal to learn more about terrestrial alteration in Antarctica we are obtaining reflectance spectra of CCs, but also performing ICP-MS bulk chemistry of the different CC groups. A direct comparison with the mean bulk elemental composition of recovered falls might inform us on the effects of terrestrial alteration in finds. With such a goal, in the current work we have analyzed some members representative of CO and CM chondrite groups.

  9. Bulk ordering and surface segregation in Ni50Pt50

    DEFF Research Database (Denmark)

    Pourovskii, L.P.; Ruban, Andrei; Abrikosov, I.A.

    2001-01-01

    in the bulk compare well with experimental data. The surface-alloy compositions for the (111) and (110) facets above the ordering transition temperature are also found to be in a good agreement with experiments. It is demonstrated that the segregation profile at the (110) surface of NiPt is mainly caused...... by the unusually strong segregation of Pt into the second layer and the interlayer ordering due to large chemical nearest-neighbor interactions....

  10. Extremal surfaces as bulk probes in AdS/CFT

    Science.gov (United States)

    Hubeny, Veronika E.

    2012-07-01

    Motivated by the need for further insight into the emergence of AdS bulk spacetime from CFT degrees of freedom, we explore the behaviour of probes represented by specific geometric quantities in the bulk. We focus on geodesics and n-dimensional extremal surfaces in a general static asymptotically AdS spacetime with spherical and planar symmetry, respectively. While our arguments do not rely on the details of the metric, we illustrate some of our findings explicitly in spacetimes of particular interest (specifically AdS, Schwarzschild-AdS and extreme Reissner-Nordstrom-AdS). In case of geodesics, we find that for a fixed spatial distance between the geodesic endpoints, spacelike geodesics at constant time can reach deepest into the bulk. We also present a simple argument for why, in the presence of a black hole, geodesics cannot probe past the horizon whilst anchored on the AdS boundary at both ends. The reach of an extremal n-dimensional surface anchored on a given region depends on its dimensionality, the shape and size of the bounding region, as well as the bulk metric. We argue that for a fixed extent or volume of the boundary region, spherical regions give rise to the deepest reach of the corresponding extremal surface. Moreover, for physically sensible spacetimes, at fixed extent of the boundary region, higher-dimensional surfaces reach deeper into the bulk. Finally, we show that in a static black hole spacetime, no extremal surface (of any dimensionality, anchored on any region in the boundary) can ever penetrate the horizon.

  11. Introduction to Applied Colloid and Surface Chemistry

    DEFF Research Database (Denmark)

    Kontogeorgis, Georgios; Kiil, Søren

    Colloid and Surface Chemistry is a subject of immense importance and implications both to our everyday life and numerous industrial sectors, ranging from coatings and materials to medicine and biotechnology. How do detergents really clean? (Why can’t we just use water ?) Why is milk “milky” Why do......, to the benefit of both the environment and our pocket. Cosmetics is also big business! Creams, lotions and other personal care products are really just complex emulsions. All of the above can be explained by the principles and methods of colloid and surface chemistry. A course on this topic is truly valuable...

  12. Understanding surface structure and chemistry of single crystal lanthanum aluminate

    KAUST Repository

    Pramana, Stevin S.

    2017-03-02

    The surface crystallography and chemistry of a LaAlO3 single crystal, a material mainly used as a substrate to deposit technologically important thin films (e.g. for superconducting and magnetic devices), was analysed using surface X-ray diffraction and low energy ion scattering spectroscopy. The surface was determined to be terminated by Al-O species, and was significantly different from the idealised bulk structure. Termination reversal was not observed at higher temperature (600 °C) and chamber pressure of 10−10 Torr, but rather an increased Al-O occupancy occurred, which was accompanied by a larger outwards relaxation of Al from the bulk positions. Changing the oxygen pressure to 10−6 Torr enriched the Al site occupancy fraction at the outermost surface from 0.245(10) to 0.325(9). In contrast the LaO, which is located at the next sub-surface atomic layer, showed no chemical enrichment and the structural relaxation was lower than for the top AlO2 layer. Knowledge of the surface structure will aid the understanding of how and which type of interface will be formed when LaAlO3 is used as a substrate as a function of temperature and pressure, and so lead to improved design of device structures.

  13. Surface processing for bulk niobium superconducting radio frequency cavities

    Science.gov (United States)

    Kelly, M. P.; Reid, T.

    2017-04-01

    The majority of niobium cavities for superconducting particle accelerators continue to be fabricated from thin-walled (2-4 mm) polycrystalline niobium sheet and, as a final step, require material removal from the radio frequency (RF) surface in order to achieve performance needed for use as practical accelerator devices. More recently bulk niobium in the form of, single- or large-grain slices cut from an ingot has become a viable alternative for some cavity types. In both cases the so-called damaged layer must be chemically etched or electrochemically polished away. The methods for doing this date back at least four decades, however, vigorous empirical studies on real cavities and more fundamental studies on niobium samples at laboratories worldwide have led to seemingly modest improvements that, when taken together, constitute a substantial advance in the reproducibility for surface processing techniques and overall cavity performance. This article reviews the development of niobium cavity surface processing, and summarizes results of recent studies. We place some emphasis on practical details for real cavity processing systems which are difficult to find in the literature but are, nonetheless, crucial for achieving the good and reproducible cavity performance. New approaches for bulk niobium surface treatment which aim to reduce cost or increase performance, including alternate chemical recipes, barrel polishing and ‘nitrogen doping’ of the RF surface, continue to be pursued and are closely linked to the requirements for surface processing.

  14. Strong surface effect on direct bulk flexoelectric response in solids

    International Nuclear Information System (INIS)

    Yurkov, A. S.; Tagantsev, A. K.

    2016-01-01

    In the framework of a continuum theory, it is shown that the direct bulk flexoelectric response of a finite sample essentially depends on the surface polarization energy, even in the thermodynamic limit where the body size tends to infinity. It is found that a modification of the surface energy can lead to a change in the polarization response by a factor of two. The origin of the effect is an electric field produced by surface dipoles induced by the strain gradient. The unexpected sensitivity of the polarization response to the surface energy in the thermodynamic limit is conditioned by the fact that the moments of the surface dipoles may scale as the body size

  15. Tapping of Love waves in an isotropic surface waveguide by surface-to-bulk wave transduction.

    Science.gov (United States)

    Tuan, H.-S.; Chang, C.-P.

    1972-01-01

    A theoretical study of tapping a Love wave in an isotropic microacoustic surface waveguide is given. The surface Love wave is tapped by partial transduction into a bulk wave at a discontinuity. It is shown that, by careful design of the discontinuity, the converted bulk wave power and the radiation pattern may be controlled. General formulas are derived for the calculation of these important characteristics from a relatively general surface contour deformation.

  16. Bulk and surface controlled diffusion of fission gas atoms

    Energy Technology Data Exchange (ETDEWEB)

    Andersson, Anders D. [Los Alamos National Laboratory

    2012-08-09

    in UO{sub 2{+-}x}, which compare favorably to available experiments. This is an extension of previous work [13]. In particular, it applies improved chemistry models for the UO{sub 2{+-}x} nonstoichiometry and its impact on the fission gas activation energies. The derivation of these models follows the approach that used in our recent study of uranium vacancy diffusion in UO{sub 2} [14]. Also, based on the calculated DFT data we analyze vacancy enhanced diffusion mechanisms in the intermediate temperature regime. In addition to vacancy enhanced diffusion we investigate species transport on the (111) UO{sub 2} surface. This is motivated by the formation of small voids partially filled with fission gas atoms (bubbles) in UO{sub 2} under irradiation, for which surface diffusion could be the rate-limiting transport step. Diffusion of such bubbles constitutes an alternative mechanism for mass transport in these materials.

  17. Homogeneous bulk, surface, and edge nucleation in crystalline nanodroplets

    Science.gov (United States)

    Carvalho, Jessica L.; Dalnoki-Veress, Kari

    2011-03-01

    We present a study on the homogeneous nucleation of dewetted poly(ethylene oxide) droplets on a substrate that is itself crystallisable. While the chemical properties of the substrate prepared in either the amorphous or crystalline state are identical, the surface landscape varies widely. We observe a large difference in the substrate's nucleating ability depending on how it is prepared. Furthermore, the scaling dependence of the nucleation rate on the size of the droplets depends on the substrate surface properties. The birth of the crystalline state can be directed to originate predominantly within the bulk, at the substrate surface or at the droplet's edge depending on how we tune the substrate. J.L. Carvalho and K. Dalnoki-Veress, Phys. Rev. Lett in press, 2010.

  18. Grain surface chemistry in protoplanetary disks

    International Nuclear Information System (INIS)

    Reboussin, Laura

    2015-01-01

    Planetary formation occurs in the protoplanetary disks of gas and dust. Although dust represents only 1% of the total disk mass, it plays a fundamental role in disk chemical evolution since it acts as a catalyst for the formation of molecules. Understanding this chemistry is therefore essential to determine the initial conditions from which planets form. During my thesis, I studied grain-surface chemistry and its impact on the chemical evolution of molecular cloud, initial condition for disk formation, and protoplanetary disk. Thanks to numerical simulations, using the gas-grain code Nautilus, I showed the importance of diffusion reactions and gas-grain interactions for the abundances of gas-phase species. Model results combined with observations also showed the effects of the physical structure (in temperature, density, AV) on the molecular distribution in disks. (author)

  19. Operando chemistry of catalyst surfaces during catalysis.

    Science.gov (United States)

    Dou, Jian; Sun, Zaicheng; Opalade, Adedamola A; Wang, Nan; Fu, Wensheng; Tao, Franklin Feng

    2017-04-03

    Chemistry of a catalyst surface during catalysis is crucial for a fundamental understanding of mechanism of a catalytic reaction performed on the catalyst in the gas or liquid phase. Due to the pressure- or molecular density-dependent entropy contribution of gas or liquid phase of the reactants and the potential formation of a catalyst surface during catalysis different from that observed in an ex situ condition, the characterization of the surface of a catalyst under reaction conditions and during catalysis can be significant and even necessary for understanding the catalytic mechanism at a molecular level. Electron-based analytical techniques are challenging for studying catalyst nanoparticles in the gas or liquid phase although they are necessary techniques to employ. Instrumentation and further development of these electron-based techniques have now made in situ/operando studies of catalysts possible. New insights into the chemistry and structure of catalyst nanoparticles have been uncovered over the last decades. Herein, the origin of the differences between ex situ and in situ/operando studies of catalysts, and the technical challenges faced as well as the corresponding instrumentation and innovations utilized for characterizing catalysts under reaction conditions and during catalysis, are discussed. The restructuring of catalyst surfaces driven by the pressure of reactant(s) around a catalyst, restructuring in reactant(s) driven by reaction temperature and restructuring during catalysis are also reviewed herein. The remaining challenges and possible solutions are briefly discussed.

  20. Criegee Chemistry on Aqueous Organic Surfaces.

    Science.gov (United States)

    Enami, Shinichi; Colussi, A J

    2017-04-06

    In the troposphere, the fate of gas-phase Criegee intermediates (CIs) is deemed to be determined by their reactions with water molecules. Here it is shown that CIs produced in situ on the surface of water/acetonitrile (W/AN) solutions react competitively with millimolar carboxylic acids. Present experiments probe, via online electrospray mass spectrometry, CIs' chemistry on the surface of α-humulene and β-caryophyllene in W/AN microjets exposed to O 3 (g) for competitiveness being an increasing function of n. Present findings demonstrate that CIs can react with species other than H 2 O on the surface of aqueous organic aerosols due to the low water concentrations prevalent in the outermost interfacial layers.

  1. Adsorção e propriedades de volume de misturas binárias água álcool: um experimento didático com base em medidas de tensão superficial An undergraduate experiment in physical chemistry: adsorption and bulk properties of alcohol-water mixtures based on surface tension measurements

    Directory of Open Access Journals (Sweden)

    Michelly C. dos Santos

    2010-01-01

    Full Text Available An undergraduate physical chemistry experiment based on the drop counting method for surface tension measurements is proposed to demonstrate adsorption isotherms of binary aqueous solutions of ethanol, n-propanol, and n-butanol. Excess surface is obtained by the derivative of surface tension taken with respect to alcohol activity, after this activity calculation using van Laar equation. Laboratory class contents are surface tension, excess surface, percolation of hydrogen bonds, micelle, activity, and ideal solution.

  2. From helical to planar chirality by on-surface chemistry

    Czech Academy of Sciences Publication Activity Database

    Stetsovych, Oleksandr; Švec, Martin; Vacek, Jaroslav; Vacek Chocholoušová, Jana; Jančařík, Andrej; Rybáček, Jiří; Kośmider, K.; Stará, Irena G.; Jelínek, Pavel; Starý, Ivo

    2017-01-01

    Roč. 9, č. 3 (2017), s. 213-218 ISSN 1755-4330 R&D Projects: GA ČR(CZ) GC14-16963J; GA ČR(CZ) GA14-29667S Institutional support: RVO:68378271 ; RVO:61388963 Keywords : chirality * AFM * STM * helicene * on surface chemistry * DFT Subject RIV: CF - Physical ; Theoretical Chemistry; CC - Organic Chemistry (UOCHB-X) OBOR OECD: Physical chemistry; Organic chemistry (UOCHB-X) Impact factor: 25.870, year: 2016

  3. Dissociative electron attachment on surfaces and in bulk media

    International Nuclear Information System (INIS)

    Fabrikant, Ilya I.

    2007-01-01

    A theory of dissociative electron attachment to molecules condensed at surfaces and embedded within bulk media is developed. The theory of low-energy electron diffraction is used to obtain the width for electron-molecule resonance scattering in the condensed phase from the width for the gas phase. It is then employed for the calculation of dissociative attachment in the framework of the nonlocal complex potential theory. Specific calculations using the effective mass approximation are carried out for electron attachment to CH 3 Cl and CF 3 Cl molecules physisorbed on the surface of a Kr film. The role of image states and image-potential resonances is analyzed. The results show an increase by several orders of magnitude in the cross section for physisorbed molecules as compared with gas-phase molecules. This is in general agreement with the measured cross sections. However, the position of the peak in the cross section for CH 3 Cl is significantly shifted towards higher energies as compared to experiment [K. Nagesha et al., J. Chem. Phys. 114, 4934 (2001)], and the magnitude of the calculated cross section for CF 3 Cl at the surface is significantly higher than the measured value. Possible reasons for disagreements are analyzed

  4. Surface barrier and bulk pinning in MgB$_2$ superconductor

    OpenAIRE

    Pissas, M.; Moraitakis, E.; Stamopoulos, D.; Papavassiliou, G.; Psycharis, V.; Koutandos, S.

    2001-01-01

    We present a modified method of preparation of the new superconductor MgB$_2$. The polycrystalline samples were characterized using x-ray and magnetic measurements. The surface barriers control the isothermal magnetization loops in powder samples. In bulk as prepared samples we always observed symmetric magnetization loops indicative of the presence of a bulk pinning mechanism. Magnetic relaxation measurements in the bulk sample reveal a crossover of surface barrier to bulk pinning.

  5. Ferroelectric based catalysis: Switchable surface chemistry

    Science.gov (United States)

    Kakekhani, Arvin; Ismail-Beigi, Sohrab

    2015-03-01

    We describe a new class of catalysts that uses an epitaxial monolayer of a transition metal oxide on a ferroelectric substrate. The ferroelectric polarization switches the surface chemistry between strongly adsorptive and strongly desorptive regimes, circumventing difficulties encountered on non-switchable catalytic surfaces where the Sabatier principle dictates a moderate surface-molecule interaction strength. This method is general and can, in principle, be applied to many reactions, and for each case the choice of the transition oxide monolayer can be optimized. Here, as a specific example, we show how simultaneous NOx direct decomposition (into N2 and O2) and CO oxidation can be achieved efficiently on CrO2 terminated PbTiO3, while circumventing oxygen (and sulfur) poisoning issues. One should note that NOx direct decomposition has been an open challenge in automotive emission control industry. Our method can expand the range of catalytically active elements to those which are not conventionally considered for catalysis and which are more economical, e.g., Cr (for NOx direct decomposition and CO oxidation) instead of canonical precious metal catalysts. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.

  6. Characterisation of the inorganic chemistry of surface waters in ...

    African Journals Online (AJOL)

    The main purpose of this study was to determine a simple inorganic chemistry index that can be used for all surface waters in South Africa, in order to characterise the inorganic chemistry of surface waters. Water quality data collected up until 1999 from all sample monitoring stations (2 068 monitoring stations, 364 659 ...

  7. Surface Chemistry and Spectroscopy of Chromium in Inorganic Oxides

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Wachs, I.E.; Schoonheydt, R.A.

    1996-01-01

    Focuses on the surface chemistry and spectroscopy of chromium in inorganic oxides. Characterization of the molecular structures of chromium; Mechanics of hydrogenation-dehydrogenation reactions; Mobility and reactivity on oxidic surfaces.

  8. Evaluation of Color Stability and Surface Roughness of Bulk-Fill Resin Composites and Nanocomposites

    OpenAIRE

    Muhammet Karadaş; Sezer Demirbuğa

    2017-01-01

    Objective: The purpose of this study was to evaluate the color stability and surface roughness of four bulk-fill resin composites (SonicFill, Filtek Bulk Fill Flowable, X-tra fil, Filtek Bulk Fill Posterior) and three nanocomposites (G-aenial Universal Flo, Herculite XRV Ultra, Filtek Ultimate) after an aging simulation. Materials and Methods: The upper surfaces of prepared composite discs were polished with Sof-Lex discs. The samples were subjected to a thermocycling process for 3000 cyc...

  9. Chemical, electronic, and magnetic structure of LaFeCoSi alloy: Surface and bulk properties

    Energy Technology Data Exchange (ETDEWEB)

    Lollobrigida, V. [Dipartimento di Scienze, Università Roma Tre, I-00146 Rome (Italy); Dipartimento di Matematica e Fisica, Università Roma Tre, I-00146 Rome (Italy); Basso, V.; Kuepferling, M.; Coïsson, M.; Olivetti, E. S.; Celegato, F. [Istituto Nazionale di Ricerca Metrologica (INRIM), I-10135 Torino (Italy); Borgatti, F. [CNR, Istituto per lo Studio dei Materiali Nanostrutturati (ISMN), I-40129 Bologna (Italy); Torelli, P.; Panaccione, G. [CNR, Istituto Officina dei Materiali (IOM), Lab. TASC, I-34149 Trieste (Italy); Tortora, L. [Laboratorio di Analisi di Superficie, Dipartimento di Matematica e Fisica, Università Roma Tre, I-00146 Rome (Italy); Dipartimento di Ingegneria Meccanica, Università Tor Vergata, I-00133 Rome (Italy); Stefani, G.; Offi, F. [Dipartimento di Scienze, Università Roma Tre, I-00146 Rome (Italy)

    2014-05-28

    We investigate the chemical, electronic, and magnetic structure of the magnetocaloric LaFeCoSi compound with bulk and surface sensitive techniques. We put in evidence that the surface retains a soft ferromagnetic behavior at temperatures higher than the Curie temperature of the bulk due to the presence of Fe clusters at the surface only. This peculiar magnetic surface effect is attributed to the exchange interaction between the ferromagnetic Fe clusters located at the surface and the bulk magnetocaloric alloy, and it is used here to monitor the magnetic properties of the alloy itself.

  10. Chemical, electronic, and magnetic structure of LaFeCoSi alloy: Surface and bulk properties

    International Nuclear Information System (INIS)

    Lollobrigida, V.; Basso, V.; Kuepferling, M.; Coïsson, M.; Olivetti, E. S.; Celegato, F.; Borgatti, F.; Torelli, P.; Panaccione, G.; Tortora, L.; Stefani, G.; Offi, F.

    2014-01-01

    We investigate the chemical, electronic, and magnetic structure of the magnetocaloric LaFeCoSi compound with bulk and surface sensitive techniques. We put in evidence that the surface retains a soft ferromagnetic behavior at temperatures higher than the Curie temperature of the bulk due to the presence of Fe clusters at the surface only. This peculiar magnetic surface effect is attributed to the exchange interaction between the ferromagnetic Fe clusters located at the surface and the bulk magnetocaloric alloy, and it is used here to monitor the magnetic properties of the alloy itself.

  11. Simultaneous surface engineering and bulk hardening of precipitation hardening stainless steel

    DEFF Research Database (Denmark)

    Frandsen, Rasmus Berg; Christiansen, Thomas; Somers, Marcel A. J.

    2006-01-01

    This article addresses simultaneous bulk precipitation hardening and low temperature surface engineering of two commercial precipitation hardening stainless steels: Sandvik Nanoflex® and Uddeholm Corrax®. Surface engineering comprised gaseous nitriding or gaseous carburising. Microstructural char....... The duration and temperature of the nitriding/carburising surface hardening treatment can be chosen in agreement with the thermal treatment for obtaining optimal bulk hardness in the precipitation hardening stainless steel.......This article addresses simultaneous bulk precipitation hardening and low temperature surface engineering of two commercial precipitation hardening stainless steels: Sandvik Nanoflex® and Uddeholm Corrax®. Surface engineering comprised gaseous nitriding or gaseous carburising. Microstructural...

  12. Bulk and Surface Aqueous Speciation of Calcite: Implications for Low-Salinity Waterflooding of Carbonate Reservoirs

    KAUST Repository

    Yutkin, Maxim P.

    2017-08-25

    Low-salinity waterflooding (LSW) is ineffective when reservoir rock is strongly water-wet or when crude oil is not asphaltenic. Success of LSW relies heavily on the ability of injected brine to alter surface chemistry of reservoir crude-oil brine/rock (COBR) interfaces. Implementation of LSW in carbonate reservoirs is especially challenging because of high reservoir-brine salinity and, more importantly, because of high reactivity of the rock minerals. Both features complicate understanding of the COBR surface chemistries pertinent to successful LSW. Here, we tackle the complex physicochemical processes in chemically active carbonates flooded with diluted brine that is saturated with atmospheric carbon dioxide (CO2) and possibly supplemented with additional ionic species, such as sulfates or phosphates. When waterflooding carbonate reservoirs, rock equilibrates with the injected brine over short distances. Injected-brine ion speciation is shifted substantially in the presence of reactive carbonate rock. Our new calculations demonstrate that rock-equilibrated aqueous pH is slightly alkaline quite independent of injected-brine pH. We establish, for the first time, that CO2 content of a carbonate reservoir, originating from CO2-rich crude oil and gas, plays a dominant role in setting aqueous pH and rock-surface speciation. A simple ion-complexing model predicts the calcite-surface charge as a function of composition of reservoir brine. The surface charge of calcite may be positive or negative, depending on speciation of reservoir brine in contact with the calcite. There is no single point of zero charge; all dissolved aqueous species are charge determining. Rock-equilibrated aqueous composition controls the calcite-surface ion-exchange behavior, not the injected-brine composition. At high ionic strength, the electrical double layer collapses and is no longer diffuse. All surface charges are located directly in the inner and outer Helmholtz planes. Our evaluation of

  13. Effects of bulk charged impurities on the bulk and surface transport in three-dimensional topological insulators

    International Nuclear Information System (INIS)

    Skinner, B.; Chen, T.; Shklovskii, B. I.

    2013-01-01

    In the three-dimensional topological insulator (TI), the physics of doped semiconductors exists literally side-by-side with the physics of ultrarelativistic Dirac fermions. This unusual pairing creates a novel playground for studying the interplay between disorder and electronic transport. In this mini-review, we focus on the disorder caused by the three-dimensionally distributed charged impurities that are ubiquitous in TIs, and we outline the effects it has on both the bulk and surface transport in TIs. We present self-consistent theories for Coulomb screening both in the bulk and at the surface, discuss the magnitude of the disorder potential in each case, and present results for the conductivity. In the bulk, where the band gap leads to thermally activated transport, we show how disorder leads to a smaller-than-expected activation energy that gives way to variable-range hopping at low temperatures. We confirm this enhanced conductivity with numerical simulations that also allow us to explore different degrees of impurity compensation. For the surface, where the TI has gapless Dirac modes, we present a theory of disorder and screening of deep impurities, and we calculate the corresponding zero-temperature conductivity. We also comment on the growth of the disorder potential in passing from the surface of the TI into the bulk. Finally, we discuss how the presence of a gap at the Dirac point, introduced by some source of time-reversal symmetry breaking, affects the disorder potential at the surface and the mid-gap density of states

  14. Surface chemistry: Key to control and advance myriad technologies

    Science.gov (United States)

    Yates, John T.; Campbell, Charles T.

    2011-01-01

    This special issue on surface chemistry is introduced with a brief history of the field, a summary of the importance of surface chemistry in technological applications, a brief overview of some of the most important recent developments in this field, and a look forward to some of its most exciting future directions. This collection of invited articles is intended to provide a snapshot of current developments in the field, exemplify the state of the art in fundamental research in surface chemistry, and highlight some possibilities in the future. Here, we show how those articles fit together in the bigger picture of this field. PMID:21245359

  15. Variability in chemistry of surface and soil waters of an ...

    African Journals Online (AJOL)

    Water chemistry is important for the maintenance of wetland structure and function. Interpreting ecological patterns in a wetland system therefore requires an in-depth understanding of the water chemistry of that system. We investigated the spatial distribution of chemical solutes both in soil pore water and surface water, ...

  16. Surface and Bulk Nanostructuring of Insulators by Ultrashort Laser Pulses

    Science.gov (United States)

    2017-04-05

    photoionization yield in diamond. More recently, it was experimentally found that high-harmonic generation in bulk solids [30] is char - acteristic of...Such experimental studies were devoted to the design and fabrication of bio -sensors, employing the biocompatibility of the material, by ablative...HHG. Experimental and theoretical study of HHG spectra from rare-gas solids [17] exposed char - acteristic features of HHG in solids: abrupt appearance

  17. Effects of surface and bulk transverse fields on critical behaviour of ferromagnetic films

    International Nuclear Information System (INIS)

    Saber, A.; Lo Russo, S.; Mattei, G.

    2002-02-01

    The influence of surface and bulk transverse fields on the critical behaviour of a ferromagnetic Ising film is studied using the effective field theory based on a single-site cluster method. Surface exchange enhancement is considered and a critical value is obtained. The dependence of the critical uniform transverse field on film thickness, phase diagrams in the fields, critical surface transverse field versus the bulk one, and exchange coupling ratio are presented. (author)

  18. Ferromagnetic transitions of a spin-one Ising film in a surface and bulk transverse fields

    International Nuclear Information System (INIS)

    Saber, A.; Lo Russo, S.; Mattei, G.; Mattoni, A.

    2002-01-01

    Using the effective field theory method, we have calculated the Curie temperature of a spin-one Ising ferromagnetic film in a surface and bulk transverse fields. Numerical calculations give phase diagrams under various parameters. Surface exchange enhancement is considered. The dependence of the critical transverse field on film thickness, and phase diagrams in the fields, critical surface transverse field versus the bulk one are presented

  19. Fingerprinting young ignimbrites in Dominica (Lesser Antilles): Constraints from bulk REEs, apatite chemistry, and U-Th zircon chronology

    Science.gov (United States)

    Frey, H. M.; Manon, M. R.; Brehm, S.

    2015-12-01

    Multiple methods of fingerprinting tephra deposits enable distinction of separate magma batches beneath the island of Dominica. Previous studies have invoked a single large batholith but apatite REE chemistry is inconsistent with generation of multiple ignimbrites by fractional crystallization. The crystal-rich, andesite-dacite (58-66 wt% SiO2) ignimbrites comprise the largest explosive eruption in the Caribbean in the last 200 kyr, erupting a magma volume >58 km3 (Carey and Sigurdsson, 1980). Although the ignimbrites appear to emanate from several vents, their broad similarity in bulk chemistry, phase assemblage (pl + opx + cpx + hbl + ilm + mag + zrn + ap), and mineral composition, has led previous workers to suggest that Dominica is underlain by a single large batholith eruptions younging from north to south. However, bulk REE chemistry, solution ICP-MS chemistry of individual apatite grains, and ion microprobe U-Th dating of zircon rims from pumice clasts suggest a more complex plumbing system. More than 150 pumice clasts from northernmost (Morne aux Diables), northern (Wesley, Pointe Ronde, Grand Savanne), central (Layou, Roseau, Rosalie), and southern (Grand Bay, Grand Fonde) ignimbrites were analyzed for bulk chemistry. Geographically controlled differences exist in the concavity of the middle-heavy REE (Dy*). In central Dominica, apatites from the more evolved Layou Ignimbrite are depleted in middle REE compared to the nearby Roseau Ignimbrite, belying a genetic relationship via fractional crystallization. U-Th zircon rim ages in the northernmost and northern deposits were in secular equilibrium (>350 ka), whereas the central and southern ignimbrites yielded several populations of crystallization ages: Layou (99±12 ka), Roseau (139±12 ka; 65±17 ka), and Grand Bay (107±15 ka; 211±61 ka). Collectively, these observations are consistent with partial melting of magma batches prior to eruption rather than fractional crystallization of a single magma chamber.

  20. Surface wear reduction of bulk solids handling equipment using bionic design

    NARCIS (Netherlands)

    Chen, G.

    2017-01-01

    Bulk solids handling continues to play an important role in a number of industries. One of the issues during bulk solids handling processes is equipment surface wear. Wear results in high economic loss and increases downtime. Current wear reduction methods such as optimizing transfer conditions or

  1. Development of a novel once-through flow visualization technique for kinetic study of bulk and surface scaling

    Science.gov (United States)

    Sanni, O.; Bukuaghangin, O.; Huggan, M.; Kapur, N.; Charpentier, T.; Neville, A.

    2017-10-01

    There is a considerable interest to investigate surface crystallization in order to have a full mechanistic understanding of how layers of sparingly soluble salts (scale) build on component surfaces. Despite much recent attention, a suitable methodology to improve on the understanding of the precipitation/deposition systems to enable the construction of an accurate surface deposition kinetic model is still needed. In this work, an experimental flow rig and associated methodology to study mineral scale deposition is developed. The once-through flow rig allows us to follow mineral scale precipitation and surface deposition in situ and in real time. The rig enables us to assess the effects of various parameters such as brine chemistry and scaling indices, temperature, flow rates, and scale inhibitor concentrations on scaling kinetics. Calcium carbonate (CaCO3) scaling at different values of the saturation ratio (SR) is evaluated using image analysis procedures that enable the assessment of surface coverage, nucleation, and growth of the particles with time. The result for turbidity values measured in the flow cell is zero for all the SR considered. The residence time from the mixing point to the sample is shorter than the induction time for bulk precipitation; therefore, there are no crystals in the bulk solution as the flow passes through the sample. The study shows that surface scaling is not always a result of pre-precipitated crystals in the bulk solution. The technique enables both precipitation and surface deposition of scale to be decoupled and for the surface deposition process to be studied in real time and assessed under constant condition.

  2. Quantum effects on propagation of bulk and surface waves in a thin quantum plasma film

    Energy Technology Data Exchange (ETDEWEB)

    Moradi, Afshin, E-mail: a.moradi@kut.ac.ir [Department of Engineering Physics, Kermanshah University of Technology, Kermanshah (Iran, Islamic Republic of); Department of Nano Sciences, Institute for Studies in Theoretical Physics and Mathematics (IPM), Tehran (Iran, Islamic Republic of)

    2015-06-19

    The propagation of bulk and surface plasma waves in a thin quantum plasma film is investigated, taking into account the quantum effects. The generalized bulk and surface plasma dispersion relation due to quantum effects is derived, using the quantum hydrodynamic dielectric function and applying appropriate additional boundary conditions. The quantum mechanical and film geometric effects on the bulk and surface modes are discussed. It is found that quantum effects become important for a thin film of small thickness. - Highlights: • New bulk and surface plasma dispersion relations due to quantum effects are derived, in a thin quantum plasma film. • It is found that quantum effects become important for a thin quantum film of small thickness.

  3. Multilayered nanoclusters of platinum and gold: insights on electrodeposition pathways, electrocatalysis, surface and bulk compositional properties

    CSIR Research Space (South Africa)

    Mkwizu, TS

    2013-06-01

    Full Text Available Electrochemical, surface and bulk compositional properties of multilayered nanoclusters of Pt and Au, electrochemically deposited on glassy carbon under conditions involving sequential surface–limited redox–replacement reactions (performed at open...

  4. Surface wear reduction of bulk solids handling equipment using bionic design

    OpenAIRE

    Chen, G.

    2017-01-01

    Bulk solids handling continues to play an important role in a number of industries. One of the issues during bulk solids handling processes is equipment surface wear. Wear results in high economic loss and increases downtime. Current wear reduction methods such as optimizing transfer conditions or using wear-resistant materials, have brought notable progress. Nevertheless, the wear loss is still significant. Therefore, new solutions for reducing the surface wear must be investigated.Because w...

  5. Effects of bulk and surface conductivity on the performance of CdZnTe pixel detectors

    DEFF Research Database (Denmark)

    Bolotnikov, A.E.; Chen, C.M.H.; Cook, W.R.

    2002-01-01

    We studied the effects of bulk and surface conductivity on the performance of high-resistivity CdZnTe (CZT) pixel detectors with Pt contacts. We emphasize the difference in mechanisms of the bulk and surface conductivity as indicated by their different temperature behaviors. In addition...... with two back-to-back Schottky-barrier contacts. The high-surface leakage. current is apparently due to the presence of a low-resistivity surface layer that has characteristics that differ considerably from those of the bulk material. This surface layer has a profound effect on the charge......-collection efficiency in detectors with multicontact geometry; some fraction of the electric field lines that originated on the cathode intersects the surface areas between the pixel contacts where the charge produced by an ionizing particle gets trapped. To overcome this effect, we place a grid of thin electrodes...

  6. Concentration polarization, surface currents, and bulk advection in a microchannel

    DEFF Research Database (Denmark)

    Nielsen, Christoffer Peder; Bruus, Henrik

    2014-01-01

    We present a comprehensive analysis of salt transport and overlimiting currents in a microchannel during concentration polarization. We have carried out full numerical simulations of the coupled Poisson-Nernst-Planck-Stokes problem governing the transport and rationalized the behavior of the syst...... as in the limit of negligible surface charge. By including the effects of diffusion and advection in the diffuse part of the electric double layers, we extend a recently published analytical model of overlimiting current due to surface conduction....

  7. The Hydrated Electron at the Surface of Neat Liquid Water Appears To Be Indistinguishable from the Bulk Species.

    Science.gov (United States)

    Coons, Marc P; You, Zhi-Qiang; Herbert, John M

    2016-08-31

    Experiments have suggested that the aqueous electron, e(-)(aq), may play a significant role in the radiation chemistry of DNA. A recent measurement of the energy (below vacuum level) of the putative "interfacial" hydrated electron at the water/vacuum interface, performed using liquid microjet photoelectron spectroscopy, has been interpreted to suggest that aqueous electrons at the water/biomolecule interface may possess the appropriate energetics to induce DNA strand breaks, whereas e(-)(aq) in bulk water lies too far below the vacuum level to induce such reactions. Other such experiments, however, find no evidence of a long-lived feature at low binding energy. We employ a variety of computational strategies to demonstrate that the energetics of the hydrated electron at the surface of neat liquid water are not significantly different from those of e(-)(aq) in bulk water and as such are incompatible with dissociative electron attachment reactions in DNA. We furthermore suggest that no stable interfacial species may exist at all, consistent with the interpretation of certain surface-sensitive spectroscopy measurements, and that even if a short-lived, metastable species does exist at the vacuum/water interface, it would be extremely difficult to distinguish, experimentally, from e(-)(aq) in bulk water, using either optical absorption or photoelectron spectroscopy.

  8. Electrospray deposition of organic molecules on bulk insulator surfaces.

    Science.gov (United States)

    Hinaut, Antoine; Pawlak, Rémy; Meyer, Ernst; Glatzel, Thilo

    2015-01-01

    Large organic molecules are of important interest for organic-based devices such as hybrid photovoltaics or molecular electronics. Knowing their adsorption geometries and electronic structures allows to design and predict macroscopic device properties. Fundamental investigations in ultra-high vacuum (UHV) are thus mandatory to analyze and engineer processes in this prospects. With increasing size, complexity or chemical reactivity, depositing molecules by thermal evaporation becomes challenging. A recent way to deposit molecules in clean conditions is Electrospray Ionization (ESI). ESI keeps the possibility to work with large molecules, to introduce them in vacuum, and to deposit them on a large variety of surfaces. Here, ESI has been successfully applied to deposit triply fused porphyrin molecules on an insulating KBr(001) surface in UHV environment. Different deposition coverages have been obtained and characterization of the surface by in-situ atomic force microscopy working in the non-contact mode shows details of the molecular structures adsorbed on the surface. We show that UHV-ESI, can be performed on insulating surfaces in the sub-monolayer regime and to single molecules which opens the possibility to study a variety of complex molecules.

  9. Surface chemistry: Single handedness in flatland

    Science.gov (United States)

    Ernst, Karl-Heinz

    2017-03-01

    Planar molecules may break mirror symmetry when aligned on a surface, but both right- and left-handed forms will be created. Starting with a single-handed precursor, chiral adsorbates of planar hydrocarbons with a single handedness are formed in on-surface reactions.

  10. Chemistry - Toward efficient hydrogen production at surfaces

    DEFF Research Database (Denmark)

    Nørskov, Jens Kehlet; Christensen, Claus H.

    2006-01-01

    Calculations are providing a molecular picture of hydrogen production on catalytic surfaces and within enzymes, knowledge that may guide the design of new, more efficient catalysts for the hydrogen economy.......Calculations are providing a molecular picture of hydrogen production on catalytic surfaces and within enzymes, knowledge that may guide the design of new, more efficient catalysts for the hydrogen economy....

  11. Surface and Bulk Reactivity of Iron Oxyhydroxides : A Molecular Perspective

    OpenAIRE

    Song, Xiaowei

    2013-01-01

    Iron oxyhydroxide (FeOOH) mineral plays an important role in a variety of atmospheric, terrestrial and technological settings. Molecular resolution of reactions involving these minerals is thereby required to develop a fundamental understanding of their contributions in processes taking place in the atmosphere, Earth’s upper crust as well as the hydrosphere. This study resolves interactions involving four different types of synthetic FeOOH particles with distinct and well-defined surfaces, na...

  12. Clean Air Markets - Monitoring Surface Water Chemistry

    Science.gov (United States)

    Learn about how EPA uses Long Term Monitoring (LTM) and Temporily Integrated Monitoring of Ecosystems (TIME) to track the effect of the Clean Air Act Amendments on acidity of surface waters in the eastern U.S.

  13. Surface flux density distribution characteristics of bulk high-T c superconductor in external magnetic field

    International Nuclear Information System (INIS)

    Nishikawa, H.; Torii, S.; Yuasa, K.

    2005-01-01

    This paper describes the measured results of the two-dimensional flux density distribution of a YBCO bulk under applied AC magnetic fields with various frequency. Melt-processed oxide superconductors have been developed in order to obtain strong pinning forces. Various electric mechanical systems or magnetic levitation systems use those superconductors. The major problem is that cracks occur because the bulk superconductors are brittle. The bulk may break in magnetizing process after cracks make superconducting state instable. The trapped flux density and the permanent current characteristics of bulk superconductors have been analyzed, so as to examine the magnetizing processes or superconducting states of the bulk. In those studies, the two-dimensional surface flux density distributions of the bulk in static fields are discussed. On the other hand, the distributions in dynamic fields are little discussed. We attempted to examine the states of the bulk in the dynamic fields, and made a unique experimental device which has movable sensors synchronized with AC applied fields. As a result, the two-dimensional distributions in the dynamic fields are acquired by recombining the one-dimensional distributions. The dynamic states of the flux of the bulk and the influences of directions of cracks are observed from the distributions. In addition, a new method for measuring two-dimensional flux density distribution under dynamic magnetic fields is suggested

  14. Adsorption of trace gases to ice surfaces: surface, bulk and co-adsorbate effects

    Science.gov (United States)

    Kerbrat, Michael; Bartels-Rausch, Thorsten; Huthwelker, Thomas; Schneebeli, Martin; Pinzer, Bernd; Ammann, Markus

    2010-05-01

    Atmospheric ices frequently interact with trace gases and aerosol making them an important storage, transport or reaction medium in the global ecosystem. Further, this also alters the physical properties of the ice particles with potential consequences for the global irradiation balance and for the relative humidity of surrounding air masses. We present recent results from a set of laboratory experiments of atmospheric relevance to investigate the nature of the uptake processes. The focus of this talk will be placed on the partitioning of acidic acid and nitrous acid on ice surfaces.The presented results span from very simple reversible adsorption experiments of a single trace gas onto ice surfaces to more complex, but well controlled, experimental procedures that successfully allowed us to - Disentangle surface adsorption and uptake into the ice matrix using radioactive labelled trace gases. - Show that simultaneous adsorption of acetic acid and nitrous acid to an ice surface is consistent with the Langmuir co-adsorption model. The experiments were done in a packed ice bed flow tube at atmospheric pressure and at temperatures between 213 and 253 K. The HONO gas phase mixing ratio was between 0.4 and 137 ppbv, the mixing ratio of acetic acid between 5 and 160 ppbv . The use of the radioactive labelled nitrous acid molecules for these experiments enabled in situ monitoring of the migration of trace gas in the flow tube. The measurements showed that the interactions do not only occur through adsorption but also via diffusion into polycrystalline ice. A method is suggested to disentangle the bulk and the surface processes. The co-adsorption of acetic and nitrous acids was also investigated. The measurements are well reproduced by a competitive Langmuir adsorption model.

  15. Surface ferro (or antiferro) magnetism in bulk antiferro (or ferro) magnets: renormalization group analysis

    International Nuclear Information System (INIS)

    Sarmento, E.F.; Tsallis, C.

    1985-01-01

    The renormalization group techniques are applied, for the first time, to surface magnetism in bulk magnets, for all signs of surface and bulk coupling constants. The g-state Potts model is specifically focused, and a interesting q-evolution of the phase diagram is exhibited. In particular the Ising model (q=2) presents a remarkable feature: surface ferro (or antiferro) magnetism can disappear while heating an antiferro (or ferro) magnet, and reappear again for higher temperatures, before entering in the paramagnetic phase. (Author) [pt

  16. Disentangling surface, bulk, and space-charge-layer conductivity in Si(111)-(7x7)

    DEFF Research Database (Denmark)

    Wells, J.W.; Kallehauge, J.F.; Hansen, Torben Mikael

    2006-01-01

    A novel approach for extracting genuine surface conductivities is presented and illustrated using the unresolved example of Si(111)-(7x7). Its temperature-dependent conductivity was measured with a microscopic four point probe between room temperature and 100 K. At room temperature the measured......), irrespective of bulk doping. This abrupt transition is interpreted as the switching from bulk to surface conduction, an interpretation which is supported by a numerical model for the measured four point probe conductance. The value of the surface conductance is considerably lower than that of a good metal....

  17. Covalent-Bond Formation via On-Surface Chemistry.

    Science.gov (United States)

    Held, Philipp Alexander; Fuchs, Harald; Studer, Armido

    2017-05-02

    In this Review article pioneering work and recent achievements in the emerging research area of on-surface chemistry is discussed. On-surface chemistry, sometimes also called two-dimensional chemistry, shows great potential for bottom-up preparation of defined nanostructures. In contrast to traditional organic synthesis, where reactions are generally conducted in well-defined reaction flasks in solution, on-surface chemistry is performed in the cavity of a scanning probe microscope on a metal crystal under ultrahigh vacuum conditions. The metal first acts as a platform for self-assembly of the organic building blocks and in many cases it also acts as a catalyst for the given chemical transformation. Products and hence success of the reaction are directly analyzed by scanning probe microscopy. This Review provides a general overview of this chemistry highlighting advantages and disadvantages as compared to traditional reaction setups. The second part of the Review then focuses on reactions that have been successfully conducted as on-surface processes. On-surface Ullmann and Glaser couplings are addressed. In addition, cyclodehydrogenation reactions and cycloadditions are discussed and reactions involving the carbonyl functionality are highlighted. Finally, the first examples of sequential on-surface chemistry are considered in which two different functionalities are chemoselectively addressed. The Review gives an overview for experts working in the area but also offers a starting point to non-experts to enter into this exciting new interdisciplinary research field. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. On the interrelation between bulk and thin-film Fermi surfaces

    KAUST Repository

    Schwingenschlögl, Udo

    2010-12-01

    A general scheme for inferring the Fermi surface of a finite slab from ab initio electronic-structure calculations for the parent bulk system is introduced. The simple cubic ReO 3 oxide is studied as an example system. We show that our scheme provides an accurate approximation of the Fermi surface even for very thin slabs. © 2010 Europhysics Letters Association.

  19. Surface and bulk dissolution properties, and selectivity of DNA-linked nanoparticle assemblies

    NARCIS (Netherlands)

    Lukatsky, D.B.; Frenkel, D.

    2005-01-01

    Using a simple mean-field model, we analyze the surface and bulk dissolution properties of DNA-linked nanoparticle assemblies. We find that the dissolution temperature and the sharpness of the dissolution profiles increase with the grafting density of the single-stranded DNA "probes" on the surface

  20. Manganese phospate physical chemistry and surface properties

    International Nuclear Information System (INIS)

    Najera R, N.; Romero G, E. T.

    2008-01-01

    This paper presents the methodology for the manganese phosphate (III) synthesis (MnP0 4 H 2 0) from manganese chloride. The physicochemical characterization was carried out by: X-ray diffraction, scanning electron microscopy, infrared analysis and thermal gravimetric analysis. The surface characterization is obtained through the determination of surface area, point of zero charge and kinetics of moisture. As a phosphate compound of a metal with low oxidation state is a promising compound for removal pollutants from water and soil, can be used for the potential construction of containment barriers for radioactive wastes. (Author)

  1. The Chemistry and Physics of Molecular Surfaces

    Science.gov (United States)

    Kaldor, A.; Cox, D. M.; Trevor, D. J.; Zakin, M. R.

    1986-06-01

    This article reviews the results of several recent experiments performed in our laboratory designed to elucidate the fundamental chemical and physical properties of clusters of both transition metals and other refractory elements containing from one to several hundred atoms. The gas-phase reactivity of clusters towards a variety of reagents is explored using a fast-flow reactor system. Strong cluster size-dependent variations in reactivity are observed, especially for the case of hydrogen chemisorption. Measurement of cluster photoionization thresholds (IPs) provides a sensitive probe of the evolution of cluster electronic structure as a function of the number of constituent atoms. Cluster ionization potentials are observed to exhibit fluctuations about the smooth global falloff predicted by the classical drop model, indicating the non-bulk-like behavior of small clusters. Measurement of shifts in IP induced by chemisorption of different reagents provides insight into the nature of adsorbate-cluster bonding. The formation and properties of bare and metal-doped carbon clusters are explored, with particular emphasis on elucidating the photophysics and photochemistry of the postulated ultrastable larger clusters. The results suggest that further work is required to prove soccer ball-like structures for C50, C60, etc. Finally, infrared multiple-photon dissociation (IR-MPD) is demonstrated to be a viable technique for obtaining infrared spectra of absorbate-cluster complexes. This technique is an important new tool for obtaining information about the molecularity of gas-phase reactions beyond that currently available from mass spectrometric analysis. As an illustration of the method, IR-MPD spectra of methanol chemisorbed on small iron clusters are obtained.

  2. Organic chemistry on Titan: Surface interactions

    Science.gov (United States)

    Thompson, W. Reid; Sagan, Carl

    1992-01-01

    The interaction of Titan's organic sediments with the surface (solubility in nonpolar fluids) is discussed. How Titan's sediments can be exposed to an aqueous medium for short, but perhaps significant, periods of time is also discussed. Interactions with hydrocarbons and with volcanic magmas are considered. The alteration of Titan's organic sediments over geologic time by the impacts of meteorites and comets is discussed.

  3. Surface chemistry and microscopy of food powders

    Science.gov (United States)

    Burgain, Jennifer; Petit, Jeremy; Scher, Joël; Rasch, Ron; Bhandari, Bhesh; Gaiani, Claire

    2017-12-01

    Despite high industrial and scientific interest, a comprehensive review of the surface science of food powders is still lacking. There is a real gap between scientific concerns of the field and accessible reviews on the subject. The global description of the surface of food powders by multi-scale microscopy approaches seems to be essential in order to investigate their complexity and take advantage of their high innovation potential. Links between these techniques and the interest to develop a multi-analytical approach to investigate scientific questions dealing with powder functionality are discussed in the second part of the review. Finally, some techniques used in others fields and showing promising possibilities in the food powder domain will be highlighted.

  4. Quantification of air plasma chemistry for surface disinfection

    Science.gov (United States)

    Pavlovich, Matthew J.; Clark, Douglas S.; Graves, David B.

    2014-12-01

    Atmospheric-pressure air plasmas, created by a variety of discharges, are promising sources of reactive species for the emerging field of plasma biotechnology because of their convenience and ability to operate at ambient conditions. One biological application of ambient-air plasma is microbial disinfection, and the ability of air plasmas to decontaminate both solid surfaces and liquid volumes has been thoroughly established in the literature. However, the mechanism of disinfection and which reactive species most strongly correlate with antimicrobial effects are still not well understood. We describe quantitative gas-phase measurements of plasma chemistry via infrared spectroscopy in confined volumes, focusing on air plasma generated via surface micro-discharge (SMD). Previously, it has been shown that gaseous chemistry is highly sensitive to operating conditions, and the measurements we describe here extend those findings. We quantify the gaseous concentrations of ozone (O3) and nitrogen oxides (NO and NO2, or NOx) throughout the established ‘regimes’ for SMD air plasma chemistry: the low-power, ozone-dominated mode; the high-power, nitrogen oxides-dominated mode; and the intermediate, unstable transition region. The results presented here are in good agreement with previously published experimental studies of aqueous chemistry and parameterized models of gaseous chemistry. The principal finding of the present study is the correlation of bacterial inactivation on dry surfaces with gaseous chemistry across these time and power regimes. Bacterial decontamination is most effective in ‘NOx mode’ and less effective in ‘ozone mode’, with the weakest antibacterial effects in the transition region. Our results underscore the dynamic nature of air plasma chemistry and the importance of careful chemical characterization of plasma devices intended for biological applications.

  5. Evaluation of Color Stability and Surface Roughness of Bulk-Fill Resin Composites and Nanocomposites

    Directory of Open Access Journals (Sweden)

    Muhammet Karadaş

    2017-11-01

    Full Text Available Objective: The purpose of this study was to evaluate the color stability and surface roughness of four bulk-fill resin composites (SonicFill, Filtek Bulk Fill Flowable, X-tra fil, Filtek Bulk Fill Posterior and three nanocomposites (G-aenial Universal Flo, Herculite XRV Ultra, Filtek Ultimate after an aging simulation. Materials and Methods: The upper surfaces of prepared composite discs were polished with Sof-Lex discs. The samples were subjected to a thermocycling process for 3000 cycles, then immersed in the prepared mixture solution for two weeks. Before and after the aging simulation, profilometer and spectrophotometer were used to measure surface roughness (Ra and color of the composite discs. The color change (ΔE of each material was calculated. Results: The ΔE values showed a statistically significant difference among the studied materials (p<0.001. The Ra values of X-tra fil, Filtek Bulk Fill Flowable, SonicFill, and Filtek Bulk Fill Posterior were significantly increased by the aging process (p<0.001, while G-aenial Universal Flo, Filtek Ultimate, and Herculite XRV Ultra showed steady roughness (p<0.001. Conclusion: Filtek Ultimate showed greater susceptibility to staining. Microhybrid X-tra fil and nanohybrid SonicFill with higher filler amounts revealed more surface deterioration.

  6. Near-surface and bulk behavior of Ag in SiC

    International Nuclear Information System (INIS)

    Xiao, H.Y.; Zhang, Y.; Snead, L.L.; Shutthanandan, V.; Xue, H.Z.; Weber, W.J.

    2012-01-01

    Highlights: ► Ag release from SiC poses problems in safe operation of nuclear reactors. ► Near-surface and bulk behavior of Ag are studied by ab initio and ion beam methods. ► Ag prefers to adsorb on the surface rather than in the bulk SiC. ► At high temperature Ag desorbs from the surface instead of diffusion into bulk SiC. ► Surface diffusion may be a dominating mechanism accounting for Ag release from SiC. - Abstract: The diffusive release of fission products, such as Ag, from TRISO particles at high temperatures has raised concerns regarding safe and economic operation of advanced nuclear reactors. Understanding the mechanisms of Ag diffusion is thus of crucial importance for effective retention of fission products. Two mechanisms, i.e., grain boundary diffusion and vapor or surface diffusion through macroscopic structures such as nano-pores or nano-cracks, remain in debate. In the present work, an integrated computational and experimental study of the near-surface and bulk behavior of Ag in silicon carbide (SiC) has been carried out. The ab initio calculations show that Ag prefers to adsorb on the SiC surface rather than in the bulk, and the mobility of Ag on the surface is high. The energy barrier for Ag desorption from the surface is calculated to be 0.85–1.68 eV, and Ag migration into bulk SiC through equilibrium diffusion process is not favorable. Experimentally, Ag ions are implanted into SiC to produce Ag profiles buried in the bulk and peaked at the surface. High-temperature annealing leads to Ag release from the surface region instead of diffusion into the interior of SiC. It is suggested that surface diffusion through mechanical structural imperfection, such as vapor transport through cracks in SiC coatings, may be a dominating mechanism accounting for Ag release from the SiC in the nuclear reactor.

  7. A new approach to the problem of bulk-mediated surface diffusion.

    Science.gov (United States)

    Berezhkovskii, Alexander M; Dagdug, Leonardo; Bezrukov, Sergey M

    2015-08-28

    This paper is devoted to bulk-mediated surface diffusion of a particle which can diffuse both on a flat surface and in the bulk layer above the surface. It is assumed that the particle is on the surface initially (at t = 0) and at time t, while in between it may escape from the surface and come back any number of times. We propose a new approach to the problem, which reduces its solution to that of a two-state problem of the particle transitions between the surface and the bulk layer, focusing on the cumulative residence times spent by the particle in the two states. These times are random variables, the sum of which is equal to the total observation time t. The advantage of the proposed approach is that it allows for a simple exact analytical solution for the double Laplace transform of the conditional probability density of the cumulative residence time spent on the surface by the particle observed for time t. This solution is used to find the Laplace transform of the particle mean square displacement and to analyze the peculiarities of its time behavior over the entire range of time. We also establish a relation between the double Laplace transform of the conditional probability density and the Fourier-Laplace transform of the particle propagator over the surface. The proposed approach treats the cases of both finite and infinite bulk layer thicknesses (where bulk-mediated surface diffusion is normal and anomalous at asymptotically long times, respectively) on equal footing.

  8. Tuning apparent friction coefficient by controlled patterning bulk metallic glasses surfaces

    Science.gov (United States)

    Li, Ning; Xu, Erjiang; Liu, Ze; Wang, Xinyun; Liu, Lin

    2016-12-01

    Micro-honeycomb structures with various pitches between adjacent cells were hot-embossed on Zr35Ti30Cu8.25Be26.75 bulk metallic glass surface. The effect of pitch geometry on the frictional behavior of metallic glass surface was systematically investigated. The results revealed that all textured metallic glass surfaces show a reduction in friction coefficient compared to smooth surface. More intriguingly, the friction coefficient first decreased and then increased gradually with increasing pitches. Such unique behavior can be understood fundamentally from the perspective of competing effects between contact area and local stress level with increasing pitches. This finding not only enhance the in-depth understanding of the mechanism of the significant role of surface topography on the frictional behavior of metallic glass surface, but also opens a new route towards other functional applications for bulk metallic glasses.

  9. Density functional theory in surface chemistry and catalysis

    Science.gov (United States)

    Nørskov, Jens K.; Abild-Pedersen, Frank; Studt, Felix; Bligaard, Thomas

    2011-01-01

    Recent advances in the understanding of reactivity trends for chemistry at transition-metal surfaces have enabled in silico design of heterogeneous catalysts in a few cases. The current status of the field is discussed with an emphasis on the role of coupling theory and experiment and future challenges. PMID:21220337

  10. Density functional theory in surface chemistry and catalysis

    DEFF Research Database (Denmark)

    Nørskov, Jens Kehlet; Abild-Pedersen, Frank; Studt, Felix

    2011-01-01

    Recent advances in the understanding of reactivity trends for chemistry at transition-metal surfaces have enabled in silico design of heterogeneous catalysts in a few cases. The current status of the field is discussed with an emphasis on the role of coupling theory and experiment and future...

  11. Density Functional Theory in Surface Chemistry and Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Norskov, Jens

    2011-05-19

    Recent advances in the understanding of reactivity trends for chemistry at transition metal surfaces have enabled in silico design of heterogeneous catalysts in a few cases. Current status of the field is discussed with an emphasis on the role of coupling between theory and experiment and future challenges.

  12. Neutron skin thickness in neutron-rich nuclei: bulk and surface contributions and shell effects

    International Nuclear Information System (INIS)

    Vinas, X.; Centelles, M.; Warda, M.; Roca-Maza, X.

    2012-01-01

    We analyze theoretically the neutron skin thickness in nuclei and its correlation with the symmetry energy by using semiclassical and mean field approaches together with nuclear effective interactions. Semiclassical approaches reveal that the neutron skin thickness in nuclei is formed by a combination of bulk and surface contributions. To investigate the neutron skin thickness predicted by mean field models, we fit the corresponding densities by two-parameter Fermi distributions. Using these parametrized densities, we study the neutron skin thickness as well as its bulk and surface contributions in 208 Pb and in Zr isotopes, where the influence of shell effects along the isotopic chain is discussed. (author)

  13. Smart Surface Chemistries of Conducting Polymers

    DEFF Research Database (Denmark)

    Lind, Johan Ulrik

    In this thesis we investigate post-polymerization covalent modifications of poly(3,4-dioxythiophene (PEDOT)-type conducting polymers. The aim of the modifications is to gain specific control of the interaction between the material and living mammalian cells. The use of “click-chemistry” to modify...... film substrates. Complementing these findings, we introduce a novel technique for fabricating surface chemical gradients on PEDOT-N3 substrates. The technique is based on applying “electro-click chemistry” to locally induce covalent modifications. Further supplementing these results, we develop......-ethylene-glycol-coatings of the conducting polymer substrates. These coatings render the substrates resistant to protein adsorption. Hence, the choice of solvent is found to be a key parameter for achieving functional post-polymerization modifications of PEDOT-N3. The methods developed in this thesis are highly generic, and can therefore...

  14. Heterogeneous catalytic materials solid state chemistry, surface chemistry and catalytic behaviour

    CERN Document Server

    Busca, Guido

    2014-01-01

    Heterogeneous Catalytic Materials discusses experimental methods and the latest developments in three areas of research: heterogeneous catalysis; surface chemistry; and the chemistry of catalysts. Catalytic materials are those solids that allow the chemical reaction to occur efficiently and cost-effectively. This book provides you with all necessary information to synthesize, characterize, and relate the properties of a catalyst to its behavior, enabling you to select the appropriate catalyst for the process and reactor system. Oxides (used both as catalysts and as supports for cata

  15. Microstructure and surface chemistry of amorphous alloys important to their friction and wear behavior

    Science.gov (United States)

    Miyoshi, K.; Buckley, D. H.

    1986-01-01

    An investigation was conducted to examine the microstructure and surface chemistry of amorphous alloys, and their effects on tribological behavior. The results indicate that the surface oxide layers present on amorphous alloys are effective in providing low friction and a protective film against wear in air. Clustering and crystallization in amorphous alloys can be enhanced as a result of plastic flow during the sliding process at a low sliding velocity, at room temperature. Clusters or crystallines with sizes to 150 nm and a diffused honeycomb-shaped structure are produced on sizes to 150 nm and a diffused honeycomb-shaped structure are produced on the wear surface. Temperature effects lead to drastic changes in surface chemistry and friction behavior of the alloys at temperatures to 750 C. Contaminants can come from the bulk of the alloys to the surface upon heating and impart to the surface oxides at 350 C and boron nitride above 500 C. The oxides increase friction while the boron nitride reduces friction drastically in vacuum.

  16. Bulk-Induced 1/f Noise at the Surface of Three-Dimensional Topological Insulators.

    Science.gov (United States)

    Bhattacharyya, Semonti; Banerjee, Mitali; Nhalil, Hariharan; Islam, Saurav; Dasgupta, Chandan; Elizabeth, Suja; Ghosh, Arindam

    2015-12-22

    Slow intrinsic fluctuations of resistance, also known as the flicker noise or 1/f-noise, in the surface transport of strong topological insulators (TIs) is a poorly understood phenomenon. Here, we have systematically explored the 1/f-noise in field-effect transistors (FET) of mechanically exfoliated Bi1.6Sb0.4Te2Se TI films when transport occurs predominantly via the surface states. We find that the slow kinetics of the charge disorder within the bulk of the TI induces mobility fluctuations at the surface, providing a new source of intrinsic 1/f-noise that is unique to bulk TI systems. At small channel thickness, the noise magnitude can be extremely small, corresponding to the phenomenological Hooge parameter γH as low as ≈10(-4), but it increases rapidly when channel thickness exceeds ∼1 μm. From the temperature (T)-dependence of noise, which displayed sharp peaks at characteristic values of T, we identified generation-recombination processes from interband transitions within the TI bulk as the dominant source of the mobility fluctuations in surface transport. Our experiment not only establishes an intrinsic microscopic origin of noise in TI surface channels, but also reveals a unique spectroscopic information on the impurity bands that can be useful in bulk TI systems in general.

  17. Surface-spin magnetism of antiferromagnetic NiO in nanoparticle and bulk morphology

    International Nuclear Information System (INIS)

    Jagodic, M; Jaglicic, Z; Jelen, A; Dolinsek, J; Lee, Jin Bae; Kim, Hae Jin; Kim, Young-Min

    2009-01-01

    The surface-spin magnetism of the antiferromagnetic (AFM) material NiO in nanoparticle and bulk morphology was investigated by magnetic measurements (temperature-dependent zero-field-cooled (zfc) and field-cooled (fc) dc susceptibility, ac susceptibility and zfc and fc hysteresis loops). We addressed the question of whether the multisublattice ordering of the uncompensated surface spins and the exchange bias (EB) effect are only present in the nanoparticles, originating from their high surface-to-volume ratio or if these surface phenomena are generally present in the AFM materials regardless of their bulky or nanoparticle morphology, but the effect is just too small to be detected experimentally in the bulk due to a very small surface magnetization. Performing experiments on the NiO nanoparticles of different sizes and bulk NiO grains, we show that coercivity enhancement and hysteresis loop shift in the fc experiments, considered to be the key experimental manifestations of multisublattice ordering and the EB effect, are true nanoscale phenomena only present in the nanoparticles and absent in the bulk.

  18. Linear magnetoresistance and surface to bulk coupling in topological insulator thin films.

    Science.gov (United States)

    Singh, Sourabh; Gopal, R K; Sarkar, Jit; Pandey, Atul; Patel, Bhavesh G; Mitra, Chiranjib

    2017-12-20

    We explore the temperature dependent magnetoresistance of bulk insulating topological insulator thin films. Thin films of Bi 2 Se 2 Te and BiSbTeSe 1.6 were grown using the pulsed laser deposition technique and subjected to transport measurements. Magnetotransport measurements indicate a non-saturating linear magnetoresistance (LMR) behavior at high magnetic field values. We present a careful analysis to explain the origin of LMR taking into consideration all the existing models of LMR. Here we consider that the bulk insulating states and the metallic surface states constitute two parallel conduction channels. Invoking this, we were able to explain linear magnetoresistance behavior as a competition between these parallel channels. We observe that the cross-over field, where LMR sets in, decreases with increasing temperature. We propose that this cross-over field can be used phenomenologically to estimate the strength of surface to bulk coupling.

  19. Recent advances in study of uranium surface chemistry in China

    International Nuclear Information System (INIS)

    Luo, Lizhu; Lai, Xinchun; Wang, Xiaolin

    2014-01-01

    Uranium is very important in nuclear energy industry; however, uranium and its alloys corrode seriously in various atmospheres because of their chemical reactivities. In China, continuous investigations focused on surface chemistry have been carried out for a thorough understanding of uranium in order to provide technical support for its engineering applications. Oxidation kinetics of uranium and its alloys in oxidizing atmospheres are in good agreement with those in the literature. In addition to the traditional techniques, non-traditional methods have been applied for oxidation kinetics of uranium, and it has been verified that spectroscopic ellipsometry and X-ray diffraction are effective and nondestructive tools for in situ kinetic studies. The inhibition efficiency of oxidizing gas impurities on uranium hydrogenation is found to follow the order CO 2 > CO > O 2 , and the broadening of XPS shoulders with temperature in depth profile of hydrogenated uranium surface is discussed, which is not mentioned in the literature. Significant progress on surface chemistry of alloyed uranium (U-Nb and U-Ti) in hydrogen atmosphere is reported, and it is revealed that the hydrating nucleation and subsequent growth of alloyed uranium are closely connected with the surface states, underlying metal matrix, and it is microstructure-dependent. In this review, the recent advances in uranium surface chemistry in China, published so far mostly in Chinese language, are briefly summarized. Suggestions for further study are made. (orig.)

  20. Decoupling Bulk and Surface Contributions in Water- Splitting Photocatalysts by In Situ Ultrafast Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Appavoo, Kannatassen [Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials; Mingzhao, Liu [Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials; Black, Charles T. [Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials; Sfeir, Matthew Y. [Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials

    2015-05-10

    By performing ultrafast emission spectroscopy in an operating, bias-controlled photoelectrochemical cell, we distinguish between bulk (charge transport) and surface (chemical reaction) recombination processes in a nanostructured photocatalyst and correlate its electronic properties directly with its incident-photon-to-current efficiency.

  1. Surface and bulk-loss reduction research by low-energy hydrogen doping

    Science.gov (United States)

    Fonash, S.

    1985-01-01

    Surface and bulk loss reduction by low energy hydrogen doping of silicon solar cells was examined. Hydrogen ions provided a suppression of space charge recombination currents. Implantation of hydrogen followed by the anneal cycle caused more redistribution of boron than the anneal which could complicate processing. It was demonstrated that passivation leads to space charge current reduction.

  2. Optical find of hypersonic surface acoustic waves in bulk transparent materials

    Science.gov (United States)

    Jiménez Riobóo, Rafael J.; Sánchez-Sánchez, Alberto; Prieto, Carlos

    2016-07-01

    It is shown that direct information from surface acoustic waves (SAWs) of bulk transparent materials can be obtained by using Brillouin light scattering (BLS). The study of surface phonons by means of an optical spectroscopy such as BLS has been historically constrained to nontransparent and highly reflecting bulk and film samples or even to very thin films deposited on reflecting substrates. Probably due to its low signal and to the narrow window in experimental conditions, it was assumed for years that bulk transparent samples were not suited for Brillouin spectroscopy in order to get information on SAWs, negating this optical technique in the search for SAW properties. The reported experiments on transparent glasses and single crystals (cubic MgO and trigonal sapphire) prove that there is no intrinsic physical reason not to collect SAW propagation velocity data from transparent bulk samples and opens a challenge to apply the Brillouin spectroscopy in a wider scenario to obtain direct information, in a nondestructive and contactless way, about SAWs in bulk materials.

  3. Influence of surface structure and chemistry on water droplet splashing.

    Science.gov (United States)

    Koch, Kerstin; Grichnik, Roland

    2016-08-06

    Water droplet splashing and aerosolization play a role in human hygiene and health systems as well as in crop culturing. Prevention or reduction of splashing can prevent transmission of diseases between animals and plants and keep technical systems such as pipe or bottling systems free of contamination. This study demonstrates to what extent the surface chemistry and structures influence the water droplet splashing behaviour. Smooth surfaces and structured replicas of Calathea zebrina (Sims) Lindl. leaves were produced. Modification of their wettability was done by coating with hydrophobizing and hydrophilizing agents. Their wetting was characterized by contact angle measurement and splashing behaviour was observed with a high-speed video camera. Hydrophobic and superhydrophilic surfaces generally showed fewer tendencies to splash than hydrophobic ones. Structuring amplified the underlying behaviour of the surface chemistries, increasing hydrophobic surfaces' tendency to splash and decreasing splash on hydrophilic surfaces by quickly transporting water off the impact point by capillary forces. The non-porous surface structures found in C. zebrina could easily be applied to technical products such as plastic foils or mats and coated with hydrophilizing agents to suppress splash in areas of increased hygiene requirements or wherever pooling of liquids is not desirable.This article is part of the themed issue 'Bioinspired hierarchically structured surfaces for green science'. © 2016 The Author(s).

  4. Bulk measurements of messy chemistries are needed for a theory of the origins of life

    Science.gov (United States)

    Guttenberg, Nicholas; Virgo, Nathaniel; Chandru, Kuhan; Scharf, Caleb; Mamajanov, Irena

    2017-11-01

    A feature of many of the chemical systems plausibly involved in the origins of terrestrial life is that they are complex and messy-producing a wide range of compounds via a wide range of mechanisms. However, the fundamental behaviour of such systems is currently not well understood; we do not have the tools to make statistical predictions about such complex chemical networks. This is, in part, due to a lack of quantitative data from which such a theory could be built; specifically, functional measurements of messy chemical systems. Here, we propose that the pantheon of experimental approaches to the origins of life should be expanded to include the study of `functional measurements'-the direct study of bulk properties of chemical systems and their interactions with other compounds, the formation of structures and other behaviours, even in cases where the precise composition and mechanisms are unknown. This article is part of the themed issue 'Reconceptualizing the origins of life'.

