WorldWideScience

Sample records for surface kinetic roughening

  1. Kinetic roughening of the Kossel (1 0 0) surface

    NARCIS (Netherlands)

    van Veenendaal, E.; van Hoof, P.J.C.M.; van Suchtelen, J.; van Enckevort, W.J.P.; Bennema, P.

    1999-01-01

    Kinetic roughening is not a phase transition and, as such, it lacks a sharp definition. Therefore, the many criteria used to mark the onset of kinetic roughening, are expected to give different results. Criteria stemming from the classical two-dimensional nucleation theory are frequently used.

  2. Kinetic roughening of the Kossel (100) surface: comparison of classical criteria with Monte Carlo results

    NARCIS (Netherlands)

    van Veenendaal, E.; van Hoof, P.J.C.M.; van Suchtelen, J.; van Enckevort, W.J.P.; Bennema, P.

    1998-01-01

    Kinetic roughening is not a phase transition and, as such, it lacks an exact definition. Many criteria are used to mark the onset of kinetic roughening. Criteria stemming from the classical two-dimensional nucleation theory are widely used. On the other hand, experimentalists observe a transition

  3. On the roughening of solid surfaces

    Science.gov (United States)

    Rys, Franz S.

    1986-12-01

    Two roughening phenomena are discussed. The kink-driven line roughening of high-indexed surfaces (such as fcc(113), (115) and (117), discussed in various papers recently) is presumably undergoing an Ising-type transition in contrast to the step-driven surface roughening which shows either a Kosterlitz-Thouless-type infinite-order phase transition, or, depending on the step energy parameters, a smooth cross-over only.

  4. Critical and noncritical roughening of surfaces

    Science.gov (United States)

    Rys, Franz S.

    1986-02-01

    The equilibrium roughening of perfect, clean, crystalline surfaces is described in terms of thermally created atomic steps in the frame of a lattice model (loop gas). If the bending energies for convex and concave step corners are different, the ``particle-hole'' symmetry is destroyed and the sharp infinite-order roughening transition disappears. Instead, a rather smooth crossover from a smooth to a rough surface occurs. A simple model illustrates this result, which is expected to be important for the crystal-growth process and for surface-catalytic reactions.

  5. Generic Dynamic Scaling in Kinetic Roughening

    OpenAIRE

    Ramasco, JJ; Lopez, JM; Rodriguez, MA

    2000-01-01

    We study the dynamic scaling hypothesis in invariant surface growth. We show that the existence of power-law scaling of the correlation functions (scale invariance) does not determine a unique dynamic scaling form of the correlation functions, which leads to the different anomalous forms of scaling recently observed in growth models. We derive all the existing forms of anomalous dynamic scaling from a new generic scaling ansatz. The different scaling forms are subclasses of this generic scali...

  6. Oxidation-reduction induced roughening of platinum (111) surface

    International Nuclear Information System (INIS)

    You, H.; Nagy, Z.

    1993-06-01

    Platinum (111) single crystal surface was roughened by repeated cycles of oxidation and reduction to study dynamic evolution of surface roughening. The interface roughens progressively upon repeated cycles. The measured width of the interface was fit to an assumed pow law, W ∼t β , with β = 0.38(1). The results are compared with a simulation based on a random growth model. The fraction of the singly stepped surface apparently saturates to 0. 25 monolayer, which explains the apparent saturation to a steady roughness observed in previous studies

  7. Kinetic Roughening and Energetics of Tetragonal Lysozyme Crystal Growth: A Preliminary Atomic Force Microscopy Investigation

    Science.gov (United States)

    Gorti, Sridhar; Forsythe, Elizabeth L.; Pusey, Marc L.

    2004-01-01

    We examined particulars of crystal growth from measurements obtained at both microscopic and molecular levels. The crystal growth measurements performed at the microscopic level are well characterized by a model that balances the flux of macromolecules towards the crystal surface with the flux of the crystal surface. Numerical evaluation of model with measurements of crystal growth, in time, provided accurate estimates for the average growth velocities. Growth velocities thus obtained were also interpreted using well-established phenomenological theories. Moreover, we find that microscopic measurements of growth velocity measurements obtained as a function of temperature best characterizes changes in crystal growth modes, when present. We also examined the possibility of detecting a change in crystal growth modes at the molecular level using atomic force microscopy, AFM. From preliminary AFM measurements performed at various supersaturations, we find that magnitude of surface height fluctuations, h(x), increases with supersaturation. Further examination of surface height fluctuations using methods established for fluctuation spectroscopy also enabled the discovery of the existence of a characteristic length, c, which may possibly determine the mode of crystal growth. Although the results are preliminary, we establish the non- critical divergence of 5 and the root-mean-square (rms) magnitude of height-height fluctuations as the kinetic roughening transition temperatures are approached. Moreover, we also examine approximate models for interpreting the non-critical behavior of both 6 and rms magnitude of height-height fluctuations, as the solution supersaturation is increased towards the kinetic roughening supersaturation.

  8. Roughening instability and ion-induced viscous relaxation of SiO2 surfaces

    International Nuclear Information System (INIS)

    Mayer, T.M.; Chason, E.; Howard, A.J.

    1994-01-01

    We characterize the development of nanometer scale topography (roughness) on SiO 2 surfaces as a result of low energy, off-normal ion bombardment, using in situ energy dispersive x-ray reflectivity and atomic force microscopy. Surfaces roughen during sputtering by heavy ions (Xe), with roughness increasing approximately linearly with ion fluence up to 10 17 cm -2 . A highly coherent ripple structure with wavelength of 30 nm and oriented with the wave vector parallel to the direction of incidence is observed after Xe sputtering at 1 keV. Lower frequency, random texture is also observed. Subsequent light ion (H, He) bombardment smoothens preroughened surfaces. The smoothing kinetics are first order with ion fluence and strongly dependent on ion energy in the range 0.2--1 eV. We present a linear model to account for the experimental observations which includes roughening both by random stochastic processes and by development of a periodic surface instability due to sputter yield variations with surface curvature which leads to ripple development. Smoothing occurs via ion bombardment induced viscous flow and surface diffusion. From the smoothing kinetics with H and He irradiation we measure the radiation enhanced viscosity of SiO 2 and find values on the order of 1--20x10 12 N s m -2 . The viscous relaxation per ion scales as the square root of the ion induced displacements in the film over the range of the ion penetration, suggesting short-lived defects with a bimolecular annihilation mechanism. The surface instability mechanism accounts for the ripple formation, while inclusion of stochastic roughening produces the random texture and reproduces the observed linear roughening kinetics and the magnitude of the overall roughness

  9. Kinetic roughening and pinning of coupled precursor and impregnation fronts in porous media

    International Nuclear Information System (INIS)

    Balankin, Alexander S.; Garcia Paredes, Rafael; Marquez Gonsalez, Jesus; Susarrey Huerta, Orlando; Morales Matamoros, Daniel; Castrejon Vacio, Fernando

    2006-01-01

    In the paper wetting experiments at low evaporation rate, after a short Washburn regime the film flow of filtered water overtakes the main impregnation front. Accordingly, we study the kinetic roughening dynamics and pinning of two strongly coupled fronts moving in different papers. We find that the kinetic roughening dynamics of precursor and main fronts belongs to different universality classes, nevertheless, at the final stage the distance between the fronts decrease until both fronts are pinned in the same configuration z P (x,y), the scaling properties of which are determined by the long-range correlations in the pore network

  10. Two modes of surface roughening during plasma etching of silicon: Role of ionized etch products

    OpenAIRE

    Nakazaki, Nobuya; Tsuda, Hirotaka; Takao, Yoshinori; Eriguchi, Koji; Ono, Kouichi

    2014-01-01

    Atomic- or nanometer-scale surface roughening has been investigated during Si etching in inductively coupled Cl{2} plasmas, as a function of rf bias power or ion incident energy E{i} , by varying feed gas flow rate, wafer stage temperature, and etching time. The experiments revealed two modes of surface roughening which occur depending on E{i} : one is the roughening mode at low E{i}  

  11. Osteogenic potential of bone marrow stromal cells on smooth, roughened, and tricalcium phosphate-modified titanium alloy surfaces.

    LENUS (Irish Health Repository)

    Colombo, John S

    2012-09-01

    This study investigated the influence of smooth, roughened, and tricalcium phosphate (TCP)-coated roughened titanium-aluminum-vanadium (Ti-6Al-4V) surfaces on the osteogenic potential of rat bone marrow stromal cells (BMSCs).

  12. Physical mechanism of surface roughening on the radial core-shell nanowire heterostructure with alloy shell

    Science.gov (United States)

    Cao, Yuanyuan; Diao, Dongfeng

    2017-05-01

    We proposed a quantitative thermodynamic theory to address the physical process of surface roughening during the epitaxial growth of core-shell NW with alloy layer. The surface roughening origins from the transformation of the Frank-van der Merwe (FM) mode to the Stranski-Krastanow (SK) mode. In addition to the radius of NW core, the composition and thickness of alloy shell could determine the growth behaviors due to their modulation to the strain. The established theoretical model not only explains the surface roughening caused by the alloy shell layer, but also provides a new way to control the growth of core-shell NW.

  13. Physical mechanism of surface roughening on the radial core-shell nanowire heterostructure with alloy shell

    Directory of Open Access Journals (Sweden)

    Yuanyuan Cao

    2017-05-01

    Full Text Available We proposed a quantitative thermodynamic theory to address the physical process of surface roughening during the epitaxial growth of core-shell NW with alloy layer. The surface roughening origins from the transformation of the Frank-van der Merwe (FM mode to the Stranski-Krastanow (SK mode. In addition to the radius of NW core, the composition and thickness of alloy shell could determine the growth behaviors due to their modulation to the strain. The established theoretical model not only explains the surface roughening caused by the alloy shell layer, but also provides a new way to control the growth of core-shell NW.

  14. Surface Roughening Behavior of 6063 Aluminum Alloy during Bulging by Spun Tubes

    Directory of Open Access Journals (Sweden)

    Yang Cai

    2017-03-01

    Full Text Available Severe surface roughening during the hydroforming of aluminum alloy parts can produce surface defects that severely restrict their application in the automobile and aerospace industry. To understand the relation between strain, grain size and surface roughness under biaxial stress conditions, hydro-bulging tests of aluminum alloy tubes were carried out, and the tubes with different grain sizes were prepared by a spinning and annealing process. The surface roughness was measured by a laser scanning confocal microscope to evaluate the surface roughening macroscopical behavior, and the corresponding microstructures were observed using electron back-scattered diffraction (EBSD to reveal the roughening microscopic behavior. The results obtained show that the surface roughness increased with both strain and grain size under biaxial stress. No surface defects were observed on the surface when the grain size was less than 105 μm if the strain was less than 18%, or when the grain size was between 130 and 175 μm if the strain was less than 15.88% and 7.15%, respectively. The surface roughening microscopic behavior was identified as an inhomogeneous grain size distribution, which became more pronounced with increasing grain size and resulted in greater local deformation. Concentrated grain orientation also results in severe inhomogeneous deformation during plastics deformation, and serious surface roughening.

  15. Two modes of surface roughening during plasma etching of silicon: Role of ionized etch products

    Science.gov (United States)

    Nakazaki, Nobuya; Tsuda, Hirotaka; Takao, Yoshinori; Eriguchi, Koji; Ono, Kouichi

    2014-12-01

    Atomic- or nanometer-scale surface roughening has been investigated during Si etching in inductively coupled Cl2 plasmas, as a function of rf bias power or ion incident energy Ei, by varying feed gas flow rate, wafer stage temperature, and etching time. The experiments revealed two modes of surface roughening which occur depending on Ei: one is the roughening mode at low Ei rms) roughness of etched surfaces increases with increasing Ei, exhibiting an almost linear increase with time during etching (t rms surface roughness decreases substantially with Ei down to a low level etch rate versus √{Ei } curve, and in the evolution of the power spectral density distribution of surfaces. Such changes from the roughening to smoothing modes with increasing Ei were found to correspond to changes in the predominant ion flux from feed gas ions Clx+ to ionized etch products SiClx+ caused by the increased etch rates at increased Ei, in view of the results of several plasma diagnostics. Possible mechanisms for the formation and evolution of surface roughness during plasma etching are discussed with the help of Monte Carlo simulations of the surface feature evolution and classical molecular dynamics simulations of etch fundamentals, including stochastic roughening and effects of ion reflection and etch inhibitors.

  16. Effect of the roughening transition on the vicinal surface in the step droplet zone

    Science.gov (United States)

    Akutsu, Noriko

    2017-06-01

    For vicinal surfaces around the (001) surface inclined towards the 〈 111 〉 direction, the influence of roughening transitions on the surface tension and on step droplets is studied numerically. The surface tension is calculated using a restricted solid-on-solid model with a point-contact type step-step attraction (p-RSOS model) on a square lattice. To ensure the reliability of the calculations, the density matrix renormalization group method is used. The growth rate of the vicinal surface near equilibrium is also calculated by the Monte Carlo method. It is found that the roughening transition changes the morphology around the (001) surface, and the roughening transition affects the size of locally merged steps (step droplets).

  17. Directed Polymers in Random Media and Kinetic Roughening in Interface Growth.

    Science.gov (United States)

    Yu, Yi-Kuo

    The DPRM problem is the simplest model known thus far exhibiting randomness-dominated phases. Variations on the DPRM are closely related to problems like the directed waves scattered through random media and variable range hopping conductivity. Kinetic roughening phenomena arise from the pattern growth in clusters and solidification fronts. A Hopf transformation somehow links these two seemingly unrelated topics together. Both problems exhibit lattice-continuum crossovers. In the DPRM context, the problems associated with taking replica number n to 0 as well as some analytical results are studied and criticized. The two-replica analytic result we obtained is important in determining the transition temperature of the DPRM system as well as in calculating the wave front spread of the directed waves in random media problem. To understand more about the macroscopic stochastic differential equations describing kinetic roughening phenomena, we studied the growth process with correlated noise. We solved the Edwards-Wilkinson stochastic equation with power -law correlated noise. A new algorithm to generate truly power-law correlated noises is presented. The algorithm we present here can be applied to generate noise with arbitrary spatial correlations.

  18. Nanometer-scale sharpening and surface roughening of ZnO nanorods by argon ion bombardment

    Science.gov (United States)

    Chatterjee, Shyamal; Behera, Akshaya K.; Banerjee, Amarabha; Tribedi, Lokesh C.; Som, Tapobrata; Ayyub, Pushan

    2012-07-01

    We report the effects of exposing a hydrothermally grown, single crystalline ZnO nanorod array to a beam of 50 keV argon ions at room temperature. High resolution electron microscopy reveals that the ion bombardment results in a nanometer-scale roughening of the nanorod sidewalls, which were almost atomically flat in the pristine sample. Ion bombardment further causes the flat, ≈100 nm diameter nanorod tips to get sharpened to ultrafine points less than 10 nm across. While tip sharpening is attributed to preferential sputtering, the formation of crystalline surface protuberances can be ascribed to surface instability due to curvature dependent sputtering and surface diffusion under argon-ion bombardment. Both the nanoscale roughening as well as the tip sharpening are expected to favorably impact a wide variety of applications, such as those involving catalysis, gas sensing, solar cells, field emission and gas discharge.

  19. Nanometer-scale sharpening and surface roughening of ZnO nanorods by argon ion bombardment

    Energy Technology Data Exchange (ETDEWEB)

    Chatterjee, Shyamal, E-mail: shyamal@iitbbs.ac.in [School of Basic Sciences, Indian Institute of Technology, Bhubaneswar 751013 (India); Behera, Akshaya K. [School of Basic Sciences, Indian Institute of Technology, Bhubaneswar 751013 (India); Banerjee, Amarabha; Tribedi, Lokesh C. [Tata Institute of Fundamental Research, Homi Bhabha Road, Mumbai 400005 (India); Som, Tapobrata [Institute of Physics, Sachivalaya Marg, Bhubaneswar 751005 (India); Ayyub, Pushan, E-mail: pushan@tifr.res.in [Tata Institute of Fundamental Research, Homi Bhabha Road, Mumbai 400005 (India)

    2012-07-01

    We report the effects of exposing a hydrothermally grown, single crystalline ZnO nanorod array to a beam of 50 keV argon ions at room temperature. High resolution electron microscopy reveals that the ion bombardment results in a nanometer-scale roughening of the nanorod sidewalls, which were almost atomically flat in the pristine sample. Ion bombardment further causes the flat, Almost-Equal-To 100 nm diameter nanorod tips to get sharpened to ultrafine points less than 10 nm across. While tip sharpening is attributed to preferential sputtering, the formation of crystalline surface protuberances can be ascribed to surface instability due to curvature dependent sputtering and surface diffusion under argon-ion bombardment. Both the nanoscale roughening as well as the tip sharpening are expected to favorably impact a wide variety of applications, such as those involving catalysis, gas sensing, solar cells, field emission and gas discharge.

  20. Entanglement in correlated random spin chains, RNA folding and kinetic roughening

    International Nuclear Information System (INIS)

    Rodríguez-Laguna, Javier; Santalla, Silvia N; Ramírez, Giovanni; Sierra, Germán

    2016-01-01

    Average block entanglement in the 1D XX-model with uncorrelated random couplings is known to grow as the logarithm of the block size, in similarity to conformal systems. In this work we study random spin chains whose couplings present long range correlations, generated as gaussian fields with a power-law spectral function. Ground states are always planar valence bond states, and their statistical ensembles are characterized in terms of their block entropy and their bond-length distribution, which follow power-laws. We conjecture the existence of a critical value for the spectral exponent, below which the system behavior is identical to the case of uncorrelated couplings. Above that critical value, the entanglement entropy violates the area law and grows as a power law of the block size, with an exponent which increases from zero to one. Interestingly, we show that XXZ models with positive anisotropy present the opposite behavior, and strong correlations in the couplings lead to lower entropies. Similar planar bond structures are also found in statistical models of RNA folding and kinetic roughening, and we trace an analogy between them and quantum valence bond states. Using an inverse renormalization procedure we determine the optimal spin-chain couplings which give rise to a given planar bond structure, and study the statistical properties of the couplings whose bond structures mimic those found in RNA folding. (paper)

  1. Surface roughening and rippling during plasma etching of silicon: Numerical investigations and a comparison with experiments

    OpenAIRE

    Tsuda, Hirotaka; Nakazaki, Nobuya; Takao, Yoshinori; Eriguchi, Koji; Ono, Kouichi

    2014-01-01

    Atomic- or nanometer-scale surface roughening and rippling during Si etching in high-density Cl2 and Cl2/O2 plasmas have been investigated by developing a three-dimensional atomic-scale cellular model (ASCeM-3D), which is a 3D Monte Carlo-based simulation model for plasma-surface interactions and the feature profile evolution during plasma etching. The model took into account the behavior of Cl+ ions, Cl and O neutrals, and etch products and byproducts of SiClx and SiClxOy in microstructures ...

  2. Analysis of Surface Roughening in AA6111 Automotive Sheet Under Pure Bending

    Science.gov (United States)

    Shi, Y.; Zhao, P. Z.; Jin, H.; Wu, P. D.; Lloyd, D. J.

    2016-02-01

    The finite element method is used to numerically simulate the topographic development in an aluminum sheet, AA6111, under pure bending. The measured electron backscatter diffraction data are directly incorporated into the finite element model, and the constitutive response at an integration point is described by the single crystal plasticity theory. The effects of strain-rate sensitivity, work hardening, and imposed initial surface roughness on surface roughening are studied. It is found that the grains in top surface layers of the sheet play a big role in controlling the outer surface roughness due to the strain gradient across sheet thickness in bending, while the grain size and texture of the surface layers have a direct impact on finishing surface qualities.

  3. Submonolayer nucleation and growth and the initial stage of multilayer kinetic roughening during Ag/Ag (100) homoepitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, C.

    1996-08-01

    A comprehensive Scanning Tunneling Microscopy (STM) study of submonolayer nucleation and growth of 2D islands in Ag/Ag(100) homoepitaxy for temperature between 295K and 370K is presented. The initial stages of multilayer kinetic roughening is also studied. Analysis of an appropriate model for metal (100) homoepitaxy, produces estimates of 350 meV for the terrace diffusion barrier, 400 meV for the adatom bond energy, and 25 meV for the additional Ehrlich-Schwoebel step-edge barrier.

  4. Roughened titanium surfaces with silane and further RGD peptide modification in vitro

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Wen-Cheng, E-mail: wencchen@fcu.edu.tw [Advanced Medical Devices and Composites Laboratory, Department of Fiber and Composite Materials, College of Engineering, Feng Chia University, Taichung 40724, Taiwan, ROC (China); Ko, Chia-Ling [School of Dentistry, College of Dental Medicine, Kaohsiung Medical University, Kaohsiung 807, Taiwan, ROC (China)

    2013-07-01

    The strategy to achieve osteoregeneration of dental implants during early-stage regeneration is strongly related to surface conditions for achieving highly successful effects after implantation. Surface modifications, namely, mechanical ground, silanization, bonded and sandblasted with pentasequence Gly-Arg-Gly-Asp-Ser (GRGDS) peptide, and acid-etched with Arg-Gly-Asp (RGD) peptide, were compared for their ability to support cell attachment, proliferation, and differentiation on titanium surfaces. The characteristics and comparative in vitro bio-interactions toward osteoprogenitor cells were tested in the four groups with various surface modifications. Compared with the other groups, the sandblasted and acid-etched, and silane with subsequent RGD peptide modified surfaces had the smallest wetting angle, absence of a significant cell viability difference, and largest quantity of alkaline phosphatase production during the expressions of early-stage cell differentiation. The method of synthesizing GRGDS peptides on roughened titanium surfaces has the potential to provide a combination of early bone regeneration and implant of long-term anchored capabilities. Highlights: • The osteoregeneration during early-stage is strongly related to surface conditions. • The wettability with RGD peptide treated surfaces can be enhanced. • Rougher surface binding with RGD peptide can achieve better osseogeneration. • Surfaces with RGD peptide accelerate the progenitor bone cell mineralization.

  5. Computational prediction of heat transfer to gas turbine nozzle guide vanes with roughened surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Guo, S.M.; Jones, T.V. [Univ. of Oxford (United Kingdom). Dept. of Engineering Science; Lock, G.D. [Univ. of Bath (United Kingdom). Dept. of Mechanical Engineering; Dancer, S.N. [Rolls-Royce PLC, Derby (United Kingdom)

    1998-04-01

    The local Mach number and heat transfer coefficient over the aerofoil surfaces and endwalls of a transonic gas turbine nozzle guide vane have been calculated. the computations were performed by solving the time-averaged Navier-Stokes equations using a fully three-dimensional computational code (CFDS), which is well established at Rolls-Royce. A model to predict the effects of roughness has been incorporated into CFDS and heat transfer levels have been calculated for both hydraulically smooth and transitionally rough surfaces. The roughness influences the calculations in two ways; first the mixing length at a certain height above the surface is increased; second the wall function used to reconcile the wall condition with the first grid point above the wall is also altered. The first involves a relatively straightforward shift of the origin in the van Driest damping function description, the second requires an integration of the momentum equation across the wall layer. A similar treatment applies to the energy equation. The calculations are compared with experimental contours of heat transfer coefficient obtained using both thin-film gages and the transient liquid crystal technique. Measurements were performed using both hydraulically smooth and roughened surfaces, and at engine-representative Mach and Reynolds numbers. The heat transfer results are discussed and interpreted in terms of surface-shear flow visualization using oil and dye techniques.

  6. Fouling of roughened stainless steel surfaces during convective heat transfer to aqueous solutions

    International Nuclear Information System (INIS)

    Herz, A.; Malayeri, M.R.; Mueller-Steinhagen, H.

    2008-01-01

    The deterioration of heat transfer performance due to fouling is the prime cause for higher energy consumption and inefficiency in many industrial heat exchangers such as those in power plants, refineries, food and dairy industries. Fouling is also a very complex process in which many geometrical, physical and operating parameters are involved with poorly understood interaction. Among them, the surface roughness is an important surface characteristic that would greatly influence crystallisation fouling mechanisms and hence deposition morphology and stickability to the surface. In this work, the effect of the surface roughness of AISI 304 BA stainless steel surfaces on fouling of an aqueous solution with inverse solubility behaviour has been investigated under convective heat transfer. Several experiments have been performed on roughened surfaces ranging from 0.18 to 1.55 μm for different bulk concentrations and heat fluxes. The EDTA titration method was used to measure the concentration of the calcium sulphate salt in order to maintain it at constant value during each fouling run. Experimental results show that the heat transfer coefficient of very rough surfaces (1.55 μm) decreases more rapidly than that of 0.54 μm. Several facts contribute to this behaviour notably (1) increased of primary heterogeneous nucleation rate on the surfaces; (2) reduction of local shear stress in the valleys and (3) reduced removal rate of the crystals from the surfaces where the roughness elements protrude out of the viscous sub-layer. The results also show linear and proportional variation of the fouling rate and heat flux within the range of operating conditions. In addition, the deposition process in terms of fouling rate could only be affected at lower surface contact angles. Such results would particularly be of interest for new surface treatment technologies which aim at altering the surface texture

  7. Effect of nanotubular-micro-roughened titanium surface on cell response in vitro and osseointegration in vivo

    Energy Technology Data Exchange (ETDEWEB)

    Yun, Kwi-Dug [Department of Prosthodontics, School of Dentistry, Chonnam National University, Gwangju 504-190 (Korea, Republic of); Yang, Yunzhi, E-mail: Yunzhi.yang@uth.tmc.edu [Department of Restorative Dentistry and Biomaterials, University of Texas Health Science Center at Houston,6516 M.D. Anderson Blvd., Ste. 4.133, Houston, TX 77030 (United States); Lim, Hyun-Pil [Department of Prosthodontics, School of Dentistry, Chonnam National University, Gwangju 504-190 (Korea, Republic of); Oh, Gye-Jeong; Koh, Jeong-Tae; Bae, In-Ho; Kim, Jaehyung [Dental Science Research Institute and BK21 Project, School of Dentistry, Chonnam National University, Gwangju 504-190 (Korea, Republic of); Lee, Kwang-Min [Division of Materials Science and Engineering, Research Institute for Functional Surface Engineering, Chonnam National University, Gwangju 500-757 (Korea, Republic of); Park, Sang-Won, E-mail: psw320@chonnam.ac.kr [Dental Science Research Institute and BK21 Project, School of Dentistry, Chonnam National University, Gwangju 504-190 (Korea, Republic of)

    2010-01-01

    This study was to evaluate wettability, cell response, and osseointegration of nanotubular titanium (Ti) surface by anodic oxidation. Commercially pure Ti discs were treated by polishing, sandblasting, and anodizing. These surfaces were characterized by scanning electron microscopy and contact angle measurement. MC3T3-E1 osteoblast cell was used to evaluate cell response in vitro. The cell morphology, cell viability, and alkaline phosphatase (ALP) specific activity were assessed. The Ti implants of 2.0 mm diameter and 5.0 mm long treated by anodizing and sandblasting/anodizing were inserted into the tibia of rats. After 3 weeks, the histology of the Ti-bone interface was examined. SEM observations showed that the anodizing and sandblasting/anodizing created the nanotubular surface and graded nanotubular-micro-roughened surfaces, respectively. The anodizing and sandblasting/anodizing significantly improved the hydrophilicity of Ti. The significant greatest cell spreading and ALP specific activity were observed on the graded nanotubular-micro-roughened surfaces treated by sandblasting/anodizing. The in vivo study shows that newly formed bone was intimately in contact with the nanotubular surfaces without adverse immune response. This study has suggested that the graded nanotubular-micro-roughened surface of Ti treated with sandblasting/anodizing is very promising in implantology due to improved hydrophilicity, favorable cell response, and excellent osseointegration.

  8. Electrical characteristics of a vertical light emitting diode with n-type contacts on a selectively wet-etching roughened surface

    International Nuclear Information System (INIS)

    Wang Liancheng; Guo Enqing; Liu Zhiqiang; Yi Xiaoyan; Wang Guohong

    2011-01-01

    Low resistance and thermally stable n-type contacts to N-polar GaN are essentially important for vertical light emitting diodes (VLEDs). The electrical characteristics of VLEDs with n-type contacts on a roughened and flat N-polar surface have been compared. VLEDs with contacts deposited on a roughened surface exhibit lower leakage currents yet a higher operating voltage. Based on this, a new scheme by depositing metallization contacts on a selectively wet-etching roughened surface has been developed. Excellent electrical and optical characteristics have been achieved with this method. An aging test further confirmed its stability. (semiconductor devices)

  9. Enhancing biodegradation and energy generation via roughened surface graphite electrode in microbial desalination cell.

    Science.gov (United States)

    Ebrahimi, Atieh; Yousefi Kebria, Daryoush; Najafpour Darzi, Ghasem

    2017-09-01

    The microbial desalination cell (MDC) is known as a newly developed technology for water and wastewater treatment. In this study, desalination rate, organic matter removal and energy production in the reactors with and without desalination function were compared. Herein, a new design of plain graphite called roughened surface graphite (RSG) was used as the anode electrode in both microbial fuel cell (MFC) and MDC reactors for the first time. Among the three type of anode electrodes investigated in this study, RSG electrode produced the highest power density and salt removal rate of 10.81 W/m 3 and 77.6%, respectively. Such a power density was 2.33 times higher than the MFC reactor due to the junction potential effect. In addition, adding the desalination function to the MFC reactor enhanced columbic efficiency from 21.8 to 31.4%. These results provided a proof-of-concept that the use of MDC instead of MFC would improve wastewater treatment efficiency and power generation, with an added benefit of water desalination. Furthermore, RSG can successfully be employed in an MDC or MFC, enhancing the bio-electricity generation and salt removal.

  10. Roughening Conjugated Polymer Surface for Enhancing the Charge Collection Efficiency of Sequentially Deposited Polymer/Fullerene Photovoltaics

    Directory of Open Access Journals (Sweden)

    Yoonhee Jang

    2015-08-01

    Full Text Available A method that enables the formation of a rough nano-scale surface for conjugated polymers is developed through the utilization of a polymer chain ordering agent (OA. 1-Chloronaphthalene (1-CN is used as the OA for the poly(3-hexylthiophene-2,5-diyl (P3HT layer. The addition of 1-CN to the P3HT solution improves the chain ordering of the P3HT during the film formation process and increases the surface roughness of the P3HT film compared to the film prepared without 1-CN. The roughened surface of the P3HT film is utilized to construct a P3HT/fullerene bilayer organic photovoltaic (OPV by sequential solution deposition (SqSD without thermal annealing process. The power conversion efficiency (PCE of the SqSD-processed OPV utilizing roughened P3HT layer is 25% higher than that utilizing a plain P3HT layer. It is revealed that the roughened surface of the P3HT increases the heterojunction area at the P3HT/fullerene interface and this resulted in improved internal charge collection efficiency, as well as light absorption efficiency. This method proposes a novel way to improve the PCE of the SqSD-processed OPV, which can be applied for OPV utilizing low band gap polymers. In addition, this method allows for the reassessment of polymers, which have shown insufficient performance in the BSD process.

  11. Optical properties and kinetic roughening influence on dispersive casimir and van der Waals forces

    NARCIS (Netherlands)

    Palasantzas, G.; Svetovoy, Vitaly; van Zwol, P.J.

    2010-01-01

    Casimir and van der Waals dispersive forces between real material surfaces can be strongly influenced by surface roughness and the frequency dependent dielectric functions of the interacting materials. The Lifshitz theory allows calculations of these forces between two flat plates if the frequency

  12. Optical Properties and Kinetic Roughening Influence on Dispersive Casimir and van der Waals Forces

    NARCIS (Netherlands)

    Palasantzas, G.; Svetovoy, V. B.; Van Zwol, P. J.

    2010-01-01

    Casimir and van der Waals dispersive forces between real material surfaces can be strongly influenced by surface roughness and the frequency dependent dielectric functions of the interacting materials. The Lifshitz theory allows calculations of these forces between two flat plates if the frequency

  13. Kinetic Roughening and Material Optical Properties Influence on Van der Waals/Casimir Forces

    NARCIS (Netherlands)

    van Zwol, P. J.; Palasantzas, G.

    Atomic force microscopy measurements and force theory calculations using the Lifshitz theory show that van der Waals/Casimir dispersive forces have a strong dependence on surface roughness and material optical properties. It is found that at separations below 100 nm the roughness effect is

  14. Kinetic roughening of a soft dewetting line under quenched disorder: A numerical study

    Science.gov (United States)

    Tyukodi, B.; Bréchet, Y.; Néda, Z.

    2014-11-01

    An elegant simulation method, suitable for investigating the dewetting dynamics of thin and viscous liquid layers, is discussed. The efficiency of the method is exemplified by studying a two-parameter depinninglike model defined on inhomogeneous solid surfaces. The morphology and the statistical properties of the contact line are mapped in the relevant parameter space, and as a result critical behavior in the vicinity of the depinning transition is revealed. The model allows for the tearing of the layer, which leads to a new propagation regime resulting in nontrivial collective behavior. The large deformations observed for the interface are a result of the interplay between the substrate inhomogeneities and the capillary forces.

  15. Some causes and a consequence of epitaxial roughening

    Science.gov (United States)

    Zangwill, A.

    1996-05-01

    This article consists of two related parts. In the first part, a review is presented of the theory of surface roughening during homoepitaxial growth or lattice-matched heteroepitaxial growth. Emphasis is placed on qualitative concepts and general mechanisms. Rate equations, Monte Carlo simulations, and continuum equations of motion are used to illustrate roughening due to asymmetric diffusion barriers to interlayer mass transport and from statistical fluctuations in the incident deposition flux. In the second part, we report new results regarding one consequence of such roughening that is pertinent to the growth of semiconductor alloys that exhibit long-range order induced by local thermodynamics at the free surface. The qualitative ingredients for a kinetic mean field theory are described along with preliminary results that indicate that surface roughness induces the injection of anti-phase domains that progressively destroy the lateral coherence of order in a growing film.

  16. Improved adhesion at titanium surfaces via laser-induced surface oxidation and roughening

    Energy Technology Data Exchange (ETDEWEB)

    Zimmermann, S. [Fraunhofer-Institut fuer Fertigungstechnik und Angewandte Materialforschung, Wiener Str. 12, 28359 Bremen (Germany); Institut fuer Mikro- und Nanotechnologien, Technische Universitaet Ilmenau, PF 100565, 98684 Ilmenau (Germany); Specht, U., E-mail: uwe.specht@ifam.fraunhofer.de [Fraunhofer-Institut fuer Fertigungstechnik und Angewandte Materialforschung, Wiener Str. 12, 28359 Bremen (Germany); Spiess, L.; Romanus, H.; Krischok, S.; Himmerlich, M. [Institut fuer Mikro- und Nanotechnologien, Technische Universitaet Ilmenau, PF 100565, 98684 Ilmenau (Germany); Ihde, J. [Fraunhofer-Institut fuer Fertigungstechnik und Angewandte Materialforschung, Wiener Str. 12, 28359 Bremen (Germany)

    2012-12-15

    Commercial titanium was treated in ambient atmosphere using pulsed Nd:YAG ({lambda}=1064nm) laser irradiation. Repeated laser treatments induce a removal of surface contaminants as well as the formation of a nanostructured top layer exhibiting a large effective surface and nanometer roughness. The laser induced oxidation leads to the presence of a surface layer with strongly improved, hydrothermally stable adhesion when joined to a one-component, hot-curing epoxy-based adhesive. Changes in the material properties have been characterized with respect to the topography, the chemical composition and the crystal structure using SEM, cross-beam FIB, XPS and XRD analyses in order to correlate the adhesion behavior with the structural and chemical characteristics of the surface.

  17. Highly porous micro-roughened structures developed on aluminum surface using the jet of rotating arc discharges at atmospheric pressure

    Science.gov (United States)

    Asadollahi, Siavash; Farzaneh, Masoud; Stafford, Luc

    2018-02-01

    Aluminum 6061 samples were exposed to the jet of an atmospheric pressure rotating arc discharge operated in either nitrogen or air. After multiple passes of treatment with an air-based plasma jet at very short source-to-substrate distances, scanning electron microscopy combined with x-ray photoelectron spectroscopy revealed a highly porous micro-roughened alumina-based structure on the surface of aluminum. Based on optical emission spectroscopy and high-speed optical imaging of the jet interacting with aluminum samples, it was found that the process is mainly driven by the energy transfer from the plasma source to the surface through transient plasma-transferred arcs. The occurrence of multiple arc discharges over very short time scales can induce rapid phase transformations of aluminum with characteristics similar to the ones usually observed during laser ablation of materials with femto- to nanosecond laser pulses or during the formation of cathode spots on the surface of metals.

  18. Avalanche dynamics, surface roughening, and self-organized criticality: Experiments on a three-dimensional pile of rice

    NARCIS (Netherlands)

    Aegerter, C.M.; Gunther, R.; Wijngaarden, R.J.

    2003-01-01

    The results of both the avalanche and the roughening behavior of an experimental self-organized criticality (SOC) system are presented. In addition, simple arguments for universal scaling relations, derived by Paczuski et al. on general grounds, connecting the avalanche and the roughening behavior

  19. Two or three machined vs roughened surface dental implants loaded immediately supporting total fixed prostheses: 1-year results from a randomised controlled trial.

    Science.gov (United States)

    Cannizzaro, Gioacchino; Gastaldi, Giorgio; Gherlone, Enrico; Vinci, Raffaele; Loi, Ignazio; Trullenque-Eriksson, Anna; Esposito, Marco

    To compare implants with machined vs roughened surfaces placed flapless in totally edentulous jaws and immediately restored with metal-resin screw-retained cross-arch prostheses. Mandibles were rehabilitated with two implants (Fixed-on-2 or Fo2) and maxillae with three implants (Fixed-on-3 or Fo3). Forty edentulous or to be rendered edentulous patients (20 in the mandible and 20 in the maxilla) were randomised to the machined group (20 patients: 10 mandibles and 10 maxillae) and to the roughened group (20 patients: 10 mandibles and 10 maxillae) according to a parallel group design. To be immediately loaded implants had to be inserted with a minimum torque of 60 Ncm. Outcome measures were prosthesis and implant failures, complications and peri-implant marginal bone level changes evaluated up to 1 year post-loading. Flaps were raised in four patients from the machined group. Four prostheses on machined implants and three on roughened implants were delayed for loading because a sufficient insertion torque was not obtained. There were no dropouts 1 year after loading. Two maxillary machined implants were lost in two patients (difference in proportions = 0.10; 95% CI = -0.03 to 0.23; P (Fisher's exact test) = 0.487); one maxillary Fo3 prosthesis on machined implants and one mandibular Fo2 prosthesis on roughened implants had to be remade (difference in proportions = 0; 95% CI = -0.14 to 0.14; P (Fisher's exact test) = 1.000). Five patients with machined implants had six complications vs seven patients who had eight complications at roughened implants (difference in proportions = -0.10; 95% CI = -0.38 to 0.18; P (Fisher's exact test) = 0.731). There were no statistically significant differences for implant failures, prosthetic failures or complications between groups. There were no statistically significant differences for marginal peri-implant bone levels between the two groups (estimate of the difference = -0.06 mm; 95% CI = -0.23 to 0.10; P (ANCOVA) = 0.445), with

  20. Effect of input power and gas pressure on the roughening and selective etching of SiO2/Si surfaces in reactive plasmas

    International Nuclear Information System (INIS)

    Zhong, X. X.; Huang, X. Z.; Tam, E.; Ostrikov, K.; Colpo, P.; Rossi, F.

    2010-01-01

    We report on the application low-temperature plasmas for roughening Si surfaces which is becoming increasingly important for a number of applications ranging from Si quantum dots to cell and protein attachment for devices such as 'laboratory on a chip' and sensors. It is a requirement that Si surface roughening is scalable and is a single-step process. It is shown that the removal of naturally forming SiO 2 can be used to assist in the roughening of the surface using a low-temperature plasma-based etching approach, similar to the commonly used in semiconductor micromanufacturing. It is demonstrated that the selectivity of SiO 2 /Si etching can be easily controlled by tuning the plasma power, working gas pressure, and other discharge parameters. The achieved selectivity ranges from 0.4 to 25.2 thus providing an effective means for the control of surface roughness of Si during the oxide layer removal, which is required for many advance applications in bio- and nanotechnology.

  1. Enhanced visible light photocatalytic property of red phosphorus via surface roughening

    International Nuclear Information System (INIS)

    Li, Weibing; Yue, Jiguang; Hua, Fangxia; Feng, Chang; Bu, Yuyu; Chen, Zhuoyuan

    2015-01-01

    Highlights: • Photocatalytic RhB degradation of red phosphorus was studied for the first time. • Surface rough can increase the photocatalysis reaction active sites. • Surface rough red phosphorus possesses high photocatalytic performance. • Surface rough red phosphorus has high industrial application value. - Abstract: Red phosphorus with rough surface (SRP) was prepared by catalyst-assisted hydrothermal synthesis using Co 2+ catalyst. The photocatalytic Rhodamine B (RhB) degradation of red phosphorus (RP) and SRP was studied for the first time in this work. Rough surface can enhance the dye adsorption ability of RP. About 75% RhB was absorbed by SRP after 30-min adsorption in 100 ml RhB solution with concentration of 10 mg l −1 in dark. After only 10 min of illumination by visible light, more than 95% RhB was degraded, indicating that SRP has a great application potential in the area of photocatalysis. The photocatalytic RhB degradation properties of RP are much weaker than those of SRP. The increase of the number of the active sites for the photocatalytic reactions, the electron mobility and the lifetime of the photogenerated electrons cause the significant improvement of the photocatalytic performance of SRP based on the experimental results obtained

  2. Near- and supercritical water as a diameter manipulation and surface roughening agent in fused silica capillaries

    Czech Academy of Sciences Publication Activity Database

    Karásek, Pavel; Planeta, Josef; Roth, Michal

    2013-01-01

    Roč. 85, č. 1 (2013), s. 327-333 ISSN 0003-2700 R&D Projects: GA ČR(CZ) GAP106/12/0522; GA ČR(CZ) GAP206/11/0138 Institutional support: RVO:68081715 Keywords : supercritical water * fused silica capillary * surface treatment Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 5.825, year: 2013

  3. Improving Dry Powder Inhaler Performance by Surface Roughening of Lactose Carrier Particles.

    Science.gov (United States)

    Tan, Bernice Mei Jin; Chan, Lai Wah; Heng, Paul Wan Sia

    2016-08-01

    This study investigated the impact of macro-scale carrier surface roughness on the performance of dry powder inhaler (DPI) formulations. Fluid-bed processing and roller compaction were explored as processing methods to increase the surface roughness (Ra) of lactose carrier particles. DPI formulations containing either (a) different concentrations of fine lactose at a fixed concentration of micronized drug (isoniazid) or (b) various concentrations of drug in the absence of fine lactose were prepared. The fine particle fraction (FPF) and aerodynamic particle size of micronized drug of all formulations were determined using the Next Generation Impactor. Fluid-bed processing resulted in a modest increase in the Ra from 562 to 907 nm while roller compaction led to significant increases in Ra > 1300 nm. The roller compacted carriers exhibited FPF > 35%, which were twice that of the smoothest carriers. The addition of up to 5%, w/w of fine lactose improved the FPF of smoother carriers by 60-200% whereas only lactose carrier particles by roller compaction was immensely beneficial to improving DPI performance, primarily due to increased surface roughness at the macro-scale.

  4. Surface Roughening of Polystyrene and Poly(methyl methacrylate in Ar/O2 Plasma Etching

    Directory of Open Access Journals (Sweden)

    Amy E. Wendt

    2010-12-01

    Full Text Available Selectively plasma-etched polystyrene-block-poly(methyl methacrylate (PS-b-PMMA diblock copolymer masks present a promising alternative for subsequent nanoscale patterning of underlying films. Because mask roughness can be detrimental to pattern transfer, this study examines roughness formation, with a focus on the role of cross-linking, during plasma etching of PS and PMMA. Variables include ion bombardment energy, polymer molecular weight and etch gas mixture. Roughness data support a proposed model in which surface roughness is attributed to polymer aggregation associated with cross-linking induced by energetic ion bombardment. In this model, RMS roughness peaks when cross-linking rates are comparable to chain scissioning rates, and drop to negligible levels for either very low or very high rates of cross-linking. Aggregation is minimal for very low rates of cross-linking, while very high rates produce a continuous cross-linked surface layer with low roughness. Molecular weight shows a negligible effect on roughness, while the introduction of H and F atoms suppresses roughness, apparently by terminating dangling bonds. For PS etched in Ar/O2 plasmas, roughness decreases with increasing ion energy are tentatively attributed to the formation of a continuous cross-linked layer, while roughness increases with ion energy for PMMA are attributed to increases in cross-linking from negligible to moderate levels.

  5. Physical mechanism of surface roughening of the radial Ge-core/Si-shell nanowire heterostructure and thermodynamic prediction of surface stability of the InAs-core/GaAs-shell nanowire structure.

    Science.gov (United States)

    Cao, Y Y; Ouyang, G; Wang, C X; Yang, G W

    2013-02-13

    As a promising and typical semiconductor heterostructure at the nanoscale, the radial Ge/Si NW heterostructure, that is, the Ge-core/Si-shell NW structure, has been widely investigated and used in various nanodevices such as solar cells, lasers, and sensors because of the strong changes in the band structure and increased charge carrier mobility. Therefore, to attain high quality radial semiconductor NW heterostructures, controllable and stable epitaxial growth of core-shell NW structures has become a major challenge for both experimental and theoretical evaluation. Surface roughening is usually undesirable for the epitaxial growth of high quality radial semiconductor NW heterostructures, because it would destroy the core-shell NW structures. For example, the surface of the Ge-core/Si-shell NWs always exhibits a periodic modulation with island-like morphologies, that is, surface roughening, during epitaxial growth. Therefore, the physical understanding of the surface roughening behavior during the epitaxial growth of core-shell NW structures is essential and urgent for theoretical design and experimentally controlling the growth of high quality radial semiconductor NW heterostructures. Here, we proposed a quantitative thermodynamic theory to address the physical process of epitaxial growth of core-shell NW structures and surface roughening. We showed that the transformation from the Frank-van der Merwe mode to the Stranski-Krastanow mode during the epitaxial growth of radial semiconductor NW heterostructures is the physical origin of surface roughening. We deduced the thermodynamic criterion for the formation of the surface roughening and the phase diagram of growth and showed that the radius of the NWs and the thickness of the shell layer can not only determine the formation of the surface roughening in a core-shell NW structure, but also control the periodicity and amplitude of the surface roughness. The agreement between the theoretical results and the

  6. QCM and AFM Study of atomic scale polishing and roughening of surfaces exposed to nanoparticle suspensions of diamond, Al2O3 and SiO2.

    Science.gov (United States)

    Krim, Jacqueline; Acharya, Biplav; Chestnut, Melanie; Marek, Antonin; Shendarova, Olga; Smirnov, Alex

    The addition of nanoparticles to conventional automotive lubricants is known in many cases to result in increased energy efficiency, but the atomic scale mechanisms leading to the increased efficiency are yet to be established. To explore this issue, we studied surface uptake and nanotribological properties of nanoparticle suspensions of diamond, Al2O3 and SiO2 dispersed in water and/or oil (PAO6) in real time by means of an in situ Quartz Crystal Microbalance (QCM) technique, with a focus on the impact of the suspension on the surface roughness and texture of the QCM electrode and how the results compared to macroscopic reductions in friction and increased energy efficiency for the same materials' combinations. The frequency and dissipative properties (mechanical resistance) of QCM's with both gold and nickel surface electrodes were first studied for immersed samples upon addition of the nanoparticles. Nanodiamonds resulted in an increased mechanical resistance while the addition of Al2O3 and SiO2 nanoparticles resulted in a decreased resistance, indicating a reduced resistance of the fluid to the motion of the QCM. Atomic Force Microscope (AFM) measurements were then performed on the QCM electrodes after exposure to the suspensions, to explore potential polishing and/or roughening effects. The results are closely linked to the macroscopic friction and wear attributes. Work supported by NSF.

  7. Thermodynamical and structural properties of solid surfaces in the high temperature range by molecular dynamics solution: evidence for a roughening transition on the F.C.C. {110} surface

    International Nuclear Information System (INIS)

    Rosato, Vittorio

    1986-01-01

    We have studied by Molecular Dynamics simulation the thermodynamical and structural properties of the {110} solid Argon surface as a function of temperature up to T m . The following results have been obtained: 1) the Arrhenius plot indicates that for T> 0.7 T m the defect creation becomes a nearly athermal process. The measured surface diffusion coefficients are very high and are comparable with those observed in the liquid state. 2) the long range order is preserved at least up to T= 0.94 T m . The thermal disorder is related to the onset of a roughening transition on that surface at T ≅ 0.7 T m . Surface layers are not melted in the whole range of temperature we have studied. Furthermore we have investigated the influence of constraints on the surface structure for the same model system previously used at T = 0.48 T m . We have shown that both temperature and constraints induce disorder on surface: for constraints corresponding to elastic deformations of -5 pc applied along the dense axis {110}, the surface structure results to be very similar to that obtained, without constraints, at a higher temperature (T = 0.68 T m ). The implications of our bindings in several areas of Materials Science are briefly discussed. (author) [fr

  8. Making waves: Kinetic processes controlling surface evolution during low energy ion sputtering

    International Nuclear Information System (INIS)

    Chan, W.L.; Chason, Eric

    2007-01-01

    When collimated beams of low energy ions are used to bombard materials, the surface often develops a periodic pattern or ''ripple'' structure. Different types of patterns are observed to develop under different conditions, with characteristic features that depend on the substrate material, the ion beam parameters, and the processing conditions. Because the patterns develop spontaneously, without applying any external mask or template, their formation is the expression of a dynamic balance among fundamental surface kinetic processes, e.g., erosion of material from the surface, ion-induced defect creation, and defect-mediated evolution of the surface morphology. In recent years, a comprehensive picture of the different kinetic mechanisms that control the different types of patterns that form has begun to emerge. In this article, we provide a review of different mechanisms that have been proposed and how they fit together in terms of the kinetic regimes in which they dominate. These are grouped into regions of behavior dominated by the directionality of the ion beam, the crystallinity of the surface, the barriers to surface roughening, and nonlinear effects. In sections devoted to each type of behavior, we relate experimental observations of patterning in these regimes to predictions of continuum models and to computer simulations. A comparison between theory and experiment is used to highlight strengths and weaknesses in our understanding. We also discuss the patterning behavior that falls outside the scope of the current understanding and opportunities for advancement

  9. 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.

  10. Roughness evolution of Si surfaces upon Ar ion erosion

    NARCIS (Netherlands)

    de Rooij-Lohmann, Vita; Kozhevnikov, I. V.; Peverini, L.; Ziegler, E.; Cuerno, R.; F. Bijkerk,; Yakshin, A. E.

    2010-01-01

    We studied the roughness evolution of Si surfaces upon Ar ion erosion in real time. Following the theory of surface kinetic roughening, a model proposed by Majaniemi was used to obtain the value of the dynamic scaling exponent beta from our data. The model was found to explain both the observed

  11. Surface kinetic temperature mapping using satellite spectral data in ...

    African Journals Online (AJOL)

    The result revealed that despite the limited topographic differences of the rift lakes and their proximity, the surface kinetic temperature difference is high, mainly due to groundwater and surface water fluxes. From thermal signature analysis two hot springs below the lake bed of Ziway were discovered. The various hot springs ...

  12. Fundamental Mechanisms of Roughening and Smoothing During Thin Film Deposition

    Energy Technology Data Exchange (ETDEWEB)

    Headrick, Randall [Univ. of Vermont, Burlington, VT (United States)

    2016-03-18

    pulsed nature of the deposition where particles arrive at the growth surface in an interval of a few microseconds. We have observed effects such as transient formation of two dimensional islands on elemental crystalline surfaces. Pulsed deposition may also lead to non-equilibrium phases in some cases, such as the observation anomalously high tetragonality for ferroelectric thin films. All of the results described above feature in-situ synchrotron X-ray scattering as the main experimental method, which has become an indispensable technique for observing the kinetics of structures forming in real-time. We have also investigated in-situ coherent X-ray scattering and have developed methods to characterize temporal correlations that are not possible to observe with low-coherence X-rays. A high profile result of this work is a new technique to monitor defect propagation velocities in thin films. This has practical significance since defects limit the properties of thin films and it is desirable to understand their properties and origin in order to control them for practical applications. More broadly, amorphous thin films and multilayers have applications in optical devices, including mirrors and filters. Epitaxial thin films and multilayers have applications in electronic devices such as ferroelectric multilayers for non-volatile data storage, and thermoelectric nanostructures for energy conversion. Our progress in this project points the way for improved deposition methods and for improved simulation and modeling of thin film deposition processes for nanoscale control of materials with novel applications in these areas.

  13. Kinetics of Microstructure Evolution during Gaseous Thermochemical Surface Treatment

    DEFF Research Database (Denmark)

    Somers, Marcel A.J.; Christiansen, Thomas

    2005-01-01

    ) precipitation of alloying element nitrides/carbides or by the development of a continuous layer of iron-based (carbo-) nitrides. The evolution of the microstructure during thermochemical treatments is not only determined by solid state diffusion, but in many cases also by the kinetics of the surface reactions...

  14. Oxygen surface exchange kinetics of erbia-stabilized bismuth oxide

    NARCIS (Netherlands)

    Yoo, C.-Y.; Boukamp, Bernard A.; Bouwmeester, Henricus J.M.

    2011-01-01

    The surface oxygen exchange kinetics of bismuth oxide stabilized with 25 mol% erbia (BE25) has been studied in the temperature and pO2 ranges 773–1,023 K and 0.1– 0.95 atm, respectively, using pulse-response 18O–16O isotope exchange measurements. The results indicate that BE25 exhibits a

  15. Thin film growth by 3D multi-particle diffusion limited aggregation model: Anomalous roughening and fractal analysis

    Science.gov (United States)

    Nasehnejad, Maryam; Nabiyouni, G.; Gholipour Shahraki, Mehran

    2018-03-01

    In this study a 3D multi-particle diffusion limited aggregation method is employed to simulate growth of rough surfaces with fractal behavior in electrodeposition process. A deposition model is used in which the radial motion of the particles with probability P, competes with random motions with probability 1 - P. Thin films growth is simulated for different values of probability P (related to the electric field) and thickness of the layer(related to the number of deposited particles). The influence of these parameters on morphology, kinetic of roughening and the fractal dimension of the simulated surfaces has been investigated. The results show that the surface roughness increases with increasing the deposition time and scaling exponents exhibit a complex behavior which is called as anomalous scaling. It seems that in electrodeposition process, radial motion of the particles toward the growing seeds may be an important mechanism leading to anomalous scaling. The results also indicate that the larger values of probability P, results in smoother topography with more densely packed structure. We have suggested a dynamic scaling ansatz for interface width has a function of deposition time, scan length and probability. Two different methods are employed to evaluate the fractal dimension of the simulated surfaces which are "cube counting" and "roughness" methods. The results of both methods show that by increasing the probability P or decreasing the deposition time, the fractal dimension of the simulated surfaces is increased. All gained values for fractal dimensions are close to 2.5 in the diffusion limited aggregation model.

  16. Surfaces of Microparticles in Colloids: Structure and Molecular Adsorption Kinetics

    Science.gov (United States)

    Dai, Hai-Lung

    2002-03-01

    Surfaces of micron and sub-micron size particles in liquid solution are probed by second harmonic generation (SHG) facilitated with femtosecond laser pulses. The particles probed include inorganic objects such as carbon black and color pigments, polymeric species like polystyrene beads, and biological systems such as blood cells and ecoli. In the experiments, dye molecules are first adsorbed onto the particle surface to allow generation of second harmonics upon light irradiation. Competition for adsorption between these surface dye molecules and the molecules of interest in the solution is then monitored by the SHG signal to reveal the molecular adsorption kinetics and surface structure. Specifically, surfactant adsorption on polymer surfaces, the structure of carbon black surface, and protein adsorption on biological surfaces, monitored by this technique, will be discussed.

  17. Kinetic computer modeling of microwave surface-wave plasma production

    International Nuclear Information System (INIS)

    Ganachev, Ivan P.

    2004-01-01

    Kinetic computer plasma modeling occupies an intermediate position between the time consuming rigorous particle dynamic simulation and the fast but rather rough cold- or warm-plasma fluid models. The present paper reviews the kinetic modeling of microwave surface-wave discharges with accent on recent kinetic self-consistent models, where the external input parameters are reduced to the necessary minimum (frequency and intensity of the applied microwave field and pressure and geometry of the discharge vessel). The presentation is limited to low pressures, so that Boltzmann equation is solved in non-local approximation and collisional electron heating is neglected. The numerical results reproduce correctly the bi-Maxwellian electron energy distribution functions observed experimentally. (author)

  18. Kinetics of enzyme action on surface-attached substrates: a practical guide to progress curve analysis in any kinetic situation.

    Science.gov (United States)

    Anne, Agnès; Demaille, Christophe

    2012-10-16

    In the present work, exact kinetic equations describing the action of an enzyme in solution on a substrate attached to a surface have been derived in the framework of the Michaelis-Menten mechanism but without resorting to the often-used steady-state approximation. The here-derived kinetic equations are cast in a workable format, allowing us to introduce a simple and universal procedure for the quantitative analysis of enzyme surface kinetics that is valid for any kinetic situation. The results presented here should allow experimentalists studying the kinetics of enzyme action on immobilized substrates to analyze their data in a perfectly rigorous way.

  19. Kinetics and thermodynamics of Si(111) surface nitridation in ammonia

    Science.gov (United States)

    Mansurov, Vladimir G.; Malin, Timur V.; Galitsyn, Yurij G.; Shklyaev, Alexander A.; Zhuravlev, Konstantin S.

    2016-05-01

    Kinetics and thermodynamics of Si(111) surface nitridation under an ammonia flux at different substrate temperatures are investigated by reflection high-energy electron diffraction. Two different stages of the nitridation process were revealed. The initial stage is the fast (within few seconds) formation of ordered two-dimensional SiN phase, occuring due to the topmost active surface Si atom (Sisurf) interaction with ammonia molecules. It is followed by the late stage consisting in the slow (within few minutes) amorphous Si3N4 phase formation as a result of the interaction of Si atoms in the lattice site (Siinc) with chemisorbed ammonia molecules. It was found that the ordered SiN phase formation rate decreases, as the temperature increases. The kinetic model of the initial stage was developed, in which the ordered SiN phase formation is the two-dimensional phase transition in the lattice gas with SiN cells. The enthalpy of the active surface Si atom generation on the clean Si(111) surface was estimated to be about 1.5 eV. In contrast, the amorphous Si3N4 phase formation is the normal (thermally activated) chemical process with the first-order kinetics, whose activation energy and pre-exponential factor are 2.4 eV and 108 1/s, respectively.

  20. Wetting kinetics of oil mixtures on fluorinated model cellulose surfaces.

    Science.gov (United States)

    Aulin, Christian; Shchukarev, Andrei; Lindqvist, Josefina; Malmström, Eva; Wågberg, Lars; Lindström, Tom

    2008-01-15

    The wetting of two different model cellulose surfaces has been studied; a regenerated cellulose (RG) surface prepared by spin-coating, and a novel multilayer film of poly(ethyleneimine) and a carboxymethylated microfibrillated cellulose (MFC). The cellulose films were characterized in detail using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). AFM indicates smooth and continuous films on a nanometer scale and the RMS roughness of the RG cellulose and MFC surfaces was determined to be 3 and 6 nm, respectively. The cellulose films were modified by coating with various amounts of an anionic fluorosurfactant, perfluorooctadecanoic acid, or covalently modified with pentadecafluorooctanyl chloride. The fluorinated cellulose films were used to follow the spreading mechanisms of three different oil mixtures. The viscosity and surface tension of the oils were found to be essential parameters governing the spreading kinetics on these surfaces. XPS and dispersive surface energy measurements were made on the cellulose films coated with perfluorooctadecanoic acid. A strong correlation was found between the surface concentration of fluorine, the dispersive surface energy and the contact angle of castor oil on the surface. A dispersive surface energy less than 18 mN/m was required in order for the cellulose surface to be non-wetting (theta e>90 degrees ) by castor oil.

  1. Kinetics of Microstructure Evolution during Gaseous Thermochecical Surface Treatment

    DEFF Research Database (Denmark)

    Somers, Marcel A.J.; Christiansen, Thomas

    2005-01-01

    The incorporation of nitrogen or carbon in steel is widely applied to provide major improvements in-materials performance with respect to fatigue, weaif tribology, and atmospheric corrosion. These improvements rely on a modification of the surface-adjacent region of the materiat by tl.re (internalf...... precipitation 6f ailoying element nitrides/carbides"or by thE development of a continuo_us laye_r of iron-based (carbo-) nitrides. The evolution of the microstructure during thermochemical treatme_nts is not only determined by solid-state diffusion, but in many cases also by the kinetics of the surface...

  2. Lateral interactions and non-equilibrium in surface kinetics

    Science.gov (United States)

    Menzel, Dietrich

    2016-08-01

    Work modelling reactions between surface species frequently use Langmuir kinetics, assuming that the layer is in internal equilibrium, and that the chemical potential of adsorbates corresponds to that of an ideal gas. Coverage dependences of reacting species and of site blocking are usually treated with simple power law coverage dependences (linear in the simplest case), neglecting that lateral interactions are strong in adsorbate and co-adsorbate layers which may influence kinetics considerably. My research group has in the past investigated many co-adsorbate systems and simple reactions in them. We have collected a number of examples where strong deviations from simple coverage dependences exist, in blocking, promoting, and selecting reactions. Interactions can range from those between next neighbors to larger distances, and can be quite complex. In addition, internal equilibrium in the layer as well as equilibrium distributions over product degrees of freedom can be violated. The latter effect leads to non-equipartition of energy over molecular degrees of freedom (for products) or non-equal response to those of reactants. While such behavior can usually be described by dynamic or kinetic models, the deeper reasons require detailed theoretical analysis. Here, a selection of such cases is reviewed to exemplify these points.

  3. Kinetics of conformational changes of fibronectin adsorbed onto model surfaces.

    Science.gov (United States)

    Baujard-Lamotte, L; Noinville, S; Goubard, F; Marque, P; Pauthe, E

    2008-05-01

    Fibronectin (FN), a large glycoprotein found in body fluids and in the extracellular matrix, plays a key role in numerous cellular behaviours. We investigate FN adsorption onto hydrophilic bare silica and hydrophobic polystyrene (PS) surfaces using Fourier transform infrared spectroscopy-attenuated total reflection (FTIR-ATR) in aqueous medium. Adsorption kinetics using different bulk concentrations of FN were followed for 2h and the surface density of adsorbed FN and its time-dependent conformational changes were determined. When adsorption occurs onto the hydrophilic surface, FN molecules keep their native conformation independent of the adsorption conditions, but the amount of adsorbed FN increases with time and the bulk concentration. Although the protein surface density is the same on the hydrophobic PS surface, this has a strong impact on the average conformation of the adsorbed FN layer. Indeed, interfacial hydration changes induced by adsorption onto the hydrophobic surface lead to a decrease in unhydrated beta-sheet content and cause an increase in hydrated beta-strand and hydrated random domain content of adsorbed FN. This conformational change is mainly dependent on the bulk concentration. Indeed, at low bulk concentrations, the secondary structures of adsorbed FN molecules undergo strong unfolding, allowing an extended and hydrated conformation of the protein. At high bulk concentrations, the molecular packing reduces the unfolding of the stereoregular structures of the FN molecules, preventing stronger spreading of the protein.

  4. Self-organization of decaying surface corrugations: a numerical study.

    Science.gov (United States)

    Bonito, Andrea; Nochetto, Ricardo H; Quah, John; Margetis, Dionisios

    2009-05-01

    We study numerically the interplay of surface topography and kinetics in the relaxation of crystal surface corrugations below roughening in two independent space dimensions. The kinetic processes are isotropic diffusion of adatoms across terraces and attachment-detachment of atoms at steps. We simulate the corresponding anisotropic partial differential equation for the surface height via the finite element method. The numerical results show a sharp transition from initially biperiodic surface profiles to one-dimensional surface morphologies. This transition is found to be enhanced by an applied electric field. Our predictions demonstrate the dramatic influence on morphological relaxation of geometry-induced asymmetries in the adatom fluxes transverse and parallel to step edges.

  5. Retrieved Magnesia-Stabilized Zirconia Femoral Heads Exhibit Minimal Roughening and Abrasive Potential.

    Science.gov (United States)

    Roy, Marie E; Whiteside, Leo A; Sebastian, Arun M

    2017-12-01

    The degradation of ceramic femoral heads made of yttria-stabilized zirconia (Y-TZP) because of tetragonal-to-monoclinic phase transformation in vivo is well-described, whereas magnesia-stabilized zirconia (Mg-PSZ) ceramics resist phase transformation in a warm aqueous environment. The purpose of this study was to evaluate phase transformation, changes in surface topography, and roughness parameters, including changes in surface polarity and abrasiveness, among retrieved zirconia femoral heads. A total of 69 Y-TZP and 86 Mg-PSZ-retrieved femoral heads were examined, with 5 never-implanted heads of each type as controls. Selected heads were scanned by x-ray diffraction, to measure % monoclinic phase. All heads were scanned by optical profilometry to find visual evidence of degradation and to measure surface roughness, surface polarity, and the functional roughness parameters. Monoclinic phase % and roughness data were plotted vs time in vivo. Visual evidence of phase transformation was observed among Y-TZP femoral heads, and some exhibited pitting. Y-TZP femoral heads roughened and become more abrasive in vivo, although those made by CeramTec exhibited less degradation than those by Morgan and Saint Gobain. In contrast, Mg-PSZ heads did not exhibit pitting, undergo phase transformation, or roughen in vivo, and retained a negative surface polarity. All Y-TZP femoral heads exhibited increased phase transformation with time in vivo, although not all Y-TZP heads exhibited catastrophic roughening. No phase transformation was observed on Mg-PSZ femoral heads after up to 19.2 years in vivo. The lack of degradation among Mg-PSZ retrievals suggests a lower wear potential in joint replacement. Copyright © 2017 Elsevier Inc. All rights reserved.

  6. Heat transfer augmentation for high heat flux removal in rib-roughened narrow channels

    International Nuclear Information System (INIS)

    Islam, M.S.; Hino, Ryutaro; Haga, Katsuhiro; Sudo, Yukio; Monde, Masanori.

    1997-03-01

    Heat transfer augmentation in narrow rectangular channels in a target system is a very important method to remove high heat flux up to 12 MW/m 2 generated at target plates of a high-intensity proton accelerator of 1.5 GeV and 1 mA with a proton beam power of 1.5 MW. In this report, heat transfer coefficients and friction factors in narrow rectangular channels with one-sided rib-roughened surface were evaluated for fully developed flows in the range of the Reynolds number from 6,000 to 1,00,000; the rib pitch-to-height ratios (p/k) were 10,20 and 30; the rib height-to-equivalent diameter ratios (k/De) were 0.025, 0.03 and 0.1 by means of previous existing experimental correlations. The rib-roughened surface augmented heat transfer coefficients approximately 4 times higher than the smooth surface at Re=10,000, p/k=10 and k/De=0.1; friction factors increase around 22 times higher. In this case, higher heat flux up to 12 MW/m 2 could be removed from the rib-roughened surface without flow boiling which induces flow instability; but pressure drop reaches about 1.8 MPa. Correlations obtained by air-flow experiments have showed lower heat transfer performance with the water-flow conditions. The experimental apparatus was proposed for further investigation on heat transfer augmentation in very narrow channels under water-flow conditions. This report presents the evaluation results and an outline of the test apparatus. (author)

  7. Hydrocarbon decomposition kinetics on the Ir(111) surface.

    Science.gov (United States)

    Tetlow, H; Curcio, D; Baraldi, A; Kantorovich, L

    2018-02-28

    The kinetics of the thermal decomposition of hydrocarbons on the Ir(111) surface is determined using kinetic Monte Carlo (kMC) and rate equations simulations, both based on the density functional theory (DFT) calculated energy barriers of the involved reaction processes. This decomposition process is important for understanding the early stages of epitaxial graphene growth where the deposited hydrocarbon acts as a carbon feedstock for graphene formation. The methodology of the kMC simulations and the rate equation approaches is discussed and a comparison between the results obtained from both approaches is made in the case of the temperature programmed decomposition of ethylene for different initial coverages. The theoretical results are verified against experimental data from in situ X-ray photoelectron spectroscopy (XPS) experiments. Both theoretical approaches give reasonable results; however we find that, as expected, rate equations are less reliable at high coverages. We find that the agreement between experiment and theory can be improved in all cases if slight adjustments are made to the energy barriers in order to account for the intrinsic errors in DFT. Finally we extend our approach to the case where hydrocarbon species are dosed onto the substrate continuously, as in the chemical vapour deposition (CVD) graphene growth method. For ethylene and methane the thermal decomposition mechanism is determined, and it is found that in both cases the formation of C monomers is to be expected, which is limited by the presence of hydrogen atoms.

  8. Kinetics of hydrogen evolution lon strained iron surface

    International Nuclear Information System (INIS)

    Dikij, I.I.; Protsiv, I.M.

    1994-01-01

    The influence of the degree of plastic deformation on overstrain of hydrogen evolution on the surface of armco iron from 3 % NaCl solution with pH=2, pH=7 was studied. It is shown that plastic deformation decreases overstrain of hydrogen evolution. At low densities of the polarizing current plastic deformation (δ=15 %) increases the reaction rate 1.6-1.65 fold, whereas at higher densities of current the reaction rate increases 1.65-2 fold. On the basis of the data obtained the regularities of crack propagation rate are explained, making allowance for the effect of plastic deformation of the crack vertex metal on kinetics of hydrogen evolution

  9. Heat transfer in smooth and roughened rod bundles near spacer grids

    International Nuclear Information System (INIS)

    Marek, J.; Rehme, K.

    1975-03-01

    An experimental investigation was performed of the heat transfer in smooth and rough rod bundles near spacer grids. Detailed wall temperature distributions were measured which clearly demonstrated that even in rod bundles roughened by artificial roughnesses there are no hot spots near spacer grids. On the basis of the few experimental results from the literature and the new data, heat transfer correlations are proposed for smooth and rough surfaces near spacer grids. These correlations allow a prediction to be made in a good approximation of the heat transfer near spacer grids as a function of the flow contraction due to the spacer. (orig.) [de

  10. Atomic-scale observation of temperature and pressure driven preroughening and roughening

    International Nuclear Information System (INIS)

    Ding, Z.; Bullock, D.W.; Thibado, P.M.; LaBella, V.P.; Mullen, Kieran

    2003-01-01

    Preroughening and roughening transitions are observed on the GaAs(001) surface using scanning tunneling microscopy. By tuning the substrate temperature or As 4 pressure the surface morphology can be made free of islands, covered with one monolayer high islands or covered with islands on top of islands forming a wedding-cake-type structure. These three distinct surface morphologies are classified as ordered flat (OF), disordered flat (DOF), and rough within the restricted solid-on-solid model. Here, the DOF phase is macroscopically flat; however, an up-down-up-down step pattern persists across the entire surface. Using this model we have determined the next-nearest-neighbor interaction energy to be about 0.05 eV

  11. Near-surface circulation and kinetic energy in the tropical Indian Ocean derived from lagrangian drifters

    Digital Repository Service at National Institute of Oceanography (India)

    Shenoi, S.S.C.; Saji, P.K.; Almeida, A.M.

    Trajectories of 412 satellite-tracked drifting buoys deployed in the tropical Indian Ocean have been analyzed to document the surface circulation and kinetic energy field. Only drifters drogued at 15 m depth and having drag area ratio greater than...

  12. Reaction Kinetic Parameters and Surface Thermodynamic Properties of Cu2O Nanocubes

    Directory of Open Access Journals (Sweden)

    Xingxing Li

    2015-07-01

    Full Text Available Cuprous oxide (Cu2O nanocubes were synthesized by reducing Cu(OH2 in the presence of sodium citrate at room temperature. The samples were characterized in detail by field-emission scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, X-ray powder diffraction, and N2 absorption (BET specific surface area. The equations for acquiring reaction kinetic parameters and surface thermodynamic properties of Cu2O nanocubes were deduced by establishment of the relations between thermodynamic functions of Cu2O nanocubes and these of the bulk Cu2O. Combined with thermochemical cycle, transition state theory, basic theory of chemical thermodynamics, and in situ microcalorimetry, reaction kinetic parameters, specific surface enthalpy, specific surface Gibbs free energy, and specific surface entropy of Cu2O nanocubes were successfully determined. We also introduced a universal route for gaining reaction kinetic parameters and surface thermodynamic properties of nanomaterials.

  13. Extracting surface diffusion coefficients from batch adsorption measurement data: application of the classic Langmuir kinetics model.

    Science.gov (United States)

    Chu, Khim Hoong

    2017-11-09

    Surface diffusion coefficients may be estimated by fitting solutions of a diffusion model to batch kinetic data. For non-linear systems, a numerical solution of the diffusion model's governing equations is generally required. We report here the application of the classic Langmuir kinetics model to extract surface diffusion coefficients from batch kinetic data. The use of the Langmuir kinetics model in lieu of the conventional surface diffusion model allows derivation of an analytical expression. The parameter estimation procedure requires determining the Langmuir rate coefficient from which the pertinent surface diffusion coefficient is calculated. Surface diffusion coefficients within the 10 -9 to 10 -6  cm 2 /s range obtained by fitting the Langmuir kinetics model to experimental kinetic data taken from the literature are found to be consistent with the corresponding values obtained from the traditional surface diffusion model. The virtue of this simplified parameter estimation method is that it reduces the computational complexity as the analytical expression involves only an algebraic equation in closed form which is easily evaluated by spreadsheet computation.

  14. Surface Area, and Oxidation Effects on Nitridation Kinetics of Silicon Powder Compacts

    Science.gov (United States)

    Bhatt, R. T.; Palczer, A. R.

    1998-01-01

    Commercially available silicon powders were wet-attrition-milled from 2 to 48 hr to achieve surface areas (SA's) ranging from 1.3 to 70 sq m/g. The surface area effects on the nitridation kinetics of silicon powder compacts were determined at 1250 or 1350 C for 4 hr. In addition, the influence of nitridation environment, and preoxidation on nitridation kinetics of a silicon powder of high surface area (approximately equals 63 sq m/g) was investigated. As the surface area increased, so did the percentage nitridation after 4 hr in N2 at 1250 or 1350 C. Silicon powders of high surface area (greater than 40 sq m/g) can be nitrided to greater than 70% at 1250 C in 4 hr. The nitridation kinetics of the high-surface-area powder compacts were significantly delayed by preoxidation treatment. Conversely, the nitridation environment had no significant influence on the nitridation kinetics of the same powder. Impurities present in the starting powder, and those accumulated during attrition milling, appeared to react with the silica layer on the surface of silicon particles to form a molten silicate layer, which provided a path for rapid diffusion of nitrogen and enhanced the nitridation kinetics of high surface area silicon powder.

  15. Evolution of kinetically controlled In-induced surface structure on Si(5 5 7) surface

    Energy Technology Data Exchange (ETDEWEB)

    Chauhan, Amit Kumar Singh [Physics of Energy Harvesting, (CSIR-NPL), Dr. K.S. Krishnan Road, New Delhi 110012 (India); Department of Physics, JMI, New Delhi 110025 (India); Eldose, Nirosh M.; Mishra, Monu [Physics of Energy Harvesting, (CSIR-NPL), Dr. K.S. Krishnan Road, New Delhi 110012 (India); Niazi, Asad; Nair, Lekha [Department of Physics, JMI, New Delhi 110025 (India); Gupta, Govind, E-mail: govind@nplindia.org [Physics of Energy Harvesting, (CSIR-NPL), Dr. K.S. Krishnan Road, New Delhi 110012 (India)

    2014-09-30

    Highlights: • Evolution of In induced superstructures on Si(5 5 7) surface during RT and HT adsorption/desorption process. • Kinetics is governed by substrate temperature which exhibits various growth modes (FM, SK, VB) under different conditions. • Strain relaxation play significant role in the commencement of desorption/rearrangement of atoms. • A consolidated phase diagram of In/Si(5 5 7) interface has been reported with new √3 × √3-R30° and 4 × 1 phases. - Abstract: This paper introduces issue of kinetically controlled and temperature driven superstructural phase transition of Indium (In) on atomically clean high index Si(5 5 7)-7 × 1 surface. Auger electron spectroscopy analysis reveals that at room-temperature (RT) with a controlled incident flux of 0.002 ML/s; In overlayers evolve through the Frank-van der Merwe growth mode and yield a (1 × 1) diffraction pattern for coverage ≥1 ML. For substrate temperature <500°C, growth of In follows Stranski–Krastanov growth mode while for temperature >500°C island growth is observed. On annealing the In/Si(5 5 7) interface in the temperature range 250–340°C, clusters to two dimensional (2D) layer transformation on top of a stable monolayer is predominated. In-situ RT and HT adsorption and thermal desorption phenomena revealed the formation of coverage and temperature dependent thermally stable In induced superstructural phases such as (4 × 1) at 0.5 ML (520°C), (√3 × √3-R30°) at 0.3 ML (560°C) and (7 × 7) at 0.1 ML (580°C). These indium induced superstructures could be utilized as potential substrate for the growth of various exotic 1D/2D structures.

  16. Kinetic analysis of IgG antibodies to beta-amyloid oligomers with surface plasmon resonance.

    Science.gov (United States)

    Crisostomo, Amanda C; Dang, Loan; Digambaranath, Jyothi L; Klaver, Andrea C; Loeffler, David A; Payne, Jeremiah J; Smith, Lynnae M; Yokom, Adam L; Finke, John M

    2015-07-15

    Surface plasmon resonance was used to investigate the kinetics, affinity, and specificity of binding between anti-Aβ (beta-amyloid) IgG antibodies and oligomeric Aβ. Two factors were needed to accurately characterize the IgG binding kinetics. First, a bivalent model was necessary to properly fit the kinetic association and dissociation sensograms. Second, a high concentration of IgG was necessary to overcome a significant mass transport limitation that existed regardless of oligomer density on the sensor surface. Using high IgG concentrations and bivalent fits, consistent kinetic parameters were found at varying sensor surface ligand densities. A comparison of binding specificity, affinity, and kinetic flux between monoclonal and natural human anti-Aβ IgG antibodies revealed the following findings. First, monoclonal antibodies 6E10 and 4G8 single-site binding affinity is similar between Aβ oligomers and monomers. Second, natural human anti-Aβ IgG binding readily binds Aβ oligomers but does not bind monomers. Third, natural human anti-Aβ IgG binds Aβ oligomers with a higher affinity and kinetic flux than 6E10 and 4G8. Both the current analytical methodology and antibody binding profiles are important for advances in antibody drug development and kinetic biomarker applications for Alzheimer's disease. Copyright © 2015 Elsevier Inc. All rights reserved.

  17. Measuring the Electrode Kinetics of Surface Confined Electrode Reactions at a Constant Scan Rate

    OpenAIRE

    Guziejewski, Dariusz; Mirceski, Valentin; Jadresko, Dijana

    2014-01-01

    Abstract: The kinetics of surface confined electrode reactions of alizarin, vitamin B12, and vitamin K2 is measured with square-wave voltammetry over a wide pH interval, by applying the recent methodology for kinetic analysis at a constant scan rate [V. Mirceski, D. Guziejewski, K. Lisichkov, Electrochim. Acta 2013, 114, 667–673]. The reliability and the simplicity of the recent methodology is confirmed. The methodology requires analysis of the peak potential separation o...

  18. Controlling roughening processes in the stochastic Kuramoto-Sivashinsky equation

    Science.gov (United States)

    Kalliadasis, Serafim; Gomes, Susana; Papageorgiou, Demetrios; Pavliotis, Greg; Pradas, Marc

    2017-11-01

    We present a novel methodology to control the roughening processes of semilinear parabolic stochastic partial differential equations in one dimension, which we exemplify with the stochastic Kuramoto-Sivashinsky equation. The original equation is split into a linear stochastic and a nonlinear deterministic equation so that we can apply linear feedback control methods. Our control strategy is then based on two steps: first, stabilize the zero solution of the deterministic part and, second, control the roughness of the stochastic linear equation. We consider both periodic controls and point actuated ones, observing in all cases that the second moment of the solution evolves in time according to a power-law until it saturates at the desired controlled value. Furthermore, our control framework allows us to force the interfaces to have a prescribed shape. We observe from our numerical experiments that our results are valid for different types of nonlinearity (in particular, the Burgers and KPZ ones) as well as white and coloured noise.

  19. Different photolysis kinetics at the surface of frozen freshwater vs. frozen salt solutions

    Directory of Open Access Journals (Sweden)

    T. F. Kahan

    2010-11-01

    Full Text Available Reactions at air-ice interfaces can proceed at very different rates than those in aqueous solution, due to the unique disordered region at the ice surface known as the quasi-liquid layer (QLL . The physical and chemical nature of the surfacial region of ice is greatly affected by solutes such as sodium halide salts. In this work, we studied the effects of sodium chloride and sodium bromide on the photolysis kinetics of harmine, an aromatic organic compound, in aqueous solution and at the surface of frozen salt solutions above the eutectic temperature. In common with other aromatic organic compounds we have studied, harmine photolysis is much faster on ice surfaces than in aqueous solution, but the presence of NaCl or NaBr – which does not affect photolysis kinetics in solution – reduces the photolysis rate on ice. The rate decreases monotonically with increasing salt concentration; at the concentrations found in seawater, harmine photolysis at the surface of frozen salt solutions proceeds at the same rate as in aqueous solution. These results suggest that the brine excluded to the surfaces of frozen salt solutions is a true aqueous solution, and so it may be possible to use aqueous-phase kinetics to predict photolysis rates at sea ice surfaces. This is in marked contrast to the result at the surface of frozen freshwater samples, where reaction kinetics are often not well-described by aqueous-phase processes.

  20. Evolution of kinetically controlled In-induced surface structure on Si(5 5 7) surface

    Science.gov (United States)

    Chauhan, Amit Kumar Singh; Eldose, Nirosh M.; Mishra, Monu; Niazi, Asad; Nair, Lekha; Gupta, Govind

    2014-09-01

    This paper introduces issue of kinetically controlled and temperature driven superstructural phase transition of Indium (In) on atomically clean high index Si(5 5 7)-7 × 1 surface. Auger electron spectroscopy analysis reveals that at room-temperature (RT) with a controlled incident flux of 0.002 ML/s; In overlayers evolve through the Frank-van der Merwe growth mode and yield a (1 × 1) diffraction pattern for coverage ≥1 ML. For substrate temperature 500 °C island growth is observed. On annealing the In/Si(5 5 7) interface in the temperature range 250-340 °C, clusters to two dimensional (2D) layer transformation on top of a stable monolayer is predominated. In-situ RT and HT adsorption and thermal desorption phenomena revealed the formation of coverage and temperature dependent thermally stable In induced superstructural phases such as (4 × 1) at 0.5 ML (520 °C), (√3 × √3-R30°) at 0.3 ML (560 °C) and (7 × 7) at 0.1 ML (580 °C). These indium induced superstructures could be utilized as potential substrate for the growth of various exotic 1D/2D structures.

  1. 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.

  2. CHEMICAL REACTIONS ON ADSORBING SURFACE: KINETIC LEVEL OF DESCRIPTION

    Directory of Open Access Journals (Sweden)

    P.P.Kostrobii

    2003-01-01

    Full Text Available Based on the effective Hubbard model we suggest a statistical description of reaction-diffusion processes for bimolecular chemical reactions of gas particles adsorbed on the metallic surface. The system of transport equations for description of particles diffusion as well as reactions is obtained. We carry out the analysis of the contributions of all physical processes to the formation of diffusion coefficients and chemical reactions constants.

  3. A New Approach to Simulate the Kinetics of Metal Desorption from Mineral Surfaces

    Science.gov (United States)

    Tinnacher, R. M.; Powell, B. A.; Kersting, A. B.; Zavarin, M.

    2010-12-01

    The relevance of colloid-facilitated metal transport is largely dependent on metal sorption/desorption kinetics and the degree of reversibility of metal surface binding. Thus, transport predictions need to incorporate modeling concepts that can simulate time- and history-dependent surface processes on the microscale. In this study, we characterized the sorption and desorption kinetics of neptunium(V) reactions on goethite in a flow-cell experiment. Modeling was used to evaluate differences between sorption and desorption kinetics in terms of aging, hysteresis, and ‘irreversible’ sorption. First, aging represents a series of surface-chemical processes on the microscale that lead to changes in contaminant surface speciation over time. Second, hysteresis effects indicate fundamental, chemical differences in the microscopic pathways of reactions for net sorption and desorption processes. Both phenomena may result in a sorbed contaminant fraction that is not readily available for exchange with the solution phase (apparent irreversible sorption). Most currently available kinetic sorption/desorption models incorporate fundamental changes in adsorption and desorption behavior indirectly, e.g., by postulating surface sites with different kinetic rates or ‘irreversible’ sorption behavior. We propose a new approach that allows for the specific incorporation of changes in overall reaction pathways for (ad)sorption and desorption processes. Based on experimental results, observed rates for Np(V) desorption from goethite are substantially slower than for (ad)sorption processes. Differences in metal sorption and desorption kinetics can be simulated with a minimum number of fitting parameters by combining isotherm-based sorption rate laws with a modeling concept related to transition state theory (TST). This concept is based on the assumption that changes in reaction pathways for (ad)sorption and desorption processes lead to differences in overall driving forces and

  4. Surface properties, solubility and dissolution kinetics of bamboo phytoliths

    Science.gov (United States)

    Fraysse, Fabrice; Pokrovsky, Oleg S.; Schott, Jacques; Meunier, Jean-Dominique

    2006-04-01

    Although phytoliths, constituted mainly by micrometric opal, exhibit an important control on silicon cycle in superficial continental environments, their thermodynamic properties and reactivity in aqueous solution are still poorly known. In this work, we determined the solubility and dissolution rates of bamboo phytoliths collected in the Réunion Island and characterized their surface properties via electrophoretic measurements and potentiometric titrations in a wide range of pH. The solubility product of "soil" phytoliths ( pKsp0=2.74 at 25 °C) is equal to that of vitreous silica and is 17 times higher than that of quartz. Similarly, the enthalpy of phytoliths dissolution reaction (ΔHr25-80°C=10.85kJ/mol) is close to that of amorphous silica but is significantly lower than the enthalpy of quartz dissolution. Electrophoretic measurements yield isoelectric point pH IEP = 1.2 ± 0.1 and 2.5 ± 0.2 for "soil" (native) and "heated" (450 °C heating to remove organic matter) phytoliths, respectively. Surface acid-base titrations allowed generation of a 2-p K surface complexation model. Phytoliths dissolution rates, measured in mixed-flow reactors at far from equilibrium conditions at 2 ⩽ pH ⩽ 12, were found to be intermediate between those of quartz and vitreous silica. The dissolution rate dependence on pH was modeled within the concept of surface coordination theory using the equation: R=k1·{>SiOH2+}n+k2·{>SiOH0}+k3·{>SiO-}m, where {> i} stands for the concentration of the surface species present at the SiO 2-H 2O interface, ki are the rate constants of the three parallel reactions and n and m represent the order of the proton- and hydroxy-promoted reactions, respectively. It follows from the results of this study that phytoliths dissolution rates exhibit a minimum at pH ˜ 3. This can explain their good preservation in the acidic soil horizons of Réunion Island. In terms of silicon biogeochemical cycle, phytoliths represent a large buffering reservoir

  5. Adsorption of nonionic surfactants on cellulose surfaces : adsorbed amounts and kinetics

    NARCIS (Netherlands)

    Torn, L.H.; Koopal, L.K.; Keizer, de A.; Lyklema, J.

    2005-01-01

    Kinetic and equilibrium aspects of three different poly(ethylene oxide) alkylethers (C12E5, C12E7, C14E7) near a flat cellulose surface are studied. The equilibrium adsorption isotherms look very similar for these surfactants, each showing three different regions with increasing surfactant

  6. Study of Asorption Kinetics of Surfactants onto Polyethersulfone Membrane Surface Using QCM-D

    Science.gov (United States)

    The adsorption kinetics of surfactants onto the crystal surface spin-coated with a thin layer of a model membrane material, polyethersulfone was monitored through measurements of frequency and dissipation shifts simultaneously using a quartz crystal microbalance with dissipation (QCM-D) device. In ...

  7. Surface Stability and Growth Kinetics of Compound Semiconductors: An Ab Initio-Based Approach

    Directory of Open Access Journals (Sweden)

    Takashi Nakayama

    2013-08-01

    Full Text Available We review the surface stability and growth kinetics of III-V and III-nitride semiconductors. The theoretical approach used in these studies is based on ab initio calculations and includes gas-phase free energy. With this method, we can investigate the influence of growth conditions, such as partial pressure and temperature, on the surface stability and growth kinetics. First, we examine the feasibility of this approach by comparing calculated surface phase diagrams of GaAs(001 with experimental results. In addition, the Ga diffusion length on GaAs(001 during molecular beam epitaxy is discussed. Next, this approach is systematically applied to the reconstruction, adsorption and incorporation on various nitride semiconductor surfaces. The calculated results for nitride semiconductor surface reconstructions with polar, nonpolar, and semipolar orientations suggest that adlayer reconstructions generally appear on the polar and the semipolar surfaces. However, the stable ideal surface without adsorption is found on the nonpolar surfaces because the ideal surface satisfies the electron counting rule. Finally, the stability of hydrogen and the incorporation mechanisms of Mg and C during metalorganic vapor phase epitaxy are discussed.

  8. Effect of microwave-assisted heating on chalcopyrite leaching of kinetics, interface temperature and surface energy

    Directory of Open Access Journals (Sweden)

    Tong Wen

    Full Text Available The microwave-assisted leaching was a new approach to intensify the copper recovery from chalcopyrite by hydrometallurgy. In this work, the effect of microwave-assisted heating on chalcopyrite leaching of kinetics, interfacial reaction temperature and surface energy were investigated. The activation energy of chalcopyrite leaching was affected indistinctively by the microwave-assisted heating (39.1 kJ/mol compared with the conventional heating (43.9 kJ/mol. However, the boiling point of the leaching system increased through microwave-assisted heating. Because of the improved boiling point and the selective heating of microwave, the interfacial reaction temperature increased significantly, which gave rise to the increase of the leaching recovery of copper. Moreover, the surface energy of the chalcopyrite through microwave-assisted heating was also enhanced, which was beneficial to strengthen the leaching of chalcopyrite. Keywords: Microwave-assisted heating, Chalcopyrite, Leaching kinetics, Interface temperature, Surface energy

  9. Influence of radioactivity on surface charging and aggregation kinetics of particles in the atmosphere.

    Science.gov (United States)

    Kim, Yong-Ha; Yiacoumi, Sotira; Lee, Ida; McFarlane, Joanna; Tsouris, Costas

    2014-01-01

    Radioactivity can influence surface interactions, but its effects on particle aggregation kinetics have not been included in transport modeling of radioactive particles. In this research, experimental and theoretical studies have been performed to investigate the influence of radioactivity on surface charging and aggregation kinetics of radioactive particles in the atmosphere. Radioactivity-induced charging mechanisms have been investigated at the microscopic level, and heterogeneous surface potential caused by radioactivity is reported. The radioactivity-induced surface charging is highly influenced by several parameters, such as rate and type of radioactive decay. A population balance model, including interparticle forces, has been employed to study the effects of radioactivity on particle aggregation kinetics in air. It has been found that radioactivity can hinder aggregation of particles because of similar surface charging caused by the decay process. Experimental and theoretical studies provide useful insights into the understanding of transport characteristics of radioactive particles emitted from severe nuclear events, such as the recent accident of Fukushima or deliberate explosions of radiological devices.

  10. Kinetic Monte Carlo simulation of surface segregation in Pd–Cu alloys

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Feng [Institute of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Key Laboratory of Mesoscopic Chemistry of MOE, Nanjing University (China); He, Xiang [Nanjing Institute of Geography and Limnology, Chinese Academy of Sciences, Nanjing 210008 (China); Chen, Zhao-Xu, E-mail: zxchen@nju.edu.cn [Institute of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Key Laboratory of Mesoscopic Chemistry of MOE, Nanjing University (China); Huang, Yu-Gai [Institute of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Key Laboratory of Mesoscopic Chemistry of MOE, Nanjing University (China); JiangSu Second Normal University, Nanjing (China)

    2015-11-05

    The knowledge of surface composition and atomic arrangement is prerequisite for understanding of catalytic properties of an alloy catalyst. Gaining such knowledge is rather difficult, especially for those possessing surface segregation. Pd–Cu alloy is used in many fields and possesses surface segregation. In this paper kinetic Monte Carlo method is used to explore the surface composition and structure and to examine the effects of bulk composition and temperature on the surface segregation of Pd–Cu alloys. It is shown that the segregation basically completes within 900 s at 500 K. Below 900 K and within 20 min the enriched surface Cu atoms mainly come from the top five layers. For the first time we demonstrate that there exists a “bulk-inside flocking” or clustering phenomenon (the same component element congregates in bulk) in Pd–Cu alloys. Our results indicate that for alloys with higher Cu content there are small Pd ensembles like monomers, dimers and trimers with contiguous subsurface Pd atoms. - Highlights: • Kinetic Monte Carlo was first used to study surface segregation of Pd–Cu alloys. • Bulk-inside flocking (the same component element congregates in bulk) was observed. • Small Pd ensembles with contiguous subsurface Pd exist on surfaces of Cu-rich alloys.

  11. Kinetic Monte Carlo simulation of surface segregation in Pd–Cu alloys

    International Nuclear Information System (INIS)

    Cheng, Feng; He, Xiang; Chen, Zhao-Xu; Huang, Yu-Gai

    2015-01-01

    The knowledge of surface composition and atomic arrangement is prerequisite for understanding of catalytic properties of an alloy catalyst. Gaining such knowledge is rather difficult, especially for those possessing surface segregation. Pd–Cu alloy is used in many fields and possesses surface segregation. In this paper kinetic Monte Carlo method is used to explore the surface composition and structure and to examine the effects of bulk composition and temperature on the surface segregation of Pd–Cu alloys. It is shown that the segregation basically completes within 900 s at 500 K. Below 900 K and within 20 min the enriched surface Cu atoms mainly come from the top five layers. For the first time we demonstrate that there exists a “bulk-inside flocking” or clustering phenomenon (the same component element congregates in bulk) in Pd–Cu alloys. Our results indicate that for alloys with higher Cu content there are small Pd ensembles like monomers, dimers and trimers with contiguous subsurface Pd atoms. - Highlights: • Kinetic Monte Carlo was first used to study surface segregation of Pd–Cu alloys. • Bulk-inside flocking (the same component element congregates in bulk) was observed. • Small Pd ensembles with contiguous subsurface Pd exist on surfaces of Cu-rich alloys

  12. Plasma surface functionalization and dyeing kinetics of Pan-Pmma copolymers

    OpenAIRE

    Labay, C.; Canal, C.; Rodríguez, C.; Caballero, G.; Canal, J.M.

    2013-01-01

    Fiber surface modification with air corona plasma has been studied through dyeing kinetics under isothermal conditions at 30 °C on an acrylic-fiber fabric with a cationic dye (CI Basic Blue 3) analyzing the absorption, desorption and fixing on the surface of molecules having defined cationic character. The initial dyeing rate in the first 60 s indicates an increase of 58.3% in the dyeing rate due to the effect of corona plasma on the acrylic fiber surface. At the end of the dyeing process...

  13. Evaluation of the effects of different sand particles that used in dental implant roughened for osseointegration.

    Science.gov (United States)

    Yurttutan, Mehmet Emre; Keskin, Ahmet

    2018-03-20

    Successful dental implant treatment is directly related to osseointegration. In achieving osseointegration, the surface property of the implant is of great importance. Sandblasting is the most commonly used basic method for modifying the surface. Many companies use different sand particles for surface roughening and claim their sand is the best. This leads clinicians to mix their minds in product selection. In this study, we tried to find the appropriate sand material by working objectively without praising any brand. We believe that the results of the study will help clinicians choose the right dental implant. In this study, machined-surfaced implants and implants sandblasted with Aluminum oxide (Al 2 O 3 ), Titanium dioxide (TiO 2 ) and Silicon dioxide (SiO 2 ) were compared via biomechanical testing. For the study, four 2 year-old sheep, weighing 45 kilograms (kg), were used. Eight implants (Al 2 O 3 , TiO 2 , and SiO 2 sandblasted implants and machined-surfaced implants), each with different surface characteristics, were inserted into the bilateral tibia of each sheep under general anesthesia. Results of the initial Resonance Frequency Analysis (RFA) were recorded just after implant insertion. The sheep were then randomly divided into two groups, each with 2 sheep, to undergo either a 1-month or a 3-month assessment. At the end of the designated evaluation period, RFA and removal torque tests were performed. Although there were no statistically significant differences between the groups, the implants sandblasted with Al 2 O 3 showed a higher Implant Stability Quotient (ISQ) and removal torque value at the end of the 1st and 3rd month. In short, the results of the study demonstrate that Aluminum oxide is superior to other sand particles.

  14. The kinetics of formation and transformation of silver atoms on solid surfaces subjected to ionizing irradiation

    International Nuclear Information System (INIS)

    Popovich, G.M.

    1988-01-01

    The paper discusses the results obtained in ESR-assisted studies of the kinetics of formation and transformation of silver atoms generated by γ-irradiation of silver-containing carriers. Three types of dependences have been established: (1) extreme; (2) saturation curves and (3) step-like. All the kinetic curves display, after a definite period of time, stable concentrations of adsorbed silver atoms per unit of the surface at a given temperature. Depending on the temperature of the experiment, the composition and nature of the carrier, the number of adsorbed silver ions, the irradiation dose and conditions of the experiment, a stable concentration of silver atoms at a given temperature may be equal to, higher or lower than the number of silver atoms measured immediately after γ-irradiation at a temperature of liquid nitrogen. A kinetic scheme is proposed to explain the obtained curves. The model suggests that the silver atoms adsorbed on the surface, as well as those formed after γ-irradiation, are bonded to the surface by various energies, which are related to heterogeneity of the carrier surface. (author)

  15. Use of molecular beams for kinetic measurements of chemical reactions on solid surfaces

    Science.gov (United States)

    Zaera, Francisco

    2017-05-01

    In this review we survey the contributions that molecular beam experiments have provided to our understanding of the dynamics and kinetics of chemical interactions of gas molecules with solid surfaces. First, we describe the experimental details of the different instrumental setups and approaches available for the study of these systems under the ultrahigh vacuum conditions and with the model planar surfaces often used in modern surface-science experiments. Next, a discussion is provided of the most important fundamental aspects of the dynamics of chemical adsorption that have been elucidated with the help of molecular beam experiments, which include the development of potential energy surfaces, the determination of the different channels for energy exchange between the incoming molecules and the surface, the identification of adsorption precursor states, the understanding of dissociative chemisorption, the determination of the contributions of corrugation, steps, and other structural details of the surface to the adsorption process, the effect to molecular steering, the identification of avenues for assisting adsorption, and the molecular details associated with the kinetics of the uptake of adsorbates as a function of coverage. We follow with a summary of the work directed at the determination of kinetic parameters and mechanistic details of surface reactions associated with catalysis, mostly those promoted by late transition metals. This discussion we initiate with an overview of what has been learned about simple bimolecular reactions such as the oxidation of CO and H2 with O2 and the reaction of CO with NO, and continue with the review of the studies of more complex systems such as the oxidation of alcohols, the conversion of organic acids, the hydrogenation and isomerization of olefins, and the oxidative activation of alkanes under conditions of short contact times. Sections 6 and 7 of this review deal with the advances made in the use of molecular beams with

  16. Long term kinetic measurements revealing precision and general performance of surface plasmon resonance biosensors.

    Science.gov (United States)

    Steinicke, Franziska; Oltmann-Norden, Imke; Wätzig, Hermann

    2017-08-01

    This work presents an extensive parameter list that facilitates a survey of biosensor performance using Biacore instruments for kinetic binding studies. Six long term measurements were performed using a strongly interacting antigen-antibody (β2 microglobulin) system. Both Single Cycle Kinetic (SCK) and Multi Cycle Kinetic (MCK) were executed each with five different analyte concentrations. The overall comparison of the long term monitored parameters, like the dissociation constant (K D with approximately 3-6% relative percental standard deviation), the association and dissociation rate constants (k a , k d ), the analyte binding capacity (R max ), chi 2 and the sum of the absolute values of the residuals, revealed the delicate factors that make the system performance vulnerable. The main influential factors on kinetic performance were the regeneration conditions, the quality of the sensor surface, the usage time and alteration of the sensor surface, the dilution series and the number of run cycles (about 250-600 per chip). Moreover the direct comparison of MCK and SCK uncovered distinct differences in the accuracy of the K D values. The study of sensor chips from two manufacturers showed distinct differences in the precision of the data. Using control charts for the surveillance of these parameters contributes to an overall better system performance. Copyright © 2017 Elsevier Inc. All rights reserved.

  17. Measuring binding kinetics of aromatic thiolated molecules with nanoparticles via surface-enhanced Raman spectroscopy

    Science.gov (United States)

    Devetter, Brent M.; Mukherjee, Prabuddha; Murphy, Catherine J.; Bhargava, Rohit

    2015-05-01

    Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this study, we report the development of surface-enhanced Raman spectroscopy (SERS) as a method to monitor the kinetics of gold-thiolate bond formation on colloidal gold nanoparticles. A theoretical model combining SERS enhancement with the Beer-Lambert law is proposed to explain ensemble scattering and absorption effects in colloids during chemisorption. In order to maximize biological relevance and signal reproducibility, experiments used to validate the model focused on maintaining nanoparticle stability after the addition of water-soluble aromatic thiolated molecules. Our results indicate that ligand exchange on gold nanoparticles follow a first-order Langmuir adsorption model with rate constants on the order of 0.01 min-1. This study demonstrates an experimental spectroscopic method and theoretical model for monitoring binding kinetics that may prove useful for designing novel probes.Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this

  18. Final Report: Mechanisms of sputter ripple formation: coupling among energetic ions, surface kinetics, stress and composition

    Energy Technology Data Exchange (ETDEWEB)

    Chason, Eric; Shenoy, Vivek

    2013-01-22

    Self-organized pattern formation enables the creation of nanoscale surface structures over large areas based on fundamental physical processes rather than an applied template. Low energy ion bombardment is one such method that induces the spontaneous formation of a wide variety of interesting morphological features (e.g., sputter ripples and/or quantum dots). This program focused on the processes controlling sputter ripple formation and the kinetics controlling the evolution of surfaces and nanostructures in high flux environments. This was done by using systematic, quantitative experiments to measure ripple formation under a variety of processing conditions coupled with modeling to interpret the results.

  19. In situ studies of the kinetics of surface topography development during ion irradiation

    International Nuclear Information System (INIS)

    Levinskas, R.; Pranevicius, L.

    1996-01-01

    Studies of the mechanical properties of the materials affected by 25-200 keV H + , He + , Ne + and Ar + ion irradiation in the range of fluences up to 2 · 10 17 cm -2 based on the analysis of acoustic emission signals, kinetics of the surface deformations measured by laser interferometric technique and the variations of the surface acoustic waves propagation velocity are conducted. The acoustic emissions source mechanisms under various ion irradiation conditions are discussed and relative contribution various possible mechanism are indicated. The correlation of experimental results obtained by different methods of analysis is done. (author). 11 refs, 5 figs

  20. Non-equilibrium Thermodynamic Dissolution Theory for Multi-Component Solid/Liquid Surfaces Involving Surface Adsorption and Radiolysis Kinetics

    International Nuclear Information System (INIS)

    Stout, R B

    2001-01-01

    A theoretical expression is developed for the dissolution rate response for multi-component radioactive materials that have surface adsorption kinetics and radiolysis kinetics when wetted by a multi-component aqueous solution. An application for this type of dissolution response is the performance evaluation of multi-component spent nuclear fuels (SNFs) for long term interim storage and for geological disposition. Typically, SNF compositions depend on initial composition, uranium oxide and metal alloys being most common, and on reactor burnup which results in a wide range of fission product and actinide concentrations that decay by alpha, beta, and gamma radiation. These compositional/burnup ranges of SNFs, whether placed in interim storage or emplaced in a geologic repository, will potentially be wetted by multi-component aqueous solutions, and these solutions may be further altered by radiolytic aqueous species due to three radiation fields. The solid states of the SNFs are not thermodynamically stable when wetted and will dissolve, with or without radiolysis. The following development of a dissolution theory is based on a non-equilibrium thermodynamic analysis of energy reactions and energy transport across a solid-liquid phase change discontinuity that propagates at a quasi-steady, dissolution velocity. The integral form of the energy balance equation is used for this spatial surface discontinuity analysis. The integral formulation contains internal energy functional of classical thermodynamics for both the SNFs' solid state and surface adsorption species, and the adjacent liquid state, which includes radiolytic chemical species. The steady-state concentrations of radiolytic chemical species are expressed by an approximate analysis of the decay radiation transport equation. For purposes of illustration a modified Temkin adsorption isotherm was assumed for the surface adsorption kinetics on an arbitrary, finite area of the solid-liquid dissolution interface. For

  1. Cd(II) removal on surface-modified activated carbon: equilibrium, kinetics and mechanism.

    Science.gov (United States)

    Liang, Jianjun; Liu, Meiling; Zhang, Yufei

    2016-10-01

    Commercial pulverous activated carbon (AC-0) was modified through two steps: oxidize AC-0 acid firstly, impregnate it with iron using ferric chloride secondly. Orthogonal experiment was conducted then to prepare modified activated carbon with high Cd(II) adsorption capacity (ACNF). Batch adsorption experiments were undertaken to determine the adsorption characteristics of Cd(II) from aqueous solution onto AC-0 and ACNF and the effect of pH, contact time and initial Cd(II) concentration. The results indicate that: the adsorption behavior of Cd(II) on ACNF can be well fitted with Langmuir model, and the maximum adsorption capacity of ACNF was 2.3 times higher than that of AC-0, supporting a monolayer coverage of Cd(II) on the surface. The kinetics of the adsorption process can be described by pseudo-second-order rate equation very well, and the adsorption capacity increased from 0.810 mg/g to 0.960 mg/g after modification. Compared with AC-0, the kinetic parameters of ACNF showed a higher adsorption rate through the aqueous solution to the solid surface and a lower intraparticle diffusion rate. Surface modification resulted in a lower Brunauer-Emmett-Teller (BET) surface area and pore size because of the collapse and blockage of pores, according to the X-ray diffraction (XRD) analysis, while the total number of surface oxygen acid groups increased, and this was supposed to contribute to the enhanced adsorption capacity of modified activated carbon.