  5. Automated Clean Chemistry for Bulk Analysis of Environmental Swipe Samples - FY17 Year End Report

    Energy Technology Data Exchange (ETDEWEB)

    Ticknor, Brian W. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Metzger, Shalina C. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); McBay, Eddy H. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Hexel, Cole R. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Tevepaugh, Kayron N. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Bostick, Debra A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2017-11-30

    Sample preparation methods for mass spectrometry are being automated using commercial-off-the-shelf (COTS) equipment to shorten lengthy and costly manual chemical purification procedures. This development addresses a serious need in the International Atomic Energy Agency’s Network of Analytical Laboratories (IAEA NWAL) to increase efficiency in the Bulk Analysis of Environmental Samples for Safeguards program with a method that allows unattended, overnight operation. In collaboration with Elemental Scientific Inc., the prepFAST-MC2 was designed based on COTS equipment. It was modified for uranium/plutonium separations using renewable columns packed with Eichrom TEVA and UTEVA resins, with a chemical separation method based on the Oak Ridge National Laboratory (ORNL) NWAL chemical procedure. The newly designed prepFAST-SR has had several upgrades compared with the original prepFAST-MC2. Both systems are currently installed in the Ultra-Trace Forensics Science Center at ORNL.

  6. Surface/state correspondence and bulk local operators in pp-wave holography

    Directory of Open Access Journals (Sweden)

    Nakwoo Kim

    2015-12-01

    Full Text Available We apply the surface/state correspondence proposal of Miyaji et al. to IIB pp-waves and propose that the bulk local operators should be instantonic D-branes. In line with ordinary AdS/CFT correspondence, the bulk local operators in pp-waves also create a hole, or a boundary, in the dual gauge theory as pointed out by H. Verlinde, and by Y. Nakayama and H. Ooguri. We also present simple calculations which illustrate how to extract the spacetime metric of pp-waves from instantonic D-branes in boundary state formalism.

  7. Formation of CaCO3 deposits on hard surfaces--effect of bulk solution conditions and surface properties.

    Science.gov (United States)

    Wang, Hao; Alfredsson, Viveka; Tropsch, Juergen; Ettl, Roland; Nylander, Tommy

    2013-05-22

    We have studied nucleation and crystal growth of calcium carbonate on hard surfaces, i.e. stainless steel and silica, at different temperatures, in relation to the corresponding bulk processes, using scanning electron microscopy (SEM), X-ray diffraction (XRD), and ellipsometry. In the bulk solution, a mixture of all three calcium carbonate crystalline polymorphs, calcite, aragonite, and vaterite, as well as amorphous particles was observed at 25 °C, while at 55 °C aragonite and calcite crystals dominated. On surfaces only calcite crystals were observed at 25 °C, whereas aragonite and calcite crystal adsorbed on the surfaces at 55 °C. Two kinds of nucleation and adsorption mechanism of CaCO3 crystals on hard surfaces were observed, depending on the surface orientation (vertical or horizontal, i.e., subject to sedimentation) in the bulk solution. A model for the relation between interfacial layer structure, the substrate, and the solution crystallization is discussed based on the observed difference in deposition between type of surfaces and surface orientation. In addition, the effect of magnesium ion on the morphology of calcium carbonate crystals is discussed.

  8. Next Steps Forward in Understanding Martian Surface and Subsurface Chemistry

    Science.gov (United States)

    Carrier, Brandi L.

    2017-09-01

    The presence of oxidants such as hydrogen peroxide (H2O2) and perchlorate (ClO4-), which have been detected on Mars, has significant implications for chemistry and astrobiology. These oxidants can increase the reactivity of the Martian soil, accelerate the decomposition of organic molecules, and depress the freezing point of water. The study by Crandall et al. "Can Perchlorates be Transformed to Hydrogen Peroxide Products by Cosmic Rays on the Martian Surface" reveals a new formation mechanism by which hydrogen peroxide and other potential oxidants can be generated via irradiation of perchlorate by cosmic rays. This study represents an important next step in developing a full understanding of Martian surface and subsurface chemistry, particularly with respect to degradation of organic molecules and potential biosignatures.

  9. Surface Chemistry of CWAs for Decon Enabling Sciences

    Science.gov (United States)

    2014-11-04

    Ultraviolet and Visible Photochemistry of Methanol at 3D Mesoporous Networks: TiO, The Journal of Physical Chemistry C, (07 2013): 15035. doi...A for none) Presentations since most recent interim report for this project: " Photochemistry of Methanol at 3-D Networked Aerogels of TiO2 and...evaporation • Studied the uptake, thermal, and photochemistry of agent simulants on TiO2 surfaces • Initiated experiments on the uptake and

  10. Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors

    Directory of Open Access Journals (Sweden)

    Wei Zheng

    2016-03-01

    Full Text Available Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors.

  11. Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors

    Science.gov (United States)

    Zheng, Wei; van den Hurk, Remko; Cao, Yong; Du, Rongbing; Sun, Xuejun; Wang, Yiyu; McDermott, Mark T.; Evoy, Stephane

    2016-01-01

    Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors. PMID:26985910

  12. Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors.

    Science.gov (United States)

    Zheng, Wei; van den Hurk, Remko; Cao, Yong; Du, Rongbing; Sun, Xuejun; Wang, Yiyu; McDermott, Mark T; Evoy, Stephane

    2016-03-14

    Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors.

  13. The effect of bulk/surface defects ratio change on the photocatalysis of TiO{sub 2} nanosheet film

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Fangfang [CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026 (China); Ge, Wenna [State Key Laboratory of Particle Detection and Electronics, University of Science and Technology of China, Hefei 230026 (China); Department of Modern Physics, University of Science and Technology of China, Hefei 230026 (China); Shen, Tong [CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026 (China); Ye, Bangjiao [State Key Laboratory of Particle Detection and Electronics, University of Science and Technology of China, Hefei 230026 (China); Department of Modern Physics, University of Science and Technology of China, Hefei 230026 (China); Fu, Zhengping, E-mail: fuzp@ustc.edu.cn [CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026 (China); Lu, Yalin, E-mail: yllu@ustc.edu.cn [CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026 (China); Synergetic Innovation Center of Quantum Information & Stop Quantum Physics, University of Science and Technology of China, Hefei 230026 (China); National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230026, Anhui (China)

    2017-07-15

    Highlights: • The defect behaviors of TiO{sub 2} nanosheet array films were studied by positron annihilation spectroscopy. • Different bulk/surface defect ratios were realized by annealing at different temperature. • It was concluded that bulk defects are mainly Ti{sup 3+} vacancy defects. • The separation efficiency of photogenerated electrons and holes could be significantly improved by optimizing the bulk/surface defects ratio. - Abstract: The photocatalysis behavior of TiO{sub 2} nanosheet array films was studied, in which the ratio of bulk/surface defects were adjusted by annealing at different temperature. Combining positron annihilation spectroscopy, EPR and XPS, we concluded that the bulk defects belonged to Ti{sup 3+} related vacancy defects. The results show that the separation efficiency of photogenerated electrons and holes could be significantly improved by optimizing the bulk/surface defects ratio of TiO{sub 2} nanosheet films, and in turn enhancing the photocatalysis behaviors.

  14. The effect of bulk/surface defects ratio change on the photocatalysis of TiO2 nanosheet film

    International Nuclear Information System (INIS)

    Wang, Fangfang; Ge, Wenna; Shen, Tong; Ye, Bangjiao; Fu, Zhengping; Lu, Yalin

    2017-01-01

    Highlights: • The defect behaviors of TiO 2 nanosheet array films were studied by positron annihilation spectroscopy. • Different bulk/surface defect ratios were realized by annealing at different temperature. • It was concluded that bulk defects are mainly Ti 3+ vacancy defects. • The separation efficiency of photogenerated electrons and holes could be significantly improved by optimizing the bulk/surface defects ratio. - Abstract: The photocatalysis behavior of TiO 2 nanosheet array films was studied, in which the ratio of bulk/surface defects were adjusted by annealing at different temperature. Combining positron annihilation spectroscopy, EPR and XPS, we concluded that the bulk defects belonged to Ti 3+ related vacancy defects. The results show that the separation efficiency of photogenerated electrons and holes could be significantly improved by optimizing the bulk/surface defects ratio of TiO 2 nanosheet films, and in turn enhancing the photocatalysis behaviors.

  15. Recyclable surfaces for amine conjugation chemistry via redox reaction

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Inseong; Yeo, Woon Seok [Dept. of Bioscience and Biotechnology, Bio/Molecular Informatics Center, Konkuk University, Seoul (Korea, Republic of); Bae, Se Won [Green Materials and Process Group, Research Institute of Sustainable Manufacturing System, Korea Institute of Industrial Technology, Cheonan (Korea, Republic of)

    2017-02-15

    In this study, we extended this strategy to present a switchable surface that allows surface functionalization and removal of functional groups repeatedly. The substrate presenting a benzoquinone acid group is first used to immobilize with an amine-containing (bio)molecule using well-known conjugation chemistry. The benzoquinone group is then converted to the corresponding hydroquinone by treating with a reducing agent. We have described a strategy for the dynamic control of surface properties with recyclability via a simple reduction/ oxidation reaction. A stimuli-responsive quinone derivative was harnessed for the repeated immobilization and release of (bio)molecules, and thus, for the repeated dynamic change of the surface properties according to the characteristics of the immobilized (bio)molecules.

  16. Viscous surface flow induced on Ti-based bulk metallic glass by heavy ion irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Kun [Key Laboratory of Microgravity (National Microgravity Laboratory), Institute of Mechanics, Chinese Academy of Sciences, Beijing 100190 (China); Hu, Zheng [Key Laboratory of Microgravity (National Microgravity Laboratory), Institute of Mechanics, Chinese Academy of Sciences, Beijing 100190 (China); Science and Technology on Vehicle Transmission Laboratory, China North Vehicle Research Institute, Beijing 100072 (China); Li, Fengjiang [Key Laboratory of Microgravity (National Microgravity Laboratory), Institute of Mechanics, Chinese Academy of Sciences, Beijing 100190 (China); Wei, Bingchen, E-mail: weibc@imech.ac.cn [Key Laboratory of Microgravity (National Microgravity Laboratory), Institute of Mechanics, Chinese Academy of Sciences, Beijing 100190 (China)

    2016-12-30

    Highlights: • Obvious smoothing and roughening phases on the Ti-based MG surface resulted, which correspond respectively to the normal and off-normal incidence angles. • Atomic force microscopy confirms two types of periodic ripples distributed evenly over the rough surface. • The irradiation-induced viscosity of MG is about 4×10{sup 12} Pa·s, which accords with the theoretical prediction for metallic glasses close to glass transition temperature. • Surface-confined viscous flow plays a dominant quantitative role, which is due to radiation-induced softening of the low-viscosity surface layer. - Abstract: Ti-based bulk metallic glass was irradiated by a 20 MeV Cl{sup 4+} ion beam under liquid-nitrogen cooling, which produced remarkable surface smoothing and roughening that respectively correspond to normal and off-normal incidence angles of irradiation. Atomic force microscopy confirms two types of periodic ripples distributed evenly over the rough glass surface. In terms of mechanism, irradiation-induced viscosity agrees with the theoretical prediction for metallic glasses near glass transition temperature. Here, a model is introduced, based on relaxation of confined viscous flow with a thin liquid-like layer, that explains both surface smoothing and ripple formation. This study demonstrates that bulk metallic glass has high morphological instability and low viscosity under ion irradiation, which assets can pave new paths for metallic glass applications.

  17. Glass Formation, Chemical Properties and Surface Analysis of Cu-Based Bulk Metallic Glasses

    Directory of Open Access Journals (Sweden)

    Akihisa Inoue

    2011-04-01

    Full Text Available This paper reviews the influence of alloying elements Mo, Nb, Ta and Ni on glass formation and corrosion resistance of Cu-based bulk metallic glasses (BMGs. In order to obtain basic knowledge for application to the industry, corrosion resistance of the Cu–Hf–Ti–(Mo, Nb, Ta, Ni and Cu–Zr–Ag–Al–(Nb bulk glassy alloy systems in various solutions are reported in this work. Moreover, X-ray photoelectron spectroscopy (XPS analysis is performed to clarify the surface-related chemical characteristics of the alloy before and after immersion in the solutions; this has lead to a better understanding of the correlation between the surface composition and the corrosion resistance.

  18. Surface and bulk modified high capacity layered oxide cathodes with low irreversible capacity loss

    Science.gov (United States)

    Manthiram, Arumugam (Inventor); Wu, Yan (Inventor)

    2010-01-01

    The present invention includes compositions, surface and bulk modifications, and methods of making of (1-x)Li[Li.sub.1/3Mn.sub.2/3]O.sub.2.xLi[Mn.sub.0.5-yNi.sub.0.5-yCo.sub.2- y]O.sub.2 cathode materials having an O3 crystal structure with a x value between 0 and 1 and y value between 0 and 0.5, reducing the irreversible capacity loss in the first cycle by surface modification with oxides and bulk modification with cationic and anionic substitutions, and increasing the reversible capacity to close to the theoretical value of insertion/extraction of one lithium per transition metal ion (250-300 mAh/g).

  19. Surface chemistry, microstructure and friction properties of some ferrous-base metallic glasses at temperatures to 750 C

    Science.gov (United States)

    Miyoshi, K.; Buckley, D. H.

    1982-01-01

    X-ray photoelectron spectroscopy analysis, transmission electron microscopy, diffraction studies, and sliding friction experiments were conducted with ferrous-base metallic glasses in sliding contact with aluminum oxide at temperatures from room to 750 C in a vacuum of 30 nPa. The results indicate that there is a significant temperature influence on the friction properties, surface chemistry, and microstructure of metallic glasses. The relative concentrations of the various constituents at the surface of the sputtered specimens were very different from the normal bulk compositions. Contaminants can come from the bulk of the material to the surface upon heating and impart boric oxide and silicon oxide at 350 C and boron nitride above 500 C. The coefficient of friction increased with increasing temperature to 350 C. Above 500 C the coefficient of friction decreased rapidly. The segregation of contaminants may be responsible for the friction behavior.

  20. Surface critical magnetic field Hc3(T) of a bulk superconductor MgB2 ...

    Indian Academy of Sciences (India)

    Abstract. Two-band Ginzburg–Landau (TB G–L) equations for a bulk MgB2 were solved analyti- cally to determine the temperature dependence of surface critical magnetic field Hc3(T). It is shown that Hc3(T) has the same temperature dependence with Hc2(T), similar to the case of a single-band superconductor, Hc3(T) ...

  1. Discerning the Location and Nature of Coke Deposition from Surface to Bulk of Spent Zeolite Catalysts

    OpenAIRE

    Devaraj, Arun; Vijayakumar, Murugesan; Bao, Jie; Guo, Mond F.; Derewinski, Miroslaw A.; Xu, Zhijie; Gray, Michel J.; Prodinger, Sebastian; Ramasamy, Karthikeyan K.

    2016-01-01

    The formation of carbonaceous deposits (coke) in zeolite pores during catalysis leads to temporary deactivation of catalyst, necessitating regeneration steps, affecting throughput, and resulting in partial permanent loss of catalytic efficiency. Yet, even to date, the coke molecule distribution is quite challenging to study with high spatial resolution from surface to bulk of the catalyst particles at a single particle level. To address this challenge we investigated the coke molecules in HZS...

  2. Superconducting topological surface states in the noncentrosymmetric bulk superconductor PbTaSe2.

    Science.gov (United States)

    Guan, Syu-You; Chen, Peng-Jen; Chu, Ming-Wen; Sankar, Raman; Chou, Fangcheng; Jeng, Horng-Tay; Chang, Chia-Seng; Chuang, Tien-Ming

    2016-11-01

    The search for topological superconductors (TSCs) is one of the most urgent contemporary problems in condensed matter systems. TSCs are characterized by a full superconducting gap in the bulk and topologically protected gapless surface (or edge) states. Within each vortex core of TSCs, there exists the zero-energy Majorana bound states, which are predicted to exhibit non-Abelian statistics and to form the basis of the fault-tolerant quantum computation. To date, no stoichiometric bulk material exhibits the required topological surface states (TSSs) at the Fermi level ( E F ) combined with fully gapped bulk superconductivity. We report atomic-scale visualization of the TSSs of the noncentrosymmetric fully gapped superconductor PbTaSe 2 . Using quasi-particle scattering interference imaging, we find two TSSs with a Dirac point at E ≅ 1.0 eV, of which the inner TSS and the partial outer TSS cross E F , on the Pb-terminated surface of this fully gapped superconductor. This discovery reveals PbTaSe 2 as a promising candidate for TSC.

  3. Interplay between surface and bulk states in the Topological Kondo Insulator SmB6

    Science.gov (United States)

    Biswas, Sangram; Hatnean, Monica Ciomaga; Balakrishnan, Geetha; Bid, Aveek

    Kondo insulator SmB6 is predicted to have topologically protected conducting surface states(TSS). We have studied electrical transport through surface states(SS) at ultra-low temperatures in single crystals of SmB6 using local-nonlocal transport scheme and found a large nonlocal signal at temperatures lower than bulk Kondo gap scale. Using resistance fluctuation spectroscopy, we probed the local and nonlocal transport channels and showed that at low temperatures, transport in this system takes place only through SS. The measured noise in this temperature range arises due to Universal Conductance Fluctuations whose statistics was found to be consistent with theoretical predictions for that of 2D systems in the Symplectic symmetry class. We studied the temperature dependence of noise and found that, unlike the topological insulators of the dichalcogenide family, the noise in surface and bulk conduction channels in SmB6 are uncorrelated - at sufficiently low temperatures, the bulk has no discernible contribution to electrical transport in SmB6 making it an ideal platform for probing the physics of TSS. Nanomission, Department of Science & Technology (DST) and Indian Institute of Scienc and EPSRC, UK, Grant EP/L014963/1.

  4. Analysis of bulk and surface contributions in the neutron skin of nuclei

    International Nuclear Information System (INIS)

    Warda, M.; Vinas, X.; Roca-Maza, X.; Centelles, M.

    2010-01-01

    The neutron skin thickness of nuclei is a sensitive probe of the nuclear symmetry energy and has multiple implications for nuclear and astrophysical studies. However, precision measurements of this observable are difficult to obtain. The analysis of the experimental data may imply some assumptions about the bulk or surface nature of the formation of the neutron skin. Here we study the bulk or surface character of neutron skins of nuclei following from calculations with Gogny, Skyrme, and covariant nuclear mean-field interactions. These interactions are successful in describing nuclear charge radii and binding energies but predict different values for neutron skins. We perform the study by fitting two-parameter Fermi distributions to the calculated self-consistent neutron and proton densities. We note that the equivalent sharp radius is a more suitable reference quantity than the half-density radius parameter of the Fermi distributions to discern between the bulk and surface contributions in neutron skins. We present calculations for nuclei in the stability valley and for the isotopic chains of Sn and Pb.

  5. The physics of water droplets on surfaces: exploring the effects of roughness and surface chemistry

    Science.gov (United States)

    Eid, K. F.; Panth, M.; Sommers, A. D.

    2018-03-01

    This paper explores the fluid property commonly called surface tension, its effect on droplet shape and contact angle, and the major influences of contact angle behaviour (i.e. surface roughness and surface chemistry). Images of water droplets placed on treated copper surfaces are used to measure the contact angles between the droplets and the surface. The surface wettability is manipulated either by growing a self-assembled monolayer on the surface to make it hydrophobic or by changing the surface roughness. The main activities in this experiment, then, are (1) preparing and studying surfaces with different surface wettability and roughness; (2) determining the shape and contact angles of water droplets on these surfaces; and (3) demonstrating the spontaneous motion of water droplets using surface tension gradients.

  6. Near-surface bulk densities of asteroids derived from dual-polarization radar observations

    Science.gov (United States)

    Virkki, A.; Taylor, P. A.; Zambrano-Marin, L. F.; Howell, E. S.; Nolan, M. C.; Lejoly, C.; Rivera-Valentin, E. G.; Aponte, B. A.

    2017-09-01

    We present a new method to constrain the near-surface bulk density and surface roughness of regolith on asteroid surfaces using planetary radar measurements. The number of radar observations has increased rapidly during the last five years, allowing us to compare and contrast the radar scattering properties of different small-body populations and compositional types. This provides us with new opportunities to investigate their near-surface physical properties such as the chemical composition, bulk density, porosity, or the structural roughness in the scale of centimeters to meters. Because the radar signal can penetrate into a planetary surface up to a few decimeters, radar can reveal information that is hidden from other ground-based methods, such as optical and infrared measurements. The near-surface structure of asteroids and comets in centimeter-to-meter scale is essential information for robotic and human space missions, impact threat mitigation, and understanding the history of these bodies as well as the formation of the whole Solar System.

  7. Surface and bulk behaviour of some (n-hexane + chloroalkane) mixtures

    International Nuclear Information System (INIS)

    Perez-Gregorio, V.; Montano, D.; Giner, B.; Lafuente, C.; Royo, F.M.

    2009-01-01

    Surface tensions at the temperatures of (283.15, 288.15, 293.15, 298.15, 303.15, 308.15, and 313.15) K and isothermal (vapour + liquid) equilibrium at the temperatures of (288.15, 298.15, and 308.15) K of n-hexane with 1-chlorobutane or 1-chloropentane mixtures have been measured. Surface tension measurements were carried out with a drop volume tensiometer while the (vapour + liquid) equilibrium was obtained using an all-glass dynamic recirculating type still. Several bulk thermodynamic properties of the studied mixtures have been used together with the experimental measurements to analyse the results. Furthermore, a thermodynamic study of surface formation, including interesting properties such as excess surface compositions and excess properties of surface formation, is also presented

  8. Surface and bulk behaviour of some (n-hexane + chloroalkane) mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Perez-Gregorio, V.; Montano, D.; Giner, B.; Lafuente, C. [Departamento de Quimica Organica-Quimica Fisica, Facultad de Ciencias, Universidad de Zaragoza, 50009 Zaragoza (Spain); Royo, F.M. [Departamento de Quimica Organica-Quimica Fisica, Facultad de Ciencias, Universidad de Zaragoza, 50009 Zaragoza (Spain)], E-mail: femer@unizar.es

    2009-04-15

    Surface tensions at the temperatures of (283.15, 288.15, 293.15, 298.15, 303.15, 308.15, and 313.15) K and isothermal (vapour + liquid) equilibrium at the temperatures of (288.15, 298.15, and 308.15) K of n-hexane with 1-chlorobutane or 1-chloropentane mixtures have been measured. Surface tension measurements were carried out with a drop volume tensiometer while the (vapour + liquid) equilibrium was obtained using an all-glass dynamic recirculating type still. Several bulk thermodynamic properties of the studied mixtures have been used together with the experimental measurements to analyse the results. Furthermore, a thermodynamic study of surface formation, including interesting properties such as excess surface compositions and excess properties of surface formation, is also presented.

  9. Photocatalysis with chromium-doped TiO2: Bulk and surface doping

    KAUST Repository

    Ould-Chikh, Samy

    2014-04-15

    The photocatalytic properties of TiO2 modified by chromium are usually found to depend strongly on the preparation method. To clarify this problem, two series of chromium-doped titania with a chromium content of up to 1.56 wt % have been prepared under hydrothermal conditions: the first series (Cr:TiO2) is intended to dope the bulk of TiO2, whereas the second series (Cr/TiO2) is intended to load the surface of TiO2 with Cr. The catalytic properties have been compared in the photocatalytic oxidation of formic acid. Characterization data provides evidence that in the Cr/TiO2 catalysts chromium is located on the surface of TiO2 as amorphous CrOOH clusters. In contrast, in the Cr:TiO 2 series, chromium is mostly dissolved in the titania lattice, although a minor part is still present on the surface. Photocatalytic tests show that both series of chromium-doped titania demonstrate visible-light-driven photo-oxidation activity. Surface-doped Cr/TiO2 solids appear to be more efficient photocatalysts than the bulk-doped Cr:TiO2 counterparts. It\\'s classified! The photocatalytic properties of TiO2 modified by chromium depend strongly on the preparation method. To clarify this problem, two types of modified titania are discussed: one with CrIII doped in the bulk and one with CrOOH clusters on the TiO2 surface (see picture). Both series show visible-light-driven photo-oxidation activity. However, surface modification appears to be a more efficient strategy. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Bulk and surface event identification in p-type germanium detectors

    Science.gov (United States)

    Yang, L. T.; Li, H. B.; Wong, H. T.; Agartioglu, M.; Chen, J. H.; Jia, L. P.; Jiang, H.; Li, J.; Lin, F. K.; Lin, S. T.; Liu, S. K.; Ma, J. L.; Sevda, B.; Sharma, V.; Singh, L.; Singh, M. K.; Singh, M. K.; Soma, A. K.; Sonay, A.; Yang, S. W.; Wang, L.; Wang, Q.; Yue, Q.; Zhao, W.

    2018-04-01

    The p-type point-contact germanium detectors have been adopted for light dark matter WIMP searches and the studies of low energy neutrino physics. These detectors exhibit anomalous behavior to events located at the surface layer. The previous spectral shape method to identify these surface events from the bulk signals relies on spectral shape assumptions and the use of external calibration sources. We report an improved method in separating them by taking the ratios among different categories of in situ event samples as calibration sources. Data from CDEX-1 and TEXONO experiments are re-examined using the ratio method. Results are shown to be consistent with the spectral shape method.

  11. Bulk and surface properties of magnesium peroxide MgO2

    Science.gov (United States)

    Esch, Tobit R.; Bredow, Thomas

    2016-12-01

    Magnesium peroxide has been identified in Mg/air batteries as an intermediate in the oxygen reduction reaction (ORR) [1]. It is assumed that MgO2 is involved in the solid-electrolyte interphase on the cathode surface. Therefore its structure and stability play a crucial role in the performance of Mg/air batteries. In this work we present a theoretical study of the bulk and low-index surface properties of MgO2. All methods give a good account of the experimental lattice parameters for MgO2 and MgO bulk. The reaction energies, enthalpies and free energies for MgO2 formation from MgO are compared among the different DFT methods and with the local MP2 method. A pronounced dependence from the applied functional is found. At variance with a previous theoretical study but in agreement with recent experiments we find that the MgO2 formation reaction is endothermic (HSE06-D3BJ: ΔH = 51.9 kJ/mol). The stability of low-index surfaces MgO2 (001) (Es = 0.96 J/m2) and (011) (Es = 1.98 J/m2) is calculated and compared to the surface energy of MgO (001). The formation energy of neutral oxygen vacancies in the topmost layer of the MgO2 (001) surface is calculated and compared with defect formation energies for MgO (001).

  12. Roles of surface chemistry on safety and electrochemistry in lithium ion batteries.

    Science.gov (United States)

    Lee, Kyu Tae; Jeong, Sookyung; Cho, Jaephil

    2013-05-21

    Motivated by new applications including electric vehicles and the smart grid, interest in advanced lithium ion batteries has increased significantly over the past decade. Therefore, research in this field has intensified to produce safer devices with better electrochemical performance. Most research has focused on the development of new electrode materials through the optimization of bulk properties such as crystal structure, ionic diffusivity, and electric conductivity. More recently, researchers have also considered the surface properties of electrodes as critical factors for optimizing performance. In particular, the electrolyte decomposition at the electrode surface relates to both a lithium ion battery's electrochemical performance and safety. In this Account, we give an overview of the major developments in the area of surface chemistry for lithium ion batteries. These ideas will provide the basis for the design of advanced electrode materials. Initially, we present a brief background to lithium ion batteries such as major chemical components and reactions that occur in lithium ion batteries. Then, we highlight the role of surface chemistry in the safety of lithium ion batteries. We examine the thermal stability of cathode materials: For example, we discuss the oxygen generation from cathode materials and describe how cells can swell and heat up in response to specific conditions. We also demonstrate how coating the surfaces of electrodes can improve safety. The surface chemistry can also affect the electrochemistry of lithium ion batteries. The surface coating strategy improved the energy density and cycle performance for layered LiCoO2, xLi2MnO3·(1 - x)LiMO2 (M = Mn, Ni, Co, and their combinations), and LiMn2O4 spinel materials, and we describe a working mechanism for these enhancements. Although coating the surfaces of cathodes with inorganic materials such as metal oxides and phosphates improves the electrochemical performance and safety properties of

  13. Degradation Potential of Bulk Versus Incrementally Applied and Indirect Composites: Color, Microhardness, and Surface Deterioration.

    Science.gov (United States)

    El Gezawi, M; Kaisarly, D; Al-Saleh, H; ArRejaie, A; Al-Harbi, F; Kunzelmann, K H

    This study investigated the color stability and microhardness of five composites exposed to four beverages with different pH values. Composite discs were produced (n=10); Filtek Z250 (3M ESPE) and Filtek P90 (3M ESPE) were applied in two layers (2 mm, 20 seconds), and Tetric N-Ceram Bulk Fill (TetricBF, Ivoclar Vivadent) and SonicFill (Kerr) were applied in bulk (4 mm) and then light cured (40 seconds, Ortholux-LED, 1600 mW/cm 2 ). Indirect composite Sinfony (3M ESPE) was applied in two layers (2 mm) and cured (Visio system, 3M ESPE). The specimens were polished and tested for color stability; ΔE was calculated using spectrophotometer readings. Vickers microhardness (50 g, dwell time=45 seconds) was assessed on the top and bottom surfaces at baseline, 40 days of storage, subsequent repolishing, and 60 days of immersion in distilled water (pH=7.0), Coca-Cola (pH=2.3), orange juice (pH=3.75), or anise (pH=8.5) using scanning electron microscopy (SEM). The materials had similar ΔE values (40 days, p>0.05), but TetricBF had a significantly greater ΔE than P90 or SF (40 days). The ΔE was less for P90 and TetricBF than for Z250, SonicFill, and Sinfony (60 days). Repolishing and further immersion significantly affected the ΔE (pBulk-fill composites differ regarding color-stability and top-to-bottom microhardness changes compared with those of other composites. P90 showed better surface degradation resistance. In conclusion, bulk-fill composites are not promising alternatives to incremental and indirect composites regarding biodegradation.

  14. Evidence of a Transition Layer between the Free Surface and the Bulk

    KAUST Repository

    Ogieglo, Wojciech

    2018-02-21

    The free surface, a very thin layer at the interface between polymer and air, is considered the main source of the perturbations in the properties of ultrathin polymer films, i.e., nanoconfinement effects. The structural relaxation of such a layer is decoupled from the molecular dynamics of the bulk. The free surface is, in fact, able to stay liquid even below the temperature where the polymer resides in the glassy state. Importantly, this surface layer is expected to have a very sharp interface with the underlying bulk. Here, by analyzing the penetration of n-hexane into polystyrene films, we report on the existence of a transition region, not observed by previous investigations, extending for 12 nm below the free surface. The presence of such a layer permits reconciling the behavior of interfacial layers with current models and has profound implications on the performance of ultrathin membranes. We show that the expected increase in the flux of the permeating species is actually overruled by nanoconfinement.

  15. Electronic and structural properties of TiB2: Bulk, surface, and nanoscale effects

    International Nuclear Information System (INIS)

    Volonakis, George; Tsetseris, Leonidas; Logothetidis, Stergios

    2011-01-01

    Titanium diboride (TiB 2 ), is a widely used hard material that comprises graphene-like layers of B and intercalated Ti atoms. Here we report the results of extensive first-principles calculations on key properties of bulk TiB 2 , TiB 2 surfaces, and TiB 2 nanocrystals (NCs). The computational approach is first validated based on the agreement between calculated structural and electronic properties of bulk TiB 2 and available experimental and theoretical data. We then obtain the formation energies for several surface cuts and use these values to construct TiB 2 NCs based on the Wulff theorem. Finally, we demonstrate by studying the adsorption of small molecules that hydrogen and oxygen adatoms can be attached through strongly exothermic chemisorption reactions on TiB 2 surfaces. Likewise, water molecules bind on various TiB 2 surfaces and NC facets, with an energetic preference for the latter. The results are relevant to applications that depend on reactivity-related TiB 2 properties, for example resistance to corrosion and interactions with water-based solutions.

  16. Modifying Thermal Transport in Colloidal Nanocrystal Solids with Surface Chemistry.

    Science.gov (United States)

    Liu, Minglu; Ma, Yuanyu; Wang, Robert Y

    2015-12-22

    We present a systematic study on the effect of surface chemistry on thermal transport in colloidal nanocrystal (NC) solids. Using PbS NCs as a model system, we vary ligand binding group (thiol, amine, and atomic halides), ligand length (ethanedithiol, butanedithiol, hexanedithiol, and octanedithiol), and NC diameter (3.3-8.2 nm). Our experiments reveal several findings: (i) The ligand choice can vary the NC solid thermal conductivity by up to a factor of 2.5. (ii) The ligand binding strength to the NC core does not significantly impact thermal conductivity. (iii) Reducing the ligand length can decrease the interparticle distance, which increases thermal conductivity. (iv) Increasing the NC diameter increases thermal conductivity. (v) The effect of surface chemistry can exceed the effect of NC diameter and becomes more pronounced as NC diameter decreases. By combining these trends, we demonstrate that the thermal conductivity of NC solids can be varied by an overall factor of 4, from ∼0.1-0.4 W/m-K. We complement these findings with effective medium approximation modeling and identify thermal transport in the ligand matrix as the rate-limiter for thermal transport. By combining these modeling results with our experimental observations, we conclude that future efforts to increase thermal conductivity in NC solids should focus on the ligand-ligand interface between neighboring NCs.

  17. Surface Crystallization in Mg-Based Bulk Metallic Glass during Copper Mold Casting

    Directory of Open Access Journals (Sweden)

    Xin Wang

    2014-01-01

    Full Text Available The localized crystallization of Mg54Cu28Ag7Y11 bulk metallic glass (BMG in the injection casting process using a copper mold was investigated. It has been found that several crystalline phases were formed close to the as-cast surface but did not exist in the internal part of the BMG plate. It is abnormal that the as-cast surface is partially crystallized with higher cooling rate than that of inside. Overheating of the melt and nucleation induced by the surface of copper mold play key roles in the abnormal crystallization. It is suggested that the function of copper mold to trigger heterogeneous nucleation cannot be totally ignored, although it provides the high cooling rate for the glass formation during casting.

  18. Surface and bulk composition of YBa 2Cu 3O 6+x compounds studied by XPS

    Science.gov (United States)

    Andersson, S. Lars T.; Otamiri, Jonathan C.

    1990-08-01

    YBa 2Cu 3O 6+ x compounds prepared by a formic acid route where characterized by XPS. The samples were investigated both after scraping in air and in vacuum to reveal the surface composition after partial degradation during short time air exposure and to gather data on the pure bulk state. The surface layer is characterized by the XPS data of O 1s = 530.8-531.5 eV, Y3d 5/2 = 157.5 eV, Ba3d 5/2 = 779.9 eV , Ba4d 5/2 = 89.4 eV and Cu2p 3/2 = 934.4 eV with a strong satellite structure at 942.5 eV. The data indicate the presence of barium hydroxide and carbonate, copper(II) oxide, the green phase and some yttrium compound. The bulk state is characterized by XPS data of O 1 s = 528.8 eV, Y3d 5/2 = 156.2 eV , Ba3d 5/2 = 778.6 eV , Ba4d 5/2 = 88.3 eV and Cu2p 3/2 = 932.6 eV without a satellite and a similar copper state as for the surface layer. There exist single states of yttrium and barium in the bulk, both copper(I) and copper(II) valence states and for oxygen possibly several components closely spaced accounting for the structurally different oxide ions.

  19. Experimental study on the surface characteristics of Pd-based bulk metallic glass

    International Nuclear Information System (INIS)

    Zhang, Xiang; Sun, Bingli; Zhao, Na; Li, Qian; Hou, Jianhua; Feng, Weina

    2014-01-01

    Highlights: • Wetting behavior of four polymer melts on Pd-based bulk metallic glass was investigated. • From results, in general, the contact angle of polymer on Pd-based BMG decreases with temperature increasing. • We find a critical temperature for each polymer, above this temperature, contact angle on Pd-based BMG does not decrease with temperature increasing. • Surface free energy of Pd-based BMG was estimated by Owens–Wendt method. - Abstract: The metallic glass has many unique and desirable physical and chemical characteristics for their long-range disordered atomic structure, among them the interfacial properties of the metallic glasses are crucial for their applications and manufacturing. In this work, the contact wetting angles between the polymer melts and Pd 40 Cu 30 Ni 10 P 20 bulk metallic glass (Pd-BMG) with four kinds of roughness were analyzed. Experiments show the order of four polymers wettability on Pd-BMG was PP > HDPE > COC > PC. The surface free energy of Pd-BMG was estimated by Owens–Wendt method using the contact angles of three testing liquids. Neumann method was also used to further evidence the surface free energy of Pd-BMG comparing with PTFE, mold steels NAK80 and LKM2343ESR. The results provide theoretical and technical supports for the fabrication of metallic glass micro mold and the parameter optimization of polymer micro injection molding

  20. Temperature-dependent electronic decay profiles in CZT: probe of bulk and surface properties

    Science.gov (United States)

    Kessick, Royal; Maupin, Hugh; Tepper, Gary C.; Szeles, Csaba

    2003-01-01

    The electronic performance of CZT-based gamma radiation spectrometers is governed by a synergism of bulk and surface properties. Compensation is used to increase the bulk resistivity of Cd1-xZnxTe (x~0.1), but the same electronic states that are introduced to increase the material resistivity can also trap charge and reduce the carrier lifetime. Electrical and mechanical surface defects introduced during or subsequent to crystal harvesting are also known to interfere with device performance. Using a contactless, pulsed laser microwave cavity perturbation technique, electronic decay profiles were studied in high pressure Bridgman CZT as a function of temperature. The electronic decay profile was found to depend very strongly on temperature and was modeled using a function consisting of two exponential terms with temperature-dependent amplitudes and time constants. The model was used to relate the observed temperature dependent decay kinetics in CZT to specific trap energies. It was found that, at low temperatures, the electronic decay process is dominated by a deep trap with an energy of approximately 0.69 +/- 0.1 eV from the band edge. As the temperature is increased, the charge trapping becomes dominated by a second trap with an energy of approximately 0.60 +/- 0.1 eV from the band edge. Surface damage introduces additional charge traps that significantly alter the decay kinetics particularly at low temperatures.

  1. Improvement of flow and bulk density of pharmaceutical powders using surface modification.

    Science.gov (United States)

    Jallo, Laila J; Ghoroi, Chinmay; Gurumurthy, Lakxmi; Patel, Utsav; Davé, Rajesh N

    2012-02-28

    Improvement in flow and bulk density, the two most important properties that determine the ease with which pharmaceutical powders can be handled, stored and processed, is done through surface modification. A limited design of experiment was conducted to establish a standardized dry coating procedure that limits the extent of powder attrition, while providing the most consistent improvement in angle of repose (AOR). The magnetically assisted impaction coating (MAIC) was considered as a model dry-coater for pharmaceutical powders; ibuprofen, acetaminophen, and ascorbic acid. Dry coated drug powders were characterized by AOR, particle size as a function of dispersion pressure, particle size distribution, conditioned bulk density (CBD), Carr index (CI), flow function coefficient (FFC), cohesion coefficient using different instruments, including a shear cell in the Freeman FT4 powder rheometer, and Hansen flowability index. Substantial improvement was observed in all the measured properties after dry coating relative to the uncoated powders, such that each powder moved from a poorer to a better flow classification and showed improved dispersion. The material intrinsic property such as cohesion, plotted as a function of particle size, gave a trend similar to those of bulk flow properties, AOR and CI. Property improvement is also illustrated in a phase map of inverse cohesion (or FFC) as a function of bulk density, which also indicated a significant positive shift due to dry coating. It is hoped that such phase maps are useful in manufacturing decisions regarding the need for dry coating, which will allow moving from wet granulation to roller compaction or to direct compression based formulations. Copyright © 2011 Elsevier B.V. All rights reserved.

  2. Mechanically durable underwater superoleophobic surfaces based on hydrophilic bulk metals for oil/water separation

    Science.gov (United States)

    Yu, Huadong; Lian, Zhongxu; Xu, Jinkai; Wan, Yanling; Wang, Zuobin; Li, Yiquan; Yu, Zhanjiang; Weng, Zhankun

    2018-04-01

    Despite the success of previous methods for fabricating underwater superoleophobic surfaces, most of the surfaces based on soft materials are prone to collapse and deformation due to their mechanically fragile nature, and they fail to perform their designed functions after the surface materials are damaged in water. In this work, the nanosecond laser-induced oxide coatings on hydrophilic bulk metals are reported which overcomes the limitation and shows the robust underwater superoleophobicity to a mechanical challenge encountered by surfaces deployed in water environment. The results show that the surface materials have the advantage that the underwater superoleophobicity is still preserved after the surfaces are scratched by knife or sandpaper and even completely destroyed because of the hydrophilic property of damaged materials in water. It is important that the results provide a guide for the design of durable underwater superoleophobic surfaces, and the development of superoleophobic materials in many potential applications such as the oil-repellent and the oil/water separation. Additionally, the nanosecond laser technology is simple, cost-effective and suitable for the large-area and mass fabrication of mechanically durable underwater superoleophobic metal materials.

  3. On-surface covalent linking of organic building blocks on a bulk insulator.

    Science.gov (United States)

    Kittelmann, Markus; Rahe, Philipp; Nimmrich, Markus; Hauke, Christopher M; Gourdon, André; Kühnle, Angelika

    2011-10-25

    On-surface synthesis in ultrahigh vacuum provides a promising strategy for creating thermally and chemically stable molecular structures at surfaces. The two-dimensional confinement of the educts, the possibility of working at higher (or lower) temperatures in the absence of solvent, and the templating effect of the surface bear the potential of preparing compounds that cannot be obtained in solution. Moreover, covalently linked conjugated molecules allow for efficient electron transport and are, thus, particularly interesting for future molecular electronics applications. When having these applications in mind, electrically insulating substrates are mandatory to provide sufficient decoupling of the molecular structure from the substrate surface. So far, however, on-surface synthesis has been achieved only on metallic substrates. Here we demonstrate the covalent linking of organic molecules on a bulk insulator, namely, calcite. We deliberately employ the strong electrostatic interaction between the carboxylate groups of halide-substituted benzoic acids and the surface calcium cations to prevent molecular desorption and to reach homolytic cleavage temperatures. This allows for the formation of aryl radicals and intermolecular coupling. By varying the number and position of the halide substitution, we rationally design the resulting structures, revealing straight lines, zigzag structures, and dimers, thus providing clear evidence for the covalent linking. Our results constitute an important step toward exploiting on-surface synthesis for molecular electronics and optics applications, which require electrically insulating rather than metallic supporting substrates.

  4. The surface chemistry of 3-mercaptopropyltrimethoxysilane films deposited on magnesium alloy AZ91

    International Nuclear Information System (INIS)

    Scott, A.; Gray-Munro, J.E.

    2009-01-01

    Magnesium and its alloys have desirable physical and mechanical properties for a number of applications. Unfortunately, these materials are highly susceptible to corrosion, particularly in the presence of aqueous solutions. The purpose of this study is to develop a uniform, non-toxic surface treatment to enhance the corrosion resistance of magnesium alloys. This paper reports the influence of the coating bath parameters and alloy microstructure on the deposition of 3-mercaptopropyltrimethoxysilane (MPTS) coatings on magnesium alloy AZ91. The surface chemistry at the magnesium/MPTS interface has also been explored. The results indicate that the deposition of MPTS onto AZ91 was influenced by both the pH and MPTS concentration in the coating bath. Furthermore, scanning electron microscopy results showed that the MPTS film deposited uniformly on all phases of the magnesium alloy surface. X-ray photoelectron spectroscopy studies revealed that at the magnesium/MPTS interface, the molecules bond to the surface through the thiol group in an acid-base interaction with the Mg(OH) 2 layer, whereas in the bulk of the film, the molecules are randomly oriented.

  5. The surface chemistry of 3-mercaptopropyltrimethoxysilane films deposited on magnesium alloy AZ91

    Energy Technology Data Exchange (ETDEWEB)

    Scott, A. [Dept. of Chemistry and Biochemistry, Laurentian University, Sudbury, Ontario, P3E 2C6 (Canada); Gray-Munro, J.E., E-mail: jgray@laurentian.c [Dept. of Chemistry and Biochemistry, Laurentian University, Sudbury, Ontario, P3E 2C6 (Canada)

    2009-10-30

    Magnesium and its alloys have desirable physical and mechanical properties for a number of applications. Unfortunately, these materials are highly susceptible to corrosion, particularly in the presence of aqueous solutions. The purpose of this study is to develop a uniform, non-toxic surface treatment to enhance the corrosion resistance of magnesium alloys. This paper reports the influence of the coating bath parameters and alloy microstructure on the deposition of 3-mercaptopropyltrimethoxysilane (MPTS) coatings on magnesium alloy AZ91. The surface chemistry at the magnesium/MPTS interface has also been explored. The results indicate that the deposition of MPTS onto AZ91 was influenced by both the pH and MPTS concentration in the coating bath. Furthermore, scanning electron microscopy results showed that the MPTS film deposited uniformly on all phases of the magnesium alloy surface. X-ray photoelectron spectroscopy studies revealed that at the magnesium/MPTS interface, the molecules bond to the surface through the thiol group in an acid-base interaction with the Mg(OH){sub 2} layer, whereas in the bulk of the film, the molecules are randomly oriented.

  6. X-Ray photoelectron spectroscopy and diffractometry of MnOx catalysts: surface to bulk composition relationships

    International Nuclear Information System (INIS)

    Zaki, M.I.; Kappenstein, C.

    1992-01-01

    Surface and bulk analyses of variously-composed, synthetic MnO x catalysts were carried out by means of X-ray photoelectron spectroscopy (XPS) and diffractometry (XRD), respectively. The data obtained were processed for a comprehensive assessment of bulk and surface compositions, surface oxidation state, and crystalline size. The XPS data processing revealed that a credible assessment of the surface composition (MnO x (OH) y (OH 2 ) z necessitates: (i) the implementation of experimental sensitivity factors determined on a local reference surface maintaining a close chemical similarity to the test materials, and (ii) the fine evaluation of contributions of various oxygen-containing surface species to the O 1s electron emission. The most prominent result of the present investigation is that the exposure of the bulk composition at the surface is quite proportioned. Such a surface to bulk intimacy is thought to enable genesizing the surface composition appropriate for certain catalytic and selectivity, via a possible control over the bulk formation events. (orig.)

  7. Effect of non-equilibrium flow chemistry and surface catalysis on surface heating to AFE

    Science.gov (United States)

    Stewart, David A.; Henline, William D.; Chen, Yih-Kanq

    1991-01-01

    The effect of nonequilibrium flow chemistry on the surface temperature distribution over the forebody heat shield on the Aeroassisted Flight Experiment (AFE) vehicle was investigated using a reacting boundary-layer code. Computations were performed by using boundary-layer-edge properties determined from global iterations between the boundary-layer code and flow field solutions from a viscous shock layer (VSL) and a full Navier-Stokes solution. Surface temperature distribution over the AFE heat shield was calculated for two flight conditions during a nominal AFE trajectory. This study indicates that the surface temperature distribution is sensitive to the nonequilibrium chemistry in the shock layer. Heating distributions over the AFE forebody calculated using nonequilibrium edge properties were similar to values calculated using the VSL program.

  8. Surface chemistry governs cellular tropism of nanoparticles in the brain

    Science.gov (United States)

    Song, Eric; Gaudin, Alice; King, Amanda R.; Seo, Young-Eun; Suh, Hee-Won; Deng, Yang; Cui, Jiajia; Tietjen, Gregory T.; Huttner, Anita; Saltzman, W. Mark

    2017-05-01

    Nanoparticles are of long-standing interest for the treatment of neurological diseases such as glioblastoma. Most past work focused on methods to introduce nanoparticles into the brain, suggesting that reaching the brain interstitium will be sufficient to ensure therapeutic efficacy. However, optimized nanoparticle design for drug delivery to the central nervous system is limited by our understanding of their cellular deposition in the brain. Here, we investigated the cellular fate of poly(lactic acid) nanoparticles presenting different surface chemistries, after administration by convection-enhanced delivery. We demonstrate that nanoparticles with `stealth' properties mostly avoid internalization by all cell types, but internalization can be enhanced by functionalization with bio-adhesive end-groups. We also show that association rates measured in cultured cells predict the extent of internalization of nanoparticles in cell populations. Finally, evaluating therapeutic efficacy in an orthotopic model of glioblastoma highlights the need to balance significant uptake without inducing adverse toxicity.

  9. Discerning the Location and Nature of Coke Deposition from Surface to Bulk of Spent Zeolite Catalysts

    Science.gov (United States)

    Devaraj, Arun; Vijayakumar, Murugesan; Bao, Jie; Guo, Mond F.; Derewinski, Miroslaw A.; Xu, Zhijie; Gray, Michel J.; Prodinger, Sebastian; Ramasamy, Karthikeyan K.

    2016-11-01

    The formation of carbonaceous deposits (coke) in zeolite pores during catalysis leads to temporary deactivation of catalyst, necessitating regeneration steps, affecting throughput, and resulting in partial permanent loss of catalytic efficiency. Yet, even to date, the coke molecule distribution is quite challenging to study with high spatial resolution from surface to bulk of the catalyst particles at a single particle level. To address this challenge we investigated the coke molecules in HZSM-5 catalyst after ethanol conversion treatment by a combination of C K-edge X-ray absorption spectroscopy (XAS), 13C Cross polarization-magic angle spinning nuclear magnetic resonance (CP-MAS NMR) spectroscopy, and atom probe tomography (APT). XAS and NMR highlighted the aromatic character of coke molecules. APT permitted the imaging of the spatial distribution of hydrocarbon molecules located within the pores of spent HZSM-5 catalyst from surface to bulk at a single particle level. 27Al NMR results and APT results indicated association of coke molecules with Al enriched regions within the spent HZSM-5 catalyst particles. The experimental results were additionally validated by a level-set-based APT field evaporation model. These results provide a new approach to investigate catalytic deactivation due to hydrocarbon coking or poisoning of zeolites at an unprecedented spatial resolution.

  10. Electronic transport through Si nanowires: Role of bulk and surface disorder

    DEFF Research Database (Denmark)

    Markussen, Troels; Rurali, R.; Brandbyge, Mads

    2006-01-01

    on the situation a preferable method can be identified. Several numerical results are presented to illustrate the relative merits of the two methods. Our calculations of relaxed atomic structures and their conductance properties are based on density functional theory without introducing adjustable parameters. Two...... specific models of disorder are considered: Unpassivated, surface reconstructed SiNW's are perturbed by random on-site (Anderson) disorder whereas defects in hydrogen passivated wires are introduced by randomly removed H atoms. The unpassivated wires are very sensitive to disorder in the surface whereas...... bulk disorder has almost no influence. For the passivated wires, the scattering by the hydrogen vacancies is strongly energy dependent and for relatively long SiNW's (L > 200 nm) the resistance changes from the Ohmic to the localization regime within a 0.1-eV shift of the Fermi energy. This high...

  11. Effect of bulk chemistry in the spectral variability of igneous rocks in VIS-NIR region: Implications to remote compositional mapping

    Science.gov (United States)

    Nair, Archana M.; Mathew, George

    2014-08-01

    In the present study, a range of igneous rocks with weight percentage of silica ranging from 45% to 70% were used to generate reflectance spectra in the VIS-NIR region. The laboratory generated reflectance spectra of these rocks were used to study the effect of chemical composition and mineralogy on the spectral properties. The characteristic spectral features were evaluated based on the mineralogical and chemical characteristics of the rocks. The main spectral features in the VIS-NIR region are the 0.7 μm absorption band due to the inter valance charge transfer between Fe2+ and Fe3+ termed as Band F, the 1 μm broad absorption band from Fe2+ at the octahedral sites in pyroxene termed as Band I, the 1.9 μm and 2.3 μm narrow absorption bands due to H2O or OH functional group in hydrated minerals. The 2 μm absorption feature (Band II; Cloutis and Gaffey, 1991) is observed as a weak feature in all the mafic rocks. The analysis of Band I with the bulk chemistry and mineralogy, we observed a positive correlation to the bulk Ca abundance. Rocks with high bulk calcic content exemplify Band I as a prominent spectral feature towards longer wavelength. Consequently, basalt, gabbro and anorthositic rocks show Band I as a strong feature. However, rocks with low bulk Calcic content show Band I as weak absorption feature observed towards shorter wavelength. Thus, igneous rocks of alkaline affinity have subdued Band I feature that appears towards shorter wavelength. The analysis of Band F with the bulk chemistry and mineralogy showed a positive correlation to the bulk Fe abundance. The results of the present study have implications towards remote compositional mapping and lithological discrimination for Planetary Studies.

  12. Theoretical investigation of bulk ordering and surface segregation in Ag-Pd and other isoelectornic alloys

    Science.gov (United States)

    Ruban, A. V.; Simak, S. I.; Korzhavyi, P. A.; Johansson, B.

    2007-02-01

    Bulk ordering in Ag-Pd and other isoelectronic alloys is investigated theoretically by a number of first-principles techniques. The electronic structure and total energy have been calculated by the Green’s function Korringa-Kohn-Rostocker and full-potential plane wave methods. The effective cluster interactions of the Ising-type Hamiltonian have been obtained by the screened generalized perturbation method. They reveal a complex concentration-dependent ordering behavior in these alloys due to band filling and Fermi surface effects. In particular we show that long-period superstructures are gradually stabilized by a great number of relatively weak long-range effective pair- and three-site interactions, which can be seen as “collective” effect. A similar complex concentration dependence is also found for surfaces of Ag-Pd alloys. The surface composition of the (111) and (100) surface of Ag75Pd25 , Ag50Pd50 , and Ag33Pd67 alloys have been then investigated by the surface Green’s function technique and the screened generalized perturbation method for the effective interactions of the Ising-type Hamiltonian and the grand canonical Monte Carlo method for statistical thermodynamic simulations at finite temperatures. We compare our results with experimental data and other theoretical calculations.

  13. Shear bond strength of different surface treatments in bulk fill, microhybrid, and nanoparticle repair resins

    Directory of Open Access Journals (Sweden)

    de Jesus Tavarez RR

    2017-07-01

    Full Text Available Rudys Rodolfo de Jesus Tavarez,1 Lauber Jose dos Santos Almeida Júnior,2 Tayanne Christine Gomes Guará,1 Izabella Santos Ribeiro,1 Etevaldo Matos Maia Filho,1 Leily Macedo Firoozmand2 1Department of Restorative Dentistry, Ceuma University (CEUMA, 2Department of Dentistry I, University Federal of Maranhão (UFMA, São Luís, Maranhão, Brazil Objectives: The purpose of this study was to evaluate the influence of surface treatment and different types of composite resin on the microshear bond strength of repairs. Materials and methods: Seventy-two specimens (n=72 were prepared using a nanoparticle resin and stored in artificial saliva at 37 ± 1°C for 24 h. After this period, the specimens (n=24 were restored with microhybrid resin P60 (3M ESPE, nanoparticle resin Filtek Z350 (3M ESPE, and Bulk Fill Surefil SDR Flow (Dentsply composite resins. Previously, the surfaces of the samples were treated, forming the following subgroups (n=12: (A conditioned with 37% phosphoric acid for 30 s, and (B abrasioned with a diamond tip for 3 s and conditioned with 37% phosphoric acid. In all groups, before insertion of the composite resin, the adhesive system Adper Single Bond 2 was actively applied and photopolymerized for 20 s. Results: The microshear test was executed to assess bond strength. Kruskal–Wallis (p<0.05 and Mann–Whitney statistical tests showed significant statistical difference considering that the bulk-fill resin turned out to have a lower bond strength than the conventional nanoparticle and microhybrid composites. With regard to the technique, the roughening with diamond bur followed by the application of phosphoric acid exhibited values higher than the exclusive use of acid. Conclusion: The microshear bond strength of the composite resin repairs varies in accordance with the type of composite resin utilized, and roughening the surface increased the bond strength of these materials. Keywords: bulk-fill resins, composite resins, dental

  14. Periodic density functional theory calculations of bulk and the (010 surface of goethite

    Directory of Open Access Journals (Sweden)

    Sparks Donald L

    2008-05-01

    Full Text Available Abstract Background Goethite is a common and reactive mineral in the environment. The transport of contaminants and anaerobic respiration of microbes are significantly affected by adsorption and reduction reactions involving goethite. An understanding of the mineral-water interface of goethite is critical for determining the molecular-scale mechanisms of adsorption and reduction reactions. In this study, periodic density functional theory (DFT calculations were performed on the mineral goethite and its (010 surface, using the Vienna Ab Initio Simulation Package (VASP. Results Calculations of the bulk mineral structure accurately reproduced the observed crystal structure and vibrational frequencies, suggesting that this computational methodology was suitable for modeling the goethite-water interface. Energy-minimized structures of bare, hydrated (one H2O layer and solvated (three H2O layers (010 surfaces were calculated for 1 × 1 and 3 × 3 unit cell slabs. A good correlation between the calculated and observed vibrational frequencies was found for the 1 × 1 solvated surface. However, differences between the 1 × 1 and 3 × 3 slab calculations indicated that larger models may be necessary to simulate the relaxation of water at the interface. Comparison of two hydrated surfaces with molecularly and dissociatively adsorbed H2O showed a significantly lower potential energy for the former. Conclusion Surface Fe-O and (FeO-H bond lengths are reported that may be useful in surface complexation models (SCM of the goethite (010 surface. These bond lengths were found to change significantly as a function of solvation (i.e., addition of two extra H2O layers above the surface, indicating that this parameter should be carefully considered in future SCM studies of metal oxide-water interfaces.

  15. Is the surface oxygen exchange rate linked to bulk ion diffusivity in mixed conducting Ruddlesden-Popper phases?

    Science.gov (United States)

    Tomkiewicz, Alex C; Tamimi, Mazin A; Huq, Ashfia; McIntosh, Steven

    2015-01-01

    The possible link between oxygen surface exchange rate and bulk oxygen anion diffusivity in mixed ionic and electronic conducting oxides is a topic of great interest and debate. While a large body of experimental evidence and theoretical analyses support a link, observed differences between bulk and surface composition of these materials are hard to reconcile with this observation. This is further compounded by potential problems with simultaneous measurement of both parameters. Here we utilize separate techniques, in situ neutron diffraction and pulsed isotopic surface exchange, to examine bulk ion mobility and surface oxygen exchange rates of three Ruddlesden-Popper phases, general form A(n-1)A(2)'B(n)O(3n+1), A(n-1)A(2)'B(n)X(3n+1); LaSrCo(0.5)Fe(0.5)O(4-δ) (n = 1), La(0.3)Sr(2.7)CoFeO(7-δ) (n = 2) and LaSr3Co(1.5)Fe(1.5)O(10-δ) (n = 3). These measurements are complemented by surface composition determination via high sensitivity-low energy ion scattering. We observe a correlation between bulk ion mobility and surface exchange rate between materials. The surface exchange rates vary by more than one order of magnitude with high anion mobility in the bulk of an oxygen vacancy-rich n = 2 Ruddlesden-Popper material correlating with rapid oxygen exchange. This is in contrast with the similar surface exchange rates which we may expect due to similar surface compositions across all three samples. We conclude that experimental limitations lead to inherent convolution of surface and bulk rates, and that surface exchange steps are not likely to be rate limiting in oxygen incorporation.

  16. The Impact of Nanoparticle Surface Chemistry on Biological Systems

    Science.gov (United States)

    Thorn, Angie Sue Morris

    because they are easy to synthesize and their properties (such as size, porosity and surface chemistry) can be fine-tuned. Silica nanoparticles can be found in thousands of commercially available products such as toothpastes, cosmetics and detergents and are currently being developed for biomedical applications such as drug delivery and biomedical imaging. Our findings herein indicate that the surface chemistry of silica nanoparticles can have an effect on lung inflammation after exposure. Specifically, amine-modified silica NPs are considered to be less toxic compared to bare silica nanoparticles. Together, these studies provide insight into the role that material properties have on toxicity and allow for a better understanding of their impact on human and environmental health. The final aim of this thesis was to develop surface-modified nanoparticles for drug delivery applications. For this, biodegradable, polymeric NPs were used due to their inert nature and biocompatibility. Furthermore, polymeric NPs are excellent for loading drugs and using them as drug delivery vehicles. In this work, poly (lactic-co-glycolic acid) (PLGA) NPs were loaded with a therapeutic peptide. These NPs were then coated with chitosan (a mucoadhesive polymer) for the treatment of allergic asthma or coated with a small cationic mitochondrial targeting agent for the treatment of ischemia/reperfusion injury. Taken as a whole, this thesis sheds light on the impact of NPs on human health. First by providing useful toxological data for CuO and silica NPs as well as highlighting the potential of surface-modified polymeric NPs to be used in drug delivery-based applications.

  17. Gas-grain chemistry in cold interstellar cloud cores with a microscopic Monte Carlo approach to surface chemistry

    Science.gov (United States)

    Chang, Q.; Cuppen, H. M.; Herbst, E.

    2007-07-01

    Aims:We have recently developed a microscopic Monte Carlo approach to study surface chemistry on interstellar grains and the morphology of ice mantles. The method is designed to eliminate the problems inherent in the rate-equation formalism to surface chemistry. Here we report the first use of this method in a chemical model of cold interstellar cloud cores that includes both gas-phase and surface chemistry. The surface chemical network consists of a small number of diffusive reactions that can produce molecular oxygen, water, carbon dioxide, formaldehyde, methanol and assorted radicals. Methods: The simulation is started by running a gas-phase model including accretion onto grains but no surface chemistry or evaporation. The starting surface consists of either flat or rough olivine. We introduce the surface chemistry of the three species H, O and CO in an iterative manner using our stochastic technique. Under the conditions of the simulation, only atomic hydrogen can evaporate to a significant extent. Although it has little effect on other gas-phase species, the evaporation of atomic hydrogen changes its gas-phase abundance, which in turn changes the flux of atomic hydrogen onto grains. The effect on the surface chemistry is treated until convergence occurs. We neglect all non-thermal desorptive processes. Results: We determine the mantle abundances of assorted molecules as a function of time through 2 × 105 yr. Our method also allows determination of the abundance of each molecule in specific monolayers. The mantle results can be compared with observations of water, carbon dioxide, carbon monoxide, and methanol ices in the sources W33A and Elias 16. Other than a slight underproduction of mantle CO, our results are in very good agreement with observations.

  18. Unraveling surface and bulk trap states in lead halide perovskite solar cells using impedance spectroscopy

    Science.gov (United States)

    Han, Changfeng; Wang, Kai; Zhu, Xixiang; Yu, Haomiao; Sun, Xiaojuan; Yang, Qin; Hu, Bin

    2018-03-01

    Organic-inorganic hybrid perovskites (OIHPs) have been widely recognized as an excellent candidate for next-generation photovoltaic materials because of their highly efficient power conversion. Acquiring a complete understanding of trap states and dielectric properties in OIHP-based solar cells at the steady state is highly desirable in order to further explore and improve their optoelectronic functionalities and properties. We report CH3NH3PbI3-x Cl x -based planar solar cells with a power conversion efficiency (PCE) of 15.8%. The illumination intensity dependence of the current density-voltage (J-V) revealed the presence of trap-assisted recombination at low fluences. Non-destructive ac impedance spectroscopy (ac-IS) was applied to characterize the device at the steady state. The capacitance-voltage (C-V) spectra exhibited some distinct variations at a wide range of ac modulation frequencies with and without photo-excitations. Since the frequency-dependent chemical capacitance ({{C}μ }) is concerned with the surface and bulk related density of states (DOS) in CH3NH3PbI3-x Cl x , we verified this by fitting the corresponding DOS by a Gaussian distribution function. We ascertained that the electronic sub-gap trap states present in the solution processed CH3NH3PbI3-x Cl x and their distribution differs from the surface to the bulk. In fact, we demonstrated that both surfaces that were adjacent to the electron and hole transport layers featured analogous DOS. Despite this, photo- and bias-induced giant dielectric responses (i.e. both real and imaginary parts) were detected. A remarkable reduction of {{C}μ } at higher frequencies (i.e. more than 100 kHz) was ascribed to the effect of dielectric loss in CH3NH3PbI3-x Cl x .

  19. Surface Chemistry at Size-Selected Nano-Aerosol Particles

    Science.gov (United States)

    Roberts, Jeffrey

    2005-03-01

    A method has been developed to conduct surface chemistry and extract surface kinetic rates from size-selected aerosol nanoparticles. The measurements encompass broad ranges of particle size, phase, and composition. Results will be presented on the uptake of water by aerosolized soot nanoparticles of radius between 10 and 40 nm. Water uptake was monitored by tandem differential mobility analysis (T-DMA), which is capable of measuring changes in particle diameter as little as 0.2 nm. Soot particles were produced in an ethene diffusion flame and extracted into an atmospheric pressure aerosol flow tube reactor. The particles were subjected to various thermal and oxidative treatments, and the effects of these treatments on the ability of soot to adsorb monolayer quantities of water was determined. The results are important because soot nucleates atmospheric cloud particles. More generally, the results represent one of the first kinetic and mechanistic studies of gas-phase nanoparticle reactivity. Co-author: Henry Ajo, University of Minnesota

  20. Surface composition, chemistry, and structure of polystyrene modified by electron-beam-generated plasma.

    Science.gov (United States)

    Lock, Evgeniya H; Petrovykh, Dmitri Y; Mack, Paul; Carney, Tim; White, Richard G; Walton, Scott G; Fernsler, Richard F

    2010-06-01

    Polystyrene (PS) surfaces were treated by electron-beam-generated plasmas in argon/oxygen, argon/nitrogen, and argon/sulfur hexafluoride environments. The resulting modifications of the polymer surface energy, morphology, and chemical composition were analyzed by a suite of complementary analytical techniques: contact angle goniometry, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and reflection electron energy loss spectroscopy (REELS). The plasma treatments produced only minimal increases in the surface roughness while introducing the expected chemical modifications: oxygen-based after Ar/O(2) plasma, oxygen- and nitrogen-based after Ar/N(2) plasma, and fluorine-based after Ar/SF(6) plasma. Fluorinated PS surfaces became hydrophobic and did not significantly change their properties over time. In contrast, polymer treated in Ar/O(2) and Ar/N(2) plasmas initially became hydrophilic but underwent hydrophobic recovery after 28 days of aging. The aromatic carbon chemistry in the top 1 nm of these aged surfaces clearly indicated that the hydrophobic recovery was produced by reorientation/diffusion of undamaged aromatic polymer fragments from the bulk rather than by contamination. Nondestructive depth profiles of aged plasma-treated PS films were reconstructed from parallel angle-resolved XPS (ARXPS) measurements using a maximum-entropy algorithm. The salient features of reconstructed profiles were confirmed by sputter profiles obtained with 200 eV Ar ions. Both types of depth profiles showed that the electron-beam-generated plasma modifications are confined to the topmost 3-4 nm of the polymer surface, while valence band measurements and unsaturated carbon signatures in ARXPS and REELS data indicated that much of the PS structure was preserved below 9 nm.

  1. Mutual conversion of bulk and surface acoustic waves in gratings of finite length on half-infinite substrates. I. FE analysis of surface wave generation.

    Science.gov (United States)

    Darinskii, A N; Weihnacht, M; Schmidt, H

    2013-07-01

    A numerical study is carried out of the surface acoustic wave generation by a bulk acoustic wave in a half-infinite anisotropic half-space without piezoeffect. The efficient conversion of bulk waves into surface waves occurs due to a grating area created on the surface of the substrate. Our simulations are fully based on the finite element method. Given the incident bulk wave, we directly determine the amplitude of the surface wave and investigate its dependence on various parameters specifying the situation under consideration, such as the frequency and the polarization of the bulk wave, the length of the grating, the geometrical size of grooves or strips forming the grating. Copyright © 2013 Elsevier B.V. All rights reserved.

  2. Size constraints on a Majorana beam-splitter interferometer: Majorana coupling and surface-bulk scattering

    Science.gov (United States)

    Røising, Henrik Schou; Simon, Steven H.

    2018-03-01

    Topological insulator surfaces in proximity to superconductors have been proposed as a way to produce Majorana fermions in condensed matter physics. One of the simplest proposed experiments with such a system is Majorana interferometry. Here we consider two possibly conflicting constraints on the size of such an interferometer. Coupling of a Majorana mode from the edge (the arms) of the interferometer to vortices in the center of the device sets a lower bound on the size of the device. On the other hand, scattering to the usually imperfectly insulating bulk sets an upper bound. From estimates of experimental parameters, we find that typical samples may have no size window in which the Majorana interferometer can operate, implying that a new generation of more highly insulating samples must be explored.

  3. Hofmeister Effect on PNIPAM in Bulk and at an Interface: Surface Partitioning of Weakly Hydrated Anions

    DEFF Research Database (Denmark)

    Moghaddam, Saeed Zajforoushan; Thormann, Esben

    2017-01-01

    The effect of sodium fluoride, sodium trichloroacetate, and sodium thiocyanate on the stability and conformation of poly(N-isopropylacrylamide), in bulk solution and at the gold-aqueous interface, is investigated by differential scanning calorimetry, dynamic light scattering, quartz crystal...... microbalance, and atomic force microscopy. The results indicate a surface partitioning of the weakly hydrated anions, i.e., thiocyanate and trichloroacetate, and the findings are discussed in terms of anion-induced electrostatic stabilization. Although attractive polymer-ion interactions are suggested...... for thiocyanate and trichloroacetate, a salting-out effect is found for sodium trichloroacetate. This apparent contradiction is explained by a combination of previously suggested mechanisms for the salting-out effect by weakly hydrated anions....

  4. Evaluation of Bulk and Surface Radiation Damage of Silicon Sensors for the ATLAS Upgrade

    CERN Document Server

    Mikeštíková, Marcela; Št'astný, Jan

    2015-01-01

    The electrical characteristics of different types of end-cap miniature n + -in- p strip sensors, ATLAS12A, were evaluated in Institute of Physics in Prague before and after proton and gamma irradiation. We report here on the bulk damage aspects, including the increase of leakage current and evaluation of the full depletion voltage and the surface damage, including the decrease of inter-strip resistance, changes in inter-strip capacitance and the effectiveness of punch-through protection structure. It was verified that different geometries of end-cap sensors do not influence their stability; the sensors should provide acceptable strip isolation and n ew gate PTP structure functions well even at the highest tested proton fluence 2× 10 15 n eq / cm 2

  5. Systematic study of transport via surface and bulk states in Bi2Te3 topological insulator

    Science.gov (United States)

    de Castro, S.; Peres, M. L.; Chitta, V. A.; Gratens, X.; Soares, D. A. W.; Fornari, C. I.; Rappl, P. H. O.; Abramof, E.; Oliveira, N. F., Jr.

    2016-07-01

    We performed magnetoresistance measurements on Bi2Te3 thin film in the temperature range of T = 1.2-4.0 K and for magnetic fields up to 2 T. The curves exhibited anomalous behavior for temperatures below 4.0 K. Different temperature intervals revealed electrical transport through different conductive channels with clear signatures of weak antilocalization. The magnetoresistance curves were explained using the Hikami-Larkin-Nagaoka model and the 2D Dirac modified model. The comparison between the parameters obtained from the two models revealed the transport via topological surface states and bulk states. In addition, a superconductive like transition is observed for the lowest temperatures and we suggest that this effect can be originated from the misfit dislocations caused by strain, giving rise to a superconductive channel between the interface of the film and the substrate.

  6. Hydrogen interstitials inside bulk reduced-CeO2: charge state, defect chemistry and dynamics by ab-initio calculations

    Science.gov (United States)

    Zhang, Lei; Liu, Meilin; Meilin Liu Team

    CeO2 is a well-known and widely-used solid oxide fuel cells (SOFC) electrolyte and catalyst anode support, due to its facile oxygen vacancy formation and diffusion within its symmetric and capacious fluorite lattice. In real SOFC working conditions, hydrogen fuels will dissociate on anode surface and possibly permeate inside CeO2-based anode support and electrolyte. Studying hydrogen defect inside CeO2 lattice thus has two significant impacts: To see how hydrogen alters the ``oxygen buffering'' inside CeO2 as an anode support, and to see how it affects oxygen vacancy's diffusion and clustering inside electrolyte CeO2. Hereby ab-initio calculations in Kohn-Sham Density Functional Theory with Hubbard model of self-interaction correction is carried out to investigate the electron polaron and vacancy formation in CeO2 affected by hydrogen, the hydrogen defect state within the band gap of CeO2, the chemistry of defect interactions and its effect on oxygen vacancy mobility. The authors acknowledge financial support from ARPA-E REBELS Program DE-AR0000502, and computation resources from National Energy Research Scientific Computing Center DE-AC02-05CH11231 and Extreme Science and Engineering Discovery Environment ACI-1053575.

  7. Don Quixote Pond Sediments: Surface and Subsurface Chemistry and Mineralogy

    Science.gov (United States)

    Englert, P. A. J.; Bishop, J. L.; Patel, S.; Gibson, E. K.; Koeberl, C.

    2014-12-01

    Don Quixote Pond, like Don Juan Pond in the South Fork of Wright Valley, Antarctica, is a model for calcium and chlorine weathering and distribution on Mars. It is located in the western part of the North Fork about 100 m above Mean Seawater Level; its brine is seasonally frozen [1]. Field observations show zones of discoloration which grow lighter with distance from the pond edges. Four sediment cores, a set of radial surface samples, special surface samples, and samples of local rocks were obtained [2]. We report on chemical and mineral analyses of traverse samples and on two cores. Core DQ20 is a northeastern shoreline core. Its soluble salt concentration exceeds 200 micromoles/g in the top 5 cm, and then falls to less than 70 micromoles/g at the permafrost depth of 15 cm. These concentrations are low when compared to similarly positioned locations at Don Juan Pond and to cores from Prospect Mesa close to Lake Vanda, Wright Valley. Halite, soda niter, tachyhydrite and/bischovite are suggested from the ionic molar relationships Measured halite concentrations of surface samples, collected along a traverse of 35 m from the pond outwards, range from over 5% to trace amounts, decreasing with distance. Gypsum is also present in almost all of these samples ranging from 0.2% to 2.6%, but does not exhibit a trend. However, in core DQ35, located at a distance of 15 m along the traverse, gypsum decreases from 2.5% to 0.6% from the surface to the permafrost depth of 12 cm. While DQ35 and radial samples show high quartz and albite abundance, samples that contained visible encrustations and evaporites are low in these minerals and rich in highly diverse alteration products. Don Juan Basin ponds may have formed by a complex surface water mobilization of weathering products [3] and local groundwater action [4,5]. In contrast, Don Quixote pond mineralogy and chemistry may be consistent with a less complex shallow and deep groundwater system origin [1]. [1] Harris H

  8. Genotoxicity of copper oxide nanoparticles with different surface chemistry on rat bone marrow mesenchymal stem cells

    DEFF Research Database (Denmark)

    Zhang, Wenjing; Jiang, Pengfei; Chen, Wei

    2016-01-01

    The surface chemistry of nanoparticles (NPs) is one of the critical factors determining their cellular responses. In this study, the cytotoxicity and genotoxicity of copper oxide (CuO) NPs with a similar size but different surface chemistry to rat bone marrow mesenchymal stem cells (MSCs) were in...

  9. Ab-initio investigation of structural, electronic and optical properties BSb compound in bulk and surface (110 states

    Directory of Open Access Journals (Sweden)

    H A Badehian

    2015-07-01

    Full Text Available In recent work the structural, electronic and optical properties of BSb compound in bulk and surface (110 states have been studied. Calculations have been performed using Full-Potential Augmented Plane Wave (FP-LAPW method by WIEN2k code in Density Functional Theory (DFT framework. The structural properties of the bulk such as lattice constant, bulk module and elastic constants have been investigated using four different approximations. The band gap energy of the bulk and the (110 surface of BSb were obtained about 1.082 and 0.38 eV respectively. Moreover the surface energy, the work function, the surface relaxation, surface state and the band structure of BSb (110 were investigated using symmetric and stoichiometric 15 layers slabs with the vacuum of 20 Bohr. In addition, the real and imaginary parts of the dielectric function of the bulk and the BSb (110 slab were calculated and compared to each other. Our obtained results have a good agreement with the available results.

  10. Mutual conversion of bulk and surface acoustic waves in gratings of finite length on half-infinite substrates. II. FE analysis of bulk wave generation.

    Science.gov (United States)

    Darinskii, A N; Weihnacht, M; Schmidt, H

    2013-07-01

    The paper studies numerically the bulk acoustic wave generation by the surface acoustic wave propagating across a grating created on the surface of an elastically anisotropic half-infinite substrate. The computations are fully based on the finite element method. Applying the discrete Fourier transformation to the displacement field found inside the substrate and using an orthogonality relation valid for plane modes we determine separately the spatial spectrum of the quasi longitudinal and the quasi transverse bulk waves, that is, the dependence of the amplitudes of these waves on the tangential component of the wave vector. The dependence is investigated of the central spectral peak height and shape on the frequency of the incident surface wave as well as on the thickness, the width, and the number of strips forming the grating. In particular, it is found that under certain conditions the central peak can be approximated fairly precisely by the central peak of a sinc-function describing the spectrum of the bounded acoustic beam of rectangular shape and of width equal to the length of the grating. Copyright © 2013 Elsevier B.V. All rights reserved.

  11. Nanosegregation and Structuring in the Bulk and at the Surface of Ionic-Liquid Mixtures.

    Science.gov (United States)

    Bruce, Duncan W; Cabry, Christopher P; Lopes, José N Canongia; Costen, Matthew L; D'Andrea, Lucía; Grillo, Isabelle; Marshall, Brooks C; McKendrick, Kenneth G; Minton, Timothy K; Purcell, Simon M; Rogers, Sarah; Slattery, John M; Shimizu, Karina; Smoll, Eric; Tesa-Serrate, María A

    2017-06-22

    Ionic-liquid (IL) mixtures hold great promise, as they allow liquids with a wide range of properties to be formed by mixing two common components rather than by synthesizing a large array of pure ILs with different chemical structures. In addition, these mixtures can exhibit a range of properties and structural organization that depend on their composition, which opens up new possibilities for the composition-dependent control of IL properties for particular applications. However, the fundamental properties, structure, and dynamics of IL mixtures are currently poorly understood, which limits their more widespread application. This article presents the first comprehensive investigation into the bulk and surface properties of IL mixtures formed from two commonly encountered ILs: 1-ethyl-3-methylimidazolium and 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C 2 mim][Tf 2 N] and [C 12 mim][Tf 2 N]). Physical property measurements (viscosity, conductivity, and density) reveal that these IL mixtures are not well described by simple mixing laws, implying that their structure and dynamics are strongly composition dependent. Small-angle X-ray and neutron scattering measurements, alongside molecular dynamics (MD) simulations, show that at low mole fractions of [C 12 mim][Tf 2 N], the bulk of the IL is composed of small aggregates of [C 12 mim] + ions in a [C 2 mim][Tf 2 N] matrix, which is driven by nanosegregation of the long alkyl chains and the polar parts of the IL. As the proportion of [C 12 mim][Tf 2 N] in the mixtures increases, the size and number of aggregates increases until the C12 alkyl chains percolate through the system and a bicontinuous network of polar and nonpolar domains is formed. Reactive atom scattering-laser-induced fluorescence experiments, also supported by MD simulations, have been used to probe the surface structure of these mixtures. It is found that the vacuum-IL interface is enriched significantly in C12 alkyl chains, even in

  12. Influence of the carbon fiber surface microstructure on the surface chemistry generated by a thermo-chemical surface treatment

    International Nuclear Information System (INIS)

    Vautard, F.; Ozcan, S.; Paulauskas, F.; Spruiell, J.E.; Meyer, H.; Lance, M.J.

    2012-01-01

    Highlights: ► Continuous thermo-chemical surface treatment used to functionalize different types of carbon fibers. ► Surface density of functional groups directly correlated to the size of the surface microstructure. ► Preferential creation of hydroxyls and carboxylic acids confirmed regardless of the type of carbon fiber. ► Effective surface treatment regardless of the fiber surface microstructure. ► Potential alternative to electro-chemical surface treatment. - Abstract: Carbon fibers made of textile and aerospace grade polyacrylonitrile precursor fibers were surface treated by a continuous gas phase thermochemical treatment. The surface chemistry generated by the surface treatment was characterized by X-ray photoelectron spectroscopy. The surface and the average entire microstructure of the fibers were characterized by Raman spectroscopy and X-ray diffraction, respectively. Depending on the grade of the precursor, the final surface concentration of oxygen was comprised between 14% and 24%, whereas the typical commercial electrochemical surface treatments led to concentrations of around 8% with the same fibers. The final concentration of oxygen was directly correlated to the size of the crystallites which was a function of the grade of the polyacrylonitrile precursor and to the corresponding surface microstructure. The thermochemical surface treatment enabled a better control of the nature of the oxygen-containing functionalities as well. Whatever the grade of the precursor, desired hydroxyl groups and carboxylic acid functionalities were preferably generated, which is observed to be difficult with electrochemical surface treatments.

  13. Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons.

    Science.gov (United States)

    Külah, Elçin; Marot, Laurent; Steiner, Roland; Romanyuk, Andriy; Jung, Thomas A; Wäckerlin, Aneliia; Meyer, Ernst

    2017-03-22

    Rare-earth (RE) oxide surfaces are of significant importance for catalysis and were recently reported to possess intrinsic hydrophobicity. The surface chemistry of these oxides in the low temperature regime, however, remains to a large extent unexplored. The reactions occurring at RE surfaces at room temperature (RT) in real air environment, in particular, in presence of polycyclic aromatic hydrocarbons (PAHs), were not addressed until now. Discovering these reactions would shed light onto intermediate steps occurring in automotive exhaust catalysts before reaching the final high operational temperature and full conversion of organics. Here we first address physical properties of the RE oxide, nitride and fluoride surfaces modified by exposure to ambient air and then we report a room temperature reaction between PAH and RE oxide surfaces, exemplified by tetracene (C 18 H 12 ) on a Gd 2 O 3 . Our study evidences a novel effect - oxidation of higher hydrocarbons at significantly lower temperatures (~300 K) than previously reported (>500 K). The evolution of the surface chemical composition of RE compounds in ambient air is investigated and correlated with the surface wetting. Our surprising results reveal the complex behavior of RE surfaces and motivate follow-up studies of reactions between PAH and catalytic surfaces at the single molecule level.

  14. Models of gas-grain chemistry in interstellar cloud cores with a stochastic approach to surface chemistry

    Science.gov (United States)

    Stantcheva, T.; Herbst, E.

    2004-08-01

    We present a gas-grain model of homogeneous cold cloud cores with time-independent physical conditions. In the model, the gas-phase chemistry is treated via rate equations while the diffusive granular chemistry is treated stochastically. The two phases are coupled through accretion and evaporation. A small network of surface reactions accounts for the surface production of the stable molecules water, formaldehyde, methanol, carbon dioxide, ammonia, and methane. The calculations are run for a time of 107 years at three different temperatures: 10 K, 15 K, and 20 K. The results are compared with those produced in a totally deterministic gas-grain model that utilizes the rate equation method for both the gas-phase and surface chemistry. The results of the different models are in agreement for the abundances of the gaseous species except for later times when the surface chemistry begins to affect the gas. The agreement for the surface species, however, is somewhat mixed. The average abundances of highly reactive surface species can be orders of magnitude larger in the stochastic-deterministic model than in the purely deterministic one. For non-reactive species, the results of the models can disagree strongly at early times, but agree to well within an order of magnitude at later times for most molecules. Strong exceptions occur for CO and H2CO at 10 K, and for CO2 at 20 K. The agreement seems to be best at a temperature of 15 K. As opposed to the use of the normal rate equation method of surface chemistry, the modified rate method is in significantly better agreement with the stochastic-deterministic approach. Comparison with observations of molecular ices in dense clouds shows mixed agreement.

  15. Pyridine coordination chemistry for molecular assemblies on surfaces.

    Science.gov (United States)

    de Ruiter, Graham; Lahav, Michal; van der Boom, Milko E

    2014-12-16

    CONSPECTUS: Since the first description of coordination complexes, many types of metal-ligand interactions have creatively been used in the chemical sciences. The rich coordination chemistry of pyridine-type ligands has contributed significantly to the incorporation of diverse metal ions into functional materials. Here we discuss molecular assemblies (MAs) formed with a variety of pyridine-type compounds and a metal containing cross-linker (e.g., PdCl2(PhCN2)). These MAs are formed using Layer-by-Layer (LbL) deposition from solution that allows for precise fitting of the assembly properties through molecular programming. The position of each component can be controlled by altering the assembly sequence, while the degree of intermolecular interactions can be varied by the level of π-conjugation and the availability of metal coordination sites. By setting the structural parameters (e.g., bond angles, number of coordination sites, geometry) of the ligand, control over MA structure was achieved, resulting in surface-confined metal-organic networks and oligomers. Unlike MAs that are constructed with organic ligands, MAs with polypyridyl complexes of ruthenium, osmium, and cobalt are active participants in their own formation and amplify the growth of the incoming molecular layer. Such a self-propagating behavior for molecular systems is rare, and the mechanism of their formation will be discussed. These exponentially growing MAs are capable of storing metal salts that can be used during the buildup of additional molecular layers. Various parameters influencing the film growth mechanism will be presented, including (i) the number of binding sites and geometry of the organic ligands, (ii) the metal and the structure of the polypyridyl complexes, (iii) the influence of the metal cross-linker (e.g., second or third row transition metals), and (iv) the deposition conditions. By systematic variation of these parameters, switching between linear and exponential growth could

  16. Interaction of hydrogen and oxygen with bulk defects and surfaces of metals

    International Nuclear Information System (INIS)

    Besenbacher, F.

    1994-05-01

    that STM can be used as an in situ probe to provide unique insight into the mechanisms and dynamics of surface reactions, i.e. for atom-resolved surface chemistry. (au) (158 refs.)

  17. Evaluation of bulk and surfaces absorption edge energy of sol-gel-dip-coating SnO2 thin films

    Directory of Open Access Journals (Sweden)

    Emerson Aparecido Floriano

    2010-12-01

    Full Text Available The absorption edge and the bandgap transition of sol-gel-dip-coating SnO2 thin films, deposited on quartz substrates, are evaluated from optical absorption data and temperature dependent photoconductivity spectra. Structural properties of these films help the interpretation of bandgap transition nature, since the obtained nanosized dimensions of crystallites are determinant on dominant growth direction and, thus, absorption energy. Electronic properties of the bulk and (110 and (101 surfaces are also presented, calculated by means of density functional theory applied to periodic calculations at B3LYP hybrid functional level. Experimentally obtained absorption edge is compared to the calculated energy band diagrams of bulk and (110 and (101 surfaces. The overall calculated electronic properties in conjunction with structural and electro-optical experimental data suggest that the nature of the bandgap transition is related to a combined effect of bulk and (101 surface, which presents direct bandgap transition.

  18. First bulk and surface results for the ATLAS ITk stereo annulus sensors

    CERN Document Server

    Abidi, Syed Haider; The ATLAS collaboration; Bohm, Jan; Botte, James Michael; Ciungu, Bianca; Dette, Karola; Dolezal, Zdenek; Escobar, Carlos; Fadeyev, Vitaliy; Fernandez-Tejero, Xavi; Garcia-Argos, Carlos; Gillberg, Dag; Hara, Kazuhiko; Hunter, Robert Francis Holub

    2018-01-01

    A novel microstrip sensor geometry, the “stereo annulus”, has been developed for use in the end-cap of the ATLAS experiment’s strip tracker upgrade at the High-Luminosity Large Hadron Collider (HL- LHC). The radiation-hard, single-sided, ac-coupled, n + -in-p microstrip sensors are designed by the ITk Strip Sensor Collaboration and produced by Hamamatsu Photonics. The stereo annulus design has the potential to revolutionize the layout of end-cap microstrip trackers promising better tracking performance and more complete coverage than the contemporary configurations. These advantages are achieved by the union of equal length, radially oriented strips with a small stereo angle implemented directly into the sensor surface. The first-ever results for the stereo annulus geometry have been collected across several sites world- wide and are presented here. A number of full-size, unirradiated sensors were evaluated for their mechanical, bulk, and surface properties. The new device, the ATLAS12EC, is compared ag...

  19. Bulk chirality effect for symmetric bistable switching of liquid crystals on topologically self-patterned degenerate anchoring surface.

    Science.gov (United States)

    Park, Min-Kyu; Joo, Kyung-Il; Kim, Hak-Rin

    2017-06-26

    We demonstrate a bistable switching liquid crystal (LC) mode utilizing a topologically self-structured dual-groove surface for degenerated easy axes of LC anchoring. In our study, the effect of the bulk elastic distortion of the LC directors on the bistable anchoring surface is theoretically analyzed for balanced bistable states based on a free energy diagram. By adjusting bulk LC chirality, we developed ideally symmetric and stable bistable anchoring and switching properties, which can be driven by a low in-plane pulsed field of about 0.7 V/µm. The fabricated device has a contrast ratio of 196:1.

  20. Surface Redox Chemistry of Immobilized Nanodiamond: Effects of Particle Size and Electrochemical Environment

    Science.gov (United States)

    Gupta, S.; McDonald, B.; Carrizosa, S. B.

    2017-07-01

    The size of the diamond particle is tailored to nanoscale (nanodiamond, ND), and the ND surface is engineered targeting specific (electrochemical and biological) applications. In this work, we investigated the complex surface redox chemistry of immobilized ND layer on conductive boron-doped diamond electrode with a broad experimental parameter space such as particle size (nano versus micron), scan rate, pH (cationic/acidic versus anionic/basic), electrolyte KCl concentration (four orders of magnitude), and redox agents (neutral and ionic). We reported on the significant enhancement of ionic currents while recording reversible oxidation of neutral ferrocene methanol (FcMeOH) by almost one order of magnitude than traditional potassium ferricyanide (K3Fe(CN)6) redox agent. The current enhancement is inversely related to ND particle diameter in the following order: 1 μm << 1000 nm < 100 nm < 10 nm ≤ 5 nm < 2 nm. We attribute the current enhancement to concurrent electrocatalytic processes, i.e. the electron transfer between redox probes and electroactive surface functional (e.g. hydroxyl, carboxyl, epoxy) moieties and the electron transfer mediated by adsorbed FcMeOH+ (or Fe(CN) 6 3+ ) ions onto ND surface. The first process is pH dependent since it depends upon ND surface functionalities for which the electron transfer is coupled to proton transfer. The adsorption mediated process is observed most apparently at slower scan rates owing to self-exchange between adsorbed FcMeOH+ ions and FcMeOH redox agent molecules in diffusion-limited bulk electrolyte solution. Alternatively, it is hypothesized that the surface functionality and defect sites ( sp 2-bonded C shell and unsaturated bonds) give rise to surface electronic states with energies within the band gap (midgap states) in undoped ND. These surface states serve as electron donors (and acceptors) depending upon their bonding (and antibonding) character and, therefore, they can support electrocatalytic redox

  1. Chemistry and catalysis at the surface of nanomaterials

    Science.gov (United States)

    White, Brian Edward

    This thesis will delve into three main areas of nanomaterials research: (I) Designing, building, and utilizing a chemical vapor deposition (CVD) system for the growth of CNTs; (II) Aqueous suspensions of carbon nanotubes (CNT) solubilized by various surfactants, and the oxidative chemistry that can occur at CNT surfaces; (III) Catalytic CO oxidation over supported Cu2O nanoparticle systems. An introduction to nanomaterials in general, with a particular emphasis on carbon nanotubes and nanoparticles will be given in Chapter one. Chapter two provides a summary of common techniques used to grow carbon nanotubes, and introduces a new method we have developed. This method is based on previous chemical vapor deposition techniques, but uses liquids, specifically ethanol, as the carbon source. Using ethanol has several advantages, including ease of use and safety, as well as chemical benefits. Our new process affords long, aligned, single-walled nanotubes, with a relatively narrow diameter distribution. This method can also be used to grow CNTs across slits, which can then be studied spectroscopically. In Chapter three CNT-surfactant aqueous suspensions will be discussed in depth, including a new robust polymer surfactant. Poly(maleic acid/octyl vinyl ether) (PMAOVE) is stable over a large range of temperatures and pH values, and is well suited for the study of the oxidative chemistry that can occur on SWNT surfaces. Our aqueous suspensions were found to be quite stable by zeta potential studies and their emissive properties exhibited a pH dependence, quenching at higher concentrations of H+. We attribute this dependence to chemisorbed oxygen and its protonation at lower pH values. By heating the suspensions of SWNTs, O2 can be driven off, thus eliminating the dependence on pH. We also reproducibly add oxygen back into the system in the form of 1DeltaO2 , obtained from an endoperoxide. This method allows us to calculate the number of oxygen molecules needed for

  2. Molecular metal catalysts on supports: organometallic chemistry meets surface science.

    Science.gov (United States)

    Serna, Pedro; Gates, Bruce C

    2014-08-19

    -support bonding and structure, which identify the supports as ligands with electron-donor properties that influence reactivity and catalysis. Each of the catalyst design variables has been varied independently, illustrated by mononuclear and tetranuclear iridium on zeolite HY and on MgO and by isostructural rhodium and iridium (diethylene or dicarbonyl) complexes on these supports. The data provide examples resolving the roles of the catalyst design variables and place the catalysis science on a firm foundation of organometallic chemistry linked with surface science. Supported molecular catalysts offer the advantages of characterization in the absence of solvents and with surface-science methods that do not require ultrahigh vacuum. Families of supported metal complexes have been made by replacement of ligands with others from the gas phase. Spectroscopically identified catalytic reaction intermediates help to elucidate catalyst performance and guide design. The methods are illustrated for supported complexes and clusters of rhodium, iridium, osmium, and gold used to catalyze reactions of small molecules that facilitate identification of the ligands present during catalysis: alkene dimerization and hydrogenation, H-D exchange in the reaction of H2 with D2, and CO oxidation. The approach is illustrated with the discovery of a highly active and selective MgO-supported rhodium carbonyl dimer catalyst for hydrogenation of 1,3-butadiene to give butenes.

  3. Electrical conductivity of conductive carbon blacks: influence of surface chemistry and topology

    International Nuclear Information System (INIS)

    Pantea, Dana; Darmstadt, Hans; Kaliaguine, Serge; Roy, Christian

    2003-01-01

    Conductive carbon blacks from different manufacturers were studied in order to obtain some insight into the relation between their electrical conductivity and their surface properties. The surface chemistry was studied by X-ray photoelectron spectroscopy (XPS) and static secondary ion mass spectroscopy (SIMS), whereas the topology of the carbon black surface was investigated using low-pressure nitrogen adsorption. All these techniques yield information on the graphitic character of the surface. In general, the electrical conductivity of the conductive blacks increases with the graphitic character of the surface. For low surface area conductive blacks, the electrical conductivity correlates well with the surface chemistry. In the case of the XPS and SIMS data, this correlation is also valid when other types of carbon blacks such as thermal and furnace blacks are included, confirming the determining influence of the carbon black surface chemistry on the electrical conductivity

  4. Bulk and surface electron transport in topological insulator candidate YbB{sub 6-δ}

    Energy Technology Data Exchange (ETDEWEB)

    Glushkov, Vladimir V.; Demishev, Sergey V.; Sluchanko, Nikolay E. [Prokhorov General Physics Institute of RAS, Vavilov str. 38, 119991, Moscow (Russian Federation); Moscow Institute of Physics and Technology, Institutskii per. 9, 141700, Dolgoprudny, Moscow Region (Russian Federation); Bozhko, Alexey D.; Bogach, Alexey V.; Semeno, Alexey V.; Voronov, Valeriy V. [Prokhorov General Physics Institute of RAS, Vavilov str. 38, 119991, Moscow (Russian Federation); Dukhnenko, Anatoliy V.; Filipov, Volodimir B.; Shitsevalova, Natalya Yu. [Frantsevich Institute for Problems of Materials Science NAS, Krzhyzhanovsky str. 3, 03680, Kiev (Ukraine); Kondrin, Mikhail V. [Vereshchagin Institute of High Pressure Physics of RAS, 142190, Troitsk, Moscow (Russian Federation); Kuznetsov, Alexey V.; Sannikov, Ilia I. [National Research Nuclear University ' ' MEPhI' ' , Kashirskoe Shosse 31, 115409, Moscow (Russian Federation)

    2016-04-15

    We report the study of transport and magnetic properties of the YbB{sub 6-δ}single crystals grown by inductive zone melting. A strong disparity in the low temperature resistivity, Seebeck and Hall coefficients is established for the samples with the different level of boron deficiency. The effective parameters of the charge transport in YbB{sub 6-δ} are shown to depend on the concentration of intrinsic defects, which is estimated to range from 0.09% to 0.6%. The pronounced variation of Hall mobility μ{sub H} found for bulk holes is induced by the decrease of transport relaxation time from τ ∼ 7.7 fs for YbB{sub 5.994} to τ ∼ 2.2 fs for YbB{sub 5.96}. An extra contribution to conductivity from electrons with μ{sub H}∼ -1000 cm{sup 2} V{sup -1} s{sup -1} and the very low concentration n /n{sub Yb}∼ 10{sup -6} discovered below 20 K for all the single crystals under investigation is suggested to arise from the surface electron states appeared in the inversion layer due to the band bending. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Fast inspection of bulk and surface defects of large aperture optics in high power lasers

    Science.gov (United States)

    Zhao, Yuan'an; Hu, Guohang; Liu, Shijie; Yi, Kui; Shao, Jianda

    2015-05-01

    Laser induced damage for nanosecond pulse duration is attributed to the existence of defects. The growth and polishing, as well as coating deposition, may induce versatile kinds of defects, including dig, scratch and inclusion. It is special important to get the information of the defects, such as size and location, which is the basis to know the origin of the defects and figures out effective techniques to eliminate it. It is quite easy to get the information of the defects with micron-level resolution, but it is time-consuming and is not suitable for fast inspection of the large aperture (hundreds of millimeters). In this work, on-the-fly image capture technique was employed to realize fast inspection of large aperture optics. A continuous green laser was employed as illumination source to enhance and enlarge the image of bulk defects. So it could detect the submicron-scale defects. A transmission microscopy with white light illumination was employed to detect the surface defect. Its field of view was about 2.8mm×1.6mm. The sample was raster scanned driving by a stepper motor through the stationary illumination laser and digital camera, and the speed to scan the sample was about 10mm/s. The results of large aperture optics proved the functions of this fast inspection technique.

  6. Subthreshold radiation-induced processes in the bulk and on surfaces and interfaces of solids

    International Nuclear Information System (INIS)

    Itoh, N.

    1998-01-01

    A review is given on the processes induced under irradiation by electronic encounters and by elastic encounters below the knock-on threshold. It is pointed out that electronic encounters cause bond scission that results in defect formation and sputtering in a variety of materials. The conditions for generation of permanent radiation-induced process as a consequence of electronic encounters are critically examined. Two critical issues are localization of electronic excitation energy and energetics. Self-trapping of excitons is one way of localization; otherwise defects are involved in localization and therefore in radiation-induced processes (RIP) by electronic excitation. Arguments on energetics indicate presence of linear and nonlinear electronic process with respect to the density of excitation. The registration of energetic heavy-ion tracks is explained in terms of non-linear electronic processes. The difference in the processes in the bulk, on surfaces and at interfaces is critically discussed. The possible contribution of subthreshold elastic encounters to thermodynamically driven interface reaction is also discussed. (orig.)

  7. Bulk conductivity of soft surface layers : experimental measurement and electrokinetic implications

    NARCIS (Netherlands)

    Yezek, L.P.

    2005-01-01

    Conductivity measurements were carried out on a family of polyacrylamide-co-sodium acrylate gels cross-linked with N,N¿ -methylenebisacrylamide in a homemade electrokinetic cell. The conductivity data allowed the equilibrium Donnan potential difference between the bulk gel and the bulk electrolyte

  8. Periodic DFT+U investigation of the bulk and surface properties of marcasite (FeS2)

    NARCIS (Netherlands)

    Dzade, Nelson Y.; de Leeuw, Nora H.

    2017-01-01

    Marcasite FeS2 and its surface properties have been investigated by Hubbard-corrected Density Functional Theory (DFT+U) calculations. The calculated structural parameters, interatomic bond distances, elastic constants and electronic properties of the bulk mineral were determined and compared with

  9. Surface properties and color stability of incrementally-filled and bulk-fill composites after in vitro toothbrushing.

    Science.gov (United States)

    Lai, Guangyun; Zhao, Liya; Wang, Jun; Kunzelmann, Karl-Heinz

    2017-10-01

    To evaluate the effect of simulated toothbrush abrasion on the surface gloss, the surface roughness and the color stability of incrementally-filled and bulk-fill composites. 48 dimensionally standardized composite specimens (n= 8/group) were made from four incrementally-filled composites (Tetric EvoCeram, IPS Empress Direct Enamel, Ceram X mono and Arabesk) and two bulk-fill composites (Quix fil and Tetric EvoCeram Bulk). Before and after toothbrushing simulation the surface gloss was measured by a glossmeter, the surface roughness was evaluated with a profilometer, and the color was measured using a spectrophotometer. Before and after the toothbrush abrasion, IPS Empress Direct Enamel yielded the highest gloss value, while Ceram X mono exhibited the lowest gloss value. Quix fil showed the highest Ra value before the toothbrushing simulation, however, it showed similar Ra value with Ceram X mono and Arabesk after the toothbrushing simulation. IPS Empress Direct Enamel showed the lowest ΔE after the simulated toothbrushing. Tetric EvoCeram Bulk showed similar gloss value, Ra value, and ΔE to Tetric EvoCeram after the toothbrushing simulation. Simple regression analysis showed no correlation between the roughness and the gloss, but it showed a positive linear relationship between ΔE and ΔRa. (R2= 0.863, P= 0.027). The evaluated bulk-fill composites did not exhibit significantly worse surface properties and color stability than incrementally-filled materials after toothbrush abrasion. Color changes of composites caused by toothbrush abrasion were acceptable on the premise that 3.3ΔE units were considered as acceptable threshold values.

  10. Bactericidal effects of plasma-modified surface chemistry of silicon nanograss

    Science.gov (United States)

    Ostrikov, Kola; Macgregor-Ramiasa, Melanie; Cavallaro, Alex; (Ken Ostrikov, Kostya; Vasilev, Krasimir

    2016-08-01

    The surface chemistry and topography of biomaterials regulate the adhesion and growth of microorganisms in ways that are still poorly understood. Silicon nanograss structures prepared via inductively coupled plasma etching were coated with plasma deposited nanometer-thin polymeric films to produce substrates with controlled topography and defined surface chemistry. The influence of surface properties on Staphylococcus aureus proliferation is demonstrated and explained in terms of nanograss substrate wetting behaviour. With the combination of the nanograss topography; hydrophilic plasma polymer coatings enhanced antimicrobial activity while hydrophobic coatings reduced it. This study advances the understanding of the effects of surface wettability on the bactericidal properties of reactive nano-engineered surfaces.

  11. Bactericidal effects of plasma-modified surface chemistry of silicon nanograss

    International Nuclear Information System (INIS)

    Ostrikov, Kola; Macgregor-Ramiasa, Melanie; Cavallaro, Alex; Ostrikov, Kostya; Vasilev, Krasimir

    2016-01-01

    The surface chemistry and topography of biomaterials regulate the adhesion and growth of microorganisms in ways that are still poorly understood. Silicon nanograss structures prepared via inductively coupled plasma etching were coated with plasma deposited nanometer-thin polymeric films to produce substrates with controlled topography and defined surface chemistry. The influence of surface properties on Staphylococcus aureus proliferation is demonstrated and explained in terms of nanograss substrate wetting behaviour. With the combination of the nanograss topography; hydrophilic plasma polymer coatings enhanced antimicrobial activity while hydrophobic coatings reduced it. This study advances the understanding of the effects of surface wettability on the bactericidal properties of reactive nano-engineered surfaces. (paper)

  12. Anisotropic surface chemistry properties and adsorption behavior of silicate mineral crystals.

    Science.gov (United States)

    Xu, Longhua; Tian, Jia; Wu, Houqin; Fang, Shuai; Lu, Zhongyuan; Ma, Caifeng; Sun, Wei; Hu, Yuehua

    2018-03-07

    Anisotropic surface properties of minerals play an important role in a variety of fields. With a focus on the two most intensively investigated silicate minerals (i.e., phyllosilicate minerals and pegmatite aluminosilicate minerals), this review highlights the research on their anisotropic surface properties based on their crystal structures. Four surface features comprise the anisotropic surface chemistry of minerals: broken bonds, energy, wettability, and charge. Analysis of surface broken bond and energy anisotropy helps to explain the cleavage and growth properties of mineral crystals, and understanding surface wettability and charge anisotropy is critical to the analysis of minerals' solution behavior, such as their flotation performance and rheological properties. In a specific reaction, the anisotropic surface properties of minerals are reflected in the adsorption strengths of reagents on different mineral surfaces. Combined with the knowledge of mineral crushing and grinding, a thorough understanding of the anisotropic surface chemistry properties and the anisotropic adsorption behavior of minerals will lead to the development of effective relational models comprising their crystal structure, surface chemistry properties, and targeted reagent adsorption. Overall, such a comprehensive approach is expected to firmly establish the connection between selective cleavage of mineral crystals for desired surfaces and designing novel reagents selectively adsorbed on the mineral surfaces. As tools to characterize the anisotropic surface chemistry properties of minerals, DLVO theory, atomic force microscopy (AFM), and molecular dynamics (MD) simulations are also reviewed. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Surface and Bulk Electronic Structure and Chemisorption Properties of Titanium and Vanadium Oxides

    Science.gov (United States)

    Smith, Kevin Eugene

    The unusual electronic properties of Ti _2O_3 and V _2O_3, in particular the metal-insulator transitions which they undergo, have produced widespread interest in the physics of these materials, while the use of titanium and vanadium oxides as catalysts and catalyst supports makes a detailed understanding of their surface properties of great importance. The electronic structure and gas adsorption properties of single crystal titanium and vanadium oxides have been studied here using ultraviolet and x-ray photoemission spectroscopy, synchrotron radiation, Auger electron spectroscopy and low energy electron diffraction. Spatially anisotropic resonant photoemission from 3d states in Ti_2O_3 and V_2O_3 was observed and shown to originate from localised molecular orbitals. This contrasts with an energy analysis of the photoemission data which revealed dispersing, delocalised d-bands in both oxides. A large resonance was observed in the O 2p emission at the cation 3p to 3d absorption edge in Ti_2O _3 which is inconsistent with hybridisation, indicating the possible existence of inter-atomic resonances. The first detailed photoemission observation of metal-insulator transitions in Cr-doped V_2O _3 is reported; large changes in the density of states at the Fermi level are seen at these transitions. The surface electronic structure of single crystal TiO_2, Ti_2O _3 and V_2O _3 was found to be indistinguishable from that of the bulk. The interaction of SO_2 with these oxides was extensively studied since sulfur is a notorious catalyst poison. SO_2 reacts vigorously with the titanium oxides, dissociating in the presence of Ti^{3+} cations to form TiO_2 and TiS _2; in their absence no reaction occurs. Surprisingly, SO_2 reacts very weakly with V _2O_3, adsorbing in both dissociated and molecular form. Additionally, only a weak reaction of H_2S and TiO _2 was found. The electronic structure of these oxides is shown to be extremely complex, displaying both localised and

  14. Electrochemical Characteristics of Layered Transition Metal Oxide Cathode Materials for Lithium Ion Batteries: Surface, Bulk Behavior, and Thermal Properties.

    Science.gov (United States)

    Tian, Chixia; Lin, Feng; Doeff, Marca M

    2018-01-16

    Layered lithium transition metal oxides, in particular, NMCs (LiNi x Co y Mn z O 2 ) represent a family of prominent lithium ion battery cathode materials with the potential to increase energy densities and lifetime, reduce costs, and improve safety for electric vehicles and grid storage. Our work has focused on various strategies to improve performance and to understand the limitations to these strategies, which include altering compositions, utilizing cation substitutions, and charging to higher than usual potentials in cells. Understanding the effects of these strategies on surface and bulk behavior and correlating structure-performance relationships advance our understanding of NMC materials. This also provides information relevant to the efficacy of various approaches toward ensuring reliable operation of these materials in batteries intended for demanding traction and grid storage applications. In this Account, we start by comparing NMCs to the isostructural LiCoO 2 cathode, which is widely used in consumer batteries. Effects of changing the metal content (Ni, Mn, Co) upon structure and performance of NMCs are briefly discussed. Our early work on the effects of partial substitution of Al, Fe, and Ti for Co on the electrochemical and bulk structural properties is then covered. The original aim of this work was to reduce the Co content (and thus the raw materials cost) and to determine the effect of the substitutions on the electrochemical and bulk structural properties. More recently, we have turned to the application of synchrotron and advanced microscopy techniques to understand both bulk and surface characteristics of the NMCs. Via nanoscale-to-macroscale spectroscopy and atomically resolved imaging techniques, we were able to determine that the surfaces of NMC undergo heterogeneous reconstruction from a layered structure to rock salt under a variety of conditions. Interestingly, formation of rock salt also occurs under abuse conditions. The surface

  15. On-Surface Synthesis by Click Chemistry Investigated by STM and XPS

    DEFF Research Database (Denmark)

    Vadapoo, Sundar Raja

    2014-01-01

    such as molecular electronics and surface functionalization. In this thesis, a well-defined click chemistry approach is followed, with the study of azide-alkyne cycloaddition on Cu(111) surface in UHV environment. A successful achievement of the click reaction product via on-surface synthesis has been shown, which...

  16. Seventh BES (Basic Energy Sciences) catalysis and surface chemistry research conference

    Energy Technology Data Exchange (ETDEWEB)

    1990-03-01

    Research programs on catalysis and surface chemistry are presented. A total of fifty-seven topics are included. Areas of research include heterogeneous catalysis; catalysis in hydrogenation, desulfurization, gasification, and redox reactions; studies of surface properties and surface active sites; catalyst supports; chemical activation, deactivation; selectivity, chemical preparation; molecular structure studies; sorption and dissociation. Individual projects are processed separately for the data bases. (CBS)

  17. Seventh BES [Basic Energy Sciences] catalysis and surface chemistry research conference

    International Nuclear Information System (INIS)

    1990-03-01

    Research programs on catalysis and surface chemistry are presented. A total of fifty-seven topics are included. Areas of research include heterogeneous catalysis; catalysis in hydrogenation, desulfurization, gasification, and redox reactions; studies of surface properties and surface active sites; catalyst supports; chemical activation, deactivation; selectivity, chemical preparation; molecular structure studies; sorption and dissociation. Individual projects are processed separately for the data bases

  18. Chemistry

    International Nuclear Information System (INIS)

    Gomez G, H.

    1989-01-01

    A brief description about the development and activities executed in chemistry, in the Instituto de Asuntos Nucleares, during the last years is presented. The plans and feasibility of nuclear techniques in Colombia are also described

  19. The effect of surface-bulk potential difference on the kinetics of intercalation in core-shell active cathode particles

    Science.gov (United States)

    Kazemiabnavi, Saeed; Malik, Rahul; Orvananos, Bernardo; Abdellahi, Aziz; Ceder, Gerbrand; Thornton, Katsuyo

    2018-04-01

    Surface modification of active cathode particles is commonly observed in battery research as either a surface phase evolving during the cycling process, or intentionally engineered to improve capacity retention, rate capability, and/or thermal stability of the cathode material. Here, a continuum-scale model is developed to simulate the galvanostatic charge/discharge of a cathode particle with core-shell heterostructure. The particle is assumed to be comprised of a core material encapsulated by a thin layer of a second phase that has a different open-circuit voltage. The effect of the potential difference between the surface and bulk phases (Ω) on the kinetics of lithium intercalation and the galvanostatic charge/discharge profiles is studied at different values of Ω, C-rates, and exchange current densities. The difference between the Li chemical potential in the surface and bulk phases of the cathode particle results in a concentration difference between these two phases. This leads to a charge/discharge asymmetry in the galvanostatic voltage profiles, causing a decrease in the accessible capacity of the particle. These effects are more significant at higher magnitudes of surface-bulk potential difference. The proposed model provides detailed insight into the kinetics and voltage behavior of the intercalation/de-intercalation processes in core-shell heterostructure cathode particles.

  20. Quantum and Classical Magnetoresistance in Ambipolar Topological Insulator Transistors with Gate-tunable Bulk and Surface Conduction

    Science.gov (United States)

    Tian, Jifa; Chang, Cuizu; Cao, Helin; He, Ke; Ma, Xucun; Xue, Qikun; Chen, Yong P.

    2014-01-01

    Weak antilocalization (WAL) and linear magnetoresistance (LMR) are two most commonly observed magnetoresistance (MR) phenomena in topological insulators (TIs) and often attributed to the Dirac topological surface states (TSS). However, ambiguities exist because these phenomena could also come from bulk states (often carrying significant conduction in many TIs) and are observable even in non-TI materials. Here, we demonstrate back-gated ambipolar TI field-effect transistors in (Bi0.04Sb0.96)2Te3 thin films grown by molecular beam epitaxy on SrTiO3(111), exhibiting a large carrier density tunability (by nearly 2 orders of magnitude) and a metal-insulator transition in the bulk (allowing switching off the bulk conduction). Tuning the Fermi level from bulk band to TSS strongly enhances both the WAL (increasing the number of quantum coherent channels from one to peak around two) and LMR (increasing its slope by up to 10 times). The SS-enhanced LMR is accompanied by a strongly nonlinear Hall effect, suggesting important roles of charge inhomogeneity (and a related classical LMR), although existing models of LMR cannot capture all aspects of our data. Our systematic gate and temperature dependent magnetotransport studies provide deeper insights into the nature of both MR phenomena and reveal differences between bulk and TSS transport in TI related materials. PMID:24810663

  1. Desorption of 1,3,5-Trichlorobenzene from Multi-Walled Carbon Nanotubes: Impact of Solution Chemistry and Surface Chemistry

    Directory of Open Access Journals (Sweden)

    Sheikh Uddin

    2013-05-01

    Full Text Available The strong affinity of carbon nanotubes (CNTs to environmental contaminants has raised serious concern that CNTs may function as a carrier of environmental pollutants and lead to contamination in places where the environmental pollutants are not expected. However, this concern will not be realized until the contaminants are desorbed from CNTs. It is well recognized that the desorption of environmental pollutants from pre-laden CNTs varies with the environmental conditions, such as the solution pH and ionic strength. However, comprehensive investigation on the influence of solution chemistry on the desorption process has not been carried out, even though numerous investigations have been conducted to investigate the impact of solution chemistry on the adsorption of environmental pollutants on CNTs. The main objective of this study was to determine the influence of solution chemistry (e.g., pH, ionic strength and surface functionalization on the desorption of preloaded 1,3,5-trichlorobenzene (1,3,5-TCB from multi-walled carbon nanotubes (MWNTs. The results suggested that higher pH, ionic strength and natural organic matter in solution generally led to higher desorption of 1,3,5-TCB from MWNTs. However, the extent of change varied at different values of the tested parameters (e.g., pH 7. In addition, the impact of these parameters varied with MWNTs possessing different surface functional groups, suggesting that surface functionalization could considerably alter the environmental behaviors and impact of MWNTs.

  2. Bulk Fermi surface of the Weyl type-II semimetallic candidate γ -MoTe2

    Science.gov (United States)

    Rhodes, D.; Schönemann, R.; Aryal, N.; Zhou, Q.; Zhang, Q. R.; Kampert, E.; Chiu, Y.-C.; Lai, Y.; Shimura, Y.; McCandless, G. T.; Chan, J. Y.; Paley, D. W.; Lee, J.; Finke, A. D.; Ruff, J. P. C.; Das, S.; Manousakis, E.; Balicas, L.

    2017-10-01

    The electronic structure of semimetallic transition-metal dichalcogenides, such as WTe2 and orthorhombic γ -MoTe2 , are claimed to contain pairs of Weyl points or linearly touching electron and hole pockets associated with a nontrivial Chern number. For this reason, these compounds were recently claimed to conform to a new class, deemed type-II, of Weyl semimetallic systems. A series of angle-resolved photoemission experiments (ARPES) claim a broad agreement with these predictions detecting, for example, Fermi arcs at the surface of these crystals. We synthesized single crystals of semimetallic MoTe2 through a Te flux method to validate these predictions through measurements of its bulk Fermi surface (FS) via quantum oscillatory phenomena. We find that the superconducting transition temperature of γ -MoTe2 depends on disorder as quantified by the ratio between the room- and low-temperature resistivities, suggesting the possibility of an unconventional superconducting pairing symmetry. Similarly to WTe2, the magnetoresistivity of γ -MoTe2 does not saturate at high magnetic fields and can easily surpass 106%. Remarkably, the analysis of the de Haas-van Alphen (dHvA) signal superimposed onto the magnetic torque indicates that the geometry of its FS is markedly distinct from the calculated one. The dHvA signal also reveals that the FS is affected by the Zeeman effect precluding the extraction of the Berry phase. A direct comparison between the previous ARPES studies and density-functional-theory (DFT) calculations reveals a disagreement in the position of the valence bands relative to the Fermi level ɛF. Here, we show that a shift of the DFT valence bands relative to ɛF, in order to match the ARPES observations, and of the DFT electron bands to explain some of the observed dHvA frequencies, leads to a good agreement between the calculations and the angular dependence of the FS cross-sectional areas observed experimentally. However, this relative displacement

  3. Functional surface chemistry of carbon-based nanostructures

    Science.gov (United States)

    Abdula, Daner

    The recently discovered abilities to synthesize single-walled carbon nanotubes and prepare single layer graphene have spurred interest in these sp2-bonded carbon nanostructures. In particular, studies of their potential use in electronic devices are many as silicon integrated circuits are encountering processing limitations, quantum effects, and thermal management issues due to rapid device scaling. Nanotube and graphene implementation in devices does come with significant hurdles itself. Among these issues are the ability to dope these materials and understanding what influences defects have on expected properties. Because these nanostructures are entirely all-surface, with every atom exposed to ambient, introduction of defects and doping by chemical means is expected to be an effective route for addressing these issues. Raman spectroscopy has been a proven characterization method for understanding vibrational and even electronic structure of graphene, nanotubes, and graphite, especially when combined with electrical measurements, due to a wealth of information contained in each spectrum. In Chapter 1, a discussion of the electronic structure of graphene is presented. This outlines the foundation for all sp2-bonded carbon electronic properties and is easily extended to carbon nanotubes. Motivation for why these materials are of interest is readily gained. Chapter 2 presents various synthesis/preparation methods for both nanotubes and graphene, discusses fabrication techniques for making devices, and describes characterization methods such as electrical measurements as well as static and time-resolved Raman spectroscopy. Chapter 3 outlines changes in the Raman spectra of individual metallic single-walled carbon nantoubes (SWNTs) upon sidewall covalent bond formation. It is observed that the initial degree of disorder has a strong influence on covalent sidewall functionalization which has implications on developing electronically selective covalent chemistries and

  4. Molecular dynamics study on mechanism of preformed particle gel transporting through nanopores: Surface chemistry and heterogeneity

    Science.gov (United States)

    Cui, Peng; Zhang, Heng; Ma, Ying; Hao, Qingquan; Liu, Gang; Sun, Jichao; Yuan, Shiling

    2017-10-01

    The translocation behavior of preformed particle gel (PPG) in porous media is crucial for its application in enhanced oil recovery. By means of non-equilibrium molecular dynamics simulation, the translocation mechanism of PPG confined in different silica nanopores were investigated. The influence of surface chemistry and chemical heterogeneity of silica nanopore on the translocation process was revealed. As the degree of surface hydroxylation increases and the heterogeneity decreases, the pulling force needed to drive PPG decreases. We infer that the nanopore's surface (i.e. surface chemistry and heterogeneity) affects the translocation of PPG indirectly by forming different hydration layers.

  5. ARPES view on surface and bulk hybridization phenomena in the antiferromagnetic Kondo lattice CeRh2Si2.

    Science.gov (United States)

    Patil, S; Generalov, A; Güttler, M; Kushwaha, P; Chikina, A; Kummer, K; Rödel, T C; Santander-Syro, A F; Caroca-Canales, N; Geibel, C; Danzenbächer, S; Kucherenko, Yu; Laubschat, C; Allen, J W; Vyalikh, D V

    2016-03-18

    The hybridization between localized 4f electrons and itinerant electrons in rare-earth-based materials gives rise to their exotic properties like valence fluctuations, Kondo behaviour, heavy-fermions, or unconventional superconductivity. Here we present an angle-resolved photoemission spectroscopy (ARPES) study of the Kondo lattice antiferromagnet CeRh2Si2, where the surface and bulk Ce-4f spectral responses were clearly resolved. The pronounced 4f (0) peak seen for the Ce terminated surface gets strongly suppressed in the bulk Ce-4f spectra taken from a Si-terminated crystal due to much larger f-d hybridization. Most interestingly, the bulk Ce-4f spectra reveal a fine structure near the Fermi edge reflecting the crystal electric field splitting of the bulk magnetic 4f (1)5/2 state. This structure presents a clear dispersion upon crossing valence states, providing direct evidence of f-d hybridization. Our findings give precise insight into f-d hybridization penomena and highlight their importance in the antiferromagnetic phases of Kondo lattices.

  6. Effect of the Ultrasonic Nanocrystalline Surface Modification (UNSM on Bulk and 3D-Printed AISI H13 Tool Steels

    Directory of Open Access Journals (Sweden)

    In-Sik Cho

    2017-11-01

    Full Text Available A comparative study of the microstructure, hardness, and tribological properties of two different AISI H13 tool steels—classified as the bulk with no heat treatment steel or the 3D-printed steel—was undertaken. Both samples were subjected to ultrasonic nanocrystalline surface modification (UNSM to further enhance their mechanical properties and improve their tribological behavior. The objective of this study was to compare the mechanical properties and tribological behavior of these tool steels since steel can exhibit a wide variety of mechanical properties depending on different manufacturing processes. The surface hardness of the samples was measured using a micro-Vickers hardness tester. The hardness of the 3D-printed AISI H13 tool steel was found to be much higher than that of the bulk one. The surface morphology of the samples was characterized by electron backscattered diffraction (EBSD in order to analyze the grain size and number of fractions with respect to the misorientation angle. The results revealed that the grain size of the 3D-printed AISI H13 tool steel was less than 0.5 μm, whereas that of the bulk tool steel was greater than 4 μm. The number of fractions of the bulk tool steel was about 0.5 μm at a low misorientation angle, and it decreased gradually with increasing misorientation angle. The low-angle grain boundary (LAGB and high-angle grain boundary (HAGB of the bulk sample were about 21% and 79%, respectively, and those of the 3D-printed sample were about 8% and 92%, respectively. Moreover, the friction and wear behavior of the UNSM-treated AISI H13 tool steel specimen was better than those of the untreated one. This study demonstrated the capability of 3D-printed AISI H13 tool steel to exhibit excellent mechanical and tribological properties for industrial applications.

  7. The Role of Surface Chemistry in Adhesion and Wetting of Gecko Toe Pads

    Science.gov (United States)

    Badge, Ila; Stark, Alyssa Y.; Paoloni, Eva L.; Niewiarowski, Peter H.; Dhinojwala, Ali

    2014-10-01

    An array of micron-sized setal hairs offers geckos a unique ability to walk on vertical surfaces using van der Waals interactions. Although many studies have focused on the role of surface morphology of the hairs, very little is known about the role of surface chemistry on wetting and adhesion. We expect that both surface chemistry and morphology are important, not only to achieve optimum dry adhesion but also for increased efficiency in self-cleaning of water and adhesion under wet conditions. Here, we used a plasma-based vapor deposition process to coat the hairy patterns on gecko toe pad sheds with polar and non-polar coatings without significantly perturbing the setal morphology. By a comparison of wetting across treatments, we show that the intrinsic surface of gecko setae has a water contact angle between 70-90°. As expected, under wet conditions, adhesion on a hydrophilic surface (glass) was lower than that on a hydrophobic surface (alkyl-silane monolayer on glass). Surprisingly under wet and dry conditions the adhesion was comparable on the hydrophobic surface, independent of the surface chemistry of the setal hairs. This work highlights the need to utilize morphology and surface chemistry in developing successful synthetic adhesives with desirable adhesion and self-cleaning properties.

  8. Analytical Chemistry of Surfaces: Part III. Ion Spectroscopy.

    Science.gov (United States)

    Hercules, David M.; Hercules, Shirley H.

    1984-01-01

    The fundamentals of two surface techniques--secondary-ion mass spectrometry (SIMS) and ion-scattering spectrometry (ISS)--are discussed. Examples of how these techniques have been applied to surface problems are provided. (JN)

  9. Cancer cell proliferation controlled by surface chemistry in its microenvironment

    Science.gov (United States)

    Yu, Xiao-Long; Zhang, Bin; Wang, Xiu-Mei; Wang, Ying; Qiao, Lin; He, Jin; Wang, Juan; Chen, Shuang-Feng; Lee, In-Seop; Cui, Fu-Zhai

    2011-12-01

    Hepatoma cells (Hepg2s) as typical cancer cells cultured on hydroxyl (-OH) and methyl (-CH3) group surfaces were shown to exhibit different proliferation and morphological changes. Hepg2s cells on -OH surfaces grew much more rapidly than those on -CH3 surfaces. Hepg2s cells on -OH surfaces had the larger contact area and the more flattened morphology, while those on -CH3 surfaces exhibited the smaller contact area and the more rounded morphology. After 7 days of culture, the migration of Hepg2s cells into clusters on the -CH3 surfaces behaved significantly slower than that on the -OH surfaces. These chemically modified surfaces exhibited regulation of Hepg2s cells on proliferation, adhesion, and migration, providing a potential treatment of liver cancer.

  10. Millimeter wave surface resistance of grain-aligned Y1Ba2Cu3O(x) bulk material

    International Nuclear Information System (INIS)

    Wosik, J.; Kranenburg, R.A.; Wolfe, J.C.; Selvamanickam, V.; Salama, K.

    1990-04-01

    Measurements are reported of the millimeter-wave surface resistance of grain-aligned YBa2Cu3O(x) bulk material grown by a liquid-phase process. The measurements were performed by replacing the endplate of a TE(011) cylindrical copper cavity with the superconducting sample. Surface resistance was measured for samples with surfaces oriented perpendicular and parallel to the c-axis of the grains. For the parallel configuration, the surface resistance at 77 K and 80 GHz is given. For a very well-aligned sample with a very low density of Y2BaCuO(y) precipitates, measured in the perpendicular configuration, the transition width (10-90 percent) is about 2 K and the surface resistance is derived at 88 K. The effect of microstructure on surface resistance is discussed. 19 refs

  11. Millimeter wave surface resistance of grain-aligned Y1Ba2Cu3O(x) bulk material

    Science.gov (United States)

    Wosik, J.; Kranenburg, R. A.; Wolfe, J. C.; Selvamanickam, V.; Salama, K.

    1991-01-01

    Measurements of the millimeter wave surface resistance of grain-aligned YBa2Cu3O(x) bulk material grown by a liquid phase process are reported. The measurements were performed by replacing the endplate of a TE011 cylindrical copper cavity with the superconducting sample. Surface resistance was measured for samples with surfaces oriented perpendicular and parallel to the c-axis of the grains. It is shown that, for the parallel configuration, the surface resistance at 77 K and 80 GHz is typically near 100 milliohms. For a very well-aligned sample with a very low density of Y2BaCuO(y) precipitates, measured in the perpendicular configuration, the transition width (10-90 percent) is about 2 K, and the surface resistance is less than 50 milliohms at 88 K. The effect of microstructure on surface resistance is discussed.

  12. Millimeter wave surface resistance of grain-aligned Y1Ba2Cu3Ox bulk material

    International Nuclear Information System (INIS)

    Wosik, J.; Kranenburg, R.A.; Wolfe, J.C.; Selvamanickam, V.; Salama, K.

    1991-01-01

    We report measurements of the millimeter wave surface resistance of grain-aligned YBa 2 Cu 3 O x bulk material grown by a liquid phase process. The measurements were performed by replacing the endplate of a TE 011 cylindrical copper cavity with the superconducting sample. Surface resistance was measured for samples with surfaces oriented perpendicular and parallel to the c-axis of the grains. We show that, for the parallel configuration, the surface resistance at 77 K and 80 GHz is typically near 100 mΩ. For a very well-aligned sample with a very low density of Y 2 BaCuO y precipitates, measured in the perpendicular configuration, the transition width (10%--90%) is about 2 K and the surface resistance is less than 50 mΩ at 88 K. The effect of microstructure on surface resistance is discussed

  13. Relationships Among Intrinsic Properties of Ordinary Chondrites: Oxidation State, Bulk Chemistry, Oxygen-isotopic Composition, Petrologic Type, and Chondrule Size

    Science.gov (United States)

    Rubin, Alan E.

    2006-01-01

    The properties of ordinary chondrites (OC) reflect both nebular and asteroidal processes. OC are modeled here as having acquired nebular water, probably contained within phyllosilicates, during agglomeration. This component had high Ai70 and acted like an oxidizing agent during thermal metamorphism. The nebular origin of this component is consistent with negative correlations in H, L, and LL chondrites between oxidation state (represented by olivine Fa) and bulk concentration ratios of elements involved in the metal-silicate fractionation (e.g., NdSi, Ir/Si, Ir/Mn, Ir/Cr, Ir/Mg, Ni/Mg, As/Mg, Ga/Mg). LL chondrites acquired the greatest abundance of phyllosilicates with high (delta)O-17 among OC (and thus became the most oxidized group and the one with the heaviest O isotopes); H chondrites acquired the lowest abundance, becoming the most reduced OC group with the lightest O isotopes. Chondrule precursors may have grown larger and more ferroan with time in each OC agglomeration zone. Nebular turbulence may have controlled the sizes of chondrule precursors. H-chondrite chondrules (which are the smallest among OC) formed from the smallest precursors. In each OC region, low-FeO chondrules formed before high-FeO chondrules during repeated episodes of chondrule formation. During thermal metamorphism, phyllosilicates were dehydrated; the liberated water oxidized metallic Fe-Ni. This caused correlated changes with petrologic type including decreases in the modal abundance of metal, increases in olivine Fa and low-Ca pyroxene Fs, increases in the olivine/pyroxene ratio, and increases in the kamacite Co and Ni contents. As water (with its heavy 0 isotopes) was lost during metamorphism, inverse correlations between bulk (delta)O-18 and bulk (delta)O-17 with petrologic type were produced. The H5 chondrites that were ejected from their parent body approx.7.5 Ma ago during a major impact event probably had been within a few kilometers of each other since they accreted approx.4

  14. Combined Bulk and Surface Radiation Damage Effects at Very High Fluences in Silicon Detectors: Measurements and TCAD Simulations

    CERN Document Server

    Moscatelli, F; Morozzi, A; Mendicino, R; Dalla Betta, G F; Bilei, G M

    2016-01-01

    In this work we propose a new combined TCAD radiation damage modelling scheme, featuring both bulk and surface radiation damage effects, for the analysis of silicon detectors aimed at the High Luminosity LHC. In particular, a surface damage model has been developed by introducing the relevant parameters (NOX, NIT) extracted from experimental measurements carried out on p-type substrate test structures after gamma irradiations at doses in the range 10-500 Mrad(Si). An extended bulk model, by considering impact ionization and deep-level cross-sections variation, was included as well. The model has been validated through the comparison of the simulation findings with experimental measurements carried out at very high fluences (2×1016 1 MeV equivalent n/cm2) thus fostering the application of this TCAD approach for the design and optimization of the new generation of silicon detectors to be used in future HEP experiments.

  15. The surface chemistry of metal-oxygen interactions

    DEFF Research Database (Denmark)

    Stokbro, Kurt; Baroni, Stefano

    1997-01-01

    We report on a computational study of the clean and oxygen-covered Rh(110) surface, based on density-functional theory within the local-density approximation. We have used plane-wave basis sets and Vanderbilt ultra-soft pseudopotentials. For the clean surface, we present results for the equilibrium...... structure, surface energy and surface stress of the unreconstructed and (1 x 2) reconstructed structures. For the oxygen-covered surface we have performed a geometry optimization at 0.5, 1, and 2 monolayer oxygen coverages, and we present results for the equilibrium configurations, workfunctions and oxygen...

  16. THE INTEGRATED USE OF COMPUTATIONAL CHEMISTRY, SCANNING PROBE MICROSCOPY, AND VIRTUAL REALITY TO PREDICT THE CHEMICAL REACTIVITY OF ENVIRONMENTAL SURFACES

    Science.gov (United States)

    In the last decade three new techniques scanning probe microscopy (SPM), virtual reality (YR) and computational chemistry ave emerged with the combined capability of a priori predicting the chemically reactivity of environmental surfaces. Computational chemistry provides the cap...

  17. Using advanced surface complexation models for modelling soil chemistry under forests: Solling forest, Germany

    International Nuclear Information System (INIS)

    Bonten, Luc T.C.; Groenenberg, Jan E.; Meesenburg, Henning; Vries, Wim de

    2011-01-01

    Various dynamic soil chemistry models have been developed to gain insight into impacts of atmospheric deposition of sulphur, nitrogen and other elements on soil and soil solution chemistry. Sorption parameters for anions and cations are generally calibrated for each site, which hampers extrapolation in space and time. On the other hand, recently developed surface complexation models (SCMs) have been successful in predicting ion sorption for static systems using generic parameter sets. This study reports the inclusion of an assemblage of these SCMs in the dynamic soil chemistry model SMARTml and applies this model to a spruce forest site in Solling Germany. Parameters for SCMs were taken from generic datasets and not calibrated. Nevertheless, modelling results for major elements matched observations well. Further, trace metals were included in the model, also using the existing framework of SCMs. The model predicted sorption for most trace elements well. - Highlights: → Surface complexation models can be well applied in field studies. → Soil chemistry under a forest site is adequately modelled using generic parameters. → The model is easily extended with extra elements within the existing framework. → Surface complexation models can show the linkages between major soil chemistry and trace element behaviour. - Surface complexation models with generic parameters make calibration of sorption superfluous in dynamic modelling of deposition impacts on soil chemistry under nature areas.

  18. Complex Surface Concentration Gradients by Stenciled "Electro Click Chemistry"

    DEFF Research Database (Denmark)

    Hansen, Thomas Steen; Lind, Johan Ulrik; Daugaard, Anders Egede

    2010-01-01

    Complex one- or two-dimensional concentration gradients of alkynated molecules are produced on azidized conducting polymer substrates by stenciled "electro click chemistry". The latter describes the local electrochemical generation of catalytically active Cu(I) required to complete a "click...... reaction" between alkynes and azides at room temperature. A stencil on the counter electrode defines the shape and multiplicity of the gradient(s) on the conducting polymer substrate, while the specific reaction conditions control gradient steepness and the maximum concentration deposited. Biologically...

  19. Chemistry

    International Nuclear Information System (INIS)

    Ferris, L.M.

    1975-01-01

    The chemical research and development efforts related to the design and ultimate operation of molten-salt breeder reactor systems are concentrated on fuel- and coolant-salt chemistry, including the development of analytical methods for use in these systems. The chemistry of tellurium in fuel salt is being studied to help elucidate the role of this element in the intergranular cracking of Hastelloy N. Studies were continued of the effect of oxygen-containing species on the equilibrium between dissolved UF 3 and dissolved UF 4 , and, in some cases, between the dissolved uranium fluorides and graphite, and the UC 2 . Several aspects of coolant-salt chemistry are under investigation. Hydroxy and oxy compounds that could be formed in molten NaBF 4 are being synthesized and characterized. Studies of the chemistry of chromium (III) compounds in fluoroborate melts were continued as part of a systematic investigation of the corrosion of structural alloys by coolant salt. An in-line voltammetric method for determining U 4+ /U 3+ ratios in fuel salt was tested in a forced-convection loop over a six-month period. (LK)

  20. New superjuction LDMOS with surface and bulk electric field modulation by buffered step doping and multi floating buried layers

    Science.gov (United States)

    Cao, Zhen; Duan, Baoxing; Yuan, Song; Shi, Tongtong; Yang, Yintang

    2017-11-01

    A new superjunction lateral double diffused MOSFET with surface and bulk electric field modulation (SBEFM SJ-LDMOS) by applying of multiple floating buried layers and buffered step doping is proposed in this paper. The Multiple N-type floating buried layers are embedded in P-substrate, to reduce the amount of field crowding at N+/N-buffer/P-substrate junction by spreading the vertical depletion layer, which effectively improves the bulk electric field distribution in SJ-LDMOS, and the N+/N-buffer/P-substrate junction and the auxiliary MFB layers/substrate junctions jointly sustain a high vertical breakdown voltage (BV). In addition, based on the buffered step doping layer under the SJ layer, a uniform lateral electric field at the drift region surface of the device is obtained. Therefore, the bulk and surface electric field are both optimized simultaneously in SBEFM SJ-LDMOS. Simulated results show that compared with the conventional Buffered SJ-LDMOS and BSD SJ-LDMOS, the proposed SBEFM SJ-LDMOS improves BV by 131.7% and 80.4%, respectively, at the same drift region length and with low specific ON-resistance (RON,sp). SBEFM SJ-LDMOS exhibits excellent performance with the power figure-of-merit (FOM=BV2/RON,sp) of 13.07 MW/cm2.

  1. Bulk and surface morphologies of ABC miktoarm star terpolymers comprised of PDMS, PI and PMMA arms

    DEFF Research Database (Denmark)

    Chernyy, Sergey; Kirkensgaard, Jacob Judas Kain; Mahalik, Jyoti P.

    2018-01-01

    . The thin film morphologies, which differ from those found in the bulk, were identified by scanning electron microscopy, coupled with oxygen plasma etching. Square arrays of the PDMS nanodots and empty core cylinders were formed on silica after oxygen plasma removal of the poly(1,4-isoprene) and poly...

  2. NOx Binding and Dissociation: Enhanced Ferroelectric Surface Chemistry by Catalytic Monolayers

    Science.gov (United States)

    Kakekhani, Arvin; Ismail-Beigi, Sohrab

    2013-03-01

    NOx molecules are regulated air pollutants produced during automotive combustion. As part of an effort to design viable catalysts for NOx decomposition operating at higher temperatures that would allow for improved fuel efficiency, we examine NOx chemistry on ferroelectric perovskite surfaces. Changing the direction of ferroelectric polarization can modify surface electronic properties and may lead to switchable surface chemistry. Here, we describe our recent work on potentially enhanced surface chemistry using catalytic RuO2 monolayers on perovskite ferroelectric substrates. In addition to thermodynamic stabilization of the RuO2 layer, we present results on the polarization-dependent binding of NO, O2, N2, and atomic O and N. We present results showing that one key problem with current catalysts, involving the difficulty of releasing dissociation products (especially oxygen), can be ameliorated by this method. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.

  3. Investigations of nitrogen oxide plasmas: Fundamental chemistry and surface reactivity and monitoring student perceptions in a general chemistry recitation

    Science.gov (United States)

    Blechle, Joshua M.