  2. Modeling surface disinfection kinetics of fresh tomato (Lycopersicum esculentum using chlorine solutions

    Directory of Open Access Journals (Sweden)

    Miguel Ángel Solano Cornejo

    2013-03-01

    Full Text Available Fresh tomatoes Italian variety were subjected to surface disinfection processes using calcium hypochlorite solutions to determine their germicidal efficiency and kinetics that governs the surface inactivation process in aerobic mesophilic bacteria, yeasts and molds. Chlorine as surface disinfectant was effective against aerobic mesophilic bacteria, yeasts and molds in this order, the resistance of aerobic mesophilic bacteria, yeasts and molds of their values expressed in zchlorine was 455, 500 and 625 ppm respectively. Aerobic mesophilic bacteria present in the tomato surface show a higher resistance to chlorine disinfection according contact time germtomato skin is greater due to a better adherence to the tomato skin making it difficult for the action of chlorine on germs; this effect is not present in the case of yeasts or molds. Experimental Dchlorine 20°C values and Dchlorine_20°C values predicted by the First Bigelow’s Model were fit with a correlation of between 0.91 and 0.99. The experimental zchlorine values and values zchlorine predicted by the Second Bigelow’s Model were adjusted with a correlation of 0.72 to 0.86. The variability in the values zchlorine was because germs analyzed to validate the proposed model were composed of various genera. So, the Bigelow’s Method applied to inactivation kinetics of surface chlorine was validated.

  3. Effect of Ingredient Loading on Surface Migration Kinetics of Additives in Vulcanized Natural Rubber Compounds

    Directory of Open Access Journals (Sweden)

    Bryan B. Pajarito

    2014-12-01

    Full Text Available Surface migration kinetics of chemical additives in vulcanized natural rubber compounds were studied as function of ingredient loading. Rubber sheets were compounded according to a 212-8 fractional factorial design of experiment, where ingredients were treated as factors varied at two levels of loading. Amount of migrated additives in surface of rubber sheets was monitored through time at ambient conditions. The maximum amount and estimated rate of additive migration were determined from weight loss kinetic curves. Attenuated total reflection–Fourier transform infrared (ATR-FTIR spectroscopy and optical microscopy were used to characterize the chemical structure and surface morphology of sheet specimens during additive migration. ANOVA results showed that increased loading of reclaimed rubber, CaCO3, and paraffin wax signif icantly decreased the maximum amount of additive migration; by contrast, increased loading of used oil, asphalt, and mercaptobenzothiazole disulphide (MBTS increased the maximum amount. Increased loading of sulfur, diphenylguanidine (DPG, and paraffin wax significantly decreased the additive migration rate; increased loading of used oil, asphalt, and stearic acid elicited an opposite effect. Comparison of ATRFTIR spectra of migrated and cleaned rubber surfaces showed signif icant variation in intensity of specif ic absorbance bands that are also present in infrared spectra of migrating chemicals. Paraffin wax, used oil, stearic acid, MBTS, asphalt, and zinc stearate were identified to bloom and bleed in the rubber sheets. Optical micrographs of migrated rubber surfaces revealed formation of white precipitates due to blooming and of semi-transparent wet patches due to bleeding.

  4. Kinetic analysis of inhibition of glucoamylase and active site mutants via chemoselective oxime immobilization of acarbose on SPR chip surfaces

    DEFF Research Database (Denmark)

    Sauer, Jørgen; Abou Hachem, Maher; Svensson, Birte

    2013-01-01

    We here report a quantitative study on the binding kinetics of inhibition of the enzyme glucoamylase and how individual active site amino acid mutations influence kinetics. To address this challenge, we have developed a fast and efficient method for anchoring native acarbose to gold chip surfaces...

  5. Plasma surface functionalization and dyeing kinetics of Pan-Pmma copolymers

    Science.gov (United States)

    Labay, C.; Canal, C.; Rodríguez, C.; Caballero, G.; Canal, J. M.

    2013-10-01

    Fiber surface modification with air corona plasma has been studied through dyeing kinetics under isothermal conditions at 30 °C on an acrylic-fiber fabric with a cationic dye (CI Basic Blue 3) analyzing the absorption, desorption and fixing on the surface of molecules having defined cationic character. The initial dyeing rate in the first 60 s indicates an increase of 58.3% in the dyeing rate due to the effect of corona plasma on the acrylic fiber surface. At the end of the dyeing process, the plasma-treated fabrics absorb 24.7% more dye, and the K/S value of the acrylic fabric increases by 8.8%. With selected dyestuff molecules, new techniques can be designed to amplify the knowledge about plasma-treated surface modifications of macromolecules.

  6. Kinetics of interaction from low-energy-ion bombardment of surfaces

    International Nuclear Information System (INIS)

    Horton, C.C.

    1988-01-01

    The kinetics of interaction from low energy oxygen ion bombardment of carbon and Teflon surfaces have been investigated. The surfaces were bombarded with 4.5 to 93 eV oxygen ions and emitted species were observed with a mass spectrometer. To obtain the kinetic information, the ion beam was square pulse modulated and reaction products were observed as a function of time. The kinetic information is contained in the response of the emitted species to the pulsed ion beam. Oxygen bombardment of carbon produced CO in three parallel branches with each following an adsorption-desorption process. The fast branch, with a rate constants of 12,000/sec, appeared to be sputter induced an was absent below about 19 eV. The medium and slow branches, with rate constants of 850/sec and 45/sec respectively, has little energy dependence and appeared to be due to chemical sputtering from two sites. The ratio of the fraction of the medium branch to that of the slow was constant at 1:3. The bombardment of Teflon produced CF in two parallel branches, with one following a series process and the other an adsorb-desorb process. The rate constant of the other branch were 22,000/sec and 7,000/sec and the rate constant of the other branch was 90/sec. The total signal fell monotonically with decreasing ion energy with the fraction for each branch holding constant at 71% for the series and 29% for the adsorb-desorb

  7. Quantitative kinetics of proteolytic enzymes determined by a surface concentration-based assay using peptide arrays.

    Science.gov (United States)

    Jung, Se-Hui; Kong, Deok-Hoon; Park, Seoung-Woo; Kim, Young-Myeong; Ha, Kwon-Soo

    2012-08-21

    Peptide arrays have emerged as a key technology for drug discovery, diagnosis, and cell biology. Despite the promise of these arrays, applications of peptide arrays to quantitative analysis of enzyme kinetics have been limited due to the difficulty in obtaining quantitative information of enzymatic reaction products. In this study, we developed a new approach for the quantitative kinetics analysis of proteases using fluorescence-conjugated peptide arrays, a surface concentration-based assay with solid-phase peptide standards using dry-off measurements, and compared it with an applied concentration-based assay. For fabrication of the peptide arrays, substrate peptides of cMMP-3, caspase-3, caspase-9, and calpain-1 were functionalized with TAMRA and cysteine, and were immobilized onto amine-functionalized arrays using a heterobifunctional linker, N-[γ-maleimidobutyloxy]succinimide ester. The proteolytic activities of the four enzymes were quantitatively analyzed by calculating changes induced by enzymatic reactions in the concentrations of peptides bound to array surfaces. In addition, this assay was successfully applied for calculating the Michaelis constant (K(m,surf)) for the four enzymes. Thus, this new assay has a strong potential for use in the quantitative evaluation of proteases, and for drug discovery through kinetics studies including the determination of K(m) and V(max).

  8. Turing Systems, Entropy, and Kinetic Models for Self-Healing Surfaces

    Directory of Open Access Journals (Sweden)

    Eugene Kagan

    2010-03-01

    Full Text Available The paper addresses the methods of description of friction-induced self-healing at the interface between two solid bodies. A macroscopic description of self-healing is based on a Turing system for the transfer of matter that leads to self-organization at the interface in the case of an unstable state. A microscopic description deals with a kinetic model of the process and entropy production during self-organization. The paper provides a brief overview of the Turing system approach and statistical kinetic models. The relation between these methods and the description of the self-healing surfaces is discussed, as well as results of their application. The analytical considerations are illustrated by numerical simulations.

  9. Kinetic Control of Histidine-Tagged Protein Surface Density on Supported Lipid Bilayers

    Energy Technology Data Exchange (ETDEWEB)

    Nye, Jeffrey A. [Univ. of California, Berkeley, CA (United States); Groves, Jay T. [Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2008-02-28

    Nickel-chelating lipids are general tools for anchoring polyhistidine-tagged proteins to supported lipid bilayers (SLBs), but controversy exists over the stability of the protein-lipid attachment. In this study, we show that chelator lipids are suitable anchors for building stable, biologically active surfaces but that a simple Langmuirian model is insufficient to describe their behavior. Desorption kinetics from chelator lipids are governed by the valency of surface binding: monovalently bound proteins desorb within minutes (t1/2 ≈ 6 min), whereas polyvalently bound species remain bound for hours (t1/2 ≈ 12 h). Evolution between surface states is slow, so equilibrium is unlikely to be reached on experimental timescales. However, by tuning incubation conditions, the populations of each species can be kinetically controlled, providing a wide range of protein densities on SLBs with a single concentration of chelator lipid. In conclusion, we propose guidelines for the assembly of SLB surfaces functionalized with specific protein densities and demonstrate their utility in the formation of hybrid immunological synapses.

  10. Comparative study of binding constants from Love wave surface acoustic wave and surface plasmon resonance biosensors using kinetic analysis.

    Science.gov (United States)

    Lee, Sangdae; Kim, Yong-Il; Kim, Ki-Bok

    2013-11-01

    Biosensors are used in a variety of fields for early diagnosis of diseases, measurement of toxic contaminants, quick detection of pathogens, and separation of specific proteins or DNA. In this study, we fabricated and evaluated the capability of a high sensitivity Love wave surface acoustic wave (SAW) biosensor. The experimental setup was composed of the fabricated 155-MHz Love wave SAW biosensor, a signal measurement system, a liquid flow system, and a temperature-control system. Subsequently, we measured the lower limit of detection (LOD) of the 155-MHz Love wave SAW biosensor, and calculated the association and dissociation constants between protein G and anti-mouse IgG using kinetic analysis. We compared these results with those obtained using a commercial surface plasmon resonance (SPR) biosensor. We found that the LOD of the SAW biosensor for anti-mouse IgG and mouse IgG was 0.5 and 1 microg/ml, respectively, and the resultant equilibrium association and dissociation constants were similar to the corresponding values obtaining using the commercial SPR biosensor. Thus, we conclude that the fabricated 155-MHz Love wave SAW biosensor exhibited the high sensitivity of the commercial SPR biosensor and was able to analyze the binding properties of the ligand and receptor by kinetic analysis similarly to the commercial SPR biosensor.

  11. Adsorption/desorption kinetics of Na atoms on reconstructed Si (111)-7 x 7 surface

    International Nuclear Information System (INIS)

    Chauhan, Amit Kumar Singh; Govind; Shivaprasad, S.M.

    2010-01-01

    Self-assembled nanostructures on a periodic template are fundamentally and technologically important as they put forward the possibility to fabricate and pattern micro/nano-electronics for sensors, ultra high-density memories and nanocatalysts. Alkali-metal (AM) nanostructure grown on a semiconductor surface has received considerable attention because of their simple hydrogen like electronic structure. However, little efforts have been made to understand the fundamental aspects of the growth mechanism of self-assembled nanostructures of AM on semiconductor surfaces. In this paper, we report organized investigation of kinetically controlled room-temperature (RT) adsorption/desorption of sodium (Na) metal atoms on clean reconstructed Si (111)-7 x 7 surface, by X-ray photoelectron spectroscopy (XPS). The RT uptake curve shows a layer-by-layer growth (Frank-vander Merve growth) mode of Na on Si (111)-7 x 7 surfaces and a shift is observed in the binding energy position of Na (1s) spectra. The thermal stability of the Na/Si (111) system was inspected by annealing the system to higher substrate temperatures. Within a temperature range from RT to 350 o C, the temperature induced mobility to the excess Na atoms sitting on top of the bilayer, allowing to arrange themselves. Na atoms desorbed over a wide temperature range of 370 o C, before depleting the Si (111) surface at temperature 720 o C. The acquired valence-band (VB) spectra during Na growth revealed the development of new electronic-states near the Fermi level and desorption leads the termination of these. For Na adsorption up to 2 monolayers, decrease in work function (-1.35 eV) was observed, whereas work function of the system monotonically increases with Na desorption from the Si surface as observed by other studies also. This kinetic and thermodynamic study of Na adsorbed Si (111)-7 x 7 system can be utilized in fabrication of sensors used in night vision devices.

  12. AFM stochastic analysis of surface twisted nanograin chains of iron oxide: a kinetic study

    International Nuclear Information System (INIS)

    Akhavan, O; Azimirad, R

    2009-01-01

    We have studied the stochastic parameters of surface iron oxide nanograin chains, 97 nm in diameter and 2.4 μm in length, prepared at different annealing temperatures, using atomic force microscopy (AFM) spectral analysis. In this regard, the roughness of the thin films including self-assembled twisted nanograin chains has been analysed and characterized using the height-height correlation function, the roughness exponent as well as the power spectrum density of the AFM profiles and their gradient, for the different annealing temperatures. The tip convolution effect on the stochastic parameters under study has also been investigated. The kinetics of the formation of nanograins on the film surface has been obtained using the AFM spectral analysis of the profiles and their gradient. The activation energy needed for the formation of surface nanograin chains was found to be 0.55 eV. It has been shown that the tip-surface interaction affects mainly the diffusion parameters obtained by using the surface roughness analysis of the profiles, while use of the surface roughness analysis of the gradient of the profiles results in a nearly independent tip convolution effect on the diffusion parameters. Hence, this work also provides a method for calculating the required activation energy for the formation of self-assembled nanostructures affecting the roughness of a surface.

  13. Analyzing the Molecular Kinetics of Water Spreading on Hydrophobic Surfaces via Molecular Dynamics Simulation.

    Science.gov (United States)

    Zhao, Lei; Cheng, Jiangtao

    2017-09-07

    In this paper, we report molecular kinetic analyses of water spreading on hydrophobic surfaces via molecular dynamics simulation. The hydrophobic surfaces are composed of amorphous polytetrafluoroethylene (PTFE) with a static contact angle of ~112.4° for water. On the basis of the molecular kinetic theory (MKT), the influences of both viscous damping and solid-liquid retarding were analyzed in evaluating contact line friction, which characterizes the frictional force on the contact line. The unit displacement length on PTFE was estimated to be ~0.621 nm and is ~4 times as long as the bond length of C-C backbone. The static friction coefficient was found to be ~[Formula: see text] Pa·s, which is on the same order of magnitude as the dynamic viscosity of water, and increases with the droplet size. A nondimensional number defined by the ratio of the standard deviation of wetting velocity to the characteristic wetting velocity was put forward to signify the strength of the inherent contact line fluctuation and unveil the mechanism of enhanced energy dissipation in nanoscale, whereas such effect would become insignificant in macroscale. Moreover, regarding a liquid droplet on hydrophobic or superhydrophobic surfaces, an approximate solution to the base radius development was derived by an asymptotic expansion approach.

  14. The role of surface oxides on hydrogen sorption kinetics in titanium thin films

    Science.gov (United States)

    Hadjixenophontos, Efi; Michalek, Lukas; Roussel, Manuel; Hirscher, Michael; Schmitz, Guido

    2018-05-01

    Titanium is presently discussed as a catalyst to accelerate the hydrogenation kinetics of hydrogen storage materials. It is however known that H absorption in Ti decisively depends on the surface conditions (presence or absence of the natural surface oxide). In this work, we use Ti thin films of controlled thickness (50-800 nm) as a convenient tool for quantifying the atomic transport. XRD and TEM investigations allow us to follow the hydrogenation progress inside the film. Hydrogenation of TiO2/Ti bi-layers is studied at 300 °C, for different durations (10 s to 600 min) and at varying pressures of pure H2 atmosphere. Under these conditions, the hydrogenation is found to be linear in time. By comparing films with and without TiO2, as well as by studying the pressure dependence of hydrogenation, it is demonstrated that hydrogen transport across the oxide represents the decisive kinetic barrier rather than the splitting of H2 molecules at the surface. Hydrogenation appears by a layer-like reaction initiated by heterogeneous nucleation at the backside interface to the substrate. The linear growth constant and the H diffusion coefficient inside the oxide are quantified, as well as a reliable lower bound to the hydrogen diffusion coefficient in Ti is derived. The pressure dependence of hydrogen absorption is quantitatively modelled.

  15. Kinetics studies of the F + HCl → HF + Cl reaction on an accurate potential energy surface

    Science.gov (United States)

    Lu, Dandan; Zhang, Ying; Li, Jun

    2018-02-01

    A full-dimensional electronic ground state potential energy surface for the hydrogen abstraction reaction F + HCl → HF + Cl is developed by using the permutation invariant polynomial neural network approach based on 6509 points computed at the level of CCSD(T)-F12a/AVTZ. Spin-orbit correction is also taken into account at the complete active space self-consistent field level. Theoretical thermal rate coefficients determined by the ring polymer molecular dynamics (RPMD) approach agree well with experiment, validating the accuracy of the PES. Kinetic isotope effect is also investigated.

  16. Ozone kinetics in low-pressure discharges: vibrationally excited ozone and molecule formation on surfaces

    International Nuclear Information System (INIS)

    Marinov, Daniil; Guaitella, Olivier; Booth, Jean-Paul; Rousseau, Antoine; Guerra, Vasco

    2013-01-01

    A combined experimental and modeling investigation of the ozone kinetics in the afterglow of pulsed direct current discharges in oxygen is carried out. The discharge is generated in a cylindrical silica tube of radius 1 cm, with short pulse durations between 0.5 and 2 ms, pressures in the range 1–5 Torr and discharge currents ∼40–120 mA. Time-resolved absolute concentrations of ground-state atoms and ozone molecules were measured simultaneously in situ, by two-photon absorption laser-induced fluorescence and ultraviolet absorption, respectively. The experiments were complemented by a self-consistent model developed to interpret the results and, in particular, to evaluate the roles of vibrationally excited ozone and of ozone formation on surfaces. It is found that vibrationally excited ozone, O 3 * , plays an important role in the ozone kinetics, leading to a decrease in the ozone concentration and an increase in its formation time. In turn, the kinetics of O 3 * is strongly coupled with those of atomic oxygen and O 2 (a 1 Δ g ) metastables. Ozone formation at the wall does not contribute significantly to the total ozone production under the present conditions. Upper limits for the effective heterogeneous recombination probability of O atoms into ozone are established. (paper)

  17. Ozone kinetics in low-pressure discharges: vibrationally excited ozone and molecule formation on surfaces

    Science.gov (United States)

    Marinov, Daniil; Guerra, Vasco; Guaitella, Olivier; Booth, Jean-Paul; Rousseau, Antoine

    2013-10-01

    A combined experimental and modeling investigation of the ozone kinetics in the afterglow of pulsed direct current discharges in oxygen is carried out. The discharge is generated in a cylindrical silica tube of radius 1 cm, with short pulse durations between 0.5 and 2 ms, pressures in the range 1-5 Torr and discharge currents ˜40-120 mA. Time-resolved absolute concentrations of ground-state atoms and ozone molecules were measured simultaneously in situ, by two-photon absorption laser-induced fluorescence and ultraviolet absorption, respectively. The experiments were complemented by a self-consistent model developed to interpret the results and, in particular, to evaluate the roles of vibrationally excited ozone and of ozone formation on surfaces. It is found that vibrationally excited ozone, O_3^{*} , plays an important role in the ozone kinetics, leading to a decrease in the ozone concentration and an increase in its formation time. In turn, the kinetics of O_3^{*} is strongly coupled with those of atomic oxygen and O2(a 1Δg) metastables. Ozone formation at the wall does not contribute significantly to the total ozone production under the present conditions. Upper limits for the effective heterogeneous recombination probability of O atoms into ozone are established.

  18. Effect of grain size on uranium(VI) surface complexation kinetics and adsorption additivity.

    Science.gov (United States)

    Shang, Jianying; Liu, Chongxuan; Wang, Zheming; Zachara, John M

    2011-07-15

    The contribution of variable grain sizes to uranium adsorption/desorption was studied using a sediment from the US DOE Hanford site. The sediment was wet sieved into four size fractions: coarse sand (1-2 mm), medium sand (0.2-1 mm), fine sand (0.053-0.2 mm), and clay/silt fraction (effects of size-specific adsorption site concentration and kinetic rate constants. The larger-size fraction had a larger mass percentage in the sediment but with a smaller adsorption site concentration and generally a slower uranium adsorption/desorption rate. The same equilibrium surface complexation reaction and reaction constant could describe uranium adsorption isotherms for all size fractions and the composite after accounting for the effect of adsorption site concentration. Mass-weighted, linear additivity was observed for both uranium adsorption isotherms and adsorption/desorption kinetics in the composite. One important implication of this study is that grain-size distribution may be used to estimate uranium adsorption site and adsorption/desorption kinetic rates in heterogeneous sediments from a common location.

  19. Dynamic scaling and kinetic roughening of poly(ethylene) islands grown by vapor phase deposition

    Czech Academy of Sciences Publication Activity Database

    Choukourov, A.; Melnichuk, I.; Gordeev, I.; Kylián, O.; Hanuš, J.; Kousal, J.; Solař, P.; Hanyková, L.; Brus, Jiří; Slavínská, D.; Biederman, H.

    2014-01-01

    Roč. 565, 28 August (2014), s. 249-260 ISSN 0040-6090 Institutional support: RVO:61389013 Keywords : poly(ethylene) * physical vapor deposition * island growth Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.759, year: 2014

  20. Effect of fulvic acid surface coatings on plutonium sorption and desorption kinetics on goethite.

    Science.gov (United States)

    Tinnacher, Ruth M; Begg, James D; Mason, Harris; Ranville, James; Powell, Brian A; Wong, Jennifer C; Kersting, Annie B; Zavarin, Mavrik

    2015-03-03

    The rates and extent of plutonium (Pu) sorption and desorption onto mineral surfaces are important parameters for predicting Pu mobility in subsurface environments. The presence of natural organic matter, such as fulvic acid (FA), may influence these parameters. We investigated the effects of FA on Pu(IV) sorption/desorption onto goethite in two scenarios: when FA was (1) initially present in solution or (2) found as organic coatings on the mineral surface. A low pH was used to maximize FA coatings on goethite. Experiments were combined with kinetic modeling and speciation calculations to interpret variations in Pu sorption rates in the presence of FA. Our results indicate that FA can change the rates and extent of Pu sorption onto goethite at pH 4. Differences in the kinetics of Pu sorption were observed as a function of the concentration and initial form of FA. The fraction of desorbed Pu decreased in the presence of FA, indicating that organic matter can stabilize sorbed Pu on goethite. These results suggest that ternary Pu-FA-mineral complexes could enhance colloid-facilitated Pu transport. However, more representative natural conditions need to be investigated to quantify the relevance of these findings.

  1. Adsorption of surfactants on sand surface in enhanced oil recovery: Isotherms, kinetics and thermodynamic studies

    Energy Technology Data Exchange (ETDEWEB)

    Bera, Achinta; Kumar, T.; Ojha, Keka; Mandal, Ajay, E-mail: mandal_ajay@hotmail.com

    2013-11-01

    Adsorption of surfactants onto reservoir rock surface may result in the loss and reduction of their concentrations in surfactant flooding, which may render them less efficient or ineffective in practical applications of enhanced oil recovery (EOR) techniques. Surfactant flooding for EOR received attraction due to its ability to increase the displacement efficiency by lowering the interfacial tension between oil and water and mobilizing the residual oil. This article highlights the adsorption of surfactants onto sand surface with variation of different influencing factors. It has been experimentally found that adsorption of cationic surfactant on sand surface is more and less for anionic surfactant, while non-ionic surfactant shows intermediate behaviour. X-ray diffraction (XRD) study of clean sand particles has been made to determine the main component present in the sand particles. The interaction between sand particles and surfactant has been studied by Fourier Transform Infrared (FTIR) Spectroscopy of the sand particles before and after aging with surfactant. Salinity plays an important role in adsorption of anionic surfactant. Batch experiments were also performed to understand the effects of pH and adsorbent dose on the sorption efficiency. The sand particles exhibited high adsorption efficiency at low pH for anionic and nonionic surfactants. But opposite trend was found for cationic surfactant. Adsorption data were analyzed by fitting with Langmuir, Freundlich, Redlich-Peterson, and Sips isotherm models. Results show that the Langmuir isotherm and pseudo-second order kinetics models suit the equilibrium and kinetics of adsorption on sand surface. Thermodynamics feasibility of the adsorption process was also studied to verify the spontaneity of the process.

  2. Effects of airway surface liquid height on the kinetics of extracellular nucleotides in airway epithelia.

    Science.gov (United States)

    Amarante, Tauanne D; da Silva, Jafferson K L; Garcia, Guilherme J M

    2014-12-21

    Experimental techniques aimed at measuring the concentration of signaling molecules in the airway surface liquid (ASL) often require an unrealistically large ASL volume to facilitate sampling. This experimental limitation, prompted by the difficulty of pipetting liquid from a very shallow layer (~15 μm), leads to dilution and the under-prediction of physiologic concentrations of signaling molecules that are vital to the regulation of mucociliary clearance. Here, we use a computational model to describe the effect of liquid height on the kinetics of extracellular nucleotides in the airway surface liquid coating respiratory epithelia. The model consists of a reaction-diffusion equation with boundary conditions that represent the enzymatic reactions occurring on the epithelial surface. The simulations reproduce successfully the kinetics of extracellular ATP following hypotonic challenge for ASL volumes ranging from 25 μl to 500 μl in a 12-mm diameter cell culture. The model reveals that [ATP] and [ADO] reach 1200 nM and 2200 nM at the epithelial surface, respectively, while their volumetric averages remain less than 200 nM at all times in experiments with a large ASL volume (500 μl). These findings imply that activation of P2Y2 and A2B receptors is robust after hypotonic challenge, in contrast to what could be concluded based on experimental measurements of volumetric concentrations in large ASL volumes. Finally, given the central role that ATP and ADO play in regulating mucociliary clearance, we investigated which enzymes, when inhibited, provide the greatest increase in ATP and ADO concentrations. Our findings suggest that inhibition of NTPDase1/highTNAP would cause the greatest increase in [ATP] after hypotonic challenge, while inhibition of the transporter CNT3 would provide the greatest increase in [ADO]. Copyright © 2014 Elsevier Ltd. All rights reserved.

  3. Climatic variability of near-surface turbulent kinetic energy over the United States: implications for fire-weather predications

    Science.gov (United States)

    Warren E. Heilman; Xindi. Bain

    2013-01-01

    Recent research suggests that high levels of ambient near-surface atmospheric turbulence are often associated with rapid and sometimes erratic wildland fire spread that may eventually lead to large burn areas. Previous research has also examined the feasibility of using near-surface atmospheric turbulent kinetic energy (TKEs) alone or in...

  4. THE SURFACE-MEDIATED UNFOLDING KINETICS OF GLOBULAR PROTEINS IS DEPENDENT ON MOLECULAR WEIGHT AND TEMPERATURE

    Energy Technology Data Exchange (ETDEWEB)

    Patananan, A.N.; Goheen, S.C.

    2008-01-01

    The adsorption and unfolding pathways of proteins on rigid surfaces are essential in numerous complex processes associated with biomedical engineering, nanotechnology, and chromatography. It is now well accepted that the kinetics of unfolding are characterized by chemical and physical interactions dependent on protein deformability and structure, as well as environmental pH, temperature, and surface chemistry. Although this fundamental process has broad implications in medicine and industry, little is known about the mechanism because of the atomic lengths and rapid time scales involved. Therefore, the unfolding kinetics of myoglobin, β-glucosidase, and ovalbumin were investigated by adsorbing the globular proteins to non-porous cationic polymer beads. The protein fractions were adsorbed at different residence times (0, 9, 10, 20, and 30 min) at near-physiological conditions using a gradient elution system similar to that in high-performance liquid chromatography. The elution profi les and retention times were obtained by ultraviolet/visible spectrophotometry. A decrease in recovery was observed with time for almost all proteins and was attributed to irreversible protein unfolding on the non-porous surfaces. These data, and those of previous studies, fi t a positively increasing linear trend between percent unfolding after a fi xed (9 min) residence time (71.8%, 31.1%, and 32.1% of myoglobin, β-glucosidase, and ovalbumin, respectively) and molecular weight. Of all the proteins examined so far, only myoglobin deviated from this trend with higher than predicted unfolding rates. Myoglobin also exhibited an increase in retention time over a wide temperature range (0°C and 55°C, 4.39 min and 5.74 min, respectively) whereas ovalbumin and β-glucosidase did not. Further studies using a larger set of proteins are required to better understand the physiological and physiochemical implications of protein unfolding kinetics. This study confi rms that surface

  5. Surface kinetic model for isotopic and trace element fractionation during precipitation of calcite from aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    DePaolo, D.

    2010-10-15

    A surface reaction kinetic model is developed for predicting Ca isotope fractionation and metal/Ca ratios of calcite as a function of rate of precipitation from aqueous solution. The model is based on the requirements for dynamic equilibrium; i.e. proximity to equilibrium conditions is determined by the ratio of the net precipitation rate (R{sub p}) to the gross forward precipitation rate (R{sub f}), for conditions where ionic transport to the growing crystal surface is not rate-limiting. The value of R{sub p} has been experimentally measured under varying conditions, but the magnitude of R{sub f} is not generally known, and may depend on several factors. It is posited that, for systems with no trace constituents that alter the surface chemistry, R{sub f} can be estimated from the bulk far-from-equilibrium dissolution rate of calcite (R{sub b} or k{sub b}), since at equilibrium R{sub f} = R{sub b}, and R{sub p} = 0. Hence it can be inferred that R{sub f} {approx} R{sub p} + R{sub b}. The dissolution rate of pure calcite is measureable and is known to be a function of temperature and pH. At given temperature and pH, equilibrium precipitation is approached when R{sub p} (= R{sub f} - R{sub b}) << R{sub b}. For precipitation rates high enough that R{sub p} >> R{sub b}, both isotopic and trace element partitioning are controlled by the kinetics of ion attachment to the mineral surface, which tend to favor more rapid incorporation of the light isotopes of Ca and discriminate weakly between trace metals and Ca. With varying precipitation rate, a transition region between equilibrium and kinetic control occurs near R{sub p} {approx} R{sub b} for Ca isotopic fractionation. According to this model, Ca isotopic data can be used to estimate R{sub f} for calcite precipitation. Mechanistic models for calcite precipitation indicate that the molecular exchange rate is not constant at constant T and pH, but rather is dependent also on solution saturation state and hence R{sub p

  6. Static and kinetic friction force and surface roughness of different archwire-bracket sliding contacts.

    Science.gov (United States)

    Carrion-Vilches, Francisco J; Bermudez, María-Dolores; Fructuoso, Paula

    2015-01-01

    The aim of this study was to determine the static and kinetic friction forces of the contact bracket-archwire with different dental material compositions in order to select those materials with lower resistance to sliding. We carried out sliding friction tests by means of a universal testing machine following an experimental procedure as described in ASTM D1894 standard. We determined the static and kinetic friction forces under dry and lubricating conditions using an artificial saliva solution at 36.5ºC. The bracket-archwire pairs studied were: stainless steel-stainless steel; stainless steel-glass fiber composite; stainless steel-Nitinol 60; sapphire-stainless steel; sapphire-glass fiber composite; and sapphire-Nitinol 60. The best performance is obtained for Nitinol 60 archwire sliding against a stainless steel bracket, both under dry and lubricated conditions. These results are in agreement with the low surface roughness of Nitinol 60 with respect to the glass fiber composite archwire. The results described here contribute to establishing selection criteria for materials for dental archwire-brackets.

  7. Comparison of kinetic models for atom recombination on high-temperature reusable surface insulation

    Science.gov (United States)

    Willey, Ronald J.

    1993-01-01

    Five kinetic models are compared for their ability to predict recombination coefficients for oxygen and nitrogen atoms over high-temperature reusable surface insulation (HRSI). Four of the models are derived using Rideal-Eley or Langmuir-Hinshelwood catalytic mechanisms to describe the reaction sequence. The fifth model is an empirical expression that offers certain features unattainable through mechanistic description. The results showed that a four-parameter model, with temperature as the only variable, works best with data currently available. The model describes recombination coefficients for oxygen and nitrogen atoms for temperatures from 300 to 1800 K. Kinetic models, with atom concentrations, demonstrate the influence of atom concentration on recombination coefficients. These models can be used for the prediction of heating rates due to catalytic recombination during re-entry or aerobraking maneuvers. The work further demonstrates a requirement for more recombination experiments in the temperature ranges of 300-1000 K, and 1500-1850 K, with deliberate concentration variation to verify model requirements.

  8. Solid oxide electrode kinetics in light of in situ surface studies

    DEFF Research Database (Denmark)

    Mogensen, Mogens Bjerg

    2014-01-01

    The combination of in situ and in particular in operando characterization methods such as electrochemical impedance spectroscopy (EIS) on both technical and model electrode are well known ways to gain some practical insight in electrode reaction kinetics. Yet, is has become clear that in spite...... of the strengths it is not sufficient to reveal much details of the electrode mechanisms mainly because it provide average values only. Therefore it has to be combined with surface science methods in order to reveal the interface structure and composition. Ex situ methods have been very useful over the latest....... Furthermore, it seems that detailed mathematical modeling using new tools like COMSOL is necessary for the synthesis of the large amount of data for a well-characterized electrode into one physical meaningful picture. A brief review of literature an own data will be presented with a practical example of SOFC...

  9. Potential and Kinetic Electron Emissions from HOPG Surface Irradiated by Highly Charged Xenon and Neon Ions

    International Nuclear Information System (INIS)

    Yu-Yu, Wang; Yong-Tao, Zhao; Jian-Rong, Sun; De-Hui, Li; Jin-Yu, Li; Ping-Zhi, Wang; Guo-Qing, Xiao; Abdul, Qayyum

    2011-01-01

    Highly charged 129 Xe q+ (q = 10−30) and 40 Ne q+ (q = 4−8) ion-induced secondary electron emissions on the surface of highly oriented pyrolytic graphite (HOPG) are reported. The total secondary electron yield is measured as a function of the potential energy of incident ions. The experimental data are used to separate contributions of kinetic and potential electron yields. Our results show that about 4.5% and 13.2% of ion's potential energies are consumed in potential electron emission due to different Xe q+ -HOPG and Ne q+ -HOPG combinations. A simple formula is introduced to estimate the fraction of ion's potential energy for potential electron emission. (atomic and molecular physics)

  10. Dry heat treatment affects wheat bran surface properties and hydration kinetics.

    Science.gov (United States)

    Jacobs, Pieter J; Hemdane, Sami; Delcour, Jan A; Courtin, Christophe M

    2016-07-15

    Heat stabilization of wheat bran aims at inactivation of enzymes which may cause rancidity and processability issues. Such treatments may however cause additional unanticipated phenomena which may affect wheat bran technological properties. In this work, the impact of toasting on wheat bran hydration capacity and hydration kinetics was studied. Hydration properties were assessed using the Enslin-Neff and drainage centrifugation water retention capacity methods, thermogravimetric analysis and contact angle goniometry, next to more traditional methods. While equilibrium hydration properties of bran were not affected by the heat treatment, the rate at which the heat treated bran hydrated was, however, very significantly reduced compared to the untreated bran. This phenomenon was found to originate from the formation of a lipid coating during the treatment rendering the bran surface hydrophobic. These insights help to understand and partially account for the modified processability of heat treated bran in food applications. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Surface chemistry of ferrihydrite: Part 2. Kinetics of arsenate adsorption and coprecipitation

    Science.gov (United States)

    Fuller, C.C.; Dadis, J.A.; Waychunas, G.A.

    1993-01-01

    The kinetics of As(V) adsorption by ferrihydrite was investigated in coprecipitation and postsynthesis adsorption experiments conducted in the pH range 7.5-9.0. In coprecipitation experiments, As(V) was present in solution during the hydrolysis and precipitation of iron. In adsorption experiments, a period of rapid (kinetics of As(V) desorption after an increase in pH were also consistent with diffusion as a rate-limiting process. Aging of pure ferrihydrite prior to As(V) adsorption caused a decrease in adsorption sites on the precipitate owing to crystallite growth. In coprecipitation experiments, the initial As(V) uptake was significantly greater than in post-synthesis adsorption experiments, and the rate of uptake was not diffusion limited because As(V) was coordinated by surface sites before crystallite growth and coagulation processes could proceed. After the initial adsorption, As(V) was slowly released from coprecipitates for at least one month, as crystallite growth caused desorption of As(V). Adsorption densities as high as 0.7 mole As(V) per mole of Fe were measured in coprecipitates, in comparison to 0.25 mole As(V) per mole of Fe in post-synthesis adsorption experiments. Despite the high Concentration of As(V) in the precipitates, EXAFS spectroscopy (Waychunas et al., 1993) showed that neither ferric arsenate nor any other As-bearing surface precipitate or solid solution was formed. The high adsorption densities are possible because the ferrihydrite particles are extremely small, approaching the size of small dioctahedral chains at the highest As(V) adsorption density. The results suggest that the solid solution model proposed by Fox (1989, 1992) for control of arsenate and phosphate concentrations in natural waters may be invalid. ?? 1993.

  12. Reaction kinetics of metal deposition via surface limited red-ox replacement of underpotentially deposited metal monolayers

    International Nuclear Information System (INIS)

    Gokcen, Dincer; Bae, Sang-Eun; Brankovic, Stanko R.

    2011-01-01

    The study of the kinetics of metal deposition via surface limited red-ox replacement of underpotentially deposited metal monolayers is presented. The model system was Pt submonolayer deposition on Au(1 1 1) via red-ox replacement of Pb and Cu UPD monolayers on Au(1 1 1). The kinetics of a single replacement reaction was studied using the formalism of the comprehensive analytical model developed to fit the open circuit potential transients from deposition experiments. The practical reaction kinetics parameters like reaction half life, reaction order and reaction rate constant are determined and discussed with their relevance to design and control of deposition experiments. The effects of transport limitation and the role of the anions/electrolyte on deposition kinetics are investigated and their significance to design of effective deposition process is discussed.

  13. A study of charge transfer kinetics in dye-sensitized surface conductivity solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Friedrich, Dennis

    2011-05-15

    The efficiency of the quasi-solid-state dye-sensitized solar cell developed by Junghaenel and Tributsch, the so-called Nano Surface Conductivity Solar Cell (NSCSC), was improved from 2% to 3.5% introducing a compact TiO{sub 2} underlayer, modifying the surface of the mesoporous TiO{sub 2} electrode, optimizing the deposition process of the electrolyte film, and replacing the platinum counter electrode by a carbon layer. Space-resolved photocurrent images revealed the importance of a homogeneous distribution of the electrolyte film. An uneven dispersion led to localized areas of high and low photocurrents, whereas the latter were attributed to an insufficient concentration of the redox couple. Impedance spectroscopy was performed on cells containing different concentrations of the redox couple. By modeling the spectra using an equivalent circuit with a transmission line of resistive and capacitive elements, the characteristic parameters of electron transport in the TiO{sub 2}, such as diffusion length and electron lifetime were obtained. The measurements indicated that the transport of the positive charge to the counter electrode is the main process limiting the efficiency of the cells. Excess charge carrier decay in functioning devices was analyzed by contactless transient photoconductance measurements in the microwave frequency range (TRMC). The lifetime of the photogenerated charge carriers was observed to decrease with increasing applied potential, reaching its maximum close to the opencircuit potential of the cell, where the photocurrent density was minimal, i.e. the potential dependent decay observed was limited by the injection of electrons into the front contact. The functioning of this NSCSC indicated that the transport of the positive charge occurs by solid-state diffusion at the surface of the TiO{sub 2} particles. TRMC measurements on subset devices in the form of sensitized TiO{sub 2} layers revealed charge carrier kinetics strongly dependent on the

  14. A radiotracer study on the kinetics of gold sorption by mineral surfaces

    Science.gov (United States)

    Heinhorst, J. P.; Lehmann, B.

    1994-09-01

    Aqueous solutions with about 10 ppt195Au and [HCl] of 10-2.3 and 10-1.3 m were exposed to solid minerals for several months. The gold uptake with time was observed by time-stepped sampling and radiochemical Au analysis. Sorbants were polished thick sections of quartz, pyrite, pyrrhotite and elemental gold, as well as crushed grains and sawed mineral cubes of quartz and pyrite (all randomly oriented). The kinetics of gold sorption strongly varied with the surface area of the sorbents, the type of mineral and the pH of the solution. Mineral-specific differences in reaction rates were observed only at experimental pH values around 2.3, where sorption on pyrrhotite and elemental gold was much more rapid than by quartz and pyrite. At pH around 1.3 gold sorption was rapid on all minerals. This finding is thought to reflect the gold speciation, i.e. neutral hydroxo-gold complexes above pH 1.5, for which only chemisorption is possible, versus dominantly AuCl{4/-} below pH 1.5, where unspecific electrostatic interaction enhances reaction rates with all protonated mineral surfaces.

  15. Oxygen Reduction Kinetics Enhancement on a Heterostructured Oxide Surface for Solid Oxide Fuel Cells

    KAUST Repository

    Crumlin, Ethan J.

    2010-11-04

    Heterostructured interfaces of oxides, which can exhibit transport and reactivity characteristics remarkably different from those of bulk oxides, are interesting systems to explore in search of highly active cathodes for the oxygen reduction reaction (ORR). Here, we show that the ORR of ∼85 nm thick La0.8Sr0.2CoO3-δ (LSC113) films prepared by pulsed laser deposition on (001)-oriented yttria-stabilized zirconia (YSZ) substrates is dramatically enhanced (∼3-4 orders of magnitude above bulk LSC113) by surface decorations of (La 0.5Sr0.5)2CoO4±δ (LSC214) with coverage in the range from ∼0.1 to ∼15 nm. Their surface and atomic structures were characterized by atomic force, scanning electron, and scanning transmission electron microscopy, and the ORR kinetics were determined by electrochemical impedance spectroscopy. Although the mechanism for ORR enhancement is not yet fully understood, our results to date show that the observed ORR enhancement can be attributed to highly active interfacial LSC113/LSC214 regions, which were shown to be atomically sharp. © 2010 American Chemical Society.

  16. Coupling between different superficial kinetics: segregation, precipitation and dissolution; Cinetiques couplees au voisinage des surfaces: segregation, precipitation et dissolution

    Energy Technology Data Exchange (ETDEWEB)

    Delage, St

    1998-12-31

    In most of alloys, the surface composition is different from bulk one. This phenomenon, called `surface segregation` have drawn up to now much attention in this case of alloys which have reached thermodynamic equilibrium in the solid solution. Using a kinetic model including bulk and surface driving forces, we study segregation phenomenon during dissolution and precipitation kinetics, in the case of the Fe-Cu alloy. Within a mean field approximation, we point out the dissolution modes for Fe/Cu and Cu/Fe deposit. If the substrate surface energy is lower than the deposit one (case of Fe/Cu deposit) the substrate element climbs through the deposit to reach the surface and forms a layer of the substrate element floating on the deposit. In the case of thick deposit (typically 10 monolayers), a competition between two layer by layer dissolution modes leads to a wide range of behaviours, depending on temperature and deposit thickness. Furthermore, the major part of the concentration profiles obtained during kinetics is at local equilibrium in a region near the surface. In the second part of this work, we study the surface influence during phase separation kinetics in thin layers using Monte-Carlo simulations. A surface directed spinodal decomposition occurs, leading to the appearance of a Cu-rich layer at the surface, which goes toward the layer`s core with time. This process is linked with bulk precipitation in layer`s core, and leads to different behaviours depending on average concentration and layer thickness. (authors) 125 refs.

  17. Self-organized criticality in proteins: Hydropathic roughening profiles of G-protein-coupled receptors

    Science.gov (United States)

    Phillips, J. C.

    2013-03-01

    Proteins appear to be the most dramatic natural example of self-organized criticality (SOC), a concept that explains many otherwise apparently unlikely phenomena. Protein conformational functionality is often dominated by long-range hydrophobic or hydrophilic interactions which both drive protein compaction and mediate protein-protein interactions. Superfamily transmembrane G-protein-coupled receptors (GPCRs) are the largest family of proteins in the human genome; their amino acid sequences form the largest database for protein-membrane interactions. While there are now structural data on the heptad transmembrane structures of representatives of several heptad families, here we show how fresh insights into global and some local chemical trends in GPCR properties can be obtained accurately from sequences alone, especially by algebraically separating the extracellular and cytoplasmic loops from transmembrane segments. The global mediation of long-range water-protein interactions occurs in conjunction with modulation of these interactions by roughened interfaces. Hydropathic roughening profiles are defined here solely in terms of amino acid sequences, and knowledge of protein coordinates is not required. Roughening profiles both for GPCR and some simpler protein families display accurate and transparent connections to protein functionality, and identify natural length scales for protein functionality.

  18. Osteoclast cell-surface specializations and nuclear kinetics during egg-laying in Japanese quail

    International Nuclear Information System (INIS)

    Miller, S.C.

    1981-01-01

    Medullary bone deposits serve as a reservoir of labile calcium for egg-shell calcification in birds. Quantitative transmission-electron-microscope methods and light-microscope autoradiographic cell-population-kinetic analyses were used to determine changes in cell-surface specializations and population dynamics of medullary bone osteoclasts during egg-laying in Japanese quail. Prior to egg-shell formation, from 0 to about 8 hours after the previous oviposition, very few osteoclast profiles had ruffled borders. The appearance of ruffled borders coincided with the beginning of egg-shell calcification, about 9-10 hours after the previous oviposition. During egg-shell calcification, about 10-21 hours after the previous oviposition, most osteoclast profiles had ruffled borders. Ruffled borders disappeared at the completion of egg-shell calcification and commencement of egg-shell pigmentation. Thus, functional activities of medullary bone osteoclasts appear to be closely synchronized with egg-shell calcification during egg-laying. From 1 to 48 hours after a single injection of 3H-thymidine (3H-TdR), very few labeled osteoclast nuclei were seen during egg-laying. Following multiple injections of 3H-TdR, the percentage of labeled nuclei reached a peak at about 170 hours after the first injection. At this peak-labeling time, relatively few of the osteoclast profiles that had labeled nuclei had two or more; although the average number of nuclei per osteoclast profile was about 3.6. These kinetic data suggest that the medullary bone osteoclast population has a prolonged rate of turnover compared to rapid changes in cell activities associated with each 24-hour egg-laying cycle; and collectively they would suggest that rapid changes in osteoclast functions occur independently of changes in cell-population dynamics

  19. A kinetic analysis of manual wheelchair propulsion during start-up on select indoor and outdoor surfaces

    NARCIS (Netherlands)

    Koontz, AM; Cooper, RA; Boninger, ML; Yang, YS; Impink, BG; van der Woude, LHV

    2005-01-01

    The objective of this study was to conduct a kinetic analysis of manual wheelchair propulsion during start-LIP on select indoor and Outdoor surfaces. Eleven manual wheelchairs were fitted with a SMART(Wheel) and their users were asked to Push on a Course consisting of high- and low-pile carpet,

  20. ULTRASOUND PRETREATMENT OF ELEMENTAL IRON: KINETIC STUDIES OF DEHALOGENATION REACTION ENHANCEMENT AND SURFACE EFFECTS. (R828598C743)

    Science.gov (United States)

    This work presents data showing the kinetic improvement afforded by ultrasound pretreatment and illustrates the physical and chemical changes that take place at the iron surface. First-order rate constants improved as much as 78% with 2 h of ultrasound pretreatment. Scann...

  1. Kinetics and mechanisms of the oxide film growth on the surface of α-Fe in transitional domains

    International Nuclear Information System (INIS)

    Mukhambetov, D.G.; Berber, N.N.; Kargin, D.B.; Chalaya, O.V.

    2003-01-01

    The object of this work was to study the kinetics of the α-Fe surface oxidation with prevailing cubic texture at temperatures of 450-500 deg. C. The basic conformity to natural laws and mechanisms of the two-phase thin oxide films grows are determined. (author)

  2. Ozone-surface interactions: Investigations of mechanisms, kinetics, mass transport, and implications for indoor air quality

    Energy Technology Data Exchange (ETDEWEB)

    Morrison, Glenn Charles [Univ. of California, Berkeley, CA (United States)

    1999-12-01

    In this dissertation, results are presented of laboratory investigations and mathematical modeling efforts designed to better understand the interactions of ozone with surfaces. In the laboratory, carpet and duct materials were exposed to ozone and measured ozone uptake kinetics and the ozone induced emissions of volatile organic compounds. To understand the results of the experiments, mathematical methods were developed to describe dynamic indoor aldehyde concentrations, mass transport of reactive species to smooth surfaces, the equivalent reaction probability of whole carpet due to the surface reactivity of fibers and carpet backing, and ozone aging of surfaces. Carpets, separated carpet fibers, and separated carpet backing all tended to release aldehydes when exposed to ozone. Secondary emissions were mostly n-nonanal and several other smaller aldehydes. The pattern of emissions suggested that vegetable oils may be precursors for these oxidized emissions. Several possible precursors and experiments in which linseed and tung oils were tested for their secondary emission potential were discussed. Dynamic emission rates of 2-nonenal from a residential carpet may indicate that intermediate species in the oxidation of conjugated olefins can significantly delay aldehyde emissions and act as reservoir for these compounds. The ozone induced emission rate of 2-nonenal, a very odorous compound, can result in odorous indoor concentrations for several years. Surface ozone reactivity is a key parameter in determining the flux of ozone to a surface, is parameterized by the reaction probability, which is simply the probability that an ozone molecule will be irreversibly consumed when it strikes a surface. In laboratory studies of two residential and two commercial carpets, the ozone reaction probability for carpet fibers, carpet backing and the equivalent reaction probability for whole carpet were determined. Typically reaction probability values for these materials were 10

  3. New Approach for Studying Slow Fragmentation Kinetics in FT-ICR: Surface-Induced Dissociation Combined with Resonant Ejection

    Energy Technology Data Exchange (ETDEWEB)

    Laskin, Julia; Futrell, Jean H.

    2015-02-01

    We introduce a new approach for studying the kinetics of large ion fragmentation in the gas phase by coupling surface-induced dissociation (SID) in a Fourier transform ion cyclotron resonance mass spectrometer with resonant ejection of selected fragment ions using a relatively short (5 ms) ejection pulse. The approach is demonstrated for singly protonated angiotensin III ions excited by collisions with a self-assembled monolayer of alkylthiol on gold (HSAM). The overall decomposition rate and rate constants of individual reaction channels are controlled by varying the kinetic energy of the precursor ion in a range of 65–95 eV. The kinetics of peptide fragmentation are probed by varying the delay time between resonant ejection and fragment ion detection at a constant total reaction time. RRKM modeling indicates that the shape of the kinetics plots is strongly affected by the shape and position of the energy deposition function (EDF) describing the internal energy distribution of the ion following ion-surface collision. Modeling of the kinetics data provides detailed information on the shape of the EDF and energy and entropy effects of individual reaction channels.

  4. Surface controlled dissolution rates of gypsum in aqueous solutions exhibit nonlinear dissolution kinetics

    Science.gov (United States)

    Jeschke, Alexander A.; Vosbeck, Katrin; Dreybrodt, Wolfgang

    2001-01-01

    The effective dissolution rates of gypsum are determined by mixed kinetics, where the rate constants of dissolution at the surface and the transport constant of molecular diffusion of dissolved material are similar. To obtain the surface reaction rate law it is necessary to know the transport constant. We have determined the surface rate law for monocrystalline selenite by using a rotating disc set-up, where the transport coefficients are well known. As a result, up to a calcium concentration of 0.6 · ceq, we find a nearly linear rate law Rs = ksl (1- cs/ ceq) n1, where cs is the total calcium concentration at the surface and ceq the equilibrium concentration with respect to gypsum, n1 = 1.2 ± 0.2, and ksl = 1.1 · 10 -4 mmol cm -2 s -1 ± 15%. We also employed batch-experiments for selenite, alabaster and gypsum rock samples. The result of these experiments were interpreted by using a transport constant determined by NaCl dissolution experiments under similar physical conditions. The batch experiments reveal a dissolution rate law Rs = ksl (1- cs/ ceq) n1, ksl = 1.3 · 10 -4 mmol · cm -2 s -1, n1 = 1.2 ± 0.2 for c ≤ 0.94 · ceq. Close to equilibrium a nonlinear rate law, Rs = ks2 (1- cs/ ceq) n2, is observed, where ks2 is in the order of 10 mmol · cm -2 s -1 and n2 ≈ 4.5. The experimentally observed gypsum dissolution rates from the batch experiments could be accurately fitted, with only minor variations of the surface reaction constant obtained from the rotating disk experiment and the transport coefficient from the NaCl dissolution batch experiment. Batch experiments on pure synthetic gypsum, reveal a linear rate law up to equilibrium. This indicates inhibition of dissolution in natural samples close to equilibrium, as is known also for calcite minerals.

  5. Variations in calcite growth kinetics with surface topography: molecular dynamics simulations and process-based growth kinetics modelling

    NARCIS (Netherlands)

    Wolthers, M.; Di Tommaso, D.; Du, Zhimei; de Leeuw, Nora H.

    2013-01-01

    It is generally accepted that cation dehydration is the rate-limiting step to crystal growth from aqueous solution. Here we employ classical molecular dynamics simulations to show that the water exchange frequency at structurally distinct calcium sites in the calcite surface varies by about two

  6. Control of surface ripple amplitude in ion beam sputtered polycrystalline cobalt films

    Energy Technology Data Exchange (ETDEWEB)

    Colino, Jose M., E-mail: josemiguel.colino@uclm.es [Institute of Nanoscience, Nanotechnology and Molecular Materials, University of Castilla-La Mancha, Campus de la Fabrica de Armas, Toledo 45071 (Spain); Arranz, Miguel A. [Facultad de Ciencias Quimicas, University of Castilla-La Mancha, Ciudad Real 13071 (Spain)

    2011-02-15

    We have grown both polycrystalline and partially textured cobalt films by magnetron sputter deposition in the range of thickness (50-200 nm). Kinetic roughening of the growing film leads to a controlled rms surface roughness values (1-6 nm) increasing with the as-grown film thickness. Ion erosion of a low energy 1 keV Ar+ beam at glancing incidence (80{sup o}) on the cobalt film changes the surface morphology to a ripple pattern of nanometric wavelength. The wavelength evolution at relatively low fluency is strongly dependent on the initial surface topography (a wavelength selection mechanism hereby confirmed in polycrystalline rough surfaces and based on the shadowing instability). At sufficiently large fluency, the ripple wavelength steadily increases on a coarsening regime and does not recall the virgin surface morphology. Remarkably, the use of a rough virgin surface makes the ripple amplitude in the final pattern can be controllably increased without affecting the ripple wavelength.

  7. Structure elucidation and degradation kinetic study of Ofloxacin using surface enhanced Raman spectroscopy

    Science.gov (United States)

    El-Zahry, Marwa R.; Lendl, Bernhard

    2018-03-01

    A simple, fast and sensitive surface enhanced Raman spectroscopy (SERS) method for quantitative determination of fluoroquinolone antibiotic Ofloxacin (OFX) is presented. Also the stability behavior of OFX was investigated by monitoring the SERS spectra of OFX after various degradation processes. Acidic, basic and oxidative force degradation processes were applied at different time intervals. The forced degradation conditions were conducted and followed using SERS method utilizing silver nanoparticles (Ag NPs) as a SERS substrate. The Ag NPs colloids were prepared by reduction of silver nitrate using polyethyelene glycol (PEG) as a reducing and stabilizing agent. Validation tests were done in accordance with International Conference on Harmonization (ICH) guidelines. The calibration curve with a correlation coefficient (R = 0.9992) was constructed as a relationship between the concentration range of OFX (100-500 ng/ml) and SERS intensity at 1394 cm- 1 band. LOD and LOQ values were calculated and found to be 23.5 ng/ml and 72.6 ng/ml, respectively. The developed method was applied successfully for quantitation of OFX in different pharmaceutical dosage forms. Kinetic parameters were calculated including rate constant of the degradation of the studied antibiotic.

  8. Kinetic modeling for thermal dehydration of ferrous oxalate dihydrate polymorphs: a combined model for induction period-surface reaction-phase boundary reaction.

    Science.gov (United States)

    Ogasawara, Haruka; Koga, Nobuyoshi

    2014-04-03

    In this study, ferrous oxalate dihydrate polymorph particles, α- and β-phases, with square bipyramidal and quadratic prismatic shapes, respectively, were synthesized. Thermal dehydration of the samples was subjected to kinetic study as a typical reaction that indicates a significant induction period and a sigmoidal mass-loss behavior. On the basis of the formal kinetic analysis of the mass-loss traces recorded under isothermal, nonisothermal, and constant transformation rate conditions and the morphological observations of the surface textures of the partially reacted sample particles, a combined kinetic model for the induction period-surface reaction-phase boundary reaction was developed. The sigmoidal mass-loss behavior after the significant induction period under isothermal conditions was satisfactorily simulated by the combined kinetic model. The kinetic parameters for the component processes of induction period, surface reaction, and phase boundary reaction were separately determined from the kinetic simulation. The differences in the kinetic behaviors of the induction period and the phase boundary reaction between α- and β-phase samples were well described by the kinetic parameters. The applicability of the combined kinetic model to practical systems was demonstrated through characterizing the physicogeometrical kinetics of the thermal dehydration of ferrous oxalate dihydrate polymorphs.

  9. Thermalhydraulic experiments with a cluster of 19 rods roughened by a novel type of roughness

    International Nuclear Information System (INIS)

    Rehme, K.; Kernforschungszentrum Karlsruhe G.m.b.H.

    1981-02-01

    Distributions of temperature and pressure were measured on cluster of 19 electrically heated tubes. 400 thermocouples were used for temperature measurements. The tubes were partly roughened by a novel type of roughness with a thermal performance superior to that of transverse ribs. The experiments bot with helium and nitrogen as coolants covered a range of Reynolds numbers between 450 and 1.8 x 10 5 . The maximum linear rod power achived was 43 kWm -1 , the maximum measured wall temperature 1271 K (998 0 C). The report contains the description of the test section together with all tabulated results. (orig.) [de

  10. Thermal-hydraulic experiments with a cluster of 12 roughened rods

    International Nuclear Information System (INIS)

    Rehme, K.

    1981-02-01

    Distributions of temperatures and pressures were measured on a cluster of 12 electrically heated tubes. 84 thermocouples were used to measure the temperatures. The heated part of the tubes was artificially roughened by trapezoidal transverse ribs. The experiments with helium and nitrogen as coolants covered a range of Reynolds numbers between 470 and 1.8 x 10 5 . The maximum linear rod power was 45.8 kWm -1 , the maximum measured wall temperature 1062K (789 0 C). The report contains the description of the test section and all tabulated experimental results. (orig.) [de

  11. Heat and turbulent kinetic energy budgets for surface layer cooling induced by the passage of Hurricane Frances (2004)

    Science.gov (United States)

    Huang, Peisheng; Sanford, Thomas B.; Imberger, JöRg

    2009-12-01

    Heat and turbulent kinetic energy budgets of the ocean surface layer during the passage of Hurricane Frances were examined using a three-dimensional hydrodynamic model. In situ data obtained with the Electromagnetic-Autonomous Profiling Explorer (EM-APEX) floats were used to set up the initial conditions of the model simulation and to compare to the simulation results. The spatial heat budgets reveal that during the hurricane passage, not only the entrainment in the bottom of surface mixed layer but also the horizontal water advection were important factors determining the spatial pattern of sea surface temperature. At the free surface, the hurricane-brought precipitation contributed a negligible amount to the air-sea heat exchange, but the precipitation produced a negative buoyancy flux in the surface layer that overwhelmed the instability induced by the heat loss to the atmosphere. Integrated over the domain within 400 km of the hurricane eye on day 245.71 of 2004, the rate of heat anomaly in the surface water was estimated to be about 0.45 PW (1 PW = 1015 W), with about 20% (0.09 PW in total) of this was due to the heat exchange at the air-sea interface, and almost all the remainder (0.36 PW) was downward transported by oceanic vertical mixing. Shear production was the major source of turbulent kinetic energy amounting 88.5% of the source of turbulent kinetic energy, while the rest (11.5%) was attributed to the wind stirring at sea surface. The increase of ocean potential energy due to vertical mixing represented 7.3% of the energy deposited by wind stress.

  12. Equilibrium Isotherm, Kinetic Modeling, Optimization, and Characterization Studies of Cadmium Adsorption by Surface-Engineered Escherichia coli

    Science.gov (United States)

    Tafakori, Vida; Zadmard, Reza; Tabandeh, Fatemeh; Amoozegar, Mohammad Ali; Ahmadian, Gholamreza

    2017-11-01

    Amongst the methods that remove heavy metals from environment, biosorption approaches have received increased attention because of their environmentally friendly and cost-effective feature, as well as their superior performances. In the present study, we investigated the ability of a surface-engineered Escherichia coli, carrying the cyanobacterial metallothionein on the cell surface, in the removal of Ca (II) from solution under different experimental conditions. The biosorption process was optimized using central composite design. In parallel, the kinetics of metal biosorption was studied, and the rate constants of different kinetic models were calculated. Cadmium biosorption is followed by the second-order kinetics. Freundlich and Langmuir equations were used to analyze sorption data; characteristic parameters were determined for each adsorption isotherm. The biosorption process was optimized using the central composite design. The optimal cadmium sorption capacity (284.69 nmol/mg biomass) was obtained at 40°C (pH 8) and a biomass dosage of 10 mg. The influence of two elutants, EDTA and CaCl2, was also assessed on metal recovery. Approximately, 68.58% and 56.54% of the adsorbed cadmium were removed by EDTA and CaCl2 during desorption, respectively. The Fourier transform infrared spectrophotometer (FTIR) analysis indicated that carboxyl, amino, phosphoryl, thiol, and hydroxyl are the main chemical groups involved in the cadmium bioadsorption process. Results from this study implied that chemical adsorption on the heterogeneous surface of E. coli E and optimization of adsorption parameters provides a highly efficient bioadsorbent.

  13. Palladium mixed-metal surface-modified AB5-type intermetallides enhance hydrogen sorption kinetics

    Directory of Open Access Journals (Sweden)

    Roman V. Denys

    2010-09-01

    Full Text Available Surface engineering approaches were adopted in the preparation of advanced hydrogen sorption materials, based on ‘low-temperature’, AB5-type intermetallides. The approaches investigated included micro-encapsulation with palladium and mixed-metal mantles using electroless plating. The influence of micro-encapsulation on the surface morphology and kinetics of hydrogen charging were investigated. It was found that palladium-nickel (Pd-Ni co-deposition by electroless plating significantly improved the kinetics of hydrogen charging of the AB5-type intermetallides at low hydrogen pressure and temperature, after long-term pre-exposure to air. The improvement in the kinetics of hydrogen charging was credited to a synergistic effect between the palladium and nickel atoms in the catalytic mantle and the formation of an ‘interfacial bridge’ for hydrogen diffusion by the nickel atoms in the deposited layer. The developed surface-modified materials may find application in highly selective hydrogen extraction, purification, and storage from impure hydrogen feeds.

  14. Improved Oxygen Evolution Kinetics and Surface States Passivation of Ni-Bi Co-Catalyst for a Hematite Photoanode

    Directory of Open Access Journals (Sweden)

    Ke Dang

    2017-06-01

    Full Text Available This paper describes the combinational surface kinetics enhancement and surface states passivation of nickel-borate (Ni-Bi co-catalyst for a hematite (Fe2O3 photoanode. The Ni-Bi-modified Fe2O3 photoanode exhibits a cathodic onset potential shift of 230 mV and a 2.3-fold enhancement of the photocurrent at 1.23 V, versus the reversible hydrogen electrode (RHE. The borate (Bi in the Ni-Bi film promotes the release of protons for the oxygen evolution reaction (OER.

  15. Full-dimensional analytical potential energy surface describing the gas-phase Cl + C2H6 reaction and kinetics study of rate constants and kinetic isotope effects.

    Science.gov (United States)

    Rangel, Cipriano; Espinosa-Garcia, Joaquin

    2018-02-07

    Within the Born-Oppenheimer approximation a full-dimensional analytical potential energy surface, PES-2017, was developed for the gas-phase hydrogen abstraction reaction between the chlorine atom and ethane, which is a nine body system. This surface presents a valence-bond/molecular mechanics functional form dependent on 60 parameters and is fitted to high-level ab initio calculations. This reaction presents little exothermicity, -2.30 kcal mol -1 , with a low height barrier, 2.44 kcal mol -1 , and intermediate complexes in the entrance and exit channels. We found that the energetic description was strongly dependent on the ab initio level used and it presented a very flat topology in the entrance channel, which represents a theoretical challenge in the fitting process. In general, PES-2017 reproduces the ab initio information used as input, which is merely a test of self-consistency. As a first test of the quality of the PES-2017, a theoretical kinetics study was performed in the temperature range 200-1400 K using two approaches, i.e. the variational transition-state theory and quasi-classical trajectory calculations, with spin-orbit effects. The rate constants show reasonable agreement with experiments in the whole temperature range, with the largest differences at the lowest temperatures, and this behaviour agrees with previous theoretical studies, thus indicating the inherent difficulties in the theoretical simulation of the kinetics of the title reaction. Different sources of error were analysed, such as the limitations of the PES and theoretical methods, recrossing effects, and the tunnelling effect, which is negligible in this reaction, and the manner in which the spin-orbit effects were included in this non-relativistic study. We found that the variation of spin-orbit coupling along the reaction path, and the influence of the reactivity of the excited Cl( 2 P 1/2 ) state, have relative importance, but do not explain the whole discrepancy. Finally, the

  16. 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.

  17. 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.

  18. The importance of kinetics and redox in the biogeochemical cycling of iron in the surface ocean.

    Directory of Open Access Journals (Sweden)

    Peter L. Croot

    2012-06-01

    Full Text Available It is now well established that Iron (Fe is a limiting element in many regions of the open ocean. Our current understanding of the key processes which control iron distribution in the open ocean have been largely based on thermodynamic measurements performed under the assumption of equilibrium conditions. Using this equilibrium approach, researchers have been able to detect and quantify organic complexing ligands in seawater and examine their role in increasing the overall solubility of iron. Our current knowledge about iron bioavailability to phytoplankton and bacteria is also based heavily on carefully controlled laboratory studies where it is assumed the chemical species are in equilibrium in line with the free ion association model (FIAM and/or its successor the biotic ligand model (BLM. Similarly most field work on Fe biogeochemistry generally consists of a single profile which is in essence a ‘snap-shot’ in time of the system under investigation. However it is well known that the surface ocean is an extremely dynamic environment and it is unlikely if thermodynamic equilibrium between all the iron species present is ever truly achieved. In sunlit waters this is mostly due to the daily passage of the sun across the sky leading to photoredox processes which alter Fe speciation by cycling between redox states and between inorganic and organic species. Episodic deposition events, are also important perturbations to iron cycling as they bring new iron to the system altering the equilibrium between species and phases. Over the last 20 years the mesoscale iron enrichment experiments (e.g. IronEx I /II, SOIREE, EisenEx, SOFeX, EIFeX, SAGE, SEEDS and SERIES I /II and the FeCycle (I/II experiments have provided the first insights into processes altering iron speciation and distribution which occur over temporal scales of days to weeks. Here we utilize new field data collected in the open ocean on the redox and complexation kinetics of iron in the

  19. Kinetics of ultraviolet and plasma surface modification of poly(dimethylsiloxane) probed by sum frequency vibrational spectroscopy.

    Science.gov (United States)

    Ye, Hongke; Gu, Zhiyong; Gracias, David H

    2006-02-14

    In numerous applications in microfluidics, cell growth, soft lithography, and molecular imprinting, the surface of poly(dimethylsiloxane) (PDMS) is modified from a hydrophobic methyl-terminated surface to a hydrophilic hydroxyl-terminated surface. In this study, we investigated molecular structural and orientational changes at the PDMS-air interface in response to three commonly used surface modification processes: exposure to long-wavelength ultraviolet light (UV), exposure to short-wavelength UV that generates ozone (UVO), and exposure to oxygen plasma (OP). The surfaces of two PDMS compositions (10:1 and 4:1 of base polymer/curing agent) were probed during modification, using monolayer-sensitive IR + visible sum frequency generation (SFG) vibrational spectroscopy, with two different polarization combinations. During PDMS surface modification, the peak intensities of CH3 side groups and CH2 cross-link groups decreased, while peak intensities of Si-OH groups increased. There was no significant change in the average orientation of the CH3 groups on the PDMS surface during modification. The concentration of CH3 groups on the surface decreased exponentially with time, for all three UV, UVO, and OP modification processes, with first order kinetics and time constants of approximately 160, 66, and 0.3 min, respectively. At steady state, residual CH3 groups were detected at the PDMS surface for UV and UVO treatments; however, there were negligible CH3 groups detected after OP modification.

  20. Experimental study on heat transfer augmentation for high heat flux removal in rib-roughened narrow channels

    International Nuclear Information System (INIS)

    Islam, M.S.; Monde, Masanori; Hino, Ryutaro; Haga, Katsuhiro; Sudo, Yukio.

    1997-07-01

    Frictional pressure drop and heat transfer performance in a very narrow rectangular channel having one-sided constant heat flux and repeated-ribs for turbulent flow have been investigated experimentally, and their experimental correlations were obtained using the least square method. The rib pitch-to-height ratios(p/k) were 10 and 20 while holding the rib height constant at 0.2mm, the Reynolds number(Re) from 2,414 to 98,458 under different channel heights of 1.2mm, 2.97mm, and 3.24mm, the rib height-to-channel equivalent diameter(k/De) of 0.03, 0.04, and 0.09 respectively. The results show that the rib-roughened surface augments heat transfer 2-3 times higher than that of the smooth surface with the expense of 2.8-4 times higher frictional pressure drop under Re=5000-10 5 , p/k=10, and H=1.2mm. Experimental results obtained by channel height, H=1.2mm shows a little bit higher heat transfer and friction factor performance than the higher channel height, H=3.24mm. The effect of fin and consequently higher turbulence intensity are responsible for producing higher heat transfer rates. The obtained correlations could be used to design the cooling passages between the target plates to remove high heat flux up to 12MW/m 2 generated at target plates in a high-intensity proton accelerator system. (author). 54 refs

  1. TiNOx coatings on roughened titanium and CoCr alloy accelerate early osseointegration of dental implants in minipigs.

    Science.gov (United States)

    Durual, Stéphane; Rieder, Philippe; Garavaglia, Giovanni; Filieri, Anna; Cattani-Lorente, Maria; Scherrer, Susanne S; Wiskott, H W Anselm

    2013-01-01

    Titanium nitride oxide (TiNOx) coatings are known for their biocompatibility, hardness and high resistance to corrosion and wear. Further, they can be applied by plasma vapor deposition onto a wide variety of metallic, mineral, or organic substrates. In cell cultures, TiNOx coatings applied onto SLA (sandblasted, large grit, acid etched)-roughened titanium surfaces increased human primary osteoblast proliferation by 1.5 times in the first 2 weeks after seeding, while maintaining a high degree of cell differentiation. Therefore, the objectives of the present study were (i) to determine whether these findings would translate into the enhanced osseointegration of TiNOx-coated implants in vivo and (ii) to compare the osseointegration of Ti-SLA (titanium-SLA) and CoCr-SLA (cobalt-chromium-SLA) implants coated with TiNOx. Forty-eight cylinders made of Ti-SLA, Ti-SLA-TiNOx (TiNOx-coated Ti-SLA) and CoCr-SLA-TiNOx (TiNOx-coated CoCr-SLA) were implanted into the lower jawbone of 8 minipigs. The bone-to-implant contact was determined after 1 week, 2 weeks, 1 month and 3 months. Osseointegration proceeded normally on all 3 surfaces, with equal activity after the first week of healing. After 2 weeks, bone-to-implant contact was 1.8 times higher on TiNOx coatings, either deposited on Ti or on CoCr. These differences fell off after 1 and 3 months of healing. When compared to standard SLA titanium, TiNOx coatings enhance implant osseointegration during the first month of healing. Furthermore, this stimulating effect is independent of the substrate, leading to similar results whether the coating is applied onto SLA-Ti or onto SLA-CoCr. Copyright © 2012 Elsevier Inc. All rights reserved.

  2. 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.

  3. Effect of Basic Residue on the Kinetics of Peptide Fragmentation Examined Using Surface-Induced Dissociation Combined with Resonant Ejection

    Energy Technology Data Exchange (ETDEWEB)

    Laskin, Julia

    2015-11-30

    In this work, resonant ejection coupled with surface-induced dissociation (SID) in a Fourier transform ion cyclotron resonance mass spectrometer is used to examine fragmentation kinetics of two singly protonated hexapeptides, RYGGFL and KYGGFL, containing the basic arginine residue and less basic lysine residue at the N-terminus. The kinetics of individual reaction channels at different collision energies are probed by applying a short ejection pulse (1 ms) in resonance with the cyclotron frequency of a selected fragment ion and varying the delay time between ion-surface collision and resonant ejection while keeping total reaction delay time constant. Rice-Ramsperger-Kassel-Marcus (RRKM) modeling of the experimental data provides accurate threshold energies and activation entropies of individual reaction channels. Substitution of arginine with less basic lysine has a pronounced effect on the observed fragmentation kinetics of several pathways, including the b2 ion formation, but has little or no effect on formation of the b5+H2O fragment ion. The combination of resonant ejection SID, time- and collision energy-resolved SID, and RRKM modeling of both types of experimental data provides a detailed mechanistic understanding of the primary dissociation pathways of complex gaseous ions.

  4. Kinetics and thermodynamics studies on the BMP-2 adsorption onto hydroxyapatite surface with different multi-morphological features

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Zhiwei; Huangfu, Changxin; Wang, Yanying; Ge, Hongwei; Yao, Yao; Zou, Ping; Wang, Guangtu [College of Science, Sichuan Agricultural University, Ya' an 625014 (China); He, Hua [Institute of Animal Genetics and Breeding, Sichuan Agricultural University, Wenjiang, Sichuan 611130 (China); Rao, Hanbing, E-mail: rhbscu@gmail.com [College of Science, Sichuan Agricultural University, Ya' an 625014 (China)

    2015-07-01

    The effect of the surface topography on protein adsorption process is of great significance for designing hydroxyapatite (HA) ceramic material surfaces. In this work, three different topographies of HA materials HA-sheet, HA-rod, and HA-whisker were synthesized and testified by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Brunauer–Emmett–Teller (BET) and a field emission scanning electron microscopy (FE-SEM). We have systematically investigated the adsorption kinetics and thermodynamics of bone morphogenetic proteins (BMP-2) on the three different topography surfaces of HA, respectively. The results showed that the maximum adsorption capacities of HA-sheet, HA-rod and HA-whisker were (219.96 ± 10.18), (247.13 ± 12.35), and (354.67 ± 17.73) μg · g{sup −1}, respectively. Kinetic parameters, rate constants, equilibrium adsorption capacities and related correlation coefficients, for each kinetic model were calculated as well as discussed. It demonstrated that the adsorption of BMP-2 onto HA could be described by the pseudo second-order equation. Adsorption of BMP-2 onto HA followed the Langmuir isotherm. It confirmed that compared with other samples HA-whisker had more adsorption sites for its high specific surface area which could provide more opportunities for protein molecules. The adsorption processes were endothermic (ΔH > 0), spontaneous (ΔG < 0) and entropy increasing (ΔS > 0). A possible adsorption mechanism has been proposed. In addition, the BMP-2 could be adsorbed to the surface which existed slight conformational changes by FT-IR. - Highlights: • A novel protein adsorption studies based on sheet, rod and whisker of HA were designed. • Kinetic and thermodynamics parameters of BMP-2 and HA bonded materials were evaluated. • Surface topographies of the HA effect BMP-2 adsorption • The HA-whisker material had excellent adsorption performance for protein enrichment. • The electrostatic interaction is responsible for the

  5. Kinetics and thermodynamics studies on the BMP-2 adsorption onto hydroxyapatite surface with different multi-morphological features

    International Nuclear Information System (INIS)

    Lu, Zhiwei; Huangfu, Changxin; Wang, Yanying; Ge, Hongwei; Yao, Yao; Zou, Ping; Wang, Guangtu; He, Hua; Rao, Hanbing

    2015-01-01

    The effect of the surface topography on protein adsorption process is of great significance for designing hydroxyapatite (HA) ceramic material surfaces. In this work, three different topographies of HA materials HA-sheet, HA-rod, and HA-whisker were synthesized and testified by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Brunauer–Emmett–Teller (BET) and a field emission scanning electron microscopy (FE-SEM). We have systematically investigated the adsorption kinetics and thermodynamics of bone morphogenetic proteins (BMP-2) on the three different topography surfaces of HA, respectively. The results showed that the maximum adsorption capacities of HA-sheet, HA-rod and HA-whisker were (219.96 ± 10.18), (247.13 ± 12.35), and (354.67 ± 17.73) μg · g −1 , respectively. Kinetic parameters, rate constants, equilibrium adsorption capacities and related correlation coefficients, for each kinetic model were calculated as well as discussed. It demonstrated that the adsorption of BMP-2 onto HA could be described by the pseudo second-order equation. Adsorption of BMP-2 onto HA followed the Langmuir isotherm. It confirmed that compared with other samples HA-whisker had more adsorption sites for its high specific surface area which could provide more opportunities for protein molecules. The adsorption processes were endothermic (ΔH > 0), spontaneous (ΔG < 0) and entropy increasing (ΔS > 0). A possible adsorption mechanism has been proposed. In addition, the BMP-2 could be adsorbed to the surface which existed slight conformational changes by FT-IR. - Highlights: • A novel protein adsorption studies based on sheet, rod and whisker of HA were designed. • Kinetic and thermodynamics parameters of BMP-2 and HA bonded materials were evaluated. • Surface topographies of the HA effect BMP-2 adsorption • The HA-whisker material had excellent adsorption performance for protein enrichment. • The electrostatic interaction is responsible for the BMP-2

  6. Kinetic modeling and determination of reaction constants of Alzheimer's beta-amyloid fibril extension and dissociation using surface plasmon resonance.

    Science.gov (United States)

    Hasegawa, Kazuhiro; Ono, Kenjiro; Yamada, Masahito; Naiki, Hironobu

    2002-11-19

    To establish the kinetic model of the extension and dissociation of beta-amyloid fibrils (f(A)beta) in vitro, we analyzed these reactions using a surface plasmon resonance (SPR) biosensor. Sonicated f(A)beta were immobilized on the surface of the SPR sensor chip as seeds. The SPR signal increased linearly as a function of time after amyloid beta-peptides (Abeta) were injected into the f(A)beta-immobilized chips. The extension of f(A)beta was confirmed by atomic force microscopy. When flow cells were washed with running buffer, the SPR signal decreased with time after the extension reaction. The curve fitting resolved the dissociation reaction into the fast exponential and slow linear decay phases. Kinetic analysis of the effect of Abeta/f(A)beta concentrations on the reaction rate indicated that both the extension reaction and the slow linear phase of the dissociation were consistent with a first-order kinetic model; i.e., the extension/dissociation reactions proceed via consecutive association/dissociation of Abeta onto/from the end of existing fibrils. On the basis of this model, the critical monomer concentration ([M](e)) and the equilibrium association constant (K) were calculated, for the first time, to be 20 nM and 5 x 10(7) M(-1), respectively. Alternatively, [M](e) was directly measured as 200 nM, which may represent the equilibrium between the extension reaction and the fast phase of the dissociation. The SPR biosensor is a useful quantitative tool for the kinetic and thermodynamic study of the molecular mechanisms of f9A)beta formation in vitro.

  7. Generalized Temporal Acceleration Scheme for Kinetic Monte Carlo Simulations of Surface Catalytic Processes by Scaling the Rates of Fast Reactions.

    Science.gov (United States)

    Dybeck, Eric C; Plaisance, Craig P; Neurock, Matthew

    2017-04-11

    A novel algorithm is presented that achieves temporal acceleration during kinetic Monte Carlo (KMC) simulations of surface catalytic processes. This algorithm allows for the direct simulation of reaction networks containing kinetic processes occurring on vastly disparate time scales which computationally overburden standard KMC methods. Previously developed methods for temporal acceleration in KMC were designed for specific systems and often require a priori information from the user such as identifying the fast and slow processes. In the approach presented herein, quasi-equilibrated processes are identified automatically based on previous executions of the forward and reverse reactions. Temporal acceleration is achieved by automatically scaling the intrinsic rate constants of the quasi-equilibrated processes, bringing their rates closer to the time scales of the slow kinetically relevant nonequilibrated processes. All reactions are still simulated directly, although with modified rate constants. Abrupt changes in the underlying dynamics of the reaction network are identified during the simulation, and the reaction rate constants are rescaled accordingly. The algorithm was utilized here to model the Fischer-Tropsch synthesis reaction over ruthenium nanoparticles. This reaction network has multiple time-scale-disparate processes which would be intractable to simulate without the aid of temporal acceleration. The accelerated simulations are found to give reaction rates and selectivities indistinguishable from those calculated by an equivalent mean-field kinetic model. The computational savings of the algorithm can span many orders of magnitude in realistic systems, and the computational cost is not limited by the magnitude of the time scale disparity in the system processes. Furthermore, the algorithm has been designed in a generic fashion and can easily be applied to other surface catalytic processes of interest.

  8. Kinetic electron emission due to perpendicular impact of carbon ions on tungsten surfaces

    Czech Academy of Sciences Publication Activity Database

    Lorinčík, Jan; Šroubek, Zdeněk; Brunmayr, M.; Kowarik, G.; Aumayr, F.

    2009-01-01

    Roč. 255, č. 12 (2009), s. 6303-6307 ISSN 0169-4332 Institutional research plan: CEZ:AV0Z20670512 Keywords : Kinetic electron emission * Carbon Subject RIV: JB - Sensors, Measurment, Regulation Impact factor: 1.616, year: 2009

  9. Kinetic electron emission from metal surfaces induced by impact of slow ions

    Czech Academy of Sciences Publication Activity Database

    Šroubek, Zdeněk; Lorinčík, Jan

    -, č. 625 (2014), s. 7-9 ISSN 0039-6028 R&D Projects: GA MŠk(CZ) ME10086 Institutional support: RVO:67985882 Keywords : Ion induced kinetic electron emission * Electronic excitation Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering Impact factor: 1.925, year: 2014

  10. Elucidating the Kinetics of Expression and Immune Cell Infiltration Resulting from Plasmid Gene Delivery Enhanced by Surface Dermal Electroporation

    Directory of Open Access Journals (Sweden)

    Kate E. Broderick

    2013-08-01

    Full Text Available The skin is an attractive tissue for vaccination in a clinical setting due to the accessibility of the target, the ease of monitoring and most importantly the immune competent nature of the dermal tissue. While skin electroporation offers an exciting and novel future methodology for the delivery of DNA vaccines in the clinic, little is known about the actual mechanism of the approach and the elucidation of the resulting immune responses. To further understand the mechanism of this platform, the expression kinetics and localization of a reporter plasmid delivered via a surface dermal electroporation (SEP device as well as the effect that this treatment would have on the resident immune cells in that tissue was investigated. Initially a time course (day 0 to day 21 of enhanced gene delivery with electroporation (EP was performed to observe the localization of green fluorescent protein (GFP expression and the kinetics of its appearance as well as clearance. Using gross imaging, GFP expression was not detected on the surface of the skin until 8 h post treatment. However, histological analysis by fluorescent microscopy revealed GFP positive cells as early as 1 h after plasmid delivery and electroporation. Peak GFP expression was observed at 24 h and the expression was maintained in skin for up to seven days. Using an antibody specific for a keratinocyte cell surface marker, reporter gene positive keratinocytes in the epidermis were identified. H&E staining of treated skin sections demonstrated an influx of monocytes and granulocytes at the EP site starting at 4 h and persisting up to day 14 post treatment. Immunological staining revealed a significant migration of lymphocytic cells to the EP site, congregating around cells expressing the delivered antigen. In conclusion, this study provides insights into the expression kinetics following EP enhanced DNA delivery targeting the dermal space. These findings may have implications in the future to design

  11. Controlling drug delivery kinetics from mesoporous titania thin films by pore size and surface energy

    Directory of Open Access Journals (Sweden)

    Karlsson J

    2015-07-01

    Full Text Available Johan Karlsson, Saba Atefyekta, Martin Andersson Department of Chemical and Biological Engineering, Chalmers University of Technology, Gothenburg, Sweden Abstract: The osseointegration capacity of bone-anchoring implants can be improved by the use of drugs that are administrated by an inbuilt drug delivery system. However, to attain superior control of drug delivery and to have the ability to administer drugs of varying size, including proteins, further material development of drug carriers is needed. Mesoporous materials have shown great potential in drug delivery applications to provide and maintain a drug concentration within the therapeutic window for the desired period of time. Moreover, drug delivery from coatings consisting of mesoporous titania has shown to be promising to improve healing of bone-anchoring implants. Here we report on how the delivery of an osteoporosis drug, alendronate, can be controlled by altering pore size and surface energy of mesoporous titania thin films. The pore size was varied from 3.4 nm to 7.2 nm by the use of different structure-directing templates and addition of a swelling agent. The surface energy was also altered by grafting dimethylsilane to the pore walls. The drug uptake and release profiles were monitored in situ using quartz crystal microbalance with dissipation (QCM-D and it was shown that both pore size and surface energy had a profound effect on both the adsorption and release kinetics of alendronate. The QCM-D data provided evidence that the drug delivery from mesoporous titania films is controlled by a binding–diffusion mechanism. The yielded knowledge of release kinetics is crucial in order to improve the in vivo tissue response associated to therapeutic treatments. Keywords: mesoporous titania, controlled drug delivery, release kinetics, alendronate, QCM-D

  12. SURFACE CHEMKIN-III: A Fortran package for analyzing heterogeneous chemical kinetics at a solid-surface - gas-phase interface

    Energy Technology Data Exchange (ETDEWEB)

    Coltrin, M.E.; Kee, R.J.; Rupley, F.M.; Meeks, E.

    1996-05-01

    This document is the user`s manual for the SURFACE CHEMKIN-III package. Together with CHEMKIN-III, this software facilitates the formation, solution, and interpretation of problems involving elementary heterogeneous and gas-phase chemical kinetics in the presence of a solid surface. The package consists of two major software components: an Interpreter and a Surface Subroutine Library. The Interpreter is a program that reads a symbolic description of a user-specified chemical reaction mechanism. One output from the Interpreter is a data file that forms a link to the Surface Subroutine Library, which is a collection of about seventy modular Fortran subroutines that may be called from a user`s application code to return information on chemical production rates and thermodynamic properties. This version of SURFACE CHEMKIN-III includes many modifications to allow treatment of multi-fluid plasma systems, for example modeling the reactions of highly energetic ionic species with a surface. Optional rate expressions allow reaction rates to depend upon ion energy rather than a single thermodynamic temperature. In addition, subroutines treat temperature as an array, allowing an application code to define a different temperature for each species. This version of SURFACE CHEMKIN-III allows use of real (non-integer) stoichiometric coefficients; the reaction order with respect to species concentrations can also be specified independent of the reaction`s stoichiometric coefficients. Several different reaction mechanisms can be specified in the Interpreter input file through the new construct of multiple materials.

  13. Evaluation of Degradation Kinetic of Tomato Paste Color in Heat Processing and Modeling of These Changes by Response Surface Methodology

    Directory of Open Access Journals (Sweden)

    M. Ganjeh

    2015-12-01

    Full Text Available Color is an important qualitative factor in tomato products such as tomato paste which is affected by heat processing. The main goal of this study was to evaluate the degradation kinetics of tomato paste color during heat processing by Arrhenius equation and modeling of these changes by response surface methodology (RSM. Considering this purpose, tomato paste was processed at three temperatures of 60, 70 and 80 °C for 25-100 minutes and by three main color indices including L, a and b, a/b ratio, total color difference (TCD, Saturation index (SI and hue angle (HU was analyzed. Degradation kinetics of these parameters was evaluated by Arrhenius equation and their changing trends were modeled by RSM. All parameters except TCA (zero order followed a first order reaction. The b index by highest and TCA and a/b by least activation energies had the maximum and minimum sensitivity to the temperature changes, respectively. Also, TCD and b had the maximum and minimum changing rates, respectively. All responses were influenced by independent parameters (the influence of temperature was more than time and RSM was capable of modeling and predicting these responses. In general, Arrhenius equation was appropriate to evaluate degradation kinetics of tomato paste color changes and RSM was able to estimate independent and interaction effects of time and temperature so that quadratic models were capable to predict these changes by a high accuracy (R2 > 0.95.

  14. Changes in surface electromyography signals and kinetics associated with progression of fatigue at two speeds during wheelchair propulsion.

    Science.gov (United States)

    Qi, Liping; Wakeling, James; Grange, Simon; Ferguson-Pell, Martin

    2012-01-01

    The purpose of this study was to determine whether muscle balance is influenced by fatigue in a recordable way, toward creating novel defensive activity strategies for manual wheelchair users (MWUs). Wheelchair propulsion to a point of mild fatigue, level 15 on the Rating of Perceived Exertion scale, was investigated at two different speeds. Surface electromyographic (EMG) activity of 7 muscles was recorded on 14 nondisabled participants. Kinetic variables were measured using a SmartWheel. No significant effect was found of percentage endurance time on kinetic variables for the two propulsion speeds. Fatigue-related changes in the EMG spectra were identified as an increase of EMG intensity and a decrease of mean power frequency as a function of percent endurance time for the tested muscles under both fast and slow speed conditions. The greater increases in activity for propulsive muscles compared with recovery muscles during fast speed wheelchair propulsion indicated muscle imbalance associated with fatiguing wheelchair propulsion. This study shows how kinetic and EMG information might be used as feedback to MWUs to ensure that they conduct activity in ways that do not precipitate injury.

  15. Study on fermentation conditions of palm juice vinegar by response surface methodology and development of a kinetic model

    Directory of Open Access Journals (Sweden)

    S. Ghosh

    2012-09-01

    Full Text Available Natural vinegar is one of the fermented products which has some potentiality with respect to a nutraceutical standpoint. The present study is an optimization of the fermentation conditions for palm juice vinegar production from palm juice (Borassus flabellifer wine, this biochemical process being aided by Acetobacter aceti (NCIM 2251. The physical parameters of the fermentation conditions such as temperature, pH, and time were investigated by Response Surface Methodology (RSM with 2³ factorial central composite designs (CCD. The optimum pH, temperature and time were 5.5, 30 °C and 72 hrs for the highest yield of acetic acid (68.12 g / L. The quadratic model equation had a R² value of 0.992. RSM played an important role in elucidating the basic mechanisms in a complex situation, thus providing better process control by maximizing acetic acid production with the respective physical parameters. At the optimized conditions of temperature, pH and time and with the help of mathematical kinetic equations, the Monod specific growth rate ( µ max= 0.021 h-1, maximum Logistic specific growth rate ( µ 'max = 0.027 h-1 and various other kinetic parameters were calculated, which helped in validation of the experimental data. Therefore, the established kinetic models may be applied for the production of natural vinegar by fermentation of low cost palm juice.

  16. Direct observation of the kinetics and dynamics of molecular desorption from liquid surfaces

    Science.gov (United States)

    Quintella, Cristina M.; McCaffery, Anthony J.; Zidan, Mohammed D.

    1993-11-01

    We report measurement of the kinetics and dynamics of I 2 molecules scattered off liquid polydimethylsiloxane. Time-resolved LIF spectra give number densities and quantum state populations throughout the trapping and desorption process. Temperature dependence yields desorption enthalpy Ed=30(±4) kJ mol -1, frequency factor 3 × 10 10. Dynamical behaviour indicates more than one mechanism for activation of trapped species, i.e. conversion of internal energy into translation and energising via interaction with liquid molecules.

  17. Measuring oxygen surface exchange kinetics on mixed-conducting composites by electrical conductivity relaxation

    NARCIS (Netherlands)

    Hu, Bobing; Wang, Yunlong; Zhu, Zhuoying; Xia, Changrong; Bouwmeester, Henricus J.M.

    2015-01-01

    The oxygen release kinetics of mixed-conducting Sr2Fe1.5Mo0.5O6 d–Sm0.2Ce0.8O2 d (SFM–SDC) dualphase composites has been investigated, at 750 C, as a function of the SDC phase volume fraction using electrical conductivity relaxation (ECR) under reducing atmospheres, extending our previous work on

  18. A consistent hierarchy of generalized kinetic equation approximations to the master equation applied to surface catalysis.

    Science.gov (United States)

    Herschlag, Gregory J; Mitran, Sorin; Lin, Guang

    2015-06-21

    We develop a hierarchy of approximations to the master equation for systems that exhibit translational invariance and finite-range spatial correlation. Each approximation within the hierarchy is a set of ordinary differential equations that considers spatial correlations of varying lattice distance; the assumption is that the full system will have finite spatial correlations and thus the behavior of the models within the hierarchy will approach that of the full system. We provide evidence of this convergence in the context of one- and two-dimensional numerical examples. Lower levels within the hierarchy that consider shorter spatial correlations are shown to be up to three orders of magnitude faster than traditional kinetic Monte Carlo methods (KMC) for one-dimensional systems, while predicting similar system dynamics and steady states as KMC methods. We then test the hierarchy on a two-dimensional model for the oxidation of CO on RuO2(110), showing that low-order truncations of the hierarchy efficiently capture the essential system dynamics. By considering sequences of models in the hierarchy that account for longer spatial correlations, successive model predictions may be used to establish empirical approximation of error estimates. The hierarchy may be thought of as a class of generalized phenomenological kinetic models since each element of the hierarchy approximates the master equation and the lowest level in the hierarchy is identical to a simple existing phenomenological kinetic models.

  19. Kinetic analysis of the inhibition of the drug efflux protein AcrB using surface plasmon resonance.

    Science.gov (United States)

    Mowla, Rumana; Wang, Yinhu; Ma, Shutao; Venter, Henrietta

    2018-04-01

    Multidrug efflux protein complexes such as AcrAB-TolC from Escherichia coli are paramount in multidrug resistance in Gram-negative bacteria and are also implicated in other processes such as virulence and biofilm formation. Hence efflux pump inhibition, as a means to reverse antimicrobial resistance in clinically relevant pathogens, has gained increased momentum over the past two decades. Significant advances in the structural and functional analysis of AcrB have informed the selection of efflux pump inhibitors (EPIs). However, an accurate method to determine the kinetics of efflux pump inhibition was lacking. In this study we standardised and optimised surface plasmon resonance (SPR) to probe the binding kinetics of substrates and inhibitors to AcrB. The SPR method was also combined with a fluorescence drug binding method by which affinity of two fluorescent AcrB substrates were determined using the same conditions and controls as for SPR. Comparison of the results from the fluorescent assay to those of the SPR assay showed excellent correlation and provided validation for the methods and conditions used for SPR. The kinetic parameters of substrate (doxorubicin, novobiocin and minocycline) binding to AcrB were subsequently determined. Lastly, the kinetics of inhibition of AcrB were probed for two established inhibitors (phenylalanine arginyl β-naphthylamide and 1-1-naphthylmethyl-piperazine) and three novel EPIs: 4-isobutoxy-2-naphthamide (A2), 4-isopentyloxy-2-naphthamide (A3) and 4-benzyloxy-2-naphthamide (A9) have also been probed. The kinetic data obtained could be correlated with inhibitor efficacy and mechanism of action. This study is the first step in the quantitative analysis of the kinetics of inhibition of the clinically important RND-class of multidrug efflux pumps and will allow the design of improved and more potent inhibitors of drug efflux pumps. This article is part of a Special Issue entitled: Beyond the Structure-Function Horizon of Membrane

  20. Evaluation of kinetic constants of biomolecular interaction on optical surface plasmon resonance sensor with Newton Iteration Method

    Science.gov (United States)

    Zhao, Yuanyuan; Jiang, Guoliang; Hu, Jiandong; Hu, Fengjiang; Wei, Jianguang; Shi, Liang

    2010-10-01

    In the immunology, there are two important types of biomolecular interaction: antigens-antibodies and receptors-ligands. Monitoring the response rate and affinity of biomolecular interaction can help analyze the protein function, drug discover, genomics and proteomics research. Moreover the association rate constant and dissociation rate constant of receptors-ligands are the important parameters for the study of signal transmission between cells. Recent advances in bioanalyzer instruments have greatly simplified the measurement of the kinetics of molecular interactions. Non-destructive and real-time monitoring the response to evaluate the parameters between antigens and antibodies can be performed by using optical surface plasmon resonance (SPR) biosensor technology. This technology provides a quantitative analysis that is carried out rapidly with label-free high-throughput detection using the binding curves of antigens-antibodies. Consequently, the kinetic parameters of interaction between antigens and antibodies can be obtained. This article presents a low cost integrated SPR-based bioanalyzer (HPSPR-6000) designed by ourselves. This bioanalyzer is mainly composed of a biosensor TSPR1K23, a touch-screen monitor, a microprocessor PIC24F128, a microflow cell with three channels, a clamp and a photoelectric conversion device. To obtain the kinetic parameters, sensorgrams may be modeled using one of several binding models provided with BIAevaluation software 3.0, SensiQ or Autolab. This allows calculation of the association rate constant (ka) and the dissociation rate constant (kd). The ratio of ka to kd can be used to estimate the equilibrium constant. Another kind is the analysis software OriginPro, which can process the obtained data by nonlinear fitting and then get some correlative parameters, but it can't be embedded into the bioanalyzer, so the bioanalyzer don't support the use of OriginPro. This paper proposes a novel method to evaluate the kinetic parameters

  1. Ion-induced pattern formation on Co surfaces: An x-ray scattering and kinetic Monte Carlo study

    International Nuclear Information System (INIS)

    Malis, O.; Brock, J.D.; Headrick, R.L.; Yi, M.-S.; Pomeroy, J.M.

    2002-01-01

    We report time-resolved grazing incidence small-angle x-ray scattering and atomic force microscope studies of the evolution of the surface morphology of the Co(0001) surface during low-energy Ar + ion sputtering. At temperatures greater than 573 K, the surface is smooth, erosion proceeding in either a layer-by-layer mode or a step retraction mode. In contrast, at temperatures below 573 K, the surface develops a correlated pattern of mounds and/or pits with a characteristic length scale, λ. At room temperature, the surface morphology is dominated by mounds, and coarsens as time progresses. The characteristic length scale obeys the apparent power law, λ=Axt n with n=0.20±0.02. The rms roughness of the surface increases in time according to a similar power law with a slightly larger exponent β=0.28±0.02. Kinetic Monte Carlo simulations of a simple model of Cu(111) were also performed. These simulations suggest that mound formation and coarsening at low temperatures is due to the slow diffusion of sputter-created adatoms on step edges. The morphological transition from mounds to pits is associated with activation of kink diffusion. These simple simulations produce values for the scaling exponents that agree with the experimental measurements

  2. Surface kinetics for catalytic combustion of hydrogen-air mixtures on platinum at atmospheric pressure in stagnation flows

    Science.gov (United States)

    Ikeda, H.; Sato, J.; Williams, F. A.

    1995-03-01

    Experimental studies of the combustion of premixed hydrogen-air mixtures impinging on the surface of a heated platinum plate at normal atmospheric pressure were performed and employed to draw inferences concerning surface reaction mechanisms and rate parameters applicable under practical conditions of catalytic combustion. Plate and gas temperatures were measured by thermocouples, and concentration profiles of major stable species in the gas were measured by gas-chromatographic analyses of samples withdrawn by quartz probes. In addition, ignition and extinction phenomena were recorded and interpreted with the aid of a heat balance at the surface and a previous flow-field analysis of the stagnation-point boundary layer. From the experimental and theoretical results, conclusions were drawn concerning the surface chemical-kinetic mechanisms and values of the elementary rate parameters that are consistent with the observations. In particular, the activation energy for the surface oxidation step H + OH → H 2O is found to be appreciably less at these high surface coverages than in the low-coverage limit.

  3. Surface Rheology and Adsorption Kinetics Reveal the Relative Amphiphilicity, Interfacial Activity, and Stability of Human Exchangeable Apolipoproteins☆

    Science.gov (United States)

    Bolanos-Garcia, Victor Martin; Renault, Anne; Beaufils, Sylvie

    2008-01-01

    Exchangeable apolipoproteins are located in the surface of lipoprotein particles and regulate lipid metabolism through direct protein-protein and protein-lipid interactions. These proteins are characterized by the presence of tandem repeats of amphiphatic α-helix segments and a high surface activity in monolayers and lipoprotein surfaces. A noteworthy aspect in the description of the function of exchangeable apolipoproteins is the requirement of a quantitative account of the relation between their physicochemical and structural characteristics and changes in the mesoscopic system parameters such as the maximum surface pressure and relative stability at interfaces. To comply with this demand, we set out to establish the relations among α-helix amphiphilicity, surface concentration, and surface rheology of apolipoproteins ApoA-I, ApoA-II, ApoC-I, ApoC-II, and ApoC-III adsorbed at the air-water interface. Our studies render further insights into the interfacial properties of exchangeable apolipoproteins, including the kinetics of their adsorption and the physical properties of the interfacial layer. PMID:17993480

  4. Iron oxidation kinetics and phosphorus immobilization at the groundwater-surface water interface

    NARCIS (Netherlands)

    van der Grift, Bas|info:eu-repo/dai/nl/373433484; Rozemeijer, Joachim|info:eu-repo/dai/nl/304838403; Griffioen, Jasper|info:eu-repo/dai/nl/091129265; van der Velde, Ype

    2014-01-01

    Eutrophication of freshwater environments following diffuse nutrient loads is a widely recognized water quality problem in catchments. Fluxes of non-point P sources to surface waters originate from surface runoff and flow from soil water and groundwater into surface water. The availability of P in

  5. Effect of structural modifications on the drying kinetics of foods: changes in volume, surface area and product shape

    Directory of Open Access Journals (Sweden)

    Antonio De Michelis

    2013-10-01

    Full Text Available Macro and micro-structural changes take place during food dehydration. Macro-structural changes encompass modifications in shape, area and volume. Studies of such changes are important because dehydration kinetics (essential for calculating industrial dryers may be highly influenced by changes in food shape and dimensions. The overall changes in volume, surface area (“shrinkage” and shape (Heywood factor, with provides a close description of food shape were determined experimentally, and the results were correlated with simple expressions. Hence, although dehydration kinetics can be modeled with simplified overall shrinkage expressions, the possibility of selecting a suitable geometry and predicting the characteristics dimensions will provide higher accuracy. An additional unresolved problem is the lack of a general model that predicts macro-structural changes for various foods and diverse geometries. In this work, based on experimental data of sweet and sour cherries, and rose hip fruits, a simplified general model to predict changes in volume and surface area are proposed. To estimate how the changes in characteristic dimensions affect the kinetic studies, experimental drying curves for the three fruits by means of a diffusional model considered the following variants for the characteristic dimensions: (i The radius of the fresh food, assumed constant; (ii The radius of the partially dehydrated product; (iii The radius predicted by the correlation for structural changes, especially volume, obtained in this work and generalized for the three fruits, and (iv to demonstrate the need to study the macro-structural changes for all dehydrated foods, also be present the case of a restructured food.

  6. Effects of Iron-Oxide Nanoparticle Surface Chemistry on Uptake Kinetics and Cytotoxicity in CHO-K1 Cells

    Directory of Open Access Journals (Sweden)

    Camille C. Hanot

    2015-12-01

    Full Text Available Superparamagnetic iron-oxide nanoparticles (SPIONs show great promise for multiple applications in biomedicine. While a number of studies have examined their safety profile, the toxicity of these particles on reproductive organs remains uncertain. The goal of this study was to evaluate the cytotoxicity of starch-coated, aminated, and PEGylated SPIONs on a cell line derived from Chinese Hamster ovaries (CHO-K1 cells. We evaluated the effect of particle diameter (50 and 100 nm and polyethylene glycol (PEG chain length (2k, 5k and 20k Da on the cytotoxicity of SPIONs by investigating cell viability using the tetrazolium dye 3-(4,5-dimethylthiazol-2-yl-2,5-diphenyltetrazolium bromide (MTT and sulforhodamine B (SRB assays. The kinetics and extent of SPION uptake by CHO-K1 cells was also studied, as well as the resulting generation of intracellular reactive oxygen species (ROS. Cell toxicity profiles of SPIONs correlated strongly with their cellular uptake kinetics, which was strongly dependent on surface properties of the particles. PEGylation caused a decrease in both uptake and cytotoxicity compared to aminated SPIONs. Interestingly, 2k Da PEG-modifed SPIONs displayed the lowest cellular uptake and cytotoxicity among all studied particles. These results emphasize the importance of surface coatings when engineering nanoparticles for biomedical applications.

  7. Surface plasmon resonance imaging based multiplex biosensor: Integration of biomolecular screening, detection and kinetics estimation.

    NARCIS (Netherlands)

    Krishnamoorthy, G.; Carlen, Edwin; van den Berg, Albert; Schasfoort, Richardus B.M.

    2010-01-01

    We present a multiplex biosensing method to simultaneously screen targets of interest in a multiple target analyte sample and to extract the binding affinities of all interactant pairs from a single sensor surface using a commercial surface plasmon resonance imaging system. For demonstration, we

  8. In situ photoemission spectroscopy using synchrotron radiation for O2 translational kinetic energy induced oxidation processes of partially-oxidized Si(001) surfaces

    International Nuclear Information System (INIS)

    Teraoka, Yuden; Yoshigoe, Akitaka

    2001-01-01

    The influence of translational kinetic energy of incident O 2 molecules for the passive oxidation process of partially-oxidized Si(001) surfaces has been studied by photoemission spectroscopy. The translational kinetic energy of O 2 molecules was controlled up to 3 eV by a supersonic seed beam technique using a high temperature nozzle. Two translational kinetic energy thresholds (1.0 eV and 2.6 eV) were found out in accordance with the first-principles calculation for the oxidation of clean surfaces. Si-2p photoemission spectra measured in representative translational kinetic energies revealed that the translational kinetic energy dependent oxidation of dimers and the second layer (subsurface) backbonds were caused by the direct dissociative chemisorption of O 2 molecules. Moreover, the difference in chemical bonds for oxygen atoms was found out to be as low and high binding energy components in O-1s photoemission spectra. Especially, the low binding energy component increased with increasing the translational kinetic energy that indicates the translational kinetic energy induced oxidation in backbonds. (author)

  9. Morphology of ion-sputtered surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Makeev, Maxim A. E-mail: makeev@baton.phys.lsu.edu; Cuerno, Rodolfo; Barabasi, Albert-Laszlo

    2002-12-01

    We derive a stochastic nonlinear continuum equation to describe the morphological evolution of amorphous surfaces eroded by ion bombardment. Starting from Sigmund's theory of sputter erosion, we calculate the coefficients appearing in the continuum equation in terms of the physical parameters characterizing the sputtering process. We analyze the morphological features predicted by the continuum theory, comparing them with the experimentally reported morphologies. We show that for short time scales, where the effect of nonlinear terms is negligible, the continuum theory predicts ripple formation. We demonstrate that in addition to relaxation by thermal surface diffusion, the sputtering process can also contribute to the smoothing mechanisms shaping the surface morphology. We explicitly calculate an effective surface diffusion constant characterizing this smoothing effect and show that it is responsible for the low temperature ripple formation observed in various experiments. At long time scales the nonlinear terms dominate the evolution of the surface morphology. The nonlinear terms lead to the stabilization of the ripple wavelength and we show that, depending on the experimental parameters, such as angle of incidence and ion energy, different morphologies can be observed: asymptotically, sputter eroded surfaces could undergo kinetic roughening, or can display novel ordered structures with rotated ripples. Finally, we discuss in detail the existing experimental support for the proposed theory and uncover novel features of the surface morphology and evolution, that could be directly tested experimentally.