    Part I of this dissertation focuses on investigations of nitrogen oxide plasma systems. With increasing concerns over the environmental presence of NxOy species, there is growing interest in utilizing plasma-assisted conversion techniques. Advances, however, have been limited because of the lack of knowledge regarding the fundamental chemistry of these plasma systems. Understanding the kinetics and thermodynamics of processes in these systems is vital to realizing their potential in a range of applications. Unraveling the complex chemical nature of these systems, however, presents numerous challenges. As such, this work serves as a foundational step in the diagnostics and assessment of these NxOy plasmas. The partitioning of energy within the plasma system is essential to unraveling these complications as it provides insight into both gas and surface reactivity. To obtain this information, techniques such as optical emission spectroscopy (OES), broadband absorption spectroscopy (BAS), and laser induced fluorescence (LIF) were utilized to determine species energetics (vibrational, rotational, translational temperatures). These temperature data provide mechanistic insight and establish the relationships between system parameters and energetic outcomes. Additionally, these data are also correlated to surface reactivity data collected with the Imaging of Radicals Interacting with Surfaces (IRIS) technique. IRIS data demonstrate the relationship between internal temperatures of radicals and their observed surface scatter coefficients (S), the latter of which is directly related to surface reactivity (R) [R = 1-S]. Furthermore, time-resolved (TR) spectroscopic techniques, specifically TR-OES, revealed kinetic trends in NO and N2 formation from a range of precursors (NO, N2O, N2/O2). By examining the rate constants associated with the generation and destruction of various plasma species we can investigate possible mechanistic implications. All told, such data provides

  4. 3D Printed Potential and Free Energy Surfaces for Teaching Fundamental Concepts in Physical Chemistry

    Science.gov (United States)

    Kaliakin, Danil S.; Zaari, Ryan R.; Varganov, Sergey A.

    2015-01-01

    Teaching fundamental physical chemistry concepts such as the potential energy surface, transition state, and reaction path is a challenging task. The traditionally used oversimplified 2D representation of potential and free energy surfaces makes this task even more difficult and often confuses students. We show how this 2D representation can be…

  5. The role of electron scattering in electron-induced surface chemistry

    NARCIS (Netherlands)

    van Dorp, Willem F.

    2012-01-01

    Electron-induced chemistry on surfaces plays a key role in focused electron beam induced processing (FEBIP), a single-step lithography technique that has increasingly gained interest in the past decade. It is crucial for the understanding and modelling of this process to know the role of the surface

  6. Flame Treatment of Low-Density Polyethylene: Surface Chemistry Across the Length Scale

    NARCIS (Netherlands)

    Song, Jing; Gunst, Ullrich; Arlinghaus, Heinrich F.; Vancso, Gyula J.

    2007-01-01

    The relationship between surface chemistry and morphology of flame treated low-density polyethylene (LDPE) was studied by various characterization techniques across different length scales. The chemical composition of the surface was determined on the micrometer scale by X-ray photoelectron

  7. Rock-Eval analysis of French forest soils: the influence of depth, soil and vegetation types on SOC thermal stability and bulk chemistry

    Science.gov (United States)

    Soucemarianadin, Laure; Cécillon, Lauric; Baudin, François; Cecchini, Sébastien; Chenu, Claire; Mériguet, Jacques; Nicolas, Manuel; Savignac, Florence; Barré, Pierre

    2017-04-01

    Soil organic matter (SOM) is the largest terrestrial carbon pool and SOM degradation has multiple consequences on key ecosystem properties like nutrients cycling, soil emissions of greenhouse gases or carbon sequestration potential. With the strong feedbacks between SOM and climate change, it becomes particularly urgent to develop reliable routine methodologies capable of indicating the turnover time of soil organic carbon (SOC) stocks. Thermal analyses have been used to characterize SOM and among them, Rock-Eval 6 (RE6) analysis of soil has shown promising results in the determination of in-situ SOC biogeochemical stability. This technique combines a phase of pyrolysis followed by a phase of oxidation to provide information on both the SOC bulk chemistry and thermal stability. We analyzed with RE6 a set of 495 soils samples from 102 permanent forest sites of the French national network for the long-term monitoring of forest ecosystems (''RENECOFOR'' network). Along with covering pedoclimatic variability at a national level, these samples include a range of 5 depths up to 1 meter (0-10 cm, 10-20 cm, 20-40 cm, 40-80 cm and 80-100 cm). Using RE6 parameters that were previously shown to be correlated to short-term (hydrogen index, HI; T50 CH pyrolysis) or long-term (T50 CO2 oxidation and HI) SOC persistence, and that characterize SOM bulk chemical composition (oxygen index, OI and HI), we tested the influence of depth (n = 5), soil class (n = 6) and vegetation type (n = 3; deciduous, coniferous-fir, coniferous-pine) on SOM thermal stability and bulk chemistry. Results showed that depth was the dominant discriminating factor, affecting significantly all RE6 parameters. With depth, we observed a decrease of the thermally labile SOC pool and an increase of the thermally stable SOC pool, along with an oxidation and a depletion of hydrogen-rich moieties of the SOC. Soil class and vegetation type had contrasted effects on the RE6 parameters but both affected significantly T

  8. Geochemistry and Organic Chemistry on the Surface of Titan

    Science.gov (United States)

    Lunine, J. I.; Beauchamp, P.; Beauchamp, J.; Dougherty, D.; Welch, C.; Raulin, F.; Shapiro, R.; Smith, M.

    2001-01-01

    Titan's atmosphere produces a wealth of organic products from methane and nitrogen. These products, deposited on the surface in liquid and solid form, may interact with surface ices and energy sources to produce compounds of exobiological interest. Additional information is contained in the original extended abstract.

  9. Analytical Chemistry of Surfaces: Part II. Electron Spectroscopy.

    Science.gov (United States)

    Hercules, David M.; Hercules, Shirley H.

    1984-01-01

    Discusses two surface techniques: X-ray photoelectron spectroscopy (ESCA) and Auger electron spectroscopy (AES). Focuses on fundamental aspects of each technique, important features of instrumentation, and some examples of how ESCA and AES have been applied to analytical surface problems. (JN)

  10. Sampling procedure for lake or stream surface water chemistry

    Science.gov (United States)

    Robert Musselman

    2012-01-01

    Surface waters collected in the field for chemical analyses are easily contaminated. This research note presents a step-by-step detailed description of how to avoid sample contamination when field collecting, processing, and transporting surface water samples for laboratory analysis.

  11. In situ investigation of titanium nitride surface dynamics: The role of surface and bulk mass transport processes

    Science.gov (United States)

    Bareno, Javier

    NaCl-structure TiN and related transition-metal (TM) nitrides are widely used as hard wear-resistant coatings on cutting tools, diffusion-barriers in microelectronic devices, corrosion-resistant layers on mechanical components, and abrasion-resistant thin films on optics and architectural glass. Since the elastic and physical properties of TiN are highly anisotropic, controlling the microstructural and surface morphological evolution of polycrystalline TM nitride films is important for all of the above applications. In this thesis, I used in-situ high-temperature low-energy electron microscopy (LEEM) to gain insight into film growth and microstructure development dynamics by studying mass-transport processes occurring during annealing of three dimensional (3D) structures on TiN surfaces. Additionally, in order to extend the current understanding of nanostructure development in binary nitride films to more complex ternary TM-nitride-based nanocomposites, I employed in-situ scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED), as well as ab-initio modeling, to investigate the atomic structure of the SiNx/TiN heterointerfaces which control the properties of SiNx-TiN nanocomposites. The LEEM studies of mass transport on TiN(111) focus on two specific surface morphologies which are observed to be present during growth of TiN single-crystals. (1) I investigated the temperature-dependent coarsening/decay kinetics of three-dimensional TiN island mounds on large (>1000 A) atomically-flat terraces; showing that TiN(111) steps are highly permeable and exhibit strong repulsive temperature-dependent step-step interactions that vary from 0.03 eV-A at 1559 K to 0.76 eV-A at 1651 K. (2) I studied the nucleation and growth of spiral steps originating at surface-terminated screw dislocations; I developed a model of spiral growth relating the emission rate of point defects from the bulk to the temperature-dependent spiral rotation frequency o(T); and I

  12. Surface chemistry of a hydrogenated mesoporous p-type silicon

    Energy Technology Data Exchange (ETDEWEB)

    Media, El-Mahdi, E-mail: belhadidz@tahoo.fr; Outemzabet, Ratiba, E-mail: oratiba@hotmail.com

    2017-02-15

    Highlights: • Due to its large specific surface porous silicon is used as substrate for drug therapy and biosensors. • We highlight the evidency of the contribution of the hydrides (SiHx) in the formation of the porous silicon. • The responsible species in the porous silicon formation are identified and quantified at different conditions. • By some chemical treatments we show that silicon surface can be turn from hydrophobic to hydrophilic. - Abstract: The finality of this work is devoted to the grafting of organic molecules on hydrogen passivated mesoporous silicon surfaces. The study would aid in the development for the formation of organic monolayers on silicon surface to be exploited for different applications such as the realisation of biosensors and medical devices. The basic material is silicon which has been first investigated by FTIR at atomistic plane during the anodic forward and backward polarization (i.e. “go” and “return”). For this study, we applied a numerical program based on least squares method to infrared absorbance spectra obtained by an in situ attenuated total reflection on p-type silicon in diluted HF electrolyte. Our numerical treatment is based on the fitting of the different bands of IR absorbance into Gaussians corresponding to the different modes of vibration of molecular groups such as siloxanes and hydrides. An adjustment of these absorbance bands is done systematically. The areas under the fitted bands permit one to follow the intensity of the different modes of vibration that exist during the anodic forward and backward polarization in order to compare the reversibility of the phenomenon of the anodic dissolution of silicon. It permits also to follow the evolution between the hydrogen silicon termination at forward and backward scanning applied potential. Finally a comparison between the states of the initial and final surface was carried out. We confirm the presence of clearly four and three distinct vibration modes

  13. Surface chemistry interventions to control boiler tube fouling

    Energy Technology Data Exchange (ETDEWEB)

    Turner, C.W.; Guzonas, D.A.; Klimas, S.J

    2000-06-01

    The adsorption of ammonia, morpholine, ethanolamine, and dimethylamine onto the surfaces of colloidal magnetite and hematite was measured at 25{sup o}C. The effect of the adsorption on the surface potential was quantified by measuring the resulting shift in the isoelectric point of the corrosion products and by the direct measurement of the surface interaction force between the corrosion products and Inconel 600. These measurements have served to support the hypothesis that adsorption of amine affects the magnetite deposition rate by lowering the force of repulsion between magnetite and the surface of Inconel 600. The deposition rate of hematite increased as the oxygen concentration increased. A mechanism to account for enhanced deposition rates at high mixture qualities (> 0.35) has been identified and shown to predict behaviour that is consistent with both experimental and plant data. As a result of this investigation, several criteria are proposed to reduce the extent of corrosion product deposition on the tube bundle. Low hematite deposition is favoured by a low concentration of dissolved oxygen, and low magnetite deposition is favoured by choosing an amine for pH control that has little tendency to adsorb onto the surface of magnetite. To minimize adsorption the amine should have a high base strength and a large 'footprint' on the surface of magnetite. To prevent enhanced deposition at high mixture qualities, it is proposed that a modified amine be used that will reduce the surface tension or the elasticity of the steam-water interface or both.

  14. Surface chemistry interventions to control boiler tube fouling

    International Nuclear Information System (INIS)

    Turner, C.W.; Guzonas, D.A.; Klimas, S.J.

    2000-06-01

    The adsorption of ammonia, morpholine, ethanolamine, and dimethylamine onto the surfaces of colloidal magnetite and hematite was measured at 25 o C. The effect of the adsorption on the surface potential was quantified by measuring the resulting shift in the isoelectric point of the corrosion products and by the direct measurement of the surface interaction force between the corrosion products and Inconel 600. These measurements have served to support the hypothesis that adsorption of amine affects the magnetite deposition rate by lowering the force of repulsion between magnetite and the surface of Inconel 600. The deposition rate of hematite increased as the oxygen concentration increased. A mechanism to account for enhanced deposition rates at high mixture qualities (> 0.35) has been identified and shown to predict behaviour that is consistent with both experimental and plant data. As a result of this investigation, several criteria are proposed to reduce the extent of corrosion product deposition on the tube bundle. Low hematite deposition is favoured by a low concentration of dissolved oxygen, and low magnetite deposition is favoured by choosing an amine for pH control that has little tendency to adsorb onto the surface of magnetite. To minimize adsorption the amine should have a high base strength and a large 'footprint' on the surface of magnetite. To prevent enhanced deposition at high mixture qualities, it is proposed that a modified amine be used that will reduce the surface tension or the elasticity of the steam-water interface or both

  15. The Effect of Bulk Depth and Irradiation Time on the Surface Hardness and Degree of Cure of Bulk-Fill Composites

    Directory of Open Access Journals (Sweden)

    Farahat F

    2016-09-01

    Full Text Available Statement of Problem: For many years, application of the composite restoration with a thickness less than 2 mm for achieving the minimum polymerization contraction and stress has been accepted as a principle. But through the recent development in dental material a group of resin based composites (RBCs called Bulk Fill is introduced whose producers claim the possibility of achieving a good restoration in bulks with depths of 4 or even 5 mm. Objectives: To evaluate the effect of irradiation times and bulk depths on the degree of cure (DC of a bulk fill composite and compare it with the universal type. Materials and Methods: This study was conducted on two groups of dental RBCs including Tetric N Ceram Bulk Fill and Tetric N Ceram Universal. The composite samples were prepared in Teflon moulds with a diameter of 5 mm and height of 2, 4 and 6 mm. Then, half of the samples in each depth were cured from the upper side of the mould for 20s by LED light curing unit. The irradiation time for other specimens was 40s. After 24 hours of storage in distilled water, the microhardness of the top and bottom of the samples was measured using a Future Tech (Japan- Model FM 700 Vickers hardness testing machine. Data were analyzed statistically using the one and multi way ANOVAand Tukey’s test (p = 0.050. Results: The DC of Tetric N Ceram Bulk Fill in defined irradiation time and bulk depth was significantly more than the universal type (p < 0.001. Also, the DC of both composites studied was significantly (p < 0.001 reduced by increasing the bulk depths. Increasing the curing time from 20 to 40 seconds had a marginally significant effect (p ≤ 0.040 on the DC of both bulk fill and universal studied RBC samples. Conclusions: The DC of the investigated bulk fill composite was better than the universal type in all the irradiation times and bulk depths. The studied universal and bulk fill RBCs had an appropriate DC at the 2 and 4 mm bulk depths respectively and

  16. Plasma Processing with Fluorine Chemistry for Modification of Surfaces Wettability

    Directory of Open Access Journals (Sweden)

    Veronica Satulu

    2016-12-01

    Full Text Available Using plasma in conjunction with fluorinated compounds is widely encountered in material processing. We discuss several plasma techniques for surface fluorination: deposition of fluorocarbon thin films either by magnetron sputtering of polytetrafluoroethylene targets, or by plasma-assisted chemical vapor deposition using tetrafluoroethane as a precursor, and modification of carbon nanowalls by plasma treatment in a sulphur hexafluoride environment. We showed that conformal fluorinated thin films can be obtained and, according to the initial surface properties, superhydrophobic surfaces can be achieved.

  17. Surface chemistry controls crystallinity of ZnS nanoparticles.

    Science.gov (United States)

    Gilbert, Benjamin; Huang, Feng; Lin, Zhang; Goodell, Carmen; Zhang, Hengzhong; Banfield, Jillian F

    2006-04-01

    Combined small-angle and high energy wide-angle X-ray scattering measurements of nanoparticle size and structure permit interior strain and disorder to be observed directly in the real-space pair distribution function (PDF). PDF analysis showed that samples of ZnS nanoparticles with similar mean diameters (3.2-3.6 nm) but synthesized and treated with different low-temperature procedures possess a dramatic range of interior disorder. We used Fourier transform infrared spectroscopy to detect the surface species and the nature of surface chemical interactions. Our results suggest that there is a direct correlation between the strength of surface-ligand interactions and interior crystallinity.

  18. Impact of Molecular Orientation and Packing Density on Electronic Polarization in the Bulk and at Surfaces of Organic Semiconductors

    KAUST Repository

    Ryno, Sean

    2016-05-16

    The polarizable environment surrounding charge carriers in organic semiconductors impacts the efficiency of the charge transport process. Here, we consider two representative organic semiconductors, tetracene and rubrene, and evaluate their polarization energies in the bulk and at the organic-vacuum interface using a polarizable force field that accounts for induced-dipole and quadrupole interactions. Though both oligoacenes pack in a herringbone motif, the tetraphenyl substituents on the tetracene backbone of rubrene alter greatly the nature of the packing. The resulting change in relative orientations of neighboring molecules is found to reduce the bulk polarization energy of holes in rubrene by some 0.3 eV when compared to tetracene. The consideration of model organic-vacuum interfaces highlights the significant variation in the electrostatic environment for a charge carrier at a surface although the net change in polarization energy is small; interestingly, the environment of a charge even just one layer removed from the surface can be viewed already as representative of the bulk. Overall, it is found that in these herringbone-type layered crystals the polarization energy has a much stronger dependence on the intralayer packing density than interlayer packing density.

  19. Spin-orbit torque in 3D topological insulator-ferromagnet heterostructure: crossover between bulk and surface transport

    KAUST Repository

    Ghosh, Sumit

    2017-11-29

    Current-driven spin-orbit torques are investigated in a heterostructure composed of a ferromagnet deposited on top of a three dimensional topological insulator using the linear response formalism. We develop a tight-binding model of the heterostructure adopting a minimal interfacial hybridization scheme that promotes induced magnetic exchange on the topological surface states, as well as induced Rashba-like spin-orbit coupling in the ferromagnet. Therefore, our model accounts for spin Hall effect from bulk states together with inverse spin galvanic and magnetoelectric effects at the interface on equal footing. By varying the transport energy across the band structure, we uncover a crossover from surface-dominated to bulk-dominated transport regimes. We show that the spin density profile and the nature of the spin-orbit torques differ substantially in both regimes. Our results, which compare favorably with experimental observations, demonstrate that the large damping torque reported recently is more likely attributed to interfacial magnetoelectric effect, while spin Hall torque remains small even in the bulk-dominated regime.

  20. Spin-orbit torque in a three-dimensional topological insulator–ferromagnet heterostructure: Crossover between bulk and surface transport

    KAUST Repository

    Ghosh, Sumit

    2018-04-02

    Current-driven spin-orbit torques are investigated in a heterostructure composed of a ferromagnet deposited on top of a three-dimensional topological insulator using the linear response formalism. We develop a tight-binding model of the heterostructure adopting a minimal interfacial hybridization scheme that promotes induced magnetic exchange on the topological surface states, as well as induced Rashba-like spin-orbit coupling in the ferromagnet. Therefore our model accounts for the spin Hall effect from bulk states together with inverse spin galvanic and magnetoelectric effects at the interface on equal footing. By varying the transport energy across the band structure, we uncover a crossover from surface-dominated to bulk-dominated transport regimes. We show that the spin density profile and the nature of the spin-orbit torques differ substantially in both regimes. Our results, which compare favorably with experimental observations, demonstrate that the large dampinglike torque reported recently is more likely attributed to the Berry curvature of interfacial states, while spin Hall torque remains small even in the bulk-dominated regime.

  1. Role of the substrate reflectance and surface-bulk treatments in CsI quantum efficiency

    CERN Document Server

    Singh, B K; Nitti, M A; Valentini, A

    2003-01-01

    We have experimentally investigated the following aspects related to the quantum efficiency of CsI photocathodes: the type of substrate, the film thickness and the effect of a 'bulk treatment' during the film growth. We discovered that, using a high reflectivity aluminium substrate, the photoemission of very thin CsI film is enhanced. Our study also revealed that photocathodes become less sensitive to moisture when a negative bias voltage is applied to the substrate during the film deposition process.

  2. Reaction chemistry and ligand exchange at cadmium selenide nanocrystal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Owen, Jonathan; Park, Jungwon; Trudeau, Paul-Emile; Alivisatos, A. Paul

    2008-12-02

    Chemical modification of nanocrystal surfaces is fundamentally important to their assembly, their implementation in biology and medicine, and greatly impacts their electrical and optical properties. However, it remains a major challenge owing to a lack of analytical tools to directly determine nanoparticle surface structure. Early nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) studies of CdSe nanocrystals prepared in tri-n-octylphosphine oxide (1) and tri-n-octylphosphine (2), suggested these coordinating solvents are datively bound to the particle surface. However, assigning the broad NMR resonances of surface-bound ligands is complicated by significant concentrations of phosphorus-containing impurities in commercial sources of 1, and XPS provides only limited information about the nature of the phosphorus containing molecules in the sample. More recent reports have shown the surface ligands of CdSe nanocrystals prepared in technical grade 1, and in the presence of alkylphosphonic acids, include phosphonic and phosphinic acids. These studies do not, however, distinguish whether these ligands are bound datively, as neutral, L-type ligands, or by X-type interaction of an anionic phosphonate/phosphinate moiety with a surface Cd{sup 2+} ion. Answering this question would help clarify why ligand exchange with such particles does not proceed generally as expected based on a L-type ligand model. By using reagents with reactive silicon-chalcogen and silicon-chlorine bonds to cleave the ligands from the nanocrystal surface, we show that our CdSe and CdSe/ZnS core-shell nanocrystal surfaces are likely terminated by X-type binding of alkylphosphonate ligands to a layer of Cd{sup 2+}/Zn{sup 2+} ions, rather than by dative interactions. Further, we provide spectroscopic evidence that 1 and 2 are not coordinated to our purified nanocrystals.

  3. Attachment chemistry of aromatic compounds on a Silicon(100) surface

    Science.gov (United States)

    Henriksson, Anders; Nishiori, Daiki; Maeda, Hiroaki; Miyachi, Mariko; Yamanoi, Yoshinori; Nishihara, Hiroshi

    2018-03-01

    A mild method was developed for the chemical attachment of aromatic compounds directly onto a hydrogen-terminated Si(100) (H-Si(100)) surface. In the presence of palladium catalyst and base, 4-iodophenylferrocene and a π-conjugated iron complex were attached to H-Si(100) electrodes and hydrogen-terminated silicon nanowires (H-SiNWs), both of which have predominant dihydride species on their surfaces. The reactions were conducted in 1,4-dioxane at 100 °C and the immobilization of both 4-ferrocenylphenyl group and π-conjugated molecular wires were confirmed and quantified by XPS and electrochemical measurements. We reported densely packed monolayer whose surface coverage (Γ), estimated from the electrochemical measurements are in analogue to similar monolayers prepared via thermal or light induced hydrosilylation reactions with alkenes or alkynes. The increase in electrochemical response observed on nanostructured silicon surfaces corresponds well to the increase in surface area, those strongly indicating that this method may be applied for the functionalization of electrodes with a variety of surface topographies.

  4. A comparative study on optical and magnetic resonance properties of near-surface NV centers in nano and bulk diamond

    International Nuclear Information System (INIS)

    Frederico Brandao

    2014-01-01

    Using shallow nitrogen-vacancy (NV) centers in diamond for applications in magnetometry requires the generation of stable defects in the NV charge state in sufficiently high density and high quality spin properties. Recent studies reported about NV defects close to the surface created by ion implantation or during chemical vapor deposition growth technique and in nanodiamonds point to a scenario where defects are stabilized in the neutral charge state and that the minority of negatively charged state defects have poor spin properties, i.e.g shorter coherence times compared to NV defects deeply localized in bulk diamond. This undesirable behavior appears to result from the interaction with rapidly fluctuating electric fields created by moving charges at the surface and with interface effects associated with the termination of the diamond surface. Here we report studies of photoluminescence and magnetic resonance properties of shallow NV ensembles created by low energy nitrogen ion implantation in electronic grade diamond substrate and nanodiamonds with low nitrogen concentration. We verified the shallow NV center spin properties through pulsed optically detected magnetic resonance (ODMR) protocols and found longitudinal time constant (T1) of a few milliseconds and transversal relaxation time constant (T2) of a few microseconds for shallow defects implanted in bulk diamond. For nanodiamonds, the T2 coherence time is similar to the case in bulk sample but on the other hand the T1 coherence time is ten times shorter than in bulk. Additionally was found the T2* is around one microsecond for shallow NV defects in bulk samples meanwhile in nanodiamonds it is around twenty nanoseconds. It worth to mention that all the measurements were performed in NV ensembles which show just two ODMR resonance lines with applied magnetic field as if they were magnetically equivalent. In that sense we are trying to apply chirped pulses and Ramsey pulse sequence to check this assumption

  5. Surface and bulk investigation of ZSM5 and Al-MCM-41 usingsynchrotron XPS, XANES, and hexane cracking

    Energy Technology Data Exchange (ETDEWEB)

    Jalil, P.A.; Kariapper, M.S.; Faiz, Z.; Tabet, N.; Hamdan, N.M.; Diaz, J.; Hussain, Z.

    2005-05-12

    We present a comparative study of ZSM5 and Al-MCM-41 catalysts using spectroscopic and chemical techniques. The analysis of conventional and synchrotron XPS spectra of these catalysts reveals the presence of a topmost surface-related Si peak in addition to the bulk peak. XANES results suggest structural modification upon heating Al-MCM-41 at 500 C. Depth-resolved XPS data show Al depletion from the surface of Al-MCM-41 in contrast to surface enrichment of Al in ZSM5. These surface modifications could be one of the reasons for the weak acidity of Al-MCM-41 in chemical reactions such as hexane cracking at different temperatures.

  6. Affinity Induced Surface Functionalization of Liposomes Using Cu-Free Click Chemistry

    DEFF Research Database (Denmark)

    Bak, Martin; Jølck, Rasmus Irming; Eliasen, Rasmus

    2016-01-01

    be used for functionalization of other nanoparticles or solid surfaces. The method exploits a synergistic effect of having both affinity and covalent anchoring tags on the surface of the liposome. This was achieved by synthesizing a peptide linker system that uses Cu-free strain-promoted click chemistry.......2%. The reaction kinetics and overall yield were quantified by HPLC. The results presented here open new possibilities for constructing complex nanostructures and functionalized surfaces....

  7. Rate equation model of bulk optical damage of silica, and the influence of polishing on surface optical damage of silica

    Science.gov (United States)

    Smith, Arlee; Do, Binh; Schuster, Rod; Collier, David

    2008-02-01

    Our objective is to understand the mechanism that generates catastrophic optical damage in pulsed fiber amplifiers. We measured optical damage thresholds of bulk fused silica at 1064 nm for 8 ns and 14 ps pulses. The 8 ns pulse is single longitudinal mode from a Q-switched laser, and the 14 ps pulse is from a Q-switched mode-lock laser. The beams in both cases are TEM 00 mode, and they are focused to a 7.5 μm spot inside a fused silica window. The pulse-to-pulse energy variations are 1% for 8 ns pulses and 5% for 14 ps pulses. Under these conditions optical damage is always accompanied by plasma formation at the focal spot; we found the damage threshold fluences are 3854 +/- 85 J/cm2 for the 8 ns pulses and 25.4 +/- 1.0 J/cm2 for the 14 ps pulses. These fluences are corrected for self focusing. Both damage thresholds are deterministic, in contrast to the claim often made in the literature that optical damage is statistical in the nanosecond range. The measured damage threshold fluences for 8 ns and 14 ps pulses do not fit a square root of pulse duration scaling rule. We interpret the damage in terms of plasma formation initiated by multiphoton ionization and amplified by an electron avalanche. The damage threshold irradiance can be matched with a simple rate equation model that includes multiphoton ionization, electron avalanche, and electron-hole recombination. The damage morphologies are dramatically different in the nanosecond and picosecond cases because of the large difference in deposited energy. However, both morphologies are reproducible from pulse to pulse. We also measured surface damage thresholds for silica windows polished by different methods. We find that cerium oxide polished surfaces damage at approximately 40% of the bulk threshold, with a large statistical spread. Surfaces prepared using an Al IIO 3 polish damaged between 50% and 100% of the bulk damage limit, with a substantial fraction at 100%. Surfaces polished using first the Al IIO 3 polish

  8. Surface chemistry and morphology in single particle optical imaging

    Science.gov (United States)

    Ekiz-Kanik, Fulya; Sevenler, Derin Deniz; Ünlü, Neşe Lortlar; Chiari, Marcella; Ünlü, M. Selim

    2017-05-01

    Biological nanoparticles such as viruses and exosomes are important biomarkers for a range of medical conditions, from infectious diseases to cancer. Biological sensors that detect whole viruses and exosomes with high specificity, yet without additional labeling, are promising because they reduce the complexity of sample preparation and may improve measurement quality by retaining information about nanoscale physical structure of the bio-nanoparticle (BNP). Towards this end, a variety of BNP biosensor technologies have been developed, several of which are capable of enumerating the precise number of detected viruses or exosomes and analyzing physical properties of each individual particle. Optical imaging techniques are promising candidates among broad range of label-free nanoparticle detectors. These imaging BNP sensors detect the binding of single nanoparticles on a flat surface functionalized with a specific capture molecule or an array of multiplexed capture probes. The functionalization step confers all molecular specificity for the sensor's target but can introduce an unforeseen problem; a rough and inhomogeneous surface coating can be a source of noise, as these sensors detect small local changes in optical refractive index. In this paper, we review several optical technologies for label-free BNP detectors with a focus on imaging systems. We compare the surface-imaging methods including dark-field, surface plasmon resonance imaging and interference reflectance imaging. We discuss the importance of ensuring consistently uniform and smooth surface coatings of capture molecules for these types of biosensors and finally summarize several methods that have been developed towards addressing this challenge.

  9. Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

    International Nuclear Information System (INIS)

    Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing; Gong, Yongkuan

    2016-01-01

    Highlights: • Biomimetic surface modification of PP was successfully conducted by integrating mussel-inspired technology, thiol chemistry and cell outer membranes-like structures. • The resultant biomimetic surface exhibits good interface and surface stability. • The obvious suppression of protein adsorption and platelet adhesion is also achieved. • The residue thoil groups on the surface could be further functionalized. - Abstract: Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH 2 ) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such

  10. Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing, E-mail: shisq@nwu.edu.cn; Gong, Yongkuan

    2016-11-15

    Highlights: • Biomimetic surface modification of PP was successfully conducted by integrating mussel-inspired technology, thiol chemistry and cell outer membranes-like structures. • The resultant biomimetic surface exhibits good interface and surface stability. • The obvious suppression of protein adsorption and platelet adhesion is also achieved. • The residue thoil groups on the surface could be further functionalized. - Abstract: Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH{sub 2}) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such

  11. Importance of the carbon surface chemistry: methods of characterization; Importance de la chimie de surface des materiaux carbones

    Energy Technology Data Exchange (ETDEWEB)

    Burg, Ph. [Universite Paul Verlaine, Lab. de Chimie et Applications, UFR Sciences, 57 - Metz (France); Vix-Guterl, C. [Centre National de la Recherche Scientifique, Institut de Chimie des Surfaces et Interfaces (ICSI) UPR CNRS 9069, 68 - Mulhouse (France)

    2006-03-15

    The diversity of the carbonaceous materials in terms of chemical composition and porous texture explains their large field of applications. The performances of such materials are often influenced by their surface chemistry that is not easy to investigate. Thus a large range of complementary analytical methods is necessary. (authors)

  12. Understanding colloidal charge renormalization from surface chemistry: Experiment and theory

    Science.gov (United States)

    Gisler, T.; Schulz, S. F.; Borkovec, M.; Sticher, H.; Schurtenberger, P.; D'Aguanno, B.; Klein, R.

    1994-12-01

    In this paper we report on the charging behavior of latex particles in aqueous suspensions. We use static light scattering and acid-base titrations as complementary techniques to observe both effective and bare particle charges. Acid-base titrations at various ionic strengths provide the pH dependent charging curves. The surface chemical parameters (dissociation constant of the acidic carboxylic groups, total density of ionizable sites and Stern capacitance) are determined from fits of a Stern layer model to the titration data. We find strong evidence that the dissociation of protons is the only specific adsorption process. Effective particle charges are determined by fits of integral equation calculations of the polydisperse static structure factor to the static light scattering data. A generalization of the Poisson-Boltzmann cell model including the dissociation of the acidic surface groups and the autodissociation of water is used to predict effective particle charges from the surface chemical parameters determined by the titration experiments. We find that the light scattering data are best described by a model where a small fraction of the ionizable surface sites are sulfate groups which are completely dissociated at moderate pH. These effective charges are comparable to the predictions by a basic cell model where charge regulation is absent.

  13. Progression towards optimization of viscosity of highly concentrated carbonaceous solid-water slurries by incorporating and modifying surface chemistry parameters with and without additives

    Science.gov (United States)

    Mukherjee, Amrita

    electrostatic interaction energy, and the van der Waals interaction energy, was clearly the dominant interaction energy for such a system. Hydrophobic interactions lead to the formation of aggregation networks of solids in the suspensions, entrapping a part of the bulk water, whereas hydrophilic interactions result in the formation of hydration layers around carbonaceous solids. Both of these phenomena cause a loss of bulk water from the slurry and increase the effective solid volume fraction, resulting in an increase in slurry viscosity. The water in the bulk of the slurry, responsible for the fluidity of the slurry is called free water. The amount of free water was determined using thermogravimetric analysis and was observed to increase with an increase in the O/C ratio of a carbonaceous solid (up to ˜20%). The free water to total water ratio was observed to be constant for the slurry of a particular carbonaceous solid for various loadings of solids (44 wt.% to 67 wt.%). The increase in the effective solid volume fractions of slurries was determined using viscosity measurements. A relationship between the effective solid volume fraction and the O/C ratio of the carbonaceous solid was developed. This correlation was then incorporated into the existing equation for viscosity prediction (developed based on particle size distribution and solid volume fraction), to account for the surface chemistry of the carbonaceous solid and hence improve the predictive capabilities. This modified equation was validated using three concentrated carbonaceous slurries with different particle size distributions and was observed to significantly improve accuracy of prediction (deviation of predicted results decreased from up to 96% to 25%). The validation was performed with a lignite, bituminous coal and a petcoke-all with low ash yield. Additives modify the surface chemistry of the carbonaceous solids, thereby affecting the interfacial interactions. Through this research, the effects of additives

  14. Nanocrystalline Sm{sub 0.5}Sr{sub 0.5}CoO{sub 3−δ} synthesized using a chelating route for use in IT-SOFC cathodes: Microstructure, surface chemistry and electrical conductivity

    Energy Technology Data Exchange (ETDEWEB)

    Scurtu, Rares [“IlieMurgulescu” Institute of Physical Chemistry, Romanian Academy, 202 SplaiulIndependentei, 060021 Bucharest (Romania); Romania National Institute for Research and Development in Microtechnologies(IMT), 023573 Bucharest (Romania); Somacescu, Simona, E-mail: ssimona@icf.ro [“IlieMurgulescu” Institute of Physical Chemistry, Romanian Academy, 202 SplaiulIndependentei, 060021 Bucharest (Romania); Calderon-Moreno, Jose Maria; Culita, Daniela [“IlieMurgulescu” Institute of Physical Chemistry, Romanian Academy, 202 SplaiulIndependentei, 060021 Bucharest (Romania); Bulimestru, Ion; Popa, Nelea; Gulea, Aurelian [Faculty of Chemistry and Chemical Technology State University of Moldova 60 Mateevici, Chisinau MD 2009 Republic of Moldova (Moldova, Republic of); Osiceanu, Petre [“IlieMurgulescu” Institute of Physical Chemistry, Romanian Academy, 202 SplaiulIndependentei, 060021 Bucharest (Romania)

    2014-02-15

    Nanocrystalline Sm{sub 0.5}Sr{sub 0.5}CoO{sub 3−δ} powders were synthesized by a chelating route using different polyfunctional H{sub x}APC acids (APC=aminopolycarboxylate; x=3, 4, 5). Different homologous aminopolycarboxylic acids, namely nitrilotriacetic (H{sub 3}nta), ethylenediaminetetraacetic (H{sub 4}edta), 1,2-cyclohexanediaminetetracetic (H{sub 4}cdta) and diethylenetriaminepentaacetic (H{sub 5}dtpa) acid, were used as chelating agents to combine Sm, Sr, Co elements into a perovskite structure. The effects of the chelating agents on the crystalline structure, porosity, surface chemistry and electrical properties were investigated. The electrical properties of the perovskite-type materials emphasized that their conductivities in the temperature range of interest (600–800 °C) depend on the nature of the precursors as well as on the presence of a residual Co oxide phase as shown by XRD and XPS analysis. The surface chemistry and the surface stoichiometries were determined by XPS revealing a complex chemical behavior of Sr that exhibits a peculiar “surface phase” and “bulk phase” chemistry within the detected volume (<10 nm). - Graphical abstract: Synthesis of nanocrystalline Sm{sub 0.5}Sr{sub 0.5}CoO{sub 3−δ} powders by a chelating route and the investigation of the microstructure, surface chemistry and electrical properties. Display Omitted - Highlights: • Nanocrystalline Sm{sub 0.5}Sr{sub 0.5}CoO{sub 3−δ} obtained by a chelating synthesis route. • Cubic perovskite structures with crystallite sizes ∼23±2 nm. • The porous nature revealed by N{sub 2} adsorption/desorption (BET). • The surface chemistry and the surface stoichiometries highlighted by XPS. • A complex chemical behavior of Sr exhibits a peculiar “surface phase” and “bulk phase” chemistry.

  15. In-plume gas scavenging: Insights into gas adsorption, ash-surface chemistry and the role of water

    Science.gov (United States)

    Casas, Ana S.; Wadsworth, Fabian; Ayris, Paul M.; Cimarelli, Corrado; Dingwell, Donald B.

    2017-04-01

    In-plume gas scavenging-processes are well known to occur in large volcanic eruptions, where, over the range of plume conditions (temperature and gas composition) and physicochemical ash-surface properties, volcanic gases (mainly SO2, HCl, and HF) can be sequestrated by the occurrence (alone or combined) of three processes: (1) salt deposition, (2) adsorption, or (3) acidic liquid condensation on the ash-surface. Several studies have sought to constrain the diffusion-driven mechanisms through which scavenging occurs, the optimal temperatures for efficient scavenging, and the likely reaction products formed. Here we bolster these datasets with new high-resolution experimental work. Our current project additionally seeks to identify the role of water vapour in gas scavenging processes using a time- and temperature- series of experiments with well-characterized ash samples, for which, particle size distribution, surface area, and bulk chemistry were constrained. These samples will be exposed to various hydrous and anhydrous gas atmospheres with proportions of some plume-relevant gas mixtures (SO2, SO2-H2O) at high temperatures (200 to 800 °C) for various time series (1 to 60 min.) in the Advanced Ash-Gas Reactor (AGAR) available at the LMU chemistry laboratory. Post-experimental samples are analyzed by standard leachate techniques. We show that a diffusion-controlled sequestration mechanism will be strongly temperature dependent proportional to the diffusivity of the mobile species. In complex mixtures of gases, which could result in the diffusion of more than a single species, it remains to be tested whether simple diffusion models can yield average sequestration volumes. This will be tested explicitly using simple diffusion time scaling laws. Future work should target the additional combined effects of HCl, SO2 and H2O in more realistic complex volcanic atmospheres.

  16. Friction and surface chemistry of some ferrous-base metallic glasses

    Science.gov (United States)

    Miyoshi, K.; Buckley, D. H.

    1982-01-01

    The friction properties of some ferrous-base metallic glasses were measured both in argon and in vacuum to a temperature of 350 C. The alloy surfaces were also analyzed with X-ray photoelectron spectroscopy to identify the compounds and elements present on the surface. The results of the investigation indicate that even when the surfaces of the amorphous alloys, or metallic glasses, are atomically clean, bulk contaminants such as boric oxide and silicon dioxide diffuse to the surfaces. Friction measurements in both argon and vacuum indicate that the alloys exhibit higher coefficients of friction in the crystalline state than they do in the amorphous state.

  17. Understanding colloidal charge renormilization from surface chemistry : experiment and theory

    OpenAIRE

    Gisler, Thomas; Schulz, S. F.; Borkovec, Michal; Sticher, Hans; Schurtenberger, Peter; D'Aguanno, Bruno; Klein, Rudolf

    1994-01-01

    In this paper we report on the charging behavior of latex particles in aqueous suspensions. We use static light scattering and acid-base titrations as complementary techniques to observe both effective and bare particle charges. Acid-base titrations at various ionic strengths provide the pH dependent charging curves. The surface chemical parameters (dissociation constant of the acidic carboxylic groups, total density of ionizable sites and Stem capacitance) are determined from tits of a Stem ...

  18. Self-organizing cyclolinear organosilicon polymers in bulk and on the surface of water.

    Science.gov (United States)

    Makarova, Nataliya N; Astapova, Tat'yana V; Buzin, Alexander I; Polishchuk, Arkady P; Chizhova, Nataliya V; Petrova, Irina M

    2013-09-05

    Cyclolinear organocarbosiloxane polymers with varying content and location of (CH2)n groups in the monomer unit were synthesized by reactions of heterofunctional polycondensation and polyaddition of difunctional organocyclosiloxanes and organocyclocarbosiloxanes. Their bulk properties were studied by differential scanning calorimetry and X-ray structural analysis. It was shown that on introduction of CH2 groups into the methylcyclohexasiloxane unit, the polymer retains the ability to self-organize with formation of a mesomorphic state in a wide temperature range, while on introduction of (CH2)2 fragments in a cyclotetrasiloxane unit or in a bridge connecting two methylcyclotetra(hexa)siloxane units it does not. Comparison of the X-ray data of dihydroxy derivatives of decamethylcyclohexasiloxane and decamethyl-5-carbocyclohexasiloxane with packing of cyclolinear organosilicon polymers in bulk shows that the polymer inherits the layered type of crystalline structure typical for monomers. Langmuir films of cyclolinear polymethylcarbosiloxanes with different design of monomer units were studied as well. It was revealed that all polymers form monomolecular films at the air/water interface, excluding those having longer hydrophobic fragment than hydrophilic ones. The ability to form multilayers depends on the surroundings of Si atom in the bridge between the cycles.

  19. Surface modification of model hydrogel contact lenses with hyaluronic acid via thiol-ene "click" chemistry for enhancing surface characteristics.

    Science.gov (United States)

    Korogiannaki, Myrto; Zhang, Jianfeng; Sheardown, Heather

    2017-10-01

    Discontinuation of contact lens wear as a result of ocular dryness and discomfort is extremely common; as many as 26% of contact lens wearers discontinue use within the first year. While patients are generally satisfied with conventional hydrogel lenses, improving on-eye comfort continues to remain a goal. Surface modification with a biomimetic, ocular friendly hydrophilic layer of a wetting agent is hypothesized to improve the interfacial interactions of the contact lens with the ocular surface. In this work, the synthesis and characterization of poly(2-hydroxyethyl methacrylate) surfaces grafted with a hydrophilic layer of hyaluronic acid are described. The immobilization reaction involved the covalent attachment of thiolated hyaluronic acid (20 kDa) on acrylated poly(2-hydroxyethyl methacrylate) via nucleophile-initiated Michael addition thiol-ene "click" chemistry. The surface chemistry of the modified surfaces was analyzed by Fourier transform infrared spectroscopy-attenuated total reflectance and X-ray photoelectron spectroscopy. The appearance of N (1s) and S (2p) peaks on the low resolution X-ray photoelectron spectroscopy spectra confirmed successful immobilization of hyaluronic acid. Grafting hyaluronic acid to the poly(2-hydroxyethyl methacrylate) surfaces decreased the contact angle, the dehydration rate, and the amount of nonspecific sorption of lysozyme and albumin in comparison to pristine hydrogel materials, suggesting the development of more wettable surfaces with improved water-retentive and antifouling properties, while maintaining optical transparency (>92%). In vitro testing also showed excellent viability of human corneal epithelial cells with the hyaluronic acid-grafted poly(2-hydroxyethyl methacrylate) surfaces. Hence, surface modification with hyaluronic acid via thiol-ene "click" chemistry could be useful in improving contact lens surface properties, potentially alleviating symptoms of contact lens related dryness and discomfort during

  20. Block copolymer-templated chemistry on Si, Ge, InP, and GaAs surfaces.

    Science.gov (United States)

    Aizawa, Masato; Buriak, Jillian M

    2005-06-29

    Patterning of semiconductor surfaces is an area of intense interest, not only for technological applications, such as molecular electronics, sensing, cellular recognition, and others, but also for fundamental understanding of surface reactivity, general control over surface properties, and development of new surface reactivity. In this communication, we describe the use of self-assembling block copolymers to direct semiconductor surface chemistry in a spatially defined manner, on the nanoscale. The proof-of-principle class of reactions evaluated here is galvanic displacement, in which a metal ion, M+, is reduced to M0 by the semiconductor, including Si, Ge, InP, and GaAs. The block copolymer chosen has a polypyridine block which binds to the metal ions and brings them into close proximity with the surface, at which point they undergo reaction; the pattern of resulting surface chemistry, therefore, mirrors the nanoscale structure of the parent block copolymer. This chemistry has the added advantage of forming metal nanostructures that result in an alloy or intermetallic at the interface, leading to strongly bound metal nanoparticles that may have interesting electronic properties. This approach has been shown to be very general, functioning on a variety of semiconductor substrates for both silver and gold deposition, and is being extended to organic and inorganic reactions on a variety of conducting, semiconducting, and insulating substrates.

  1. Deconvoluting the effects of surface chemistry and nanoscale topography: Pseudomonas aeruginosa biofilm nucleation on Si-based substrates.

    Science.gov (United States)

    Zhang, Jing; Huang, Jinglin; Say, Carmen; Dorit, Robert L; Queeney, K T

    2018-06-01

    The nucleation of biofilms is known to be affected by both the chemistry and topography of the underlying substrate, particularly when topography includes nanoscale (topography vs. chemistry is complicated by concomitant variation in both as a result of typical surface modification techniques. Analyzing the behavior of biofilm-forming bacteria exposed to surfaces with systematic, independent variation of both topography and surface chemistry should allow differentiation of the two effects. Silicon surfaces with reproducible nanotopography were created by anisotropic etching in deoxygenated water. Surface chemistry was varied independently to create hydrophilic (OH-terminated) and hydrophobic (alkyl-terminated) surfaces. The attachment and proliferation of Psuedomonas aeruginosa to these surfaces was characterized over a period of 12 h using fluorescence and confocal microscopy. The number of attached bacteria as well as the structural characteristics of the nucleating biofilm were influenced by both surface nanotopography and surface chemistry. In general terms, the presence of both nanoscale features and hydrophobic surface chemistry enhance bacterial attachment and colonization. However, the structural details of the resulting biofilms suggest that surface chemistry and topography interact differently on each of the four surface types we studied. Copyright © 2018 Elsevier Inc. All rights reserved.

  2. Microwave surface resistance of bulk YBa2Cu3O6+x material

    Science.gov (United States)

    Fathy, A.; Kalokitis, D.; Belohoubek, E.; Sundar, H. G. K.; Safari, A.

    1988-10-01

    Superconducting Y-Ba-Cu-O samples were prepared by conventional solid-state reaction. The microwave surface resistance of 1:2:3 compound superconductor material was measured in a special disk resonator structure at 10 GHz. At liquid-nitrogen temperatures the microwave surface resistance is comparable to that of Au. At lower temperature (~10 K) the surface resistance is an order of magnitude lower than that of Au at the same temperature.

  3. Color and surface chemistry changes of extracted wood flour after heating at 120 °C

    Science.gov (United States)

    Yao Chen; Mandla A. Tshabalala; Jianmin Gao; Nicole M. Stark

    2013-01-01

    To investigate the effect of heat on color and surface chemistry of wood flour (WF), unextracted, extracted and delignified samples of commercial WF were heated at 120 °C for 24 h and analyzed by colorimetry, diffuse reflectance visible (DRV), attenuated total reflectance Fourier transform infrared (ATR-FTIR) and Fourier transform Raman (FT-Raman) spectroscopies....

  4. Challenges in Teaching "Colloid and Surface Chemistry"--A Danish Experience

    Science.gov (United States)

    Kontogeorgis, Georgios M.; Vigild, Martin E.

    2009-01-01

    Seven years ago we were asked, as one of our first teaching duties at the Technical University of Denmark (DTU), to teach a 5 ECTS point course on "Colloid and Surface Chemistry". The topic is itself at the same time exciting and demanding, largely due to its multidisciplinary nature. Several "local" requirements posed…

  5. Surface Geometry and Chemistry of Hydrothermally Synthesized Single Crystal Thorium Dioxide

    Science.gov (United States)

    2015-03-01

    Member Alex G. Li, PhD Member iv AFIT-ENP-MS-15-M-87 Abstract The surface chemistry and geometry of hydrothermally grown, single...Interactions with Materials and Atoms 268(9), pp. 1482-1485. 2010. . DOI: 10.1016/j.nimb.2010.01.027. [4] J. A. Felix , D. M. Fleetwood, R. D. Schrimpf, J. G

  6. On surface-initiated atom transfer radical polymerization using diazonium chemistry to introduce the initiator layer

    DEFF Research Database (Denmark)

    Iruthayaraj, Joseph; Chernyy, Sergey; Lillethorup, Mie

    2011-01-01

    This work features the controllability of surface-initiated atom transfer radical polymerization (SI-ATRP) of methyl methacrylate, initiated by a multilayered 2-bromoisobutyryl moiety formed via diazonium chemistry. The thickness as a function of polymerization time has been studied by varying...

  7. Laboratory Activity Worksheet to Train High Order Thinking Skill of Student on Surface Chemistry Lecture

    Science.gov (United States)

    Yonata, B.; Nasrudin, H.

    2018-01-01

    A worksheet has to be a set with activity which is help students to arrange their own experiments. For this reason, this research is focused on how to train students’ higher order thinking skills in laboratory activity by developing laboratory activity worksheet on surface chemistry lecture. To ensure that the laboratory activity worksheet already contains aspects of the higher order thinking skill, it requires theoretical and empirical validation. From the data analysis results, it shows that the developed worksheet worth to use. The worksheet is worthy of theoretical and empirical feasibility. This conclusion is based on the findings: 1) Assessment from the validators about the theoretical feasibility aspects in the category is very feasible with an assessment range of 95.24% to 97.92%. 2) students’ higher thinking skill from N Gain values ranges from 0.50 (enough) to 1.00 (high) so it can be concluded that the laboratory activity worksheet on surface chemistry lecture is empirical in terms of worth. The empirical feasibility is supported by the responses of the students in very reasonable categories. It is expected that the laboratory activity worksheet on surface chemistry lecture can train students’ high order thinking skills for students who program surface chemistry lecture.

  8. Surface chemistry of tribochemical reactions explored in ultrahigh vacuum conditions

    International Nuclear Information System (INIS)

    Lara-Romero, Javier; Maya-Yescas, Rafael; Rico-Cerda, Jose Luis; Rivera-Rojas, Jose Luis; Castillo, Fernando Chinas; Kaltchev, Matey; Tysoe, Wilfred T.

    2006-01-01

    The thermal decomposition of model extreme-pressure lubricant additives on clean iron was studied in ultrahigh vacuum conditions using molecular beam strategies. Methylene chloride and chloroform react to deposit a solid film consisting of FeCl 2 and carbon, and evolve only hydrogen into the gas phase. No gas-phase products and less carbon on the surface are detected in the case of carbon tetrachloride. Dimethyl and diethyl disulfide react on clean iron to deposit a saturated sulfur plus carbon layer at low temperatures (∼600 K) and an iron sulfide film onto a Fe + C underlayer at higher temperatures (∼950 K). Methane is the only gas-phase product when dimethyl disulfide reacts with iron. Ethylene and hydrogen are detected when diethyl disulfide is used

  9. Surface Chemistry Involved in Epitaxy of Graphene on 3C-SiC(111)/Si(111)

    OpenAIRE

    Abe Shunsuke; Handa Hiroyuki; Takahashi Ryota; Imaizumi Kei; Fukidome Hirokazu; Suemitsu Maki

    2010-01-01

    Abstract Surface chemistry involved in the epitaxy of graphene by sublimating Si atoms from the surface of epitaxial 3C-SiC(111) thin films on Si(111) has been studied. The change in the surface composition during graphene epitaxy is monitored by in situ temperature-programmed desorption spectroscopy using deuterium as a probe (D2-TPD) and complementarily by ex situ Raman and C1s core-level spectroscopies. The surface of the 3C-SiC(111)/Si(111) is Si-terminated before the graphitization, and ...

  10. Evaluation of the In Vitro Effect of Gold Nanorod Aspect Ratio, Surface Charge and Chemistry on Cellular Association and Cytotoxicity

    Science.gov (United States)

    2016-03-28

    Nanorods. Analytical Chemistry , 79(2), 572-579. doi: 10.1021/ac061730d 22 LIST OF ACRONYMS ATCC American Type Culture Collection AR Aspect...EVALUATION OF THE IN VITRO EFFECTOF GOLD NANOROD ASPECT RATIO, SURFACE CHARGE AND CHEMISTRY ON CELLULAR ASSOCIATION AND CYTOTOXICITY...July 2012 – Jan 2016 4. TITLE AND SUBTITLE EVALUATION OF THE IN VITRO EFFECT OF GOLD NANOROD ASPECT RATIO, SURFACE CHARGE AND CHEMISTRY ON

  11. Modular "click" chemistry for electrochemically and photoelectrochemically active molecular interfaces to tin oxide surfaces.

    Science.gov (United States)

    Benson, Michelle C; Ruther, Rose E; Gerken, James B; Rigsby, Matthew L; Bishop, Lee M; Tan, Yizheng; Stahl, Shannon S; Hamers, Robert J

    2011-08-01

    We demonstrate the use of "click" chemistry to form electrochemically and photoelectrochemically active molecular interfaces to SnO(2) nanoparticle thin films. By using photochemical grafting to link a short-chain alcohol to the surface followed by conversion to a surface azide group, we enable use of the Cu(I)-catalyzed azide-alkyne [3 + 2] cycloaddition (CuAAC) reaction, a form of "click" chemistry, on metal oxide surfaces. Results are shown with three model compounds to test the surface chemistry and subsequent ability to achieve electrochemical and photoelectrochemical charge transfer. Surface-tethered ferrocene groups exhibit good electron-transfer characteristics with thermal rates estimated at >1000 s(-1). Time-resolved surface photovoltage measurements using a ruthenium terpyridyl coordination compound demonstrate photoelectron charge transfer on time scales of nanoseconds or less, limited by the laser pulse width. The results demonstrate that the CuAAC "click" reaction can be used to form electrochemically and photoelectrochemically active molecular interfaces to SnO(2) and other metal oxide semiconductors.

  12. Thermal Stability of Metal Nanocrystals: An Investigation of the Surface and Bulk Reconstructions of Pd Concave Icosahedra.

    Science.gov (United States)

    Gilroy, Kyle D; Elnabawy, Ahmed O; Yang, Tung-Han; Roling, Luke T; Howe, Jane; Mavrikakis, Manos; Xia, Younan

    2017-06-14

    Despite the remarkable success in controlling the synthesis of metal nanocrystals, it still remains a grand challenge to stabilize and preserve the shapes or internal structures of metastable kinetic products. In this work, we address this issue by systematically investigating the surface and bulk reconstructions experienced by a Pd concave icosahedron when subjected to heating up to 600 °C in vacuum. We used in situ high-resolution transmission electron microscopy to identify the equilibration pathways of this far-from-equilibrium structure. We were able to capture key structural transformations occurring during the thermal annealing process, which were mechanistically rationalized by implementing self-consistent plane-wave density functional theory (DFT) calculations. Specifically, the concave icosahedron was found to evolve into a regular icosahedron via surface reconstruction in the range of 200-400 °C, and then transform into a pseudospherical crystalline structure through bulk reconstruction when further heated to 600 °C. The mechanistic understanding may lead to the development of strategies for enhancing the thermal stability of metal nanocrystals.

  13. Bulk Surfaces Coated with Triangular Silver Nanoplates: Antibacterial Action Based on Silver Release and Photo-Thermal Effect

    Directory of Open Access Journals (Sweden)

    Agnese D’Agostino

    2017-01-01

    Full Text Available A layer of silver nanoplates, specifically synthesized with the desired localized surface plasmon resonance (LSPR features, was grafted on amino-functionalized bulk glass surfaces to impart a double antibacterial action: (i the well-known, long-term antibacterial effect based on the release of Ag+; (ii an “on demand” action which can be switched on by the use of photo-thermal properties of silver nano-objects. Irradiation of these samples with a laser having a wavelength falling into the so called “therapeutic window” of the near infrared region allows the reinforcement, in the timescale of minutes, of the classical antibacterial effect of silver nanoparticles. We demonstrate how using the two actions allows for almost complete elimination of the population of two bacterial strains of representative Gram-positive and Gram-negative bacteria.

  14. Bulk Surfaces Coated with Triangular Silver Nanoplates: Antibacterial Action Based on Silver Release and Photo-Thermal Effect.

    Science.gov (United States)

    D'Agostino, Agnese; Taglietti, Angelo; Desando, Roberto; Bini, Marcella; Patrini, Maddalena; Dacarro, Giacomo; Cucca, Lucia; Pallavicini, Piersandro; Grisoli, Pietro

    2017-01-06

    A layer of silver nanoplates, specifically synthesized with the desired localized surface plasmon resonance (LSPR) features, was grafted on amino-functionalized bulk glass surfaces to impart a double antibacterial action: (i) the well-known, long-term antibacterial effect based on the release of Ag⁺; (ii) an "on demand" action which can be switched on by the use of photo-thermal properties of silver nano-objects. Irradiation of these samples with a laser having a wavelength falling into the so called "therapeutic window" of the near infrared region allows the reinforcement, in the timescale of minutes, of the classical antibacterial effect of silver nanoparticles. We demonstrate how using the two actions allows for almost complete elimination of the population of two bacterial strains of representative Gram-positive and Gram-negative bacteria.

  15. Solvent Composition Directing Click-Functionalization at the Surface or in the Bulk of Azide-Modified PEDOT

    DEFF Research Database (Denmark)

    Lind, Johan Ulrik; Hansen, Thomas Steen; Daugaard, Anders Egede

    2011-01-01

    Thin films of the conducting polymer poly(3,4-(1-azidomethylethylene)dioxythiophene) tosylate (PEDOT−N3) can be functionalized by reaction with alkynated reagents in aqueous solutions. Reaction in pure water resulted in surface specific modification of PEDOT−N3 films, whereas both surface and bulk...... reaction was achieved in solvent mixtures of water and DMSO. These reaction patterns were confirmed by a combination of AFM and XPS measurements on the front- and back-side of the film. The phenomenon is attributed to a strong dependence of the swelling of PEDOT−N3 on the solvent mixture used. Liquid AFM...... studies showed increasing film thickness with increasing DMSO content, with the measured thickness in pure DMSO being >250% of the thickness in pure water. A similar, but less pronounced, behavior was observed for unmodified poly(3,4-ethylenedioxythiophene) tosylate (PEDOT). High-density grafting...

  16. Relation between bulk compressibility and surface energy of electron-hole liquids

    International Nuclear Information System (INIS)

    Singwi, K.S.; Tosi, M.P.

    1979-08-01

    Attention is drawn to the existence of an empirical relation chiσ/asup(*)sub(B) approximately 1 between the compressibility, the surface energy and the excitonic radius in electron-hole liquids. (author)

  17. Sub-Surface and Bulk Creep Behaviour of Polyurethane/Clay Nanocomposites.

    Science.gov (United States)

    Jin, J; Yusoh, K; Zhang, H X; Song, M

    2016-03-01

    A series of exfoliated and intercalated polyurethane organoclay nanocomposites were prepared by in situ polymerization of polyol/organoclay mixture, chain extender and diisocyanate. The creep behaviour of subsurface and bulk of the polyurethane coatings was investigated by nanoindentation technique and uniaxial conventional creep testing method, respectively. The results showed that the creep resistance of the nanocomposites was significantly improved by incorporation of organoclay. The enhancement of creep resistance was dependent on clay content as well as organoclay structure (exfoliation or intercalation) in the polymer matrix. With 1 wt% organoclay, the creep resistance increased by about 50% for the intercalated organoclay and 6% for the exfoliated organoclay systems, respectively, compared to the pristine polyurethane. Viscoelastic model was employed to investigate the effect of organoclay loadings on the creep performance of the polyurethane. Results showed the model was in good agreement with the experimental data. Incorporation of clay leads to an increase in elastic deformation especially in exfoliated polyurethane nanocomposites and induces a higher initial displacement at the early stage of creep.

  18. Optimizing the bulk copolymerization of D,L-lactide and glycolide by response surface methodology

    Directory of Open Access Journals (Sweden)

    J. F. Rodriguez

    2013-11-01

    Full Text Available Poly(D,L-lactide-co-glycolide, PLGA, is a biodegradable polyester with high interest in medical industry, especially when zinc (II 2-ethylhexanoate (ZnOct2 is used as catalyst substitute in polymerization processes as a substitute of the toxic tin (II 2-ethylhexanoate (SnOct2 together an initiator such as methanol to improve the reaction rate. This article shows the optimization of the bulk copolymerization method by using a factorial design approach on three experimental parameters: temperature (T, molar ratio monomers/catalyst (MC ratio and molar ratio initiator/catalyst (IC ratio. Their influence on mass conversion (X and number-average molecular weight (Mn was also discussed. Also it provides a useful tool to select in a fast way the proper experimental conditions for the obtaining of this polymer as a previous stage in the synthesis and impregnation of biodegradable scaffolds. This analysis revealed that the most relevant variable in the process is the temperature, being desirable to use the high value (160ºC in order to obtain high values of conversion and molecular weight.

  19. Interaction between carbon fibers and polymer sizing: Influence of fiber surface chemistry and sizing reactivity

    Science.gov (United States)

    Moosburger-Will, Judith; Bauer, Matthias; Laukmanis, Eva; Horny, Robert; Wetjen, Denise; Manske, Tamara; Schmidt-Stein, Felix; Töpker, Jochen; Horn, Siegfried

    2018-05-01

    Different aspects of the interaction of carbon fibers and epoxy-based polymer sizings are investigated, e.g. the wetting behavior, the strength of adhesion between fiber and sizing, and the thermal stability of the sizing layer. The influence of carbon fiber surface chemistry and sizing reactivity is investigated using fibers of different degree of anodic oxidation and sizings with different number of reactive epoxy groups per molecule. Wetting of the carbon fibers by the sizing dispersion is found to be specified by both, the degree of fiber activation and the sizing reactivity. In contrast, adhesion strength between fibers and sizing is dominated by the surface chemistry of the carbon fibers. Here, the number of surface oxygen groups seems to be the limiting factor. We also find that the sizing and the additional functionalities induced by anodic oxidation are removed by thermal treatment at 600 °C, leaving the carbon fiber in its original state after carbonization.

  20. Colloid Surface Chemistry Critically Affects Multiple Particle Tracking Measurements of Biomaterials

    Science.gov (United States)

    Valentine, M. T.; Perlman, Z. E.; Gardel, M. L.; Shin, J. H.; Matsudaira, P.; Mitchison, T. J.; Weitz, D. A.

    2004-01-01

    Characterization of the properties of complex biomaterials using microrheological techniques has the promise of providing fundamental insights into their biomechanical functions; however, precise interpretations of such measurements are hindered by inadequate characterization of the interactions between tracers and the networks they probe. We here show that colloid surface chemistry can profoundly affect multiple particle tracking measurements of networks of fibrin, entangled F-actin solutions, and networks of cross-linked F-actin. We present a simple protocol to render the surface of colloidal probe particles protein-resistant by grafting short amine-terminated methoxy-poly(ethylene glycol) to the surface of carboxylated microspheres. We demonstrate that these poly(ethylene glycol)-coated tracers adsorb significantly less protein than particles coated with bovine serum albumin or unmodified probe particles. We establish that varying particle surface chemistry selectively tunes the sensitivity of the particles to different physical properties of their microenvironments. Specifically, particles that are weakly bound to a heterogeneous network are sensitive to changes in network stiffness, whereas protein-resistant tracers measure changes in the viscosity of the fluid and in the network microstructure. We demonstrate experimentally that two-particle microrheology analysis significantly reduces differences arising from tracer surface chemistry, indicating that modifications of network properties near the particle do not introduce large-scale heterogeneities. Our results establish that controlling colloid-protein interactions is crucial to the successful application of multiple particle tracking techniques to reconstituted protein networks, cytoplasm, and cells. PMID:15189896

  1. Influence of surface microstructure and chemistry on osteoinduction and osteoclastogenesis by biphasic calcium phosphate discs.

    Science.gov (United States)

    Davison, N L; Su, J; Yuan, H; van den Beucken, J J J P; de Bruijn, J D; Barrère-de Groot, F

    2015-06-20

    It has been reported that surface microstructural dimensions can influence the osteoinductivity of calcium phosphates (CaPs), and osteoclasts may play a role in this process. We hypothesised that surface structural dimensions of ≤ 1 μm trigger osteoinduction and osteoclast formation irrespective of macrostructure (e.g., concavities, interconnected macropores, interparticle space) or surface chemistry. To test this, planar discs made of biphasic calcium phosphate (BCP: 80% hydroxyapatite, 20% tricalcium phosphate) were prepared with different surface structural dimensions - either ~ 1 μm (BCP1150) or ~ 2-4 μm (BCP1300) - and no macropores or concavities. A third material was made by sputter coating BCP1150 with titanium (BCP1150Ti), thereby changing its surface chemistry but preserving its surface structure and chemical reactivity. After intramuscular implantation in 5 dogs for 12 weeks, BCP1150 formed ectopic bone in 4 out of 5 samples, BCP1150Ti formed ectopic bone in 3 out of 5 samples, and BCP1300 formed no ectopic bone in any of the 5 samples. In vivo, large multinucleated osteoclast-like cells densely colonised BCP1150, smaller osteoclast-like cells formed on BCP1150Ti, and osteoclast-like cells scarcely formed on BCP1300. In vitro, RAW264.7 cells cultured on the surface of BCP1150 and BCP1150Ti in the presence of osteoclast differentiation factor RANKL (receptor activator for NF-κB ligand) proliferated then differentiated into multinucleated osteoclast-like cells with positive tartrate resistant acid phosphatase (TRAP) activity. However, cell proliferation, fusion, and TRAP activity were all significantly inhibited on BCP1300. These results indicate that of the material parameters tested - namely, surface microstructure, macrostructure, and surface chemistry - microstructural dimensions are critical in promoting osteoclastogenesis and triggering ectopic bone formation.

  2. Effects of wood fiber surface chemistry on strength of wood-plastic composites

    Science.gov (United States)

    Migneault, Sébastien; Koubaa, Ahmed; Perré, Patrick; Riedl, Bernard

    2015-07-01

    Because wood-plastic composites (WPC) strength relies on fiber-matrix interaction at fiber surface, it is likely that fiber surface chemistry plays an important role in WPC strength development. The objective of the present study is to investigate the relationships between fiber surface chemical characteristics and WPC mechanical properties. Different fibers were selected and characterized for surface chemical characteristics using X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (FTIR). WPC samples were manufactured at 40% fiber content and with six different fibers. High density polyethylene was used as matrix and maleated polyethylene (MAPE) was used as compatibility agent. WPC samples were tested for mechanical properties and fiber-matrix interface was observed with scanning electron microscope. It was found WPC strength decreases as the amount of unoxidized carbon (assigned to lignin and extractives) measured with XPS on fiber surface increases. In the opposite case, WPC strength increases with increasing level of oxidized carbon (assigned to carbohydrates) on fiber surface. The same conclusions were found with FTIR where WPC strength decreases as lignin peaks intensity increases. Esterification reaction of fibers with MAPE occurs on polar sites of carbohydrates, such as hydroxyls (Osbnd H). Thus, fibers with carbohydrates-rich surface, such as cellulose pulp, produced stronger WPC samples. Other factors such as mechanical interlocking and fiber morphology interfered with the effects of fiber surface chemistry.

  3. Surface critical magnetic field Hc3 (T) of a bulk superconductor ...

    Indian Academy of Sciences (India)

    ... surface critical magnetic field Hc3(). It is shown that c3() has the same temperature dependence with c2(), similar to the case of a single-band superconductor, c3()=1.66 c2(). We use an elimination procedure for the decoupling of G–L equations of two-band superconductivity, which eases the calculations.

  4. Major Successes of Theory-and-Experiment-Combined Studies in Surface Chemistry and Heterogeneous Catalysis.

    Energy Technology Data Exchange (ETDEWEB)

    Somorjai, Gabor A.; Li, Yimin

    2009-11-21

    Experimental discoveries followed by theoretical interpretations that pave the way of further advances by experimentalists is a developing pattern in modern surface chemistry and catalysis. The revolution of modern surface science started with the development of surface-sensitive techniques such as LEED, XPS, AES, ISS and SIMS, in which the close collaboration between experimentalists and theorists led to the quantitative determination of surface structure and composition. The experimental discovery of the chemical activity of surface defects and the trends in the reactivity of transitional metals followed by the explanations from the theoretical studies led to the molecular level understanding of active sites in catalysis. The molecular level knowledge, in turn, provided a guide for experiments to search for new generation of catalysts. These and many other examples of successes in experiment-and-theory-combined studies demonstrate the importance of the collaboration between experimentalists and theorists in the development of modern surface science.