  10. Adsorptive kinetic mechanism of heavy metal cations on the surface of graphite oxide and its SiO2 composite

    Science.gov (United States)

    Sheet, Imtithal; Kabbani, Ahmad; Holail, Hanafy

    2017-02-01

    Nanomaterials have gained great attention because of their novel size- and shape-dependent properties, large specific surface area and high reaction activity. Moreover, nanomaterials have a wide range of applications, as in the technological and environmental challenges in the areas of solar energy conversion, catalysis, medicine, and water treatments. In the present study, nanostructured graphite oxide, silica/graphite oxide composites and silica nanoparticles were used for the removal of the heavy metal ions from aqueous solutions by a batch adsorption method and the adsorptive kinetic mechanism of heavy metal cations on the surface of graphite oxide and its SiO2 composite was evaluated. The experimental results revealed a strong adsorption of the metal cations on the surface of graphite oxide, this is reflected in the shifts in wave numbers after adsorption with nanostructured graphite oxide and the big shift in wave numbers (Δv¯) for nickel ions reflects chemosorption type of adsorption. This is confirmed by the coherence between Δv¯, removal percentage and crystal field stabilization energy (CFSE). Silica/ GO (2:3) composite showed the greatest removal percentage at different concentrations compared to pure graphite oxide and silica nanoparticles. The higher removal percentage of nickel ions by silica /GO composite (2:3) was observed at 180 min contact time and basic pH. The kinetic studies showed that silica/ GO (2:3) composite had rapid adsorption rate and efficiency and it was found to follow first order rate expression or an exponential decay of the metal cations from water study.

  11. Electrochemical evaluation of electron transfer kinetics of high and low redox potential laccases on gold electrode surface

    International Nuclear Information System (INIS)

    Frasconi, Marco; Boer, Harry; Koivula, Anu; Mazzei, Franco

    2010-01-01

    Laccases and other multicopper oxidases are reported to be able to carry out direct electron transfer reactions when immobilized onto electrode surface. This allows detailed research of their electron transfer mechanisms. We have recently characterized the kinetic properties of four laccases in homogenous solution and immobilized onto an electrode surface with respect to a set of different redox mediators. In this paper we report the direct electron transfer of four purified laccases from Trametes hirsuta (ThL), Trametes versicolor (TvL), Melanocarpus albomyces (r-MaL) and Rhus vernicifera (RvL), by trapping the proteins within an electrochemically inert polymer of tributylmethyl phosphonium chloride coating a gold electrode surface. In particular, we have characterized the steps involved in the laccases electron transfer mechanism as well as the factors limiting each step. During the voltammetric experiments, non-turnover Faradic signals with midpoint potential of about 790 and 400 mV were observed for high potential laccases, ThL and TvL, corresponding to redox transformations of the T1 site and the T2/T3 cluster of the enzyme, respectively, whereas low redox potential laccases r-MaL and RvL shown a redox couple with a midpoint potential around 400 mV. The electrocatalytic properties of these laccase modified electrodes for the reduction of oxygen have been evaluated demonstrating significative direct electron transfer kinetics. The biocatalytic activity of laccases was also monitored in the presence of a well known inhibitor, sodium azide. On the basis of the experimental results, a hypothesis about the electronic pathway for intramolecular electron transfer characterizing laccases has been proposed.

  12. Electrochemical evaluation of electron transfer kinetics of high and low redox potential laccases on gold electrode surface

    Energy Technology Data Exchange (ETDEWEB)

    Frasconi, Marco [Department of Chemistry and Drug Technologies, Sapienza University of Rome, P.le Aldo Moro, 5 00185 Rome (Italy); Boer, Harry; Koivula, Anu [VTT Technical Research Centre of Finland, P.O. Box 1000, FI-02044 VTT (Finland); Mazzei, Franco, E-mail: franco.mazzei@uniroma1.i [Department of Chemistry and Drug Technologies, Sapienza University of Rome, P.le Aldo Moro, 5 00185 Rome (Italy)

    2010-12-30

    Laccases and other multicopper oxidases are reported to be able to carry out direct electron transfer reactions when immobilized onto electrode surface. This allows detailed research of their electron transfer mechanisms. We have recently characterized the kinetic properties of four laccases in homogenous solution and immobilized onto an electrode surface with respect to a set of different redox mediators. In this paper we report the direct electron transfer of four purified laccases from Trametes hirsuta (ThL), Trametes versicolor (TvL), Melanocarpus albomyces (r-MaL) and Rhus vernicifera (RvL), by trapping the proteins within an electrochemically inert polymer of tributylmethyl phosphonium chloride coating a gold electrode surface. In particular, we have characterized the steps involved in the laccases electron transfer mechanism as well as the factors limiting each step. During the voltammetric experiments, non-turnover Faradic signals with midpoint potential of about 790 and 400 mV were observed for high potential laccases, ThL and TvL, corresponding to redox transformations of the T1 site and the T2/T3 cluster of the enzyme, respectively, whereas low redox potential laccases r-MaL and RvL shown a redox couple with a midpoint potential around 400 mV. The electrocatalytic properties of these laccase modified electrodes for the reduction of oxygen have been evaluated demonstrating significative direct electron transfer kinetics. The biocatalytic activity of laccases was also monitored in the presence of a well known inhibitor, sodium azide. On the basis of the experimental results, a hypothesis about the electronic pathway for intramolecular electron transfer characterizing laccases has been proposed.

  13. Kinetically induced irreversibility in electro-oxidation and reduction of Pt surface

    Science.gov (United States)

    Jinnouchi, Ryosuke; Kodama, Kensaku; Suzuki, Takahisa; Morimoto, Yu

    2015-05-01

    A mean field kinetic model was developed for electrochemical oxidations and reductions of Pt(111) on the basis of density functional theory calculations, and the reaction mechanisms were analyzed. The model reasonably describes asymmetric shapes of cyclic voltammograms and small Tafel slopes of relevant redox reactions observed in experiments without assuming any unphysical forms of rate equations. Simulations using the model indicate that the oxidation of Pt(111) proceeds via an electrochemical oxidation from Pt to PtOH and a disproportionation reaction from PtOH to PtO and Pt, while its reduction proceeds via two electrochemical reductions from PtO to PtOH and from PtOH to Pt.

  14. 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.

  15. Growth kinetics of white graphene (h-BN) on a planarised Ni foil surface.

    Science.gov (United States)

    Cho, Hyunjin; Park, Sungchan; Won, Dong-Il; Kang, Sang Ook; Pyo, Seong-Soo; Kim, Dong-Ik; Kim, Soo Min; Kim, Hwan Chul; Kim, Myung Jong

    2015-07-09

    The morphology of the surface and the grain orientation of metal catalysts have been considered to be two important factors for the growth of white graphene (h-BN) by chemical vapour deposition (CVD). We report a correlation between the growth rate of h-BN and the orientation of the nickel grains. The surface of the nickel (Ni) foil was first polished by electrochemical polishing (ECP) and subsequently annealed in hydrogen at atmospheric pressure to suppress the effect of the surface morphology. Atmospheric annealing with hydrogen reduced the nucleation sites of h-BN, which induced a large crystal size mainly grown from the grain boundary with few other nucleation sites in the Ni foil. A higher growth rate was observed from the Ni grains that had the {110} or {100} orientation due to their higher surface energy.

  16. Evaluation of Scaling Approaches for the Oceanic Dissipation Rate of Turbulent Kinetic Energy in the Surface Ocean

    Science.gov (United States)

    Esters, L. T.; Ward, B.; Sutherland, G.; Ten Doeschate, A.; Landwehr, S.; Bell, T. G.; Christensen, K. H.

    2016-02-01

    The air-sea exchange of heat, gas and momentum plays an important role for the Earth's weather and global climate. The exchange processes between ocean and atmosphere are influenced by the prevailing surface ocean dynamics. This surface ocean is a highly turbulent region where there is enhanced production of turbulent kinetic energy (TKE). The dissipation rate of TKE (ɛ) in the surface ocean is an important process for governing the depth of both the mixing and mixed layers, which are important length-scales for many aspects of ocean research. However, there exist very limited observations of ɛ under open ocean conditions and consequently our understanding of how to model the dissipation profile is very limited. The approaches to model profiles of ɛ that exist, differ by orders of magnitude depending on their underlying theoretical assumption and included physical processes. Therefore, scaling ɛ is not straight forward and requires open ocean measurements of ɛ to validate the respective scaling laws. This validated scaling of ɛ, is for example required to produce accurate mixed layer depths in global climate models. Errors in the depth of the ocean surface boundary layer can lead to biases in sea surface temperature. Here, we present open ocean measurements of ɛ from the Air-Sea Interaction Profiler (ASIP) collected during several cruises in different ocean basins. ASIP is an autonomous upwardly rising microstructure profiler allowing undisturbed profiling up to the ocean surface. These direct measurements of ɛ under various types of atmospheric and oceanic conditions along with measurements of atmospheric fluxes and wave conditions allow us to make a unique assessment of several scaling approaches based on wind, wave and buoyancy forcing. This will allow us to best assess the most appropriate ɛ-based parameterisation for air-sea exchange.

  17. Role of Microstructure and Surface Defects on the Dissolution Kinetics of CeO2, a UO2 Fuel Analogue.

    Science.gov (United States)

    Corkhill, Claire L; Bailey, Daniel J; Tocino, Florent Y; Stennett, Martin C; Miller, James A; Provis, John L; Travis, Karl P; Hyatt, Neil C

    2016-04-27

    The release of radionuclides from spent fuel in a geological disposal facility is controlled by the surface mediated dissolution of UO2 in groundwater. In this study we investigate the influence of reactive surface sites on the dissolution of a synthesized CeO2 analogue for UO2 fuel. Dissolution was performed on the following: CeO2 annealed at high temperature, which eliminated intrinsic surface defects (point defects and dislocations); CeO2-x annealed in inert and reducing atmospheres to induce oxygen vacancy defects and on crushed CeO2 particles of different size fractions. BET surface area measurements were used as an indicator of reactive surface site concentration. Cerium stoichiometry, determined using X-ray Photoelectron Spectroscopy (XPS) and supported by X-ray Diffraction (XRD) analysis, was used to determine oxygen vacancy concentration. Upon dissolution in nitric acid medium at 90 °C, a quantifiable relationship was established between the concentration of high energy surface sites and CeO2 dissolution rate; the greater the proportion of intrinsic defects and oxygen vacancies, the higher the dissolution rate. Dissolution of oxygen vacancy-containing CeO2-x gave rise to rates that were an order of magnitude greater than for CeO2 with fewer oxygen vacancies. While enhanced solubility of Ce(3+) influenced the dissolution, it was shown that replacement of vacancy sites by oxygen significantly affected the dissolution mechanism due to changes in the lattice volume and strain upon dissolution and concurrent grain boundary decohesion. These results highlight the significant influence of defect sites and grain boundaries on the dissolution kinetics of UO2 fuel analogues and reduce uncertainty in the long term performance of spent fuel in geological disposal.

  18. Elucidation of the Oxygen Surface Kinetics in a Coated Dual-Phase Membrane for Enhancing Oxygen Permeation Flux.

    Science.gov (United States)

    Na, Beom Tak; Park, Jeong Hwan; Park, Jong Hyuk; Yu, Ji Haeng; Joo, Jong Hoon

    2017-06-14

    The dual-phase membrane has received much attention as the solution to the instability of the oxygen permeation membrane. It has been reported that the oxygen flux of the dual-phase membrane is greatly enhanced by the active coating layer. However, there has been little discussion about the enhancement mechanism by surface coating in the dual-phase membrane. This study investigates the oxygen flux of the Ce 0.9 Gd 0.1 O 2-δ -La 0.7 Sr 0.3 MnO 3±δ (GDC 80 vol %/LSM 20 vol %) composite membrane depending on the oxygen partial pressure (P O 2 ) to elucidate the mechanism of enhanced oxygen flux by the surface modification in the fluorite-rich phase dual-phase membrane. The oxygen permeation resistances were obtained from the oxygen flux as a function of P O 2 using the oxygen permeation model. The surface exchange coefficient (k) and the bulk diffusion coefficient (D) were calculated from these resistances. According to the calculated k and D values, we concluded that the active coating layer (La 0.6 Sr 0.4 CoO 3-δ ) significantly increased the k value of the membrane. Furthermore, the surface exchange reaction on the permeate side was more sluggish than that at the feed side under operating conditions (feed: 0.21 atm/permeate side: 4.7 × 10 -4 atm). Therefore, the enhancement of the oxygen surface exchange kinetics at the permeate side is more important in improving the oxygen permeation flux of the thin film-based fluorite-rich dual-phase membrane. These results provide new insight about the function of the surface coating to enhance the oxygen permeation flux of the dual-phase membrane.

  19. Surface Morphology and Overlayer Formation Kinetics of OXYGEN/SILVER(110) Studied by Scanning Tunneling Microscopy

    Science.gov (United States)

    Pai, Woei Wu.

    1995-01-01

    I have applied scanning tunneling microscopy (STM) to study clean and oxygen-covered vicinal Ag(110) surfaces at room temperature. Experimental results of surface morphology/stability, surface mass transport and surface chemical reactivity are presented. On clean vicinal Ag(110) surfaces, the steps distribute under the influence of step-step interactions. The terrace width distributions indicate an additional oscillatory component besides an l^{-2} interaction term. If the surface is contaminated slightly (quasi-clean), isolated "pinning sites" impede the motion of steps. The interactions between steps push the steps across the pinning site, resulting in a curved step front. When oxygen atoms adsorb on stepped Ag(110), a dramatic change in surface morphology occurs. The surface separates into two distinct phases--step bunches and large terraces (facets). The orientational instability is closely related to the linear "added-row" structure of the oxygen overlayer, as the long O chains push steps into bunches. The O chains do not push the steps effectively when O chains orient perpendicular to steps, and the faceting proceeds through nucleation. If the O chains orient near parallel to steps, however, O chains push the steps easily and the faceting proceeds through spinodal decomposition. To understand the mass transport during faceting, I quantify the thermal step fluctuations by employing a Langevin statistical analysis. The mass transport mechanism at the step edge is shown to be by atomic exchange between steps and terraces, making the step an effective source or sink for Ag adatoms. This Ag source also proves essential in O overlayer formation, since both Ag and O atoms are incorporated into the "added -row" overlayer structure. Because an Ag source must be found during the adlayer formation, I show the surface morphology is sensitive to oxygen dosing pressure. Above a critical O pressure of 10^{-5} mbar, vacancy islands on terraces provide a second source of Ag

  20. Molecular projectile effects for kinetic electron emission from carbon- and metal-surfaces bombarded by slow hydrogen ions

    CERN Document Server

    Cernusca, S; Aumayr, F; Diez-Muino, R; Juaristi, J I

    2003-01-01

    Total yields for kinetic electron emission (KE) have been determined for impact of hydrogen monomer-, dimer- and trimer-ions (impact energy <10 keV) on atomically clean surfaces of carbon-fiber inforced graphite used as first-wall armour in magnetic fusion devices. The data are compared with KE yields for impact of same projectile ions on atomically clean highly oriented pyrolytic graphite and polycrystalline gold. We discuss KE yields for the different targets if bombarded by equally fast molecular and atomic ions in view to 'projectile molecular effects' (different yields per proton for equally fast atomic and molecular ions), which are expected from calculated electronic projectile energy losses in these target materials.

  1. Molecular projectile effects for kinetic electron emission from carbon- and metal-surfaces bombarded by slow hydrogen ions

    International Nuclear Information System (INIS)

    Cernusca, S.; Winter, H.P.; Aumayr, F.; Diez Muino, R.; Juaristi, J.I.

    2003-01-01

    Total yields for kinetic electron emission (KE) have been determined for impact of hydrogen monomer-, dimer- and trimer-ions (impact energy <10 keV) on atomically clean surfaces of carbon-fiber inforced graphite used as first-wall armour in magnetic fusion devices. The data are compared with KE yields for impact of same projectile ions on atomically clean highly oriented pyrolytic graphite and polycrystalline gold. We discuss KE yields for the different targets if bombarded by equally fast molecular and atomic ions in view to 'projectile molecular effects' (different yields per proton for equally fast atomic and molecular ions), which are expected from calculated electronic projectile energy losses in these target materials

  2. Growth kinetics and morphology of a ballistic deposition model that incorporates surface diffusion for two species

    International Nuclear Information System (INIS)

    El-Nashar, H.F.; Cerdeira, H.A.

    1998-08-01

    We introduce a ballistic deposition model for two kinds of particles (active and inactive) in (2+1) dimensions upon introducing the surface diffusion for the inactive particles. A morphological structural transition is found as the probability of being the inactive particle increases. This transition is well defined by the change in the behavior of the surface width when it is plotted versus time and probability. The exponents α and β calculated for different values of probability show the same behavior. The presence of both types of particles issues three different processes that control the growing surface: overhanging, nonlocal growth and diffusion. It finally leads to a morphological structural transition where the universality changes away from that of Kardar-Parisi-Zhang, in (2+1) dimensions, but not into Edwards-Wilkinson's. (author)

  3. 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.

  4. Adsorption kinetics of WS2 quantum dots onto a polycrystalline gold surface.

    Science.gov (United States)

    Ozhukil Valappil, Manila; Roopesh, Mekkat; Alwarappan, Subbiah; Pillai, Vijayamohanan K

    2018-04-18

    In this work, we report the adsorption kinetics of electrochemically synthesized WS2 quantum dots (ca. 3 nm) onto a polycrystalline gold electrode. Langmuir adsorption isotherm approach was employed to explore the temperature and adsorbate concentration dependence of experimentally calculated equilibrium constant of adsorption (Keq) and free energy for adsorption (ΔGads). Subsequently, we extract other thermodynamic parameters such as adsorption rate constant (Kads), desorption rate constant (Kd), the enthalpy of adsorption (ΔHads) and the entropy of adsorption (ΔSads). Our findings indicate that ΔGads is temperature dependent and ca. -1.74 kcal mol-1, ΔHads = -10.697 kcal mol-1 and ΔSads = -30 cal/(mol.K). These investigations on the contribution of the enthalpic and entropic forces to the total free energy of this system underscore the role of entropic forces on the stability of the WS2 QDs monolayer and provide new thermodynamic insights into other TMDQDs monolayers as well.

  5. Equilibrium and kinetics of Sin Nombre hantavirus binding at DAF/CD55 functionalized bead surfaces.

    Science.gov (United States)

    Buranda, Tione; Swanson, Scarlett; Bondu, Virginie; Schaefer, Leah; Maclean, James; Mo, Zhenzhen; Wycoff, Keith; Belle, Archana; Hjelle, Brian

    2014-03-10

    Decay accelerating factor (DAF/CD55) is targeted by many pathogens for cell entry. It has been implicated as a co-receptor for hantaviruses. To examine the binding of hantaviruses to DAF, we describe the use of Protein G beads for binding human IgG Fc domain-functionalized DAF ((DAF)₂-Fc). When mixed with Protein G beads the resulting DAF beads can be used as a generalizable platform for measuring kinetic and equilibrium binding constants of DAF binding targets. The hantavirus interaction has high affinity (24-30 nM; k(on) ~ 10⁵ M⁻¹ s⁻¹, k(off) ~ 0.0045 s⁻¹). The bivalent (DAF)₂-Fc/SNV data agree with hantavirus binding to DAF expressed on Tanoue B cells (K(d) = 14.0 nM). Monovalent affinity interaction between SNV and recombinant DAF of 58.0 nM is determined from competition binding. This study serves a dual purpose of presenting a convenient and quantitative approach of measuring binding affinities between DAF and the many cognate viral and bacterial ligands and providing new data on the binding constant of DAF and Sin Nombre hantavirus. Knowledge of the equilibrium binding constant allows for the determination of the relative fractions of bound and free virus particles in cell entry assays. This is important for drug discovery assays for cell entry inhibitors.

  6. Modifications of the hydriding kinetics of a metallic surface, using ion implantation

    International Nuclear Information System (INIS)

    Crusset, D.

    1992-10-01

    Uranium reacts with hydrogen to form an hydride: this reaction leads to the total destruction of the material. To modify the reactivity of an uranium surface towards hydrogen, ion implantation was selected, among surface treatments techniques. Four elements (carbon, nitrogen, oxygen, sulfur) were implanted to different doses. The results show a modification of the hydriding mechanism and a significant increase in the reaction induction times, notably at high implantation doses. Several techniques (SIMS, X-rays phases analysis and residual stresses determination) were used to characterize the samples and understand the different mechanisms involved

  7. Kinetic model for electric-field induced point defect redistribution near semiconductor surfaces

    Science.gov (United States)

    Gorai, Prashun; Seebauer, Edmund G.

    2014-07-01

    The spatial distribution of point defects near semiconductor surfaces affects the efficiency of devices. Near-surface band bending generates electric fields that influence the spatial redistribution of charged mobile defects that exchange infrequently with the lattice, as recently demonstrated for pile-up of isotopic oxygen near rutile TiO2 (110). The present work derives a mathematical model to describe such redistribution and establishes its temporal dependence on defect injection rate and band bending. The model shows that band bending of only a few meV induces significant redistribution, and that the direction of the electric field governs formation of either a valley or a pile-up.

  8. Kinetic model for electric-field induced point defect redistribution near semiconductor surfaces

    International Nuclear Information System (INIS)

    Gorai, Prashun; Seebauer, Edmund G.

    2014-01-01

    The spatial distribution of point defects near semiconductor surfaces affects the efficiency of devices. Near-surface band bending generates electric fields that influence the spatial redistribution of charged mobile defects that exchange infrequently with the lattice, as recently demonstrated for pile-up of isotopic oxygen near rutile TiO 2 (110). The present work derives a mathematical model to describe such redistribution and establishes its temporal dependence on defect injection rate and band bending. The model shows that band bending of only a few meV induces significant redistribution, and that the direction of the electric field governs formation of either a valley or a pile-up.

  9. 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

  10. Roughened glass slides and a spectrophotometer for the detection of the wavelength-dependent refractive index of transparent liquids.

    Science.gov (United States)

    Niskanen, Ilpo; Räty, Jukka; Myllylä, Risto; Sutinen, Veijo; Matsuda, Kiyofumi; Homma, Kazuhiro; Silfsten, Pertti; Peiponen, Kai-Erik

    2012-07-01

    We describe a method to determine the wavelength-dependent refractive index of liquids by measurement of light transmittance with a spectrophotometer. The method is based on using roughened glass slides with different a priori known refractive indices and immersing the slides into the transparent liquid with unknown refractive index. Using the dispersion data on the glass material it is possible to find the index match between the liquid and the glass slide, and hence the refractive index of the liquid.

  11. Mass and heat transfer between evaporation and condensation surfaces: Atomistic simulation and solution of Boltzmann kinetic equation.

    Science.gov (United States)

    Zhakhovsky, Vasily V; Kryukov, Alexei P; Levashov, Vladimir Yu; Shishkova, Irina N; Anisimov, Sergey I

    2018-04-16

    Boundary conditions required for numerical solution of the Boltzmann kinetic equation (BKE) for mass/heat transfer between evaporation and condensation surfaces are analyzed by comparison of BKE results with molecular dynamics (MD) simulations. Lennard-Jones potential with parameters corresponding to solid argon is used to simulate evaporation from the hot side, nonequilibrium vapor flow with a Knudsen number of about 0.02, and condensation on the cold side of the condensed phase. The equilibrium density of vapor obtained in MD simulation of phase coexistence is used in BKE calculations for consistency of BKE results with MD data. The collision cross-section is also adjusted to provide a thermal flux in vapor identical to that in MD. Our MD simulations of evaporation toward a nonreflective absorbing boundary show that the velocity distribution function (VDF) of evaporated atoms has the nearly semi-Maxwellian shape because the binding energy of atoms evaporated from the interphase layer between bulk phase and vapor is much smaller than the cohesive energy in the condensed phase. Indeed, the calculated temperature and density profiles within the interphase layer indicate that the averaged kinetic energy of atoms remains near-constant with decreasing density almost until the interphase edge. Using consistent BKE and MD methods, the profiles of gas density, mass velocity, and temperatures together with VDFs in a gap of many mean free paths between the evaporation and condensation surfaces are obtained and compared. We demonstrate that the best fit of BKE results with MD simulations can be achieved with the evaporation and condensation coefficients both close to unity.

  12. Enhancement of Friction against a Rough Surface by a Ridge-Channel Surface Microstructure.

    Science.gov (United States)

    Bai, Ying; Hui, Chung-Yuen; Levrard, Benjamin; Jagota, Anand

    2015-07-14

    We report on a study of the sliding friction of elastomeric surfaces patterned with ridges and channels (and unstructured flat controls), against both smooth and roughened spherical indenters. Against the smooth spherical indenter, all of the structured surfaces have highly reduced sliding friction due to the reduction in actual area of contact. Against roughened spherical indenters, however, the sliding force for structured samples can be up to 50% greater than that of an unstructured flat control. The mechanism of enhanced friction against a rough surface is due to a combination of increased actual area of contact, interlocking between roughness and the surface structure, and attendant dynamic instabilities that dissipate energy.

  13. COMBINED THEORETICAL AND EXPERIMENTAL INVESTIGATION OF MECHANISMS AND KINETICS OF VAPOR-PHASE MERCURY UPTAKE BY CARBONACEOUS SURFACES; ANNUAL

    International Nuclear Information System (INIS)

    Radisav D. Vidic; Eric V. Borguet; Karl J. Johnson

    2000-01-01

    The overall goal of this research program is to gain fundamental understanding of the important chemistry and physics involved in mercury adsorption on carbonaceous surfaces. This knowledge will then be used to optimize adsorption processes and operating conditions to maximize the uptake of mercury within the required contact time. An additional long-term benefit of this research is the basic understanding of the Hg adsorption process, which may facilitate the design of new adsorbents for more efficient and cost-effective removal of Hg from a variety of effluent streams. Molecular modeling of the adsorption of Hg on carbonaceous surfaces will greatly increase the insight into the physics of the adsorption process and combined with in situ rate measurements of mercury adsorption and desorption (conventional and pulsed laser) on graphite using linear and nonlinear optical probes with real time optical resolution have the potential to provide fundamental insight into the process of mercury uptake by carbonaceous surfaces. Besides accurate assessment of key parameters influencing adsorption equilibrium, fundamental understanding of the kinetics of mercury adsorption, desorption, and diffusion will be developed in this study. These key physical and chemical processes postulated through molecular modeling efforts and verified by in situ measurements will be utilized to select (or develop) promising sorbents for mercury control, which will be tested under dynamic conditions using simulated flue gas

  14. Survival Kinetics of Salmonella enterica and Enterohemorrhagic Escherichia coli on a Plastic Surface at Low Relative Humidity and on Low-Water Activity Foods.

    Science.gov (United States)

    Hokunan, Hidekazu; Koyama, Kento; Hasegawa, Mayumi; Kawamura, Shuso; Koseki, Shigenobu

    2016-10-01

    We investigated the survival kinetics of Salmonella enterica and enterohemorrhagic Escherichia coli under various water activity (a w ) conditions to elucidate the net effect of a w on pathogen survival kinetics and to pursue the development of a predictive model of pathogen survival as a function of a w . Four serotypes of S. enterica (Stanley, Typhimurium, Chester, and Oranienburg) and three serotypes of enterohemorrhagic E. coli ( E. coli O26, E. coli O111, and E. coli O157:H7) were examined. These bacterial strains were inoculated on a plastic plate surface at a constant relative humidity (RH) (22, 43, 58, 68, or 93% RH, corresponding to the a w ) or on a surface of almond kernels (a w 0.58), chocolate (a w 0.43), radish sprout seeds (a w 0.58), or Cheddar cheese (a w 0.93) at 5, 15, or 25°C for up to 11 months. Under most conditions, the survival kinetics were nonlinear with tailing regardless of the storage a w , temperature, and bacterial strain. For all bacterial serotypes, there were no apparent differences in pathogen survival kinetics on the plastic surface at a given storage temperature among the tested RH conditions, except for the 93% RH condition. Most bacterial serotypes were rapidly inactivated on Cheddar cheese when stored at 5°C compared with their inactivation on chocolate, almonds, and radish sprout seeds. Distinct trends in bacterial survival kinetics were also observed between almond kernels and radish sprout seeds, even though the a w s of these two foods were not significantly different. The survival kinetics of bacteria inoculated on the plastic plate surface showed little correspondence to those of bacteria inoculated on food matrices at an identical a w . Thus, these results demonstrated that, for low-a w foods and/or environments, a w alone is insufficient to account for the survival kinetics of S. enterica and enterohemorrhagic E. coli .

  15. Kinetic and Surface Study of Single-Walled Aluminosilicate Nanotubes and Their Precursors

    Directory of Open Access Journals (Sweden)

    Mauricio Molina

    2013-03-01

    Full Text Available The structural and surface changes undergone by the different precursors that are produced during the synthesis of imogolite are reported. The surface changes that occur during the synthesis of imogolite were determined by electrophoretic migration (EM measurements, which enabled the identification of the time at which the critical precursor of the nanoparticles was generated. A critical parameter for understanding the evolution of these precursors is the isoelectric point (IEP, of which variation revealed that the precursors modify the number of active ≡Al-OH and ≡Si-OH sites during the formation of imogolite. We also found that the IEP is displaced to a higher pH level as a consequence of the surface differentiation that occurs during the synthesis. At the same time, we established that the pH of the reaction (pHrx decreases with the evolution and condensation of the precursors during aging. Integration of all of the obtained results related to the structural and surface properties allows an overall understanding of the different processes that occur and the products that are formed during the synthesis of imogolite.

  16. Kinetic Electron Emission from Higly Oriented Pyrolytic Graphite Surfaces Induced by Singly Charged Ions

    Czech Academy of Sciences Publication Activity Database

    Cernusca, S.; Diem, A.; Winter, H. P.; Aumayr, F.; Lörinčík, Jan; Šroubek, Zdeněk

    2002-01-01

    Roč. 193, - (2002), s. 616-620 ISSN 0168-583X Institutional research plan: CEZ:AV0Z4040901 Keywords : clean metal-surface * slow * polycrystalline gold Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.158, year: 2002

  17. Cortical surface-based analysis reduces bias and variance in kinetic modeling of brain PET data

    DEFF Research Database (Denmark)

    Greve, Douglas N; Svarer, Claus; Fisher, Patrick M

    2014-01-01

    estimates. Volume-based smoothing resulted in large bias and intersubject variance because it smears signal across tissue types. In some cases, PVC with volume smoothing paradoxically caused the estimated BPND to be less than when no PVC was used at all. When applied in the absence of PVC, cortical surface...

  18. High-resolution mass spectrometry for the analysis of interfacial kinetics of organic surface reactions

    NARCIS (Netherlands)

    Sen, Rickdeb

    2017-01-01

    In this thesis, XPS and DART–HRMS have been used in close conjugation to supplement each other, since the latter is a relatively new addition to surface chemist’s repertoire that – after development – needed a firm comparison to build up a reputation of its own. The strength of our approach has

  19. Comparison Study of the Kinetics of Ceftizoxime Penetration into Extravascular Spaces with Known Surface Area/Volume Ratio In Vitro and In Vivo in Rabbits

    OpenAIRE

    Van Etta, Linda L.; Fasching, Claudine E.; Peterson, Lance R.; Gerding, Dale N.

    1983-01-01

    The extravascular kinetics of ceftizoxime were studied both in an in vitro kinetic model and in an in vivo rabbit model. Visking tubing chambers were used in both models to provide extravascular spaces with large or small volumes and surface areas, but identical surface area/volume ratios. Four rabbits, each implanted with two large Visking chambers and four small chambers, received 50 mg of ceftizoxime per kg intramuscularly every 3 h for eight doses. In the in vitro model, 80 mg of ceftizox...

  20. Drop entrainment from the surface of oil mist filters: mechanisms, kinetics, and drop spectra

    OpenAIRE

    Wurster, S.; Kolb, H.; Meyer, J.; Kasper, G.

    2016-01-01

    Oil entrainment from coalescence filters has been characterized by different techniques. Drop spectra and entrainment rates were measured by a combination of techniques from 1 mm over long periods of time. Dominant entrainment mechanism(s) are identified on the basis of comparisons of entrainment rates measured in different regions of the filter surface with rates of air bubble formation, measurements of oil film thickness, as well as visual observations. Experiments are supported by force es...

  1. Tunnel junction sensors for HCI-surface measurements at low kinetic energies

    Science.gov (United States)

    Pomeroy, J. M.; Lake, R. E.

    2013-12-01

    In recent years, we have developed and deployed the capability to make and use tunnel junctions sensors (TJS) as extremely sensitive tools for the measurement of surface nanofeatures created by particle-surface interactions. The focus of our interest has been highly charged ion (HCI) produced nanofeatures, which we are able to produce in situ due to a direct vacuum connection to the NIST electron beam ion trap (EBIT). Using these sensors, we make systematic studies of the role of the charge state on the size of features created by HCIs and connect those measurements to the stopping power. Recently we have begun to study reduced velocities at a fixed charge state for which little previous theoretical or experimental work has been done. Due to many technical improvements that have been made to our methods, we offer a contemporary summary of the TJS fabrication and HCI irradiation method. Further, we present early experimental results showing increased surface damage when Xe41+ is extracted at ≈4.6 kV in comparison with ≈8.1 kV.

  2. Tunnel junction sensors for HCI-surface measurements at low kinetic energies

    Energy Technology Data Exchange (ETDEWEB)

    Pomeroy, J.M., E-mail: joshua.pomeroy@nist.gov [National Institute of Standards and Technology, 100 Bureau Dr., Gaithersburg, MD 20899 (United States); Lake, R.E. [National Institute of Standards and Technology, 100 Bureau Dr., Gaithersburg, MD 20899 (United States); Department of Physics and Astronomy, Clemson University, Clemson, SC 29634 (United States)

    2013-12-15

    In recent years, we have developed and deployed the capability to make and use tunnel junctions sensors (TJS) as extremely sensitive tools for the measurement of surface nanofeatures created by particle-surface interactions. The focus of our interest has been highly charged ion (HCI) produced nanofeatures, which we are able to produce in situ due to a direct vacuum connection to the NIST electron beam ion trap (EBIT). Using these sensors, we make systematic studies of the role of the charge state on the size of features created by HCIs and connect those measurements to the stopping power. Recently we have begun to study reduced velocities at a fixed charge state for which little previous theoretical or experimental work has been done. Due to many technical improvements that have been made to our methods, we offer a contemporary summary of the TJS fabrication and HCI irradiation method. Further, we present early experimental results showing increased surface damage when Xe{sup 41+} is extracted at ≈4.6 kV in comparison with ≈8.1 kV.

  3. Tunnel junction sensors for HCI-surface measurements at low kinetic energies

    International Nuclear Information System (INIS)

    Pomeroy, J.M.; Lake, R.E.

    2013-01-01

    In recent years, we have developed and deployed the capability to make and use tunnel junctions sensors (TJS) as extremely sensitive tools for the measurement of surface nanofeatures created by particle-surface interactions. The focus of our interest has been highly charged ion (HCI) produced nanofeatures, which we are able to produce in situ due to a direct vacuum connection to the NIST electron beam ion trap (EBIT). Using these sensors, we make systematic studies of the role of the charge state on the size of features created by HCIs and connect those measurements to the stopping power. Recently we have begun to study reduced velocities at a fixed charge state for which little previous theoretical or experimental work has been done. Due to many technical improvements that have been made to our methods, we offer a contemporary summary of the TJS fabrication and HCI irradiation method. Further, we present early experimental results showing increased surface damage when Xe 41+ is extracted at ≈4.6 kV in comparison with ≈8.1 kV

  4. A means to estimate thermal and kinetic parameters of coal dust layer from hot surface ignition tests.

    Science.gov (United States)

    Park, Haejun; Rangwala, Ali S; Dembsey, Nicholas A

    2009-08-30

    A method to estimate thermal and kinetic parameters of Pittsburgh seam coal subject to thermal runaway is presented using the standard ASTM E 2021 hot surface ignition test apparatus. Parameters include thermal conductivity (k), activation energy (E), coupled term (QA) of heat of reaction (Q) and pre-exponential factor (A) which are required, but rarely known input values to determine the thermal runaway propensity of a dust material. Four different dust layer thicknesses: 6.4, 12.7, 19.1 and 25.4mm, are tested, and among them, a single steady state dust layer temperature profile of 12.7 mm thick dust layer is used to estimate k, E and QA. k is calculated by equating heat flux from the hot surface layer and heat loss rate on the boundary assuming negligible heat generation in the coal dust layer at a low hot surface temperature. E and QA are calculated by optimizing a numerically estimated steady state dust layer temperature distribution to the experimentally obtained temperature profile of a 12.7 mm thick dust layer. Two unknowns, E and QA, are reduced to one from the correlation of E and QA obtained at criticality of thermal runaway. The estimated k is 0.1 W/mK matching the previously reported value. E ranges from 61.7 to 83.1 kJ/mol, and the corresponding QA ranges from 1.7 x 10(9) to 4.8 x 10(11)J/kg s. The mean values of E (72.4 kJ/mol) and QA (2.8 x 10(10)J/kg s) are used to predict the critical hot surface temperatures for other thicknesses, and good agreement is observed between measured and experimental values. Also, the estimated E and QA ranges match the corresponding ranges calculated from the multiple tests method and values reported in previous research.

  5. The surface oxidation kinetics of zirconium-niobium alloys and aα-Fe with prevailing cubical texture

    International Nuclear Information System (INIS)

    Mukhambetov, D.G.; Kargin, D.B.; Chalaya, O. V.; Berber, N.N.

    2002-01-01

    It is known, that the kinetics of oxidation of zirconium at formed heating is characterized by two consecutive stages. At the initial stage the thin protecting film will be derived. The relation of its depth from time h (t) is described predominantly by parabolic law. Some time later there can be a transition to the linear law of oxidation. The time moment divided these areas on the kinetic relation is called as a point of break. The film is formed at the second stage, has a developed grid of pores or cracks, can be flake away and be crumbled by losing its protective properties. At the oxidation of the surface shells of the heat generating elements and the technological channels of atomic boilers both stages are proceeded simultaneously. This phenomenon is called modular corrosion. Its consequences can be dangerous for the equipment. Its mechanism is not clear till now. Similar dependencies h(t), with the break point, beginning from which the thin film is transformed into the thick one were found by us at the oxidation α-Fe with prevailing cubical texture. The task of the work was to study the oxide film growth laws in order to clarify the mechanisms of transition of the thin film into the oxide layer on the α-Fe surface and Zr-Nb alloy modular corrosion emergence. Low-carbonate steel with contents 99.43 % of α-Fe was used as a model object of our research. In the texture of the steel surface planar direction [100] was prevalent. Its part accounted for about 40 %. The isothermal air oxidation was carried out in the interval of 450-500 deg. C . Phase composition of the film was determined with X-ray diffraction. The mathematical treatment of the dependencies h(t) obtained by experiment showed that the kinetics of the film growth can be conditionally divided into 4-stages. The initial stage is described by function logarithmic function, the other stages - by the power mode h n =A n ·t, namely, the second stage - is described by function close to cubical (n≅3

  6. Kinetics, thermodynamics and surface heterogeneity assessment of uranium(VI) adsorption onto cation exchange resin derived from a lignocellulosic residue

    Energy Technology Data Exchange (ETDEWEB)

    Anirudhan, T.S., E-mail: tsani@rediffmail.com [Department of Chemistry, University of Kerala, Kariavattom, Trivandrum 695581 (India); Radhakrishnan, P.G. [Department of Chemistry, University of Kerala, Kariavattom, Trivandrum 695581 (India)

    2009-02-15

    A new cation exchange resin (PGTFS-COOH) having a carboxylate functional group at the chain end was prepared by grafting poly(hydroxyethylmethacrylate) onto tamarind fruit shell, TFS (a lignocellulosic residue) using potassium peroxydisulphate-sodium thiosulphate redox initiator, and in the presence of N,N'-methylenebisacrylamide (MBA) as a crosslinking agent, followed by functionalisation. The adsorbent was characterized with the help of FTIR, XRD, scanning electron micrographs (SEM), and potentiometric titrations. The kinetic and isotherm data, obtained at optimum pH value 6.0 at different temperatures could be fitted with pseudo-second-order equation and Sips isotherm model, respectively. An increase in temperature induces positive effect on the adsorption process. The calculated activation energy of adsorption (E{sub a}, 18.67 kJ/mol) indicates that U(VI) adsorption was largely due to diffusion-controlled process. The values of adsorption enthalpy, Gibbs free energy, and entropy were calculated using thermodynamic function relationships. The decrease in adsorption enthalpy with increasing U(VI) uploading on the adsorbent, reflects the surface energetic heterogeneity of the adsorbent. The isosteric heat of adsorption was quantitatively correlated with the fractional loading for the U(VI) ions adsorption onto PGTFS-COOH. The results showed that the PGTFS-COOH possessed heterogeneous surface with sorption sites having different activities.

  7. Kinetics, thermodynamics and surface heterogeneity assessment of uranium(VI) adsorption onto cation exchange resin derived from a lignocellulosic residue

    Science.gov (United States)

    Anirudhan, T. S.; Radhakrishnan, P. G.

    2009-02-01

    A new cation exchange resin (PGTFS-COOH) having a carboxylate functional group at the chain end was prepared by grafting poly(hydroxyethylmethacrylate) onto tamarind fruit shell, TFS (a lignocellulosic residue) using potassium peroxydisulphate-sodium thiosulphate redox initiator, and in the presence of N,N'-methylenebisacrylamide (MBA) as a crosslinking agent, followed by functionalisation. The adsorbent was characterized with the help of FTIR, XRD, scanning electron micrographs (SEM), and potentiometric titrations. The kinetic and isotherm data, obtained at optimum pH value 6.0 at different temperatures could be fitted with pseudo-second-order equation and Sips isotherm model, respectively. An increase in temperature induces positive effect on the adsorption process. The calculated activation energy of adsorption ( Ea, 18.67 kJ/mol) indicates that U(VI) adsorption was largely due to diffusion-controlled process. The values of adsorption enthalpy, Gibbs free energy, and entropy were calculated using thermodynamic function relationships. The decrease in adsorption enthalpy with increasing U(VI) uploading on the adsorbent, reflects the surface energetic heterogeneity of the adsorbent. The isosteric heat of adsorption was quantitatively correlated with the fractional loading for the U(VI) ions adsorption onto PGTFS-COOH. The results showed that the PGTFS-COOH possessed heterogeneous surface with sorption sites having different activities.

  8. Deposition of metallic clusters on a metallic surface at zero initial kinetic energy: Evidence for implantation and site exchanges

    Science.gov (United States)

    Nacer, B.; Massobrio, C.; Félix, C.

    1997-10-01

    We have investigated the deposition at zero impact kinetic energy of the Ag atom and clusters (Ag7,Ag19) on the (100) and (111) surfaces of Pd by molecular-dynamics simulations performed within the embedded-atom-method scheme. Our results elucidate the role played by the adsorption energy in determining the final morphology of the cluster/substrate system when ideal nondestructive deposition conditions are implemented. While implantation of the atom is not observed, we find a finite probability of site Ag-Pd exchanges in the case of clusters. Deposition-assisted mixing occurring at the topmost surface layer appears to be correlated to the size of the cluster and the orientation of the substrate, being higher for Ag7/Pd(100) and lower for Ag19/Pd(111). Total-energy calculations, combined with an analysis of the atomic motion, indicate that the structural transformation accompanying the deposition of the cluster provides the needed activation energy to induce the observed Ag-Pd atomic exchanges.

  9. Photolysis of polycyclic aromatic hydrocarbons (PAHs) on Fe3+-montmorillonite surface under visible light: Degradation kinetics, mechanism, and toxicity assessments.

    Science.gov (United States)

    Zhao, Song; Jia, Hanzhong; Nulaji, Gulimire; Gao, Hongwei; Wang, Fu; Wang, Chuanyi

    2017-10-01

    Photochemical behavior of various polycyclic aromatic hydrocarbons (PAHs) on Fe 3+ -modified montmorillonite was explored to determine their potential kinetics, pathways, and mechanism under visible light. Depending on the type of PAH molecules, the transformation rate follows the order of benzo[a]pyrene ≈ anthracene > benzo[a]anthracene > phenanthrene. Quantum simulation results confirm the crucial role of "cation-π" interaction between Fe 3+ and PAHs on their transformation kinetics. Primary intermediates, including quinones, ring-opening products and benzene derivatives, were identified by gas chromatography-mass spectrometer (GC-MS), and the possible photodegradation pathway of benzo[a]pyrene was proposed. Meanwhile, radical intermediates, such as reactive oxygen species (ROS) and free organic radicals, were detected by electron paramagnetic resonance (EPR) technique. The photolysis of selected PAHs, such as anthracene and benzo[a]pyrene, on clay surface firstly occurs by electron transfer from PAHs to Fe 3+ -montmorillonite, followed by degradation involving photo-induced ROS such as ·OH and ·O 2 - . To investigate the acute toxicity of photolysis products, the Microtox ® toxicity test was performed during the photodegradation processes of various PAHs. As a result, the photo-irradiation initially induces increased toxicity by generating reactive intermediates, such as free organic radicals, and then the toxicity gradually decreases with increasing of reaction time. Overall, the present study provides useful information to understand the fate and photo-transformation of PAHs in contaminated soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Superhydrophobic alumina surface based on stearic acid modification

    Energy Technology Data Exchange (ETDEWEB)

    Feng Libang, E-mail: lepond@hotmail.com [School of Mechatronic Engineering, Lanzhou Jiaotong University, Lanzhou 730070 (China); Zhang Hongxia; Mao Pengzhi; Wang Yanping; Ge Yang [School of Mechatronic Engineering, Lanzhou Jiaotong University, Lanzhou 730070 (China)

    2011-02-15

    A novel superhydrophobic alumina surface is fabricated by grafting stearic acid layer onto the porous and roughened aluminum film. The chemical and phase structure, morphology, and the chemical state of the atoms at the superhydrophobic surface were investigated by techniques as FTIR, XRD, FE-SEM, and XPS, respectively. Results show that a super water-repellent surface with a contact angle of 154.2{sup o} is generated. The superhydrophobic alumina surface takes on an uneven flowerlike structure with many nanometer-scale hollows distribute in the nipple-shaped protrusions, and which is composed of boehmite crystal and {gamma}-Al{sub 2}O{sub 3}. Furthermore, the roughened and porous alumina surface is coated with a layer of hydrophobic alkyl chains which come from stearic acid molecules. Therefore, both the roughened structure and the hydrophobic layer endue the alumina surface with the superhydrophobic behavior.

  11. Theoretical Analysis of the Relative Significance of Thermodynamic and Kinetic Dispersion in the dc and ac Voltammetry of Surface-Confined Molecules

    KAUST Repository

    Morris, Graham P.

    2015-05-05

    © 2015 American Chemical Society. Commonly, significant discrepancies are reported in theoretical and experimental comparisons of dc voltammograms derived from a monolayer or close to monolayer coverage of redox-active surface-confined molecules. For example, broader-than-predicted voltammetric wave shapes are attributed to the thermodynamic or kinetic dispersion derived from distributions in reversible potentials (E0) and electrode kinetics (k0), respectively. The recent availability of experimentally estimated distributions of E0 and k0 values derived from the analysis of data for small numbers of surface-confined modified azurin metalloprotein molecules now allows more realistic modeling to be undertaken, assuming the same distributions apply under conditions of high surface coverage relevant to voltammetric experiments. In this work, modeling based on conventional and stochastic kinetic theory is considered, and the computationally far more efficient conventional model is shown to be equivalent to the stochastic one when large numbers of molecules are present. Perhaps unexpectedly, when experimentally determined distributions of E0 and k0 are input into the model, thermodynamic dispersion is found to be unimportant and only kinetic dispersion contributes significantly to the broadening of dc voltammograms. Simulations of ac voltammetric experiments lead to the conclusion that the ac method, particularly when the analysis of kinetically very sensitive higher-order harmonics is undertaken, are far more sensitive to kinetic dispersion than the dc method. ac methods are therefore concluded to provide a potentially superior strategy for addressing the inverse problem of determining the k0 distribution that could give rise to the apparent anomalies in surface-confined voltammetry.

  12. Comparison study of the kinetics of ceftizoxime penetration into extravascular spaces with known surface area/volume ratio in vitro and in vivo in rabbits.

    Science.gov (United States)

    Van Etta, L L; Fasching, C E; Peterson, L R; Gerding, D N

    1983-01-01

    The extravascular kinetics of ceftizoxime were studied both in an in vitro kinetic model and in an in vivo rabbit model. Visking tubing chambers were used in both models to provide extravascular spaces with large or small volumes and surface areas, but identical surface area/volume ratios. Four rabbits, each implanted with two large Visking chambers and four small chambers, received 50 mg of ceftizoxime per kg intramuscularly every 3 h for eight doses. In the in vitro model, 80 mg of ceftizoxime was infused over 30 min every 3 h for eight doses. Intravascular and extravascular spaces were sampled in both models after the eighth dose. Ceftizoxime had similar intravascular kinetics in both models, i.e., the peak levels, the peak-to-trough fluctuations, and the half-life were comparable. The area under the curve (AUC) for the extravascular spaces was also similar in the two models. Large and small chambers having identical surface area/volume ratios demonstrated identical kinetics. The extravascular Visking chamber spaces achieved equilibrium with the intravascular spaces in both models, i.e., the AUC for the extravascular spaces was the same (P > 0.2) as that for the serum (rabbit model) or the test chamber (in vitro model). This study illustrates (i) that our modified in vitro model is a potentially valid model for studying extravascular kinetics; (ii) that extravascular spaces with identical surface area/volume ratios show similar penetration kinetics with a freely diffusible drug, such as ceftizoxime, despite differences in size; and (iii) that the Visking chamber extravascular-space model permits the free diffusion of the antimicrobial agent and reaches equilibrium (equivalent AUC) with the intravascular space.

  13. Nanoplasmonic sensing and QCM-D as ultrasensitive complementary techniques for kinetic corrosion studies of aluminum nanoparticles

    Science.gov (United States)

    Schwind, Markus; Langhammer, Christoph; Kasemo, Bengt; Zorić, Igor

    2011-04-01

    Corrosion (oxidation) kinetics of Al nanodisks, 262 nm in diameter and 20 nm in height, was measured in degassed Milli-Q water at 23 °C and neutral pH by quartz crystal microbalance with dissipation monitoring (QCM-D) and nanoplasmonic sensing. The former detects the changes of the resonance frequency and the damping of the oscillation of a piezoelectric quartz crystal resonator. The latter detects the changes of the localized surface plasmon resonance (LSPR) in the metallic part of the Al nanoparticle, caused both by the shrinking metallic core and the changes in the dielectric environment as the oxide grows. Highly resolved kinetic data were obtained which show different corrosion stages. The two techniques yield complementary information not obtainable with one technique alone. Two main corrosion mechanisms, namely homogeneous oxide growth and nanoparticle fragmentation and roughening, are distinguished. The time dependence of the corrosion kinetics, determined using QCM-D, is in agreement with weight gain studies of bulk Al found in literature. The nanoplasmonic sensing measurements are compared to analytical model calculations of LSPR shifts which yield an estimate for the increase of oxide thickness during homogeneous oxide growth.

  14. Thick-to-Thin Filament Surface Distance Modulates Cross-Bridge Kinetics in Drosophila Flight Muscle

    Energy Technology Data Exchange (ETDEWEB)

    Tanner, Bertrand C.W.; Farman, Gerrie P.; Irving, Thomas C.; Maughan, David W.; Palmer, Bradley M.; Miller, Mark S. (IIT); (Vermont); (BU)

    2012-09-19

    The demembranated (skinned) muscle fiber preparation is widely used to investigate muscle contraction because the intracellular ionic conditions can be precisely controlled. However, plasma membrane removal results in a loss of osmotic regulation, causing abnormal hydration of the myofilament lattice and its proteins. We investigated the structural and functional consequences of varied myofilament lattice spacing and protein hydration on cross-bridge rates of force development and detachment in Drosophila melanogaster indirect flight muscle, using x-ray diffraction to compare the lattice spacing of dissected, osmotically compressed skinned fibers to native muscle fibers in living flies. Osmolytes of different sizes and exclusion properties (Dextran T-500 and T-10) were used to differentially alter lattice spacing and protein hydration. At in vivo lattice spacing, cross-bridge attachment time (t{sub on}) increased with higher osmotic pressures, consistent with a reduced cross-bridge detachment rate as myofilament protein hydration decreased. In contrast, in the swollen lattice, t{sub on} decreased with higher osmotic pressures. These divergent responses were reconciled using a structural model that predicts t{sub on} varies inversely with thick-to-thin filament surface distance, suggesting that cross-bridge rates of force development and detachment are modulated more by myofilament lattice geometry than protein hydration. Generalizing these findings, our results suggest that cross-bridge cycling rates slow as thick-to-thin filament surface distance decreases with sarcomere lengthening, and likewise, cross-bridge cycling rates increase during sarcomere shortening. Together, these structural changes may provide a mechanism for altering cross-bridge performance throughout a contraction-relaxation cycle.

  15. Surface plasmon resonance thermodynamic and kinetic analysis as a strategic tool in drug design. Distinct ways for phosphopeptides to plug into Src- and Grb2 SH2 domains

    NARCIS (Netherlands)

    de Mol, Nico J; Dekker, Frank J; Broutin, Isabel; Fischer, Marcel J E; Liskamp, Rob M J; Dekker, Frank

    2005-01-01

    Thermodynamic and kinetic studies of biomolecular interactions give insight into specificity of molecular recognition processes and advance rational drug design. Binding of phosphotyrosine (pY)-containing peptides to Src- and Grb2-SH2 domains was investigated using a surface plasmon resonance

  16. Kinetic analysis of synthetic analogues of linear-epitope peptides of glycoprotein D of herpes simplex virus type 1 by surface plasmon resonance

    NARCIS (Netherlands)

    Lasonder, E; Schellekens, GA; Koedijk, DGAM; Damhof, RA; WellingWester, S; Feijlbrief, M; Scheffer, AJ; Welling, GW

    1996-01-01

    The interaction between mAb A16 and glycoprorein D (gD) of herpes simplex virus type 1 was analyzed by studying the kinetics of binding with a surface-plasmon-resonance biosensor. mAb A16 belongs to group VII antibodies, which recognize residues 11-19 of gD. In a previous study, three critical

  17. Kinetic model framework for aerosol and cloud surface chemistry and gas-particle interactions ─ Part 2: Exemplary practical applications and numerical simulations

    OpenAIRE

    M. Ammann; U. Pöschl

    2007-01-01

    International audience; 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., 2005), 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...

  18. Impacts of anions on the oxygen reduction reaction kinetics on platinum and palladium surfaces in alkaline solutions.

    Science.gov (United States)

    Zhu, Shangqian; Hu, Xiaomeng; Shao, Minhua

    2017-03-15

    The fundamental understanding of the impacts induced by anions on oxygen reduction reaction (ORR) in alkaline media is of great importance in the design of more advanced catalysts for alkaline fuel cells (AFC). In this study, the specific adsorption of F - , Cl - , ClO 4 - , CO 3 2- , SO 4 2- , and citrate anions on Pt/C and Pd/C catalysts, and their impacts on the ORR kinetics in alkaline solutions were systematically studied. It was found that F - , Cl - and ClO 4 - did not specifically adsorb on Pt or Pd surfaces and had no poisoning effect on ORR. CO 3 2- and SO 4 2- had significant effects on Pt/C and lowered the activity even at a very low concentration. On the other hand, their impacts on Pd/C were negligible. Self-dissociation of citrate anions was found to occur on both Pt/C and Pd/C in the H adsorption/desorption and double layer regions. For the first time, surface enhanced infrared absorption spectroscopy (SEIRAS) with the attenuated total reflection (ATR) technique was used to investigate the self-dissociation of citrate on Pt and Pd thin film electrodes. The breaking of carboxylic groups and the carbon backbone was proposed as a possible dissociation pathway for citrate. The adsorbed species have a negligible effect on ORR activity on Pt/C as they are removed by oxidation before 0.75 V. In contrast, their oxidation on Pd/C surfaces is not completed until 0.91 V, which causes a lower ORR activity observed in rotating disk electrode measurements. The findings in this paper emphasize the importance of specific adsorption of anions and double-layer interfacial effects on the ORR activity measurement in alkaline solutions.

  19. Kinetics of the homogeneous exchange of alpha-lactalbumin adsorbed on titanium oxide surface.

    Science.gov (United States)

    Bentaleb, A; Haïkel, Y; Voegel, J C; Schaaf, P

    1998-06-05

    The homogeneous exchange process whereby alpha-lactalbumine molecules adsorbed on hydrophilic titanium oxide particles are replaced by alpha-lactalbumine molecules in solution has been investigated by means of a 125I radio-labeling technique, alpha-lactalbumine is a compact and highly negatively charged protein, making this study complementary to previous work devoted to the general understanding of the exchange mechanisms of adsorbed proteins on solid surfaces. The isotherm of alpha-lactalbumine exhibits bimodal adsorption shape, and the exchange process whereby adsorbed proteins are replaced by new incoming ones from the bulk solution has been studied at both the upper and the lower plateau of the isotherm. In the upper plateau the exchange process was found to be of first order with respect to the bulk molecules, and the release rate constant was equal to 0.914 L. mol-1.s-1. This behavior is identical to what has been observed with other proteinic systems. In the lower plateau domain, in contrast, the protein release process is independent of the concentration of proteins in the bulk, but the release rates are higher than the pure desorption rates. This constitutes, to our knowledge, a behavior that never before has been observed and that remains to be explained.

  20. Release kinetics of multiwalled carbon nanotubes deposited on silica surfaces: quartz crystal microbalance with dissipation (QCM-D) measurements and modeling.

    Science.gov (United States)

    Yi, Peng; Chen, Kai Loon

    2014-04-15

    Understanding the kinetics of the release of carbon nanotubes (CNTs) from naturally occurring surfaces is crucial for the prediction of the environmental fate and transport of CNTs. In this study, the release kinetics of multiwalled CNTs (MWNTs) from silica surfaces was investigated using a quartz crystal microbalance with dissipation monitoring (QCM-D). MWNTs were first deposited on silica surfaces under favorable deposition conditions (1.50 mM CaCl2 and pH 7.1) and the deposited MWNTs were then rinsed at different electrolyte solutions to induce the release of MWNTs from the primary energy minimum. The kinetics of MWNT release was shown to be first order with respect to the deposited MWNTs when complete release took place. A model that accounts for the releasable and unreleasable components of MWNTs was used to fit the experimental data in order to derive the release rate coefficients. When the CaCl2 concentration in the eluent was decreased, a larger fraction of deposited MWNTs was released and the release rate coefficient of the releasable MWNTs also increased. The rise in the surface charges of both MWNTs and silica surfaces with the drop in CaCl2 concentration likely resulted in the decrease in the height of the energy barrier, thus facilitating the release of the nanotubes. Moreover, when the initial surface concentrations of deposited MWNTs were over 1000 ng/cm(2), the release rate coefficient was lower than expected. The reduced release kinetics was likely due to the formation of large surface-bound MWNT clusters which had considerably lower diffusion coefficients than dispersed MWNTs or MWNT aggregates.

  1. Fluorescence Techniques for Measuring Kinetics of Specific Binding of Hormone to Cell Surface Receptors.

    Science.gov (United States)

    Hellen, Edward Herbert

    This thesis presents theoretical calculations and technical advances relevant to total internal reflection/ fluorescence photobleaching recovery (tir/fpr), and results from experiments using tir/fpr to measure the dissociation rate constant of epidermal growth factor (egf) hormone interacting with its receptor molecule on A431 cells. The classical electromagnetic calculations describe fluorescence emission from fluorophores near an interface (possibly metal coated). It is well known that an interface alters the emission properties of nearby fluorophores. Most previous classical calculations model the fluorophore as a fixed-amplitude dipole oscillator. However, for fluorophores under steady illumination, a fixed-power dipole is more appropriate. This modification corresponds to normalizing the fixed-amplitude dipole's intensity by its total dissipated power. The results for the fixed-power model differ nontrivially from the fixed-amplitude model. The observation-angle -dependent intensity as a function of the fluorophore's orientation and distance from the surface is calculated. General expressions are derived for the emission power as observed through a circular-aperture collection system located on either side of the interface. A system for maintaining long-term focus of samples under high-magnification quantitative observation in an epi-illumination optical microscope is described. Focus -dependent changes in the backreflection of an off-axis HeNe laser generate negative feedback signals which drive a dc motor coupled to the fine-focus knob of the microscope. This system has several advantages: (1) it is compatible and nonobstructive with concurrent data acqusition of sample intensities; (2) it requires no alteration of the sample, stage, or objective; (3) it monitors the position of sample areas very near to those under observation; (4) it is inexpensive. The system can hold a glass coverslip sample to within 0.5 μm of its preset focus position. Prismless tir

  2. Comparative studies of H absorption/desorption kinetics and evaporation of liquid lithium in different porous systems and free surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Oyarzabal, E., E-mail: eider.oyarzabal@externos.ciemat.es [Ass. Euratom-Ciemat, Av. Complutense 22, 28040 Madrid (Spain); Calle de Guzmán el Bueno, 133, 28003 Madrid (Spain); Martín-Rojo, A.B. [Ass. Euratom-Ciemat, Av. Complutense 22, 28040 Madrid (Spain); Calle de Guzmán el Bueno, 133, 28003 Madrid (Spain); Tabarés, F.L. [Ass. Euratom-Ciemat, Av. Complutense 22, 28040 Madrid (Spain)

    2017-04-15

    In the present work, a study of the two most relevant properties of liquid lithium with respect to its suitability as a Plasma Facing Component (PFC) element in a Reactor, namely, its evaporation rate and the uptake/release of hydrogen, eventually leading to the formation of a stable hydride was carried out for Li in different porous systems and Li as a free surface. These properties were characterized in a temperature range of 200–500 °C. The H{sub 2} absorption kinetics at low pressure (<1torr) were measured for the different studied porous systems and then outgassed. Particle balance and chemical analysis were used to assess the retention properties of lithium for each case. Thermal Desorption Spectroscopy (TDS) analysis was used for the assessment of possible hydride formation. Evaporation rates were determined by using a Quartz Microbalance (QMB). A significant reduction of the evaporation rate was observed when Li was trapped in a microstructure of sintered stainless steel with a characteristic porous size of 5–10 μm. On the other hand, a negligible rate of H{sub 2} uptake was found at temperatures above 500 °C in all cases.

  3. Laser-induced oxidation kinetics of bismuth surface microdroplets on GaAsBi studied in situ by Raman microprobe analysis.

    Science.gov (United States)

    Steele, J A; Lewis, R A

    2014-12-29

    We report the cw-laser-induced oxidation of molecular-beam-epitaxy grown GaAsBi bismuth surface microdroplets investigated in situ by micro-Raman spectroscopy under ambient conditions as a function of irradiation power and time. Our results reveal the surface droplets are high-purity crystalline bismuth and the resultant Bi2O3 transformation to be β-phase and stable at room temperature. A detailed Raman study of Bi microdroplet oxidation kinetics yields insights into the laser-induced oxidation process and offers useful real-time diagnostics. The temporal evolution of new β-Bi2O3 Raman modes is shown to be well described by Johnson-Mehl-Avrami-Kolmogorov kinetic transformation theory and while this study limits itself to the laser-induced oxidation of GaAsBi bismuth surface droplets, the results will find application within the wider context of bismuth laser-induced oxidation and direct Raman laser processing.

  4. Growth kinetics of boride coatings formed at the surface AISI M2 during dehydrated paste pack boriding

    Energy Technology Data Exchange (ETDEWEB)

    Doñu Ruiz, M.A., E-mail: mdonur0800@alumno.ipn.mx [Universidad Politécnica del Valle de México UPVM, Grupo Ciencia e Ingeniería de Materiales, Av. Mexiquense S/N Esquina Av. Universidad Politécnica, Col Villa Esmeralda, 54910 Tultitlan (Mexico); López Perrusquia, N.; Sánchez Huerta, D. [Universidad Politécnica del Valle de México UPVM, Grupo Ciencia e Ingeniería de Materiales, Av. Mexiquense S/N Esquina Av. Universidad Politécnica, Col Villa Esmeralda, 54910 Tultitlan (Mexico); Torres San Miguel, C.R.; Urriolagoitia Calderón, G.M. [Instituto Politécnico Nacional, SEPI-ESIME, Unidad Profesional Adolfo López Mateos Zacatenco, Edificio 5, 2do. Piso, Col. Lindavista, CP 07738 México, D.F. (Mexico); Cerillo Moreno, E.A. [Universidad Politécnica del Valle de México UPVM, Grupo Ciencia e Ingeniería de Materiales, Av. Mexiquense S/N Esquina Av. Universidad Politécnica, Col Villa Esmeralda, 54910 Tultitlan (Mexico); Cortes Suarez, J.V. [Univerisdad Autónoma Metropolitana Unidad Azcapotzalco, Av. San Pablo 180 Azcapotzalco 02200, Área de Ciencia de los Materiales, México, D.F. (Mexico)

    2015-12-01

    The growth kinetics of the boride coatings (FeB and Fe{sub 2}B) at the surface of AISI M2 high speed steels were studied in this work. Boriding thermochemical treatment was carried out by dehydrated paste pack at three different temperatures 1173, 1223, and 1273 K and four exposure times 1, 3, 5, and 7 h, respectively. The presence of FeB and Fe{sub 2}B phases was identified by scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS) and X-ray diffraction method. In order to obtain the boron diffusion coefficients at the FeB/Fe{sub 2}B boride coatings, a mathematical model based on the mass balance at the growing interfaces was proposed under certain assumptions. Likewise the parabolic growth constants and the boride incubation time were established as a function of the parameters η (T) and ε (T). The activation energy values estimated for the FeB and Fe{sub 2}B layers were 233.42 and 211.89 kJ mol{sup −1} respectively. A good agreement was obtained between the simulated values of boride layer thicknesses and the experimental results. Finally, empirical relationships of boride coating thickness as a function of boriding temperature and time are presented. - Highlights: • Formed boride coatings at the surface of AISI M2 high speed steels by new process dehydrated paste pack boriding. • The model was based on the mass balance equation at the FeB/Fe{sub 2}B and Fe{sub 2}B/Fe interfaces by considering the boride incubation time. • A good agreement was obtained between the simulated values of boride layers coatings and the experimental results.

  5. Incorporation of velocity-dependent restitution coefficient and particle surface friction into kinetic theory for modeling granular flow cooling.

    Science.gov (United States)

    Duan, Yifei; Feng, Zhi-Gang

    2017-12-01

    Kinetic theory (KT) has been successfully used to model rapid granular flows in which particle interactions are frictionless and near elastic. However, it fails when particle interactions become frictional and inelastic. For example, the KT is not able to accurately predict the free cooling process of a vibrated granular medium that consists of inelastic frictional particles under microgravity. The main reason that the classical KT fails to model these flows is due to its inability to account for the particle surface friction and its inelastic behavior, which are the two most important factors that need be considered in modeling collisional granular flows. In this study, we have modified the KT model that is able to incorporate these two factors. The inelasticity of a particle is considered by establishing a velocity-dependent expression for the restitution coefficient based on many experimental studies found in the literature, and the particle friction effect is included by using a tangential restitution coefficient that is related to the particle friction coefficient. Theoretical predictions of the free cooling process by the classical KT and the improved KT are compared with the experimental results from a study conducted on an airplane undergoing parabolic flights without the influence of gravity [Y. Grasselli, G. Bossis, and G. Goutallier, Europhys. Lett. 86, 60007 (2009)10.1209/0295-5075/86/60007]. Our results show that both the velocity-dependent restitution coefficient and the particle surface friction are important in predicting the free cooling process of granular flows; the modified KT model that integrates these two factors is able to improve the simulation results and leads to better agreement with the experimental results.

  6. Incorporation of velocity-dependent restitution coefficient and particle surface friction into kinetic theory for modeling granular flow cooling

    Science.gov (United States)

    Duan, Yifei; Feng, Zhi-Gang

    2017-12-01

    Kinetic theory (KT) has been successfully used to model rapid granular flows in which particle interactions are frictionless and near elastic. However, it fails when particle interactions become frictional and inelastic. For example, the KT is not able to accurately predict the free cooling process of a vibrated granular medium that consists of inelastic frictional particles under microgravity. The main reason that the classical KT fails to model these flows is due to its inability to account for the particle surface friction and its inelastic behavior, which are the two most important factors that need be considered in modeling collisional granular flows. In this study, we have modified the KT model that is able to incorporate these two factors. The inelasticity of a particle is considered by establishing a velocity-dependent expression for the restitution coefficient based on many experimental studies found in the literature, and the particle friction effect is included by using a tangential restitution coefficient that is related to the particle friction coefficient. Theoretical predictions of the free cooling process by the classical KT and the improved KT are compared with the experimental results from a study conducted on an airplane undergoing parabolic flights without the influence of gravity [Y. Grasselli, G. Bossis, and G. Goutallier, Europhys. Lett. 86, 60007 (2009), 10.1209/0295-5075/86/60007]. Our results show that both the velocity-dependent restitution coefficient and the particle surface friction are important in predicting the free cooling process of granular flows; the modified KT model that integrates these two factors is able to improve the simulation results and leads to better agreement with the experimental results.

  7. A Chemical-Adsorption Strategy to Enhance the Reaction Kinetics of Lithium-Rich Layered Cathodes via Double-Shell Surface Modification.

    Science.gov (United States)

    Guo, Lichao; Li, Jiajun; Cao, Tingting; Wang, Huayu; Zhao, Naiqin; He, Fang; Shi, Chunsheng; He, Chunnian; Liu, Enzuo

    2016-09-21

    Sluggish surface reaction kinetics hinders the power density of Li-ion battery. Thus, various surface modification techniques have been applied to enhance the electronic/ionic transfer kinetics. However, it is challenging to obtain a continuous and uniform surface modification layer on the prime particles with structure integration at the interface. Instead of classic physical-adsorption/deposition techniques, we propose a novel chemical-adsorption strategy to synthesize double-shell modified lithium-rich layered cathodes with enhanced mass transfer kinetics. On the basis of experimental measurement and first-principles calculation, MoO2S2 ions are proved to joint the layered phase via chemical bonding. Specifically, the Mo-O or Mo-S bonds can flexibly rotate to bond with the cations in the layered phase, leading to the good compatibility between the thiomolybdate adsorption layer and layered cathode. Followed by annealing treatment, the lithium-excess-spinel inner shell forms under the thiomolybdate adsorption layer and functions as favorable pathways for lithium and electron. Meanwhile, the nanothick MoO3-x(SO4)x outer shell protects the transition metal from dissolution and restrains electrolyte decomposition. The double-shell modified sample delivers an enhanced discharge capacity almost twice as much as that of the unmodified one at 1 A g(-1) after 100 cycles, demonstrating the superiority of the surface modification based on chemical adsorption.

  8. Oxygen surface exchange kinetics measurement by simultaneous optical transmission relaxation and impedance spectroscopy: Sr(Ti,Fe)O3-x thin film case study

    Science.gov (United States)

    Perry, Nicola H.; Kim, Jae Jin; Tuller, Harry L.

    2018-01-01

    Abstract We compare approaches to measure oxygen surface exchange kinetics, by simultaneous optical transmission relaxation (OTR) and AC-impedance spectroscopy (AC-IS), on the same mixed conducting SrTi0.65Fe0.35O3-x film. Surface exchange coefficients were evaluated as a function of oxygen activity in the film, controlled by gas partial pressure and/or DC bias applied across the ionically conducting yttria-stabilized zirconia substrate. Changes in measured light transmission through the film over time (relaxations) resulted from optical absorption changes in the film corresponding to changes in its oxygen and oxidized Fe (~Fe4+) concentrations; such relaxation profiles were successfully described by the equation for surface exchange-limited kinetics appropriate for the film geometry. The kchem values obtained by OTR were significantly lower than the AC-IS derived kchem values and kq values multiplied by the thermodynamic factor (bulk or thin film), suggesting a possible enhancement in k by the metal current collectors (Pt, Au). Long-term degradation in kchem and kq values obtained by AC-IS was also attributed to deterioration of the porous Pt current collector, while no significant degradation was observed in the optically derived kchem values. The results suggest that, while the current collector might influence measurements by AC-IS, the OTR method offers a continuous, in situ, and contact-free method to measure oxygen exchange kinetics at the native surfaces of thin films. PMID:29511391

  9. Salt effects on the air/solution interfacial properties of PEO-containing copolymers: equilibrium, adsorption kinetics and surface rheological behavior.

    Science.gov (United States)

    Llamas, Sara; Mendoza, Alma J; Guzmán, Eduardo; Ortega, Francisco; Rubio, Ramón G

    2013-06-15

    Lithium cations are known to form complexes with the oxygen atoms of poly(oxyethylene) chains. The effect of Li(+) on the surface properties of three block-copolymers containing poly(oxyethylene) (PEO) have been studied. Two types of copolymers have been studied, a water soluble one of the pluronic family, PEO-b-PPO-b-PEO, PPO being poly(propyleneoxyde), and two water insoluble ones: PEO-b-PS and PEO-b-PS-b-PEO, PS being polystyrene. In the case of the pluronic the adsorption kinetics, the equilibrium surface tension isotherm and the aqueous/air surface rheology have been measured, while for the two insoluble copolymers only the surface pressure and the surface rheology have been studied. In all the cases two different Li(+) concentrations have been used. As in the absence of lithium ions, the adsorption kinetics of pluronic solutions shows two processes, and becomes faster as [Li(+)] increases. The kinetics is not diffusion controlled. For a given pluronic concentration the equilibrium surface pressure increases with [Li(+)], and the isotherms show two surface phase transitions, though less marked than for [Li(+)]=0. A similar behavior was found for the equilibrium isotherms of PEO-b-PS and PEO-b-PS-b-PEO. The surface elasticity of these two copolymers was found to increase with [Li(+)] over the whole surface concentration and frequency ranges studied. A smaller effect was found in the case of the pluronic solutions. The results of the pluronic solutions were modeled using a recent theory that takes into account that the molecules can be adsorbed at the surface in two different states. The theory gives a good fit for the adsorption kinetics and a reasonably good prediction of the equilibrium isotherms for low and intermediate concentrations of pluronic. However, the theory is not able to reproduce the isotherm for [Li(+)]=0. Only a semi-quantitative prediction of the surface elasticity is obtained for [pluronic]≤1×10(-3) mM. Copyright © 2013 Elsevier Inc. All

  10. Investigation of surface roughness on etched glass surfaces

    International Nuclear Information System (INIS)

    Papa, Z.; Budai, J.; Farkas, B.; Toth, Z.

    2011-01-01

    Roughening the surface of solar cells is a common practice within the photovoltaic industry as it reduces reflectance, and thus enhances the performance of devices. In this work the relationship between reflectance characterized by the haze parameter, surface roughness and optical properties was investigated. To achieve this goal, model samples were prepared by hydrofluoric acid etching of glass for various times and measured by optical microscopy, spectroscopic ellipsometry, scanning electron microscopy, and atomic force microscopy. Our investigation showed that the surface reflectance was decreased not only by the roughening of the surface but also by the modification of the depth profile and lowering of the refractive index of the surface domain of the samples.

  11. Ion beam sputter modification of the surface morphology of biological implants

    Science.gov (United States)

    Weigand, A. J.; Banks, B. A.

    1976-01-01

    The surface chemistry and texture of materials used for biological implants may significantly influence their performance and biocompatibility. Recent interest in the microscopic control of implant surface texture has led to the evaluation of ion beam sputtering as a potentially useful surface roughening technique. Ion sources, similar to electron bombardment ion thrusters designed for propulsive applications, are used to roughen the surfaces of various biocompatible alloys or polymer materials. These materials are typically used for dental implants, orthopedic prostheses, vascular prostheses, and artificial heart components. Masking techniques and resulting surface textures are described along with progress concerning evaluation of the biological response to the ion beam sputtered surfaces.

  12. Morphology and grain structure evolution during epitaxial growth of Ag films on native-oxide-covered Si surface

    International Nuclear Information System (INIS)

    Hur, Tae-Bong; Kim, Hong Koo; Perello, David; Yun, Minhee; Kulovits, Andreas; Wiezorek, Joerg

    2008-01-01

    Epitaxial nanocrystalline Ag films were grown on initially native-oxide-covered Si(001) substrates using radio-frequency magnetron sputtering. Mechanisms of grain growth and morphology evolution were investigated. An epitaxially oriented Ag layer (∼5 nm thick) formed on the oxide-desorbed Si surface during the initial growth phase. After a period of growth instability, characterized as kinetic roughening, grain growth stagnation, and increase of step-edge density, a layer of nanocrystalline Ag grains with a uniform size distribution appeared on the quasi-two-dimensional layer. This hierarchical process of film formation is attributed to the dynamic interplay between incoming energetic Ag particles and native oxide. The cyclic interaction (desorption and migration) of the oxide with the growing Ag film is found to play a crucial role in the characteristic evolution of grain growth and morphology change involving an interval of grain growth stagnation

  13. A DFT study and micro-kinetic analysis of acetylene selective hydrogenation on Pd-doped Cu(111) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Ling-Ling [Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education) and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071 (China); Lv, Cun-Qin, E-mail: lcq173@126.com [College of Chemistry and Environmental Engineering, Shanxi Datong University, Datong 037009, Shanxi Province (China); Wang, Gui-Chang, E-mail: wangguichang@nankai.edu.cn [Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education) and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071 (China)

    2017-07-15

    Semi-hydrogenation of acetylene in a hydrogen-rich stream is an industrially important process. Inspired by the recent experiments that Cu(111) surface doped by a small number of Pd atoms can exhibit excellent catalytic performance toward the dissociation of H{sub 2} molecule as well as the high selective hydrogenation of acetylene as compared with pure Cu and Pd metal alone at low-temperature, here we performed systematic first-principles calculations to investigate the corresponding reaction mechanism related to the acetylene hydrogenation processes on single atom alloys (SAAs) and monolayer Pd/Cu(111) (i.e.,1.00 ML Pd/Cu(111)) model catalysts in detail, and to explore the possible factors controlling the high selectivity on SAAs. Our results clearly demonstrate that the SAA catalyst has higher selectivity for the ethylene formation than that of 1.00 ML Pd/Cu(111), and lower activity for the acetylene conversion compared with that of 1.00 ML Pd/Cu(111). The relatively high selectivity on SAA is mainly due to the facile desorption of ethylene and moderate activity in the dissociation of molecular H{sub 2}. The main factor which lowers the selectivity towards the ethylene formation on 1.00 ML Pd/Cu(111) is that this system has a higher capacity to promote the breaking of C−H/C−C bonds, which leads to the formation of carbonaceous deposits and polymers such as benzene, and thus reduces the selectivity for the ethylene formation. Meanwhile, it was found that the desorption energy of ethylene on these two surfaces was smaller than the energy barrier of further hydrogenation, which results in the absence of ethane on these two systems. Micro-kinetic model analysis provides a further valuable insight into the evidence for the key factors controlling the catalytic activity and selectivity towards the selective hydrogenation of acetylene. Our findings may help people to design a highly selective hydrogenation catalyst by controlling the balance between the H{sub 2

  14. A DFT study and micro-kinetic analysis of acetylene selective hydrogenation on Pd-doped Cu(111) surfaces

    Science.gov (United States)

    Ma, Ling-Ling; Lv, Cun-Qin; Wang, Gui-Chang

    2017-07-01

    Semi-hydrogenation of acetylene in a hydrogen-rich stream is an industrially important process. Inspired by the recent experiments that Cu(111) surface doped by a small number of Pd atoms can exhibit excellent catalytic performance toward the dissociation of H2 molecule as well as the high selective hydrogenation of acetylene as compared with pure Cu and Pd metal alone at low-temperature, here we performed systematic first-principles calculations to investigate the corresponding reaction mechanism related to the acetylene hydrogenation processes on single atom alloys (SAAs) and monolayer Pd/Cu(111) (i.e.,1.00 ML Pd/Cu(111)) model catalysts in detail, and to explore the possible factors controlling the high selectivity on SAAs. Our results clearly demonstrate that the SAA catalyst has higher selectivity for the ethylene formation than that of 1.00 ML Pd/Cu(111), and lower activity for the acetylene conversion compared with that of 1.00 ML Pd/Cu(111). The relatively high selectivity on SAA is mainly due to the facile desorption of ethylene and moderate activity in the dissociation of molecular H2. The main factor which lowers the selectivity towards the ethylene formation on 1.00 ML Pd/Cu(111) is that this system has a higher capacity to promote the breaking of Csbnd H/Csbnd C bonds, which leads to the formation of carbonaceous deposits and polymers such as benzene, and thus reduces the selectivity for the ethylene formation. Meanwhile, it was found that the desorption energy of ethylene on these two surfaces was smaller than the energy barrier of further hydrogenation, which results in the absence of ethane on these two systems. Micro-kinetic model analysis provides a further valuable insight into the evidence for the key factors controlling the catalytic activity and selectivity towards the selective hydrogenation of acetylene. Our findings may help people to design a highly selective hydrogenation catalyst by controlling the balance between the H2 dissociation and

  15. Thermal Rate Coefficients and Kinetic Isotope Effects for the Reaction OH + CH4 → H2O + CH3 on an ab Initio-Based Potential Energy Surface.

    Science.gov (United States)

    Li, Jun; Guo, Hua

    2018-03-15

    Thermal rate coefficients for the title reaction and its various isotopologues are computed using a tunneling-corrected transition-state theory on a global potential energy surface recently developed by fitting a large number of high-level ab initio points. The calculated rate coefficients are found to agree well with the measured ones in a wide temperature range, validating the accuracy of the potential energy surface. Strong non-Arrhenius effects are found at low temperatures. In addition, the calculations reproduced the primary and secondary kinetic isotope effects. These results confirm the strong influence of tunneling to this heavy-light-heavy hydrogen abstraction reaction.

  16. 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.

  17. Heat transfer and friction correlations for artificially roughened solar air heater duct with discrete W-shaped ribs

    International Nuclear Information System (INIS)

    Kumar, Arvind; Bhagoria, J.L.; Sarviya, R.M.

    2009-01-01

    An experimental investigation has been carried out to study the heat transfer and friction characteristics in solar air heater by using discrete W-shaped roughness on one broad wall of solar air heater with an aspect ratio of 8:1, the roughened wall being heated while the remaining three walls are insulated. The experiment encompassed Reynolds number (Re) range from 3000 to 15,000, relative roughness height (e/D h ) in the range of 0.0168-0.0338, relative roughness pitch (p/e) 10 and the angle of attack (α) in the range of 30-75 deg. The effect of parameters on the heat transfer and friction are compared with the result of smooth duct under similar flow conditions. Correlations for heat transfer and friction have been developed as a function of roughness and flow parameters.

  18. Growth morphologies of crystal surfaces

    Science.gov (United States)

    Xiao, Rong-Fu; Alexander, J. Iwan D.; Rosenberger, Franz

    1991-03-01

    We have expanded our earlier Monte Carlo model [Phys. Rev. A 38, 2447 (1988); J. Crystal Growth 100, 313 (1990)] to three dimensions and included reevaporation after accommodation and growth on dislocation-induced steps. We found again that, for a given set of growth parameters, the critical size, beyond which a crystal cannot retain its macroscopically faceted shape, scales linearly with the mean free path in the vapor. However, the three-dimensional (3D) the systems show increased shape stability compared to corresponding 2D cases. Extrapolation of the model results to mean-free-path conditions used in morphological stability experiments leads to order-of-magnitude agreement of the predicted critical size with experimental findings. The stability region for macroscopically smooth (faceted) surfaces in the parameter space of temperature and supersaturation depends on both the surface and bulk diffusion. While surface diffusion is seen to smooth the growth morphology on the scale of the surface diffusion length, bulk diffusion is always destabilizing. The atomic surface roughness increases with increase in growth temperature and supersaturation. That is, the tendency of surface kinetics anisotropies to stabilize the growth shape is reduced through thermal and kinetic roughening. It is also found that the solid-on-solid assumption, which can be advantageously used at low temperatures and supersaturations, is insufficient to describe the growth dynamics of atomically rough interfaces where bulk diffusion governs the process. For surfaces with an emerging screw dislocation, we find that the spiral growth mechanism dominates at low temperatures and supersaturations. The polygonization of a growth spiral decreases with increasing temperature or supersaturation. When the mean free path in the nutrient is comparable to the lattice constant, the combined effect of bulk and surface diffusion reduces the terrace width of a growth spiral in its center region. At elevated

  19. 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.

  20. The interaction of C60 on Si(111 7x7 studied by Supersonic Molecular Beams: interplay between precursor kinetic energy and substrate temperature in surface activated processes.

    Directory of Open Access Journals (Sweden)

    Lucrezia eAversa

    2015-06-01

    Full Text Available Buckminsterfullerene (C60 is a molecule fully formed of carbon that can be used, owing to its electronic and mechanical properties, as clean precursor for the growth of carbon-based materials, ranging from -conjugated systems (graphenes to synthesized species, e.g. carbides such as silicon carbide (SiC. To this goal, C60 cage rupture is the main physical process that triggers material growth. Cage breaking can be obtained either thermally by heating up the substrate to high temperatures (630°C, after C60 physisorption, or kinetically by using Supersonic Molecular Beam Epitaxy (SuMBE techniques. In this work, aiming at demonstrating the growth of SiC thin films by C60 supersonic beams, we present the experimental investigation of C60 impacts on Si(111 7x7 kept at 500°C for translational kinetic energies ranging from 18 to 30 eV. The attained kinetically activated synthesis of SiC submonolayer films is probed by in-situ surface electron spectroscopies (XPS and UPS. Furthermore, in these experimental conditions the C60-Si(111 7×7 collision has been studied by computer simulations based on a tight-binding approximation to Density Functional Theory, DFT. Our theoretical and experimental findings point towards a kinetically driven growth of SiC on Si, where C60 precursor kinetic energy plays a crucial role, while temperature is relevant only after cage rupture to enhance Si and carbon reactivity. In particular, we observe a counterintuitive effect in which for low kinetic energy (below 22 eV, C60 bounces back without breaking more effectively at high temperature due to energy transfer from excited phonons. At higher kinetic energy (22 < K < 30 eV, for which cage rupture occurs, temperature enhances reactivity without playing a major role in the cage break. These results are in good agreement with ab-initio molecular dynamics simulations. SuMBE is thus a technique able to drive materials growth at low temperature regime.

  1. Physisorption kinetics

    CERN Document Server

    Kreuzer, Hans Jürgen

    1986-01-01

    This monograph deals with the kinetics of adsorption and desorption of molecules physisorbed on solid surfaces. Although frequent and detailed reference is made to experiment, it is mainly concerned with the theory of the subject. In this, we have attempted to present a unified picture based on the master equation approach. Physisorption kinetics is by no means a closed and mature subject; rather, in writing this monograph we intended to survey a field very much in flux, to assess its achievements so far, and to give a reasonable basis from which further developments can take off. For this reason we have included many papers in the bibliography that are not referred to in the text but are of relevance to physisorption. To keep this monograph to a reasonable size, and also to allow for some unity in the presentation of the material, we had to omit a number of topics related to physisorption kinetics. We have not covered to any extent the equilibrium properties of physisorbed layers such as structures, phase tr...

  2. Kinetics of Accumulation of Damage in Surface Layers of Lithium-Containing Aluminum Alloys in Fatigue Tests with Rigid Loading Cycle and Corrosive Effect of Environment

    Science.gov (United States)

    Morozova, L. V.; Zhegina, I. P.; Grigorenko, V. B.; Fomina, M. A.

    2017-07-01

    High-resolution methods of metal physics research including electron, laser and optical microscopy are used to study the kinetics of the accumulation of slip lines and bands and the corrosion damage in the plastic zone of specimens of aluminum-lithium alloys 1441 and B-1469 in rigid-cycle fatigue tests under the joint action of applied stresses and corrosive environment. The strain parameters (the density of slip bands, the sizes of plastic zones near fracture, the surface roughness in singled-out zones) and the damage parameters (the sizes of pits and the pitting area) are evaluated.

  3. High temperature growth kinetics and texture of surface-oxidised NiO for coated superconductor applications

    Energy Technology Data Exchange (ETDEWEB)

    Kursumovic, A.; Tomov, R.; Huehne, R.; Glowacki, B.A.; Everts, J.E.; Tuissi, A.; Villa, E.; Holzapfel, B

    2003-03-15

    Thick NiO films were grown in air, on biaxially textured (0 0 1) Ni and as-rolled Ni tapes, at temperatures from 1050 to 1350 deg. C. Ni diffusion through the NiO film mainly contributes to the growth since is much faster than oxygen diffusion and occurs by a vacancy diffusion mechanism in the lattice at high temperatures. Parabolic growth kinetics were found for both NiO film thickness and grain growth, and compared with the literature data. Competitive growth of (1 1 1) and (0 0 1) oriented grains establishes the final NiO orientation at temperatures below 1250 deg. C, while at higher temperatures leakage diffusion at/towards grain boundaries, grain coarsening and (1 1 0) oriented grains disrupt the (1 0 0) texture. Hence, development of epitaxy of NiO on textured Ni tapes was found to be largely due to growth kinetics depending on both, time and temperature. We report here a systematic study of the microstructure and kinetics of formation of textured NiO substrate for application as a buffer layer in coated conductor technology.

  4. Effects of surface treatment of provisional crowns on the shear bond strength of brackets.

    Science.gov (United States)

    de Almeida, Josiane Xavier; Deprá, Mauren Bitencourt; Marquezan, Mariana; Retamoso, Luciana Borges; Tanaka, Orlando

    2013-01-01

    To assess the adhesive resistance of metallic brackets bonded to temporary crowns made of acrylic resin after different surface treatments. 180 specimens were made of Duralay and randomly divided into 6 groups (n = 30) according to surface treatment and bonding material: G1 - surface roughening with Soflex and bonding with Duralay; G2 - roughening with aluminum oxide blasting and bonding with Duralay; G3 - application of monomer and bonding with Duralay; G4 - roughening with Soflex and bonding with Transbond XT; G5 - roughening with aluminum oxide blasting and bonding with Transbond XT and G6 - application of monomer and bonding with Transbond. The results were statistically assessed by ANOVA/Games-Howell. The means (MPa) were: G1= 18.04, G2= 22.64, G3= 22.4, G4= 9.71, G5= 11.23, G6= 9.67. The Adhesive Remnant Index (ARI) ranged between 2 and 3 on G1, G2 and G3 whereas in G4, G5 and G6 it ranged from 0 to 1, showing that only the material affects the pattern of adhesive flaw. The surface treatment and the material influenced adhesive resistance of brackets bonded to temporary crowns. Roughening by aluminum blasting increased bond strength when compared to Soflex, in the group bonded with Duralay. The bond strength of Duralay acrylic resin was superior to that of Transbond XT composite resin.

  5. Effects of surface treatment of provisional crowns on the shear bond strength of brackets

    Directory of Open Access Journals (Sweden)

    Josiane Xavier de Almeida

    2013-08-01

    Full Text Available OBJECTIVE: To assess the adhesive resistance of metallic brackets bonded to temporary crowns made of acrylic resin after different surface treatments. METHODS: 180 specimens were made of Duralay and randomly divided into 6 groups (n = 30 according to surface treatment and bonding material: G1 - surface roughening with Soflex and bonding with Duralay; G2 - roughening with aluminum oxide blasting and bonding with Duralay; G3 - application of monomer and bonding with Duralay; G4 - roughening with Soflex and bonding with Transbond XT; G5 - roughening with aluminum oxide blasting and bonding with Transbond XT and G6: application of monomer and bonding with Transbond. The results were statistically assessed by ANOVA/Games-Howell. RESULTS: The means (MPa were: G1= 18.04, G2= 22.64, G3= 22.4, G4= 9.71, G5= 11.23, G6= 9.67. The Adhesive Remnant Index (ARI ranged between 2 and 3 on G1, G2 and G3 whereas in G4, G5 and G6 it ranged from 0 to 1, showing that only the material affects the pattern of adhesive flaw. CONCLUSION: The surface treatment and the material influenced adhesive resistance of brackets bonded to temporary crowns. Roughening by aluminum blasting increased bond strength when compared to Soflex, in the group bonded with Duralay. The bond strength of Duralay acrylic resin was superior to that of Transbond XT composite resin.

  6. Influence of deuterium on kinetics of methane isotope exchange with surface deuteroxy groups of Pt/SiO2 catalysts

    International Nuclear Information System (INIS)

    Musoyan, L.M.; Aliev, R.K.

    1990-01-01

    Reaction of isotope methane exchange with surface deuteroxy groups of 2 % Pt/SiO 2 catalyst was studied. It is shown that preliminarily chemisorbed deuterium does not decelerate the exchange reaction, but changes its mechanism. Activation energy of exchange on clean surface is equal to 25 kJ/mol; it grows in the presence of deuterium on the surface

  7. "Kinetics of the adsorption of atomic oxygen (N2O) on the Si(001)2x1 surface as revealed by the change in the surface conductance"

    NARCIS (Netherlands)

    Wormeester, Herbert; Keim, Enrico G.; van Silfhout, Arend

    1992-01-01

    The adsorption behaviour of N2O on the Si(001)2 × 1 surface at 300 K substrate temperature has been investigated by measuring in situ the surface conductance during the reaction process. For comparison we monitored in the same way the adsorption of O2 on the same surface which ultimately leads to

  8. Studies of the kinetics and mechanisms of ammonia synthesis and hydrodesulfurization on metal single-crystal surfaces

    International Nuclear Information System (INIS)

    Gellman, A.J.; Asscher, M.; Somorjai, G.A.

    1985-01-01

    The authors studied the ammonia synthesis reaction over Fe and Re single crystal surfaces and the hydrodesulfurization of thiophene over the Mo(100) single crystal surface. The studies have been performed using UHV surface science tools with the capability of exposing the surfaces to high pressure, high temperature reaction conditions. The ammonia synthesis reaction was shown to be extremely sensitive to surface structure on both Fe and Re, favoring surfaces with a rough or open topography. The HDS reaction on the Mo(100) surface has been shown to be similar to that on MoS/sub 2/ and appears to proceed via a reaction path that does not produce a strong Mo-S bond as an intermediate species

  9. Biodegradation of hydrocarbon mixtures in surface waters at environmentally relevant levels - Effect of inoculum origin on kinetics and sequence of degradation.

    Science.gov (United States)

    Birch, Heidi; Hammershøj, Rikke; Comber, Mike; Mayer, Philipp

    2017-10-01

    Biodegradation is a dominant removal process for many organic pollutants, and biodegradation tests serve as tools for assessing their environmental fate within regulatory risk assessment. In simulation tests, the inoculum is not standardized, varying in microbial quantity and quality, thereby potentially impacting the observed biodegradation kinetics. In this study we investigated the effect of inoculum origin on the biodegradation kinetics of hydrocarbons for five inocula from surface waters varying in urbanization and thus expected pre-exposure to petroleum hydrocarbons. A new biodegradation method for testing mixtures of hydrophobic chemicals at trace concentrations was demonstrated: Aqueous solutions containing 9 hydrocarbons were generated by passive dosing and diluted with surface water resulting in test systems containing native microorganisms exposed to test substances at ng-μg/L levels. Automated Headspace Solid Phase Microextraction coupled to GC-MS was applied directly to these test systems to determine substrate depletion relative to abiotic controls. Lag phases were generally less than 8 days. First order rate constants were within one order of magnitude for each hydrocarbon in four of the five waters but lower in water from a rural lake. The sequence of degradation between the 9 hydrocarbons showed similar patterns in the five waters indicating the potential for using selected hydrocarbons for benchmarking between biodegradation tests. Degradation half-times were shorter than or within one order of magnitude of BioHCwin predictions for 8 of 9 hydrocarbons. These results showed that location choice is important for biodegradation kinetics and can provide a relevant input to aquatic exposure and fate models. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Enhanced photochemistry on metal surfaces

    International Nuclear Information System (INIS)

    Goncher, G.M.; Parsons, C.A.; Harris, C.B.

    1984-01-01

    Due to the fast relaxation of molecular excited states in the vicinity of a metal or semiconductor surface, few observations of surface photochemistry have been reported. The following work concerns the surface-enhanced photo-reactions of a variety of physisorbed molecules on roughened Ag surfaces. In summary, photodecomposition leads to a graphitic surface carbon product which is monitored via surface-enhanced Raman scattering. In most cases an initial two-photon molecular absorption step followed by further absorption and fragmentation is thought to occur. Enhancement of the incident fields occurs through roughness-mediated surface plasmon resonances. This mechanism provides the amplified electromagnetic surface fields responsible for the observed photodecomposition. The photodecomposition experiments are performed under ultra-high vacuum. Surface characterization of the roughened surfaces was done by Scanning Electron Microscopy (SEM), and electron-stimulated emission. The SEM revealed morphology on the order of 300-400 A. This size of roughness feature, when modelled as isolated spheres should exhibit the well-known Mie resonances for light of the correct wavelengths. For protrusions existing on a surface these Mie resonances can be thought of as a coupling of the light with the surface plasmon. Experimental verification of these resonances was provided by the electron-stimulated light emission results. These showed that a polished Ag surface emitted only the expected transition radiation at the frequency of the Ag bulk plasmon. Upon roughening, however, a broad range of lower frequencies extending well into the visible are seen from electron irradiation of the surface. Large enhancements are expected for those frequencies which are able to couple into the surface modes

  11. 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

  12. A Surface-Layer Study of the Transport and Dissipation of Turbulent Kinetic Energy and the Variances of Temperature, Humidity and CO_2

    Science.gov (United States)

    Hackerott, João A.; Bakhoday Paskyabi, Mostafa; Reuder, Joachim; de Oliveira, Amauri P.; Kral, Stephan T.; Marques Filho, Edson P.; Mesquita, Michel dos Santos; de Camargo, Ricardo

    2017-11-01

    We discuss scalar similarities and dissimilarities based on analysis of the dissipation terms in the variance budget equations, considering the turbulent kinetic energy and the variances of temperature, specific humidity and specific CO_2 content. For this purpose, 124 high-frequency sampled segments are selected from the Boundary Layer Late Afternoon and Sunset Turbulence experiment. The consequences of dissipation similarity in the variance transport are also discussed and quantified. The results show that, for the convective atmospheric surface layer, the non-dimensional dissipation terms can be expressed in the framework of Monin-Obukhov similarity theory and are independent of whether the variable is temperature or moisture. The scalar similarity in the dissipation term implies that the characteristic scales of the atmospheric surface layer can be estimated from the respective rate of variance dissipation, the characteristic scale of temperature, and the dissipation rate of temperature variance.

  13. Molecular projectile effects for kinetic electron emission from carbon- and metal-surfaces bombarded by slow hydrogen ions

    Science.gov (United States)

    Cernusca, S.; Winter, HP.; Aumayr, F.; Díez Muiño, R.; Juaristi, J. I.

    2003-04-01

    Total yields for kinetic electron emission (KE) have been determined for impact of hydrogen monomer-, dimer- and trimer-ions (impact energy armour in magnetic fusion devices. The data are compared with KE yields for impact of same projectile ions on atomically clean highly oriented pyrolytic graphite and polycrystalline gold. We discuss KE yields for the different targets if bombarded by equally fast molecular and atomic ions in view to "projectile molecular effects" (different yields per proton for equally fast atomic and molecular ions), which are expected from calculated electronic projectile energy losses in these target materials.

  14. Lectin interactions on surface-grafted glycostructures: influence of the spatial distribution of carbohydrates on the binding kinetics and rupture forces.

    Science.gov (United States)

    Yu, Kai; Creagh, A Louise; Haynes, Charles A; Kizhakkedathu, Jayachandran N

    2013-08-20

    We performed quantitative analysis of the binding kinetics and affinity of carbohydrate-lectin binding and correlated them directly with the molecular and structural features of ligands presented at the nanoscale within the glycocalyx mimicking layers on surfaces. The surface plasmon resonance analysis identified that the mode of binding changed from multivalent to monovalent, which resulted in a near 1000-fold change in the equilibrium association constant, by varying the spatial distribution of carbohydrate ligands within the surface-grafted polymer layer. We identified, for the first time, that the manner in which the ligands presented on the surface has great influence on the binding at the first stage of bivalent chelating, not on the binding at the second stage. The rupture forces measured by atomic force microscope force spectroscopy also indicated that the mode of binding between lectin and ligands changed from multiple to single with variation in the ligand presentation. The dependence of lectin binding on the glycopolymer composition and grafting density is directly correlated with the nanoscale presentation of ligands on a surface, which is a determining factor in controlling the clustering and statistical effects contributing to the enhanced binding.

  15. Understanding early serum hepatitis D virus and hepatitis B surface antigen kinetics during pegylated interferon-alpha therapy via mathematical modeling.

    Science.gov (United States)

    Guedj, Jeremie; Rotman, Yaron; Cotler, Scott J; Koh, Christopher; Schmid, Peter; Albrecht, Jeff; Haynes-Williams, Vanessa; Liang, T Jake; Hoofnagle, Jay H; Heller, Theo; Dahari, Harel

    2014-12-01

    There is little information on the early kinetics of hepatitis delta virus (HDV) and hepatitis B surface antigen (HBsAg) during interferon-α therapy. Here a mathematical model was developed and fitted to frequent HDV and HBsAg kinetic data from 10 patients during the first 28 weeks of pegylated-interferon-α2a (peg-IFN) therapy. Three patients achieved a complete virological response (CVR), defined as undetectable HDV 6 months after treatment stopped with loss of HBsAg and anti-HBsAg seroconversion. After initiation of therapy, a median delay of 9 days (interquartile range [IQR]: 5-15) was observed with no significant changes in HDV level. Thereafter, HDV declined in a biphasic manner, where a rapid first phase lasting for 25 days (IQR: 23-58) was followed by a slower or plateau second phase. The model predicts that the main effect of peg-IFN is to reduce HDV production/release with a median effectiveness of 96% (IQR: 93-99.8). Median serum HDV half-life (t1/2 ) was estimated as 2.9 days (IQR: 1.5-5.3) corresponding to a pretreatment production and clearance of about 10(10) (IQR: 10(9.7) -10(10.7) ) virions/day. None of the patients with flat second phase in HDV achieved CVR. HBsAg kinetics of decline paralleled the second phase of HDV decline consistent with HBsAg-productive-infected cells being the main source of production of HDV, with a median t1/2 of 135 days (IQR: 20-460). The interferon lambda-3 polymorphism (rs12979860) was not associated with kinetic parameters. Modeling results provide insights into HDV-host dynamics, the relationship between serum HBsAg levels and HBsAg-infected cells, IFN's mode of action, and its effectiveness. The observation that a flat second phase in HDV and HBsAg kinetics was associated with failure to achieve CVR provides the basis to develop early stopping rules during peg-IFN treatment in HDV-infected patients. © 2014 by the American Association for the Study of Liver Diseases. This article has been contributed to by U

  16. Local heat/mass transfer distributions around sharp 180 deg turns in two-pass smooth and rib-roughened channels

    Science.gov (United States)

    Han, J. C.; Chandra, P. R.; Lau, S. C.

    1988-01-01

    The napthalene sublimation technique was employed to study the detailed mass transfer distributions around the sharp 180 deg turns in a two-pass, square, smooth channel and in an identical channel with two rib-roughened opposite walls. Experiments conducted for Reynolds numbers of 15,000, 30,000, and 60,000 indicate that the Sherwood numbers on the top, outer, and inner walls around the turn in the rib-roughened channel are higher than the corresponding Sherwood numbers around the turn in the smooth channel. Sherwood numbers after the sharp turn are found to be higher than those before the turn for both the smooth and the ribbed channels.

  17. APEX (Aqueous Photochemistry of Environmentally occurring Xenobiotics): a free software tool to predict the kinetics of photochemical processes in surface waters.

    Science.gov (United States)

    Bodrato, Marco; Vione, Davide

    2014-04-01

    The APEX software predicts the photochemical transformation kinetics of xenobiotics in surface waters as a function of: photoreactivity parameters (direct photolysis quantum yield and second-order reaction rate constants with transient species, namely ˙OH, CO₃(-)˙, (1)O₂ and the triplet states of chromophoric dissolved organic matter, (3)CDOM*), water chemistry (nitrate, nitrite, bicarbonate, carbonate, bromide and dissolved organic carbon, DOC), and water depth (more specifically, the optical path length of sunlight in water). It applies to well-mixed surface water layers, including the epilimnion of stratified lakes, and the output data are average values over the considered water column. Based on intermediate formation yields from the parent compound via the different photochemical pathways, the software can also predict intermediate formation kinetics and overall yield. APEX is based on a photochemical model that has been validated against available field data of pollutant phototransformation, with good agreement between model predictions and field results. The APEX software makes allowance for different levels of knowledge of a photochemical system. For instance, the absorption spectrum of surface water can be used if known, or otherwise it can be modelled from the values of DOC. Also the direct photolysis quantum yield can be entered as a detailed wavelength trend, as a single value (constant or average), or it can be defined as a variable if unknown. APEX is based on the free software Octave. Additional applications are provided within APEX to assess the σ-level uncertainty of the results and the seasonal trend of photochemical processes.

  18. The Contribution of Antimonide Surface Reconstructions to Heterostructure Interface Roughness

    National Research Council Canada - National Science Library

    Bracker, A. S; Barvosa-Carter, W; Culbertson, J. C; Nosho, B. Z; Whitman, L. J; Shanabrook, B. V; Bennett, B. R; Yang, M. J

    1999-01-01

    ... for the 6.1 Angstrom family of compound semiconductors (InAs, GaSb, AlSb). The structure and stoichiometry of MBE-grown antimonide surfaces lead to growth and roughening mechanisms that are distinctly different from other III-V materials...

  19. 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

  20. Nano-Bio Interactions of Porous and Nonporous Silica Nanoparticles of Varied Surface Chemistry: A Structural, Kinetic, and Thermodynamic Study of Protein Adsorption from RPMI Culture Medium.