  5. Addition of carbon to anatase TiO{sub 2} by n-hexane treatment-surface or bulk doping?

    Energy Technology Data Exchange (ETDEWEB)

    Enache, Cristina S. [Delft University of Technology, Delft Institute for Sustainable Energy, Laboratory for Inorganic Chemistry, P.O. Box 5045, 2600 GA Delft (Netherlands)]. E-mail: c.s.enache@tnw.tudelft.nl; Schoonman, Joop [Delft University of Technology, Delft Institute for Sustainable Energy, Laboratory for Inorganic Chemistry, P.O. Box 5045, 2600 GA Delft (Netherlands); Krol, Roel van de [Delft University of Technology, Delft Institute for Sustainable Energy, Laboratory for Inorganic Chemistry, P.O. Box 5045, 2600 GA Delft (Netherlands)

    2006-07-15

    Anatase TiO{sub 2} can be sensitized to visible light by adding carbon as a dopant. Towards this end, TiO{sub 2} photoelectrodes were subjected to a thermal treatment in a hexane-rich environment. By comparing the optical and photoelectrochemical characteristics of both thin film and nanocrystalline nanoporous photoelectrodes, carbon is found to be located mainly at the surface of the TiO{sub 2}. The amount of carbon that diffuses into the bulk of the material is too small to significantly enhance the visible light response and only a small shift of the absorption edge towards higher wavelengths is observed. The presence of carbon in TiO{sub 2} shifts the anatase-to-rutile transformation temperature beyond 800 deg. C, and X-ray diffraction shows that spray deposition of TiO{sub 2} under a CO{sub 2} atmosphere results in a higher bulk carbon concentration than a post-deposition thermal treatment in a hexane-rich environment.

  6. The impact of surface chemistry on the performance of localized solar-driven evaporation system

    Science.gov (United States)

    Yu, Shengtao; Zhang, Yao; Duan, Haoze; Liu, Yanming; Quan, Xiaojun; Tao, Peng; Shang, Wen; Wu, Jianbo; Song, Chengyi; Deng, Tao

    2015-09-01

    This report investigates the influence of surface chemistry (or wettability) on the evaporation performance of free-standing double-layered thin film on the surface of water. Such newly developed evaporation system is composed of top plasmonic light-to-heat conversion layer and bottom porous supporting layer. Under solar light illumination, the induced plasmonic heat will be localized within the film. By modulating the wettability of such evaporation system through the control of surface chemistry, the evaporation rates are differentiated between hydrophilized and hydrophobized anodic aluminum oxide membrane-based double layered thin films. Additionally, this work demonstrated that the evaporation rate mainly depends on the wettability of bottom supporting layer rather than that of top light-to-heat conversion layer. The findings in this study not only elucidate the role of surface chemistry of each layer of such double-layered evaporation system, but also provide additional design guidelines for such localized evaporation system in applications including desalination, distillation and power generation.

  7. The impact of surface chemistry on the performance of localized solar-driven evaporation system.

    Science.gov (United States)

    Yu, Shengtao; Zhang, Yao; Duan, Haoze; Liu, Yanming; Quan, Xiaojun; Tao, Peng; Shang, Wen; Wu, Jianbo; Song, Chengyi; Deng, Tao

    2015-09-04

    This report investigates the influence of surface chemistry (or wettability) on the evaporation performance of free-standing double-layered thin film on the surface of water. Such newly developed evaporation system is composed of top plasmonic light-to-heat conversion layer and bottom porous supporting layer. Under solar light illumination, the induced plasmonic heat will be localized within the film. By modulating the wettability of such evaporation system through the control of surface chemistry, the evaporation rates are differentiated between hydrophilized and hydrophobized anodic aluminum oxide membrane-based double layered thin films. Additionally, this work demonstrated that the evaporation rate mainly depends on the wettability of bottom supporting layer rather than that of top light-to-heat conversion layer. The findings in this study not only elucidate the role of surface chemistry of each layer of such double-layered evaporation system, but also provide additional design guidelines for such localized evaporation system in applications including desalination, distillation and power generation.

  8. Versatile gas-phase reactions for surface to bulk esterification of cellulose microfibrils aerogels.

    Science.gov (United States)

    Fumagalli, Matthieu; Ouhab, Djamila; Boisseau, Sonia Molina; Heux, Laurent

    2013-09-09

    Aqueous suspensions of microfibrillated cellulose obtained by a high pressure homogenization process were freeze-dried after solvent exchange into tert-butanol. The resulting aerogels, which displayed a remarkable open morphology with a surface area reaching 100 m(2)/g, were subjected to a gas-phase esterification with palmitoyl chloride. Under these conditions, variations of the reaction temperature from 100 to 200 °C, of the reaction time from 0.5 to 2 h, and of the initial quantity of reagent, led to the preparation of a library of cellulose palmitates with DS varying from zero to 2.36. These products were characterized by gravimetry, FTIR, and (13)C solid-state NMR spectroscopy. Of special interest were the cellulose palmitate samples of low DS in the range of 0.1-0.4, which corresponded to hydrophobic cellulose microfibrils exclusively esterified at their surface while keeping intact their inner structure.

  9. Decoupling single nanowire mobilities limited by surface scattering and bulk impurity scattering

    International Nuclear Information System (INIS)

    Khanal, D. R.; Levander, A. X.; Wu, J.; Yu, K. M.; Liliental-Weber, Z.; Walukiewicz, W.; Grandal, J.; Sanchez-Garcia, M. A.; Calleja, E.

    2011-01-01

    We demonstrate the isolation of two free carrier scattering mechanisms as a function of radial band bending in InN nanowires via universal mobility analysis, where effective carrier mobility is measured as a function of effective electric field in a nanowire field-effect transistor. Our results show that Coulomb scattering limits effective mobility at most effective fields, while surface roughness scattering only limits mobility under very high internal electric fields. High-energy α particle irradiation is used to vary the ionized donor concentration, and the observed decrease in mobility and increase in donor concentration are compared to Hall effect results of high-quality InN thin films. Our results show that for nanowires with relatively high doping and large diameters, controlling Coulomb scattering from ionized dopants should be given precedence over surface engineering when seeking to maximize nanowire mobility.

  10. Bulk and surface effects in x-ray magnetic circular dichroism of iron clusters

    Czech Academy of Sciences Publication Activity Database

    Šipr, Ondřej; Ebert, H.

    2003-01-01

    Roč. 53, č. 1 (2003), s. 55-62 ISSN 0011-4626. [Symposium on Surface Physics /9./. Třešt', 02.09.2002-06.09.2002] R&D Projects: GA ČR GA202/02/0841 Institutional research plan: CEZ:AV0Z1010914 Keywords : x-ray magnetic circular dichroism * clusters * spin-polarized relativistic KKR Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.263, year: 2003

  11. The Surface and Bulk Magnetic Properties of Fe-Al Alloys

    Czech Academy of Sciences Publication Activity Database

    Hendrych, A.; Žitovsky, O.; Jirásková, Yvonna; Matko, I.

    2014-01-01

    Roč. 126, č. 1 (2014), s. 58-59 ISSN 0587-4246. [CSMAG Czech and Slovak Conference on Magnetism /15./. Košice, 17.06.2013-21.06.2013] R&D Projects: GA MŠk 7AMB12SK009 Institutional support: RVO:68081723 Keywords : Fe-Al * MOKE * Surface properties * MFM Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.530, year: 2014

  12. Surface and bulk magnetic properties of as-quenched FeNbB ribbons

    Czech Academy of Sciences Publication Activity Database

    Životský, O.; Postava, K.; Kraus, Luděk; Juraszek, J.; Jirásková, Yvonna; Teillet, J.; Barčová, K.; Švec, P.; Janičkovič, D.; Pištora, J.

    2008-01-01

    Roč. 320, č. 8 (2008), s. 1535-1540 ISSN 0304-8853 R&D Projects: GA ČR GA202/05/2111; GA AV ČR KAN400100653 Institutional research plan: CEZ:AV0Z20410507; CEZ:AV0Z10100520 Keywords : Surface nanocrystallization * Fe-based ribbon * depth profile Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.283, year: 2008

  13. Measurements and TCAD Simulations of Bulk and Surface Radiation Damage Effects

    CERN Document Server

    F. Moscatelli; G. M. Bilei; A. Morozzi; G.-F. Dalla Betta; R. Mendicino; M. Boscardin; N. Zorzi; L. Servoli; P. Maccagnani

    2016-01-01

    In this work we propose the application of a radiation damage model based on the introduction of deep level traps/recombination centers suitable for device level numerical simulation of radiation detectors at very high fluences (e.g. 1÷2×1016 1-MeV equivalent neutrons per square centimeter) combined with a surface damage model developed by using experimental parameters extracted from measurements from gamma irradiated p-type dedicated test structures.

  14. Influence of bulk and surface phenomena on the hydrogen permeation through metals

    International Nuclear Information System (INIS)

    Waelbroeck, F.; Wienhold, P.; Winter, J.; Rota, E.; Bauno, T.

    1984-12-01

    We discuss the permeation of hydrogen through metals and alloys such as iron, nickel, steels and Inconel wherein H dissolves endothermically from an H 2 gas. We assume first that trapping centers, surface contamination layers, the saturation of the H surface coverage and the implantation profile - when energetic ions drive the permeation - can be neglected, that a quasi-equilibrium exists between the H atom concentration ν in the adsorbed layer and c in the near surface layers and that the H solubility and diffusivity are homogeneous in the membrane. We evaluate thereafter separately the influence of these various effects and identify the parameter domains where appreciable corrections result. The permeation phenomenon is complex even when these simplifications are made: the penetration rate is proportional to the flux of thermal molecules, atoms or energetic ions - depending upon the case - which strike the surface; the diffusion in the metal is proportional to the gradient of c; the release rate depends on c 2 ; the time-dependent diffusion equation includes a double spatial derivative of c. Permeation can only be fully described when computer codes such as PERI is used. Simple analytical relations are however obtained in several limiting cases. They are the object of this report. Some of them had already been derived by other authors but they were not shown to be part of a single, self consistent permeation model. A comparison of predicted and experimental results shows that the simplified model describes surprisingly accurately the hydrogen exchange between gas and metal solutions. (orig./GSCH)

  15. On the modelling of semi-insulating GaAs including surface tension and bulk stresses

    Energy Technology Data Exchange (ETDEWEB)

    Dreyer, W.; Duderstadt, F.

    2004-07-01

    Necessary heat treatment of single crystal semi-insulating Gallium Arsenide (GaAs), which is deployed in micro- and opto- electronic devices, generate undesirable liquid precipitates in the solid phase. The appearance of precipitates is influenced by surface tension at the liquid/solid interface and deviatoric stresses in the solid. The central quantity for the description of the various aspects of phase transitions is the chemical potential, which can be additively decomposed into a chemical and a mechanical part. In particular the calculation of the mechanical part of the chemical potential is of crucial importance. We determine the chemical potential in the framework of the St. Venant-Kirchhoff law which gives an appropriate stress/strain relation for many solids in the small strain regime. We establish criteria, which allow the correct replacement of the St. Venant-Kirchhoff law by the simpler Hooke law. The main objectives of this study are: (i) We develop a thermo-mechanical model that describes diffusion and interface motion, which both are strongly influenced by surface tension effects and deviatoric stresses. (ii) We give an overview and outlook on problems that can be posed and solved within the framework of the model. (iii) We calculate non-standard phase diagrams, i.e. those that take into account surface tension and non-deviatoric stresses, for GaAs above 786 C, and we compare the results with classical phase diagrams without these phenomena. (orig.)

  16. Kinetic model framework for aerosol and cloud surface chemistry and gas-particle interactions - Part 1: General equations, parameters, and terminology

    Science.gov (United States)

    Pöschl, U.; Rudich, Y.; Ammann, M.

    2007-12-01

    Aerosols and clouds play central roles in atmospheric chemistry and physics, climate, air pollution, and public health. The mechanistic understanding and predictability of aerosol and cloud properties, interactions, transformations, and effects are, however, still very limited. This is due not only to the limited availability of measurement data, but also to the limited applicability and compatibility of model formalisms used for the analysis, interpretation, and description of heterogeneous and multiphase processes. To support the investigation and elucidation of atmospheric aerosol and cloud surface chemistry and gas-particle interactions, we present a comprehensive kinetic model framework with consistent and unambiguous terminology and universally applicable rate equations and parameters. It enables a detailed description of mass transport and chemical reactions at the gas-particle interface, and it allows linking aerosol and cloud surface processes with gas phase and particle bulk processes in systems with multiple chemical components and competing physicochemical processes. The key elements and essential aspects of the presented framework are: a simple and descriptive double-layer surface model (sorption layer and quasi-static layer); straightforward flux-based mass balance and rate equations; clear separation of mass transport and chemical reactions; well-defined and consistent rate parameters (uptake and accommodation coefficients, reaction and transport rate coefficients); clear distinction between gas phase, gas-surface, and surface-bulk transport (gas phase diffusion, surface and bulk accommodation); clear distinction between gas-surface, surface layer, and surface-bulk reactions (Langmuir-Hinshelwood and Eley-Rideal mechanisms); mechanistic description of concentration and time dependences (transient and steady-state conditions); flexible addition of unlimited numbers of chemical species and physicochemical processes; optional aggregation or resolution

  17. Modelling interstellar physics and chemistry: implications for surface and solid-state processes.

    Science.gov (United States)

    Williams, David; Viti, Serena

    2013-07-13

    We discuss several types of regions in the interstellar medium of the Milky Way and other galaxies in which the chemistry appears to be influenced or dominated by surface and solid-state processes occurring on or in interstellar dust grains. For some of these processes, for example, the formation of H₂ molecules, detailed experimental and theoretical approaches have provided excellent fundamental data for incorporation into astrochemical models. In other cases, there is an astrochemical requirement for much more laboratory and computational study, and we highlight these needs in our description. Nevertheless, in spite of the limitations of the data, it is possible to infer from astrochemical modelling that surface and solid-state processes play a crucial role in astronomical chemistry from early epochs of the Universe up to the present day.

  18. Quantification of Hydrogen Concentrations in Surface and Interface Layers and Bulk Materials through Depth Profiling with Nuclear Reaction Analysis.

    Science.gov (United States)

    Wilde, Markus; Ohno, Satoshi; Ogura, Shohei; Fukutani, Katsuyuki; Matsuzaki, Hiroyuki

    2016-03-29

    Nuclear reaction analysis (NRA) via the resonant (1)H((15)N,αγ)(12)C reaction is a highly effective method of depth profiling that quantitatively and non-destructively reveals the hydrogen density distribution at surfaces, at interfaces, and in the volume of solid materials with high depth resolution. The technique applies a (15)N ion beam of 6.385 MeV provided by an electrostatic accelerator and specifically detects the (1)H isotope in depths up to about 2 μm from the target surface. Surface H coverages are measured with a sensitivity in the order of ~10(13) cm(-2) (~1% of a typical atomic monolayer density) and H volume concentrations with a detection limit of ~10(18) cm(-3) (~100 at. ppm). The near-surface depth resolution is 2-5 nm for surface-normal (15)N ion incidence onto the target and can be enhanced to values below 1 nm for very flat targets by adopting a surface-grazing incidence geometry. The method is versatile and readily applied to any high vacuum compatible homogeneous material with a smooth surface (no pores). Electrically conductive targets usually tolerate the ion beam irradiation with negligible degradation. Hydrogen quantitation and correct depth analysis require knowledge of the elementary composition (besides hydrogen) and mass density of the target material. Especially in combination with ultra-high vacuum methods for in-situ target preparation and characterization, (1)H((15)N,αγ)(12)C NRA is ideally suited for hydrogen analysis at atomically controlled surfaces and nanostructured interfaces. We exemplarily demonstrate here the application of (15)N NRA at the MALT Tandem accelerator facility of the University of Tokyo to (1) quantitatively measure the surface coverage and the bulk concentration of hydrogen in the near-surface region of a H2 exposed Pd(110) single crystal, and (2) to determine the depth location and layer density of hydrogen near the interfaces of thin SiO2 films on Si(100).

  19. Surface Modification of Nanoporous 1,2-Polybutadiene by Atom Transfer Radical Polymerization or Click Chemistry

    DEFF Research Database (Denmark)

    Guo, Fengxiao; Jankova Atanasova, Katja; Schulte, Lars

    2010-01-01

    Surface-initiated atom transfer radical polymerization (ATRP) and click chemistry were used to obtain functional nanoporous polymers based oil nanoporous 1,2-polybutadiene (PB) with gyroid morphology. The ATRP monolith initiator was prepared by immobilizing bromoester initiators onto the pore walls...... ATRP-grafting of hydrophilic polyacrylates and click of MPEG, the originally hydrophobic samples transformed into hydrophilic nanoporous materials. The successful modification was confirmed by infrared spectroscopy, contact angle measurements and measurements of spontaneous water uptake, while...

  20. Effects of wood fiber surface chemistry on strength of wood–plastic composites

    Energy Technology Data Exchange (ETDEWEB)

    Migneault, Sébastien, E-mail: sebastien.migneault@uqat.ca [University of Quebec in Abitibi-Temiscamingue (UQAT), 445 boulevard de l’Université, Rouyn-Noranda, Québec J9X 5E4 (Canada); Koubaa, Ahmed, E-mail: ahmed.koubaa@uqat.ca [UQAT (Canada); Perré, Patrick, E-mail: patrick.perre@ecp.fr [École centrale de Paris, Grande Voie des Vignes, F-92 295 Chatenay-Malabry Cedex (France); Riedl, Bernard, E-mail: Bernard.Riedl@sbf.ulaval.ca [Université Laval, 2425 rue de la Terrasse, Québec City, Québec G1V 0A6 (Canada)

    2015-07-15

    Highlights: • Infrared spectroscopy and X-ray photoelectron spectroscopy analyses showed variations of surface chemical characteristics according to fiber origin. • Surface chemical characteristics of fibers could partly explain the differences in mechanical properties of the wood–plastic composites. • Fibers with carbohydrate rich surface led to stronger wood–plastic composites because the coupling between the matrix and fibers using coupling agent is achieved with polar sites mostly available on carbohydrates. • Conversely, lignin or extractives rich surface do not have oxidized functions for the esterification reaction with coupling agent and thus led to wood–plastic composites with lower mechanical properties. • Other factors such as mechanical interlocking and fiber morphology interfere with the effects of fiber surface chemistry. - Abstract: Because wood–plastic composites (WPC) strength relies on fiber-matrix interaction at fiber surface, it is likely that fiber surface chemistry plays an important role in WPC strength development. The objective of the present study is to investigate the relationships between fiber surface chemical characteristics and WPC mechanical properties. Different fibers were selected and characterized for surface chemical characteristics using X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (FTIR). WPC samples were manufactured at 40% fiber content and with six different fibers. High density polyethylene was used as matrix and maleated polyethylene (MAPE) was used as compatibility agent. WPC samples were tested for mechanical properties and fiber-matrix interface was observed with scanning electron microscope. It was found WPC strength decreases as the amount of unoxidized carbon (assigned to lignin and extractives) measured with XPS on fiber surface increases. In the opposite case, WPC strength increases with increasing level of oxidized carbon (assigned to carbohydrates) on fiber surface. The same

  1. Adsorption of Dyes in Studying the Surface Chemistry of Ultradispersed Diamond

    Science.gov (United States)

    Khokhlova, T. D.; Yunusova, G. R.; Lanin, S. N.

    2018-05-01

    The effect the surface chemistry of ultradispersed diamond (UDD) has on the adsorption of watersoluble dyes is considered. A comparison is made to adsorption on graphitized thermal carbon black (GTCB), which has a homogeneous and nonporous surface. The adsorption isotherms of dyes and the dependence of the adsorption on the pH of solutions are measured. It is found that UDD adsorbs acid (anionic) dyes—acid orange (AO) and acid anthraquinone blue (AAB)—but barely adsorbs a basic (cationic) dye, methylene blue (MB), because of the predominance of positively charged basic groups on the surface of UDD. The maximum adsorption of AO is much lower on UDD than on GTCB, while the maximum adsorption of AAB is similar for both surfaces. The adsorption of AO on UDD depends strongly on the pH of the solution, while the adsorption of AAB is independent of this parameter. It is suggested that the adsorption of AAB is determined not only by ionic and hydrophobic interactions but also by coordination interactions with impurity metal ions on a UDD surface. It is concluded that the adsorption of dyes characterizes the chemistry of a UDD surface with high sensitivity.

  2. The contribution of inflammasome components on macrophage response to surface nanotopography and chemistry

    Science.gov (United States)

    Christo, Susan; Bachhuka, Akash; Diener, Kerrilyn R.; Vasilev, Krasimir; Hayball, John D.

    2016-05-01

    Implantable devices have become an established part of medical practice. However, often a negative inflammatory host response can impede the integration and functionality of the device. In this paper, we interrogate the role of surface nanotopography and chemistry on the potential molecular role of the inflammasome in controlling macrophage responses. To achieve this goal we engineered model substrata having precisely controlled nanotopography of predetermined height and tailored outermost surface chemistry. Bone marrow derived macrophages (BMDM) were harvested from genetically engineered mice deficient in the inflammasome components ASC, NLRP3 and AIM2. These cells were then cultured on these nanoengineered substrata and assessed for their capacity to attach and express pro-inflammatory cytokines. Our data provide evidence that the inflammasome components ASC, NLRP3 and AIM2 play a role in regulating macrophage adhesion and activation in response to surface nanotopography and chemistry. The findings of this paper are important for understanding the inflammatory consequences caused by biomaterials and pave the way to the rational design of future implantable devices having controlled and predictable inflammatory outcomes.

  3. Surface thermodynamics

    International Nuclear Information System (INIS)

    Garcia-Moliner, F.

    1975-01-01

    Basic thermodynamics of a system consisting of two bulk phases with an interface. Solid surfaces: general. Discussion of experimental data on surface tension and related concepts. Adsorption thermodynamics in the Gibbsian scheme. Adsorption on inert solid adsorbents. Systems with electrical charges: chemistry and thermodynamics of imperfect crystals. Thermodynamics of charged surfaces. Simple models of charge transfer chemisorption. Adsorption heat and related concepts. Surface phase transitions

  4. The role of surface chemistry in the cytotoxicity profile of graphene.

    Science.gov (United States)

    Majeed, Waqar; Bourdo, Shawn; Petibone, Dayton M; Saini, Viney; Vang, Kieng Bao; Nima, Zeid A; Alghazali, Karrer M; Darrigues, Emilie; Ghosh, Anindya; Watanabe, Fumiya; Casciano, Daniel; Ali, Syed F; Biris, Alexandru S

    2017-04-01

    Graphene and its derivative, because of their unique physical, electrical and chemical properties, are an important class of nanomaterials being proposed as foundational materials in nanomedicine as well as for a variety of industrial applications. A major limitation for graphene, when used in biomedical applications, is its poor solubility due to its rather hydrophobic nature. Therefore, chemical functionalities are commonly introduced to alter both its surface chemistry and biochemical activity. Here, we show that surface chemistry plays a major role in the toxicological profile of the graphene structures. To demonstrate this, we chemically increased the oxidation level of the pristine graphene and compared the corresponding toxicological effects along with those for the graphene oxide. X-ray photoelectron spectroscopy revealed that pristine graphene had the lowest amount of surface oxygen, while graphene oxide had the highest at 2.5% and 31%, respectively. Low and high oxygen functionalized graphene samples were found to have 6.6% and 24% surface oxygen, respectively. Our results showed a dose-dependent trend in the cytotoxicity profile, where pristine graphene was the most cytotoxic, with decreasing toxicity observed with increasing oxygen content. Increased surface oxygen also played a role in nanomaterial dispersion in water or cell culture medium over longer periods. It is likely that higher dispersity might result in graphene entering into cells as individual flakes ~1 nm thick rather than as more cytotoxic aggregates. In conclusion, changes in graphene's surface chemistry resulted in altered solubility and toxicity, suggesting that a generalized toxicity profile would be rather misleading. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  5. 3D printed glass: surface finish and bulk properties as a function of the printing process

    Science.gov (United States)

    Klein, Susanne; Avery, Michael P.; Richardson, Robert; Bartlett, Paul; Frei, Regina; Simske, Steven

    2015-03-01

    It is impossible to print glass directly from a melt, layer by layer. Glass is not only very sensitive to temperature gradients between different layers but also to the cooling process. To achieve a glass state the melt, has to be cooled rapidly to avoid crystallization of the material and then annealed to remove cooling induced stress. In 3D-printing of glass the objects are shaped at room temperature and then fired. The material properties of the final objects are crucially dependent on the frit size of the glass powder used during shaping, the chemical formula of the binder and the firing procedure. For frit sizes below 250 μm, we seem to find a constant volume of pores of less than 5%. Decreasing frit size leads to an increase in the number of pores which then leads to an increase of opacity. The two different binders, 2- hydroxyethyl cellulose and carboxymethylcellulose sodium salt, generate very different porosities. The porosity of samples with 2-hydroxyethyl cellulose is similar to frit-only samples, whereas carboxymethylcellulose sodium salt creates a glass foam. The surface finish is determined by the material the glass comes into contact with during firing.

  6. 3He impurity states on liquid 4He: From thin films to the bulk surface

    International Nuclear Information System (INIS)

    Pavloff, N.; Treiner, J.

    1991-01-01

    The structure of the states accessible to 3 He impurities in films of liquid 4 He on Nuclepore is investigated using a density functional approach with a finite-range effective interaction. In thick films, one finds that the two lowest states are localized in the surface region. For thinner films, the variation with film thickness of the first three states results from a delicate balance between the attractive tail of the substrate potential and the quantum finite-size effect. The existence of states localized in the second layer of the films is discussed. The energy difference between the ground state and the first excited state agrees with the recent determination of Higley, Sprague, and Hallock from magnetization measurements. The effective mass of the ground state has a structure similar to that obtained by Krotscheck and coworkers and exhibits a maximum for a 4 He coverage of 0.15 angstrom -2 , in agreement with the data of Gasparini and coworkers. A similar behavior is predicted for the effective mass of the first, second, and third excited states. The structure of the energy spectrum may also explain former results on third-sound measurements in thin mixture films by Laheurte et al. and by Hallock

  7. Bioadhesion of mussels and geckos: Molecular mechanics, surface chemistry, and nanoadhesives

    Science.gov (United States)

    Lee, Haeshin

    The adhesive strategies of living creatures are diverse, ranging from temporary to permanent adhesions with various functions such as locomotion, self-defense, communication, colony formation, and so on. The classic example of temporary adhesion is the gecko, which is known for its ability to walk along vertical and even inverted surfaces; this remarkable adhesion arises from the interfacial weak interactions of van der Waals and capillary forces. In contrast, a celerbrated example of permanent adhesion is found in marine mussels which secrete protein adhesives that function in aqueous environments without mechanical failure against turbulent conditions on the seashore. In addition, mussel adhesives stick to virtually all inorganic and organic surfaces. However, most commonly used man-made adhesives lack such unique adhesion properties compared to their natural counterparts. For example, many commercial adhesives quickly lose their adhesive strength when exposed to solvents, particularly water. The first part of this thesis focused on adhesion mechanics of mussels at a single-molecule level, in which the adhesive molecule showed surprisingly strong yet reversible adhesion on inorganic surfaces but exhibited irreversible covalent bond formation on organic surfaces. Strong and reversible adhesion on mucin surfaces was found, indicating potential application for drug delivery via mucus layers. Next, inspired by the mussel's versatile adhesion on a wide variety of material surfaces, a material-independent surface modification chemistry called 'polydopamine coating' is described. This concept was subsequently adapted to develop a surface-independent polymeric primer for layer-by-layer assembly of multifunctional coatings. Finally, a new bio-hybrid adhesive 'geckel' was developed by the functional combination of adhesion strategies of geckos and mussels. The new bio-inspired adhesive and material-independent surface chemistry can revolutionize the research areas such as

  8. Metals on graphene and carbon nanotube surfaces: From mobile atoms to atomtronics to bulk metals to clusters and catalysts

    KAUST Repository

    Sarkar, Santanu C.

    2014-01-14

    In this Perspective, we present an overview of recent fundamental studies on the nature of the interaction between individual metal atoms and metal clusters and the conjugated surfaces of graphene and carbon nanotube with a particular focus on the electronic structure and chemical bonding at the metal-graphene interface. We discuss the relevance of organometallic complexes of graphitic materials to the development of a fundamental understanding of these interactions and their application in atomtronics as atomic interconnects, high mobility organometallic transistor devices, high-frequency electronic devices, organometallic catalysis (hydrogen fuel generation by photocatalytic water splitting, fuel cells, hydrogenation), spintronics, memory devices, and the next generation energy devices. We touch on chemical vapor deposition (CVD) graphene grown on metals, the reactivity of its surface, and its use as a template for asymmetric graphene functionalization chemistry (ultrathin Janus discs). We highlight some of the latest advances in understanding the nature of interactions between metals and graphene surfaces from the standpoint of metal overlayers deposited on graphene and SWNT thin films. Finally, we comment on the major challenges facing the field and the opportunities for technological applications. © 2013 American Chemical Society.

  9. Surface microstructure and chemistry of polyimide by single pulse ablation of picosecond laser

    Science.gov (United States)

    Du, Qifeng; Chen, Ting; Liu, Jianguo; Zeng, Xiaoyan

    2018-03-01

    Polyimide (PI) surface was ablated by the single pulse of picosecond laser, and the effects of laser wavelength (λ= 355 nm and 1064 nm) and fluence on surface microstructure and chemistry were explored. Scanning electron microscopy (SEM) analysis found that different surface microstructures, i.e., the concave of concentric ring and the convex of porous circular disk, were generated by 355 nm and 1064 nm picosecond laser ablation, respectively. X-ray photoelectron spectroscopy (XPS) characterization indicated that due to the high peak energy density of picosecond laser, oxygen and nitrogen from the ambient were incorporated into the PI surface mainly in the form of Cdbnd O and Csbnd Nsbnd C groups. Thus, both of the O/C and N/C atomic content ratios increased, but the increase caused by 1064 nm wavelength laser was larger. It inferred that the differences of PI surface microstructures and chemistry resulted from different laser parameters were related to different laser-matter interaction effects. For 355 nm picosecond laser, no obvious thermal features were observed and the probable ablation process of PI was mainly governed by photochemical effect; while for 1064 nm picosecond laser, obvious thermal feature appeared and photothermal effect was thought to be dominant.

  10. The Influence of Surface Chemistry on the Optoelectronic Properties of Semiconductor Quantum Dots

    Science.gov (United States)

    Harris, Rachel Dory

    This dissertation describes the relationship between the surface chemistry of colloidal semiconductor nanocrystals (quantum dots, QDs) and their optoelectronic properties, such as photoluminescence and degree of quantum confinement. We primarily focus our efforts on one particular subset of ligands known to couple strongly to the inorganic core of the QD to decrease its quantum confinement, phenyldithiocarbamates (PTCs). We focus first on the development of quantitative Nuclear Magnetic Resonance (NMR) techniques to characterize the identity and quantity of ligands (such as PTCs and oleic acid) bound to nanocrystal surfaces. When we correlate the surface chemistry information obtained from NMR with the optical spectra of our QDs, we find that for strongly-delocalizing ligands like PTC, the spatial distribution of ligands on the QD surface affects the overall degree of delocalization. In the later chapters of this thesis, we describe two avenues for exploiting the relationship between surface coverage of exciton-delocalizing ligands and quantum confinement to design strongly coupled, hierarchical nanomaterials for efficient charge transport in films or in solution. We explore the treatment of thin lead sulfide QD films with a PTC derivative to improve their overall conductivity relative to benzoic acid, a similar molecule that does not affect confinement. Finally, we describe a potential strategy to improve the yield and rate of hole transfer to a tethered phthalocyanine molecule using dithiocarbamate and thiolate linkers.

  11. Perchlorate formation on Mars through surface radiolysis-initiated atmospheric chemistry: A potential mechanism

    Science.gov (United States)

    Wilson, Eric H.; Atreya, Sushil K.; Kaiser, Ralf I.; Mahaffy, Paul R.

    2016-08-01

    Recent observations of the Martian surface by the Phoenix lander and the Sample Analysis at Mars indicate the presence of perchlorate (ClO4-). The abundance and isotopic composition of these perchlorates suggest that the mechanisms responsible for their formation in the Martian environment may be unique in our solar system. With this in mind, we propose a potential mechanism for the production of Martian perchlorate: the radiolysis of the Martian surface by galactic cosmic rays, followed by the sublimation of chlorine oxides into the atmosphere and their subsequent synthesis to form perchloric acid (HClO4) in the atmosphere, and the surface deposition and subsequent mineralization of HClO4 in the regolith to form surface perchlorates. To evaluate the viability of this mechanism, we employ a one-dimensional chemical model, examining chlorine chemistry in the context of Martian atmospheric chemistry. Considering the chlorine oxide, OClO, we find that an OClO flux as low as 3.2 × 107 molecules cm-2 s-1 sublimated into the atmosphere from the surface could produce sufficient HClO4 to explain the perchlorate concentration on Mars, assuming an accumulation depth of 30 cm and integrated over the Amazonian period. Radiolysis provides an efficient pathway for the oxidation of chlorine, bypassing the efficient Cl/HCl recycling mechanism that characterizes HClO4 formation mechanisms proposed for the Earth but not Mars.

  12. Surface chemistry and acid-base activity of Shewanella putrefaciens: Cell wall charging and metal binding to bacterial cell walls

    NARCIS (Netherlands)

    Claessens, Jacqueline Wilhelmien

    2006-01-01

    To gain insight into the surface chemistry of live microorganisms, pH stat experiments are combined with analyses of the time-dependent changes in solution chemistry using suspensions of live cells of Shewanella putrefaciens. The results of this study illustrate the complex response of the live

  13. Surface chemistry and acid-base activity of Shewanella putrefaciens : Cell wall charging and metal binding to bacterial cell walls

    NARCIS (Netherlands)

    Claessens, J.W.

    2006-01-01

    To gain insight into the surface chemistry of live microorganisms, pH stat experiments are combined with analyses of the time-dependent changes in solution chemistry using suspensions of live cells of Shewanella putrefaciens. The results of this study illustrate the complex response of the live

  14. Experimental studies of lithium-based surface chemistry for fusion plasma-facing materials applications

    International Nuclear Information System (INIS)

    Allain, J.P.; Rokusek, D.L.; Harilal, S.S.; Nieto-Perez, M.; Skinner, C.H.; Kugel, H.W.; Heim, B.; Kaita, R.; Majeski, R.

    2009-01-01

    Lithium has enhanced the operational performance of fusion devices such as: TFTR, CDX-U, FTU, T-11 M, and NSTX. Lithium in the solid and liquid state has been studied extensively in laboratory experiments including its erosion and hydrogen-retaining properties. Reductions in physical sputtering up to 40-60% have been measured for deuterated solid and liquid lithium surfaces. Computational modeling indicates that up to a 1:1 deuterium volumetric retention in lithium is possible. This paper presents the results of systematic in situ laboratory experimental studies on the surface chemistry evolution of ATJ graphite under lithium deposition. Results are compared to post-mortem analysis of similar lithium surface coatings on graphite exposed to deuterium discharge plasmas in NSTX. Lithium coatings on plasma-facing components in NSTX have shown substantial reduction of hydrogenic recycling. Questions remain on the role lithium surface chemistry on a graphite substrate has on particle sputtering (physical and chemical) as well as hydrogen isotope recycling. This is particularly due to the lack of in situ measurements of plasma-surface interactions in tokamaks such as NSTX. Results suggest that the lithium bonding state on ATJ graphite is lithium peroxide and with sufficient exposure to ambient air conditions, lithium carbonate is generated. Correlation between both results is used to assess the role of lithium chemistry on the state of lithium bonding and implications on hydrogen pumping and lithium sputtering. In addition, reduction of factors between 10 and 30 reduction in physical sputtering from lithiated graphite compared to pure lithium or carbon is also measured.

  15. New Concept of C–H and C–C Bond Activation via Surface Organometallic Chemistry

    KAUST Repository

    Samantaray, Manoja

    2015-08-18

    In this chapter we describe the recent applications of well-defined oxidesupported metal alkyls/alkylidenes/alkylidynes and hydrides of group IV, V, and VI transition metals in the field of C–H and C–C bond activation. The activation of ubiquitous C–H and C–C bonds of paraffin is a long-standing challenge because of intrinsic low reactivity. There are many concepts derived from surface organometallic chemistry (SOMC): surface organometallic fragments are always intermediates in heterogeneous catalysis. The study of their synthesis and reactivity is a way to rationalize mechanism of heterogeneous catalysis and to achieve structure activity relationship. By surface organometallic chemistry one can enter any catalytic center by a reaction intermediate leading in fine to single site catalysts. With surface organometallic chemistry one can coordinate to the metal which can play a role in different elementary steps leading for example to C–H activation and Olefin metathesis. Because of the development of SOMC there is a lot of space for the improvement of homogeneous catalysis. After the 1997 discovery of alkane metathesis using silica-supported tantalum hydride by Basset et al. at low temperature (150ºC) the focus in this area was shifted to the discovery of more and more challenging surface complexes active in the application of C–H and C–C bond activation. Here we describe the evolution of well-defined metathesis catalyst with time as well as the effect of support on catalysis. We also describe here which metal–ligand combinations are responsible for a variety of C–H and C–C bond activation.

  16. Field and laboratory emission cell automation and control system for investigating surface chemistry reactions

    Science.gov (United States)

    Flemmer, Michael M.; Ham, Jason E.; Wells, J. R.

    2007-01-01

    A novel system [field and laboratory emission cell (FLEC) automation and control system] has been developed to deliver ozone to a surface utilizing the FLEC to simulate indoor surface chemistry. Ozone, humidity, and air flow rate to the surface were continuously monitored using an ultraviolet ozone monitor, humidity, and flow sensors. Data from these sensors were used as feedback for system control to maintain predetermined experimental parameters. The system was used to investigate the chemistry of ozone with α-terpineol on a vinyl surface over 72h. Keeping all other experimental parameters the same, volatile organic compound emissions from the vinyl tile with α-terpineol were collected from both zero and 100ppb(partsper109) ozone exposures. System stability profiles collected from sensor data indicated experimental parameters were maintained to within a few percent of initial settings. Ozone data from eight experiments at 100ppb (over 339h) provided a pooled standard deviation of 1.65ppb and a 95% tolerance of 3.3ppb. Humidity data from 17 experiments at 50% relative humidity (over 664h) provided a pooled standard deviation of 1.38% and a 95% tolerance of 2.77%. Data of the flow rate of air flowing through the FLEC from 14 experiments at 300ml/min (over 548h) provided a pooled standard deviation of 3.02ml/min and a 95% tolerance range of 6.03ml/min. Initial experimental results yielded long term emissions of ozone/α-terpineol reaction products, suggesting that surface chemistry could play an important role in indoor environments.

  17. Pretreatment-dependent surface chemistry of wood nanocellulose for pH-sensitive hydrogels.

    Science.gov (United States)

    Chinga-Carrasco, Gary; Syverud, Kristin

    2014-09-01

    Nanocellulose from wood is a promising material with potential in various technological areas. Within biomedical applications, nanocellulose has been proposed as a suitable nano-material for wound dressings. This is based on the capability of the material to self-assemble into 3D micro-porous structures, which among others have an excellent capacity of maintaining a moist environment. In addition, the surface chemistry of nanocellulose is suitable for various applications. First, OH-groups are abundant in nanocellulose materials, making the material strongly hydrophilic. Second, the surface chemistry can be modified, introducing aldehyde and carboxyl groups, which have major potential for surface functionalization. In this study, we demonstrate the production of nanocellulose with tailor-made surface chemistry, by pre-treating the raw cellulose fibres with carboxymethylation and periodate oxidation. The pre-treatments yielded a highly nanofibrillated material, with significant amounts of aldehyde and carboxyl groups. Importantly, the poly-anionic surface of the oxidized nanocellulose opens up for novel applications, i.e. micro-porous materials with pH-responsive characteristics. This is due to the swelling capacity of the 3D micro-porous structures, which have ionisable functional groups. In this study, we demonstrated that nanocellulose gels have a significantly higher swelling degree in neutral and alkaline conditions, compared to an acid environment (pH 3). Such a capability can potentially be applied in chronic wounds for controlled and intelligent release of antibacterial components into biofilms. © The Author(s) 2014 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

  18. The Chemistry of Inorganic Precursors during the Chemical Deposition of Films on Solid Surfaces.

    Science.gov (United States)

    Barry, Seán T; Teplyakov, Andrew V; Zaera, Francisco

    2018-03-20

    The deposition of thin solid films is central to many industrial applications, and chemical vapor deposition (CVD) methods are particularly useful for this task. For one, the isotropic nature of the adsorption of chemical species affords even coverages on surfaces with rough topographies, an increasingly common requirement in microelectronics. Furthermore, by splitting the overall film-depositing reactions into two or more complementary and self-limiting steps, as it is done in atomic layer depositions (ALD), film thicknesses can be controlled down to the sub-monolayer level. Thanks to the availability of a vast array of inorganic and metalorganic precursors, CVD and ALD are quite versatile and can be engineered to deposit virtually any type of solid material. On the negative side, the surface chemistry that takes place in these processes is often complex, and can include undesirable side reactions leading to the incorporation of impurities in the growing films. Appropriate precursors and deposition conditions need to be chosen to minimize these problems, and that requires a proper understanding of the underlying surface chemistry. The precursors for CVD and ALD are often designed and chosen based on their known thermal chemistry from inorganic chemistry studies, taking advantage of the vast knowledge developed in that field over the years. Although a good first approximation, however, this approach can lead to wrong choices, because the reactions of these precursors at gas-solid interfaces can be quite different from what is seen in solution. For one, solvents often aid in the displacement of ligands in metalorganic compounds, providing the right dielectric environment, temporarily coordinating to the metal, or facilitating multiple ligand-complex interactions to increase reaction probabilities; these options are not available in the gas-solid reactions associated with CVD and ALD. Moreover, solid surfaces act as unique "ligands", if these reactions are to be

  19. A dynamic duo: pairing click chemistry and postpolymerization modification to design complex surfaces.

    Science.gov (United States)

    Arnold, Rachelle M; Patton, Derek L; Popik, Vladimir V; Locklin, Jason

    2014-10-21

    Advances in key 21st century technologies such as biosensors, biomedical implants, and organic light-emitting diodes rely heavily on our ability to imagine, design, and understand spatially complex interfaces. Polymer-based thin films provide many advantages in this regard, but the direct synthesis of polymers with incompatible functional groups is extremely difficult. Using postpolymerization modification in conjunction with click chemistry can circumvent this limitation and result in multicomponent surfaces that are otherwise unattainable. The two methods used to form polymer thin films include physisorption and chemisorption. Physisorbed polymers suffer from instability because of the weak intermolecular forces between the film and the substrate, which can lead to dewetting, delamination, desorption, or displacement. Covalent immobilization of polymers to surfaces through either a "grafting to" or "grafting from" approach provides thin films that are more robust and less prone to degradation. The grafting to technique consists of adsorbing a polymer containing at least one reactive group along the backbone to form a covalent bond with a complementary surface functionality. Grafting from involves polymerization directly from the surface, in which the polymer chains deviate from their native conformation in solution and stretch away from the surface because of the high density of chains. Postpolymerization modification (PPM) is a strategy used by our groups over the past several years to immobilize two or more different chemical functionalities onto substrates that contain covalently grafted polymer films. PPM exploits monomers with reactive pendant groups that are stable under the polymerization conditions but are readily modified via covalent attachment of the desired functionality. "Click-like" reactions are the most common type of reactions used for PPM because they are orthogonal, high-yielding, and rapid. Some of these reactions include thiol-based additions

  20. Surface chemistry of Ti6Al4V components fabricated using selective laser melting for biomedical applications

    Energy Technology Data Exchange (ETDEWEB)

    Vaithilingam, Jayasheelan, E-mail: Jayasheelan.Vaithilingam@nottingham.ac.uk [Additive Manufacturing and 3D Printing Research Group, EPSRC Centre for Innovative Manufacturing in Additive Manufacturing, School of Engineering, The University of Nottingham, Nottingham NG7 2RD (United Kingdom); Prina, Elisabetta [School of Pharmacy, Centre for Biomolecular Sciences, The University of Nottingham, Nottingham NG7 2RD (United Kingdom); Goodridge, Ruth D.; Hague, Richard J.M. [Additive Manufacturing and 3D Printing Research Group, EPSRC Centre for Innovative Manufacturing in Additive Manufacturing, School of Engineering, The University of Nottingham, Nottingham NG7 2RD (United Kingdom); Edmondson, Steve [School of Materials, The University of Manchester, Manchester M13 9PL (United Kingdom); Rose, Felicity R.A.J. [School of Pharmacy, Centre for Biomolecular Sciences, The University of Nottingham, Nottingham NG7 2RD (United Kingdom); Christie, Steven D.R. [Department of Chemistry, Loughborough University, Loughborough LE11 3TU (United Kingdom)

    2016-10-01

    Selective laser melting (SLM) has previously been shown to be a viable method for fabricating biomedical implants; however, the surface chemistry of SLM fabricated parts is poorly understood. In this study, X-ray photoelectron spectroscopy (XPS) was used to determine the surface chemistries of (a) SLM as-fabricated (SLM-AF) Ti6Al4V and (b) SLM fabricated and mechanically polished (SLM-MP) Ti6Al4V samples and compared with (c) traditionally manufactured (forged) and mechanically polished Ti6Al4V samples. The SLM–AF surface was observed to be porous with an average surface roughness (Ra) of 17.6 ± 3.7 μm. The surface chemistry of the SLM-AF was significantly different to the FGD-MP surface with respect to elemental distribution and their existence on the outermost surface. Sintered particles on the SLM-AF surface were observed to affect depth profiling of the sample due to a shadowing effect during argon ion sputtering. Surface heterogeneity was observed for all three surfaces; however, vanadium was witnessed only on the mechanically polished (SLM-MP and FGD-MP) surfaces. The direct and indirect 3T3 cell cytotoxicity studies revealed that the cells were viable on the SLM fabricated Ti6Al4V parts. The varied surface chemistry of the SLM-AF and SLM-MP did not influence the cell behaviour. - Highlights: • Surface chemistry of selective laser melted (SLM) Ti6Al4V parts was compared with conventionally forged Ti6Al4V parts. • The surface elemental compositions of the SLM as-fabricated surfaces were significantly different to the forged surface. • Surface oxide-layer of the SLM as-fabricated was thicker than the polished SLM surfaces and the forged Ti6Al4V surfaces.

  1. Surface Chemistry Involved in Epitaxy of Graphene on 3C-SiC(111/Si(111

    Directory of Open Access Journals (Sweden)

    Abe Shunsuke

    2010-01-01

    Full Text Available Abstract Surface chemistry involved in the epitaxy of graphene by sublimating Si atoms from the surface of epitaxial 3C-SiC(111 thin films on Si(111 has been studied. The change in the surface composition during graphene epitaxy is monitored by in situ temperature-programmed desorption spectroscopy using deuterium as a probe (D2-TPD and complementarily by ex situ Raman and C1s core-level spectroscopies. The surface of the 3C-SiC(111/Si(111 is Si-terminated before the graphitization, and it becomes C-terminated via the formation of C-rich (6√3 × 6√3R30° reconstruction as the graphitization proceeds, in a similar manner as the epitaxy of graphene on Si-terminated 6H-SiC(0001 proceeds.

  2. Multiphase chemical kinetics of OH radical uptake by molecular organic markers of biomass burning aerosols: humidity and temperature dependence, surface reaction, and bulk diffusion.

    Science.gov (United States)

    Arangio, Andrea M; Slade, Jonathan H; Berkemeier, Thomas; Pöschl, Ulrich; Knopf, Daniel A; Shiraiwa, Manabu

    2015-05-14

    Multiphase reactions of OH radicals are among the most important pathways of chemical aging of organic aerosols in the atmosphere. Reactive uptake of OH by organic compounds has been observed in a number of studies, but the kinetics of mass transport and chemical reaction are still not fully understood. Here we apply the kinetic multilayer model of gas-particle interactions (KM-GAP) to experimental data from OH exposure studies of levoglucosan and abietic acid, which serve as surrogates and molecular markers of biomass burning aerosol (BBA). The model accounts for gas-phase diffusion within a cylindrical coated-wall flow tube, reversible adsorption of OH, surface-bulk exchange, bulk diffusion, and chemical reactions at the surface and in the bulk of the condensed phase. The nonlinear dependence of OH uptake coefficients on reactant concentrations and time can be reproduced by KM-GAP. We find that the bulk diffusion coefficient of the organic molecules is approximately 10(-16) cm(2) s(-1), reflecting an amorphous semisolid state of the organic substrates. The OH uptake is governed by reaction at or near the surface and can be kinetically limited by surface-bulk exchange or bulk diffusion of the organic reactants. Estimates of the chemical half-life of levoglucosan in 200 nm particles in a biomass burning plume increase from 1 day at high relative humidity to 1 week under dry conditions. In BBA particles transported to the free troposphere, the chemical half-life of levoglucosan can exceed 1 month due to slow bulk diffusion in a glassy matrix at low temperature.

  3. Strong excitation of surface and bulk spin waves in yttrium iron garnet placed in a split ring resonator

    Science.gov (United States)

    Tay, Z. J.; Soh, W. T.; Ong, C. K.

    2018-02-01

    This paper presents an experimental study of the inverse spin Hall effect (ISHE) in a bilayer consisting of a yttrium iron garnet (YIG) and platinum (Pt) loaded on a metamaterial split ring resonator (SRR). The system is excited by a microstrip feed line which generates both surface and bulk spin waves in the YIG. The spin waves subsequently undergo spin pumping from the YIG film to an adjacent Pt layer, and is converted into a charge current via the ISHE. It is found that the presence of the SRR causes a significant enhancement of the mangetic field near the resonance frequency of the SRR, resulting in a significant increase in the ISHE signal. Furthermore, the type of spin wave generated in the system can be controlled by changing the external applied magnetic field angle (θH ). When the external applied magnetic field is near parallel to the microstrip line (θH = 0 ), magnetostatic surface spin waves are predominantly excited. On the other hand, when the external applied magnetic field is perpendicular to the microstrip line (θH = π/2 ), backward volume magnetostatic spin waves are predominantly excited. Hence, it can be seen that the SRR structure is a promising method of achieving spin-charge conversion, which has many advantages over a coaxial probe.

  4. Annealing and surface conduction on Hydrogen peroxide treated bulk melt-grown, single crystal ZnO

    International Nuclear Information System (INIS)

    Mtangi, W.; Nel, J.M.; Auret, F.D.; Chawanda, A.; Diale, M.; Nyamhere, C.

    2012-01-01

    We report on the studies carried out on hydrogen peroxide treated melt-grown, bulk single crystal ZnO samples. Results show the existence of two shallow donors in the as-received ZnO samples with energy levels (37.8±0.3) meV that has been suggested as Zn i related and possibly H-complex related and (54.5±0.9) meV, which has been assigned to an Al-related donor. Annealing studies performed on the hydrogen peroxide treated samples reveal the existence of a conductive channel in the samples in which new energy levels have been observed, Zn vacancies, related to the Group I elements, X Zn . The surface donor volume concentration of the conductive channel was calculated from a theory developed by Look (2007) . Results indicate an increase in the surface volume concentration with increasing annealing temperature from 60×10 17 cm −3 at 200 °C to 4.37×10 18 cm -3 at 800 °C.

  5. Annealing and surface conduction on Hydrogen peroxide treated bulk melt-grown, single crystal ZnO

    Energy Technology Data Exchange (ETDEWEB)

    Mtangi, W., E-mail: wilbert.mtangi@up.ac.za [University of Pretoria, Physics Department, Pretoria 0002 (South Africa); Nel, J.M.; Auret, F.D.; Chawanda, A.; Diale, M. [University of Pretoria, Physics Department, Pretoria 0002 (South Africa); Nyamhere, C. [Nelson Mandela Metropolitan University, Physics Department, P.O. Box 77000, Port Elizabeth 6031 (South Africa)

    2012-05-15

    We report on the studies carried out on hydrogen peroxide treated melt-grown, bulk single crystal ZnO samples. Results show the existence of two shallow donors in the as-received ZnO samples with energy levels (37.8{+-}0.3) meV that has been suggested as Zn{sub i} related and possibly H-complex related and (54.5{+-}0.9) meV, which has been assigned to an Al-related donor. Annealing studies performed on the hydrogen peroxide treated samples reveal the existence of a conductive channel in the samples in which new energy levels have been observed, Zn vacancies, related to the Group I elements, X{sub Zn}. The surface donor volume concentration of the conductive channel was calculated from a theory developed by Look (2007) . Results indicate an increase in the surface volume concentration with increasing annealing temperature from 60 Multiplication-Sign 10{sup 17} cm{sup -3} at 200 Degree-Sign C to 4.37 Multiplication-Sign 10{sup 18} cm{sup -3} at 800 Degree-Sign C.

  6. Investigation of the rates of surface and bulk ROS-generating reactions using indigo dye as an indicator

    Science.gov (United States)

    Anderson, Carly; Clark, Douglas; Graves, David

    2014-10-01

    We present evidence for the existence of two distinct processes that contribute to the generation of reactive oxygen and nitrogen species (RONS) in liquids exposed to cold atmospheric plasma (CAP) in air. At the plasma-liquid interface, there exists a fast surface reaction zone where RONS from the gas phase interact with species in the liquid. RONS can also be produced by ``slow'' chemical reactions in the bulk liquid, even long after plasma exposure. To separate the effects of these processes, we used indigo dye as an indicator of ROS production; specifically generation of hydroxyl radical. The rate of indigo decolorization while in direct contact with CAP is compared with the expected rate of hydroxyl radical generation at the liquid surface. When added to aqueous solutions after CAP exposure, indigo dye reacts on a time scale consistent with the production of peroxynitrous acid, ONOOH, which is known to decompose to hydroxyl radical below a pH of 6.8. In this study, the CAP used was a air corona discharge plasma run in a positive streamer mode.

  7. High resolution Brillouin scattering studies of β-Gd2(MoO4)3; the bulk and surface phase transitions

    International Nuclear Information System (INIS)

    Mielcarek, S; Trzaskowska, A; Mroz, B; Andrews, T

    2005-01-01

    We present here results of Brillouin scattering from bulk and surface phonons propagating in a well known ferroelectric-ferroelastic crystal β-Gd 2 (MoO 4 ) 3 , in the temperature range covering the phase transition. Temperature dependences of the velocity of Rayleigh surface acoustic waves, propagating in a few planes of this crystal, have been calculated. The surface phonon velocities determined experimentally have been found to show a different character of temperature dependences, especially in the phase transition range

  8. Analysis of Surface Chemistry and Detector Performance of Chemically Process CdZnTe crystals

    Energy Technology Data Exchange (ETDEWEB)

    HOSSAIN, A.; Yang, G.; Sutton, J.; Zergaw, T.; Babalola, O. S.; Bolotnikov, A. E.; Camarda. ZG. S.; Gul, R.; Roy, U. N., and James, R. B.

    2015-10-05

    The goal is to produce non-conductive smooth surfaces for fabricating low-noise and high-efficiency CdZnTe devices for gamma spectroscopy. Sample preparation and results are discussed. The researachers demonstrated various bulk defects (e.g., dislocations and sub-grain boundaries) and surface defects, and examined their effects on the performance of detectors. A comparison study was made between two chemical etchants to produce non-conductive smooth surfaces. A mixture of bromine and hydrogen peroxide proved more effective than conventional bromine etchant. Both energy resolution and detection efficiency of CZT planar detectors were noticeably increased after processing the detector crystals using improved chemical etchant and processing methods.

  9. Surface chemistry on bimetallic alloy surfaces: adsorption of anions and oxidation of CO on Pt3Sn(111).

    Science.gov (United States)

    Stamenković, Vojislav R; Arenz, Matthias; Lucas, Christopher A; Gallagher, Mark E; Ross, Philip N; Marković, Nenad M

    2003-03-05

    The microscopic structure of the Pt(3)Sn(111) surface in an electrochemical environment has been studied by a combination of ex situ low-energy electron diffraction (LEED), Auger electron spectroscopy (AES), and low-energy ion scattering (LEIS) and in situ surface X-ray scattering (SXS) and Fourier transform infrared (FTIR) spectroscopy. In ultrahigh vacuum (UHV) the clean-annealed surface produces a p(2 x 2) LEED pattern consistent with the surface composition, determined by LEIS, of 25 at. % Sn. SXS results show that the p(2 x 2) structure can be "transferred" from UHV into 0.5 M H(2)SO(4) and that the surface structure remains stable from 0.05 to 0.8 V. At 0.05 V the expansion of Pt surface atoms, ca. +2% from the bulk lattice spacing, is induced by adsorption of underpotential-deposited (UPD) hydrogen. At 0.5 V, where Pt atoms are covered by (bi)sulfate anions, the topmost layer is contracted relative to 0.05 V, although Sn atoms expand significantly, ca. 8.5%. The p(2 x 2) structure is stable even in solutions containing CO. In contrast to the Pt(111)-CO system, no ordered structures of CO are formed on the Pt(3)Sn(111) surface and the topmost layer expands relatively little (ca. 1.5%) from the bulk lattice spacing upon the adsorption of CO. The binding site geometry of CO on Pt(3)Sn(111) is determined by FTIR. In contrast to the near invariant band shape of a-top CO on Pt(111), changes in band morphology (splitting of the band) and vibrational properties (increase in the frequency mode) are clearly visible on the Pt(3)Sn(111) surface. To explain the line shape of the CO bands, we suggest that in addition to alloying effects other factors, such as intermolecular repulsion between coadsorbed CO and OH species, are controlling segregation of CO into cluster domains where the local CO coverage is different from the coverage expected for the CO-CO interaction on an unmodified Pt(111) surface.

  10. Ethers on Si(001): A prime example for the common ground between surface science and molecular organic chemistry

    KAUST Repository

    Pecher, Lisa

    2017-09-15

    Using computational chemistry, we show that the adsorption of ether molecules on Si(001) under ultra-high vacuum conditions can be understood with textbook organic chemistry. The two-step reaction mechanism of (1) dative bond formation between the ether oxygen and a Lewis acidic surface atom and (2) a nucleophilic attack of a nearby Lewis basic surface atom is analysed in detail and found to mirror the acid-catalysed ether cleavage in solution. The O-Si dative bond is found to be the strongest of its kind and reactivity from this state defies the Bell-Evans-Polanyi principle. Electron rearrangement during the C-O bond cleavage is visualized using a newly developed bonding analysis method, which shows that the mechanism of nucleophilic substitutions on semiconductor surfaces is identical to molecular chemistry SN2 reactions. Our findings thus illustrate how the fields of surface science and molecular chemistry can mutually benefit and unexpected insight can be gained.

  11. Substantial difference in target surface chemistry between reactive dc and high power impulse magnetron sputtering

    Science.gov (United States)

    Greczynski, G.; Mráz, S.; Schneider, J. M.; Hultman, L.

    2018-02-01

    The nitride layer formed in the target race track during the deposition of stoichiometric TiN thin films is a factor 2.5 thicker for high power impulse magnetron sputtering (HIPIMS), compared to conventional dc processing (DCMS). The phenomenon is explained using x-ray photoelectron spectroscopy analysis of the as-operated Ti target surface chemistry supported by sputter depth profiles, dynamic Monte Carlo simulations employing the TRIDYN code, and plasma chemical investigations by ion mass spectrometry. The target chemistry and the thickness of the nitride layer are found to be determined by the implantation of nitrogen ions, predominantly N+ and N2+ for HIPIMS and DCMS, respectively. Knowledge of this method-inherent difference enables robust processing of high quality functional coatings.

  12. Control and Characterization of Titanium Dioxide Morphology: Applications in Surface Organometallic Chemistry

    KAUST Repository

    Jeantelot, Gabriel

    2014-05-01

    Surface Organometallic Chemistry leads to the combination of the high activity and specificity of homogeneous catalysts with the recoverability and practicality of heterogeneous catalysts. Most metal complexes used in this chemistry are grafted on metal oxide supports such as amorphous silica (SiO2) and γ-alumina (Al2O3). In this thesis, we sought to enable the use of titania (TiO2) as a new support for single-site well-defined grafting of metal complexes. This was achieved by synthesizing a special type of anatase-TiO2, bearing a high density of identical hydroxyl groups, through hydrothermal synthesis then post-treatment under high vacuum followed by oxygen flow, and characterized by several analytical techniques including X-ray diffraction, transmission electron microscopy, infrared spectroscopy and nuclear magnetic resonance. Finally, as a proof of concept, the grafting of vanadium oxychloride (VOCl3) was successfully attempted.

  13. Observation of core-level binding energy shifts between (100) surface and bulk atoms of epitaxial CuInSe{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, A.J. [Colorado School of Mines, Golden, CO (United States); Berry, G.; Rockett, A. [Univ. of Illinois, Urbana-Champaign, IL (United States)] [and others

    1997-04-01

    Core-level and valence band photoemission from semiconductors has been shown to exhibit binding energy differences between surface atoms and bulk atoms, thus allowing one to unambiguously distinguish between the two atomic positions. Quite clearly, surface atoms experience a potential different from the bulk due to the lower coordination number - a characteristic feature of any surface is the incomplete atomic coordination. Theoretical accounts of this phenomena are well documented in the literature for III-V and II-VI semiconductors. However, surface state energies corresponding to the equilibrium geometry of (100) and (111) surfaces of Cu-based ternary chalcopyrite semiconductors have not been calculated or experimental determined. These compounds are generating great interest for optoelectronic and photovoltaic applications, and are an isoelectronic analog of the II-VI binary compound semiconductors. Surface core-level binding energy shifts depend on the surface cohesive energies, and surface cohesive energies are related to surface structure. For ternary compound semiconductor surfaces, such as CuInSe{sub 2}, one has the possibility of variations in surface stoichiometry. Applying standard thermodynamical calculations which consider the number of individual surface atoms and their respective chemical potentials should allow one to qualitatively determine the magnitude of surface core-level shifts and, consequently, surface state energies.

  14. Combined effects of surface conditions, boundary layer dynamics and chemistry on diurnal SOA evolution

    Directory of Open Access Journals (Sweden)

    R. H. H. Janssen

    2012-08-01

    Full Text Available We study the combined effects of land surface conditions, atmospheric boundary layer dynamics and chemistry on the diurnal evolution of biogenic secondary organic aerosol in the atmospheric boundary layer, using a model that contains the essentials of all these components. First, we evaluate the model for a case study in Hyytiälä, Finland, and find that it is able to satisfactorily reproduce the observed dynamics and gas-phase chemistry. We show that the exchange of organic aerosol between the free troposphere and the boundary layer (entrainment must be taken into account in order to explain the observed diurnal cycle in organic aerosol (OA concentration. An examination of the budgets of organic aerosol and terpene concentrations show that the former is dominated by entrainment, while the latter is mainly driven by emission and chemical transformation. We systematically investigate the role of the land surface, which governs both the surface energy balance partitioning and terpene emissions, and the large-scale atmospheric process of vertical subsidence. Entrainment is especially important for the dilution of organic aerosol concentrations under conditions of dry soils and low terpene emissions. Subsidence suppresses boundary layer growth while enhancing entrainment. Therefore, it influences the relationship between organic aerosol and terpene concentrations. Our findings indicate that the diurnal evolution of secondary organic aerosols (SOA in the boundary layer is the result of coupled effects of the land surface, dynamics of the atmospheric boundary layer, chemistry, and free troposphere conditions. This has potentially some consequences for the design of both field campaigns and large-scale modeling studies.

  15. Unravelling the surface chemistry of metal oxide nanocrystals, the role of acids and bases.

    Science.gov (United States)

    De Roo, Jonathan; Van den Broeck, Freya; De Keukeleere, Katrien; Martins, José C; Van Driessche, Isabel; Hens, Zeger

    2014-07-09

    We synthesized HfO2 nanocrystals from HfCl4 using a surfactant-free solvothermal process in benzyl alcohol and found that the resulting nanocrystals could be transferred to nonpolar media using a mixture of carboxylic acids and amines. Using solution (1)H NMR, FTIR, and elemental analysis, we studied the details of the transfer reaction and the surface chemistry of the resulting sterically stabilized nanocrystals. As-synthesized nanocrystals are charge-stabilized by protons, with chloride acting as the counterion. Treatment with only carboxylic acids does not lead to any binding of ligands to the HfO2 surface. On the other hand, we find that the addition of amines provides the basic environment in which carboxylic acids can dissociate and replace chloride. This results in stable, aggregate-free dispersions of HfO2 nanocrystals, sterically stabilized by carboxylate ligands. Moreover, titrations with deuterated carboxylic acid show that the charge on the carboxylate ligands is balanced by coadsorbed protons. Hence, opposite from the X-type/nonstoichiometric nanocrystals picture prevailing in literature, one should look at HfO2/carboxylate nanocrystals as systems where carboxylic acids are dissociatively adsorbed to bind to the nanocrystals. Similar results were obtained with ZrO2 NCs. Since proton accommodation on the surface is most likely due to the high Brønsted basicity of oxygen, our model could be a more general picture for the surface chemistry of metal oxide nanocrystals with important consequences on the chemistry of ligand exchange reactions.

  16. Do organic surface films on sea salt aerosols influence atmospheric chemistry? ─ a model study

    Directory of Open Access Journals (Sweden)

    R. von Glasow

    2007-11-01

    Full Text Available Organic material from the ocean's surface can be incorporated into sea salt aerosol particles often producing a surface film on the aerosol. Such an organic coating can reduce the mass transfer between the gas phase and the aerosol phase influencing sea salt chemistry in the marine atmosphere. To investigate these effects and their importance for the marine boundary layer (MBL we used the one-dimensional numerical model MISTRA. We considered the uncertainties regarding the magnitude of uptake reduction, the concentrations of organic compounds in sea salt aerosols and the oxidation rate of the organics to analyse the possible influence of organic surfactants on gas and liquid phase chemistry with a special focus on halogen chemistry. By assuming destruction rates for the organic coating based on laboratory measurements we get a rapid destruction of the organic monolayer within the first meters of the MBL. Larger organic initial concentrations lead to a longer lifetime of the coating but lead also to an unrealistically strong decrease of O3 concentrations as the organic film is destroyed by reaction with O3. The lifetime of the film is increased by assuming smaller reactive uptake coefficients for O3 or by assuming that a part of the organic surfactants react with OH. With regard to tropospheric chemistry we found that gas phase concentrations for chlorine and bromine species decreased due to the decreased mass transfer between gas phase and aerosol phase. Aqueous phase chlorine concentrations also decreased but aqueous phase bromine concentrations increased. Differences for gas phase concentrations are in general smaller than for liquid phase concentrations. The effect on gas phase NO2 or NO is very small (reduction less than 5% whereas liquid phase NO2 concentrations increased in some cases by nearly 100%. We list suggestions for further laboratory studies which are needed for improved model studies.

  17. Influence of solution chemistry on the deposition and detachment kinetics of RNA on silica surfaces.

    Science.gov (United States)

    Shen, Yun; Kim, Hyunjung; Tong, Meiping; Li, Qingyun

    2011-02-01

    The deposition kinetics of RNA extracted from both virus and bacteria on silica surfaces were examined in both monovalent (NaCl) and divalent (CaCl(2)) solutions under a wide range of environmentally relevant ionic strength and pH conditions by utilizing a quartz crystal microbalance with dissipation (QCM-D). To better understand the RNA deposition mechanisms, QCM-D data were complemented by diffusion coefficients and zeta potentials of RNA as a function of examined solution chemistry conditions. Favorable deposition of RNA on poly-l-lysine-coated (positively charged) silica surfaces was governed by the convective-diffusive transport of RNA to the surfaces. The deposition kinetics of RNA on bare silica surfaces were controlled by classic Derjaguin-Landau-Verwey-Overbeek (DLVO) interactions. The presence of divalent cations (Ca(2+)) in solutions greatly enhanced the deposition kinetics of RNA on silica surfaces. Solution pH also affected the deposition behavior of RNA on silica surfaces. Release experiments showed that detachment of RNA from silica surfaces was significant in NaCl solutions, whereas, the deposited RNA on silica surfaces in CaCl(2) solutions was more likely to be irreversible. Copyright © 2010 Elsevier B.V. All rights reserved.

  18. Surface chemistry of Ti6Al4V components fabricated using selective laser melting for biomedical applications.

    Science.gov (United States)

    Vaithilingam, Jayasheelan; Prina, Elisabetta; Goodridge, Ruth D; Hague, Richard J M; Edmondson, Steve; Rose, Felicity R A J; Christie, Steven D R

    2016-10-01

    Selective laser melting (SLM) has previously been shown to be a viable method for fabricating biomedical implants; however, the surface chemistry of SLM fabricated parts is poorly understood. In this study, X-ray photoelectron spectroscopy (XPS) was used to determine the surface chemistries of (a) SLM as-fabricated (SLM-AF) Ti6Al4V and (b) SLM fabricated and mechanically polished (SLM-MP) Ti6Al4V samples and compared with (c) traditionally manufactured (forged) and mechanically polished Ti6Al4V samples. The SLM-AF surface was observed to be porous with an average surface roughness (Ra) of 17.6±3.7μm. The surface chemistry of the SLM-AF was significantly different to the FGD-MP surface with respect to elemental distribution and their existence on the outermost surface. Sintered particles on the SLM-AF surface were observed to affect depth profiling of the sample due to a shadowing effect during argon ion sputtering. Surface heterogeneity was observed for all three surfaces; however, vanadium was witnessed only on the mechanically polished (SLM-MP and FGD-MP) surfaces. The direct and indirect 3T3 cell cytotoxicity studies revealed that the cells were viable on the SLM fabricated Ti6Al4V parts. The varied surface chemistry of the SLM-AF and SLM-MP did not influence the cell behaviour. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

  19. Controlled surface chemistry of diamond/β-SiC composite films for preferential protein adsorption.

    Science.gov (United States)

    Wang, Tao; Handschuh-Wang, Stephan; Yang, Yang; Zhuang, Hao; Schlemper, Christoph; Wesner, Daniel; Schönherr, Holger; Zhang, Wenjun; Jiang, Xin

    2014-02-04

    Diamond and SiC both process extraordinary biocompatible, electronic, and chemical properties. A combination of diamond and SiC may lead to highly stable materials, e.g., for implants or biosensors with excellent sensing properties. Here we report on the controllable surface chemistry of diamond/β-SiC composite films and its effect on protein adsorption. For systematic and high-throughput investigations, novel diamond/β-SiC composite films with gradient composition have been synthesized using the hot filament chemical vapor deposition (HFCVD) technique. As revealed by scanning electron microscopy (SEM), the diamond/β-SiC ratio of the composite films shows a continuous change from pure diamond to β-SiC over a length of ∼ 10 mm on the surface. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) was employed to unveil the surface termination of chemically oxidized and hydrogen treated surfaces. The surface chemistry of the composite films was found to depend on diamond/β-SiC ratio and the surface treatment. As observed by confocal fluorescence microscopy, albumin and fibrinogen were preferentially adsorbed from buffer: after surface oxidation, the proteins preferred to adsorb on diamond rather than on β-SiC, resulting in an increasing amount of proteins adsorbed to the gradient surfaces with increasing diamond/β-SiC ratio. By contrast, for hydrogen-treated surfaces, the proteins preferentially adsorbed on β-SiC, leading to a decreasing amount of albumin adsorbed on the gradient surfaces with increasing diamond/β-SiC ratio. The mechanism of preferential protein adsorption is discussed by considering the hydrogen bonding of the water self-association network to OH-terminated surfaces and the change of the polar surface energy component, which was determined according to the van Oss method. These results suggest that the diamond/β-SiC gradient film can be a promising material for biomedical applications which

  20. Evidence for near-Surface NiOOH Species in Solution-Processed NiOx Selective Interlayer Materials: Impact on Energetics and the Performance of Polymer Bulk Heterojunction Photovoltaics

    Energy Technology Data Exchange (ETDEWEB)

    Ratcliff, Erin L.; Meyer, Jens; Steirer, K. Xerxes; Garcia, Andres; Berry, Joseph J.; Ginley, David S.; Olson, Dana C.; Kahn, Antoine; Armstrong, Neal R.