    Science.gov (United States)

    Lehman, Sean E; Mudunkotuwa, Imali A; Grassian, Vicki H; Larsen, Sarah C

    2016-01-26

    Understanding complex chemical changes that take place at nano-bio interfaces is of great concern for being able to sustainably implement nanomaterials in key applications such as drug delivery, imaging, and environmental remediation. Typical in vitro assays use cell viability as a proxy to understanding nanotoxicity but often neglect how the nanomaterial surface can be altered by adsorption of solution-phase components in the medium. Protein coronas form on the nanomaterial surface when incubated in proteinaceous solutions. Herein, we apply a broad array of techniques to characterize and quantify protein corona formation on silica nanoparticle surfaces. The porosity and surface chemistry of the silica nanoparticles have been systematically varied. Using spectroscopic tools such as FTIR and circular dichroism, structural changes and kinetic processes involved in protein adsorption were evaluated. Additionally, by implementing thermogravimetric analysis, quantitative protein adsorption measurements allowed for the direct comparison between samples. Taken together, these measurements enabled the extraction of useful chemical information on protein binding onto nanoparticles in solution. Overall, we demonstrate that small alkylamines can increase protein adsorption and that even large polymeric molecules such as poly(ethylene glycol) (PEG) cannot prevent protein adsorption in these systems. The implications of these results as they relate to further understanding nano-bio interactions are discussed.

  1. Development of a Surface Plasmon Resonance Assay for the Characterization of Small-Molecule Binding Kinetics and Mechanism of Binding to Kynurenine 3-Monooxygenase.

    Science.gov (United States)

    Poda, Suresh B; Kobayashi, Masakazu; Nachane, Ruta; Menon, Veena; Gandhi, Adarsh S; Budac, David P; Li, Guiying; Campbell, Brian M; Tagmose, Lena

    2015-10-01

    Kynurenine 3-monooxygenase (KMO), a pivotal enzyme in the kynurenine pathway, was identified as a potential therapeutic target for treating neurodegenerative and psychiatric disorders. In this article, we describe a surface plasmon resonance (SPR) assay that delivers both kinetics and the mechanism of binding (MoB) data, enabling a detailed characterization of KMO inhibitors for the enzyme in real time. SPR assay development included optimization of the protein construct and the buffer conditions. The stability and inhibitor binding activity of the immobilized KMO were significantly improved when the experiments were performed at 10°C using a buffer containing 0.05% n-dodecyl-β-d-maltoside (DDM) as the detergent. The KD values of the known KMO inhibitors (UPF648 and RO61-8048) from the SPR assay were in good accordance with the biochemical LC/MS/MS assay. Also, the SPR assay was able to differentiate the binding kinetics (k(a) and k(d)) of the selected unknown KMO inhibitors. For example, the inhibitors that showed comparable IC50 values in the LC/MS/MS assay displayed differences in their residence time (τ = 1/k(d)) in the SPR assay. To better define the MoB of the inhibitors to KMO, an SPR-based competition assay was developed, which demonstrated that both UPF648 and RO61-8048 bound to the substrate-binding site. These results demonstrate the potential of the SPR assay for characterizing the affinity, the kinetics, and the MoB profiles of the KMO inhibitors.

  2. COMBINED THEORETICAL AND EXPERIMENTAL INVESTIGATION OF MECHANISMS AND KINETICS OF VAPOR-PHASE MERCURY UPTAKE BY CARBONACOUES SURFACES

    Energy Technology Data Exchange (ETDEWEB)

    Radisav D. Vidic

    2002-05-01

    The first part of this study evaluated the application of a versatile optical technique to study the adsorption and desorption of model adsorbates representative of volatile polar (acetone) and non-polar (propane) organic compounds on a model carbonaceous surface under ultra high vacuum (UHV) conditions. The results showed the strong correlation between optical differential reflectance (ODR) and adsorbate coverage determined by temperature programmed desorption (TPD). ODR technique was proved to be a powerful tool to investigate surface adsorption and desorption from UHV to high pressure conditions. The effects of chemical functionality and surface morphology on the adsorption/desorption behavior of acetone, propane and mercury were investigated for two model carbonaceous surfaces, namely air-cleaved highly oriented pyrolytic graphite (HOPG) and plasma-oxidized HOPG. They can be removed by thermal treatment (> 500 K). The presence of these groups almost completely suppresses propane adsorption at 90K and removal of these groups leads to dramatic increase in adsorption capacity. The amount of acetone adsorbed is independent of surface heat treatment and depends only on total exposure. The effects of morphological heterogeneity is evident for plasma-oxidized HOPG as this substrate provides greater surface area, as well as higher energy binding sites. Mercury adsorption at 100 K on HOPG surfaces with and without chemical functionalities and topological heterogeneity created by plasma oxidation occurs through physisorption. The removal of chemical functionalities from HOPG surface enhances mercury physisorption. Plasma oxidation of HOPG provides additional surface area for mercury adsorption. Mercury adsorption by activated carbon at atmospheric pressure occurs through two distinct mechanisms, physisorption below 348 K and chemisorption above 348 K. No significant impact of oxygen functionalities was observed in the chemisorption region. The key findings of this study

  3. Crystallite growth kinetics of TiO2 surface modification with 9 mol% ZnO prepared by a coprecipitation process

    International Nuclear Information System (INIS)

    Ko, Horng-Huey; Hsi, Chi-Shiung; Wang, Moo-Chin; Zhao, Xiujian

    2014-01-01

    Highlights: • TiO 2 powder surface modification with 9 mol% ZnO was obtained. • Phase transformation from anatase to rutile was hindered by ZnO added. • Growth kinetic of anatase TiO 2 nanocrystallites in T-9Z powders was described as: D A,9 2 =2.42×10 5 ×exp(-39.9×10 3 /RT). • Growth kinetic of rutile TiO 2 nanocrystallites in T-9Z powders was described as: D R,9 2 =8.49×10 5 ×exp(-47.6×10 3 /RT) rutile TiO 2 . -- Abstract: The nanocrystallite growth of TiO 2 surface modification with 9 mol% ZnO prepared by a coprecipitation process has been studied. Thermogravimetric and differential thermal analysis (TG/DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and UV–VIS–NIR spectrophotometry have been utilized to characterize the TiO 2 nanocrystallites surface modification with 9 mol% ZnO (denoted by T-9Z). The DTA result shows that the anatase TiO 2 first formed at 533 K and the completion of anatase TiO 2 crystallization occurred at 745 K for the T-9Z freeze-dried precursor powders. XRD results reveal that the anatase and rutile TiO 2 coexist when the T-9Z freeze-dried precursor powders were calcined at 523–973 K for 2 h. When the T-9Z freeze-dried precursor powders were calcined at 973 K for 2 h, rutile TiO 2 was the major phase, and the minor phases were anatase TiO 2 and Zn 2 Ti 3 O 8 . The phase was composed of the rutile TiO 2 and Zn 2 TiO 4 for the T-9Z freeze-dried precursor powders after calcination at 1273 K for 2 h. The growth kinetics of TiO 2 nanocrystallites in T-9Z powders were described as: D A,9 2 =2.42×10 5 ×exp(-39.9×10 3 /RT)and D R,9 2 =8.49×10 5 ×exp(-47.6×10 3 /RT) for anatase and rutile TiO 2 nanocrystallites respectively. The analysis results of UV/VIS/NIR spectra reveal that the T-9Z freeze-dried precursor powders after calcination have a red-shifted effect with increasing calcination temperature and can be used as a UVA-attenuating agent

  4. Kinetic Typography

    DEFF Research Database (Denmark)

    van Leeuwen, Theo; Djonov, Emilia

    2014-01-01

    After discussing broad cultural drivers behind the development of kinetic typography, the chapter outlines an approach to analysing kinetic typography which is based on Halliday's theory of transitivity, as applied by Kress and Van Leeuwen to visual images....

  5. Kinetic Typography

    DEFF Research Database (Denmark)

    van Leeuwen, Theo; Djonov, Emilia

    2014-01-01

    After discussing broad cultural drivers behind the development of kinetic typography, the chapter outlines an approach to analysing kinetic typography which is based on Halliday's theory of transitivity, as applied by Kress and Van Leeuwen to visual images.......After discussing broad cultural drivers behind the development of kinetic typography, the chapter outlines an approach to analysing kinetic typography which is based on Halliday's theory of transitivity, as applied by Kress and Van Leeuwen to visual images....

  6. Theoretical Kinetics Analysis for Ḣ Atom Addition to 1,3-Butadiene and Related Reactions on the Ċ4H7 Potential Energy Surface.

    Science.gov (United States)

    Li, Yang; Klippenstein, Stephen J; Zhou, Chong-Wen; Curran, Henry J

    2017-10-12

    The oxidation chemistry of the simplest conjugated hydrocarbon, 1,3-butadiene, can provide a first step in understanding the role of polyunsaturated hydrocarbons in combustion and, in particular, an understanding of their contribution toward soot formation. On the basis of our previous work on propene and the butene isomers (1-, 2-, and isobutene), it was found that the reaction kinetics of Ḣ-atom addition to the C═C double bond plays a significant role in fuel consumption kinetics and influences the predictions of high-temperature ignition delay times, product species concentrations, and flame speed measurements. In this study, the rate constants and thermodynamic properties for Ḣ-atom addition to 1,3-butadiene and related reactions on the Ċ 4 H 7 potential energy surface have been calculated using two different series of quantum chemical methods and two different kinetic codes. Excellent agreement is obtained between the two different kinetics codes. The calculated results including zero-point energies, single-point energies, rate constants, barrier heights, and thermochemistry are systematically compared among the two quantum chemical methods. 1-Methylallyl (Ċ 4 H 7 1-3) and 3-buten-1-yl (Ċ 4 H 7 1-4) radicals and C 2 H 4 + Ċ 2 H 3 are found to be the most important channels and reactivity-promoting products, respectively. We calculated that terminal addition is dominant (>80%) compared to internal Ḣ-atom addition at all temperatures in the range 298-2000 K. However, this dominance decreases with increasing temperature. The calculated rate constants for the bimolecular reaction C 4 H 6 + Ḣ → products and C 2 H 4 + Ċ 2 H 3 → products are in excellent agreement with both experimental and theoretical results from the literature. For selected C 4 species, the calculated thermochemical values are also in good agreement with literature data. In addition, the rate constants for H atom abstraction by Ḣ atoms have also been calculated, and it is

  7. Bond strength of resin cement to dentin and to surface-treated posts of titanium alloy, glass fiber, and zirconia

    DEFF Research Database (Denmark)

    Sahafi, Alireza; Peutzfeldt, Anne; Asmussen, Erik

    2003-01-01

    PURPOSE: To determine the effect of surface treatments on bond strength of two resin cements (ParaPost Cement and Panavia F) to posts of titanium alloy (ParaPost XH), glass fiber (ParaPost Fiber White), and zirconia (Cerapost), and to dentin. MATERIALS AND METHODS: After embedding, planar surfaces...... of posts (n = 9 to 14) and human dentin (n = 10) were obtained by grinding. The posts received one of three surface treatments: 1. roughening (sandblasting, hydrofluoric acid etching), 2. application of primer (Alloy Primer, Metalprimer II, silane), or 3. roughening followed by application of primer...

  8. Rational Design of Thermodynamic and Kinetic Binding Profiles by Optimizing Surface Water Networks Coating Protein-Bound Ligands.

    Science.gov (United States)

    Krimmer, Stefan G; Cramer, Jonathan; Betz, Michael; Fridh, Veronica; Karlsson, Robert; Heine, Andreas; Klebe, Gerhard

    2016-12-08

    A previously studied congeneric series of thermolysin inhibitors addressing the solvent-accessible S 2 ' pocket with different hydrophobic substituents showed modulations of the surface water layers coating the protein-bound inhibitors. Increasing stabilization of water molecules resulted in an enthalpically more favorable binding signature, overall enhancing affinity. Based on this observation, we optimized the series by designing tailored P 2 ' substituents to improve and further stabilize the surface water network. MD simulations were applied to predict the putative water pattern around the bound ligands. Subsequently, the inhibitors were synthesized and characterized by high-resolution crystallography, microcalorimetry, and surface plasmon resonance. One of the designed inhibitors established the most pronounced water network of all inhibitors tested so far, composed of several fused water polygons, and showed 50-fold affinity enhancement with respect to the original methylated parent ligand. Notably, the inhibitor forming the most perfect water network also showed significantly prolonged residence time compared to the other tested inhibitors.

  9. Influence of kinetics on the determination of the surface reactivity of oxide suspensions by acid-base titration.

    Science.gov (United States)

    Duc, M; Adekola, F; Lefèvre, G; Fédoroff, M

    2006-11-01

    The effect of acid-base titration protocol and speed on pH measurement and surface charge calculation was studied on suspensions of gamma-alumina, hematite, goethite, and silica, whose size and porosity have been well characterized. The titration protocol has an important effect on surface charge calculation as well as on acid-base constants obtained by fitting of the titration curves. Variations of pH versus time after addition of acid or base to the suspension were interpreted as diffusion processes. Resulting apparent diffusion coefficients depend on the nature of the oxide and on its porosity.

  10. The Influence of implant geometry and surface composition on bone response

    NARCIS (Netherlands)

    Al Farraj Aldosari, A.; Anil, S.; Alasqah, M.; Wazzan, K.A. Al; Jetaily, S.A. Al; Jansen, J.A.

    2014-01-01

    OBJECTIVES: The implant design and surface modification are independent conditions that can alter the implant bone response. The objective of this study is to compare the bone response to roughened tapered and cylindrical screw-type implants with and without hydroxyapatite (HA) surface coating in

  11. Gold Cluster Diffusion Kinetics on Stoichiometric and Reduced Surfaces of Rutile TiO 2 (110)

    Energy Technology Data Exchange (ETDEWEB)

    Goldman, Nir; Browning, Nigel D.

    2011-06-16

    Gold clusters on rutile TiO2 are known to serve as efficient oxidation catalysts for pollutants and environmental contaminants. However, the mechanism by which highly mobile small clusters migrate and aggregate into larger species relevant to gold’s catalytic activity remains unresolved. We report herein on ab initio simulations of the diffusion of atomic gold clusters up to the trimer on rutile TiO2(110) surfaces. We show that, on the stoichiometric surface, both the dimer and the trimer can exhibit relatively low surface mobility due to high energetic barriers for diffusion out of their energetic minima coupled with low barriers for the reverse motion. On the reduced surface, these clusters can diffuse relatively quickly between energetic minima within the oxygen vacancy site due to the large degree of vibrational entropy in their transition states. Our computed diffusion times provide a point of comparison for future experiments and will aid in development of models of gold cluster island sintering.

  12. New Combinatorial Approach for the Investigation of Kinetics and Temperature Dependence of Surface Reactions in Thin Organic Films

    NARCIS (Netherlands)

    Shovsky, A.; Schönherr, Holger

    2005-01-01

    In this paper we present a new, simple, and reproducible method for the rapid determination of the temperature dependence of solution phase surface reactions of organic thin films on solid supports. Instead of estimating the extent of reaction for many separate samples for many different

  13. Simulation analysis of air flow and turbulence statistics in a rib grit roughened duct.

    Science.gov (United States)

    Vogiatzis, I I; Denizopoulou, A C; Ntinas, G K; Fragos, V P

    2014-01-01

    The implementation of variable artificial roughness patterns on a surface is an effective technique to enhance the rate of heat transfer to fluid flow in the ducts of solar air heaters. Different geometries of roughness elements investigated have demonstrated the pivotal role that vortices and associated turbulence have on the heat transfer characteristics of solar air heater ducts by increasing the convective heat transfer coefficient. In this paper we investigate the two-dimensional, turbulent, unsteady flow around rectangular ribs of variable aspect ratios by directly solving the transient Navier-Stokes and continuity equations using the finite elements method. Flow characteristics and several aspects of turbulent flow are presented and discussed including velocity components and statistics of turbulence. The results reveal the impact that different rib lengths have on the computed mean quantities and turbulence statistics of the flow. The computed turbulence parameters show a clear tendency to diminish downstream with increasing rib length. Furthermore, the applied numerical method is capable of capturing small-scale flow structures resulting from the direct solution of Navier-Stokes and continuity equations.

  14. Quantum-kinetic modeling of electron release in low-energy surface collisions of atoms and molecules

    Energy Technology Data Exchange (ETDEWEB)

    Marbach, Johannes

    2012-09-20

    In this work we present a theoretical description of electron release in the collision of atomic and molecular projectiles with metallic and especially dielectric surfaces. The associated electron yield, the secondary electron emission coefficient, is an important input parameter for numerical simulations of dielectric barrier discharges and other bounded low-temperature gas discharges. The available reference data for emission coefficients is, however, very sparse and often uncertain, especially for molecular projectiles. With the present work we aim to contribute to the filling of these gaps by providing a flexible and easy-to-use model that allows for a convenient calculation of the emission coefficient and related quantities for a wide range of projectile-surface systems and the most dominant reaction channels.

  15. Photochemical transformation of anionic 2-nitro-4-chlorophenol in surface waters: Laboratory and model assessment of the degradation kinetics, and comparison with field data

    Energy Technology Data Exchange (ETDEWEB)

    Sur, Babita [Dipartimento di Chimica, Universita di Torino, Via P. Giuria 5, 10125 Torino (Italy); Department of Chemical Engineering, Calcutta University, 92 Acharya P. C. Road, Kolkata 700009 (India); De Laurentiis, Elisa; Minella, Marco; Maurino, Valter; Minero, Claudio [Dipartimento di Chimica, Universita di Torino, Via P. Giuria 5, 10125 Torino (Italy); Vione, Davide [Dipartimento di Chimica, Universita di Torino, Via P. Giuria 5, 10125 Torino (Italy); Centro Interdipartimentale NatRisk, Universita di Torino, Via Leonardo da Vinci 44, 10095 Grugliasco (Italy)

    2012-06-01

    Anionic 2-nitro-4-chlorophenol (NCP) may occur in surface waters as a nitroderivative of 4-chlorophenol, which is a transformation intermediate of the herbicide dichlorprop. Here we show that NCP would undergo efficient photochemical transformation in environmental waters, mainly by direct photolysis and reaction with {center_dot}OH. NCP has a polychromatic photolysis quantum yield {Phi}{sub NCP} = (1.27 {+-} 0.22) {center_dot} 10{sup -5}, a rate constant with {center_dot}OH k{sub NCP,}{center_dot}{sub OH} = (1.09 {+-} 0.09) {center_dot} 10{sup 10} M{sup -1} s{sup -1}, a rate constant with {sup 1}O{sub 2}k{sub NCP,1O2} = (2.15 {+-} 0.38) {center_dot} 10{sup 7} M{sup -1} s{sup -1}, a rate constant with the triplet state of anthraquinone-2-sulphonate k{sub NCP,3AQ2S*} = (5.90 {+-} 0.43) {center_dot} 10{sup 8} M{sup -1} s{sup -1}, and is poorly reactive toward CO{sub 3}{sup -}{center_dot}. The k{sub NCP,3AQ2S*} value is representative of reaction with the triplet states of chromophoric dissolved organic matter. The inclusion of photochemical reactivity data into a model of surface-water photochemistry allowed the NCP transformation kinetics to be predicted as a function of water chemical composition and column depth. Very good agreement between model predictions and field data was obtained for the shallow lagoons of the Rhone delta (Southern France). Highlights: Black-Right-Pointing-Pointer Phototransformation kinetics of 2-nitro-4-chlorophenol, relevant to surface waters. Black-Right-Pointing-Pointer Determination of photochemical reactivity data in the laboratory. Black-Right-Pointing-Pointer Model approach to combine photochemical reactivity with environmental variables. Black-Right-Pointing-Pointer Good agreement with field data in lagoon water (Rhone delta, Southern France). Black-Right-Pointing-Pointer Direct photolysis and reaction with {center_dot}OH as main photoprocesses in the environment.

  16. Technical note: Influence of surface roughness and local turbulence on coated-wall flow tube experiments for gas uptake and kinetic studies

    Directory of Open Access Journals (Sweden)

    G. Li

    2018-02-01

    Full Text Available Coated-wall flow tube reactors are frequently used to investigate gas uptake and heterogeneous or multiphase reaction kinetics under laminar flow conditions. Coating surface roughness may potentially distort the laminar flow pattern, induce turbulence and introduce uncertainties in the calculated uptake coefficient based on molecular diffusion assumptions (e.g., Brown/Cooney–Kim–Davis (CKD/Knopf–Pöschl–Shiraiwa (KPS methods, which has not been fully resolved in earlier studies. Here, we investigate the influence of surface roughness and local turbulence on coated-wall flow tube experiments for gas uptake and kinetic studies. According to laminar boundary theory and considering the specific flow conditions in a coated-wall flow tube, we derive and propose a critical height δc to evaluate turbulence effects in the design and analysis of coated-wall flow tube experiments. If a geometric coating thickness δg is larger than δc, the roughness elements of the coating may cause local turbulence and result in overestimation of the real uptake coefficient (γ. We further develop modified CKD/KPS methods (i.e., CKD-LT/KPS-LT to account for roughness-induced local turbulence effects. By combination of the original methods and their modified versions, the maximum error range of γCKD (derived with the CKD method or γKPS (derived with the KPS method can be quantified and finally γ can be constrained. When turbulence is generated, γCKD or γKPS can bear large difference compared to γ. Their difference becomes smaller for gas reactants with lower uptake (i.e., smaller γ and/or for a smaller ratio of the geometric coating thickness to the flow tube radius (δg ∕ R0. On the other hand, the critical height δc can also be adjusted by optimizing flow tube configurations and operating conditions (i.e., tube diameter, length, and flow velocity, to ensure not only unaffected laminar flow patterns but also other specific requirements for an

  17. Technical note: Influence of surface roughness and local turbulence on coated-wall flow tube experiments for gas uptake and kinetic studies

    Science.gov (United States)

    Li, Guo; Su, Hang; Kuhn, Uwe; Meusel, Hannah; Ammann, Markus; Shao, Min; Pöschl, Ulrich; Cheng, Yafang

    2018-02-01

    Coated-wall flow tube reactors are frequently used to investigate gas uptake and heterogeneous or multiphase reaction kinetics under laminar flow conditions. Coating surface roughness may potentially distort the laminar flow pattern, induce turbulence and introduce uncertainties in the calculated uptake coefficient based on molecular diffusion assumptions (e.g., Brown/Cooney-Kim-Davis (CKD)/Knopf-Pöschl-Shiraiwa (KPS) methods), which has not been fully resolved in earlier studies. Here, we investigate the influence of surface roughness and local turbulence on coated-wall flow tube experiments for gas uptake and kinetic studies. According to laminar boundary theory and considering the specific flow conditions in a coated-wall flow tube, we derive and propose a critical height δc to evaluate turbulence effects in the design and analysis of coated-wall flow tube experiments. If a geometric coating thickness δg is larger than δc, the roughness elements of the coating may cause local turbulence and result in overestimation of the real uptake coefficient (γ). We further develop modified CKD/KPS methods (i.e., CKD-LT/KPS-LT) to account for roughness-induced local turbulence effects. By combination of the original methods and their modified versions, the maximum error range of γCKD (derived with the CKD method) or γKPS (derived with the KPS method) can be quantified and finally γ can be constrained. When turbulence is generated, γCKD or γKPS can bear large difference compared to γ. Their difference becomes smaller for gas reactants with lower uptake (i.e., smaller γ) and/or for a smaller ratio of the geometric coating thickness to the flow tube radius (δg / R0). On the other hand, the critical height δc can also be adjusted by optimizing flow tube configurations and operating conditions (i.e., tube diameter, length, and flow velocity), to ensure not only unaffected laminar flow patterns but also other specific requirements for an individual flow tube

  18. Electrochemical Oxidation of Resorcinol in Aqueous Medium Using Boron-Doped Diamond Anode: Reaction Kinetics and Process Optimization with Response Surface Methodology.

    Science.gov (United States)

    Körbahti, Bahadır K; Demirbüken, Pelin

    2017-01-01

    Electrochemical oxidation of resorcinol in aqueous medium using boron-doped diamond anode (BDD) was investigated in a batch electrochemical reactor in the presence of Na 2 SO 4 supporting electrolyte. The effect of process parameters such as resorcinol concentration (100-500 g/L), current density (2-10 mA/cm 2 ), Na 2 SO 4 concentration (0-20 g/L), and reaction temperature (25-45°C) was analyzed on electrochemical oxidation using response surface methodology (RSM). The optimum operating conditions were determined as 300 mg/L resorcinol concentration, 8 mA/cm 2 current density, 12 g/L Na 2 SO 4 concentration, and 34°C reaction temperature. One hundred percent of resorcinol removal and 89% COD removal were obtained in 120 min reaction time at response surface optimized conditions. These results confirmed that the electrochemical mineralization of resorcinol was successfully accomplished using BDD anode depending on the process conditions, however the formation of intermediates and by-products were further oxidized at much lower rate. The reaction kinetics were evaluated at optimum conditions and the reaction order of electrochemical oxidation of resorcinol in aqueous medium using BDD anode was determined as 1 based on COD concentration with the activation energy of 5.32 kJ/mol that was supported a diffusion-controlled reaction.

  19. Electrochemical Oxidation of Resorcinol in Aqueous Medium Using Boron-Doped Diamond Anode: Reaction Kinetics and Process Optimization with Response Surface Methodology

    Directory of Open Access Journals (Sweden)

    Bahadır K. Körbahti

    2017-10-01

    Full Text Available Electrochemical oxidation of resorcinol in aqueous medium using boron-doped diamond anode (BDD was investigated in a batch electrochemical reactor in the presence of Na2SO4 supporting electrolyte. The effect of process parameters such as resorcinol concentration (100–500 g/L, current density (2–10 mA/cm2, Na2SO4 concentration (0–20 g/L, and reaction temperature (25–45°C was analyzed on electrochemical oxidation using response surface methodology (RSM. The optimum operating conditions were determined as 300 mg/L resorcinol concentration, 8 mA/cm2 current density, 12 g/L Na2SO4 concentration, and 34°C reaction temperature. One hundred percent of resorcinol removal and 89% COD removal were obtained in 120 min reaction time at response surface optimized conditions. These results confirmed that the electrochemical mineralization of resorcinol was successfully accomplished using BDD anode depending on the process conditions, however the formation of intermediates and by-products were further oxidized at much lower rate. The reaction kinetics were evaluated at optimum conditions and the reaction order of electrochemical oxidation of resorcinol in aqueous medium using BDD anode was determined as 1 based on COD concentration with the activation energy of 5.32 kJ/mol that was supported a diffusion-controlled reaction.

  20. Kinetic sculpture

    OpenAIRE

    Joneta Witabora; Jonata Witabora

    2014-01-01

    Kinetic Sculpture was born from a long process of searching new approach in sculpture. The artists tried to escape from 'static' paradigm and tried to implement movement into their works: a sculpture that is mobile. Movement is always a fascinating phenomenon to eyes. Kinetic sculpture strength lies in its unique character in combining science and art. Kinetic Sculptures are really interesting pieces of art. It succeeds to fascinate human everytime. 

  1. Bond strength of resin cement to dentin and to surface-treated posts of titanium alloy, glass fiber, and zirconia

    DEFF Research Database (Denmark)

    Sahafi, Alireza; Peutzfeldt, Anne; Asmussen, Erik

    2003-01-01

    of posts (n = 9 to 14) and human dentin (n = 10) were obtained by grinding. The posts received one of three surface treatments: 1. roughening (sandblasting, hydrofluoric acid etching), 2. application of primer (Alloy Primer, Metalprimer II, silane), or 3. roughening followed by application of primer...... with and without silane treatment significantly decreased the bond strength of Panavia F to the post. CONCLUSION: The bond strength of resin cements to the posts was affected by the material of the post, the surface treatment of the post, and by the type of resin cement. The bond strength of resin cement to dentin...

  2. Crystallite growth kinetics of TiO{sub 2} surface modification with 9 mol% ZnO prepared by a coprecipitation process

    Energy Technology Data Exchange (ETDEWEB)

    Ko, Horng-Huey [Department of Fragrance and Cosmetic Science, Kaohsiung Medical University, 100 Shih-Chuan 1st Road, Kaohsiung 80708, Taiwan (China); Hsi, Chi-Shiung [Department of Materials Science and Engineering, National United University, 1 Lein-Da, Kung-Ching Li, Miao-Li 36003, Taiwan (China); Wang, Moo-Chin, E-mail: mcwang@kmu.edu.tw [Department of Fragrance and Cosmetic Science, Kaohsiung Medical University, 100 Shih-Chuan 1st Road, Kaohsiung 80708, Taiwan (China); Zhao, Xiujian, E-mail: opluse@whut.edu.cn [State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070 (China)

    2014-03-05

    Highlights: • TiO{sub 2} powder surface modification with 9 mol% ZnO was obtained. • Phase transformation from anatase to rutile was hindered by ZnO added. • Growth kinetic of anatase TiO{sub 2} nanocrystallites in T-9Z powders was described as: D{sub A,9}{sup 2}=2.42×10{sup 5}×exp(-39.9×10{sup 3}/RT). • Growth kinetic of rutile TiO{sub 2} nanocrystallites in T-9Z powders was described as: D{sub R,9}{sup 2}=8.49×10{sup 5}×exp(-47.6×10{sup 3}/RT) rutile TiO{sub 2}. -- Abstract: The nanocrystallite growth of TiO{sub 2} surface modification with 9 mol% ZnO prepared by a coprecipitation process has been studied. Thermogravimetric and differential thermal analysis (TG/DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and UV–VIS–NIR spectrophotometry have been utilized to characterize the TiO{sub 2} nanocrystallites surface modification with 9 mol% ZnO (denoted by T-9Z). The DTA result shows that the anatase TiO{sub 2} first formed at 533 K and the completion of anatase TiO{sub 2} crystallization occurred at 745 K for the T-9Z freeze-dried precursor powders. XRD results reveal that the anatase and rutile TiO{sub 2} coexist when the T-9Z freeze-dried precursor powders were calcined at 523–973 K for 2 h. When the T-9Z freeze-dried precursor powders were calcined at 973 K for 2 h, rutile TiO{sub 2} was the major phase, and the minor phases were anatase TiO{sub 2} and Zn{sub 2}Ti{sub 3}O{sub 8}. The phase was composed of the rutile TiO{sub 2} and Zn{sub 2}TiO{sub 4} for the T-9Z freeze-dried precursor powders after calcination at 1273 K for 2 h. The growth kinetics of TiO{sub 2} nanocrystallites in T-9Z powders were described as: D{sub A,9}{sup 2}=2.42×10{sup 5}×exp(-39.9×10{sup 3}/RT)and D{sub R,9}{sup 2}=8.49×10{sup 5}×exp(-47.6×10{sup 3}/RT) for anatase and rutile TiO{sub 2} nanocrystallites respectively. The analysis results of UV/VIS/NIR spectra reveal that the T-9Z freeze

  3. On the photocatalytic reduction of MTT tetrazolium salt on the surface of TiO2 nanoparticles: Formazan production kinetics and mechanism.

    Science.gov (United States)

    Popescu, Traian; Lupu, Andreea R; Raditoiu, Valentin; Purcar, Violeta; Teodorescu, Valentin S

    2015-11-01

    The MTT [3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium-bromide] cell cytotoxicity indicator is photocatalytically reduced on the surface of TiO2 nanoparticles in phosphate-buffered-saline (PBS) environment. We hypothesize that specific phosphate adsorption may be used to modulate the efficiency of the TiO2-MTT reaction through colloidal and semiconductor-liquid interface processes. The TiO2-MTT reaction kinetics was studied in PBS, with respect to photocatalyst and MTT concentrations and irradiation wavelength. The effects of PBS and electron scavengers (Fe(3+) ions) on reaction efficiency and the role of colloidal surface charge in the photocatalytic process were investigated. The structural and spectroscopic characteristics of relevant TiO2-formazan systems were studied by X-ray diffraction, transmission electron microscopy and IR-spectroscopy. The reaction was pseudo-first order with respect to photocatalyst and showed a negative and fractional partial order with respect to MTT. Formazan production rates were directly proportional to radiation wavelength and TiO2 concentration and inversely proportional to the MTT initial concentration. The addition of Fe(3+) ions, as well as the absence of PBS, induced strong reaction inhibition. Reaction efficiency and catalyst Zeta potential were enhanced by Na2HPO4 (PBS component) and showed a maximum around the phosphate concentration 0.005 M. Structural/spectroscopic characterization confirmed the formation of amorphous MTT-formazan on the surface of TiO2 and the TiO2-phosphate binding. Copyright © 2015 Elsevier Inc. All rights reserved.

  4. Thermodynamics and kinetics of reduction and species conversion at a hydrophobic surface for mitochondrial cytochromes c and their cardiolipin adducts

    International Nuclear Information System (INIS)

    Ranieri, Antonio; Di Rocco, Giulia; Millo, Diego; Battistuzzi, Gianantonio; Bortolotti, Carlo A.; Lancellotti, Lidia; Borsari, Marco; Sola, Marco

    2015-01-01

    Highlights: • Cytochrome c and its adduct with cardiolipin can be immobilized on a hydrophobic SAM. • Adsorbed cytochrome c and its adduct undergo extensive unfolding and axial ligand substitution. • An equilibrium between a six-coordinated and a five-coordinated form is observed in both cases. • The reduced five-coordinated form is stabilized by cardiolipin binding. • Immobilized cytochrome c exchanges electrons more slowly upon cardiolipin binding. - Abstract: Cytochrome c (cytc) and its adduct with cardiolipin (CL) were immobilized on a hydrophobic SAM-coated electrode surface yielding a construct which mimics the environment experienced by the complex at the inner mitochondrial membrane where it plays a role in cell apoptosis. Under these conditions, both species undergo an equilibrium between a six-coordinated His/His-ligated and a five-coordinated His/- ligated forms stable in the oxidized and in the reduced state, respectively. The thermodynamics of the oxidation-state dependent species conversion were determined by temperature-dependent diffusionless voltammetry experiments. CL binding stabilizes the immobilized reduced His/- ligated form of cytc which was found previously to catalytically reduce dioxygen. Here, this adduct is also found to show pseudoperoxidase activity, catalysing reduction of hydrogen peroxide. These effects would impart CL with an additional role in the cytc-mediated peroxidation leading to programmed cell death. Moreover, immobilized cytc exchanges electrons more slowly upon CL binding possibly due to changes in solvent reorganization effects at the protein-SAM interface

  5. Swelling-induced morphology reconstruction in block copolymer nanorods: kinetics and impact of surface tension during solvent evaporation.

    Science.gov (United States)

    Wang, Yong; Tong, Ling; Steinhart, Martin

    2011-03-22

    Nanoscopic domain structures of BCP nanorods can be converted into well-defined mesopore systems by swelling the BCP minority component with a selective solvent at temperatures below the bulk glass transition temperature of the nonswelling matrix. The initial stage of this process involves rapid morphology reconstruction of the nonswelling majority domains to accommodate the increased volume of the swelling minority domains caused by rapid solvent uptake. Morphology reconstruction slows down once entropic restoring forces of the swelling chains impede further uptake of swelling agent. Upon evaporation of the swelling agent, mesopores form in place of the swollen domains as the swollen minority blocks undergo entropic relaxation while intermediate nonequilibrium morphologies in the BCP nanorods are fixated by the reconstructed majority component. The surface area of mesopores developing when swollen cylindrical minority domains collapse may be minimized by the growth of Rayleigh instabilities. Depending on swelling temperature, swelling agent, and BCP architecture, BCP nanorods with one or several cylindrical channels undulated or uniform in diameter running along their long axes, linear strings of spherical cavities, and continuous mesopore systems can be obtained.

  6. Kinetic approach

    Indian Academy of Sciences (India)

    Collapse of a Bose gas: Kinetic approach ... Thermodynamical, statistical and static properties of condensates; Ultracold and trapped gases; matter waves. ... of a harmonically trapped attractively interacting Bose gas below the condensation point by introducing a kinetic approach within the Hartee-Fock approximation.

  7. Heparin kinetics

    International Nuclear Information System (INIS)

    Swart, C.A.M. de.

    1983-01-01

    The author has studied the kinetics of heparin and heparin fractions after intravenous administration in humans and in this thesis the results of this study are reported. Basic knowledge about the physico-chemical properties of heparin and its interactions with proteins resulting in anticoagulant and lipolytic effects are discussed in a review (chapter II), which also comprises some clinical aspects of heparin therapy. In chapter III the kinetics of the anticoagulant effect are described after intravenous administration of five commercial heparin preparations. A mathematical model is presented that fits best to these kinetics. The kinetics of the anticoagulant and lipolytic effects after intravenous injection of various 35 S-radiolabelled heparin fractions and their relationship with the disappearance of the radiolabel are described in chapter IV. Chapter V gives a description of the kinetics of two radiolabels after injection of in vitro formed complexes consisting of purified, 125 I-radiolabelled antithrombin III and various 35 S-radiolabelled heparin fractions. (Auth.)

  8. Kinetic and isotherm analyses for thorium (IV) adsorptive removal from aqueous solutions by modified magnetite nanoparticle using response surface methodology (RSM)

    Science.gov (United States)

    Karimi, Mohammad; Milani, Saeid Alamdar; Abolgashemi, Hossein

    2016-10-01

    In this study, the ability and the adsorption capacity of magnetite/aminopropyltriethoxysilane/glutaraldehyde (Fe3O4/APTES/GA) adsorbent were evaluated for the adsorption of thorium (IV) ions from aqueous solutions. The influence of the several variables such as pH (1-5), Th (IV) initial concentration (50-300 mg L-1) and adsorbent concentration (1-5 g L-1) on the Th (IV) adsorption were investigated by response surface methodology (RSM). The results showed that the highest absorption capacity (q) was 107.23 mg g-1 with respect to pH = 4.5, initial concentration of 250 mg L-1 and adsorbent concentration of 1 g L-1 for 90 min. Modeling equilibrium sorption data with the Langmuir, Freundlich and Dubinin-Radushkevich models pointed out that the results were in good agreement with Langmuir model. The experimental kinetic data were well fitted to pseudo-second-order equation with R2 = 0.9739. Also thermodynamic parameters (ΔGo, ΔHo, ΔSo) declared that the Th (IV) adsorption was endothermic and spontaneous.

  9. Aging Versus Postmenopausal Osteoporosis: Bone Composition and Maturation Kinetics at Actively-Forming Trabecular Surfaces of Female Subjects Aged 1 to 84 Years.

    Science.gov (United States)

    Paschalis, Eleftherios P; Fratzl, Peter; Gamsjaeger, Sonja; Hassler, Norbert; Brozek, Wolfgang; Eriksen, Erik F; Rauch, Frank; Glorieux, Francis H; Shane, Elizabeth; Dempster, David; Cohen, Adi; Recker, Robert; Klaushofer, Klaus

    2016-02-01

    Bone strength depends on the amount of bone, typically expressed as bone mineral density (BMD), determined by dual-energy X-ray absorptiometry (DXA), and on bone quality. Bone quality is a multifactorial entity including bone structural and material compositional properties. The purpose of the present study was to examine whether bone material composition properties at actively-forming trabecular bone surfaces in health are dependent on subject age, and to contrast them with postmenopausal osteoporosis patients. To achieve this, we analyzed by Raman microspectroscopy iliac crest biopsy samples from healthy subjects aged 1.5 to 45.7 years, paired biopsy samples from females before and immediately after menopause aged 46.7 to 53.6 years, and biopsy samples from placebo-treated postmenopausal osteoporotic patients aged 66 to 84 years. The monitored parameters were as follows: the mineral/matrix ratio; the mineral maturity/crystallinity (MMC); nanoporosity; the glycosaminoglycan (GAG) content; the lipid content; and the pyridinoline (Pyd) content. The results indicate that these bone quality parameters in healthy, actively-forming trabecular bone surfaces are dependent on subject age at constant tissue age, suggesting that with advancing age the kinetics of maturation (either accumulation, or posttranslational modifications, or both) change. For most parameters, the extrapolation of models fitted to the individual age dependence of bone in healthy individuals was in rough agreement with their values in postmenopausal osteoporotic patients, except for MMC, lipid, and Pyd content. Among these three, Pyd content showed the greatest deviation between healthy aging and disease, highlighting its potential to be used as a discriminating factor. © 2015 American Society for Bone and Mineral Research.

  10. Spectrophotometric evaluation of surface morphology dependent catalytic activity of biosynthesized silver and gold nanoparticles using UV–vis spectra: A comparative kinetic study

    International Nuclear Information System (INIS)

    Ankamwar, Balaprasad; Kamble, Vaishali; Sur, Ujjal Kumar; Santra, Chittaranjan

    2016-01-01

    Graphical abstract: - Highlights: • The biosynthesized silver nanoparticles were stable for 6 months and used as effective SERS active substrate. • They are effective catalyst in the chemical reduction of 4-nitrophenol to 4-aminophenol. • Comparative catalytic efficiency of both silver and gold nanoparticles was studied spectrophotometrically. • Our results demonstrate surface morphology dependent catalytic activity of both nanoparticles. - Abstract: The development of eco-friendly and cost-effective synthetic protocol for the preparation of nanomaterials, especially metal nanoparticles is an emerging area of research in nanotechnology. These metal nanoparticles, especially silver can play a crucial role in various catalytic reactions. The biosynthesized silver nanoparticles described here was very stable up to 6 months and can be further exploited as an effective catalyst in the chemical reduction of 4-nitrophenol to 4-aminophenol. The silver nanoparticles were utilized as an efficient surface-enhanced Raman scattering (SERS) active substrate using Rhodamine 6G as Raman probe molecule. We have also carried out systematic comparative studies on the catalytic efficiency of both silver and gold nanoparticles using UV–vis spectra to monitor the above reaction spectrophotometrically. We find that the reaction follows pseudo-first order kinetics and the catalytic activity can be explained by a simple model based on Langmuir–Hinshelwood mechanism for heterogeneous catalysis. We also find that silver nanoparticles are more efficient as a catalyst compare to gold nanoparticles in the reduction of 4-nitrophenol to 4-aminophenol, which can be explained by the morphology of the nanoparticles as determined by transmission electron microscopy.

  11. Formation of vanadium carbide precipitations at the surface of alloys: Thermodynamics and kinetics aspects; Bildung von Vanadiumcarbid-Ausscheidungen auf Legierungsoberflaechen: Thermodynamische und kinetische Aspekte

    Energy Technology Data Exchange (ETDEWEB)

    Schneider, A.; Uebing, C. [Max-Planck-Institut fuer Eisenforschung GmbH, Duesseldorf (Germany)

    1998-12-31

    The paper describes the formation of vanadium carbides on the surface layers of Fe-3%V-C(100) alloys. The phase diagram calculated for this alloyed material using the ThermoCalc program package reveals a co-existence of ferritic matrix and V{sub 3}C{sub 2} at temperatures of T{<=}650 C. This carbide is instable at elevated temperatures, leading to co-existence of ferrite and the cubic VC{sub 1-x}. Experimental analyses revealed the formation of a 2D VC compound in the top layers of the surface of Fe-3%V-C(100) alloys, induced by equilibrium segregation. The paper explains the usefulness of thermodynamic and kinetic calculations for interpretation of precipitation phenomena in steels. Mathematically derived and experimental results of analyses for the case of non-equilibrium segregation showed excellent agreement in the determination of carbide thickness (nanometer scale) and time dependence of segregation under fast cooling conditions. (orig./CB) [Deutsch] In der vorliegenden Arbeit wurde die Bildung von Vanadiumcarbiden auf Fe-3%V-C(100)-Legierungsoberflaechen beschrieben. Das anhand des ThermoCalc-Programmpakets fuer diese Legierungszusammensetzung berechnete Phasendiagramm zeigt bei niedrigen Temperaturen T{<=}650 C die Koexistenz von ferritischer Matrix und V{sub 3}C{sub 2}. Bei hoeheren Temperaturen ist dieses Carbid instabil und es liegt Koexistenz von Ferrit und dem kubischen VC{sub 1-x} vor. Die experimentellen Untersuchungen zeigen die Ausbildung einer zweidimensionalen VC-Oberflaechenverbindung auf Fe-3%V-C(100)-Legierungsoberflaechen durch Gleichgewichtssegregation. Diese Arbeit zeigt, dass thermodynamische und kinetische Rechnungen bei der Deutung von Ausscheidungsphaenomenen in Staehlen sinnvoll eingesetzt werden koennen. Bei der Nichtgleichgewichtssegregation wurde bezueglich Carbiddicke (im Nanometerbereich) und Zeitabhaengigkeit der Ausscheidung bei schneller Abkuehlung eine hervorragende Uebereinstimmung zwischen Simulation und Experiment gefunden

  12. Kinetic energy budget details

    Indian Academy of Sciences (India)

    Abstract. This paper presents the detailed turbulent kinetic energy budget and higher order statistics of flow behind a surface-mounted rib with and without superimposed acoustic excitation. Pattern recognition technique is used to determine the large-scale structure magnitude. It is observed that most of the turbulence ...

  13. The influence of shale depositional fabric on the kinetics of hydrocarbon generation through control of mineral surface contact area on clay catalysis

    Science.gov (United States)

    Rahman, Habibur M.; Kennedy, Martin; Löhr, Stefan; Dewhurst, David N.; Sherwood, Neil; Yang, Shengyu; Horsfield, Brian

    2018-01-01

    Accurately assessing the temperature and hence the depth and timing of hydrocarbon generation is a critical step in the characterization of a petroleum system. Clay catalysis is a potentially significant modifier of hydrocarbon generation temperature, but experimental studies of clay catalysis show inconsistent or contradictory results. This study tests the hypothesis that source rock fabric itself is an influence on clay mineral catalysis as it controls the extent to which organic matter and clay minerals are physically associated. Two endmember clay-organic fabrics distinguish the source rocks studied: (1) a particulate fabric where organic matter is present as discrete, >5 μm particles and (2) a nanocomposite fabric in which amorphous organic matter is associated with clay mineral surfaces at sub-micron scale. High-resolution electron imaging and bulk geochemical characterisation confirm that samples of the Miocene Monterey Formation (California) are representative of the nanocomposite source rock endmember, whereas samples from the Permian Stuart Range Formation (South Australia) represent the particulate source rock endmember. Kinetic experiments are performed on paired whole rock and kerogen isolate samples from these two formations using open system, non-isothermal pyrolysis at three different heating rates (0.7, 2 and 5 K/min) to determine the effects of the different shale fabrics on hydrocarbon generation kinetics. Extrapolation to a modelled geological heating rate shows a 20 °C reduction in the onset temperature of hydrocarbon generation in Monterey Formation whole rock samples relative to paired kerogen isolates. This result is consistent with the Monterey Formations's nanocomposite fabric where clay catalysis can proceed because reactive clay minerals are intimately associated with organic matter. By contrast, there is no significant difference in the modelled hydrocarbon generation temperature of paired whole rock and kerogen isolates from the

  14. Roughening plastic foils as polymer substrates for efficient light trapping in amorphous solar cells; Aufrauhen von Polymersubstraten. Gezieltes Aufrauhen von Plastikfolien fuer ein effizientes Light-Trapping in amorphen Solarzellen

    Energy Technology Data Exchange (ETDEWEB)

    Keppner, H.; Fischer, D.

    2003-07-01

    The objective of the project was the introduction of light-trapping for a-Si:H solar cells deposited on polymer foils by applying plasma roughening of the substrate. The preliminary experiments showed that Reactive Ion Etching (RIE) using SF{sub 6} / O{sub 2} mixtures can result in surface roughnesses of the order of 0.1 to 1 {mu}m. Such surfaces were analysed and compared by using AFM, scanning electron microscopy and angular resolved reflection. Here, the angular resolved reflection proved to be particularly useful as a clear quantitative interpretation is possible on the basis of the critical angle of escape of 28 {sup o}C. Regarding etching parameters to obtain useful roughnesses, it turned out that the electrode configuration plays a predominant role. The best results were obtained by applying a set of powered linear electrode bars in front of the substrate foil. To apply such textured etched substrates to actual solar cell manufacturing, a continuous etching system was realized comprising a linear etching electrode and a roll-to-roll foil transport mechanism capable of treating 300 mm wide foils. In solar cell manufacturing on textured etched films, at first the yield was very low. This was related to a coverage of the etched film with a layer of reaction products. These structures could be eliminated by a cleaning step, leading to an again reasonably high yield. Based on this procedure, n-i-p type solar cells could be successfully manufactured on textured etched polyimide substrates. The increase of the photocurrent and efficiency compared to flat substrates was +10%, with the best solar cell reaching an initial conversion efficiency of 6.9 %. (author)

  15. Kinetic Interface

    DEFF Research Database (Denmark)

    2009-01-01

    A kinetic interface for orientation detection in a video training system is disclosed. The interface includes a balance platform instrumented with inertial motion sensors. The interface engages a participant's sense of balance in training exercises.......A kinetic interface for orientation detection in a video training system is disclosed. The interface includes a balance platform instrumented with inertial motion sensors. The interface engages a participant's sense of balance in training exercises....

  16. Effect of surface roughness on the heating rates of large-angled hypersonic blunt cones

    Science.gov (United States)

    Irimpan, Kiran Joy; Menezes, Viren

    2018-03-01

    Surface-roughness caused by the residue of an ablative Thermal Protection System (TPS) can alter the turbulence level and surface heating rates on a hypersonic re-entry capsule. Large-scale surface-roughness that could represent an ablated TPS, was introduced over the forebody of a 120° apex angle blunt cone, in order to test for its influence on surface heating rates in a hypersonic freestream of Mach 8.8. The surface heat transfer rates measured on smooth and roughened models under the same freestream conditions were compared. The hypersonic flow-fields of the smooth and rough-surfaced models were visualized to analyse the flow physics. Qualitative numerical simulations and pressure measurements were carried out to have an insight into the high-speed flow physics. Experimental observations under moderate Reynolds numbers indicated a delayed transition and an overall reduction of 17-46% in surface heating rates on the roughened model.

  17. Kinetics and

    Directory of Open Access Journals (Sweden)

    Mojtaba Ahmadi

    2016-11-01

    Full Text Available The aqueous degradation of Reactive Yellow 84 (RY84 by potassium peroxydisulfate (K2S2O8 has been studied in laboratory scale experiments. The effect of the initial concentrations of potassium peroxydisulfate and RY84, pH and temperature on RY84 degradation were also examined. Experimental data were analyzed using first and second-order kinetics. The degradation kinetics of RY84 of the potassium peroxydisulfate process followed the second-order reaction kinetics. These rate constants have an extreme values similar to of 9.493 mM−1min−1 at a peroxydisulfate dose of 4 mmol/L. Thermodynamic parameters such as activation (Ea and Gibbs free energy (ΔG° were also evaluated. The negative value of ΔGo and Ea shows the spontaneous reaction natural conditions and exothermic nature.

  18. Early-stage roughening of the polymer-polymer interface approaching the glass transition temperature by real-time neutron reflection.

    Science.gov (United States)

    Carelli, C; Higgins, A M; Jones, R A L; Sferrazza, M

    2006-06-01

    The early-stage roughening of the interface between thin deuterated poly(methyl methacrylate) (d-PMMA) layers on thick polystyrene (PS) films was studied as a function of the temperature using real-time specular neutron reflectivity. By measuring the growth of the interface roughness as a precursor of the dewetting, the characteristic time constant of the early stages of the process was studied as a function of the temperature approaching the glass transition temperature (T(g)) of the two polymers from above and compared with the prediction of the growth of the interface by the spinodal process. Both solid and liquid regimes were probed, in which the viscosity of the thin film or the substrate dominates respectively. The characteristic growth time of the process also depends on the upper film thickness to a power of 5 or 6 in the solid or liquid regimes, respectively, as predicted by the theory of spinodal dewetting.

  19. Manufacturing and characterisation of water repellent surfaces

    DEFF Research Database (Denmark)

    De Grave, Arnaud; Botija, Pablo; Hansen, Hans Nørgaard

    2006-01-01

    The leaves of some natural plants show a micro structure that gives them the capacity of being cleaned from any undesired particles on them by rainfall. A thorough study of the physical laws that lay behind this phenomenon, known as the lotus effect was conducted in order to obtain a set of useful...... design criteria for such surfaces. The problem of adapting this behaviour to artificially roughened surfaces is addressed by providing design criteria for superhydrophobic, water-repellent and self-cleaning surfaces according to the concrete performance desired for them. Different kind of manufacturing...

  20. Kinetic bridges.

    Science.gov (United States)

    1980-01-01

    This report on kinetic bridges is essentially a state-of-the-art study on two types of bridges whose location or physical characteristics are designed to be time dependent. The first type, called a "relocatable bridge", is essentially for use as a te...

  1. An anti-bacterial approach to nanoscale roughening of biomimetic rice-like pattern PP by thermal annealing

    Science.gov (United States)

    Jafari Nodoushan, Emad; Ebrahimi, Nadereh Golshan; Ayazi, Masoumeh

    2017-11-01

    In this paper, we introduced thermal annealing treatment as an effective way of increasing the nanoscale roughness of a semi-crystalline polymer surface. Annealing treatment applied to a biomimetic microscale pattern of rice leaf to achieve a superhydrophobic surface with a hierarchical roughness. Resulted surfaces was characterized by XRD, AFM and FE-SEM instruments and showed an increase of roughness and cristallinity within both time and temperature of treatment. These two parameters also impact on measured static contact angle up to 158°. Bacterial attachment potency has an inverse relationship with the similarity of surface pattern dimensions and bacterial size and due to that, thermal annealing could be an effective way to create anti-bacterial surface beyond its effect on water repellency. Point in case, the anti-bacterial properties of produced water-repellence surfaces of PP were measured and counted colonies of both gram-negative (E. coli) and gram-positive (S. aureus) bacteria reduced with the nature of PP and hierarchical pattern on that. Anti-bacterial characterization of the resulted surface reveals a stunning reduction in adhesion of gram-positive bacteria to the surface. S. aureus reduction rates equaled to 95% and 66% when compared to control blank plate and smooth surface of PP. Moreover, it also could affect the other type of bacteria, gram-negative (E. coli). In the latter case, adhesion reduction rates calculated 66% and 53% when against to the same controls, respectively.