    2011-11-22

    The characterization and implementation of solution-processed, wide bandgap nickel oxide (NiO{sub x}) hole-selective interlayer materials used in bulk-heterojunction (BHJ) organic photovoltaics (OPVs) are discussed. The surface electrical properties and charge selectivity of these thin films are strongly dependent upon the surface chemistry, band edge energies, and midgap state concentrations, as dictated by the ambient conditions and film pretreatments. Surface states were correlated with standards for nickel oxide, hydroxide, and oxyhydroxide components, as determined using monochromatic X-ray photoelectron spectroscopy. Ultraviolet and inverse photoemission spectroscopy measurements show changes in the surface chemistries directly impact the valence band energies. O₂-plasma treatment of the as-deposited NiO{sub x} films was found to introduce the dipolar surface species nickel oxyhydroxide (NiOOH), rather than the p-dopant Ni₂O₃, resulting in an increase of the electrical band gap energy for the near-surface region from 3.1 to 3.6 eV via a vacuum level shift. Electron blocking properties of the as-deposited and O₂-plasma treated NiO{sub x} films are compared using both electron-only and BHJ devices. O₂-plasma-treated NiO{sub x} interlayers produce electron-only devices with lower leakage current and increased turn on voltages. The differences in behavior of the different pretreated interlayers appears to arise from differences in local density of states that comprise the valence band of the NiO{sub x} interlayers and changes to the band gap energy, which influence their hole-selectivity. The presence of NiOOH states in these NiO{sub x} films and the resultant chemical reactions at the oxide/organic interfaces in OPVs is predicted to play a significant role in controlling OPV device efficiency and lifetime.

  1. The surface chemistry determines the spatio-temporal interaction dynamics of quantum dots in atherosclerotic lesions.

    Science.gov (United States)

    Uhl, Bernd; Hirn, Stephanie; Mildner, Karina; Coletti, Raffaele; Massberg, Steffen; Reichel, Christoph A; Rehberg, Markus; Zeuschner, Dagmar; Krombach, Fritz

    2018-03-01

    To optimize the design of nanoparticles for diagnosis or therapy of vascular diseases, it is mandatory to characterize the determinants of nano-bio interactions in vascular lesions. Using ex vivo and in vivo microscopy, we analyzed the interactive behavior of quantum dots with different surface functionalizations in atherosclerotic lesions of ApoE-deficient mice. We demonstrate that quantum dots with different surface functionalizations exhibit specific interactive behaviors with distinct molecular and cellular components of the injured vessel wall. Moreover, we show a role for fibrinogen in the regulation of the spatio-temporal interaction dynamics in atherosclerotic lesions. Our findings emphasize the relevance of surface chemistry-driven nano-bio interactions on the differential in vivo behavior of nanoparticles in diseased tissue.

  2. Nanoporous Anodic Alumina Platforms: Engineered Surface Chemistry and Structure for Optical Sensing Applications

    Directory of Open Access Journals (Sweden)

    Tushar Kumeria

    2014-07-01

    Full Text Available Electrochemical anodization of pure aluminum enables the growth of highly ordered nanoporous anodic alumina (NAA structures. This has made NAA one of the most popular nanomaterials with applications including molecular separation, catalysis, photonics, optoelectronics, sensing, drug delivery, and template synthesis. Over the past decades, the ability to engineer the structure and surface chemistry of NAA and its optical properties has led to the establishment of distinctive photonic structures that can be explored for developing low-cost, portable, rapid-response and highly sensitive sensing devices in combination with surface plasmon resonance (SPR and reflective interference spectroscopy (RIfS techniques. This review article highlights the recent advances on fabrication, surface modification and structural engineering of NAA and its application and performance as a platform for SPR- and RIfS-based sensing and biosensing devices.

  3. Surface Chemistry and Spectroscopic Study of a Cholera Toxin B Langmuir Monolayer.

    Science.gov (United States)

    Sharma, Shiv K; Seven, Elif S; Micic, Miodrag; Li, Shanghao; Leblanc, Roger M

    2018-02-20

    In this article, we explored the surface chemistry properties of a cholera toxin B (CTB) monolayer at the air-subphase interface and investigated the change in interfacial properties through in situ spectroscopy. The study showed that the impact of the blue shift was negligible, suggesting that the CTB molecules were minimally affected by the subphase molecules. The stability of the CTB monolayer was studied by maintaining the constant surface pressure for a long time and also by using the compression-decompression cycle experiments. The high stability of the Langmuir monolayer of CTB clearly showed that the driving force of CTB going to the amphiphilic membrane was its amphiphilic nature. In addition, no major change was detected in the various in situ spectroscopy results (such as UV-vis, fluorescence, and IR ER) of the CTB Langmuir monolayer with the increase in surface pressure. This indicates that no aggregation occurs in the Langmuir monolayer of CTB.

  4. Investigation of silicate surface chemistry and reaction mechanisms associated with mass transport in geologic media

    International Nuclear Information System (INIS)

    White, A.F.; Perry, D.L.

    1982-01-01

    The concentration and rate of transport of radionuclides through geologic media can be strongly influenced by the extent of sorption on aquifer surfaces. Over time intervals relevant to such transport processes, rock and mineral surfaces cannot be considered as inert, unreactive substrates but rather as groundwater/solidphase interfaces which are commonly in a state of natural or artificially induced disequilibrium. The goal of the present research is to define experimentally the type of water/rock interactions that will influence surface chemistry and hence sorption characteristics and capacities of natural aquifers. As wide a range of silicate minerals as possible was selected for study to represent rock-forming minerals in basalt, tuff, and granite. The minerals include K-feldspar, plagioclase feldspar, olivine, hornblende, biotite, and volcanic glass

  5. Surface chemistry of K-montmorillonite: ionic strength, temperature dependence and dissolution kinetics.

    Science.gov (United States)

    Rozalén, Marisa; Brady, Patrick V; Huertas, F Javier

    2009-05-15

    The surface chemistry of K-montmorillonite was investigated by potentiometric titrations conducted at 25, 50 and 70 degrees C and at ionic strengths of 0.001, 0.01 and 0.1 M KNO(3). Proton adsorption decreases with electrolyte concentration at all pHs. The pH of zero net proton charge (PZNPC) decreases from 8.1 to 7.6 when the ionic strength increases from 0.001 to 0.1 M. Temperature has a very small effect on surface charge. A constant capacitance model that accounts for protonation/deprotonation of aluminol and silanol edge sites and basal plane H(+)/K(+) exchange is used to fit the experimental data. H(+) and OH(-) adsorption to specific surface sites appear to account for the pH-dependence of the K-montmorillonite dissolution.

  6. Tuning the surface chemistry of lubricant-derived phosphate thermal films: The effect of boron

    Energy Technology Data Exchange (ETDEWEB)

    Spadaro, F. [Laboratory for Surface Science and Technology, Department of Materials, ETH Zurich, Vladimir-Prelog-Weg 5, CH-8093 Zurich (Switzerland); Rossi, A., E-mail: antonella.rossi@mat.ethz.ch [Laboratory for Surface Science and Technology, Department of Materials, ETH Zurich, Vladimir-Prelog-Weg 5, CH-8093 Zurich (Switzerland); Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, Cittadella Universitaria di Monserrato, I-09100, Cagliari (Italy); Lainé, E.; Woodward, P. [Enabling Research, Infineum UK Ltd., Milton Hill, Steventon, Oxfordshire OX13 6BD (United Kingdom); Spencer, N.D., E-mail: nicholas.spencer@mat.ethz.ch [Laboratory for Surface Science and Technology, Department of Materials, ETH Zurich, Vladimir-Prelog-Weg 5, CH-8093 Zurich (Switzerland)

    2017-02-28

    Highlights: • The additives bulk interactions in “neat” blends at high temperatures is evaluated. • The competition among the different additives to react with air-oxidized steel surfaces under pure thermal condition is investigated. • Different thermal films are grown, their in depth-composition and thickness is determined by ARXPS. • A reaction mechanism is proposed for elucidating the composition of the thermals films. - Abstract: Understanding the interactions among the various additives in a lubricant is important because they can have a major influence on the performance of blends under tribological conditions. The present investigation is focused on the interactions occurring between ZnDTP and dispersant molecules in an oil formulation, and on their reactivity under purely thermal conditions in the presence of air-oxidized iron surfaces. Nuclear magnetic resonance spectroscopy (NMR) was performed on undiluted blends at different temperatures, while angle-resolved X-ray photoelectron spectroscopy (ARXPS) was exploited to investigate the surface reactivity on oxidized iron surfaces. The results indicate that the dispersant, generally added to blends for preventing the deposition of sludge, varnish and soot on the surface, might also inhibit the reaction of all other additives with the steel surface.

  7. Coordination chemistry of weathering: Kinetics of the surface-controlled dissolution of oxide minerals

    Science.gov (United States)

    Stumm, Werner; Wollast, Roland

    1990-02-01

    Chemical weathering processes, essentially caused by the interaction of water and the atmosphere with the Earth's crust, transform primary minerals into solutes and clays and, eventually, into sedimentary rocks; these processes participate in controlling the global hydrogeochemical cycles of many elements. Many mineral dissolution processes are controlled by a chemical mechanism at the solid-water interface. The reaction-controlling steps can be interpreted in terms of a surface coordination model. The tendency of a mineral to dissolve is influenced by the interaction of solutes—H+, OH-, ligands, and metal ions—with its surface. The surface reactivity is shown to depend on the surface species and their structural identity; specifically, the dependence of dissolution rates on pH and on dissolved ligand concentrations can be explained in terms of surface protonation (and deprotonation) and of ligand surface complexes. A general rate law for the dissolution of minerals is derived by considering, in addition to the surface coordination chemistry, established models of lattice statistics and activated complex theory.

  8. Effect of solution chemistry on the adsorption of perfluorooctane sulfonate onto mineral surfaces.

    Science.gov (United States)

    Tang, Chuyang Y; Shiang Fu, Q; Gao, Dawen; Criddle, Craig S; Leckie, James O

    2010-04-01

    Perfluorooctane sulfonate (PFOS) is an emergent contaminant of substantial environmental concerns, yet very limited information has been available on PFOS adsorption onto mineral surfaces. PFOS adsorption onto goethite and silica was investigated by batch adsorption experiments under various solution compositions. Adsorption onto silica was only marginally affected by pH, ionic strength, and calcium concentration, likely due to the dominance of non-electrostatic interactions. In contrast, PFOS uptake by goethite increased significantly at high [H+] and [Ca2+], which was likely due to enhanced electrostatic attraction between the negatively charged PFOS molecules and positively charged goethite surface. The effect of pH was less significant at high ionic strength, likely due to electrical double layer compression. PFOS uptake was reduced at higher ionic strength for a strongly positively charged goethite surface (pH 3), while it increased for a weakly charged surface (pH 7 and 9), which could be attributed to the competition between PFOS-surface electrostatic attraction and PFOS-PFOS electrostatic repulsion. A conceptual model that captures PFOS-surface and PFOS-PFOS electrostatic interactions as well as non-electrostatic interaction was also formulated to understand the effect of solution chemistry on PFOS adsorption onto goethite and silica surfaces. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

  9. Surface chemistry of methanol on different ZnO surfaces studied by vibrational spectroscopy.

    Science.gov (United States)

    Jin, Lanying; Wang, Yuemin

    2017-05-24

    The adsorption and reactions of CH 3 OH on nonpolar mixed-terminated ZnO(101[combining macron]0), polar O-ZnO(0001[combining macron]) and Zn-ZnO(0001) surfaces have been studied systematically using high-resolution electron energy loss spectroscopy (HREELS) in conjunction with temperature programmed desorption (TPD). For all three ZnO surfaces, exposure to methanol at room temperature leads to (partially) dissociative adsorption resulting in the formation of hydroxyl and methoxy species. Upon heating to higher temperatures, the dissociated and intact methanol species on ZnO(101[combining macron]0) predominantly undergo molecular desorption releasing CH 3 OH at 370 and 440 K. The Zn-O dimer vacancies are responsible for the decomposition of a small fraction of methanol yielding H 2 , CH 2 O and CO at 540 and 565 K. The interaction of methanol with polar O-ZnO and Zn-ZnO surfaces is dominated by thermal decomposition of CH 3 OH to produce CH 2 O, H 2 , CO, CO 2 and H 2 O at elevated temperatures. The high chemical reactivity of both polar surfaces is related to the high abundance of different types of surface defects formed via massive restructuring. Importantly, the reconstructed Zn-ZnO surface exhibits high selectivity for hydrogen production at 520 K, which was not observed for the polar O-ZnO surface. The HREELS data revealed that this low-temperature hydrogen evolution on Zn-ZnO results from methoxy oxidation to a formate species occurring at O-terminated step-edge sites.

  10. Surface chemistry manipulation of gold nanorods preserves optical properties for bio-imaging applications

    Energy Technology Data Exchange (ETDEWEB)

    Polito, Anthony B.; Maurer-Gardner, Elizabeth I.; Hussain, Saber M., E-mail: saber.hussain@us.af.mil [Air Force Research Laboratory, Molecular Bioeffects Branch, Bioeffects Division, Human Effectiveness Directorate (United States)

    2015-12-15

    Due to their anisotropic shape, gold nanorods (GNRs) possess a number of advantages for biosystem use including, enhanced surface area and tunable optical properties within the near-infrared (NIR) region. However, cetyl trimethylammonium bromide-related cytotoxicity, overall poor cellular uptake following surface chemistry modifications, and loss of NIR optical properties due to material intracellular aggregation in combination remain as obstacles for nanobased biomedical GNR applications. In this article, we report that tannic acid-coated 11-mercaptoundecyl trimethylammonium bromide (MTAB) GNRs (MTAB-TA) show no significant decrease in either in vitro cell viability or stress activation after exposures to A549 human alveolar epithelial cells. In addition, MTAB-TA GNRs demonstrate a substantial level of cellular uptake while displaying a unique intracellular clustering pattern. This clustering pattern significantly reduces intracellular aggregation, preserving the GNRs NIR optical properties, vital for biomedical imaging applications. These results demonstrate how surface chemistry modifications enhance biocompatibility, allow for higher rate of internalization with low intracellular aggregation of MTAB-TA GNRs, and identify them as prime candidates for use in nanobased bio-imaging applications.Graphical Abstract.

  11. The influence of the surface chemistry of silver nanoparticles on cell death

    International Nuclear Information System (INIS)

    Sur, Ilknur; Altunbek, Mine; Kahraman, Mehmet; Culha, Mustafa

    2012-01-01

    The influence of the surface chemistry of silver nanoparticles (AgNPs) on p53 mediated cell death was evaluated using human dermal fibroblast (HDF) and lung cancer (A549) cells. The citrate reduced AgNPs (C-AgNPs) were modified with either lactose (L-AgNPs) or a 12-base long oligonucleotide (O-AgNPs). Both unmodified and modified AgNPs showed increased concentration and time dependent cytotoxicity and genotoxicity causing an increased p53 up-regulation within 6 h and led to apoptotic or necrotic cell deaths. The C-AgNPs induced more cytotoxicity and cellular DNA damage than the surface modified AgNPs. Modifying the C-AgNPs with lactose or the oligonucleotide reduced both necrotic and apoptotic cell deaths in the HDF cells. The C-AgNPs caused an insignificant necrosis in A549 cells whereas the modified AgNPs caused necrosis and apoptosis in both cell types. Compared to the O-AgNPs, the L-AgNPs triggered more cellular DNA damage, which led to up-regulation of p53 gene inducing apoptosis in A549 cells compared to HDF cells. This suggests that the different surface chemistries of the AgNPs cause different cellular responses that may be important not only for their use in medicine but also for reducing their toxicity. (paper)

  12. Surface chemistry manipulation of gold nanorods preserves optical properties for bio-imaging applications

    Science.gov (United States)

    Polito, Anthony B.; Maurer-Gardner, Elizabeth I.; Hussain, Saber M.

    2015-12-01

    Due to their anisotropic shape, gold nanorods (GNRs) possess a number of advantages for biosystem use including, enhanced surface area and tunable optical properties within the near-infrared (NIR) region. However, cetyl trimethylammonium bromide-related cytotoxicity, overall poor cellular uptake following surface chemistry modifications, and loss of NIR optical properties due to material intracellular aggregation in combination remain as obstacles for nanobased biomedical GNR applications. In this article, we report that tannic acid-coated 11-mercaptoundecyl trimethylammonium bromide (MTAB) GNRs (MTAB-TA) show no significant decrease in either in vitro cell viability or stress activation after exposures to A549 human alveolar epithelial cells. In addition, MTAB-TA GNRs demonstrate a substantial level of cellular uptake while displaying a unique intracellular clustering pattern. This clustering pattern significantly reduces intracellular aggregation, preserving the GNRs NIR optical properties, vital for biomedical imaging applications. These results demonstrate how surface chemistry modifications enhance biocompatibility, allow for higher rate of internalization with low intracellular aggregation of MTAB-TA GNRs, and identify them as prime candidates for use in nanobased bio-imaging applications.

  13. Multifunctionality of organometallic quinonoid metal complexes: surface chemistry, coordination polymers, and catalysts.

    Science.gov (United States)

    Kim, Sang Bok; Pike, Robert D; Sweigart, Dwight A

    2013-11-19

    Quinonoid metal complexes have potential applications in surface chemistry, coordination polymers, and catalysts. Although quinonoid manganese tricarbonyl complexes have been used as secondary building units (SBUs) in the formation of novel metal-organometallic coordination networks and polymers, the potentially wider applications of these versatile linkers have not yet been recognized. In this Account, we focus on these diverse new applications of quinonoid metal complexes, and report on the variety of quinonoid metal complexes that we have synthesized. Through the use of [(η(6)-hydroquinone)Mn(CO)3](+), we are able to modify the surface of Fe3O4 and FePt nanoparticles (NPs). This process occurs either by the replacement of oleylamine with neutral [(η(5)-semiquinone)Mn(CO)3] at the NP surface, or by the binding of anionic [(η(4)-quinone)Mn(CO)3](-) upon further deprotonation of [(η(5)-semiquinone)Mn(CO)3] at the NP surface. We have demonstrated chemistry at the intersection of surface-modified NPs and coordination polymers through the growth of organometallic coordination polymers onto the surface modified Fe3O4 NPs. The resulting magnetic NP/organometallic coordination polymer hybrid material exhibited both the unique superparamagnetic behavior associated with Fe3O4 NPs and the paramagnetism attributable to the metal nodes, depending upon the magnetic range examined. By the use of functionalized [(η(5)-semiquinone)Mn(CO)3] complexes, we attained the formation of an organometallic monolayer on the surface of highly ordered pyrolitic graphite (HOPG). The resulting organometallic monolayer was not simply a random array of manganese atoms on the surface, but rather consisted of an alternating "up and down" spatial arrangement of Mn atoms extending from the HOPG surface due to hydrogen bonding of the quinonoid complexes. We also showed that the topology of metal atoms on the surface could be controlled through the use of quinonoid metal complexes. A quinonoid

  14. Carbon key-properties for microcystin adsorption in drinking water treatment: structure or surface chemistry?

    OpenAIRE

    Júlio, Maria de Fátima de Jesus Leal

    2011-01-01

    Dissertação para Obtenção de Grau de Mestre em Engenharia Química e Bioquímica The carbon key-properties (structure and surface chemistry) for microcystin-LR (MC-LR) adsorption onto activated carbon were investigated. Waters with an inorganic background matrix approaching that of the soft natural water (2.5 mM ionic strength) were used. Also, model waters with controlled ionic make-up and NOM surrogate with similar size of MC-LR (tannic acid - TA) with MC-LR extracts were tested with activ...

  15. Influence of Microstructure and Process Conditions on Simultaneous Low-Temperature Surface Hardening and Bulk Precipitation Hardening of Nanoflex®

    DEFF Research Database (Denmark)

    Bottoli, Federico; Winther, Grethe; Christiansen, Thomas L.

    2015-01-01

    Precipitation hardening martensitic stainless steel Nanoflex was low-temperature nitrided or nitrocarburized. In these treatments, simultaneous hardening of the bulk, by precipitation hardening, and the surface by dissolving nitrogen/carbon can be obtained because the treatment temperatures and t...

  16. Coarse-grained modeling of proline rich protein 1 (PRP-1) in bulk solution and adsorbed to a negatively charged surface.

    Science.gov (United States)

    Skepö, Marie; Linse, Per; Arnebrant, Thomas

    2006-06-22

    Structural properties of the acidic proline rich protein PRP-1 of salivary origin in bulk solution and adsorbed onto a negatively charged surface have been studied by Monte Carlo simulations. A simple model system with focus on electrostatic interactions and short-ranged attractions among the uncharged amino acids has been used. In addition to PRP-1, some mutants were considered to assess the role of the interactions in the systems. Contrary to polyelectrolytes, the protein has a compact structure in salt-free bulk solutions, whereas at high salt concentration the protein becomes more extended. The protein adsorbs to a negatively charged surface, although its net charge is negative. The adsorbed protein displays an extended structure, which becomes more compact upon addition of salt. Hence, the conformational response upon salt addition in the adsorbed state is the opposite as compared to that in bulk solution. The conformational behavior of PRP-1 in bulk solution and at charged surfaces as well as its propensity to adsorb to surfaces with the same net charge are rationalized by the block polyampholytic character of the protein. The presence of a triad of positively charged amino acids in the C-terminal was found to be important for the adsorption of the protein.

  17. The influence of surface nanoroughness, texture and chemistry of TiZr implant abutment on oral biofilm accumulation.

    Science.gov (United States)

    Xing, Rui; Lyngstadaas, Ståle P; Ellingsen, Jan Eirik; Taxt-Lamolle, Sébastien; Haugen, Håvard J

    2015-06-01

    The aim of the study was to examine surface nanoroughness, texture and chemistry of dental implant abutment and to investigate how these parameters influence oral biofilm formation in healthy subjects. Eight different nanorough TiZr surfaces were produced by polishing, machining, cathodic polarization and acid etching. Surface topography was examined using field emission scanning electron microscope and a blue light laser profilometer. Surface chemistry was analyzed by secondary ion mass spectrometry and X-ray photoelectron spectroscopy. Surface hydrophilicity was tested by measuring contact angle on the surfaces. A human in vivo study using a splint model was employed to evaluate oral biofilm accumulation on these surfaces. Different surface textures (flat, grooved and irregular) were created with nanoroughness from 29 to 214 nm. Some test surfaces were incorporated with hydrogen by cathodic polarization and/or acid etching with HCl/H(2)SO(4). Nanoroughness (S(a)) positively correlated with microbial adhesion. Biofilm accumulation was less pronounced on flat and grooved than on irregular surfaces. No significant association between hydrogen content or hydrophilicity of the surface and biofilm accumulation was observed. Nanoroughness (< 214 nm) and surface texture influence oral biofilm accumulation independent of surface chemistry and hydrophilicity. Surface hydrogen, which has previously been shown to promote fibroblast growth, does not affect biofilm formation. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  18. The effect of prolonged immersion of giomer bulk-fill composite resin on the pH value of artificial saliva and resin surface roughness

    Science.gov (United States)

    Ratna, A. A.; Triaminingsih, S.; Eriwati, Y. K.

    2017-08-01

    This study aimed to determine the effect of immersion time on the surface roughness of Giomer Bulk-Fill composite resin and on the pH value of artificial saliva. Sixty-three specimens were divided into nine groups and immersed in artificial saliva with pH values of 7, 5.5, and 4.5 for 1 hour, 24 hours, and 72 hours at 37 °C. The changes in artificial saliva pH were measured using a pH meter and the surface roughness was measured using a surface roughness tester. Longer immersion time increases the pH of artificial saliva and the surface roughness of Giomer Bulk-Fill composite resin.

  19. Controls on surface water chemistry in the upper Merced River basin, Yosemite National Park, California

    Science.gov (United States)

    Clow, D.W.; Mast, M.A.; Campbell, D.H.

    1996-01-01

    Surface water draining granitic bedrock in Yosemite National Park exhibits considerable variability in chemical composition, despite the relative homogeneity of bedrock chemistry. Other geological factors, including the jointing and distribution of glacial till, appear to exert strong controls on water composition. Chemical data from three surface water surveys in the upper Merced River basin conducted in August 1981, June 1988 and August 1991 were analysed and compared with mapped geological, hydrological and topographic features to identify the solute sources and processes that control water chemistry within the basin during baseflow. Water at most of the sampling sites was dilute, with alkalinities ranging from 26 to 77 ??equiv. 1-1. Alkalinity was much higher in two subcatchments, however, ranging from 51 to 302 ??equiv. 1-1. Base cations and silica were also significantly higher in these two catchments than in the rest of the watershed. Concentrations of weathering products in surface water were correlated to the fraction of each subcatchment underlain by surficial material, which is mostly glacial till. Silicate mineral weathering is the dominant control on concentrations of alkalinity, silica and base cations, and ratios of these constituents in surface water reflect the composition of local bedrock, Chloride concentrations in surface water samples varied widely, ranging from Merced River at the Happy Isles gauge from 1968 to 1990 was 26 ??equiv. 1-1, which was five times higher than in atmospheric deposition (4-5 ??equiv. 1-1), suggesting that a source of chloride exists within the watershed. Saline groundwater springs, whose locations are probably controlled by vertical jointing in the bedrock, are the most likely source of the chloride. Sulphate concentrations varied much less than most other solutes, ranging from 3 to 14 ??equiv. 1-1. Concentrations of sulphate in quarterly samples collected at the watershed outlet also showed relatively little variation

  20. Kinetic model framework for aerosol and cloud surface chemistry and gas-particle interactions ─ Part 2: Exemplary practical applications and numerical simulations

    Directory of Open Access Journals (Sweden)

    M. Ammann

    2007-12-01

    Full Text Available A kinetic model framework with consistent and unambiguous terminology and universally applicable rate equations and parameters for aerosol and cloud surface chemistry and gas-particle interactions has been presented in the preceding companion paper by Pöschl, Rudich and Ammann (Pöschl et al., 2007, abbreviated PRA. It allows to describe mass transport and chemical reaction at the gas-particle interface and to link aerosol and cloud surface processes with gas phase and particle bulk processes. Here we present multiple exemplary model systems and calculations illustrating how the general mass balance and rate equations of the PRA framework can be easily reduced to compact sets of equations which enable a mechanistic description of time and concentration dependencies of trace gas uptake and particle composition in systems with one or more chemical components and physicochemical processes. Time-dependent model scenarios show the effects of reversible adsorption, surface-bulk transport, and chemical aging on the temporal evolution of trace gas uptake by solid particles and solubility saturation of liquid particles. They demonstrate how the transformation of particles and the variation of trace gas accommodation and uptake coefficients by orders of magnitude over time scales of microseconds to days can be explained and predicted from the initial composition and basic kinetic parameters of model systems by iterative calculations using standard spreadsheet programs. Moreover, they show how apparently inconsistent experimental data sets obtained with different techniques and on different time scales can be efficiently linked and mechanistically explained by application of consistent model formalisms and terminologies within the PRA framework. Steady-state model scenarios illustrate characteristic effects of gas phase composition and basic kinetic parameters on the rates of mass transport and chemical reactions. They demonstrate how adsorption and

  1. Early osseointegration driven by the surface chemistry and wettability of dental implants.

    Science.gov (United States)

    Sartoretto, Suelen Cristina; Alves, Adriana Terezinha Neves Novellino; Resende, Rodrigo Figueiredo Britto; Calasans-Maia, José; Granjeiro, José Mauro; Calasans-Maia, Mônica Diuana

    2015-01-01

    The objective of this study was to investigate the impact of two different commercially available dental implants on osseointegration. The surfaces were sandblasting and acid etching (Group 1) and sandblasting and acid etching, then maintained in an isotonic solution of 0.9% sodium chloride (Group 2). X-ray photoelectron spectroscopy (XPS) was employed for surface chemistry analysis. Surface morphology and topography was investigated by scanning electron microscopy (SEM) and confocal microscopy (CM), respectively. Contact angle analysis (CAA) was employed for wetting evaluation. Bone-implant-contact (BIC) and bone area fraction occupied (BAFO) analysis were performed on thin sections (30 μm) 14 and 28 days after the installation of 10 implants from each group (n=20) in rabbits' tibias. Statistical analysis was performed by ANOVA at the 95% level of significance considering implantation time and implant surface as independent variables. Group 2 showed 3-fold less carbon on the surface and a markedly enhanced hydrophilicity compared to Group 1 but a similar surface roughness (p>0.05). BIC and BAFO levels in Group 2 at 14 days were similar to those in Group 1 at 28 days. After 28 days of installation, BIC and BAFO measurements of Group 2 were approximately 1.5-fold greater than in Group 1 (pimplants of Group 2 accelerate osseointegration and increase the area of the bone-to-implant interface when compared to those of Group 1.

  2. Review: Impacts of permafrost degradation on inorganic chemistry of surface fresh water

    Science.gov (United States)

    Colombo, Nicola; Salerno, Franco; Gruber, Stephan; Freppaz, Michele; Williams, Mark; Fratianni, Simona; Giardino, Marco

    2018-03-01

    Recent studies have shown that climate change is impacting the inorganic chemical characteristics of surface fresh water in permafrost areas and affecting aquatic ecosystems. Concentrations of major ions (e.g., Ca2 +, Mg2 +, SO42 -, NO3-) can increase following permafrost degradation with associated deepening of flow pathways and increased contributions of deep groundwater. In addition, thickening of the active layer and melting of near-surface ground ice can influence inorganic chemical fluxes from permafrost into surface water. Permafrost degradation has also the capability to modify trace element (e.g., Ni, Mn, Al, Hg, Pb) contents in surface water. Although several local and regional modifications of inorganic chemistry of surface fresh water have been attributed to permafrost degradation, a comprehensive review of the observed changes is lacking. The goal of this paper is to distil insight gained across differing permafrost settings through the identification of common patterns in previous studies, at global scale. In this review we focus on three typical permafrost configurations (pervasive permafrost degradation, thermokarst, and thawing rock glaciers) as examples and distinguish impacts on (i) major ions and (ii) trace elements. Consequences of warming climate have caused spatially-distributed progressive increases of major ion and trace element delivery to surface fresh water in both polar and mountain areas following pervasive permafrost degradation. Moreover, localised releases of major ions and trace elements to surface water due to the liberation of soluble materials sequestered in permafrost and ground ice have been found in ice-rich terrains both at high latitude (thermokarst features) and high elevation (rock glaciers). Further release of solutes and related transport to surface fresh water can be expected under warming climatic conditions. However, complex interactions among several factors able to influence the timing and magnitude of the impacts

  3. Effect of Polyelectrolyte and Fatty Acid Soap on the Formation of CaCO3 in the Bulk and the Deposit on Hard Surfaces.

    Science.gov (United States)

    Wang, Hao; Alfredsson, Viveka; Tropsch, Juergen; Ettl, Roland; Nylander, Tommy

    2015-09-30

    The effects of sodium polyacrylate (NaPAA) as well as potassium oleate on the nucleation and calcium carbonate crystal growth on hard surfaces, i.e., stainless steel and silica, have been investigated at different temperatures. The relation between the surface deposition and the corresponding bulk processes has been revealed by combining dynamic light scattering (DLS), scanning electron microscopy (SEM), X-ray diffraction (XRD), and ellipsometry. The aim was to further our understanding of the crystal deposition/growth mechanism and how it can be controlled by the presence of polyelectrolytes (NaPAA) or soap (potassium oleate). The addition of polyelectrolytes (NaPAA) or soap (potassium oleate) decreases the size of CaCO3 particles in bulk solution and affects both crystal structure and morphology in the bulk as well as on hard surfaces. The amount of particles on hard surfaces decreases significantly in the presence of both potassium oleate and NaPAA. This was found to be a consequence of potassium oleate or NaPAA adsorption on the hard surface as well as on the CaCO3 crystal surfaces. Here, the polymer NaPAA exhibited a stronger inhibition effect on the formation and growth of CaCO3 particles than potassium oleate.

  4. Radiofrequency electric field hyperthermia with gold nanostructures: role of particle shape and surface chemistry.

    Science.gov (United States)

    Amini, Seyed Mohammad; Kharrazi, Sharmin; Rezayat, Seyed Mahdi; Gilani, Kambiz

    2017-09-10

    Hyperthermia treatment of cancerous cells has been recently developed drastically with the help of nanostructures. Heating of gold nanoparticles in non-invasive radiofrequency electric field (RF-EF) is a promising and unique technique for cancer hyperthermia. However, because of differences between particles (i.e. their surface chemistry and dispersion medium) and between RF-EF sources, the research community has not reached a consensus yet. Here, we report the results of investigations on heating of gold nanoparticles and gold nanorods under RF-EF and feasibility of in-vitro cancer hyperthermia. The heating experiments were performed to investigate the role of particle shape and surface chemistry (CTAB, citrate and PEG molecules). In-vitro hyperthermia was performed on human pancreatic cancer cell (MIA Paca-2) with PEG-coated GNPs and GNRs at concentrations that were found non-toxic based on the results of cytotoxicity assay. Application of RF-EF on cells treated with PEG-GNPs and PEG-GNRs proved highly effective in killing cells.

  5. Tuning colloidal quantum dot band edge positions through solution-phase surface chemistry modification

    Science.gov (United States)

    Kroupa, Daniel M.; Vörös, Márton; Brawand, Nicholas P.; McNichols, Brett W.; Miller, Elisa M.; Gu, Jing; Nozik, Arthur J.; Sellinger, Alan; Galli, Giulia; Beard, Matthew C.

    2017-05-01

    Band edge positions of semiconductors determine their functionality in many optoelectronic applications such as photovoltaics, photoelectrochemical cells and light emitting diodes. Here we show that band edge positions of lead sulfide (PbS) colloidal semiconductor nanocrystals, specifically quantum dots (QDs), can be tuned over 2.0 eV through surface chemistry modification. We achieved this remarkable control through the development of simple, robust and scalable solution-phase ligand exchange methods, which completely replace native ligands with functionalized cinnamate ligands, allowing for well-defined, highly tunable chemical systems. By combining experiments and ab initio simulations, we establish clear relationships between QD surface chemistry and the band edge positions of ligand/QD hybrid systems. We find that in addition to ligand dipole, inter-QD ligand shell inter-digitization contributes to the band edge shifts. We expect that our established relationships and principles can help guide future optimization of functional organic/inorganic hybrid nanostructures for diverse optoelectronic applications.

  6. Surface chemistry and microstructure of metallic biomaterials for hip and knee endoprostheses

    Science.gov (United States)

    Jenko, Monika; Gorenšek, Matevž; Godec, Matjaž; Hodnik, Maxinne; Batič, Barbara Šetina; Donik, Črtomir; Grant, John T.; Dolinar, Drago

    2018-01-01

    The surface chemistry and microstructures of titanium alloys (both new and used) and CoCrMo alloys used for hip and knee endoprostheses were determined using SEM (morphology), EBSD (phase analysis), AES and XPS (surface chemistry). Two new and two used endoprostheses were studied. The SEM SE and BE images showed their microstructures, while the EBSD provided the phases of the materials. During the production of the hip and knee endoprostheses, these materials are subject to severe thermomechanical treatments and physicochemical processes that are decisive for CoCrMo alloys. The AES and XPS results showed that thin oxide films on (a) Ti6Al4V are primarily a mixture of TiO2 with a small amount of Al2O3, while the V is depleted, (b) Ti6Al7Nb is primarily a mixture of TiO2 with a small amount of Al2O3 and Nb2O5, and (c) the CoCrMo alloy is primarily a mixture of Cr2O3 with small amounts of Co and Mo oxides. The thin oxide film on the CoCrMo alloy should prevent intergranular corrosion and improve the biocompatibility. The thin oxide films on the Ti alloys prevent further corrosion, improve the biocompatibility, and affect the osseointegration.

  7. Reorientation of the diagonal double-stripe spin structure at Fe1+yTe bulk and thin-film surfaces

    Science.gov (United States)

    Hänke, Torben; Singh, Udai Raj; Cornils, Lasse; Manna, Sujit; Kamlapure, Anand; Bremholm, Martin; Hedegaard, Ellen Marie Jensen; Iversen, Bo Brummerstedt; Hofmann, Philip; Hu, Jin; Mao, Zhiqiang; Wiebe, Jens; Wiesendanger, Roland

    2017-01-01

    Establishing the relation between ubiquitous antiferromagnetism in the parent compounds of unconventional superconductors and their superconducting phase is important for understanding the complex physics in these materials. Going from bulk systems to thin films additionally affects their phase diagram. For Fe1+yTe, the parent compound of Fe1+ySe1-xTex superconductors, bulk-sensitive neutron diffraction revealed an in-plane oriented diagonal double-stripe antiferromagnetic spin structure. Here we show by spin-resolved scanning tunnelling microscopy that the spin direction at the surfaces of bulk Fe1+yTe and thin films grown on the topological insulator Bi2Te3 is canted out of the high-symmetry directions of the surface unit cell resulting in a perpendicular spin component, keeping the diagonal double-stripe order. As the magnetism of the Fe d-orbitals is intertwined with the superconducting pairing in Fe-based materials, our results imply that the superconducting properties at the surface of the related superconducting compounds might be different from the bulk.

  8. Surface chemistry and corrosion behavior of Inconel 625 and 718 in subcritical, supercritical, and ultrasupercritical water

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez, David; Merwin, Augustus; Karmiol, Zachary; Chidambaram, Dev, E-mail: dcc@unr.edu

    2017-05-15

    Highlights: • Mixtures of oxides containing Ni, Fe, Cr and Nb formed on the surface. • Short term exposure tests observed breakdown of native film. • Formation of a Fe rich oxide layer on Inconel 718 prevents mass loss. - Abstract: Corrosion behavior of Inconel 625 and 718 in subcritical, supercritical and ultrasupercritical water was studied as a function of temperature and time. The change in the chemistry of the as-received surface film on Inconel 625 and 718 after exposure to subcritical water at 325 °C and supercritical water at 425 °C and 527.5 °C for 2 h was studied. After exposure to 325 °C subcritical water, the CrO{sub 4}{sup 2−} based film formed; however minor quantities of NiFe{sub x}Cr{sub 2-x}O{sub 4} spinel compounds were observed. The oxide film formed on both alloys when exposed to supercritical water at 425 °C consisted of NiFe{sub x}Cr{sub 2-x}O{sub 4} spinel. The surface films on both alloys were identified as NiFe{sub 2}O{sub 4} when exposed to supercritical water at 527.5 °C. To characterize the fully developed oxide layer, studies were conducted at test solution temperatures of 527.5 and 600 °C. Samples were exposed to these temperatures for 24, 96, and 200 h. Surface chemistry was analyzed using X-ray diffraction, as well as Raman and X-ray photoelectron spectroscopies. Inconel 718 exhibited greater mass gain than Inconel 625 for all temperatures and exposure times. The differences in corrosion behavior of the two alloys are attributed to the lower content of chromium and increased iron content of Inconel 718 as compared to Inconel 625.

  9. Surface chemistry of polyacrylonitrile- and rayon-based activated carbon fibers after post-heat treatment

    International Nuclear Information System (INIS)

    Chiang Yuchun; Lee, C.-Y.; Lee, H.-C.

    2007-01-01

    Polyacrylonitrile- and rayon-based activated carbon fibers (ACFs) subject to heat treatment were investigated by means of elemental analyzer, and X-ray photoelectron spectroscopy (XPS). The total ash content of all ACFs was also analyzed. The adsorption of benzene, carbon tetrachloride and water vapor on ACFs was determined to shed light on the role of surface chemistry on gas adsorption. Results show that different precursors resulted in various elemental compositions and imposed diverse influence upon surface functionalities after heat treatment. The surface of heat-treated ACFs became more graphitic and hydrophobic. Three distinct peaks due to C, N, and O atoms were identified by XPS, and the high-resolution revealed the existence of several surface functionalities. The presence of nitride-like species, aromatic N-imines, or chemisorbed nitrogen oxides was found to be of great advantage to adsorption of water vapor or benzene, but the pyridine-N was not. Unstable complexes on the surface would hinder the fibers from adsorption of carbon tetrachloride. The rise in total ash content or hydrogen composition was of benefit to the access of water vapor. Modifications of ACFs by heat treatment have effectively improved adsorption performance

  10. PES Surface Modification Using Green Chemistry: New Generation of Antifouling Membranes

    Directory of Open Access Journals (Sweden)

    Norhan Nady

    2016-04-01

    Full Text Available A major limitation in using membrane-based separation processes is the loss of performance due to membrane fouling. This drawback can be addressed thanks to surface modification treatments. A new and promising surface modification using green chemistry has been recently investigated. This modification is carried out at room temperature and in aqueous medium using green catalyst (enzyme and nontoxic modifier, which can be safely labelled “green surface modification”. This modification can be considered as a nucleus of new generation of antifouling membranes and surfaces. In the current research, ferulic acid modifier and laccase bio-catalyst were used to make poly(ethersulfone (PES membrane less vulnerable to protein adsorption. The blank and modified PES membranes are evaluated based on e.g., their flux and protein repellence. Both the blank and the modified PES membranes (or laminated PES on silicon dioxide surface are characterized using many techniques e.g., SEM, EDX, XPS and SPM, etc. The pure water flux of the most modified membranes was reduced by 10% on average relative to the blank membrane, and around a 94% reduction in protein adsorption was determined. In the conclusions section, a comparison between three modifiers—ferulic acid, and two other previously used modifiers (4-hydroxybenzoic acid and gallic acid—is presented.

  11. PES Surface Modification Using Green Chemistry: New Generation of Antifouling Membranes.

    Science.gov (United States)

    Nady, Norhan

    2016-04-18

    A major limitation in using membrane-based separation processes is the loss of performance due to membrane fouling. This drawback can be addressed thanks to surface modification treatments. A new and promising surface modification using green chemistry has been recently investigated. This modification is carried out at room temperature and in aqueous medium using green catalyst (enzyme) and nontoxic modifier, which can be safely labelled "green surface modification". This modification can be considered as a nucleus of new generation of antifouling membranes and surfaces. In the current research, ferulic acid modifier and laccase bio-catalyst were used to make poly(ethersulfone) (PES) membrane less vulnerable to protein adsorption. The blank and modified PES membranes are evaluated based on e.g., their flux and protein repellence. Both the blank and the modified PES membranes (or laminated PES on silicon dioxide surface) are characterized using many techniques e.g., SEM, EDX, XPS and SPM, etc. The pure water flux of the most modified membranes was reduced by 10% on average relative to the blank membrane, and around a 94% reduction in protein adsorption was determined. In the conclusions section, a comparison between three modifiers-ferulic acid, and two other previously used modifiers (4-hydroxybenzoic acid and gallic acid)-is presented.

  12. Tuning Surface Chemistry of Polyetheretherketone by Gold Coating and Plasma Treatment

    Science.gov (United States)

    Novotná, Zdeňka; Rimpelová, Silvie; Juřík, Petr; Veselý, Martin; Kolská, Zdeňka; Hubáček, Tomáš; Borovec, Jakub; Švorčík, Václav

    2017-06-01

    Polyetheretherketone (PEEK) has good chemical and biomechanical properties that are excellent for biomedical applications. However, PEEK exhibits hydrophobic and other surface characteristics which cause limited cell adhesion. We have investigated the potential of Ar plasma treatment for the formation of a nanostructured PEEK surface in order to enhance cell adhesion. The specific aim of this study was to reveal the effect of the interface of plasma-treated and gold-coated PEEK matrices on adhesion and spreading of mouse embryonic fibroblasts. The surface characteristics (polarity, surface chemistry, and structure) before and after treatment were evaluated by various experimental techniques (gravimetry, goniometry, X-ray photoelectron spectroscopy (XPS), and electrokinetic analysis). Further, atomic force microscopy (AFM) was employed to examine PEEK surface morphology and roughness. The biological response of cells towards nanostructured PEEK was evaluated in terms of cell adhesion, spreading, and proliferation. Detailed cell morphology was evaluated by scanning electron microscopy (SEM). Compared to plasma treatment, gold coating improved PEEK wettability. The XPS method showed a decrease in the carbon concentration with increasing time of plasma treatment. Cell adhesion determined on the interface between plasma-treated and gold-coated PEEK matrices was directly proportional to the thickness of a gold layer on a sample. Our results suggest that plasma treatment in a combination with gold coating could be used in biomedical applications requiring enhanced cell adhesion.

  13. Tuning Surface Chemistry of Polyetheretherketone by Gold Coating and Plasma Treatment.

    Science.gov (United States)

    Novotná, Zdeňka; Rimpelová, Silvie; Juřík, Petr; Veselý, Martin; Kolská, Zdeňka; Hubáček, Tomáš; Borovec, Jakub; Švorčík, Václav

    2017-12-01

    Polyetheretherketone (PEEK) has good chemical and biomechanical properties that are excellent for biomedical applications. However, PEEK exhibits hydrophobic and other surface characteristics which cause limited cell adhesion. We have investigated the potential of Ar plasma treatment for the formation of a nanostructured PEEK surface in order to enhance cell adhesion. The specific aim of this study was to reveal the effect of the interface of plasma-treated and gold-coated PEEK matrices on adhesion and spreading of mouse embryonic fibroblasts. The surface characteristics (polarity, surface chemistry, and structure) before and after treatment were evaluated by various experimental techniques (gravimetry, goniometry, X-ray photoelectron spectroscopy (XPS), and electrokinetic analysis). Further, atomic force microscopy (AFM) was employed to examine PEEK surface morphology and roughness. The biological response of cells towards nanostructured PEEK was evaluated in terms of cell adhesion, spreading, and proliferation. Detailed cell morphology was evaluated by scanning electron microscopy (SEM). Compared to plasma treatment, gold coating improved PEEK wettability. The XPS method showed a decrease in the carbon concentration with increasing time of plasma treatment. Cell adhesion determined on the interface between plasma-treated and gold-coated PEEK matrices was directly proportional to the thickness of a gold layer on a sample. Our results suggest that plasma treatment in a combination with gold coating could be used in biomedical applications requiring enhanced cell adhesion.

  14. Chemistry on electrospun polymeric nanofibers: merely routine chemistry or a real challenge?

    Science.gov (United States)

    Agarwal, Seema; Wendorff, Joachim H; Greiner, Andreas

    2010-08-03

    Nanofiber-based non-wovens can be prepared by electrospinning. The chemical modification of such nanofibers or chemistry using nanofibers opens a multitude of application areas and challenges. A wealth of chemistry has been elaborated in recent years on and with electrospun nanofibers. Known methods as well as new methods have been applied to modify the electrospun nanofibers and thereby generate new materials and new functionalities. This Review summarizes and sorts the chemistry that has been reported in conjunction with electrospun nanofibers. The major focus is on catalysis and nanofibers, enzymes and nanofibers, surface modification for biomedical and specialty applications, coatings of fibers, crosslinking, and bulk modifications. A critical focus is on the question: what could make chemistry on or with nanofibers different from bulk chemistry? Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Investigations of Nitrogen Oxide Plasmas: Fundamental Chemistry and Surface Reactivity and Monitoring Student Perceptions in a General Chemistry Recitation

    Science.gov (United States)

    Blechle, Joshua M.

    2016-01-01

    Part I of this dissertation focuses on investigations of nitrogen oxide plasma systems. With increasing concerns over the environmental presence of NxOy species, there is growing interest in utilizing plasma-assisted conversion techniques. Advances, however, have been limited because of the lack of knowledge regarding the fundamental chemistry of…

  16. Investigation of the oxygen exchange mechanism on Pt|yttria stabilized zirconia at intermediate temperatures: Surface path versus bulk path

    International Nuclear Information System (INIS)

    Opitz, Alexander K.; Lutz, Alexander; Kubicek, Markus; Kubel, Frank; Hutter, Herbert; Fleig, Juergen

    2011-01-01

    Highlights: → Oxygen exchange kinetics of Pt on YSZ investigated by means of Pt model electrodes. → Two different geometry dependencies of the polarization resistance identified. → At higher temperatures the oxygen exchange reaction proceeds via a Pt surface path. → At lower temperatures a bulk path through the Pt thin film electrode is discussed. - Abstract: The oxygen exchange kinetics of platinum on yttria-stabilized zirconia (YSZ) was investigated by means of geometrically well-defined Pt microelectrodes. By variation of electrode size and temperature it was possible to separate two temperature regimes with different geometry dependencies of the polarization resistance. At higher temperatures (550-700 deg. C) an elementary step located close to the three phase boundary (TPB) with an activation energy of ∼1.6 eV was identified as rate limiting. At lower temperatures (300-400 deg. C) the rate limiting elementary step is related to the electrode area and exhibited a very low activation energy in the order of 0.2 eV. From these observations two parallel pathways for electrochemical oxygen exchange are concluded. The nature of these two elementary steps is discussed in terms of equivalent circuits. Two combinations of parallel rate limiting reaction steps are found to explain the observed geometry dependencies: (i) Diffusion through an impurity phase at the TPB in parallel to diffusion of oxygen through platinum - most likely along Pt grain boundaries - as area-related process. (ii) Co-limitation of oxygen diffusion along the Pt|YSZ interface and charge transfer at the interface with a short decay length of the corresponding transmission line (as TPB-related process) in parallel to oxygen diffusion through platinum.

  17. Chemistry of SOFC Cathode Surfaces: Fundamental Investigation and Tailoring of Electronic Behavior

    Energy Technology Data Exchange (ETDEWEB)

    Yildiz, Bilge; Heski, Clemens

    2013-08-31

    1) Electron tunneling characteristics on La0.7Sr0.3MnO3 (LSM) thin-film surfaces were studied up to 580oC in 10-3mbar oxygen pressure, using scanning tunneling microscopy/ spectroscopy (STM/STS). A threshold-like drop in the tunneling current was observed at positive bias in STS, which is interpreted as a unique indicator for the activation polarization in cation oxygen bonding on LSM cathodes. Sr-enrichment was found on the surface at high temperature using Auger electron spectroscopy, and was accompanied by a decrease in tunneling conductance in STS. This suggests that Sr-terminated surfaces are less active for electron transfer in oxygen reduction compared to Mn-terminated surfaces on LSM. 2) Effects of strain on the surface cation chemistry and the electronic structure are important to understand and control for attaining fast oxygen reduction kinetics on transition metal oxides. Here, we demonstrate and mechanistically interpret the strain coupling to Sr segregation, oxygen vacancy formation, and electronic structure on the surface of La0.7Sr0.3MnO3 (LSM) thin films as a model system. Our experimental results from x-ray photoelectron spectroscopy and scanning tunneling spectroscopy are discussed in light of our first principles-based calculations. A stronger Sr enrichment tendency and a more facile oxygen vacancy formation prevail for the tensile strained LSM surface. The electronic structure of the tensile strained LSM surface exhibits a larger band gap at room temperature, however, a higher tunneling conductance near the Fermi level than the compressively strained LSM at elevated temperatures in oxygen. Our findings suggest lattice strain as a key parameter to tune the reactivity of perovskite transition metal oxides with oxygen in solid oxide fuel cell cathodes. 3) Cation segregation on perovskite oxide surfaces affects vastly the oxygen reduction activity and stability of solid oxide fuel cell (SOFC) cathodes. A unified theory that explains the physical

  18. Surface chemistry and moisture sorption properties of wood coated with multifunctional alkoxysilanes by sol-gel process

    Science.gov (United States)

    Mandla A. Tshabalala; Peter Kingshott; Mark R. VanLandingham; David Plackett

    2003-01-01

    Sol-gel surface deposition of a hydrophobic polysiloxane coating on wood was accomplished by using a mixture of a low molecular weight multifunctional alkoxysilane, methyltrimethoxysilane (MTMOS), and a high molecular weight multifunctional alkoxysilane, hexadecyltrimethoxysilane (HDTMOS). Investigation of the surface chemistry and morphology of the wood specimens by...

  19. The synergy of ultrasonic treatment and organic modifiers for tuning the surface chemistry and conductivity of multiwalled carbon nanotubes

    Czech Academy of Sciences Publication Activity Database

    Omastová, M.; Mičušík, M.; Fedorko, P.; Pionteck, J.; Kovářová, Jana; Chehimi, M. M.

    2014-01-01

    Roč. 46, 10-11 (2014), s. 940-944 ISSN 0142-2421. [European Conference on Applications of Surface and Interface Analysis /15./ - ECASIA 2013. Cagliari, 13.10.2013-18.10.2013] Institutional support: RVO:61389013 Keywords : carbon nanotubes * surface modification * surfactant Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.245, year: 2014

  20. Solution electrostatic levitator for measuring surface properties and bulk structures of an extremely supersaturated solution drop above metastable zone width limit

    Science.gov (United States)

    Lee, Sooheyong; Jo, Wonhyuk; Cho, Yong chan; Lee, Hyun Hwi; Lee, Geun Woo

    2017-05-01

    We report on the first integrated apparatus for measuring surface and thermophysical properties and bulk structures of a highly supersaturated solution by combining electrostatic levitation with real-time laser/x-ray scattering. Even today, a proper characterization of supersaturated solutions far above their solubility limits is extremely challenging because heterogeneous nucleation sites such as container walls or impurities readily initiate crystallization before the measurements can be performed. In this work, we demonstrate simultaneous measurements of drying kinetics and surface tension of a potassium dihydrogen phosphate (KH2PO4) aqueous solution droplet and its bulk structural evolution beyond the metastable zone width limit. Our experimental finding shows that the noticeable changes of the surface properties are accompanied by polymerizations of hydrated monomer clusters. The novel electrostatic levitation apparatus presented here provides an effective means for studying a wide range of highly concentrated solutions and liquids in deep metastable states.

  1. Optical and terahertz measurement techniques for flat-faced pharmaceutical tablets: a case study of gloss, surface roughness and bulk properties of starch acetate tablets

    International Nuclear Information System (INIS)

    Juuti, M; Tuononen, H; Kontturi, V; Peiponen, K-E; Prykäri, T; Alarousu, E; Myllylä, R; Kuosmanen, M; Ketolainen, J

    2009-01-01

    Surface and bulk properties of flat-faced starch acetate tablets were studied. For surface quality inspection optical coherence tomography and recently developed diffractive glossmeter were utilized. Both these optical devices together provide local information on surface roughness and gloss of a tablet over a measured area. The concepts of mean topography and mean gloss profile for surface quality of a tablet are introduced. It was observed that the surface quality of the tablet varies, and compression at high pressure may not guarantee a good surface quality of the tablet. Using novel statistical parameters for gloss and relevant surface roughness parameter, it is possible to get more comprehensive quantitative data on the surface condition of a tablet. THz spectrometer was utilized for detection of THz pulse delay in transmission measurement mode from the tablets. The delay time and thickness ratio of the tablet are consistent with the porosity of the tablet as a function of compression pressure. We suggest that the multimeasurement scheme using three different devices helps tablet makers to better assess bulk and surface quality of their products

  2. Simple preparation of thiol-ene particles in glycerol and surface functionalization by thiol-ene chemistry (TEC) and surface chain transfer free radical polymerization (SCT-FRP)

    DEFF Research Database (Denmark)

    Hoffmann, Christian; Chiaula, Valeria; Pinelo, Manuel

    2018-01-01

    functionalization of excess thiol groups via photochemical thiol-ene chemistry (TEC) resulting in a functional monolayer. In addition, surface chain transfer free radical polymerization (SCT-FRP) was used for the first time to introduce a thicker polymer layer on the particle surface. The application potential...

  3. Revisiting 30 years of Biofunctionalization and Surface Chemistry of Inorganic Nanoparticles for Nanomedicine

    Directory of Open Access Journals (Sweden)

    João eConde

    2014-07-01

    Full Text Available In the last 30 years we have assisted to a massive advance of nanomaterials in material science. Nanomaterials and structures, in addition to their small size, have properties that differ from those of larger bulk materials, making them ideal for a host of novel applications. The spread of nanotechnology in the last years has been due to the improvement of synthesis and characterization methods on the nanoscale, a field rich in new physical phenomena and synthetic opportunities. In fact, the development of functional nanoparticles has progressed exponentially over the past two decades. This work aims to extensively review 30 years of different strategies of surface modification and functionalization of noble metal (gold nanoparticles, magnetic nanocrystals and semiconductor nanoparticles, such as quantum dots. The aim of this review is not only to provide in-depth insights into the different biofunctionalization and characterization methods, but also to give an overview of possibilities and limitations of the available nanoparticles.

  4. Control of pyrite surface chemistry in physical coal cleaning. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Luttrell, G.H.; Yoon, R.H.; Richardson, P.E.

    1993-05-19

    In Part I, Surface Chemistry of Coal Pyrite the mechanisms responsible for the inefficient rejection of coal pyrite were investigated using a number of experimental techniques. The test results demonstrate that the hydrophobicity of coal pyrite is related to the surface products formed during oxidation in aqueous solutions. During oxidation, a sulfur-rich surface layer is produced in near neutral pH solutions. This surface layer is composed mainly of sulfur species in the form of an iron-polysulfide along with a smaller amount of iron oxide/hydroxides. The floatability coal pyrite increases dramatically in the presence of frothers and hydrocarbon collectors. These reagents are believed to absorb on the weakly hydrophobic pyrite surfaces as a result of hydrophobic interaction forces. In Part III, Developing the Best Possible Rejection Schemes, a number of pyrite depressants were evaluated in column and conventional flotation tests. These included manganese (Mn) metal, chelating agents quinone and diethylenetriamine (DETA), and several commercially-available organic depressants. Of these, the additives which serve as reducing agents were found to be most effective. Reducing agents were used to prevent pyrite oxidation and/or remove oxidation products present on previously oxidized surfaces. These data show that Mn is a significantly stronger depressant for pyrite than quinone or DETA. Important factors in determining the pyrite depression effect of Mn include the slurry solid content during conditioning, the addition of acid (HCl), and the amount of Mn. The acid helps remove the oxide layer from the surface of Mn and promotes the depression of pyrite by Mn.

  5. Photografting of perfluoroalkanes onto polyethylene surfaces via azide/nitrene chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Siegmann, Konstantin, E-mail: konstantin.siegmann@zhaw.ch [Institute of Materials and Process Engineering (IMPE), School of Engineering (SoE), Zurich University of Applied Sciences - ZHAW, Technikumstrasse 9, CH-8401 Winterthur (Switzerland); Inauen, Jan, E-mail: jan.inauen@zhaw.ch [Institute of Materials and Process Engineering (IMPE), School of Engineering (SoE), Zurich University of Applied Sciences - ZHAW, Technikumstrasse 9, CH-8401 Winterthur (Switzerland); Villamaina, Diego, E-mail: diego.villamaina@gmail.com [Visiting scientist at IMPE, Permanent address: Rapidplatz 3, CH-8953 Dietikon (Switzerland); Winkler, Martin, E-mail: martin.winkler@zhaw.ch [Institute of Materials and Process Engineering (IMPE), School of Engineering (SoE), Zurich University of Applied Sciences - ZHAW, Technikumstrasse 9, CH-8401 Winterthur (Switzerland)

    2017-02-28

    The purpose of this study is to render polyethylene surfaces strongly and permanently hydrophobic. Polyethylene is a common plastic and, because of its inertness, difficult to graft. We chose polyethylene as example because of its ubiquity and model character. As graft chains linear perfluoroalkyl residues (−C{sub 4}F{sub 9}, −C{sub 6}F{sub 13}, −C{sub 8}F{sub 17} and −C{sub 10}F{sub 21}) were chosen, and photografting was selected as grafting method. Photolytically generated nitrenes can insert into carbon–hydrogen bonds and are therefore suited for binding to polyethylene. Hydrophobic photo reactive surface modifiers based on azide/nitrene chemistry are designed, synthesized in high yield and characterized. Four new molecules are described. Water contact angles exceeding 110° were achieved on grafted polyethylene. One problem is to demonstrate that the photografted surface modifiers are bound covalently to the polyethylene. Abrasion tests show that all new molecules, when photografted to polyethylene, have a higher abrasion resistance than a polyethylene surface coated with a long-chain perfluoroalkane. Relative abrasion resitances of 1.4, 2.0, 2.1 and 2.5 compared to the fluoroalkane coating were obtained for the four compounds. An abrasion model using ice is developed. Although all four compounds have the same λ{sub max} of 266 nm in acetonitrile solution, their molar extincition coefficients increase from 1.6·10{sup 4} to 2.2·10{sup 4} with increasing length of the fluorotelomer chain. Exitonic coupling of the chromophores of the surface modifiers is observed for specific molecules in the neat state. A linear correlation of water contact angle with fluorine surface content, as measured by photoelectron spectroscopy, in grafted polyethylene surfaces is established.

  6. Surface chemistry and corrosion behavior of Inconel 625 and 718 in subcritical, supercritical, and ultrasupercritical water

    Science.gov (United States)

    Rodriguez, David; Merwin, Augustus; Karmiol, Zachary; Chidambaram, Dev

    2017-05-01

    Corrosion behavior of Inconel 625 and 718 in subcritical, supercritical and ultrasupercritical water was studied as a function of temperature and time. The change in the chemistry of the as-received surface film on Inconel 625 and 718 after exposure to subcritical water at 325 °C and supercritical water at 425 °C and 527.5 °C for 2 h was studied. After exposure to 325 °C subcritical water, the CrO42- based film formed; however minor quantities of NiFexCr2-xO4 spinel compounds were observed. The oxide film formed on both alloys when exposed to supercritical water at 425 °C consisted of NiFexCr2-xO4 spinel. The surface films on both alloys were identified as NiFe2O4 when exposed to supercritical water at 527.5 °C. To characterize the fully developed oxide layer, studies were conducted at test solution temperatures of 527.5 and 600 °C. Samples were exposed to these temperatures for 24, 96, and 200 h. Surface chemistry was analyzed using X-ray diffraction, as well as Raman and X-ray photoelectron spectroscopies. Inconel 718 exhibited greater mass gain than Inconel 625 for all temperatures and exposure times. The differences in corrosion behavior of the two alloys are attributed to the lower content of chromium and increased iron content of Inconel 718 as compared to Inconel 625.

  7. Lake and bulk sampling chemistry, NADP, and IMPROVE air quality data analysis on the Bridger-Teton National Forest (USFS Region 4)

    Science.gov (United States)

    Jill Grenon; Terry Svalberg; Ted Porwoll; Mark Story

    2010-01-01

    Air quality monitoring data from several programs in and around the Bridger-Teton (B-T) National Forest - National Atmospheric Deposition Program (NADP), longterm lake monitoring, long-term bulk precipitation monitoring (both snow and rain), and Interagency Monitoring of Protected Visual Environments (IMPROVE) - were analyzed in this report. Trends were analyzed using...

  8. Surface chemistry of InP ridge structures etched in Cl{sub 2}-based plasma analyzed with angular XPS

    Energy Technology Data Exchange (ETDEWEB)

    Bouchoule, Sophie, E-mail: sophie.bouchoule@lpn.cnrs.fr; Cambril, Edmond; Guilet, Stephane [Laboratoire de Photonique et Nanostructure (LPN)—UPR20, CNRS, Route de Nozay, 91460 Marcoussis (France); Chanson, Romain; Pageau, Arnaud; Rhallabi, Ahmed; Cardinaud, Christophe, E-mail: christophe.cardinaud@cnrs-imn.fr [Institut des matériaux Jean Rouxel (IMN), UMR6502, Université de Nantes, CNRS, 44322 Nantes (France)

    2015-09-15

    Two x-ray photoelectron spectroscopy configurations are proposed to analyze the surface chemistry of micron-scale InP ridge structures etched in chlorine-based inductively coupled plasma (ICP). Either a classical or a grazing configuration allows to retrieve information about the surface chemistry of the bottom surface and sidewalls of the etched features. The procedure is used to study the stoichiometry of the etched surface as a function of ridge aspect ratio for Cl{sub 2}/Ar and Cl{sub 2}/H{sub 2} plasma chemistries. The results show that the bottom surface and the etched sidewalls are P-rich, and indicate that the P-enrichment mechanism is rather chemically driven. Results also evidence that adding H{sub 2} to Cl{sub 2} does not necessarily leads to a more balanced surface stoichiometry. This is in contrast with recent experimental results obtained with the HBr ICP chemistry for which fairly stoichiometric surfaces have been obtained.

  9. A study on the relationships between corrosion properties and chemistry of thermally oxidised surface films formed on polished commercial magnesium alloys AZ31 and AZ61

    Energy Technology Data Exchange (ETDEWEB)

    Feliu, Sebastián, E-mail: sfeliu@cenim.csic.es [Centro Nacional de Investigaciones Metalúrgicas CSIC, Avda. Gregorio del Amo 8, 28040 Madrid (Spain); Samaniego, Alejandro [Centro Nacional de Investigaciones Metalúrgicas CSIC, Avda. Gregorio del Amo 8, 28040 Madrid (Spain); Barranco, Violeta [Instituto de Ciencias de Materiales de Madrid, ICMM, Consejo Superior de Investigaciones Científicas, CSIC, Sor Juana Inés de la Cruz, 3, Cantoblanco, 28049, Madrid (Spain); El-Hadad, A.A. [Physics Department, Faculty of Science, Al-Azhar University, Nasr City 11884, Cairo (Egypt); Llorente, Irene [Centro Nacional de Investigaciones Metalúrgicas CSIC, Avda. Gregorio del Amo 8, 28040 Madrid (Spain); Serra, Carmen [Servicio de Nanotecnologia y Análisis de Superficies, CACTI, Universidade de Vigo, 36310 Vigo (Spain); Galván, J.C. [Centro Nacional de Investigaciones Metalúrgicas CSIC, Avda. Gregorio del Amo 8, 28040 Madrid (Spain)

    2014-03-01

    Highlights: • Surface chemistry of heat treated magnesium alloys. • Relation between heat treatment and aluminium subsurface enrichment. • Relation between surface composition and corrosion behaviour. - Abstract: This paper studies the changes in chemical composition of the thin oxide surface films induced by heating in air at 200 °C for time intervals from 5 min to 60 min on the freshly polished commercial AZ31 and AZ61 alloys with a view to better understanding their protective properties. This thermal treatment resulted in the formation of layers enriched in metallic aluminium at the interface between the outer MgO surface films and the bulk material. A strong link was found between the degree of metallic Al enrichment in the subsurface layer (from 10 to 15 at.%) observed by XPS (X-ray photoelectron spectroscopy) in the AZ61 treated samples and the increase in protective properties observed by EIS (electrochemical impedance spectroscopy) in the immersion test in 0.6 M NaCl. Heating for 5–60 min in air at 200 °C seems to be an effective, easy to perform and inexpensive method for increasing the corrosion resistance of the AZ61 alloy by approximately two or three times.

  10. Constraints on the Early Terrestrial Surface UV Environment Relevant to Prebiotic Chemistry.

    Science.gov (United States)

    Ranjan, Sukrit; Sasselov, Dimitar D

    2017-03-01

    The UV environment is a key boundary condition to abiogenesis. However, considerable uncertainty exists as to planetary conditions and hence surface UV at abiogenesis. Here, we present two-stream multilayer clear-sky calculations of the UV surface radiance on Earth at 3.9 Ga to constrain the UV surface fluence as a function of albedo, solar zenith angle (SZA), and atmospheric composition. Variation in albedo and latitude (through SZA) can affect maximum photoreaction rates by a factor of >10.4; for the same atmosphere, photoreactions can proceed an order of magnitude faster at the equator of a snowball Earth than at the poles of a warmer world. Hence, surface conditions are important considerations when computing prebiotic UV fluences. For climatically reasonable levels of CO 2 , fluence shortward of 189 nm is screened out, meaning that prebiotic chemistry is robustly shielded from variations in UV fluence due to solar flares or variability. Strong shielding from CO 2 also means that the UV surface fluence is insensitive to plausible levels of CH 4 , O 2 , and O 3 . At scattering wavelengths, UV fluence drops off comparatively slowly with increasing CO 2 levels. However, if SO 2 and/or H 2 S can build up to the ≥1-100 ppm level as hypothesized by some workers, then they can dramatically suppress surface fluence and hence prebiotic photoprocesses. H 2 O is a robust UV shield for λ levels of other atmospheric gases, fluence ≲198 nm is only available for cold, dry atmospheres, meaning sources with emission ≲198 (e.g., ArF excimer lasers) can only be used in simulations of cold environments with low abundance of volcanogenic gases. On the other hand, fluence at 254 nm is unshielded by H 2 O and is available across a broad range of [Formula: see text], meaning that mercury lamps are suitable for initial studies regardless of the uncertainty in primordial H 2 O and CO 2 levels. Key Words: Radiative transfer-Origin of life-Planetary environments

  11. An Ab Initio Approach Towards Engineering Fischer-Tropsch Surface Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Matthew Neurock

    2006-09-11

    One of the greatest societal challenges over the next decade is the production of cheap, renewable energy for the 10 billion people that inhabit the earth. This will require the development of various energy sources which will likely include fuels derived from methane, coal, and biomass and alternatives sources such as solar, wind and nuclear energy. One approach will be to synthesize gasoline and other fuels from simpler hydrocarbons such as CO derived from methane or other U.S. based sources such as coal. Syngas (CO and H{sub 2}) can be readily converted into higher molecular weight hydrocarbons through Fischer-Tropsch synthesis. Fischer-Tropsch (FT) synthesis involves the adsorption and the activation of CO and H{sub 2}, the subsequent propagation steps including hydrogenation and carbon-carbon coupling, followed by chain termination reactions. The current commercial catalysts are supported Co and Co-alloys particles. This project set out with the following objectives in mind: (1) understand the reaction mechanisms that control FT kinetics, (2) predict how the intrinsic metal-adsorbate bond affects the sequence of elementary steps in FT, (3) establish the effects of the reaction environment on catalytic activity and selectivity, (4) construct a first-principles based algorithm that can incorporate the detailed atomic surface structure and simulate the kinetics for the myriad of elementary pathways that make up FT chemistry, and (5) suggest a set of optimal features such as alloy composition and spatial configuration, oxide support, distribution of defect sites. As part of this effort we devoted a significant portion of time to develop an ab initio based kinetic Monte Carlo simulation which can be used to follow FT surface chemistry over different transition metal and alloy surfaces defined by the user. Over the life of this program, we have used theory and have developed and applied stochastic Monte Carlo simulations in order to establish the fundamental

  12. Porous structure and surface chemistry of phosphoric acid activated carbon from corncob

    International Nuclear Information System (INIS)

    Sych, N.V.; Trofymenko, S.I.; Poddubnaya, O.I.; Tsyba, M.M.; Sapsay, V.I.; Klymchuk, D.O.; Puziy, A.M.

    2012-01-01

    Highlights: ► Phosphoric acid activation results in formation of carbons with acidic surface groups. ► Maximum amount of surface groups is introduced at impregnation ratio 1.25. ► Phosphoric acid activated carbons show high capacity to copper. ► Phosphoric acid activated carbons are predominantly microporous. ► Maximum surface area and pore volume achieved at impregnation ratio 1.0. - Abstract: Active carbons have been prepared from corncob using chemical activation with phosphoric acid at 400 °C using varied ratio of impregnation (RI). Porous structure of carbons was characterized by nitrogen adsorption and scanning electron microscopy. Surface chemistry was studied by IR and potentiometric titration method. It has been shown that porosity development was peaked at RI = 1.0 (S BET = 2081 m 2 /g, V tot = 1.1 cm 3 /g), while maximum amount of acid surface groups was observed at RI = 1.25. Acid surface groups of phosphoric acid activated carbons from corncob includes phosphate and strongly acidic carboxylic (pK = 2.0–2.6), weakly acidic carboxylic (pK = 4.7–5.0), enol/lactone (pK = 6.7–7.4; 8.8–9.4) and phenol (pK = 10.1–10.7). Corncob derived carbons showed high adsorption capacity to copper, especially at low pH. Maximum adsorption of methylene blue and iodine was observed for carbon with most developed porosity (RI = 1.0).

  13. Porous structure and surface chemistry of phosphoric acid activated carbon from corncob

    Energy Technology Data Exchange (ETDEWEB)

    Sych, N.V.; Trofymenko, S.I.; Poddubnaya, O.I.; Tsyba, M.M. [Institute for Sorption and Endoecology Problems, National Academy of Sciences of Ukraine, 13 General Naumov St., 03164 Kyiv (Ukraine); Sapsay, V.I.; Klymchuk, D.O. [M.G. Kholodny Institute of Botany, National Academy of Sciences of Ukraine, 2 Tereshchenkivska St., 01601 Kyiv (Ukraine); Puziy, A.M., E-mail: alexander.puziy@ispe.kiev.ua [Institute for Sorption and Endoecology Problems, National Academy of Sciences of Ukraine, 13 General Naumov St., 03164 Kyiv (Ukraine)

    2012-11-15

    Highlights: Black-Right-Pointing-Pointer Phosphoric acid activation results in formation of carbons with acidic surface groups. Black-Right-Pointing-Pointer Maximum amount of surface groups is introduced at impregnation ratio 1.25. Black-Right-Pointing-Pointer Phosphoric acid activated carbons show high capacity to copper. Black-Right-Pointing-Pointer Phosphoric acid activated carbons are predominantly microporous. Black-Right-Pointing-Pointer Maximum surface area and pore volume achieved at impregnation ratio 1.0. - Abstract: Active carbons have been prepared from corncob using chemical activation with phosphoric acid at 400 Degree-Sign C using varied ratio of impregnation (RI). Porous structure of carbons was characterized by nitrogen adsorption and scanning electron microscopy. Surface chemistry was studied by IR and potentiometric titration method. It has been shown that porosity development was peaked at RI = 1.0 (S{sub BET} = 2081 m{sup 2}/g, V{sub tot} = 1.1 cm{sup 3}/g), while maximum amount of acid surface groups was observed at RI = 1.25. Acid surface groups of phosphoric acid activated carbons from corncob includes phosphate and strongly acidic carboxylic (pK = 2.0-2.6), weakly acidic carboxylic (pK = 4.7-5.0), enol/lactone (pK = 6.7-7.4; 8.8-9.4) and phenol (pK = 10.1-10.7). Corncob derived carbons showed high adsorption capacity to copper, especially at low pH. Maximum adsorption of methylene blue and iodine was observed for carbon with most developed porosity (RI = 1.0).

  14. Surface chemistry and cytotoxicity of reactively sputtered tantalum oxide films on NiTi plates

    Energy Technology Data Exchange (ETDEWEB)

    McNamara, K. [Materials and Surface Science Institute, University of Limerick, Limerick (Ireland); Department of Physics & Energy, University of Limerick, Limerick (Ireland); Kolaj-Robin, O.; Belochapkine, S.; Laffir, F. [Materials and Surface Science Institute, University of Limerick, Limerick (Ireland); Gandhi, A.A. [Materials and Surface Science Institute, University of Limerick, Limerick (Ireland); Department of Physics & Energy, University of Limerick, Limerick (Ireland); Tofail, S.A.M., E-mail: tofail.syed@ul.ie [Materials and Surface Science Institute, University of Limerick, Limerick (Ireland); Department of Physics & Energy, University of Limerick, Limerick (Ireland)

    2015-08-31

    NiTi, an equiatomic alloy containing nickel and titanium, exhibits unique properties such as shape memory effect and superelasticity. NiTi also forms a spontaneous protective titanium dioxide (TiO{sub 2}) layer that allows its use in biomedical applications. Despite the widely perceived biocompatibility there remain some concerns about the sustainability of the alloy's biocompatibility due to the defects in the TiO{sub 2} protective layer and the presence of high amount of sub-surface Ni, which can give allergic reactions. Many surface treatments have been investigated to try to improve both the corrosion resistance and biocompatibility of this layer. For such purposes, we have sputter deposited tantalum (Ta) oxide thin films onto the surface of the NiTi alloy. Despite being one of the promising metals for biomedical applications, Ta, and its various oxides and their interactions with cells have received relatively less attention. The oxidation chemistry, crystal structure, morphology and biocompatibility of these films have been investigated. In general, reactive sputtering especially in the presence of a low oxygen mixture yields a thicker film with better control of the film quality. The sputtering power influenced the surface oxidation states of Ta. Both microscopic and quantitative cytotoxicity measurements show that Ta films on NiTi are biocompatible with little to no variation in cytotoxic response when the surface oxidation state of Ta changes. - Highlights: • Reactive sputtering in low oxygen mixture yields thicker better quality films. • Sputtering power influenced surface oxidation states of Ta. • Cytotoxicity measurements show Ta films on NiTi are biocompatible. • Little to no variation in cytotoxic response when oxidation state changes.

  15. Nitrate pollution and surface water chemistry in Shimabara, Nagasaki Prefecture, Japan

    Science.gov (United States)

    Nakagawa, K.; Amano, H.

    2017-12-01

    Shimabara city has been experiencing serious nitrate pollution in groundwater. To evaluate nitrate pollution and water chemistry in surface water, water samples were collected at 42 sampling points in 15 rivers in Shimabara including a part of Unzen city from January to February 2017. Firstly, spatial distribution of water chemistry was assessed by describing stiff and piper-trilinear diagrams using major ions concentrations. Most of the samples showed Ca-HCO3 or Ca-(NO3+SO4) water types. It corresponds to groundwater chemistry. Some samples were classified into characteristic water types such as Na-Cl, (Na+K)-HCO3, and Ca-Cl. These results indicate sea water mixing and anthropogenic pollution. At the upstream of Nishi-river, although water chemistry showed Ca-HCO3, ions concentrations were higher than that of the other rivers. It indicates that this site was affected by the peripheral anthropogenic activities. Secondly, nitrate-pollution assessment was performed by using NO3-, NO2-, coprostanol (5β(H)-Cholestan-3β-ol), and cholestanol (5α(H)-Cholestan-3β-ol). NO2-N was detected at the 2 sampling points and exceeded drinking standard 0.9 mg L-1 for bottle-fed infants (WHO, 2011). NO3-N + NO2-N concentrations exceeded Japanese drinking standard 10 mg L-1 at 18 sampling points. The highest concentration was 27.5 mg L-1. Higher NO3-N levels were observed in the rivers in the northern parts of the study area. Coprostanol has been used as a fecal contamination indicator, since it can be found in only feces of higher animals. Coprostanol concentrations at 8 sampling points exceeded 700 ng L-1 (Australian drinking water standard). Coprostanol has a potential to distinguish the nitrate pollution sources between chemical fertilizer or livestock wastes, since water samples with similar NO3-N + NO2-N concentration showed distinct coprostanol concentration. The sterols ratio (5β/ (5β+5α)) exceeded 0.5 at 18 sampling points. This reveals that fecal pollution has occurred.

  16. Controls on Surface Water Chemistry in the Upper Merced River Basin, Yosemite National Park, California

    Science.gov (United States)

    Clow, David W.; Alisa Mast, M.; Campbell, Donald H.

    1996-05-01

    Surface water draining granitic bedrock in Yosemite National Park exhibits considerable variability in chemical composition, despite the relative homogeneity of bedrock chemistry. Other geological factors, including the jointing and distribution of glacial till, appear to exert strong controls on water composition. Chemical data from three surface water surveys in the upper Merced River basin conducted in August 1981, June 1988 and August 1991 were analysed and compared with mapped geological, hydrological and topographic features to identify the solute sources and processes that control water chemistry within the basin during baseflow. Water at most of the sampling sites was dilute, with alkalinities ranging from 26 to 77 equiv. l-1. Alkalinity was much higher in two subcatchments, however, ranging from 51 to 302 equiv. l-1. Base cations and silica were also significantly higher in these two catchments than in the rest of the watershed. Concentrations of weathering products in surface water were correlated to the fraction of each subcatchment underlain by surficial material, which is mostly glacial till. Silicate mineral weathering is the dominant control on concentrations of alkalinity, silica and base cations, and ratios of these constituents in surface water reflect the composition of local bedrock. Chloride concentrations in surface water samples varied widely, ranging from <1 to 96 equiv. l-1. The annual volume-weighted mean chloride concentration in the Merced River at the Happy Isles gauge from 1968 to 1990 was 26 equiv. l-1, which was five times higher than in atmospheric deposition (4-5 equiv. l-1), suggesting that a source of chloride exists within the watershed. Saline groundwater springs, whose locations are probably controlled by vertical jointing in the bedrock, are the most likely source of the chloride. Sulphate concentrations varied much less than most other solutes, ranging from 3 to 14 equiv. l-1. Concentrations of sulphate in quarterly samples

  17. Plains hydrology and reclamation project: Spoil ground-water chemistry and its impacts on surface water

    Energy Technology Data Exchange (ETDEWEB)

    Trudell, M.R.

    1988-01-01

    Description of the chemical makeup of spoil groundwater at Diplomat and Vesta mines in the Battle River mining area, 200 km southeast of Edmonton within the Lower Horseshoe Canyon coal zone; and at Highvale and Whitewood Mines in the Lake Wabamun mining area, 100 km west of Edmonton within the Ardley coal zone. This report compares the chemical characteristics of the spoil groundwater for each mine to those of the principal premining aquifer that is disrupted by surface mining. The characterization of spoil groundwater chemistry is based on the sampling and analyses of groundwater from piezometers installed in reclaimed areas. Forty-three samples were collected from 23 piezometers at Vesta Mine, and 54 samples were collected from 32 piezometers at Diplomat Mine. At Highvale Mine, 29 samples were collected from 13 piezometers installed in the reclaimed area at Pit 01. Eleven samples were also collected from piezometers installed in spoil at Whitewood Mine to augment a study of that site.

  18. Micropatterning of Functional Conductive Polymers with Multiple Surface Chemistries in Register

    DEFF Research Database (Denmark)

    Lind, Johan Ulrik; Acikgöz, Canet; Daugaard, Anders Egede

    2012-01-01

    A versatile procedure is presented for fast and efficient micropatterning of multiple types of covalently bound surface chemistry in perfect register on and between conductive polymer microcircuits. The micropatterning principle is applied to several types of native and functionalized PEDOT (poly(3......,4-ethylenedioxythiophene)) thin films. The method is based on contacting PEDOT-type thin films with a micropatterned agarose stamp containing an oxidant (aqueous hypochlorite) and applying a nonionic detergent. Where contacted, PEDOT not only loses its conductance but is entirely removed, thereby locally revealing...... of the method is illustrated by micropatterning cell-binding RGD-functionalized PEDOT on low cell-binding PMOXA (poly(2-methyl-2-oxazoline)) to produce cell-capturing microelectrodes on a cell nonadhesive background in a few simple steps. The method should be applicable to a wide range of native and chemically...

  19. SnSe Nanocrystals: Synthesis, Structure, Optical Properties, and Surface Chemistry

    KAUST Repository

    Baumgardner, William J.

    2010-07-21

    The colloidal synthesis of SnSe nanoparticles is accomplished through the injection of bis[bis(trimethylsilyl)amino]tin(II) into hot trioctylphosphine: selenium in the presence of oleylamine. Through the manipulation of reaction temperature particles are grown with the average diameter reliably tuned to 4-10 nm. Quantum confinement is examined by establishing a relationship between particle size and band gap while the in depth growth dynamics are illuminated through UV-vis-NIR spectroscopy. Surface chemistry effects are explored, including the demonstration of useful ligand exchanges and the development of routes toward anisotropic particle growth. Finally, transient current-voltage properties of SnSe nanocrystal films in the dark and light are examined. © 2010 American Chemical Society.

  20. Chemistry of the sea-surface microlayer. 3. Studies on the nutrient chemistry of the northern Arabian Sea

    Digital Repository Service at National Institute of Oceanography (India)

    Singbal, S.Y.S.; Narvekar, P.V.; Nagarajan, R.

    Nutrients showed enrichment in the surface microlayer compared to those in sub-surface water and there was a decreasing trend in the enrichment factor from nearshore to offshore in Northern Arabian Sea. The nutrient concentrations were correlated...

  1. Contributions of gas-phase plasma chemistry to surface modifications and gas-surface interactions: investigations of fluorocarbon rf plasmas

    Science.gov (United States)

    Cuddy, Michael F., II

    The fundamental aspects of inductively coupled fluorocarbon (FC) plasma chemistry were examined, with special emphasis on the contributions of gas-phase species to surface modifications. Characterization of the gas-phase constituents of single-source CF4-, C2F6-, C3F 8-, and C3F6-based plasmas was performed using spectroscopic and mass spectrometric techniques. The effects of varying plasma parameters, including applied rf power (P) and system pressure (p) were examined. Optical emission spectroscopy (OES) and laser-induced fluorescence (LIF) spectroscopy were employed to monitor the behavior of excited and ground CFx (x = 1,2) radicals, respectively. Mass spectrometric techniques, including ion energy analyses, elucidated behaviors of nascent ions in the FC plasmas. These gas-phase data were correlated with the net effect of substrate processing for Si and ZrO2 surfaces. Surface-specific analyses were performed for post-processed substrates via x-ray photoelectron spectroscopy (XPS) and contact angle goniometry. Generally, precursors with lower F/C ratios tended to deposit robust FC films of high surface energy. Precursors of higher F/C ratio, such as CF4, were associated with etching or removal of material from surfaces. Nonetheless, a net balance between deposition of FC moieties and etching of material exists for each plasma system. The imaging of radicals interacting with surfaces (IRIS) technique provided insight into the phenomena occurring at the interface of the plasma gas-phase and substrate of interest. IRIS results demonstrate that CFx radicals scatter copiously, with surface scatter coefficients, S, generally greater than unity under most experimental conditions. Such considerable S values imply surface-mediated production of the CFx radicals at FC-passivated sites. It is inferred that the primary route to surface production of CFx arises from energetic ion bombardment and ablation of surface FC films. Other factors which may influence the observed CFx

  2. The Materials Chemistry of Atomic Oxygen with Applications to Anisotropic Etching of Submicron Structures in Microelectronics and the Surface Chemistry Engineering of Porous Solids

    Science.gov (United States)

    Koontz, Steve L.; Leger, Lubert J.; Wu, Corina; Cross, Jon B.; Jurgensen, Charles W.

    1994-01-01

    Neutral atomic oxygen is the most abundant component of the ionospheric plasma in the low Earth orbit environment (LEO; 200 to 700 kilometers altitude) and can produce significant degradation of some spacecraft materials. In order to produce a more complete understanding of the materials chemistry of atomic oxygen, the chemistry and physics of O-atom interactions with materials were determined in three radically different environments: (1) The Space Shuttle cargo bay in low Earth orbit (the EOIM-3 space flight experiment), (2) a high-velocity neutral atom beam system (HVAB) at Los Alamos National Laboratory (LANL), and (3) a microwave-plasma flowing-discharge system at JSC. The Space Shuttle and the high velocity atom beam systems produce atom-surface collision energies ranging from 0.1 to 7 eV (hyperthermal atoms) under high-vacuum conditions, while the flowing discharge system produces a 0.065 eV surface collision energy at a total pressure of 2 Torr. Data obtained in the three different O-atom environments referred to above show that the rate of O-atom reaction with polymeric materials is strongly dependent on atom kinetic energy, obeying a reactive scattering law which suggests that atom kinetic energy is directly available for overcoming activation barriers in the reaction. General relationships between polymer reactivity with O atoms and polymer composition and molecular structure have been determined. In addition, vacuum ultraviolet photochemical effects have been shown to dominate the reaction of O atoms with fluorocarbon polymers. Finally, studies of the materials chemistry of O atoms have produced results which may be of interest to technologists outside the aerospace industry. Atomic oxygen 'spin-off' or 'dual use' technologies in the areas of anisotropic etching in microelectronic materials and device processing, as well as surface chemistry engineering of porous solid materials are described.

  3. THE EFFECTS OF SURFACE CHEMISTRY ON THE PROPERTIES OF PROTEINS CONFINED IN NANO-POROUS MATERIALS

    Energy Technology Data Exchange (ETDEWEB)

    Garrett, L. M.; O' Neill, H.

    2007-01-01

    The entrapment of proteins using the sol-gel route provides a means to retain its native properties and artifi cially reproduce the molecular crowding and confi nement experienced by proteins in the cell allowing investigation of the physico-chemical and structural properties of biomolecules at the biotic/abiotic interface. The biomolecules are spatially separated and ‘caged’ in the gel structure but solutes can freely permeate the matrix. Thus, properties such as the folding of ensembles of individual molecules can be examined in the absence of aggregation effects that can occur in solution studies. Green fl uorescent protein from Aequorea coerulescens was used as a model protein to examine the unfolding/re-folding properties of protein in silica gels. The recombinant protein was isolated and purifi ed from Escherichia coli extracts by cell lysis, three-phase partitioning, dialysis, and anion exchange chromatography. The purity of the protein was greater than 90% as judged by SDS PAGE gel analysis. Sol-gels were synthesized using tetramethylorthosilicate (TMOS) in combination with, methyltrimethoxyorthosilane (MTMOS), ethyltrimethoxyorthosilane (ETMOS), 3-aminopropyltriethoxysilane (APTES), and 3-glycidoxypropyltrimethoxysilane (GPTMS). The acid induced denaturation and renaturation of GFP was analyzed by UV-visible, fl uorescence, and circular dichroism (CD) spectroscopies. No renaturation was observed in gels that were made with TMOS only, and in the presence of APTES, MTMOS, and ETMOS. However, in gels that were made with GPTMS, the CD and UV-visible spectra indicated that the protein had refolded. The fl uorescence emission spectrum indicated that approximately 20% of fl uorescence had returned. This study highlights the importance of the surface chemistry of the silica gels for the refolding properties of the entrapped GFP. Future studies will investigate the effect of surface chemistry on the thermal and solvent stability of the entrapped protein.

  4. Graphdiyne as Electrode Material: Tuning Electronic State and Surface Chemistry for Improved Electrode Reactivity.

    Science.gov (United States)

    Guo, Shuyue; Yan, Hailong; Wu, Fei; Zhao, Lijun; Yu, Ping; Liu, Huibiao; Li, Yuliang; Mao, Lanqun

    2017-12-05

    Graphdiyne (GDY) is recently synthesized two-dimensional carbon allotrope with hexagonal rings cross-linked by diacetylene through introducing butadiyne linkages (-C≡C-C≡C-) to form 18-C hexagons and is emerging to be fundamentally interesting and particularly useful in various research fields. In this study, we for the first time find that GDY can be used as an electrode material with reactivity tunable by electronic states and surface chemistry of GDY. To demonstrate this, GDY is oxidized into graphdiyne oxide (GDYO) that is then chemically and electrochemically reduced into chemically reduced GDYO (cr-GDYO) and electrochemically reduced GDYO (er-GDYO), respectively. Electrode reactivity of GDY and its derivatives (i.e., GDYO, cr-GDYO, and er-GDYO) is studied with hexaammineruthenium chloride ([Ru(NH 3 ) 6 ]Cl 3 ) and potassium ferricyanide (K 3 Fe(CN) 6 ) as redox probes. We find that electron transfer kinetics of the redox probes employed here at GDYs depends on the density of electronic state (DOS) and the synergetic effects of the surface chemistry as well as the hydrophilicity of the materials, and that the electron transfer kinetics at cr-GDYO and er-GDYO are faster than those at GDY and GDYO, and quite comparable with those at carbon nanotubes and graphene and its derivatives (i.e., GO, cr-GO, and er-GO). These properties, combined with the unique electronic and chemical structures of GDY, essentially enable GDY as a new kind of electrode material for fundamental studies on carbon electrochemistry and various electroanalytical applications.

  5. Neutron reflectivity study of substrate surface chemistry effects on supported phospholipid bilayer formation on (1120) sapphire.

    Energy Technology Data Exchange (ETDEWEB)

    Oleson, Timothy A. [University of Wisconsin, Madison; Sahai, Nita [University of Akron; Wesolowski, David J [ORNL; Dura, Joseph A [ORNL; Majkrzak, Charles F [ORNL; Giuffre, Anthony J. [University of Wisconsin, Madison

    2012-01-01

    Oxide-supported phospholipid bilayers (SPBs) used as biomimetric membranes are significant for a broad range of applications including improvement of biomedical devices and biosensors, and in understanding biomineralization processes and the possible role of mineral surfaces in the evolution of pre-biotic membranes. Continuous-coverage and/or stacjed SPBs retain properties (e.,g. fluidity) more similar to native biological membranes, which is desirable for most applications. Using neutron reflectivity, we examined face coverage and potential stacking of dipalmitoylphosphatidylcholine (DPPC) bilayers on the (1120) face of sapphire (a-Al2O3). Nearly full bilayers were formed at low to neutral pH, when the sapphire surface is positively charged, and at low ionic strength (l=15 mM NaCl). Coverage decreased at higher pH, close to the isoelectric point of sapphire, and also at high I>210mM, or with addition of 2mM Ca2+. The latter two effects are additive, suggesting that Ca2+ mitigates the effect of higher I. These trends agree with previous results for phospholipid adsorption on a-Al2O3 particles determined by adsorption isotherms and on single-crystal (1010) sapphire by atomic force microscopy, suggesting consistency of oxide surface chemistry-dependent effects across experimental techniques.

  6. Chemistry and Photochemistry at the Surface of Urban Road Dust and Photoactive Minerals

    Science.gov (United States)

    Styler, S. A.; Abou-Ghanem, M.; Wickware, B.

    2017-12-01

    Each year, over a billion tons of dust are released into the atmosphere from arid regions. After its emission, dust can undergo efficient long-range transport to urban centres, where it can interact with local pollution sources. Another source of dust in urban regions is road dust resuspension, which is the largest anthropogenic source of primary particulate matter in both Canada and the United States. Since dust contains light-absorbing components, including iron- and titanium-containing minerals, dust-catalyzed photochemical processes have the potential to influence both the lifetime of pollutants present at the dust surface and the composition of the surrounding atmosphere. To date, most studies of dust photochemistry have focused on TiO2-mediated processes, and no studies have explored trace gas uptake at the surface of road dust. Here, we present first results from aerosol and coated-wall flow tube investigations of ozone uptake at the surface of a suite of titanium-containing minerals and road dust collected in Edmonton, Alberta. Together, this work represents a significant advance in our understanding of chemistry and photochemistry at realistic environmental interfaces.

  7. DNA damage response to different surface chemistry of silver nanoparticles in mammalian cells

    International Nuclear Information System (INIS)

    Ahamed, Maqusood; Karns, Michael; Goodson, Michael; Rowe, John; Hussain, Saber M.; Schlager, John J.; Hong Yiling

    2008-01-01

    Silver nanoparticles (Ag NPs) have recently received much attention for their possible applications in biotechnology and life sciences. Ag NPs are of interest to defense and engineering programs for new material applications as well as for commercial purposes as an antimicrobial. However, little is known about the genotoxicity of Ag NPs following exposure to mammalian cells. This study was undertaken to examine the DNA damage response to polysaccharide surface functionalized (coated) and non-functionalized (uncoated) Ag NPs in two types of mammalian cells; mouse embryonic stem (mES) cells and mouse embryonic fibroblasts (MEF). Both types of Ag NPs up-regulated the cell cycle checkpoint protein p53 and DNA damage repair proteins Rad51 and phosphorylated-H2AX expression. Furthermore both of them induced cell death as measured by the annexin V protein expression and MTT assay. Our observations also suggested that the different surface chemistry of Ag NPs induce different DNA damage response: coated Ag NPs exhibited more severe damage than uncoated Ag NPs. The results suggest that polysaccharide coated particles are more individually distributed while agglomeration of the uncoated particles limits the surface area availability and access to membrane bound organelles

  8. Porous structure and surface chemistry of phosphoric acid activated carbon from corncob

    Science.gov (United States)

    Sych, N. V.; Trofymenko, S. I.; Poddubnaya, O. I.; Tsyba, M. M.; Sapsay, V. I.; Klymchuk, D. O.; Puziy, A. M.

    2012-11-01

    Active carbons have been prepared from corncob using chemical activation with phosphoric acid at 400 °C using varied ratio of impregnation (RI). Porous structure of carbons was characterized by nitrogen adsorption and scanning electron microscopy. Surface chemistry was studied by IR and potentiometric titration method. It has been shown that porosity development was peaked at RI = 1.0 (SBET = 2081 m2/g, Vtot = 1.1 cm3/g), while maximum amount of acid surface groups was observed at RI = 1.25. Acid surface groups of phosphoric acid activated carbons from corncob includes phosphate and strongly acidic carboxylic (pK = 2.0-2.6), weakly acidic carboxylic (pK = 4.7-5.0), enol/lactone (pK = 6.7-7.4; 8.8-9.4) and phenol (pK = 10.1-10.7). Corncob derived carbons showed high adsorption capacity to copper, especially at low pH. Maximum adsorption of methylene blue and iodine was observed for carbon with most developed porosity (RI = 1.0).

  9. Preparation and application of a novel electrochemical sensing material based on surface chemistry of polyhydroquinone

    International Nuclear Information System (INIS)

    Dang, Xueping; Wang, Yingkai; Hu, Chengguo; Huang, Jianlin; Chen, Huaixia; Wang, Shengfu; Hu, Shengshui

    2014-01-01

    A new analogue of polydopamine (PDA), i.e., polyhydroquinone (PH 2 Q), was polymerized and its surface chemistry was studied by different ways of characterization. PH 2 Q was produced by the self-polymerization of H 2 Q mediated by dissolved oxygen, and the self-polymerization process was strongly dependent on the type and the pH value of the buffer solutions. PH 2 Q can not only achieve surface hydrophilization of different substrates like polyethylene terephthalate (PET) film, graphite strip, C 12 SH/Au and wax slice, but also possess several unique properties like reversible adsorption, good solubility and low cost. These properties made PH 2 Q an ideal polymeric modifier for the noncovalent functionalization of some nanomaterials. By simply grinding with PH 2 Q, pristine multi-walled carbon nanotubes (MWNTs) can be readily dispersed in water with high solubility and good stability. The resulting MWNT–PH 2 Q composite exhibited excellent electrochemical performance, which was employed for the simultaneous determination of dopamine (DA) and uric acid (UA). - Highlights: • Polyhydroquinone (PH 2 Q) was produced by the self-polymerization of hydroquinone (H 2 Q) mediated by dissolved oxygen. • PH 2 Q can achieve surface hydrophilization of a variety of substrates. • PH 2 Q is an ideal polymeric modifier for the functionalization of multi-walled carbon nanotubes (MWNTs). • The MWNT–PH 2 Q composite can be employed for the simultaneous determination of dopamine (DA) and uric acid (UA)

  10. Quantum Chemistry in Nanoscale Environments: Insights on Surface-Enhanced Raman Scattering and Organic Photovoltaics

    Science.gov (United States)

    Olivares-Amaya, Roberto

    The understanding of molecular effects in nanoscale environments is becoming increasingly relevant for various emerging fields. These include spectroscopy for molecular identification as well as in finding molecules for energy harvesting. Theoretical quantum chemistry has been increasingly useful to address these phenomena to yield an understanding of these effects. In the first part of this dissertation, we study the chemical effect of surface-enhanced Raman scattering (SERS). We use quantum chemistry simulations to study the metal-molecule interactions present in these systems. We find that the excitations that provide a chemical enhancement contain a mixed contribution from the metal and the molecule. Moreover, using atomistic studies we propose an additional source of enhancement, where a transition metal dopant surface could provide an additional enhancement. We also develop methods to study the electrostatic effects of molecules in metallic environments. We study the importance of image-charge effects, as well as field-bias to molecules interacting with perfect conductors. The atomistic modeling and the electrostatic approximation enable us to study the effects of the metal interacting with the molecule in a complementary fashion, which provides a better understanding of the complex effects present in SERS. In the second part of this dissertation, we present the Harvard Clean Energy Project, a high-throughput approach for a large-scale computational screening and design of organic photovoltaic materials. We create molecular libraries to search for candidates structures and use quantum chemistry, machine learning and cheminformatics methods to characterize these systems and find structure-property relations. The scale of this study requires an equally large computational resource. We rely on distributed volunteer computing to obtain these properties. In the third part of this dissertation we present our work related to the acceleration of electronic structure

  11. Kinetics of electrochemically controlled surface reactions on bulk and thin film metals studied with Fourier transform impedance spectroscopy and surface plasmon resonance techniques

    Science.gov (United States)

    Assiongbon, Kankoe A.

    2005-07-01

    In the work presented in this thesis, the surface sensitive electrochemical techniques of cyclic voltametry (CV), potential step (PS) and Fourier transform impedance spectroscopy (FT-EIS), as well as the optical technique of surface plasmon resonance (SPR), were used to probe a wide variety of surface processes at various metal/liquid interface. Three polycrystalline metals (Au, Ta and Cu) and a Cr-coated gold film were used for these studies in different aqueous environments. A combination of CV with FT-EIS and PS was used to investigate electronic and structural proprieties of a modified bulk electrode of Au. This experimental system involved under potential deposition (UPD) of Bi3+ on Au in a supporting aqueous electrolyte containing ClO-4 . UPD range of Bi3+ was determined, and adsorption kinetics of Bi3+ in the presence of coadsorbing anion, ClO-4 were quantified. Potentiodynamic growth of oxide films of Ta in the following electrolytes NaNO3, NaNO3 + 5wt% H2O2, NaOH and NaOH + 5wt% H2O2 had been investigated. The oxide films were grown in the range -0.1 → +0.4V (high electric field) at a scan rate of 10 mV/s. Time resolved A.C. impedance spectroscopy measurements in the frequency range (0.1--20 KHz) were performed to characterize the surface reactions of oxide formation. The results are interpreted in terms of charge conductivity O2- through the oxide film, and disintegration of H2O2 into OH-. In a high pH medium (pH 12), dissociation of H2O2 was catalytically enhanced. This led to destabilization of the electrogenerated tantalum oxide surface film in the form of a soluble hexatantalate species. In contrast with the electrolytes, NaNO3, NaNO3 + 5wt% H2O2, NaOH, where only the oxide growth was observed, the A.C. impedance spectroscopy measurements in NaOH + 5wt% H 2O2 showed competition between oxide formation and its removal. These results are relevant for chemical slurry design in chemical mechanical polishing (CMP) of Ta. Further investigations were

  12. Distinct effects of Cr bulk doping and surface deposition on the chemical environment and electronic structure of the topological insulator Bi2Se3

    Science.gov (United States)

    Yilmaz, Turgut; Hines, William; Sun, Fu-Chang; Pletikosić, Ivo; Budnick, Joseph; Valla, Tonica; Sinkovic, Boris

    2017-06-01

    In this report, it is shown that Cr doped into the bulk and Cr deposited on the surface of Bi2Se3 films produced by molecular beam epitaxy (MBE) have strikingly different effects on both the electronic structure and chemical environment. Angle resolved photoemission spectroscopy (ARPES) shows that Cr doped into the bulk opens a surface state energy gap which can be seen at room temperature; much higher than the measured ferromagnetic transition temperature of ≈10 K. On the other hand, similar ARPES measurements show that the surface states remain gapless down to 15 K for films with Cr surface deposition. In addition, core-level photoemission spectroscopy of the Bi 5d, Se 3d, and Cr 3p core levels show distinct differences in the chemical environment for the two methods of Cr introduction. Surface deposition of Cr results in the formation of shoulders on the lower binding energy side for the Bi 5d peaks and two distinct Cr 3p peaks indicative of two Cr sites. These striking differences suggests an interesting possibility that better control of doping at only near surface region may offer a path to quantum anomalous Hall states at higher temperatures than reported in the literature.

  13. Controlling the Photophysical Properties of Semiconductor Quantum Dot Arrays by Strategically Altering Their Surface Chemistry

    Science.gov (United States)

    Marshall, Ashley R.

    Semiconductor quantum dots (QDs) are interesting materials that, after less than 40 years of research, are used in commercial products. QDs are now found in displays, such as Samsung televisions and the Kindle Fire, and have applications in lighting, bio-imaging, quantum computing, and photovoltaics. They offer a large range of desirable properties: a controllable band gap, solution processability, controlled energy levels, and are currently the best materials for multiple exciton generation. The tunable optoelectronic properties of QDs can be controlled using size, shape, composition, and surface treatments--as shown here. Due to the quasi-spherical shape of QDs the surface to volume ratio is high, i.e. many of the constituent atoms are found on the QD surface. This makes QDs highly sensitive to surface chemistry modifications. This thesis encompasses the effects of surface treatments for QDs of two semiconducting materials: lead chalcogenides and CsPbI3. Our group developed a new synthetic technique for lead chalcogenide QDs via the cation exchange of cadmium chalcogenides. An in-depth chemical analysis is paired with optical and electrical studies and we find that metal halide residue contributes to the oxidative stability and decreased trap state density in cation-exchanged PbS QDs. We exploit these properties to make air-stable QD photovoltaic devices from both PbS and PbSe QD materials. Beyond the effects of residual atoms left from the synthetic technique, I investigated how to controllably add atoms onto the surface of QDs. I found that by introducing metal halides as a post-treatment in an electronically coupled array I am able to control the performance parameters in QD photovoltaic devices. These treatments fully infiltrate the assembled film, even under short exposure times and allow me to add controlled quantities of surface atoms to study their effects on film properties and photovoltaic device performance. Finally, I sought to apply the knowledge of

  14. Dust evolution, a global view: III. Core/mantle grains, organic nano-globules, comets and surface chemistry.

    Science.gov (United States)

    Jones, A P

    2016-12-01

    Within the framework of The Heterogeneous dust Evolution Model for Interstellar Solids (THEMIS), this work explores the surface processes and chemistry relating to core/mantle interstellar and cometary grain structures and their influence on the nature of these fascinating particles. It appears that a realistic consideration of the nature and chemical reactivity of interstellar grain surfaces could self-consistently and within a coherent framework explain: the anomalous oxygen depletion, the nature of the CO dark gas, the formation of 'polar ice' mantles, the red wing on the 3 μm water ice band, the basis for the O-rich chemistry observed in hot cores, the origin of organic nano-globules and the 3.2 μm 'carbonyl' absorption band observed in comet reflectance spectra. It is proposed that the reaction of gas phase species with carbonaceous a-C(:H) grain surfaces in the interstellar medium, in particular the incorporation of atomic oxygen into grain surfaces in epoxide functional groups, is the key to explaining these observations. Thus, the chemistry of cosmic dust is much more intimately related with that of the interstellar gas than has previously been considered. The current models for interstellar gas and dust chemistry will therefore most likely need to be fundamentally modified to include these new grain surface processes.

  15. Surface/Interfacial Structure and Chemistry of High-Energy Nickel-Rich Layered Oxide Cathodes: Advances and Perspectives.

    Science.gov (United States)

    Hou, Peiyu; Yin, Jiangmei; Ding, Meng; Huang, Jinzhao; Xu, Xijin

    2017-12-01

    The urgent prerequisites of high energy-density and superior electrochemical properties have been the main inspiration for the advancement of cathode materials in lithium-ion batteries (LIBs) in the last two decades. Nickel-rich layered transition-metal oxides with large reversible capacity as well as high operating voltage are considered as the most promising candidate for next-generation LIBs. Nonetheless, the poor long-term cycle-life and inferior thermal stability have limited their broadly practical applications. In the research of LIBs, it is observed that surface/interfacial structure and chemistry play significant roles in the performance of cathode cycling. This is due to the fact that they are basically responsible for the reversibility of Li + intercalation/deintercalation chemistries while dictating the kinetics of the general cell reactions. In this Review, the surface/interfacial structure and chemistry of nickel-rich layered cathodes involving structural defects, redox mechanisms, structural evolutions, side-reactions among others are initially demonstrated. Recent advancements in stabilizing the surface/interfacial structure and chemistry of nickel-rich cathodes by surface modification, core-shell/concentration-gradient structure, foreign-ion substitution, hybrid surface, and electrolyte additive are presented. Then lastly, the remaining challenges such as the fundamental studies and commercialized applications, as well as the future research directions are discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Adsorption and combing of DNA on HOPG surfaces of bulk crystals and nanosheets: application to the bridging of DNA between HOPG/Si heterostructures

    International Nuclear Information System (INIS)

    Rose, F; Martin, P; Fujita, H; Kawakatsu, H

    2006-01-01

    Controlled and reproducible combing of λ-phage DNA molecules can be realized in predetermined orientations on highly oriented pyrolitic graphite (HOPG) surfaces. Observations by atomic force microscopy (AFM) show that DNA adsorption onto HOPG surfaces leads to different hierarchical organizations such as balls, networks, films, and fractal structures. HOPG nanosheets (3.5-100 nm thick) were created by simply rubbing a HOPG crystal onto a silicon oxide surface, and then patterned with a focused ion beam (FIB) to fabricate HOPG/Si heterostructures (arrays of silicon micropillars and microtracks decorated on their top surface with HOPG nanosheets). The surface reactivity of HOPG nanosheets toward DNA is found to be the same as of HOPG bulk crystals. Finally, combing is used to attach and suspend bundles of approximately 20-50 DNA molecules between HOPG/Si heterostructures

  17. Evolution of interfacial intercalation chemistry on epitaxial graphene/SiC by surface enhanced Raman spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Ferralis, Nicola, E-mail: ferralis@mit.edu [Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States); Carraro, Carlo [Department of Chemical and Biomolecular Engineering, University of California, Berkeley, CA 94720 (United States)

    2014-11-30

    Highlights: • H-intercalated epitaxial graphene–SiC interface studied with surface enhanced Raman. • Evolution of graphene and H–Si interface with UV-ozone, annealing and O-exposure. • H–Si interface and quasi-freestanding graphene are retained after UV-ozone treatment. • Enhanced ozonolytic reactivity at the edges of H-intercalated defected graphene. • Novel SERS method for characterizing near-surface graphene–substrate interfaces. - Abstract: A rapid and facile evaluation of the effects of physical and chemical processes on the interfacial layer between epitaxial graphene monolayers on SiC(0 0 0 1) surfaces is essential for applications in electronics, photonics, and optoelectronics. Here, the evolution of the atomic scale epitaxial graphene-buffer-layer–SiC interface through hydrogen intercalation, thermal annealings, UV-ozone etching and oxygen exposure is studied by means of single microparticle mediated surface enhanced Raman spectroscopy (smSERS). The evolution of the interfacial chemistry in the buffer layer is monitored through the Raman band at 2132 cm{sup −1} corresponding to the Si-H stretch mode. Graphene quality is monitored directly by the selectively enhanced Raman signal of graphene compared to the SiC substrate signal. Through smSERS, a simultaneous correlation between optimized hydrogen intercalation in epitaxial graphene/SiC and an increase in graphene quality is uncovered. Following UV-ozone treatment, a fully hydrogen passivated interface is retained, while a moderate degradation in the quality of the hydrogen intercalated quasi-freestanding graphene is observed. While hydrogen intercalated defect free quasi-freestanding graphene is expected to be robust upon UV-ozone, thermal annealing, and oxygen exposure, ozonolytic reactivity at the edges of H-intercalated defected graphene results in enhanced amorphization of the quasi-freestanding (compared to non-intercalated) graphene, leading ultimately to its complete etching.

  18. Evolution of interfacial intercalation chemistry on epitaxial graphene/SiC by surface enhanced Raman spectroscopy

    International Nuclear Information System (INIS)

    Ferralis, Nicola; Carraro, Carlo

    2014-01-01

    Highlights: • H-intercalated epitaxial graphene–SiC interface studied with surface enhanced Raman. • Evolution of graphene and H–Si interface with UV-ozone, annealing and O-exposure. • H–Si interface and quasi-freestanding graphene are retained after UV-ozone treatment. • Enhanced ozonolytic reactivity at the edges of H-intercalated defected graphene. • Novel SERS method for characterizing near-surface graphene–substrate interfaces. - Abstract: A rapid and facile evaluation of the effects of physical and chemical processes on the interfacial layer between epitaxial graphene monolayers on SiC(0 0 0 1) surfaces is essential for applications in electronics, photonics, and optoelectronics. Here, the evolution of the atomic scale epitaxial graphene-buffer-layer–SiC interface through hydrogen intercalation, thermal annealings, UV-ozone etching and oxygen exposure is studied by means of single microparticle mediated surface enhanced Raman spectroscopy (smSERS). The evolution of the interfacial chemistry in the buffer layer is monitored through the Raman band at 2132 cm −1 corresponding to the Si-H stretch mode. Graphene quality is monitored directly by the selectively enhanced Raman signal of graphene compared to the SiC substrate signal. Through smSERS, a simultaneous correlation between optimized hydrogen intercalation in epitaxial graphene/SiC and an increase in graphene quality is uncovered. Following UV-ozone treatment, a fully hydrogen passivated interface is retained, while a moderate degradation in the quality of the hydrogen intercalated quasi-freestanding graphene is observed. While hydrogen intercalated defect free quasi-freestanding graphene is expected to be robust upon UV-ozone, thermal annealing, and oxygen exposure, ozonolytic reactivity at the edges of H-intercalated defected graphene results in enhanced amorphization of the quasi-freestanding (compared to non-intercalated) graphene, leading ultimately to its complete etching

  19. Scanning near-field optical microscopy on rough surfaces: applications in chemistry, biology, and medicine

    Directory of Open Access Journals (Sweden)

    2006-01-01

    Full Text Available Shear-force apertureless scanning near-field optical microscopy (SNOM with very sharp uncoated tapered waveguides relies on the unexpected enhancement of reflection in the shear-force gap. It is the technique for obtaining chemical (materials contrast in the optical image of “real world” surfaces that are rough and very rough without topographical artifacts, and it is by far less complicated than other SNOM techniques that can only be used for very flat surfaces. The experimental use of the new photophysical effect is described. The applications of the new technique are manifold. Important mechanistic questions in solid-state chemistry (oxidation, diazotization, photodimerization, surface hydration, hydrolysis are answered with respect to simultaneous AFM (atomic force microscopy and detailed crystal packing. Prehistoric petrified bacteria and concomitant pyrite inclusions are also investigated with local RAMAN SNOM. Polymer beads and unstained biological objects (rabbit heart, shrimp eye allow for nanoscopic analysis of cell organelles. Similarly, human teeth and a cancerous tissue are analyzed. Bladder cancer tissue is clearly differentiated from healthy tissue without staining and this opens a new highly promising diagnostic tool for precancer diagnosis. Industrial applications are demonstrated at the corrosion behavior of dental alloys (withdrawal of a widely used alloy, harmless substitutes, improvement of paper glazing, behavior of blood bags upon storage, quality assessment of metal particle preparations for surface enhanced RAMAN spectroscopy, and determination of diffusion coefficient and light fastness in textile fiber dyeing. The latter applications include fluorescence SNOM. Local fluorescence SNOM is also used in the study of partly aggregating dye nanoparticles within resin/varnish preparations. Unexpected new insights are obtained in all of the various fields that cannot be obtained by other techniques.

  20. Aqueous and Surface Chemistries of Photocatalytic Fe-Doped CeO2 Nanoparticles

    Directory of Open Access Journals (Sweden)

    Duangdao Channei

    2017-01-01

    Full Text Available The present work describes the effects of water on Fe-doped nanoparticulate CeO2, produced by flame spray pyrolysis, which is a critical environmental issue because CeO2 is not stable in typical atmospheric conditions. It is hygroscopic and absorbs ~29 wt % water in the bulk when exposed to water vapor but, more importantly, it forms a hydrated and passivating surface layer when immersed in liquid water. In the latter case, CeO2 initially undergoes direct and/or reductive dissolution, followed by the establishment of a passivating layer calculated to consist of ~69 mol % solid CeO2·2H2O and ~30 mol % gelled Ce(OH4. Under static flow conditions, a saturated boundary layer also forms but, under turbulent flow conditions, this is removed. While the passivating hydrated surface layer, which is coherent probably owing to the continuous Ce(OH4 gel, would be expected to eliminate the photoactivity, this does not occur. This apparent anomaly is explained by the calculation of (a the thermodynamic stability diagrams for Ce and Fe; (b the speciation diagrams for the Ce4+-H2O, Ce3+-H2O, Fe3+-H2O, and Fe2+-H2O systems; and (c the Pourbaix diagrams for the Ce-H2O and Fe-H2O systems. Furthermore, consideration of the probable effects of the localized chemical and redox equilibria owing to the establishment of a very low pH (<0 at the liquid-solid interface also is important to the interpretation of the phenomena. These factors highlight the critical importance of the establishment of the passivating surface layer and its role in photocatalysis. A model for the mechanism of photocatalysis by the CeO2 component of the hydrated phase CeO2·2H2O is proposed, explaining the observation of the retention of photocatalysis following the apparent alteration of the surface of CeO2 upon hydration. The model involves the generation of charge carriers at the outer surface of the hydrated surface layer, followed by the formation of radicals, which decompose organic

  1. Improving surface and defect center chemistry of fluorescent nanodiamonds for imaging purposes--a review.

    Science.gov (United States)

    Nagl, Andreas; Hemelaar, Simon Robert; Schirhagl, Romana

    2015-10-01

    Diamonds are widely used for jewelry owing to their superior optical properties accounting for their fascinating beauty. Beyond the sparkle, diamond is highly investigated in materials science for its remarkable properties. Recently, fluorescent defects in diamond, particularly the negatively charged nitrogen-vacancy (NV(-)) center, have gained much attention: The NV(-) center emits stable, nonbleaching fluorescence, and thus could be utilized in biolabeling, as a light source, or as a Förster resonance energy transfer donor. Even more remarkable are its spin properties: with the fluorescence intensity of the NV(-) center reacting to the presence of small magnetic fields, it can be utilized as a sensor for magnetic fields as small as the field of a single electron spin. However, a reproducible defect and surface and defect chemistry are crucial to all applications. In this article we review methods for using nanodiamonds for different imaging purposes. The article covers (1) dispersion of particles, (2) surface cleaning, (3) particle size selection and reduction, (4) defect properties, and (5) functionalization and attachment to nanostructures, e.g., scanning probe microscopy tips.

  2. Elucidating and exploiting the chemistry of Keggin heteropolyacids in the methanol-to-DME conversion: enabling the bulk reaction thanks to operando Raman

    OpenAIRE

    Schnee, Josefine; Gaigneaux, Eric M.

    2017-01-01

    Operando Raman spectroscopy is used here to enlighten crucial and yet unconsidered aspects of the catalytic behavior of Keggin heteropolyacids (HPAs) in the gas phase dehydration of methanol to dimethylether (DME). On one hand, HPAs are since a long time claimed as being able to absorb methanol into their bulk, but on the other hand this feature is not yet really exploited when it comes to develop/use HPA-based catalysts for the methanol-to-DME process. Actually, the conditions in which the b...

  3. Ground-Water, Surface-Water, and Water-Chemistry Data, Black Mesa Area, Northeastern Arizona - 1998

    National Research Council Canada - National Science Library

    Truini, Margot; Baum, B. M; Littin, G. R; Shingoitewa-Honanie, Gayl

    2000-01-01

    ...) flowmeter tests, and (5) ground-water and surface-water chemistry. In 1998 ,ground-water withdrawals for industrial and municipal use totaled about 7,060 acre-feet, which is less than a 1 percent decrease from 1997...

  4. Surface-Enhanced Resonance Raman Scattering and Visible Extinction Spectroscopy of Copper Chlorophyllin: An Upper Level Chemistry Experiment

    Science.gov (United States)

    Schnitzer, Cheryl S.; Reim, Candace Lawson; Sirois, John J.; House, Paul G.

    2010-01-01

    Advanced chemistry students are introduced to surface-enhanced resonance Raman scattering (SERRS) by studying how sodium copper chlorophyllin (CuChl) adsorbs onto silver colloids (CuChl/Ag) as a function of pH. Using both SERRS and visible extinction spectroscopy, the extent of CuChl adsorption and colloidal aggregation are monitored. Initially at…

  5. Surface and bulk effects of K in Cu 1-x K x In 1-y Ga y Se 2 solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Muzzillo, Christopher P.; Anderson, Timothy J.

    2017-12-01

    Two strategies for enhancing photovoltaic (PV) performance in chalcopyrite solar cells were investigated: Cu1-xKxIn1-yGaySe2 absorbers with low K content (K/(K+Cu), or x ~ 0.07) distributed throughout the bulk, and CuIn1-yGaySe2 absorbers with KIn1-yGaySe2 grown on their surfaces. Distributing K throughout the bulk absorbers improved power conversion efficiency, open-circuit voltage (VOC) and fill factor (FF) for Ga/(Ga+In) of 0, 0.3 and 0.5. Surface KIn1-yGaySe2 and bulk x ~ 0.07 Cu1-xKxIn1-yGaySe2 films with Ga/(Ga+In), or y of 0.3 and 0.5 also had improved efficiency, VOC, and FF, relative to CuIn1-yGaySe2 baselines. On the other hand, y ~ 1 absorbers did not benefit from K introduction. Similar to Cu1-xKxInSe2, the formation of Cu1-xKxGaSe2 alloys was favored at low temperatures and high Na supply by the substrate, relative to the formation of mixed-phase CuGaSe2 + KGaSe2. KIn1-yGaySe2 alloys were grown for the first time, as evidenced by X-ray diffraction and ultraviolet/visible spectroscopy. For all Ga/(Ga+In) compositions, the surface KIn1-yGaySe2 absorbers had superior PV performance in buffered and buffer-free devices. However, the bulk x ~ 0.07 absorbers only outperformed the baselines in buffered devices. The data demonstrate that KIn1-yGaySe2 passivates the surface of CuIn1-yGaySe2 to increase efficiency, VOC, and FF, while bulk Cu1-xKxIn1-yGaySe2 absorbers with x ~ 0.07 enhance efficiency, VOC, and FF by some other mechanism.

  6. Preparation and application of a novel electrochemical sensing material based on surface chemistry of polyhydroquinone

    Energy Technology Data Exchange (ETDEWEB)

    Dang, Xueping [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Ministry of Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules and College of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062 (China); State Key Laboratory of Transducer Technology, Chinese Academy of Sciences, Beijing 10080 (China); Wang, Yingkai [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); Hu, Chengguo, E-mail: cghu@whu.edu.cn [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); State Key Laboratory of Transducer Technology, Chinese Academy of Sciences, Beijing 10080 (China); Huang, Jianlin; Chen, Huaixia; Wang, Shengfu [Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Ministry of Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules and College of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062 (China); Hu, Shengshui, E-mail: sshu@whu.edu.cn [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); State Key Laboratory of Transducer Technology, Chinese Academy of Sciences, Beijing 10080 (China)

    2014-07-01

    A new analogue of polydopamine (PDA), i.e., polyhydroquinone (PH{sub 2}Q), was polymerized and its surface chemistry was studied by different ways of characterization. PH{sub 2}Q was produced by the self-polymerization of H{sub 2}Q mediated by dissolved oxygen, and the self-polymerization process was strongly dependent on the type and the pH value of the buffer solutions. PH{sub 2}Q can not only achieve surface hydrophilization of different substrates like polyethylene terephthalate (PET) film, graphite strip, C{sub 12}SH/Au and wax slice, but also possess several unique properties like reversible adsorption, good solubility and low cost. These properties made PH{sub 2}Q an ideal polymeric modifier for the noncovalent functionalization of some nanomaterials. By simply grinding with PH{sub 2}Q, pristine multi-walled carbon nanotubes (MWNTs) can be readily dispersed in water with high solubility and good stability. The resulting MWNT–PH{sub 2}Q composite exhibited excellent electrochemical performance, which was employed for the simultaneous determination of dopamine (DA) and uric acid (UA). - Highlights: • Polyhydroquinone (PH{sub 2}Q) was produced by the self-polymerization of hydroquinone (H{sub 2}Q) mediated by dissolved oxygen. • PH{sub 2}Q can achieve surface hydrophilization of a variety of substrates. • PH{sub 2}Q is an ideal polymeric modifier for the functionalization of multi-walled carbon nanotubes (MWNTs). • The MWNT–PH{sub 2}Q composite can be employed for the simultaneous determination of dopamine (DA) and uric acid (UA)

  7. Estimating the Analytical and Surface Enhancement Factors in Surface-Enhanced Raman Scattering (SERS): A Novel Physical Chemistry and Nanotechnology Laboratory Experiment

    Science.gov (United States)

    Pavel, Ioana E.; Alnajjar, Khadijeh S.; Monahan, Jennifer L.; Stahler, Adam; Hunter, Nora E.; Weaver, Kent M.; Baker, Joshua D.; Meyerhoefer, Allie J.; Dolson, David A.

    2012-01-01

    A novel laboratory experiment was successfully implemented for undergraduate and graduate students in physical chemistry and nanotechnology. The main goal of the experiment was to rigorously determine the surface-enhanced Raman scattering (SERS)-based sensing capabilities of colloidal silver nanoparticles (AgNPs). These were quantified by…

  8. Surface Chemistry Manipulation of Gold Nanorods Displays High Cellular Uptake In Vitro While Preserving Optical Properties for Bio-Imaging and Photo-Thermal Applications

    Science.gov (United States)

    2016-03-28

    its analytical applications. TrAC Trends in Analytical Chemistry , 37(0), 32-47. doi: http://dx.doi.org/10.1016/j.trac.2012.03.015 Livak, K. J...SURFACE CHEMISTRY MANIPULATION OF GOLD NANORODS DISPLAYS HIGH CELLULAR UPTAKE IN VITRO WHILE PRESERVING OPTICAL...2. REPORT TYPE Final 3. DATES COVERED (From - To) 7/2012 –1/2016 4. TITLE AND SUBTITLE SURFACE CHEMISTRY MANIPULATION OF GOLD NANORODS DISPLAYS

  9. Novel approach for a PTX/VEGF dual drug delivery system in cardiovascular applications-an innovative bulk and surface drug immobilization.

    Science.gov (United States)

    Wulf, Katharina; Teske, Michael; Matschegewski, Claudia; Arbeiter, Daniela; Bajer, Dalibor; Eickner, Thomas; Schmitz, Klaus-Peter; Grabow, Niels

    2018-03-12

    The successive incorporation of several drugs into the polymeric bulk of implants mostly results in loss of considerable quantity of one drug, and/or the loss in quality of the coating and also in changes of drug release time points. A dual drug delivery system (DDDS) based on poly-L-lactide (PLLA) copolymers combining the effective inhibition of smooth muscle cell proliferation while simultaneously promoting re-endothelialization was successfully developed. To overcome possible antagonistic drug interactions and the limitation of the polymeric bulk material as release system for dual drugs, a novel concept which combines the bulk and surface drug immobilization for a DDDS was investigated. The advantage of this DDDS is that the bulk incorporation of fluorescein diacetate (FDAc) (model drug for paclitaxel (PTX)) via spray coating enhanced the subsequent cleavable surface coupling of vascular endothelial growth factor (VEGF) via the crosslinker bissulfosuccinimidyl suberate (BS 3 ). In the presence of the embedded FDAc, the VEGF loading and release are about twice times higher than in absence. Furthermore, the DDDS combines the diffusion drug delivery (FDAc or PTX) and the chemical controlled drug release, VEGF via hydrolysable ester bonds, without loss in quantity and quality of the drug release curves. Additionally, the performed in vitro biocompatibility study showed the bimodal influences of PTX and VEGF on human endothelial EA.hy926 cells. In conclusion, it was possible to show the feasibility to develop a novel DDDS which has a high potential for the medical application due to the possible easy and short modification of a polymer-based PTX delivery system.

  10. Surface and bulk spin-wave resonances in La{sub 0.7}Mn{sub 1.3}O{sub 3} films

    Energy Technology Data Exchange (ETDEWEB)

    Dyakonov, V. [Donetsk Physics and Technology Institute, National Academy of Sciences of Ukraine, Donetsk (Ukraine); Institute of Physics, Polish Academy of Sciences, Warsaw (Poland); Prohorov, A.; Shapovalov, V.; Krivoruchko, V.; Pashchenko, V.; Zubov, E.; Mihailov, V. [Donetsk Physics and Technology Institute, National Academy of Sciences of Ukraine, Donetsk (Ukraine); Aleshkevych, P.; Berkowski, M.; Piechota, S.; Szymczak, H. [Institute of Physics, Polish Academy of Sciences, Warsaw (Poland)

    2001-05-07

    In this work, we present the measurements of exchange-dominated nonpropagating surface and bulk spin-wave modes in the La-deficient epitaxial La{sub 0.7}Mn{sub 1.3}O{sub 3} films prepared by dc-magnetron sputtering. The angular and temperature dependences of the modes observed are discussed. The main result obtained is the observation of the spin-wave resonance (SWR) consisting of a series (17) of well resolved standing spin-wave modes in the perpendicular external magnetic field geometry. The surface spin-wave modes have been observed in manganites for the first time. As the magnetization is rotated out of perpendicular to the film surface, a 'critical angle', {phi}{sub cr}, is fixed, at which the surface and first spin-wave modes have been transformed into the uniform mode. It is shown that only the uniform mode exists in the region 0<{phi}<{phi}{sub cr}. The surface mode data are consistent with the surface-inhomogeneity model in which the surface-anisotropy field acts on the surface spin. Possible origins of the surface anisotropy are discussed. Based on the temperature and angular dependences of SWR spectra, the main microscopic parameters (the spin-wave stiffness, exchange constant and g-factor value) are established. (author)

  11. Polymer dynamics near the surface and in the bulk of poly(tetrafluoroethylene) probed by zero-field muon-spin-relaxation spectroscopy.

    Science.gov (United States)

    McKenzie, Iain; Salman, Zaher; Giblin, Sean R; Han, Yun Yu; Leach, Gary W; Morenzoni, Elvezio; Prokscha, Thomas; Suter, Andreas

    2014-02-01

    The results of many experiments on polymers such as polystyrene indicate that the polymer chains near a free surface exhibit enhanced dynamics when compared with the bulk. We have investigated whether this is the case for poly(tetrafluoroethylene) (PTFE) by using zero-field muon-spin-relaxation spectroscopy to characterize a local probe, the F-Mu(+)-F state, which forms when spin-polarized positive muons are implanted in PTFE. Low-energy muons (implantation energies from 2.0 to 23.0 keV) were used to study the F-Mu(+)-F state between ∼ 23 and 191 nm from the free surface of PTFE. Measurements were also made with surface muons (4.1 MeV) where the mean implantation depth is on the order of ∼ 0.6 mm. The relaxation rate of the F-Mu(+)-F state up to ∼ 150 K was found to be significantly higher for muons implanted at 2.0 keV than for higher implantation energies, which suggests that the polymer chains in a region on the order of a few tens of nanometers from the free surface are more mobile than those in the bulk.

  12. The coupling effect of gas-phase chemistry and surface reactions on oxygen permeation and fuel conversion in ITM reactors

    KAUST Repository

    Hong, Jongsup

    2015-08-01

    © 2015 Elsevier B.V. The effect of the coupling between heterogeneous catalytic reactions supported by an ion transport membrane (ITM) and gas-phase chemistry on fuel conversion and oxygen permeation in ITM reactors is examined. In ITM reactors, thermochemical reactions take place in the gas-phase and on the membrane surface, both of which interact with oxygen permeation. However, this coupling between gas-phase and surface chemistry has not been examined in detail. In this study, a parametric analysis using numerical simulations is conducted to investigate this coupling and its impact on fuel conversion and oxygen permeation rates. A thermochemical model that incorporates heterogeneous chemistry on the membrane surface and detailed chemical kinetics in the gas-phase is used. Results show that fuel conversion and oxygen permeation are strongly influenced by the simultaneous action of both chemistries. It is shown that the coupling somewhat suppresses the gas-phase kinetics and reduces fuel conversion, both attributed to extensive thermal energy transfer towards the membrane which conducts it to the air side and radiates to the reactor walls. The reaction pathway and products, in the form of syngas and C2 hydrocarbons, are also affected. In addition, the operating regimes of ITM reactors in which heterogeneous- or/and homogeneous-phase reactions predominantly contribute to fuel conversion and oxygen permeation are elucidated.

  13. Atom-resolved surface chemistry using scanning tunneling microscopy (STM) and spectroscopy (STS)

    International Nuclear Information System (INIS)

    Avouris, P.

    1989-01-01

    The author shows that by using STM and STS one can study chemistry with atomic resolution. The author uses two examples: the reaction of Si(111)-(7x7) with (a) NH 3 and (b) decaborane (DB). In case (a) the authors can directly observe the spatial distribution of the reaction. He determined which surface atoms have reacted and how the products of the reaction are distributed. He found that the different dangling-bond sites have significantly different reactivities and explain these differences in terms of the local electronic structure. In case (b) the 7x7 reconstruction is eliminated and at high temperatures, (√3 x √3) R30 degree reconstructions are observed. Depending on the amount of DB and the annealing temperature the √3 structures contain variable numbers of B and Si adatoms on T 4 -sites. Calculations show that the structure involving B adatoms, although kinetically favored, is not the lowest energy configuration. The lowest energy state involves B in a substitutional site under a Si adatom

  14. Water chemistry of surface waters affected by the Fourmile Canyon wildfire, Colorado, 2010-2011

    Science.gov (United States)

    McCleskey, R. Blaine; Writer, Jeffrey H.; Murphy, Sheila F.

    2012-01-01

    In September 2010, the Fourmile Canyon fire burned about 23 percent of the Fourmile Creek watershed in Boulder County, Colo. Water-quality sampling of Fourmile Creek began within a month after the wildfire to assess its effects on surface-water chemistry. Water samples were collected from five sites along Fourmile Creek (above, within, and below the burned area) monthly during base flow, twice weekly during snowmelt runoff, and at higher frequencies during storm events. Stream discharge was also monitored. Water-quality samples were collected less frequently from an additional 6 sites on Fourmile Creek, from 11 tributaries or other inputs, and from 3 sites along Boulder Creek. The pH, electrical conductivity, temperature, specific ultraviolet absorbance, total suspended solids, and concentrations (dissolved and total) of major cations (calcium, magnesium, sodium, and potassium), anions (chloride, sulfate, alkalinity, fluoride, and bromide), nutrients (nitrate, ammonium, and phosphorus), trace metals (aluminum, arsenic, boron, barium, beryllium, cadmium, cobalt, chromium, copper, iron, mercury, lithium, manganese, molybdenum, nickel, lead, rubidium, antimony, selenium, strontium, vanadium, and zinc), and dissolved organic carbon are here reported for 436 samples collected during 2010 and 2011.

  15. Structure vs chemistry: friction and wear of Pt-based metallic surfaces.

    Science.gov (United States)

    Caron, A; Louzguine-Luzguin, D V; Bennewitz, R

    2013-11-13

    In comparison of a Pt57.5Cu14.7Ni5.3P22.5 metallic glass with a Pt(111) single crystal we find that wearless friction is determined by chemistry through bond formation alloying, while wear is determined by structure through plasticity mechanisms. In the wearless regime, friction is affected by the chemical composition of the counter body and involves the formation of a liquid-like neck and interfacial alloying. The wear behavior of Pt-based metallic surfaces is determined by their structural properties and corresponding mechanisms for plastic deformation. In the case of Pt(111) wear occurs by dislocation-mediated homogeneous plastic deformation. In contrast the wear of Pt57.5Cu14.7Ni5.3P22.5 metallic glass occurs through localized plastic deformation in shear bands that merge together in a single shear zone above a critical load and corresponds to the shear softening of metallic glasses. These results open a new route in the control of friction and wear of metals and are relevant for the development of self-lubricated and wear-resistant mechanical devices.

  16. Investigating thiol-modification on hyaluronan via carbodiimide chemistry using response surface methodology.

    Science.gov (United States)

    Santhanam, Sruthi; Liang, Jue; Baid, Rinku; Ravi, Nathan

    2015-07-01

    Hyaluronan (HA) is a naturally occurring glycosaminoglycan widely researched for its use as a biomaterial in tissue engineering, drug delivery, angiogenesis, and ophthalmic surgeries. The mechanical properties of this biomaterial can be altered to a required extent by chemically modifying the pendant reactive groups. However, derivatizing these polymers to a predetermined extent has been the Achilles heel for this process. In this study, we have investigated the factors controlling the derivatization of the carboxyl moieties of HA with amine containing thiol, cystamine dihydrochloride (Cys), via carbodiimide crosslinking chemistry. We used fractional factorial design to screen and identify the significant factor(s) affecting the reaction, and response surface methodology (RSM) to develop a model equation for predicting the degree of thiolation of HA. Also, we analyzed the reaction mechanism for potential side reactions. We observed that N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC) (mole ratio with repeat unit of HA) is the significant factor controlling the degree of amidation. The quadratic equations developed from RSM predict the formulation for a desired degree of amidation of HA and percentage of potential side product. Hence, derivatizing HA to a predetermined extent with minimal side product can be achieved using the statistical design of experiments. © 2014 Wiley Periodicals, Inc.

  17. Human Fetal Osteoblast Response on Poly(Methyl Methacrylate)/Polystyrene Demixed Thin Film Blends: Surface Chemistry Vs Topography Effects.

    Science.gov (United States)

    D'Sa, Raechelle A; Raj, Jog; Dickinson, Peter J; McCabe, Fiona; Meenan, Brian J

    2016-06-22

    Recent advances in materials sciences have allowed for the development and fabrication of biomaterials that are capable of providing requisite cues to instigate cells to respond in a predictable fashion. We have developed a series of poly(methyl methacrylate)/polystyrene (PMMA/PS) polymer demixed thin films with nanotopographies ranging from nanoislands to nanopits to study the response of human fetal osteoblast cells (hFOBs). When PMMA was in excess in the blend composition, a nanoisland topography dominated, whereas a nanopit topography dominated when PS was in excess. PMMA was found to segregate to the top of the nanoisland morphology with PS preferring the substrate interface. To further ascertain the effects of surface chemistry vs topography, we plasma treated the polymer demixed films using an atmospheric pressure dielectric barrier discharge reactor to alter the surface chemistry. Our results have shown that hFOBs did not have an increased short-term cellular response on pristine polymer demixed surfaces. However, increasing the hydrophilicty/wettability of the surfaces by oxygen functionalization causes an increase in the cellular response. These results indicate that topography alone is not sufficient to induce a positive cellular response, but the underlying surface chemistry is also important in regulating cell function.

  18. Sensitivity Analysis of Grain Surface Chemistry to Binding Energies of Ice Species

    Science.gov (United States)

    Penteado, E. M.; Walsh, C.; Cuppen, H. M.

    2017-07-01

    Advanced telescopes, such as ALMA and the James Webb Space Telescope, are likely to show that the chemical universe may be even more complex than currently observed, requiring astrochemical modelers to improve their models to account for the impact of new data. However, essential input information for gas-grain models, such as binding energies of molecules to the surface, have been derived experimentally only for a handful of species, leaving hundreds of species with highly uncertain estimates. We present in this paper a systematic study of the effect of uncertainties in the binding energies on an astrochemical two-phase model of a dark molecular cloud, using the rate equations approach. A list of recommended binding energy values based on a literature search of published data is presented. Thousands of simulations of dark cloud models were run, and in each simulation a value for the binding energy of hundreds of species was randomly chosen from a normal distribution. Our results show that the binding energy of H2 is critical for the surface chemistry. For high binding energies, H2 freezes out on the grain forming an H2 ice. This is not physically realistic, and we suggest a change in the rate equations. The abundance ranges found are in reasonable agreement with astronomical ice observations. Pearson correlation coefficients revealed that the binding energy of HCO, HNO, CH2, and C correlate most strongly with the abundance of dominant ice species. Finally, the formation route of complex organic molecules was found to be sensitive to the branching ratios of H2CO hydrogenation.

  19. Temporal trends of bulk precipitation and stream water chemistry (1977-1997) in a small forested area, Krusne hory, northern Bohemia, Czech Republic

    Science.gov (United States)

    Peters, N.E.; Cerny, J.; Havel, M.; Krejci, R.

    1999-01-01

    The Krusne hory (Erzgebirge or Ore Mountains) has been heavily affected by high atmospheric pollutant deposition caused by fossil fuel combustion in an adjacent Tertiary coal basin. Long-term routine sampling of bulk precipitation (1977-1996) and stream water (1977-1998) in a forested area on the south-eastern slope of the mountains were used to evaluate trends and patterns in solute concentration and flux with respect to controlling processes. From 1977 to 1996, the annual volume-weighted Ca2+ and SO42- concentrations decreased in bulk precipitation. However, after 1989, when a pronounced and continuous decrease occurred in coal production, annual volume-weighted concentrations decreased for most solutes, except H+. The concentration decreases were marked, with 1996 levels at or below 50% of those in 1989. The lack of a trend in H+ is attributed to similar decreases in both acid anions and neutralizing base cations. Stream water concentrations of most solutes, i.e. H+, Ca2+, Mg2+, SO42- and NO3-, were highest at the onset of sampling in 1977, decreased markedly from 1977 to 1983 and decreased more gradually from 1983 to 1998. The spruce forest die-back and removal reduced dry deposition of these solutes by reducing the filtering action, which was provided by the forest canopy. A notable decrease in stream water Ca2+ concentrations occurred after 1995 and may be due to the depletion of Ca2+, which was provided by catchment liming in 1986, 1988 and 1989. Solute flux trends in bulk atmospheric deposition and stream water generally were not significant and the lack of trend is attributed to the large interannual variability in precipitation quantity and runoff, respectively. All solutes except Na+ varied seasonally. The average seasonal concentrations varied between the solutes, but for most solutes were highest in winter and spring and lowest in summer, correlating with the seasonal trend and runoff. For Ca2+, Mg2+ and SO42-, the concentration minimum occurs in

  20. Inhomogeneity of surface magnetic field over a NdFeB guideway and its influence on levitation force of the HTS bulk maglev system

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Longcai [Applied Superconductivity Laboratory, Southwest Jiaotong University, P.O. Box 152, Chengdu 610031 (China)]. E-mail: zhlcai2000@163.com; Wang Jiasu [Applied Superconductivity Laboratory, Southwest Jiaotong University, P.O. Box 152, Chengdu 610031 (China); He Qingyong [Applied Superconductivity Laboratory, Southwest Jiaotong University, P.O. Box 152, Chengdu 610031 (China); Zhang Jianghua [Applied Superconductivity Laboratory, Southwest Jiaotong University, P.O. Box 152, Chengdu 610031 (China); Wang Suyu [Applied Superconductivity Laboratory, Southwest Jiaotong University, P.O. Box 152, Chengdu 610031 (China)

    2007-08-01

    Superconducting maglev vehicle system was one of the most promising applications of HTS bulks. The NdFeB guideway in this system was composed of many NdFeB permanent magnets and screws, so the air gaps (airgaps) between two permanent magnets and the screws would result in the inhomogeneity of the surface magnetic field. In this paper, we studied the magnetic inhomogeneity over the permanent magnet guideway (PMG) used in high-temperature superconducting (HTS) maglev vehicle system and its influence on the levitation force of the HTS bulk. Firstly, we measured the transverse magnetic field above the airgap, the screw and the place under where there was no airgap and screw. It was found that the magnetic field 10 mm above the guideway was roughly uniform. Secondly, we investigated the influence of the magnetic inhomogeneity of the PMG on levitation force of the bulk superconductor. From the experiment results, we found that the influence was very small, and would be ignored. Therefore, we could conclude that the PMG made by this method satisfied the requirements of the HTS maglev vehicle system in a quasi-static state.

  1. Superionic Conductivity of Sm3+, Pr3+, and Nd3+ Triple-Doped Ceria through Bulk and Surface Two-Step Doping Approach.

    Science.gov (United States)

    Liu, Yanyan; Fan, Liangdong; Cai, Yixiao; Zhang, Wei; Wang, Baoyuan; Zhu, Bin

    2017-07-19

    Sufficiently high oxygen ion conductivity of electrolyte is critical for good performance of low-temperature solid oxide fuel cells (LT-SOFCs). Notably, material conductivity, reliability, and manufacturing cost are the major barriers hindering LT-SOFC commercialization. Generally, surface properties control the physical and chemical functionalities of materials. Hereby, we report a Sm 3+ , Pr 3+ , and Nd 3+ triple-doped ceria, exhibiting the highest ionic conductivity among reported doped-ceria oxides, 0.125 S cm -1 at 600 °C. It was designed using a two-step wet-chemical coprecipitation method to realize a desired doping for Sm 3+ at the bulk and Pr 3+ /Nd 3+ at surface domains (abbreviated as PNSDC). The redox couple Pr 3+ /Pr 4+ contributes to the extraordinary ionic conductivity. Moreover, the mechanism for ionic conductivity enhancement is demonstrated. The above findings reveal that a joint bulk and surface doping methodology for ceria is a feasible approach to develop new oxide-ion conductors with high impacts on advanced LT-SOFCs.

  2. Influence of surface chemistry of carbon materials on their interactions with inorganic nitrogen contaminants in soil and water.

    Science.gov (United States)

    Sumaraj; Padhye, Lokesh P

    2017-10-01

    Inorganic nitrogen contaminants (INC) (NH 4 + , NO 3 - , NO 2 - , NH 3 , NO, NO 2 , and N 2 O) pose a growing risk to the environment, and their remediation methods are highly sought after. Application of carbon materials (CM), such as biochar and activated carbon, to remediate INC from agricultural fields and wastewater treatment plants has gained a significant interest since past few years. Understanding the role of surface chemistry of CM in adsorption of various INC is highly critical to increase adsorption efficiency as well as to assess the long term impact of using these highly recalcitrant CM for remediation of INC. Critical reviews of adsorption studies related to INC have revealed that carbon surface chemistry (surface functional groups, pH, Eh, elemental composition, and mineral content) has significant influence on adsorption of INC. Compared to basic functional groups, oxygen containing surface functional groups have been found to be more influential for adsorption of INC. However, basic sites on carbon materials still play an important role in chemisorption of anionic INC. Apart from surface functional groups, pH, Eh and pH zpc of CM and elemental and mineral composition of its surface are important properties capable of altering INC interactions with CM. This review summarizes our current understanding of INC interactions with CM's surface through the known chemisorption mechanisms: electrostatic interaction, hydrogen bonding, electron donor-acceptor mechanism, hydrophobic and hydrophilic interaction, chemisorption aided by minerals, and interactions influenced by pH and elemental composition. Change in surface chemistry of CM in soil during aging is also discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Transport of oxidized multi-walled carbon nanotubes through silica based porous media: influences of aquatic chemistry, surface chemistry, and natural organic matter.

    Science.gov (United States)

    Yang, Jin; Bitter, Julie L; Smith, Billy A; Fairbrother, D Howard; Ball, William P

    2013-12-17

    This paper provides results from studies of the transport of oxidized multi-walled carbon nanotubes (O-MWCNTs) of varying surface oxygen concentrations under a range of aquatic conditions and through uniform silica glass bead media. In the presence of Na(+), the required ionic strength (IS) for maximum particle attachment efficiency (i.e., the critical deposition concentration, or CDC) increased as the surface oxygen concentration of the O-MWCNTs or pH increased, following qualitative tenets of theories based on electrostatic interactions. In the presence of Ca(2+), CDC values were lower than those with Na(+) present, but were no longer sensitive to surface oxygen content, suggesting that Ca(2+) impacts the interactions between O-MWCNTs and glass beads by mechanisms other than electrostatic alone. The presence of Suwannee River natural organic matter (SRNOM) decreased the attachment efficiency of O-MWCNTs in the presence of either Na(+) or Ca(2+), but with more pronounced effects when Na(+) was present. Nevertheless, low concentrations of SRNOM (organic carbon) were sufficient to mobilize all O-MWCNTs studied at CaCl2 concentrations as high as 10 mM. Overall, this study reveals that NOM content, pH, and cation type show more importance than surface chemistry in affecting O-MWCNTs deposition during transport through silica-based porous media.

  4. Investigation of the extent of surface coating via mechanofusion with varying additive levels and the influences on bulk powder flow properties.

    Science.gov (United States)

    Zhou, Qi Tony; Qu, Li; Gengenbach, Thomas; Denman, John A; Larson, Ian; Stewart, Peter J; Morton, David A V

    2011-07-15

    The objective of this study was to investigate if the coating extent created by a mechanofusion process corresponded with observed changes in bulk powder properties. A fine lactose powder (approximate median diameter 20 μm) was dry coated with magnesium stearate using from 0.1 to 5% (w/w) content. An ultra-thin coating layer of magnesium stearate was anticipated, but previous attempts to determine such thin layers on these fine particles have had limited success, with poor resolution. In this study, the surface coating was examined using the state-of-the-art XPS and ToF-SIMS systems. The powder flow was characterized by Carr index and shear cell testing. XPS was successfully applied to demonstrate variations in surface coverage, as a function of additive levels, and indicated near complete coating coverage at additive levels of 1% (w/w) and above. ToF-SIMS results supported such coating coverage assessment, and indicated coating uniformly across the fine particle surfaces. The flow metrics employed could then be related to the coating coverage metrics. The mechanofusion process also modified the apparent surface roughness observed by SEM and BET. It was suggested that the changes in the surface chemical composition exerted a more evident and direct impact on the powder cohesion and flow characteristics than the changes in the surface morphological properties after the mechanofusion in this study. Copyright © 2011 Elsevier B.V. All rights reserved.

  5. Communication: Surface-to-bulk diffusion of isolated versus interacting C atoms in Ni(111) and Cu(111) substrates: A first principle investigation.

    Science.gov (United States)

    Harpale, Abhilash; Panesi, Marco; Chew, Huck Beng

    2015-02-14

    Using first principle calculations, we study the surface-to-bulk diffusion of C atoms in Ni(111) and Cu(111) substrates, and compare the barrier energies associated with the diffusion of an isolated C atom versus multiple interacting C atoms. We find that the preferential Ni-C bonding over C-C bonding induces a repulsive interaction between C atoms located at diagonal octahedral voids in Ni substrates. This C-C interaction accelerates C atom diffusion in Ni with a reduced barrier energy of ∼1 eV, compared to ∼1.4-1.6 eV for the diffusion of isolated C atoms. The diffusion barrier energy of isolated C atoms in Cu is lower than in Ni. However, bulk diffusion of interacting C atoms in Cu is not possible due to the preferential C-C bonding over C-Cu bonding, which results in C-C dimer pair formation near the surface. The dramatically different C-C interaction effects within the different substrates explain the contrasting growth mechanisms of graphene on Ni(111) and Cu(111) during chemical vapor deposition.

  6. Magnetical and optical properties of nanodiamonds can be tuned by particles surface chemistry: theoretical and experimental study

    Czech Academy of Sciences Publication Activity Database

    Kratochvílová, Irena; Šebera, Jakub; Ashcheulov, Petr; Golan, Martin; Ledvina, Miroslav; Mičová, Júlia; Mravec, F.; Kovalenko, A.; Zverev, D.; Yavkin, B.; Orlinskii, S.; Záliš, Stanislav; Fišerová, Anna; Richter, Jan; Šefc, L.; Turánek, J.

    2014-01-01

    Roč. 118, č. 43 (2014), s. 25245-25252 ISSN 1932-7447 R&D Projects: GA TA ČR TA01011165; GA ČR(CZ) GA14-10279S Institutional support: RVO:68378271 ; RVO:61388971 ; RVO:61388963 ; RVO:61388955 Keywords : nanodiamond particles * NV luminescent centers * surface functionalization * DFT Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.772, year: 2014

  7. Chemistry of Frozen NaCl and MgSO4 Brines - Implications for Surface Expression of Europa's Ocean Composition

    Science.gov (United States)

    Johnson, P. V.; Hodyss, R. P.; Choukroun, M.; Vu, T. H.

    2015-12-01

    The composition of Europa's subsurface ocean is a critical determinant of its habitability, but current analysis of the ocean composition is limited to its expression on the Europan surface. While there is observational evidence indicating that ocean materials make their way to the surface, our understanding of the chemical processes that can alter this material under Europan surface conditions is limited. We present experimental data on the chemistry of mixed solutions of NaCl and MgSO4 as they are frozen to 100 K, replicating the conditions that may occur when subsurface ocean fluids are emplaced onto Europa's surface. Confocal micro-Raman spectroscopy is used to study the formation of salts during the freezing process, and the interaction of ions in the frozen brines. Our data indicate that mixed aqueous solutions of NaCl and MgSO4 form Na2SO4 and MgCl2 preferentially when frozen, rather than making NaCl and MgSO4 precipitates. The detection of epsomite (MgSO4Ÿ•7H2O) on Europa's surface may therefore imply an ocean composition relatively low in sodium, unless radiolytic chemistry converts MgCl2 to MgSO4 as suggested by Hand and Brown 2013 (ApJ 145 110). These results have important implications for the interpretation of remote sensing data of Europa's surface.

  8. Effects of steam activation on the pore structure and surface chemistry of activated carbon derived from bamboo waste

    Science.gov (United States)

    Zhang, Yan-Juan; Xing, Zhen-Jiao; Duan, Zheng-Kang; Li, Meng; Wang, Yin

    2014-10-01

    The effects of steam activation on the pore structure evolution and surface chemistry of activated carbon (AC) obtained from bamboo waste were investigated. Nitrogen adsorption-desorption isotherms revealed that higher steam activation temperatures and/or times promoted the creation of new micropores and widened the existing micropores, consequently decreasing the surface area and total pore volume. Optimum conditions included an activation temperature of 850 °C, activation time of 120 min, and steam flush generated from deionized water of 0.2 cm3 min-1. Under these conditions, AC with a BET surface area of 1210 m2 g-1 and total pore volume of 0.542 cm-3 g-1was obtained. Changes in surface chemistry were determined through Boehm titration, pH measurement, Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). Results revealed the presence of a large number of basic groups on the surface of the pyrolyzed char and AC. Steam activation did not affect the species of oxygen-containing groups but changed the contents of these species when compared with pyrolyzed char. Scanning electron microscopy was used to observe the surface morphology of the products. AC obtained under optimum conditions showed a monolayer adsorption capacity of 330 mg g-1 for methylene blue (MB), which demonstrates its excellent potential for MB adsorption applications.

  9. Surface and bulk investigation of ZSM5 and Al-MCM-41 usingsynchrotron XPS, XANES, and hexane cracking

    Energy Technology Data Exchange (ETDEWEB)

    Jalil, P.A.; Kariapper, M.S.; Faiz, Z.; Tabet, N.; Hamdan, N.M.; Diaz, J.; Hussain, Z.

    2005-05-12

    We present a comparative study of ZSM5 and Al-MCM-41 catalysts using spectroscopic and chemical techniques. The analysis of conventional and synchrotron XPS spectra of these catalysts reveals the presence of a topmost surface-related Si peak in addition to the bulkpeak. XANES results suggest structural modification upon heating Al-MCM-41 at 500 C. Depth-resolved XPS data show Al depletion from the surface of Al-MCM-41 in contrast to surface enrichment of Al in ZSM5. These surface modifications could be one of the reasons for the weak acidity of Al-MCM-41 in chemical reactions such as hexane cracking at different temperatures.

  10. Energy-level matching of Fe(III) ions grafted at surface and doped in bulk for efficient visible-light photocatalysts.

    Science.gov (United States)

    Liu, Min; Qiu, Xiaoqing; Miyauchi, Masahiro; Hashimoto, Kazuhito

    2013-07-10

    Photocatalytic reaction rate (R) is determined by the multiplication of light absorption capability (α) and quantum efficiency (QE); however, these two parameters generally have trade-off relations. Thus, increasing α without decreasing QE remains a challenging issue for developing efficient photocatalysts with high R. Herein, using Fe(III) ions grafted Fe(III) doped TiO2 as a model system, we present a novel method for developing visible-light photocatalysts with efficient R, utilizing the concept of energy level matching between surface-grafted Fe(III) ions as co-catalysts and bulk-doped Fe(III) ions as visible-light absorbers. Photogenerated electrons in the doped Fe(III) states under visible-light efficiently transfer to the surface grafted Fe(III) ions co-catalysts, as the doped Fe(III) ions in bulk produced energy levels below the conduction band of TiO2, which match well with the potential of Fe(3+)/Fe(2+) redox couple in the surface grafted Fe(III) ions. Electrons in the surface grafted Fe(III) ions efficiently cause multielectron reduction of adsorbed oxygen molecules to achieve high QE value. Consequently, the present Fe(III)-FexTi1-xO2 nanocomposites exhibited the highest visible-light R among the previously reported photocatalysts for decomposition of gaseous organic compounds. The high R can proceed even under commercial white-light emission diode irradiation and is very stable for long-term use, making it practically useful. Further, this efficient method could be applied in other wide-band gap semiconductors, including ZnO or SrTiO3, and may be potentially applicable for other photocatalysis systems, such as water splitting, CO2 reduction, NOx removal, and dye decomposition. Thus, this method represents a strategic approach to develop new visible-light active photocatalysts for practical uses.

  11. [INVITED] Recent advances in surface plasmon resonance based fiber optic chemical and biosensors utilizing bulk and nanostructures

    Science.gov (United States)

    Gupta, Banshi D.; Kant, Ravi

    2018-05-01

    Surface plasmon resonance has established itself as an immensely acclaimed and influential optical sensing tool with quintessential applications in life sciences, environmental monitoring, clinical diagnostics, pharmaceutical developments and ensuring food safety. The implementation of sensing principle of surface plasmon resonance employing an optical fiber as a substrate has concomitantly resulted in the evolution of fiber optic surface plasmon resonance as an exceptionally lucrative scaffold for chemical and biosensing applications. This perspective article outlines the contemporary studies on fiber optic sensors founded on the sensing architecture of propagating as well as localized surface plasmon resonance. An in-depth review of the prevalent analytical and surface chemical tactics involved in configuring the sensing layer over an optical fiber for the detection of various chemical and biological entities is presented. The involvement of nanomaterials as a strategic approach to enhance the sensor sensitivity is furnished concurrently providing an insight into the diverse geometrical blueprints for designing fiber optic sensing probes. Representative examples from the literature are discussed to appreciate the latest advancements in this potentially valuable research avenue. The article concludes by identifying some of the key challenges and exploring the opportunities for expanding the scope and impact of surface plasmon resonance based fiber optic sensors.

  12. High-Performance Supercapacitor of Functionalized Carbon Fiber Paper with High Surface Ionic and Bulk Electronic Conductivity: Effect of Organic Functional Groups

    International Nuclear Information System (INIS)

    Suktha, Phansiri; Chiochan, Poramane; Iamprasertkun, Pawin; Wutthiprom, Juthaporn; Phattharasupakun, Nutthaphon; Suksomboon, Montakan; Kaewsongpol, Tanon; Sirisinudomkit, Pichamon; Pettong, Tanut; Sawangphruk, Montree

    2015-01-01

    Highlights: • A supercapacitor of organic functionalized carbon fiber paper (f-CFP) exhibits high areal and volumetric capacitances. • The performance of the supercapacitor depends on the organic functional group on the surface of the f-CFP. • Hydroxyl and carboxylic groups modified on the surface of f-CFP have higher pseudocapacitive property than amide and amine functional groups. • The f-CFP exhibits high surface ionic and bulk electrical conductivities. - Abstract: Although carbon fiber paper (CFP) or nonwovens are widely used as a non-corrosive and conductive substrate or current collector in batteries and supercapacitors as well as a gas diffusion layer in proton exchange membrane fuel cells, the CFP cannot store charges due to its poor ionic conductivity and its hydrophobic surface. In this work, the chemically functionalized CFP (f-CFP) consisting of hydroxyl and carboxylic groups on its surface was produced by an oxidation reaction of CFP in a mixed concentrated acid solution of H 2 SO 4 :HNO 3 (3:1 v/v) at 60 °C for 1 h. Other amide and amine groups modified CFP were also synthesized for comparison using a dehydration reaction of carboxylic modified CFP with ethylenediamine and n-butylamine. Interestingly, it was found that hydroxyl and carboxylic groups modified CFP behave as a pseudocapacitor electrode, which can store charges via the surface redox reaction in addition to electrochemical double layer capacitance. The aqueous-based supercapacitor of f-CFP has high areal, volumetric, and specific energy (49.0 μW.h/cm 2 , 1960 mW.h/L, and 5.2 W.h/Kg) and power (3.0 mW/cm 2 , 120 W/L, and 326.2 W/Kg) based on the total geometrical surface area and volume as well as the total weight of positive and negative electrodes. High charge capacity of the f-CFP stems from high ionic charge and pseudocapacitive behavior due to hydroxyl and carboxylic groups on its surface and high bulk electronic conductivity (2.03 mS/cm) due to 1D carbon fiber paper. The

  13. Competition of bulk trapping and surface erosion in the kinetics of tritium inventory and permeation in plasma protection metals

    International Nuclear Information System (INIS)

    Federici, G.; Holland, D.F.; Esser, B.

    1996-01-01

    A simplified transient model is presented to describe the migration of implanted tritium in the presence of trap sites across the bulk of metallic substrates whose thickness is decreasing with time due to erosion. The subject is relevant for quantifying the tritium inventory in - and permeation through -plasma facing armours in the next generation of D-T fuelled tokamak devices (i.e., the International Thermonuclear Experimental Reactor). This paper describes the equations of the physical model and the main assumptions used to simplify the complex analysis, and surveys the influence of several parameters such as the implantation flux, the erosion rate, the armour temperature, the armour thickness, the density and trapping energy of neutron-induced traps, etc., which are all expected to play a key role in the phenomena investigated. The examples presented to show the applicability of the model include the results of a study performed for beryllium armours exposed to heat and particle loads similar to those expected on the ITER divertor plasma facing components and comparison is made with cases where erosion does not play any role. (orig.)

  14. Band selection and disentanglement using maximally localized Wannier functions: the cases of Co impurities in bulk copper and the Cu(111) surface

    Energy Technology Data Exchange (ETDEWEB)

    Korytar, Richard; Pruneda, Miguel; Ordejon, Pablo; Lorente, Nicolas [Centre d' Investigacio en Nanociencia i Nanotecnologia (CSIC-ICN), Campus de la UAB, E-08193 Bellaterra (Spain); Junquera, Javier, E-mail: rkorytar@cin2.e [Departamento de Ciencias de la Tierra y Fisica de la Materia Condensada, Universidad de Cantabria, E-39005 Santander (Spain)

    2010-09-29

    We have adapted the maximally localized Wannier function approach of Souza et al (2002 Phys. Rev. B 65 035109) to the density functional theory based SIESTA code (Soler et al 2002 J. Phys.: Condens. Mater. 14 2745) and applied it to the study of Co substitutional impurities in bulk copper as well as to the Cu(111) surface. In the Co impurity case, we have reduced the problem to the Co d-electrons and the Cu sp-band, permitting us to obtain an Anderson-like Hamiltonian from well defined density functional parameters in a fully orthonormal basis set. In order to test the quality of the Wannier approach to surfaces, we have studied the electronic structure of the Cu(111) surface by again transforming the density functional problem into the Wannier representation. An excellent description of the Shockley surface state is attained, permitting us to be confident in the application of this method to future studies of magnetic adsorbates in the presence of an extended surface state.

  15. Increasing the Detection Limit of the Parkinson Disorder through a Specific Surface Chemistry Applied onto Inner Surface of the Titration Well

    Directory of Open Access Journals (Sweden)

    Fabienne Poncin-Epaillard

    2012-04-01

    Full Text Available The main objective of this paper was to illustrate the enhancement of the sensitivity of ELISA titration for neurodegenerative proteins by reducing nonspecific adsorptions that could lead to false positives. This goal was obtained thanks to the association of plasma and wet chemistries applied to the inner surface of the titration well. The polypropylene surface was plasma-activated and then, dip-coated with different amphiphilic molecules. These molecules have more or less long hydrocarbon chains and may be charged. The modified surfaces were characterized in terms of hydrophilic—phobic character, surface chemical groups and topography. Finally, the coated wells were tested during the ELISA titration of the specific antibody capture of the α-synuclein protein. The highest sensitivity is obtained with polar (Θ = 35°, negatively charged and smooth inner surface.

  16. Water adsorption on TiO2 surfaces probed by soft X-ray spectroscopies: bulk materials vs. isolated nanoparticles

    Science.gov (United States)

    Benkoula, Safia; Sublemontier, Olivier; Patanen, Minna; Nicolas, Christophe; Sirotti, Fausto; Naitabdi, Ahmed; Gaie-Levrel, François; Antonsson, Egill; Aureau, Damien; Ouf, François-Xavier; Wada, Shin-Ichi; Etcheberry, Arnaud; Ueda, Kiyoshi; Miron, Catalin

    2015-01-01

    We describe an experimental method to probe the adsorption of water at the surface of isolated, substrate-free TiO2 nanoparticles (NPs) based on soft X-ray spectroscopy in the gas phase using synchrotron radiation. To understand the interfacial properties between water and TiO2 surface, a water shell was adsorbed at the surface of TiO2 NPs. We used two different ways to control the hydration level of the NPs: in the first scheme, initially solvated NPs were dried and in the second one, dry NPs generated thanks to a commercial aerosol generator were exposed to water vapor. XPS was used to identify the signature of the water layer shell on the surface of the free TiO2 NPs and made it possible to follow the evolution of their hydration state. The results obtained allow the establishment of a qualitative determination of isolated NPs’ surface states, as well as to unravel water adsorption mechanisms. This method appears to be a unique approach to investigate the interface between an isolated nano-object and a solvent over-layer, paving the way towards new investigation methods in heterogeneous catalysis on nanomaterials. PMID:26462615

  17. High-Resolution Faraday Rotation and Electron-Phonon Coupling in Surface States of the Bulk-Insulating Topological Insulator Cu_{0.02}Bi_{2}Se_{3}.

    Science.gov (United States)

    Wu, Liang; Tse, Wang-Kong; Brahlek, M; Morris, C M; Aguilar, R Valdés; Koirala, N; Oh, S; Armitage, N P

    2015-11-20

    We have utilized time-domain magnetoterahertz spectroscopy to investigate the low-frequency optical response of the topological insulator Cu_{0.02}Bi_{2}Se_{3} and Bi_{2}Se_{3} films. With both field and frequency dependence, such experiments give sufficient information to measure the mobility and carrier density of multiple conduction channels simultaneously. We observe sharp cyclotron resonances (CRs) in both materials. The small amount of Cu incorporated into the Cu_{0.02}Bi_{2}Se_{3} induces a true bulk insulator with only a single type of conduction with a total sheet carrier density of ~4.9×10^{12}/cm^{2} and mobility as high as 4000 cm^{2}/V·s. This is consistent with conduction from two virtually identical topological surface states (TSSs) on the top and bottom of the film with a chemical potential ~145 meV above the Dirac point and in the bulk gap. The CR broadens at high fields, an effect that we attribute to an electron-phonon interaction. This assignment is supported by an extended Drude model analysis of the zero-field Drude conductance. In contrast, in normal Bi_{2}Se_{3} films, two conduction channels were observed, and we developed a self-consistent analysis method to distinguish the dominant TSSs and coexisting trivial bulk or two-dimensional electron gas states. Our high-resolution Faraday rotation spectroscopy on Cu_{0.02}Bi_{2}Se_{3} paves the way for the observation of quantized Faraday rotation under experimentally achievable conditions to push the chemical potential in the lowest Landau level.

  18. Tuning optoelectronic properties of small semiconductor nanocrystals through surface ligand chemistry

    Science.gov (United States)

    Lawrence, Katie N.

    Semiconductor nanocrystals (SNCs) are a class of material with one dimension reported. Furthermore, the outstanding increase in PL-QY was found to be a product of both passivation and delocalization effects. Next we used poly(ethylene) glycol (PEG)-thiolate ligands to passivate the SNC and provide unique solubility properties in both aqueous and organic solvents as well as utilized their highly conductive nature to explore inter-SNC electronic coupling. The electronic coupling was studied: 1) as a function of SNC size where the smallest SNC exhibited the largest coupling energy (170 meV) and 2) as a function of annealing temperature, where an exceptionally large (˜400 meV) coupling energy was observed. This strong electronic coupling in self-organized films could facilitate the large-scale production of highly efficient electronic materials for advanced optoelectronic device applications. Strong inter-SNC electronic coupling together with high solubility, such as that provided by PEG-thiolate-coated CdSe SNCs, can increase the stability of SNCs during solution-phase electrochemical characterization. Therefore, we utilized these properties to characterize solution-state electrochemical properties and photocatalytic activity of ternary copper indium diselenide (CuInSe2) SNCs as a function of their size and surface ligand chemistry. Electrochemical characterization of our PEG-thiolate-coated SNCs showed that the thermodynamic driving force (-?G) for oxygen reduction, which increased with decreasing bandgap, was a major contributor to the overall photocatalytic reaction. Additionally, phenol degradation efficiency was monitored in which the smallest diameter SNC and shortest chain length of PEG provided the highest efficiency. The information provided herein could be used to produce superior SNC photocatalysts for a variety of applications including oxidation of organic contaminants, conversion of water to hydrogen gas, and decomposition of crude oil or pesticides

  19. Evaluation of surface energy state distribution and bulk defect concentration in DSSC photoanodes based on Sn, Fe, and Cu doped TiO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Ako, Rajour Tanyi [Faculty of Science, Universiti Brunei Darussalam, Jalan Tungku Link, BE1410, Negara (Brunei Darussalam); Ekanayake, Piyaisiri, E-mail: piyasiri.ekanayake@ubd.edu.bn [Faculty of Science, Universiti Brunei Darussalam, Jalan Tungku Link, BE1410, Negara (Brunei Darussalam); Young, David James [Faculty of Science, Universiti Brunei Darussalam, Jalan Tungku Link, BE1410, Negara (Brunei Darussalam); Institute of Materials Research and Engineering (IMRE), Agency for Science, Technology and Research -A*STAR, 3 Research Link, 117602 (Singapore); Faculty of Science, Health, Education and Engineering, University of the Sunshine Coast, Locked Bag 4, Maroochydore DC, Queensland, 4558 (Australia); Hobley, Jonathan [Faculty of Science, Universiti Brunei Darussalam, Jalan Tungku Link, BE1410, Negara (Brunei Darussalam); Chellappan, Vijila [Institute of Materials Research and Engineering (IMRE), Agency for Science, Technology and Research - A*STAR, 3 Research Link, 117602 (Singapore); Tan, Ai Ling [Faculty of Science, Universiti Brunei Darussalam, Jalan Tungku Link, BE1410, Negara (Brunei Darussalam); Gorelik, Sergey; Subramanian, Gomathy Sandhya [Institute of Materials Research and Engineering (IMRE), Agency for Science, Technology and Research - A*STAR, 3 Research Link, 117602 (Singapore); Lim, Chee Ming [Faculty of Science, Universiti Brunei Darussalam, Jalan Tungku Link, BE1410, Negara (Brunei Darussalam)

    2015-10-01

    Graphical abstract: - Highlights: • The structural, optical and optoelectronic properties of 1 mol.% Fe, Sn and Cu doped TiO{sub 2} have been compared. • Transient lifetimes for pure TiO{sub 2} and Sn doped TiO{sub 2} were considerably shorter than Fe and Cu doped TiO{sub 2}. • A good correlation between the bulk defects and transient decay for the doped TiO{sub 2} powders was observed. • Photon to current conversion efficiency of DSSC based on the metal doped TiO{sub 2} were in order Sn-TiO{sub 2} > Cu-TiO{sub 2} > Pure >> Fe-TiO{sub 2}. • DSSC based on Fe doped photoanodes is limited by a high concentration of surface free holes observed at 433 nm. - Abstract: Electron transfer dynamics in the oxide layers of the working electrodes in both dye-sensitized solar cells and photocatalysts greatly influences their performance. A proper understanding of the distribution of surface and bulk energy states on/in these oxide layers can provide insights into the associated electron transfer processes. Metal ions like Iron (Fe), Copper (Cu) and Tin (Sn) doped onto TiO{sub 2} have shown enhanced photoactivity in these processes. In this work, the structural, optical and transient properties of Fe, Cu and Sn doped TiO{sub 2} nanocrystalline powders have been investigated and compared using EDX, Raman spectroscopy, X-ray Photoelectron spectroscopy (XPS), and Transient Absorption spectroscopy (TAS). Surface free energy states distributions were probed using Electrochemical Impedance spectroscopy (EIS) on Dye Sensitized Solar Cells (DSSC) based on the doped TiO{sub 2} photoanodes. Raman and XPS Ti2p{sub 3/2} peak shifts and broadening showed that the concentration of defects were in the order: Cu doped TiO{sub 2} > Fe doped TiO{sub 2} > Sn doped TiO{sub 2} > pure TiO{sub 2}. Nanosecond laser flash photolysis of Fe and Cu doped TiO{sub 2} indicated slower transient decay kinetics than that of Sn doped TiO{sub 2} or pure TiO{sub 2}. A broad absorption peak and fast

  20. Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions.

    Science.gov (United States)

    Marenich, Aleksandr V; Cramer, Christopher J; Truhlar, Donald G

    2009-05-07

    We present a new continuum solvation model based on the quantum mechanical charge density of a solute molecule interacting with a continuum description of the solvent. The model is called SMD, where the "D" stands for "density" to denote that the full solute electron density is used without defining partial atomic charges. "Continuum" denotes that the solvent is not represented explicitly but rather as a dielectric medium with surface tension at the solute-solvent boundary. SMD is a universal solvation model, where "universal" denotes its applicability to any charged or uncharged solute in any solvent or liquid medium for which a few key descriptors are known (in particular, dielectric constant, refractive index, bulk surface tension, and acidity and basicity parameters). The model separates the observable solvation free energy into two main components. The first component is the bulk electrostatic contribution arising from a self-consistent reaction field treatment that involves the solution of the nonhomogeneous Poisson equation for electrostatics in terms of the integral-equation-formalism polarizable continuum model (IEF-PCM). The cavities for the bulk electrostatic calculation are defined by superpositions of nuclear-centered spheres. The second component is called the cavity-dispersion-solvent-structure term and is the contribution arising from short-range interactions between the solute and solvent molecules in the first solvation shell. This contribution is a sum of terms that are proportional (with geometry-dependent proportionality constants called atomic surface tensions) to the solvent-accessible surface areas of the individual atoms of the solute. The SMD model has been parametrized with a training set of 2821 solvation data including 112 aqueous ionic solvation free energies, 220 solvation free energies for 166 ions in acetonitrile, methanol, and dimethyl sulfoxide, 2346 solvation free energies for 318 neutral solutes in 91 solvents (90 nonaqueous

  1. Inland dissolved salt chemistry: statistical evaluation of bivariate and ternary diagram models for surface and subsurface waters

    Directory of Open Access Journals (Sweden)

    Stephen T. THRELKELD

    2000-08-01

    Full Text Available We compared the use of ternary and bivariate diagrams to distinguish the effects of atmospheric precipitation, rock weathering, and evaporation on inland surface and subsurface water chemistry. The three processes could not be statistically differentiated using bivariate models even if large water bodies were evaluated separate from small water bodies. Atmospheric precipitation effects were identified using ternary diagrams in water with total dissolved salts (TDS 1000 mg l-1. A principal components analysis showed that the variability in the relative proportions of the major ions was related to atmospheric precipitation, weathering, and evaporation. About half of the variation in the distribution of inorganic ions was related to rock weathering. By considering most of the important inorganic ions, ternary diagrams are able to distinguish the contributions of atmospheric precipitation, rock weathering, and evaporation to inland water chemistry.

  2. Deuteration and evolution in the massive star formation process. The role of surface chemistry

    Science.gov (United States)

    Fontani, F.; Busquet, G.; Palau, Aina; Caselli, P.; Sánchez-Monge, Á.; Tan, J. C.; Audard, M.

    2015-03-01

    Context. An ever growing number of observational and theoretical evidence suggests that the deuterated fraction (column density ratio between a species containing D and its hydrogenated counterpart, Dfrac) is an evolutionary indicator both in the low- and the high-mass star formation process. However, the role of surface chemistry in these studies has not been quantified from an observational point of view. Aims: Because many abundant species, such as NH3, H2CO, and CH3OH, are actively produced on ice mantles of dust grains during the early cold phases, their Dfrac is expected to evolve differently from species formed only (or predominantly) in the gas, such as N2H+, HNC, HCN, and their deuterated isotopologues. The differences are expected to be relevant especially after the protostellar birth, in which the temperature rises, causing the evaporation of ice mantles. Methods: To compare how the deuterated fractions of species formed only in the gas and partially or uniquely on grain surfaces evolve with time, we observed rotational transitions of CH3OH, 13CH3OH, CH2DOH, and CH3OD at 3 mm and 1.3 mm, of NH2D at 3 mm with the IRAM-30 m telescope, and the inversion transitions (1, 1) and (2, 2) of NH3 with the GBT, towards most of the cores already observed in N2H+, N2D+, HNC, and DNC. Results: NH2D is detected in all but two cores, regardless of the evolutionary stage. Dfrac(NH3) is on average above 0.1 and does not change significantly from the earliest to the most evolved phases, although the highest average value is found in the protostellar phase (~0.3). Few lines of CH2DOH and CH3OD are clearly detected, and then only towards protostellar cores or externally heated starless cores. In quiescent starless cores, we have only one doubtful detection of CH2DOH. Conclusions: This work clearly confirms an expected different evolutionary trend of the species formed exclusively in the gas (N2D+ and N2H+) and those formed partially (NH2D and NH3) or totally (CH2DOH and CH3

  3. Structure formation and surface chemistry of ionic liquids on model electrode surfaces—Model studies for the electrode | electrolyte interface in Li-ion batteries

    Science.gov (United States)

    Buchner, Florian; Uhl, Benedikt; Forster-Tonigold, Katrin; Bansmann, Joachim; Groß, Axel; Behm, R. Jürgen

    2018-05-01

    decomposition products was found to sensitively change the equilibrium between surface Li and Li+ intercalated in the bulk, leading to a deintercalation from lithiated HOPG in the presence of an adsorbed IL adlayer at >230 K. Overall, these results provide detailed insights into the surface chemistry at the solid | electrolyte interface and the initial stages of SEI formation at electrode surfaces in the absence of an applied potential, which is essential for the further improvement of future Li-ion batteries.

  4. The effect of inter-granular constraints on the response of polycrystalline piezoelectric ceramics at the surface and in the bulk

    DEFF Research Database (Denmark)

    Hossain, Mohammad J.; Wang, Zhiyang; Khansur, Neamul H.

    2016-01-01

    The electro-mechanical coupling mechanisms in polycrystalline ferroelectric materials, including a soft PbZrxTi1−xO3 (PZT) and lead-free 0.9375(Bi1/2Na1/2)TiO3-0.0625BaTiO3 (BNT-6.25BT), have been studied using a surface sensitive low-energy (12.4 keV) and bulk sensitive high-energy (73 ke...... methods demonstrates that the intergranular constraints have a significant influence on the electric-field-induced electro-mechanical responses in polycrystalline ferroelectrics. These results have implications for the design of higher performance polycrystalline piezoelectrics....

  5. Color and Surface Chemistry Changes of Pine Wood Flour after Extraction and Delignification

    Science.gov (United States)

    Yao Chen; Mandla A. Tshabalala; Jianmin Gao; Nicole M. Stark; Yongming Fan

    2014-01-01

    A detailed study was undertaken to examine the color and chemistry changes of pine wood flour when its extractives are removed and when it is delignified. The solvent systems employed were toluene/ethanol (TE), acetone/water (AW), and hot-water (HW), while sodium chlorite/acetic acid were used for delignification (i.e., lignin removal (LR)). Samples were analyzed by...

  6. Nanoparticle-cell interactions: surface chemistry effects on the cellular uptake of biocompatible block copolymer assemblies

    Czech Academy of Sciences Publication Activity Database

    de Castro, C. E.; Ribeiro, C. A. S.; Alavarse, A. C.; Albuquerque, L. J. C.; da Silva, M. C. C.; Jäger, Eliezer; Surman, František; Schmidt, V.; Giacomelli, C.; Giacomelli, F. C.

    2018-01-01

    Roč. 34, č. 5 (2018), s. 2180-2188 ISSN 0743-7463 R&D Projects: GA ČR(CZ) GA17-09998S Institutional support: RVO:61389013 Keywords : biocompatibility * block copolymers * controlled drug delivery Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science Impact factor: 3.833, year: 2016

  7. Surface organization of aqueous MgCl2 and application to atmospheric marine aerosol chemistry

    Czech Academy of Sciences Publication Activity Database

    Casillas-Ituarte, N. N.; Callahan, K. M.; Tang, CH. Y.; Chen, X.; Roeselová, Martina; Tobias, D. J.; Allen, H. C.

    2010-01-01

    Roč. 107, č. 15 (2010), s. 6616-6621 ISSN 0027-8424 R&D Projects: GA MŠk LC512; GA MŠk ME09064 Institutional research plan: CEZ:AV0Z40550506 Keywords : magnesium chloride * fatty acid * air/aqueous interface Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 9.771, year: 2010

  8. Facile Synthesis of Nitrogen Doped Graphene Oxide from Graphite Flakes and Powders: A Comparison of Their Surface Chemistry.

    Science.gov (United States)

    Yokwana, Kholiswa; Ray, Sekhar C; Khenfouch, Mohammad; Kuvarega, Alex T; Mamba, Bhekie B; Mhlanga, Sabelo D; Nxumalo, Edward N

    2018-08-01

    Nitrogen-doped graphene oxide (NGO) nanosheets were prepared via a facile one-pot modified Hummer's approach at low temperatures using graphite powder and flakes as starting materials in the presence of a nitrogen precursor. It was found that the morphology, structure, composition and surface chemistry of the NGO nanosheets depended on the nature of the graphite precursor used. GO nanosheets doped with nitrogen atoms exhibited a unique structure with few thin layers and wrinkled sheets, high porosity and structural defects. NGO sheets made from graphite powder (NGOp) exhibited excellent thermal stability and remarkably high surface area (up to 240.53 m2 ·g-1) compared to NGO sheets made from graphite flakes (NGOf) which degraded at low temperatures and had an average surface area of 24.70 m2 ·g-1. NGOf sheets had a size range of 850 to 2200 nm while NGOp sheets demonstrated obviously small sizes (460-1600 nm) even when exposed to different pH conditions. The NGO nanosheets exhibited negatively charged surfaces in a wide pH range (1 to 12) and were found to be stable above pH 6. In addition, graphite flakes were found to be more suitable for the production of NGO as they produced high N-doping levels (0.65 to 1.29 at.%) compared to graphite powders (0.30 to 0.35 at.%). This study further demonstrates that by adjusting the amount of N source in the host GO, one can tailor its thermal stability, surface morphology, surface chemistry and surface area.

  9. Dynamics of cyanophenyl alkylbenzoate molecules in the bulk and in a surface layer adsorbed onto aerosil. Variation of the lengths of the alkyl chain

    Energy Technology Data Exchange (ETDEWEB)

    Frunza, Stefan [National Institute of Materials Physics, R-077125 Magurele (Romania); Schoenhals, Andreas [BAM Federal Institute of Materials Research and Testing, D-12205 Berlin (Germany); Frunza, Ligia, E-mail: lfrunza@infim.ro [National Institute of Materials Physics, R-077125 Magurele (Romania); Beica, Traian; Zgura, Irina; Ganea, Paul [National Institute of Materials Physics, R-077125 Magurele (Romania); Stoenescu, Daniel [Telecom-Bretagne, Departement d' Optique, Technopole Brest-Iroise 29238 Cedex (France)

    2010-06-16

    Graphical abstract: The temperature dependence of the molecular mobility in composites shows an Arrhenius-type regime at low temperature and a glassy-type one at higher temperature separated by a crossover phenomenon. - Abstract: The molecular mobility of 4-butyl- and 4-pentyl-4'-cyanophenyl benzoate (CP4B, CP5B) and their composites prepared from aerosil A380 was investigated by broadband dielectric spectroscopy in a large temperature range. Thermogravimetric and infrared investigations were additionally performed. High silica density (larger than 7 g aerosil/1 g of liquid crystal) was selected to observe a thin layer adsorbed on the surface of the silica particles. The data were compared with those of the member of the series with six carbon atoms in the alkyl tail. Bulk CP4B and CP5B show the dielectric behaviour expected for liquid crystals. For the composites one relaxation process is observed at frequencies much lower than those for the corresponding bulk, which was assigned to the dynamics of the molecules in a surface layer. The temperature dependence of the relaxation rates (and of the dielectric strength) shows a crossover behaviour with two distinguished regimes. At higher temperatures the data obey the Vogel-Fulcher-Tammann law, whereas an Arrhenius law is observed at lower temperature, in a close similarity to the behaviour of a constrained dynamic glass transition. The estimated Vogel and crossover temperature is independent on the tail length, while the activation energy for the low temperature branch increases weakly with increasing the alkyl tail.

  10. Simple Preparation of Thiol-Ene Particles in Glycerol and Surface Functionalization by Thiol-Ene Chemistry (TEC) and Surface Chain Transfer Free Radical Polymerization (SCT-FRP).

    Science.gov (United States)

    Hoffmann, Christian; Chiaula, Valeria; Yu, Liyun; Pinelo, Manuel; Woodley, John M; Daugaard, Anders E

    2018-01-01

    Thiol-ene (TE)-based polymer particles are traditionally prepared via emulsion polymerization in water (using surfactants, stabilizers, and cosolvents). Here, a green and simple alternative is presented with excellent control over particle size, while avoiding the addition of stabilizers. Glycerol is applied as a dispersing medium for the preparation of off-stoichiometric TE microparticles, where sizes in the range of 40-400 µm are obtained solely by changing the mixing speed of the emulsions prior to crosslinking. Control over surface chemistry is achieved by surface functionalization of excess thiol groups via photochemical thiol-ene chemistry resulting in a functional monolayer. In addition, surface chain transfer free radical polymerization is used for the first time to introduce a thicker polymer layer on the particle surface. The application potential of the system is demonstrated by using functional particles as adsorbent for metal ions and as a support for immobilized enzymes. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Biogeochemistry of bulk organic matter and biogenic elements in surface sediments of the Yangtze River Estuary and adjacent sea

    International Nuclear Information System (INIS)

    Yang, Bin; Cao, Lu; Liu, Su-Mei; Zhang, Guo-Sen

    2015-01-01

    Highlights: • Biogenic elements cycling in the YRE and adjacent sea surface sediments was discussed. • Factors influencing the biogenic elements distributions were examined. • Potential bioavailability of N and P was determined. • Burial fluxes of TOC, BSi, TN and TP were estimated. • Potential nutrient limitation factors were assessed. - Abstract: This study investigated the distribution and roles of total organic carbon (TOC), biogenic silicon (BSi), various forms of nitrogen (N) and phosphorus (P), and the stable carbon isotope (δ 13 C) in surface sediments of the Yangtze River Estuary (YRE) and adjacent sea. Terrestrial input accounted for 12–63% of total organic matter in the study area. The distribution of biogenic elements was affected by the Changjiang Diluted Water, the Jiangsu Coastal Current, human activities, marine biological processes, and the sediment grain size. Potentially bioavailable N and P accounted for an average 79.6% of the total N (TN) and 31.8% of the total P (TP), respectively. The burial fluxes for TOC, BSi, TN and TP were 39.74–2194.32, 17.34–517.48, 5.02–188.85 and 3.10–62.72 μmol cm −2 yr −1 , respectively. The molar ratios of total N/P (1.2–5.0), Si/P (5.0–14.8) and Fe/P (21–61) indicated that much of the P was sequestered in sediments

  12. Self-consistent Green’s-function technique for bulk and surface impurity calculations: Surface core-level shifts by complete screening

    DEFF Research Database (Denmark)

    Aldén, M.; Abrikosov, I. A.; Johansson, B.

    1994-01-01

    of the frozen-core and atomic-sphere approximation but, in addition, includes the dipole contribution to the intersphere potential. Within the concept of complete screening, we identify the surface core-level binding-energy shift with the surface segregation energy of a core-ionized atom and use the Green......'s-function impurity technique in a comprehensive study of the surface core-level shifts (SCLS) of the 4d and 5d transition metals. In those cases, where observed data refer to single crystals, we obtain good agreement with experiment, whereas the calculations typically underestimate the measured shift obtained from...... a polycrystalline surface. Comparison is made with independent theoretical data for the surface core-level eigenvalue shift, and the much debated role of the so-called initial-and final-state contributions to the SCLS is discussed....

  13. Chemistry in Microfluidic Channels

    Science.gov (United States)

    Chia, Matthew C.; Sweeney, Christina M.; Odom, Teri W.

    2011-01-01

    General chemistry introduces principles such as acid-base chemistry, mixing, and precipitation that are usually demonstrated in bulk solutions. In this laboratory experiment, we describe how chemical reactions can be performed in a microfluidic channel to show advanced concepts such as laminar fluid flow and controlled precipitation. Three sets of…

  14. Electronic structure in the bulk and at the surface of lanthanide materials. A detailed study with X-ray emission and inverse photoemission

    CERN Document Server

    Huebinger, F

    2000-01-01

    LaTe. With measurements of the O3-XE in the Lanthanum-Chalcogenides we could demonstrate the transfer of s-like valence electrons from the Lanthanum atom to the Chalcogen atom. Furthermore, the binding energy of the state at the Lanthanum atom was determined. The surface core-level shift is smaller by 25 % in the Chalcogenides than in La-metal. We also describe a theoretical model, which qualitatively explains the observed larger shifts of the core-level binding energy in PE than in IPE from Lanthan-Chalcogenides. This dissertation is concerned with the occupied and unoccupied electronic structure of lanthanide materials. With surface sensitive electron-excited x-ray emission spectroscopy (XES) we could experimentally determine a surface and bulk partial density of states (p-DOS) for the metals Lanthanum, Lutetium and Samarium. From calculations of the O3-XE transition probability we anticipate a three times higher probability for s-like than for d-like electrons to fill the 5p3/2-hole; this was confirmed exp...

  15. Surface and bulk 3D analysis of natural and processed ruby using electron probe micro analyzer and X-ray micro CT scan

    International Nuclear Information System (INIS)

    Sahoo, Rakesh K.; Singh, Saroj K.; Mishra, B.K.

    2016-01-01

    Highlights: • Firm linking between two advance techniques: Micro-CT and EPMA for mineral analysis. • Attempt to identify and differentiate the treated gem stone from natural counterpart. • 3D structural and surface elemental analysis of the natural gem stone. - Abstract: The change in surface compositional and bulk structural characteristics of the natural ruby stone, before and after heat treatment with lead oxide has been analyzed using two advance characterization techniques like: X-ray micro CT scan (μ-CT) and electron probe micro analyzer (EPMA). The analytical correlation between these two techniques in identification as well as in depth study of the ores and minerals before and after processing has been presented. Also, we describe the aesthetic enhancement of a low quality defective ruby stone by lead oxide filling and the sequential analysis of this ruby stone before and after treatment using these two advanced techniques to identify and to confirm the change in its aesthetic value. The cracks healing and pores filling by the metal oxide on the surface of the ruby have been analyzed using μ-CT and EPMA. Moreover, in this work we describe the advance characterization of the repaired gem stones especially ruby stones. This work will light up the path for in-depth understanding of diffusion mechanism and abstract information of impurity particles inside the minerals. Based on these observations, EPMA and micro CT are shown to be powerful tools for the identification as well as research in gem stones.

  16. Influence of surface chemistry on the structural organization of monomolecular protein layers adsorbed to functionalized aqueous interfaces

    DEFF Research Database (Denmark)

    Lösche, M.; Piepenstock, M.; Diederich, A.

    1993-01-01

    The molecular organization of streptavidin (SA) bound to aqueous surface monolayers of biotin-functionalized lipids and binary lipid mixtures has been investigated with neutron reflectivity and electron and fluorescence microscopy. The substitution of deuterons (2H) for protons (1H), both...... in subphase water molecules and in the alkyl chains of the lipid surface monolayer, was utilized to determine the interface structure on the molecular length scale. In all cases studied, the protein forms monomolecular layers underneath the interface with thickness values of apprx 40 ANG . A systematic...... dependence of the structural properties of such self-assembled SA monolayers on the surface chemistry was observed: the lateral protein density depends on the length of the spacer connecting the biotin moiety and its hydrophobic anchor. The hydration of the lipid head groups in the protein-bound state...

  17. Surface modification of carbon nanotubes via combination of mussel inspired chemistry and chain transfer free radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Wan, Qing; Tian, Jianwen; Liu, Meiying; Zeng, Guangjian; Huang, Qiang [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang, 330031 (China); Wang, Ke; Zhang, Qingsong [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing, 100084 (China); Deng, Fengjie, E-mail: fengjiedeng@aliyun.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang, 330031 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang, 330031 (China); Wei, Yen, E-mail: weiyen@tsinghua.edu.cn [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing, 100084 (China)

    2015-08-15

    Graphical abstract: A novel strategy combination of mussel inspired chemistry and chain transfer free radical polymerization has been developed for surface modification of carbon nanotubes with polymers for the first time. - Highlights: • Surface modification of CNTs via mussel inspired chemistry. • Preparation of aminated polymers through free radical polymerization. • Functionalized CNTs with aminated polymers via Michael addition reaction. • Highly dispersed CNTs in organic and aqueous solution. - Abstract: In this work, a novel strategy for surface modification of carbon nanotubes (CNTs) was developed via combination of mussel inspired chemistry and chain transfer free radical polymerization. First, pristine CNTs were functionalized with polydopamine (PDA), which is formed via self-polymerization of dopamine in alkaline conditions. These PDA functionalized CNTs can be further reacted with amino-terminated polymers (named as PDMC), which was synthesized through chain transfer free radical polymerization using cysteamine hydrochloride as chain transfer agent and methacryloxyethyltrimethyl ammonium chloride as the monomer. PDMC perfectly conjugated with CNT-PDA was ascertained by a series of characterization techniques including transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), thermal gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The dispersibility of obtained CNT nanocomposites (named as CNT-PDA-PDMC) was further examined. Results showed that the dispersibility of CNT-PDA-PDMC in aqueous and organic solutions was obviously enhanced. Apart from PDMC, many other amino-terminated polymers can also be used to functionalization of CNTs via similar strategy. Therefore, the method described in this work should be a general strategy for fabrication various polymer nanocomposites.

  18. Electron tunneling in chemistry

    International Nuclear Information System (INIS)

    Zamaraev, K.I.; Khajrutdinov, R.F.; Zhdanov, V.P.; Molin, Yu.N.

    1985-01-01

    Results of experimental and theoretical investigations are outlined systematically on electron tunnelling in chemical reactions. Mechanism of electron transport to great distances is shown to be characteristic to chemical compounds of a wide range. The function of tunnel reactions is discussed for various fields of chemistry, including radiation chemistry, electrochemistry, chemistry of solids, chemistry of surface and catalysis

  19. Surface chemistry of carbon removal from indium tin oxide by base and plasma treatment, with implications on hydroxyl termination

    International Nuclear Information System (INIS)

    Chaney, John A.; Koh, Sharon E.; Dulcey, Charles S.; Pehrsson, Pehr E.

    2003-01-01

    The surface chemistry of carbon removal from indium tin oxide (ITO) has been investigated with Auger electron spectroscopy (AES), high-resolution electron energy loss spectroscopy (HREELS), and high-resolution energy loss spectroscopy (HR-ELS). A vibrating Kelvin probe (KP) was used to monitor the work function (PHI) of ITO after cleaning, either by base-cleaning with alcoholic-KOH or by O 2 plasma-cleaning. Base-cleaning lowered PHI ITO as seen in the KP analysis, whereas plasma-cleaning slightly increased PHI ITO by an oxidative process. The degree of PHI ITO depression by base-cleaning was seen to depend on the initial surface, but the PHI depression itself was nonreductive to the ITO, as seen in the In-MNN AES lineshape. The nonreductive depression of PHI ITO by base-cleaning was further supported by a constant charge carrier density, as estimated from the HR-ELS. Base-cleaning was slightly more effective than the oxygen plasma in removing carbon from the ITO surface. However, base-cleaning preferentially removed graphitic carbon while leaving significant hydrocarbon contaminants, as determined by vibrational analysis with HREELS. All other ITO surfaces retained a significant carbon and hydrocarbon contamination as evidenced by AES and HREELS. There was little evidence of the formation of surface hydroxyl species, as expected for such an inherently contaminated surface as ITO

  20. Modulation of Protein Fouling and Interfacial Properties at Carbon Surfaces via Immobilization of Glycans Using Aryldiazonium Chemistry

    Science.gov (United States)

    Zen, Federico; Angione, M. Daniela; Behan, James A.; Cullen, Ronan J.; Duff, Thomas; Vasconcelos, Joana M.; Scanlan, Eoin M.; Colavita, Paula E.

    2016-01-01

    Carbon materials and nanomaterials are of great interest for biological applications such as implantable devices and nanoparticle vectors, however, to realize their potential it is critical to control formation and composition of the protein corona in biological media. In this work, protein adsorption studies were carried out at carbon surfaces functionalized with aryldiazonium layers bearing mono- and di-saccharide glycosides. Surface IR reflectance absorption spectroscopy and quartz crystal microbalance were used to study adsorption of albumin, lysozyme and fibrinogen. Protein adsorption was found to decrease by 30–90% with respect to bare carbon surfaces; notably, enhanced rejection was observed in the case of the tested di-saccharide vs. simple mono-saccharides for near-physiological protein concentration values. ζ-potential measurements revealed that aryldiazonium chemistry results in the immobilization of phenylglycosides without a change in surface charge density, which is known to be important for protein adsorption. Multisolvent contact angle measurements were used to calculate surface free energy and acid-base polar components of bare and modified surfaces based on the van Oss-Chaudhury-Good model: results indicate that protein resistance in these phenylglycoside layers correlates positively with wetting behavior and Lewis basicity. PMID:27108562

  1. Direct observation of bulk and surface chemical morphologies of Ginkgo biloba leaves by Fourier transform mid- and near-infrared microspectroscopic imaging.

    Science.gov (United States)

    Chen, Jianbo; Sun, Suqin; Zhou, Qun

    2013-11-01

    Fourier transform infrared microspectroscopy is a powerful tool to obtain knowledge about the spatial and/or temporal distributions of the chemical compositions of plants for better understanding of their biological properties. However, the chemical morphologies of plant leaves in the plane of the blade are barely studied, because sections in this plane for mid-infrared transmission measurements are difficult to obtain. Besides, native compositions may be changed by chemical reagents used when plant samples are microtomed. To improve methods for direct infrared microspectroscopic imaging of plant leaves in the plane of the blade, the bulk and surface chemical morphologies of nonmicrotomed Ginkgo biloba leaves were characterized by near-infrared transmission and mid-infrared attenuated total reflection microspectroscopic imaging. A new self-modeling curve resolution procedure was proposed to extract the spectral and concentration information of pure compounds. Primary and secondary metabolites of secretory cavities, veins, and mesophylls of Ginkgo biloba leaf blades were analyzed, and the distributions of cuticle, protein, calcium oxalate, cellulose, and ginkgolic acids on the adaxial surface were determined. By the integration of multiple infrared microspectroscopic imaging and chemometrics methods, it is possible to analyze nonmicrotomed leaves and other plant samples directly to understand their native chemical morphologies in detail.

  2. X-ray free electron laser as a real-time probe of chemistry on surfaces

    International Nuclear Information System (INIS)

    Katayama, Tetsuo; Ogasawara, Hirohito

    2015-01-01

    X-ray free electron laser has opened up new possibilities for the study of surface chemical reactions on ultrafast time scale. This article reviews the recent work on the desorption of a molecule from a surface, which is one of the most fundamental surface chemical process. (author)

  3. Well-Defined Molybdenum Oxo Alkyl Complex Supported on Silica by Surface Organometallic Chemistry: A Highly Active Olefin Metathesis Precatalyst

    KAUST Repository

    Merle, Nicolas

    2016-12-05

    The well-defined silica-supported molybdenum oxo alkyl species (SiO−)MoO(CH Bu) was selectively prepared by grafting of MoO(CH Bu)Cl onto partially dehydroxylated silica (silica) using the surface organometallic chemistry approach. This surface species was fully characterized by elemental analysis and DRIFT, solid-state NMR, and EXAFS spectroscopy. This new material is related to the active species of industrial supported MoO/SiO olefin metathesis catalysts. It displays very high activity in propene self-metathesis at mild (turnover number = 90 000 after 25 h). Remarkably, its catalytic performance outpaces those of the parent imido derivative and its tungsten oxo analogue.

  4. Dielectric properties of nanosilica/low-density polyethylene composites: The surface chemistry of nanoparticles and deep traps induced by nanoparticles

    Directory of Open Access Journals (Sweden)

    S. Ju

    2014-09-01

    Full Text Available Four kinds of nanosilica particles with different surface modification were employed to fabricate low-density polyethylene (LDPE composites using melt mixing and hot molding methods. The surface chemistry of modified nanosilica was analyzed by X-ray photoelectron spectroscopy. All silica nanoparticles were found to suppress the space charge injection and accumulation, increase the volume resistivity, decrease the permittivity and dielectric loss factor at low frequencies, and decrease the dielectric breakdown strength of the LDPE polymers. The modified nanoparticles, in general, showed better dielectric properties than the unmodified ones. It was found that the carrier mobility, calculated from J–V curves using the Mott-Gurney equation, was much lower for the nanocomposites than for the neat LDPE.

  5. Well-Defined Molybdenum Oxo Alkyl Complex Supported on Silica by Surface Organometallic Chemistry: A Highly Active Olefin Metathesis Precatalyst.

    Science.gov (United States)

    Merle, Nicolas; Le Quéméner, Frédéric; Bouhoute, Yassine; Szeto, Kai C; De Mallmann, Aimery; Barman, Samir; Samantaray, Manoja K; Delevoye, Laurent; Gauvin, Régis M; Taoufik, Mostafa; Basset, Jean-Marie

    2017-02-15

    The well-defined silica-supported molybdenum oxo alkyl species (≡SiO-)MoO(CH 2 t Bu) 3 was selectively prepared by grafting of MoO(CH 2 t Bu) 3 Cl onto partially dehydroxylated silica (silica 700 ) using the surface organometallic chemistry approach. This surface species was fully characterized by elemental analysis and DRIFT, solid-state NMR, and EXAFS spectroscopy. This new material is related to the active species of industrial supported MoO 3 /SiO 2 olefin metathesis catalysts. It displays very high activity in propene self-metathesis at mild (turnover number = 90 000 after 25 h). Remarkably, its catalytic performance outpaces those of the parent imido derivative and its tungsten oxo analogue.

  6. Benchtop chemistry for the rapid prototyping of label-free biosensors: Transmission localized surface plasmon resonance platforms

    Science.gov (United States)

    Liao, Wei-Ssu; Chen, Xin; Yang, Tinglu; Castellana, Edward T.; Chen, Jixin; Cremer, Paul S.

    2012-01-01

    Herein, a simple label-free biosensor fabrication method is demonstrated based on transmission localized surface plasmon resonance (T-LSPR). The platform, which consists of a silver nanoparticle array, can be prepared in just a few minutes using benchtop chemistry. The array was made by a templating technique in conjunction with the photoreduction of Ag ions from solution. This metal surface was functionalized with biotin-linked thiol ligands for binding streptavidin molecules from solution. For an array of 19 nm diameter silver nanoparticles, a redshift in the T-LSPR spectrum of 24 nm was observed upon protein-ligand binding at saturation. The binding constant was found to be 2 × 1012 M–1. Platforms were also fabricated with silver nanoparticles of 34, 55, and 72 nm diameters. The maximum LSPR wavelength shift was nanoparticle size dependent and the maximum sensitivity was obtained with the smaller nanoparticles. PMID:20408728

  7. The Role of Controlled Surface Topography and Chemistry on Mouse Embryonic Stem Cell Attachment, Growth and Self-Renewal.

    Science.gov (United States)

    Macgregor, Melanie; Williams, Rachel; Downes, Joni; Bachhuka, Akash; Vasilev, Krasimir

    2017-09-14

    The success of stem cell therapies relies heavily on our ability to control their fate in vitro during expansion to ensure an appropriate supply. The biophysical properties of the cell culture environment have been recognised as a potent stimuli influencing cellular behaviour. In this work we used advanced plasma-based techniques to generate model culture substrates with controlled nanotopographical features of 16 nm, 38 nm and 68 nm in magnitude, and three differently tailored surface chemical functionalities. The effect of these two surface properties on the adhesion, spreading, and self-renewal of mouse embryonic stem cells (mESCs) were assessed. The results demonstrated that physical and chemical cues influenced the behaviour of these stem cells in in vitro culture in different ways. The size of the nanotopographical features impacted on the cell adhesion, spreading and proliferation, while the chemistry influenced the cell self-renewal and differentiation.

  8. Modeling chemistry in PWR fuel crud

    International Nuclear Information System (INIS)

    PWR fuel crud arises from deposition of corrosion products in the coolant on clad surfaces in the core. These deposits form a porous layer through which water must pass to provide effective heat transfer from the clad surface. The usual heat transfer mechanism is by wick boiling in which water passing through the porous crud is converted to steam that escapes through steam chimneys in the deposit. This conversion of water into steam within the deposit means that dilute solutions in the bulk coolant become concentrated in the crud and this can lead to precipitation of species such as lithium borates, ZnO and Zn-silicates. Such precipitation processes may lead to problems such as crud induced power shifts (CIPS), formally known as axial off-set anomaly (AOA), or crud induced localised corrosion (CILC) of the clad, that has led to cladding failures. These precipitation processes also hinder heat transfer and can lead to hot spots on the clad surfaces that are potentially damaging. Questions such as what should be the plant limits on Zn, Si, B and Li to prevent such problems, and how should these be controlled during the cycle, are not easy to answer. With several new designs of PWR proposing high power density cores and therefore greater subcooled nucleate boiling, and with existing plants still up-rating their cores, these questions are likely to become more important in the future. It is therefore important to understand the relationship between coolant chemistry (Zn, Si, Li, B levels) and the chemistry within fuel crud. The bulk and crud chemistry are coupled along with the bulk and local heat transfer processes. This coupling of chemistry and heat transfer makes this a particularly difficult problem to investigate theoretically although the authors have previously achieved this using a number of one dimensional heat and mass transfer models. This paper discusses a new approach to this problem using finite element methods to solve the relevant coupled chemistry and

  9. Application of response surface methodology to tailor the surface chemistry of electrospun chitosan-poly(ethylene oxide) fibers.

    Science.gov (United States)

    Bösiger, Peter; Richard, Isabelle M T; Le Gat, Luce; Michen, Benjamin; Schubert, Mark; Rossi, René M; Fortunato, Giuseppino

    2018-04-15

    Chitosan is a promising biocompatible polymer for regenerative engineering applications, but its processing remains challenging due to limited solubility and rigid crystalline structure. This work represents the development of electrospun chitosan/poly(ethylene oxide) blend nanofibrous membranes by means of a numerical analysis in order to identify and tailor the main influencing parameters with respect to accessible surface nitrogen functionalities which are of importance for the biological activity as well as for further functionalization. Depending on the solution composition, both gradient fibers and homogenous blended fiber structures could be obtained with surface nitrogen concentrations varying between 0 and 6.4%. Response surface methodology (RSM) revealed chitosan/poly(ethylene oxide) ratio and chitosan molecular weight as the main influencing factors with respect to accessible nitrogen surface atoms and respective concentrations. The model showed good adequacy hence providing a tool to tailor the surface properties of chitosan/poly(ethylene oxide) blends by addressing the amount of accessible chitosan. Copyright © 2018 Elsevier Ltd. All rights reserved.

  10. Surface Chemistry Dependence of Mechanochemical Reaction of Adsorbed Molecules-An Experimental Study on Tribopolymerization of α-Pinene on Metal, Metal Oxide, and Carbon Surfaces.

    Science.gov (United States)

    He, Xin; Kim, Seong H

    2018-02-20

    Mechanochemical reactions between adsorbate molecules sheared at tribological interfaces can induce association of adsorbed molecules, forming oligomeric and polymeric products often called tribopolymers). Thi