  2. Peri-implant bone formation and surface characteristics of rough surface zirconia implants manufactured by powder injection molding technique in rabbit tibiae.

    Science.gov (United States)

    Park, Young-Seok; Chung, Shin-Hye; Shon, Won-Jun

    2013-05-01

    To evaluate osseointegration in rabbit tibiae and to investigate surface characteristics of novel zirconia implants made by powder injection molding (PIM) technique, using molds with and without roughened inner surfaces. A total of 20 rabbits received three types of external hex implants with identical geometry on the tibiae: machined titanium implants, PIM zirconia implants without mold etching, and PIM zirconia implants with mold etching. Surface characteristics of the three types of implant were evaluated. Removal torque tests and histomorphometric analyses were performed. The roughness of PIM zirconia implants was higher than that of machined titanium implants. The PIM zirconia implants exhibited significantly higher bone-implant contact and removal torque values than the machined titanium implants (P mold showed significantly higher removal torque values than PIM zirconia implants without using roughened mold (P mold etching technique can produce substantially rough surfaces on zirconia implants. © 2012 John Wiley & Sons A/S.

  3. Tungsten surface evolution by helium bubble nucleation, growth and rupture

    International Nuclear Information System (INIS)

    Sefta, Faiza; Wirth, Brian D.; Hammond, Karl D.; Juslin, Niklas

    2013-01-01

    Molecular dynamics simulations reveal sub-surface mechanisms likely involved in the initial formation of nanometre-sized ‘fuzz’ in tungsten exposed to low-energy helium plasmas. Helium clusters grow to over-pressurized bubbles as a result of repeated cycles of helium absorption and Frenkel pair formation. The self-interstitials either reach the surface as isolated adatoms or trap at the bubble periphery before organizing into prismatic 〈1 1 1〉 dislocation loops. Surface roughening occurs as single adatoms migrate to the surface, prismatic loops glide to the surface to form adatom islands, and ultimately as over-pressurized gas bubbles burst. (paper)

  4. Modelling of the kinetics of deactivation of monofunctional catalysts with an acid strength distribution in their nonhomogeneous surface. Application to the deactivation of commercial catalysts in the fcc process

    Energy Technology Data Exchange (ETDEWEB)

    Corella, J.; Menendez, M.

    1986-01-01

    A model for the kinetics of the deactivation of monofunctional catalysts with a heterogeneous or non-uniform active surface is presented. This model is based on previous work by Butt et al. (1978, Chem. Engng Sci. 33, 1321) and starts from the consideration of a function of strength distribution for the active sites. Four types of strength distribution are considered. In the model time-on-stream is used as the independent variable. The influence of the values of the parameters of the catalyst surface on the activity-time curves and the parametric sensitivity of the model are analyzed. With the consideration of the non-uniformity of the catalyst surface developed in this model one can adjust perfectly well the data of deactivation of commercial catalysts in the cracking of gas oils and the empirical correlation of a general character proposed by Pacheco and Petersen (1984a, J. Catalysis 86, 75) for a large variety of processes and catalysts.

  5. Voltammetric and surface-enhanced resonance Raman spectroscopic characterization of cytochrome C adsorbed on a 4-mercaptopyridine monolayer on silver electrodes

    NARCIS (Netherlands)

    Millo, D.; Bonifacio, A.; Ranieri, A.; Borsari, M.; Gooijer, C.; van der Zwan, G.

    2007-01-01

    To combine voltammetric techniques with surface-enhanced resonance Raman scattering (SERRS), cytochrome c (cyt c) was immobilized on a roughened silver electrode chemically modified with a self-assembled monolayer (SAM) of 4-mercaptopyridine (PySH). All measurements were performed on the same

  6. Biomimetic coating of organic polymers with a protein-functionalized layer of calcium phosphate: the surface properties of the carrier influence neither the coating characteristics nor the incorporation mechanism or release kinetics of the protein.

    Science.gov (United States)

    Wu, Gang; Liu, Yuelian; Iizuka, Tateyuki; Hunziker, Ernst B

    2010-12-01

    Polymers that are used in clinical practice as bone-defect-filling materials possess many essential qualities, such as moldability, mechanical strength and biodegradability, but they are neither osteoconductive nor osteoinductive. Osteoconductivity can be conferred by coating the material with a layer of calcium phosphate, which can be rendered osteoinductive by functionalizing it with an osteogenic agent. We wished to ascertain whether the morphological and physicochemical characteristics of unfunctionalized and bovine-serum-albumin (BSA)-functionalized calcium-phosphate coatings were influenced by the surface properties of polymeric carriers. The release kinetics of the protein were also investigated. Two sponge-like materials (Helistat® and Polyactive®) and two fibrous ones (Ethisorb™ and poly[lactic-co-glycolic acid]) were tested. The coating characteristics were evaluated using state-of-the-art methodologies. The release kinetics of BSA were monitored spectrophotometrically. The characteristics of the amorphous and the crystalline phases of the coatings were not influenced by either the surface chemistry or the surface geometry of the underlying polymer. The mechanism whereby BSA was incorporated into the crystalline layer and the rate of release of the truly incorporated depot were likewise unaffected by the nature of the polymeric carrier. Our biomimetic coating technique could be applied to either spongy or fibrous bone-defect-filling organic polymers, with a view to rendering them osteoconductive and osteoinductive.

  7. Structural kinetics studies on phase transitions of the Bi UPD layer between the (2 x 2) and (p x square root[3]) structures using surface X-ray diffraction.

    Science.gov (United States)

    Tamura, Kazuhisa; Mizuki, Jun'ichiro

    2005-07-07

    The kinetics of the phase transition between the (2 x 2) and (p x square root[3])-Bi structures on Au(111) was investigated using electrochemical methods and time-resolved surface X-ray diffraction. The temporal changes in the current value and the diffracted X-ray intensity that originated from the (2 x 2)-Bi overlayer were monitored during the phase transitions at various over-potentials. The phase transition models and kinetics parameters were deduced from each of the current and X-ray intensity transient curves. We also carried out comparative studies of the phase transition from the structural and electrochemical points of view. For the (p x square root[3]) --> (2 x 2) phase transition, the phase transition models determined by the X-ray and electrochemical measurements were a surface-diffusion controlled instantaneous nucleation-growth process and a Langmuir process, respectively. For the reverse transition, the phase transition models determined by X-ray and electrochemical measurements were a Langmuir adsorption process and a surface diffusion controlled nucleation-growth process, respectively. Our results revealed that the current transient curve does not always reflect the phase transition model in both cases and suggest that a structural analysis is fundamental in the phase transition studies. The disagreements between the phase transition models and their mechanisms are discussed.

  8. Stochastic kinetics

    International Nuclear Information System (INIS)

    Colombino, A.; Mosiello, R.; Norelli, F.; Jorio, V.M.; Pacilio, N.

    1975-01-01

    A nuclear system kinetics is formulated according to a stochastic approach. The detailed probability balance equations are written for the probability of finding the mixed population of neutrons and detected neutrons, i.e. detectrons, at a given level for a given instant of time. Equations are integrated in search of a probability profile: a series of cases is analyzed through a progressive criterium. It tends to take into account an increasing number of physical processes within the chosen model. The most important contribution is that solutions interpret analytically experimental conditions of equilibrium (moise analysis) and non equilibrium (pulsed neutron measurements, source drop technique, start up procedures)

  9. Kinetic Damage from Meteorites

    Science.gov (United States)

    Cooke, W.; Brown, P.; Matney, M.

    2017-01-01

    Comparing the natural meteorite flux at the Earth's surface to that of space debris, re-entering debris is 2 orders of magnitude less of a kinetic hazard at all but the very largest (and therefore rarest) sizes compared to natural impactors. Debris re-entries over several metric tonnes are roughly as frequent as natural impactors, but the survival fraction is expected to be much higher. Kinetic hazards from meteorites are very small, with only one recorded (indirect) injury reported. We expect fatalities to be even more rare, on the order of one person killed per several millennia. That several reports exist of small fragments/sand hitting people during meteorite falls is consistent with our prediction that this should occur every decade or so.

  10. Structural study, by surface differential diffraction of neutrons, of the surface of a nickel powder covered with deuterium

    Science.gov (United States)

    Beaufils, J. P.

    1993-01-01

    The analysis of the data of a neutron surface differential diffraction experiment, using H positions determined in the literature whenever available, supports the following model: Grains of the studied nickel powder are limited by (20 ± 10)% of (111) faces and 80% of (110) faces. The (110) faces expose (111) and (1¯11) facets because of anisotropic roughening. A new interpretation of the streaks observed in LEED patterns and a discussion of the coverage provides additional arguments in favour of the roughening. On the facets of the rough faces, the D atoms are displaced from the position they would have on a genuine (111) face. They are no longer on a C3 axis. The Ni atoms of the rough faces suffer an average displacement of 0.015 ± 0.015 nm in the [110] outward direction. The shortest NiD distance on the rough face is equal to 0.19 ± 0.015 nm.

  11. Iron cycling at corroding carbon steel surfaces

    Science.gov (United States)

    Lee, Jason S.; McBeth, Joyce M.; Ray, Richard I.; Little, Brenda J.; Emerson, David

    2013-01-01

    Surfaces of carbon steel (CS) exposed to mixed cultures of iron-oxidizing bacteria (FeOB) and dissimilatory iron-reducing bacteria (FeRB) in seawater media under aerobic conditions were rougher than surfaces of CS exposed to pure cultures of either type of microorganism. The roughened surface, demonstrated by profilometry, is an indication of loss of metal from the surface. In the presence of CS, aerobically grown FeOB produced tight, twisted helical stalks encrusted with iron oxides. When CS was exposed anaerobically in the presence of FeRB, some surface oxides were removed. However, when the same FeOB and FeRB were grown together in an aerobic medium, FeOB stalks were less encrusted with iron oxides and appeared less tightly coiled. These observations suggest that iron oxides on the stalks were reduced and solubilized by the FeRB. Roughened surfaces of CS and denuded stalks were replicated with three culture combinations of different species of FeOB and FeRB under three experimental conditions. Measurements of electrochemical polarization resistance established different rates of corrosion of CS in aerobic and anaerobic media, but could not differentiate rate differences between sterile controls and inoculated exposures for a given bulk concentration of dissolved oxygen. Similarly, total iron in the electrolyte could not be used to differentiate treatments. The experiments demonstrate the potential for iron cycling (oxidation and reduction) on corroding CS in aerobic seawater media. PMID:24093730

  12. Saffman-Taylor fingers with kinetic undercooling

    KAUST Repository

    Gardiner, Bennett P. J.

    2015-02-23

    © 2015 American Physical Society. The mathematical model of a steadily propagating Saffman-Taylor finger in a Hele-Shaw channel has applications to two-dimensional interacting streamer discharges which are aligned in a periodic array. In the streamer context, the relevant regularization on the interface is not provided by surface tension but instead has been postulated to involve a mechanism equivalent to kinetic undercooling, which acts to penalize high velocities and prevent blow-up of the unregularized solution. Previous asymptotic results for the Hele-Shaw finger problem with kinetic undercooling suggest that for a given value of the kinetic undercooling parameter, there is a discrete set of possible finger shapes, each analytic at the nose and occupying a different fraction of the channel width. In the limit in which the kinetic undercooling parameter vanishes, the fraction for each family approaches 1/2, suggesting that this "selection" of 1/2 by kinetic undercooling is qualitatively similar to the well-known analog with surface tension. We treat the numerical problem of computing these Saffman-Taylor fingers with kinetic undercooling, which turns out to be more subtle than the analog with surface tension, since kinetic undercooling permits finger shapes which are corner-free but not analytic. We provide numerical evidence for the selection mechanism by setting up a problem with both kinetic undercooling and surface tension and numerically taking the limit that the surface tension vanishes.

  13. EIR, KfK joint heat transfer experiment on a single rod, roughened with trapezoidal rounded ribs and cooled by various gases

    International Nuclear Information System (INIS)

    Hudina, M.; Huggenberger, M.; Dalle Donne, M.; Meyer, L.; Rehme, K.

    1978-10-01

    Heat transfer and pressure drop experiments with an identical fuel rod simulator have been performed at the two Research Establishments in Wuerenlingen and in Karlsruhe. The rod was artificially roughened with 'two-dimensional' ribs of trapezoidal shape and with rounded edges. The experiments at EIR were performed with CO 2 and the rough rod was contained in a smooth tube and centered by special spacers. The experiments at KfK were performed using helium and nitrogen in the same test section (rod and outer smooth tube with spacers) and air with the rod mounted in another outer smooth tube and with spacers located farther away from the measuring positions. The global measured friction factors and Stanton numbers for different gases agree reasonably well. The differences between the roughness parameters R and G are larger. The possible reasons for the uncertainties in the reduction of these parameters are discussed. It is recommended to perform further experiments with helium in a test section with spacers far apart, to investigate the effect of the temperature ratio on heat transfer and to check if the unfavourable data obtained by the experiment with air are too pessimistic for GCFR application. (orig.) [de

  14. Kinetics and Mechanisms of Oxygen Surface Exchange on La0.6Sr0.4FeO3-delta Thin Films

    OpenAIRE

    Mosleh, Majid; Søgaard, Martin; Hendriksen, Peter Vang

    2009-01-01

    The thermodynamic properties as well as oxygen exchange kinetics were examined on mixed ionic and electronic conducting (La0.6Sr0.4)0.99FeO3− (LSF64) thin films deposited on MgO single crystals. It is found that thin films and bulk material have the same oxygen stoichiometry for a given temperature and oxygen partial pressure [i.e., the incorporation reaction has the same reaction enthalpy (H0=−105 KJ/mol) and entropy (S0=−75.5 J/mol/K) as found for bulk material]. The thin film shows smaller...

  15. Kinetic buffers.

    Science.gov (United States)

    Alibrandi, Giuseppe; Fabbrizzi, Luigi; Licchelli, Maurizio; Puglisi, Antonio

    2015-01-12

    This paper proposes a new type of molecular device that is able to act as an inverse proton sponge to slowly decrease the pH inside a reaction vessel. This makes the automatic monitoring of the concentration of pH-sensitive systems possible. The device is a composite formed of an alkyl chloride, which kinetically produces acidity, and a buffer that thermodynamically modulates the variation in pH value. Profiles of pH versus time (pH-t plots) have been generated under various experimental conditions by computer simulation, and the device has been tested by carrying out automatic spectrophotometric titrations, without using an autoburette. To underline the wide variety of possible applications, this new system has been used to realize and monitor HCl uptake by a di-copper(II) bistren complex in a single run, in a completely automatic experiment. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. A Numerical Model for the Computation of Radiance Distributions in Natural Waters with Wind-Roughened Surfaces, Part 2: User’s Guide and Code Listing

    Science.gov (United States)

    1988-07-01

    8217) END IF C..... SOLUTION STEP 9 C COMPUTE THE AMPLITUDE A(A.’) C CALL AMPAP c WERKY1) NOW COtJ1AINS ACCA ,’). THE kF.,ELTED DIRECT BEAM C C END OF...FUNCTID IN IS USED;’//, SIGMA(V.COS(PSI)) = )’Y)I(44PI) wHERE/fl 2’ IV V S(V) ALPHA(Y) S,/ALPH-A!) 102 FORMAT ( H 14, F8 .IF8 .3,FI10.3, FlI1.3 END 95 §5

  17. Kinetic theory of photophoresis

    International Nuclear Information System (INIS)

    Beresnev, S.A.; Chernyak, V.G.; Fomyagin, G.A.

    1988-01-01

    The force acting on an aerosol particle in one-sided illumination is calculated on the basis of solving a linearized gas-kinetic equation. A closed system of integral-moment equations describing photophoresis with arbitrary values of the Knudsen number and an arbitrary ratio of the particle and gas thermal conductivities is constructed. The possibility of arbitrary accommodation of the momentum and energy with interaction between the gas molecules and the particle surface is taken into account. The distribution of heat sources inside the radiation-absorbing particle is described by Mie theory. The results obtained are compared with the known theoretical and experimental data

  18. TiO2 patterns with wide photo-induced wettability change by a combination of reactive sputtering process and surface modification in a microfluidic channel

    Science.gov (United States)

    Kobayashi, Taizo; Konishi, Satoshi

    2015-11-01

    This paper reports the formation of TiO2 patterns with a wide range of photo-induced wettability switching from high hydrophobic to superhydrophilic states for on-chip liquid manipulation. TiO2 thin films with rough surface morphology were formed by a combination of optimised reactive sputtering and CF4 plasma etching. Octadecylphosphonic acid self-assembled monolayer (ODP-SAM) surface modification was applied to the surface-roughened TiO2 thin films in order to obtain a highly hydrophobic surface initially. Photocatalytic decomposition of ODP-SAM on the surface-roughened TiO2 by ultraviolet (UV) irradiation caused a wetting transition from the Cassie-Baxter state to the Wenzel state. Switching of the flow direction into branch channels was also demonstrated by utilising the photoresponsive wettability of the surface-modified TiO2 patterns on a fluidic chip.

  19. Down-regulation of Cell Surface Cyclic AMP Receptors and Desensitization of Cyclic AMP-stimulated Adenylate Cyclase by Cyclic AMP in Dictyostelium discoideum. Kinetics and Concentration Dependence

    NARCIS (Netherlands)

    Haastert, Peter J.M. van

    1987-01-01

    cAMP binds to Dictyostelium discoideum surface receptors and induces a transient activation of adenylate cyclase, which is followed by desensitization. cAMP also induces a loss of detectable surface receptors (down-regulation). Cells were incubated with constant cAMP concentrations, washed free of

  20. Heat Transfer and Friction Characteristics of Artificially Roughened Duct used for Solar Air Heaters—a Review

    Science.gov (United States)

    Kumar, Khushmeet; Prajapati, D. R.; Samir, Sushant

    2018-02-01

    Solar air heater uses the energy coming from the sun to heat the air. The conversion rate of solar energy to heat depends upon the efficiency of the solar air heater and this efficiency can be increased by the use of artificial roughness on the surface of absorber plate. Various studies were carried out to analyse the effect of different roughness geometries on heat transfer and friction factor characteristics. The thermo-hydraulic performance of solar air heater can be evaluated in terms of effective efficiency, thermo-hydraulic performance parameter and exergetic efficiency. In this study various geometries used for artificial roughness and to improve the performance of solar air heaters were studied. Also correlations developed by various researchers are presented in this paper.

  1. Growth and shape of indium islands on molybdenum at micro-roughened spots created by femtosecond laser pulses

    Science.gov (United States)

    Ringleb, F.; Eylers, K.; Teubner, Th.; Schramm, H.-P.; Symietz, C.; Bonse, J.; Andree, S.; Heidmann, B.; Schmid, M.; Krüger, J.; Boeck, T.

    2017-10-01

    Indium islands on molybdenum coated glass can be grown in ordered arrays by surface structuring using a femtosecond laser. The effect of varying the molybdenum coated glass substrate temperature and the indium deposition rate on island areal density, volume and geometry is investigated and evaluated in a physical vapor deposition (PVD) process. The joined impact of growth conditions and spacing of the femtosecond laser structured spots on the arrangement and morphology of indium islands is demonstrated. The results yield a deeper understanding of the island growth and its precise adjustment to industrial requirements, which is indispensable for a technological application of such structures at a high throughput, for instance as precursors for the preparation of Cu(In,Ga)Se2 micro concentrator solar cells.

  2. Adsorption kinetics

    African Journals Online (AJOL)

    The Eucalyptus lenceolata wood was collected from Malakand division, Khyber Pakhtunkhwa Pakistan. Chemical activation of sample was conducted for surface efficiency. Batch studies were performed to address various experimental parameters like, contact time, temperature and adsorbent dosage for the removal of dye.

  3. Calcite Dissolution Kinetics

    Science.gov (United States)

    Berelson, W.; Subhas, A.; Dong, S.; Naviaux, J.; Adkins, J. F.

    2016-12-01

    A geological buffer for high atmospheric CO2 concentrations is neutralization via reaction with CaCO3. We have been studying the dissolution kinetics of carbonate minerals using labeled 13C calcite and Picarro-based measurements of 13C enrichments in solution DIC. This methodology has greatly facilitated our investigation of dissolution kinetics as a function of water carbonate chemistry, temperature and pressure. One can adjust the saturation state Omega by changing the ion activity product (e.g. adjusting carbonate ion concentration), or by changing the solubility product (e.g. adjusting temperature or pressure). The canonical formulation of dissolution rate vs. omega has been refined (Subhas et al. 2015) and shows distinct non-linear behavior near equilibrium and rates in sea water of 1-3 e-6 g/cm2day at omega = 0.8. Carbonic anhydrase (CA), an enzyme that catalyzes the hydration of dissolved CO2 to carbonic acid, was shown (in concentrations 500x. This result points to the importance of carbonic acid in enhancing dissolution at low degrees of undersaturation. CA activity and abundance in nature must be considered regarding the role it plays in catalyzing dissolution. We also have been investigating the role of temperature on dissolution kinetics. An increase of 16C yields an order of magnitude increase in dissolution rate. Temperature (and P) also change Omega critical, the saturation state where dissolution rates change substantially. Increasing pressure (achieved in a pressure reaction chamber we built) also shifts Omega critical closer to equilibrium and small pressure increases have large impact on dissolution kinetics. Dissolution rates are enhanced by an order of magnitude for a change in pressure of 1500 psi relative to the dissolution rate achieved by water chemistry effects alone for an omega of 0.8. We've shown that the thermodynamic determination of saturation state does not adequately describe the kinetics of dissolution. The interplay of mineral

  4. Theoretical Kinetics Analysis for $\\dot{H}$ Atom Addition to 1,3-Butadiene and Related Reactions on the $\\dot{C}$4H7 Potential Energy Surface

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yang [National Univ. of Ireland, Galway (Ireland). Combustion Chemistry Centre; Klippenstein, Stephen J. [Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division; Zhou, Chong-Wen [Beihang Univ., Beihang (China). School of Energy and Power Engineering; Curran, Henry J. [National Univ. of Ireland, Galway (Ireland). Combustion Chemistry Centre

    2017-09-29

    The oxidation chemistry of the simplest conjugated hydrocarbon, 1,3-butadiene, can provide a first step in understanding the role of poly-unsaturated hydrocarbons in combustion and, in particular, an understanding of their contribution towards soot formation. Based on our previous work on propene and the butene isomers (1-, 2- and isobutene), it was found that the reaction kinetics of H-atom addition to the C=C double bond plays a significant role in fuel consumption kinetics and influences the predictions of high-temperature ignition delay times, product species concentrations and flame speed measurements. In this study, the rate constants and thermodynamic properties for $\\dot{H}$-atom addition to 1,3-butadiene and related reactions on the $\\dot{C}$4H7 potential energy surface have been calculated using two different series of quantum chemical methods and two different kinetic codes. Excellent agreement is obtained between the two different kinetics codes. The calculated results including zero point energies, single point energies, rate constants, barrier heights and thermochemistry are systematically compared among the two quantum chemical methods. 1-methylallyl ($\\dot{C}$4H71-3) and 3-buten-1- yl ($\\dot{C}$4H71-4) radicals and C2H4 + $\\dot{C}$2H3 are found to be the most important channels and reactivity promoting products, respectively. We calculated that terminal addition is dominant (> 80%) compared to internal $\\dot{H}$-atom addition at all temperatures in the range 298 – 2000 K. However, this dominance decreases with increasing temperature. The calculated rate constants for the bimolecular reaction C4H6 + $\\dot{H}$ → products and C2H4 + $\\dot{C}$2H3 → products are in excellent agreement with both experimental and theoretical results from the literature. For selected C4 species the

  5. Performance Evaluation Criterion at Equal Pumping Power for Enhanced Performance Heat Transfer Surfaces

    Directory of Open Access Journals (Sweden)

    Rajendra Karwa

    2013-01-01

    Full Text Available The existing equations for the thermal performance evaluation, at equal pumping power for the artificially roughened and smooth surfaced multitube and rectangular duct heat exchangers, have been critically reviewed because the literature survey indicates that a large number of researchers have not interpreted these equations correctly. Three of the most widely used equations have been restated with clearly defined constraints and conditions for their application. Two new equations have been developed for the design constraints not covered earlier.

  6. Binding and dissociation kinetics using fractals: an analysis of electrostatic effects and randomly coupled and oriented coupled receptors on biosensor surfaces.

    Science.gov (United States)

    Butala, Harshala D; Sadana, Ajit

    2004-03-15

    A fractal analysis is used to analyze the influence of: (a) electrostatic interactions on binding and dissociation rate coefficients for antibodies HH8, HH10, and HH26 in solution to hen egg-white lysozyme (HEL) immobilized on a sensor chip surface [Biophys. J. 83 (2002) 2946]; and (b) the binding and dissociation of recombinant Fab in solution to random NHS-coupled Cys-HEL and oriented thiol-coupled Cys-HEL immobilized on a sensor chip surface [Methods 20 (2000) 310]. Single- and dual-fractal models were employed to fit the data. Values of the binding and the dissociation rate coefficient(s) and the fractal dimensions were obtained from a regression analysis provided by Corel Quattro Pro 8.0 (Corel Corporation Limited, Ottawa, Canada. 1997). The binding rate coefficients are quite sensitive to the degree of heterogeneity on the sensor chip surface. It is of interest to compare the results obtained by the fractal analysis with that of the original analysis [Biophys. J. 83 (2002) 2946]. For example, as one goes from the binding of 21 nM HH10/HEL to the binding of 640 nM HH10/HEL(K97A), Sinha et al. [Biophys. J. 83 (2002) 29461 indicate that the enhancement of diffusional encounter rates may be due to 'electrostatic steering' (a long-range interaction). Our analysis indicates that there is an increase in the value of the fractal dimension, Df1 by a factor of 1.12 from a value of 2.133-2.385. This increase in the degree of heterogeneity on the surface leads to an increase in the binding rate coefficient, k1 by a factor of 1.59 from 12.92 to 20.57. The fractal analysis of binding and dissociation of recombinant Fab in solution to random NHS-coupled Cys-HEL and oriented thiol-coupled Cys-HEL immobilized on a sensor chip [Methods 20 (2000) 310] surface are consistent with the degree of heterogeneity present on the sensor chip surface for the random and the oriented case. As expected, the random case will exhibit a higher degree of heterogeneity than the oriented case

  7. Enhancing Electrochemical Water-Splitting Kinetics by Polarization-Driven Formation of Near-Surface Iron(0): An In Situ XPS Study on Perovskite-Type Electrodes**

    Science.gov (United States)

    Opitz, Alexander K; Nenning, Andreas; Rameshan, Christoph; Rameshan, Raffael; Blume, Raoul; Hävecker, Michael; Knop-Gericke, Axel; Rupprechter, Günther; Fleig, Jürgen; Klötzer, Bernhard

    2015-01-01

    In the search for optimized cathode materials for high-temperature electrolysis, mixed conducting oxides are highly promising candidates. This study deals with fundamentally novel insights into the relation between surface chemistry and electrocatalytic activity of lanthanum ferrite based electrolysis cathodes. For this means, near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) and impedance spectroscopy experiments were performed simultaneously on electrochemically polarized La0.6Sr0.4FeO3−δ (LSF) thin film electrodes. Under cathodic polarization the formation of Fe0 on the LSF surface could be observed, which was accompanied by a strong improvement of the electrochemical water splitting activity of the electrodes. This correlation suggests a fundamentally different water splitting mechanism in presence of the metallic iron species and may open novel paths in the search for electrodes with increased water splitting activity. PMID:25557533

  8. Oxygen tracer diffusion and surface exchange kinetics in Ba0.5Sr0.5Co0.8Fe0.2O3-δ

    NARCIS (Netherlands)

    Berenov, A.; Atkinson, A.; Kilner, J.; Ananyev, M.; Eremin, V.; Porotnikova, N.; Farlenkov, A.; Kurumchin, E.; Bouwmeester, Henricus J.M.; Bucher, E.; Sitte, W.

    2014-01-01

    The oxygen tracer diffusion coefficient, Db⁎, and the oxygen tracer surface exchange coefficient, k, were measured in Ba0.5Sr0.5Co0.8Fe0.2O3 − δ (BSCF5582) over the temperature range of 310–800 °C and the oxygen partial pressure range of 1.3 × 10−3–0.21 bar. Several measurement techniques were used:

  9. Kinetic double-layer model of aerosol surface chemistry and gas-particle interactions (K2-SURF: Degradation of polycyclic aromatic hydrocarbons exposed to O3, NO2, H2O, OH and NO3

    Directory of Open Access Journals (Sweden)

    U. Pöschl

    2009-12-01

    Full Text Available We present a kinetic double-layer surface model (K2-SURF that describes the degradation of polycyclic aromatic hydrocarbons (PAHs on aerosol particles exposed to ozone, nitrogen dioxide, water vapor, hydroxyl and nitrate radicals. The model is based on multiple experimental studies of PAH degradation and on the PRA framework (Pöschl-Rudich-Ammann, 2007 for aerosol and cloud surface chemistry and gas-particle interactions. For a wide range of substrates, including solid and liquid organic and inorganic substances (soot, silica, sodium chloride, octanol/decanol, organic acids, etc., the concentration- and time-dependence of the heterogeneous reaction between PAHs and O3 can be efficiently described with a Langmuir-Hinshelwood-type mechanism. Depending on the substrate material, the Langmuir adsorption constants for O3 vary over three orders of magnitude (Kads,O3 ≈ 10−15–10−13 cm3, and the second-order rate coefficients for the surface layer reaction of O3 with different PAH vary over two orders of magnitude (kSLR,PAH,O3 ≈ 10−18–10−17 cm2 s−1. The available data indicate that the Langmuir adsorption constants for NO2 are similar to those of O3, while those of H2O are several orders of magnitude smaller (Kads,H2O ≈ 10−18–10−17 cm3. The desorption lifetimes and adsorption enthalpies inferred from the Langmuir adsorption constants suggest chemisorption of NO2 and O3 and physisorption of H2O. Note, however, that the exact reaction mechanisms, rate limiting steps and possible intermediates still remain to be resolved (e.g., surface diffusion and formation of O atoms or O3− ions at the surface. The K2-SURF model enables the calculation of ozone uptake coefficients, γO3, and of PAH concentrations in the quasi-static particle surface layer. Competitive adsorption and chemical transformation of the surface (aging lead to a strong non-linear dependence of γO3 on time and gas phase composition, with different characteristics

  10. Availability of methods of chemical thermodynamics and kinetics for the analysis of chemical transformations on metal surfaces under pulsed laser action

    Science.gov (United States)

    Veiko, V. P.; Slobodov, A. A.; Odintsova, G. V.

    2013-06-01

    A computational thermodynamic approach to determining the phase-chemical composition of films formed on the surface of metals and alloys under laser oxidation in the normal atmosphere, depending on their bulk composition, laser exposure conditions, and composition of the atmosphere, is suggested. It is demonstrated for the example of a complex alloy (alloyed steel of Russian brand 12X18H10T) subjected to laser heating in air that, among the wide variety of different possible reactions of iron, nickel, or chromium with the components of air (oxygen, nitrogen, carbon, its compounds, atmospheric moisture, etc), only strictly defined reactions can occur. First of all these are metal oxidation processes with the formation of an oxide film whose phase and chemical composition is determined by temperature and heating duration. Simulated results are confirmed by the experimental data provided by energy-dispersive x-ray spectroscopy.

  11. Hydrogen electrode reaction: A complete kinetic description

    International Nuclear Information System (INIS)

    Quaino, P.M.; Gennero de Chialvo, M.R.; Chialvo, A.C.

    2007-01-01

    The kinetic description of the hydrogen electrode reaction (HER) in the whole range of overpotentials (-0.2 < η (V) < 0.40) is presented. The Volmer-Heyrovsky-Tafel mechanism was solved considering simultaneously the following items: (i) the diffusional contribution of the molecular hydrogen from and towards the electrode surface, (ii) the forward and backward reaction rates of each elementary step and (iii) a Frumkin type adsorption for the reaction intermediate. In order to verify the descriptive capability of the kinetic expressions derived, an experimental study of the HER was carried out on a rotating platinum disc electrode in acid solution. From the correlation of these results the elementary kinetic parameters were evaluated and several aspects related to the kinetic mechanism were discussed. Finally, the use of these kinetic expressions to interpret results obtained on microelectrodes is also analysed

  12. Enhancement of the adsorption capacity of the light-weight expanded clay aggregate surface for the metronidazole antibiotic by coating with MgO nanoparticles: Studies on the kinetic, isotherm, and effects of environmental parameters.

    Science.gov (United States)

    Kalhori, Ebrahim Mohammadi; Al-Musawi, Tariq J; Ghahramani, Esmaeil; Kazemian, Hossein; Zarrabi, Mansur

    2017-05-01

    The synthesized MgO nanoparticles were used to coat the light-weight expanded clay aggregates (LECA) and as a metronidazole (MNZ) adsorbent. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Fourier-transformed infrared (FTIR) techniques were employed to study the surface morphology and characteristics of the adsorbents. MgO/LECA clearly revealed the advantages of the nanocomposite particles, showing high specific surface area (76.12 m 2 /g), significant adsorption sites and functional groups. Between pH 5 and 9, the MNZ sorption was not significantly affected. Kinetic studies revealed that the MNZ adsorption closely followed the Avrami model, with no dominant process controlling the sorption rate. The study of the effects of foreign ions revealed that the addition of carbonate raised the MNZ removal efficiency of LECA by 8% and the total removal of MNZ by MgO/LECA. Furthermore, nitrate and hardness only marginally influenced the MNZ removal efficiency and their effects can be ranked in the order of carbonate>nitrate>hardness. The isotherm adsorption of MNZ was best fitted with the Langmuir model enlighten the monolayer MNZ adsorption on the homogeneous LECA and MgO/LECA surfaces. The maximum adsorption capacity under optimum conditions was enhanced from 56.31 to 84.55 mg/g for LECA and MgO/LECA, respectively. These findings demonstrated that the MgO/LECA nanocomposite showed potential as an efficient adsorbent for MNZ removal. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Control of oil-wetting on technical textiles by means of photo-chemical surface modification and its relevance to the performance of compressed air filters

    International Nuclear Information System (INIS)

    Bahners, Thomas; Mölter-Siemens, Wolfgang; Haep, Stefan; Gutmann, Jochen S.

    2014-01-01

    Highlights: • The oil repellence of textile fabrics was increased following the Wenzel concept. • Fiber surfaces were micro-roughened by means of pulsed UV laser irradiation. • Subsequent UV-induced grafting yielded pronounced oil repellence. • The grafting process conserved the delicate topography of the fiber surfaces. • The modified fabrics showed favorable drainage behavior in oil droplet separation. - Abstract: A two-step process comprising a surface roughening step by excimer laser irradiation and a post-treatment by photo-grafting to decrease the surface free energy was employed to increase the oil repellence of technical fabrics made of poly(ethylene terephthalate) (PET). The modification was designed to improve the performance of multi-layer filters for compressed air filtration, in which the fabrics served to remove, i.e. drain, oil separated from the air stream. In detail, the fibers surfaces were roughened by applying several laser pulses at a wavelength of 248 nm and subsequently photo-grafted with 1H,1H,2H,2H-perfluoro-decyl acrylate (PPFDA). The oil wetting behavior was increased by the treatments from full wetting on the as-received fabrics to highly repellent with oil contact angles of (131 ± 7)°. On surfaces in the latter state, oil droplets did not spread or penetrate even after one day. The grafting of PPFDA alone without any surface roughening yielded an oil contact angle of (97 ± 11)°. However, the droplet completely penetrated the fabric over a period of one day. The drainage performance was characterized by recording the pressure drop over a two-layer model filter as a function of time. The results proved the potential of the treatment, which reduced the flow resistance after 1-h operation by approximately 25%

  14. Control of oil-wetting on technical textiles by means of photo-chemical surface modification and its relevance to the performance of compressed air filters

    Energy Technology Data Exchange (ETDEWEB)

    Bahners, Thomas, E-mail: bahners@dtnw.de [Deutsches Textilforschungszentrum Nord-West gGmbH (DTNW), Adlerstr. 1, 47798 Krefeld (Germany); Mölter-Siemens, Wolfgang; Haep, Stefan [Institut für Energie- und Umwelttechnik e.V. (IUTA), Bliersheimer Str. 60, 47229 Duisburg (Germany); Gutmann, Jochen S. [Deutsches Textilforschungszentrum Nord-West gGmbH (DTNW), Adlerstr. 1, 47798 Krefeld (Germany); Universität Duisburg-Essen, Physikalische Chemie and CENIDE, Universitätsstr. 2, 45141 Essen (Germany)

    2014-09-15

    Highlights: • The oil repellence of textile fabrics was increased following the Wenzel concept. • Fiber surfaces were micro-roughened by means of pulsed UV laser irradiation. • Subsequent UV-induced grafting yielded pronounced oil repellence. • The grafting process conserved the delicate topography of the fiber surfaces. • The modified fabrics showed favorable drainage behavior in oil droplet separation. - Abstract: A two-step process comprising a surface roughening step by excimer laser irradiation and a post-treatment by photo-grafting to decrease the surface free energy was employed to increase the oil repellence of technical fabrics made of poly(ethylene terephthalate) (PET). The modification was designed to improve the performance of multi-layer filters for compressed air filtration, in which the fabrics served to remove, i.e. drain, oil separated from the air stream. In detail, the fibers surfaces were roughened by applying several laser pulses at a wavelength of 248 nm and subsequently photo-grafted with 1H,1H,2H,2H-perfluoro-decyl acrylate (PPFDA). The oil wetting behavior was increased by the treatments from full wetting on the as-received fabrics to highly repellent with oil contact angles of (131 ± 7)°. On surfaces in the latter state, oil droplets did not spread or penetrate even after one day. The grafting of PPFDA alone without any surface roughening yielded an oil contact angle of (97 ± 11)°. However, the droplet completely penetrated the fabric over a period of one day. The drainage performance was characterized by recording the pressure drop over a two-layer model filter as a function of time. The results proved the potential of the treatment, which reduced the flow resistance after 1-h operation by approximately 25%.

  15. Stochastic theory of interfacial enzyme kinetics: A kinetic Monte Carlo study

    International Nuclear Information System (INIS)

    Das, Biswajit; Gangopadhyay, Gautam

    2012-01-01

    Graphical abstract: Stochastic theory of interfacial enzyme kinetics is formulated. Numerical results of macroscopic phenomenon of lag-burst kinetics is obtained by using a kinetic Monte Carlo approach to single enzyme activity. Highlights: ► An enzyme is attached with the fluid state phospholipid molecules on the Langmuir monolayer. ► Through the diffusion, the enzyme molecule reaches the gel–fluid interface. ► After hydrolysing a phospholipid molecule it predominantly leaves the surface in the lag phase. ► The enzyme is strictly attached to the surface with scooting mode of motion and the burst phase appears. - Abstract: In the spirit of Gillespie’s stochastic approach we have formulated a theory to explore the advancement of the interfacial enzyme kinetics at the single enzyme level which is ultimately utilized to obtain the ensemble average macroscopic feature, lag-burst kinetics. We have provided a theory of the transition from the lag phase to the burst phase kinetics by considering the gradual development of electrostatic interaction among the positively charged enzyme and negatively charged product molecules deposited on the phospholipid surface. It is shown that the different diffusion time scales of the enzyme over the fluid and product regions are responsible for the memory effect in the correlation of successive turnover events of the hopping mode in the single trajectory analysis which again is reflected on the non-Gaussian distribution of turnover times on the macroscopic kinetics in the lag phase unlike the burst phase kinetics.

  16. Surface- vs Diffusion-Limited Mechanisms of Anion Exchange in CsPbBr3 Nanocrystal Cubes Revealed through Kinetic Studies.

    Science.gov (United States)

    Koscher, Brent A; Bronstein, Noah D; Olshansky, Jacob H; Bekenstein, Yehonadav; Alivisatos, A Paul

    2016-09-21

    Ion-exchange transformations allow access to nanocrystalline materials with compositions that are inaccessible via direct synthetic routes. However, additional mechanistic insight into the processes that govern these reactions is needed. We present evidence for the presence of two distinct mechanisms of exchange during anion exchange in CsPbX3 nanocrystals (NCs), ranging in size from 6.5 to 11.5 nm, for transformations from CsPbBr3 to CsPbCl3 or CsPbI3. These NCs exhibit bright luminescence throughout the exchange, allowing their optical properties to be observed in real time, in situ. The iodine exchange presents surface-reaction-limited exchanges allowing all anionic sites within the NC to appear chemically identical, whereas the chlorine exchange presents diffusion-limited exchanges proceeding through a more complicated exchange mechanism. Our results represent the first steps toward developing a microkinetic description of the anion exchange, with implications not only for understanding the lead halide perovskites but also for nanoscale ion exchange in general.

  17. Methods of nonlinear kinetics

    OpenAIRE

    Gorban, A. N.; Karlin, I. V.

    2003-01-01

    Nonlinear kinetic equations are reviewed for a wide audience of specialists and postgraduate students in physics, mathematical physics, material science, chemical engineering and interdisciplinary research. Contents: The Boltzmann equation, Phenomenology and Quasi-chemical representation of the Boltzmann equation, Kinetic models, Discrete velocity models, Direct simulation, Lattice Gas and Lattice Boltzmann models, Minimal Boltzmann models for flows at low Knudsen number, Other kinetic equati...

  18. Morphological evolution of InP nano-dots and surface modifications after keV irradiation

    International Nuclear Information System (INIS)

    Paramanik, Dipak; Sahu, S N; Varma, Shikha

    2008-01-01

    Evolution and coarsening behaviour of self-assembled nano-dots fabricated on an InP surface by 3 keV Ar ion sputtering have been studied in conjunction with the structural modifications at the surface. The dots have been produced in off-normal geometry but in the absence of rotation. For small sputtering durations, the dots coarsen and agglomerate, up to a critical time t c , while the surface roughens and experiences a tensile stress. A relaxation in this stress is observed after the surface becomes amorphized at t c , beyond which an inverse coarsening, fragmentation of dots and a smoothened surface are observed

  19. Photocatalytic degradation of Reactive Red 195 using anatase/brookite TiO2 mesoporous nanoparticles: optimization using response surface methodology (RSM) and kinetics studies.

    Science.gov (United States)

    Tzikalos, Nikolaos; Belessi, Vassiliki; Lambropoulou, Dimitra

    2013-04-01

    In the present study, the photocatalytic degradation of Reactive Red 195 (RR195) from aqueous samples under UV-A irradiation by using anatase/brookite TiO2 (A/B TiO2) mesoporous nanoparticles has been investigated. Batch experiments were conducted to study the effects of the main parameters affecting the photocatalytic process. The effects and interactions of most influenced parameters, such as substrate concentration and catalyst load, were evaluated and optimized by using a central composite design model and a response surface methodology. The results indicated that the dye degradation efficiency in the experimental domain investigated was mainly affected by the tested variables, as well as their interaction effects. Analysis of variance showed a high coefficient of determination value (R(2) = 0.9947), thus ensuring a satisfactory adjustment of the first-order regression model (2FI model) with the experimental data. The obtained results also indicate that catalyst loading plays an important role in determining the removal efficiency of RR195 attributable to both photodegradation and adsorption process. Under optimal conditions (initial dye concentration (50 mg/L) and catalyst loading (2,000 mg/L), A/B TiO2 showed similar removal efficiency compared to that of commercial titania (Degussa P25). Also, at these conditions, complete degradation of RR195 can be achieved by both catalysts within 15 min under UV-A irradiation. The experiments demonstrated that dye removal on the prepared A/B TiO2 was facilitated by the synergistic effects between adsorption and photocatalysis. Photocatalytic mineralization of RR195 was monitored by total organic carbon. The recycling experiments confirmed the stability of the catalyst.

  20. Effectiveness of disinfectants on the adherence of Candida albicans to denture base resins with different surface textures.

    Science.gov (United States)

    Karakis, Duygu; Akay, Canan; Oncul, Burcin; Rad, Abbas Y; Dogan, Arife

    2016-01-01

    The aim of the present study was to compare the effects of some disinfectants, including ethanol extract of propolis (EEP), on the adhesion of Candida albicans to denture base resins. Seventy-two acrylic resin samples were prepared, half of which was polished and the other half was roughened. C. albicans strain ATCC 10231 was incubated on Sabouraud dextrose agar (SDA) at 37°C for 48 h. The adhesion period was completed by keeping the cells in this suspension for 90 min at 37°C. Specimens were then immersed in the following solutions: 1%, 2%, and 5% sodium hypochlorite; 4% chlorhexidine gluconate; and 10% EEP. Quantification of the antifungal activity of the chemical solutions was performed using the colorimetric MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide) assay test. One-way ANOVA and post-hoc Tukey tests were performed to evaluate the effectiveness of chemical agents. Polished and roughened surfaces were compared using independent sample t-test. The mean surface roughness value was 0.35 (±0.04) µm for the polished group and 1.2 (±0.2) µm for the roughened group. The contact angles of both surfaces showed statistically significant difference, and 10% EEP solution exhibited significantly less removal of adherent viable C. albicans cells in both groups. All forms of sodium hypochlorite solutions yielded higher efficiency than 4% chlorhexidine gluconate and EEP solutions (P < 0.05). (J Oral Sci 58, 431-437, 2016).

  1. Surface plasmon enhanced interfacial electron transfer and resonance Raman, surface-enhanced resonance Raman studies of cytochrome C mutants

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Junwei [Iowa State Univ., Ames, IA (United States)

    1999-11-08

    Surface plasmon resonance was utilized to enhance the electron transfer at silver/solution interfaces. Photoelectrochemical reductions of nitrite, nitrate, and CO2 were studied on electrochemically roughened silver electrode surfaces. The dependence of the photocurrent on photon energy, applied potential and concentration of nitrite demonstrates that the photoelectrochemical reduction proceeds via photoemission process followed by the capture of hydrated electrons. The excitation of plasmon resonances in nanosized metal structures resulted in the enhancement of the photoemission process. In the case of photoelectrocatalytic reduction of CO2, large photoelectrocatalytic effect for the reduction of CO2 was observed in the presence of surface adsorbed methylviologen, which functions as a mediator for the photoexcited electron transfer from silver metal to CO2 in solution. Photoinduced reduction of microperoxidase-11 adsorbed on roughened silver electrode was also observed and attributed to the direct photoejection of free electrons of silver metal. Surface plasmon assisted electron transfer at nanostructured silver particle surfaces was further determined by EPR method.

  2. Bi-stage time evolution of nano-morphology on inductively coupled plasma etched fused silica surface caused by surface morphological transformation

    Science.gov (United States)

    Jiang, Xiaolong; Zhang, Lijuan; Bai, Yang; Liu, Ying; Liu, Zhengkun; Qiu, Keqiang; Liao, Wei; Zhang, Chuanchao; Yang, Ke; Chen, Jing; Jiang, Yilan; Yuan, Xiaodong

    2017-07-01

    In this work, we experimentally investigate the surface nano-roughness during the inductively coupled plasma etching of fused silica, and discover a novel bi-stage time evolution of surface nano-morphology. At the beginning, the rms roughness, correlation length and nano-mound dimensions increase linearly and rapidly with etching time. At the second stage, the roughening process slows down dramatically. The switch of evolution stage synchronizes with the morphological change from dual-scale roughness comprising long wavelength underlying surface and superimposed nano-mounds to one scale of nano-mounds. A theoretical model based on surface morphological change is proposed. The key idea is that at the beginning, etched surface is dual-scale, and both larger deposition rate of etch inhibitors and better plasma etching resistance at the surface peaks than surface valleys contribute to the roughness development. After surface morphology transforming into one-scale, the difference of plasma resistance between surface peaks and valleys vanishes, thus the roughening process slows down.

  3. Ion beam processing of surfaces and interfaces. Modeling and atomistic simulations

    International Nuclear Information System (INIS)

    Liedke, Bartosz

    2011-01-01

    Self-organization of regular surface pattern under ion beam erosion was described in detail by Navez in 1962. Several years later in 1986 Bradley and Harper (BH) published the first self-consistent theory on this phenomenon based on the competition of surface roughening described by Sigmund's sputter theory and surface smoothing by Mullins-Herring diffusion. Many papers that followed BH theory introduced other processes responsible for the surface patterning e.g. viscous flow, redeposition, phase separation, preferential sputtering, etc. The present understanding is still not sufficient to specify the dominant driving forces responsible for self-organization. 3D atomistic simulations can improve the understanding by reproducing the pattern formation with the detailed microscopic description of the driving forces. 2D simulations published so far can contribute to this understanding only partially. A novel program package for 3D atomistic simulations called TRIDER (TRansport of Ions in matter with DEfect Relaxation), which unifies full collision cascade simulation with atomistic relaxation processes, has been developed. The collision cascades are provided by simulations based on the Binary Collision Approximation, and the relaxation processes are simulated with the 3D lattice kinetic Monte-Carlo method. This allows, without any phenomenological model, a full 3D atomistic description on experimental spatiotemporal scales. Recently discussed new mechanisms of surface patterning like ballistic mass drift or the dependence of the local morphology on sputtering yield are inherently included in our atomistic approach. The atomistic 3D simulations do not depend so much on experimental assumptions like reported 2D simulations or continuum theories. The 3D computer experiments can even be considered as 'cleanest' possible experiments for checking continuum theories. This work aims mainly at the methodology of a novel atomistic approach, showing that: (i) In general

  4. Ion beam processing of surfaces and interfaces. Modeling and atomistic simulations

    Energy Technology Data Exchange (ETDEWEB)

    Liedke, Bartosz

    2011-03-24

    Self-organization of regular surface pattern under ion beam erosion was described in detail by Navez in 1962. Several years later in 1986 Bradley and Harper (BH) published the first self-consistent theory on this phenomenon based on the competition of surface roughening described by Sigmund's sputter theory and surface smoothing by Mullins-Herring diffusion. Many papers that followed BH theory introduced other processes responsible for the surface patterning e.g. viscous flow, redeposition, phase separation, preferential sputtering, etc. The present understanding is still not sufficient to specify the dominant driving forces responsible for self-organization. 3D atomistic simulations can improve the understanding by reproducing the pattern formation with the detailed microscopic description of the driving forces. 2D simulations published so far can contribute to this understanding only partially. A novel program package for 3D atomistic simulations called TRIDER (TRansport of Ions in matter with DEfect Relaxation), which unifies full collision cascade simulation with atomistic relaxation processes, has been developed. The collision cascades are provided by simulations based on the Binary Collision Approximation, and the relaxation processes are simulated with the 3D lattice kinetic Monte-Carlo method. This allows, without any phenomenological model, a full 3D atomistic description on experimental spatiotemporal scales. Recently discussed new mechanisms of surface patterning like ballistic mass drift or the dependence of the local morphology on sputtering yield are inherently included in our atomistic approach. The atomistic 3D simulations do not depend so much on experimental assumptions like reported 2D simulations or continuum theories. The 3D computer experiments can even be considered as 'cleanest' possible experiments for checking continuum theories. This work aims mainly at the methodology of a novel atomistic approach, showing that: (i) In

  5. Gliding arc surface modification of carrot nanofibre coating - perspective for composite processing

    DEFF Research Database (Denmark)

    Kusano, Yukihiro; Berglund, L; Aitomäki, Y

    2016-01-01

    Surfaces of carrot nanofibre coatings were modified by a gliding arc in atmospheric pressure air. The treatment strengthened wetting of deionized water and glycerol, increased an oxygen content, C-O and C=O, and moderately roughened the surfaces. In the perspective of composite materials......, these changes to the nanofibres can potentially improve their processability when they are to be impregnated with a polymeric matrix. However, longer exposure to the gliding arc reduced oxidation and roughness of the surface, and thus there exists an optimum condition to achieve good wetting to solvents....

  6. Problems of surface morphology and layer deposition during plasma etching processes. 2

    International Nuclear Information System (INIS)

    Tiller, H.-J.; Krausse, J.; Voigt, R.

    1982-01-01

    The plasma etching of Si in CF 4 -, CF 4 /O 2 - and CF 4 /H 2 plasmas was investigated in dependence on the etching gas, the plasma conditions (pressure, power density) and etching time in different reactors. A roughening of the surface and the formation of a 'semi-amorphous' surface layer with a powder-like morphology was detected by TEM-and RHEED methods. It is supposed that the surface layer has a fundamental consequence as an intermediate state in the etching mechanism. (author)

  7. Applications of low-energy electron diffraction to ordering at crystal and quasicrystal surfaces

    International Nuclear Information System (INIS)

    McRae, E.G.; Malic, R.A.

    1990-01-01

    The ability to measure low-energy electron diffraction (LEED) intensity profiles has been enhanced by use of low-current well-defined primary electron beams in conjunction with position-sensitive detection (PSD) of the diffracted electrons. The following are examples of applications of LEED-PSD. Compositional ordering at ordering alloy Cu 3 Au (100) and (110) surfaces - the ordering of the (100) surface is believed to conform to a conventional picture in which the already-ordered bulk acts as a template, but the profiles measured in the course of ordering of the (110) surface are of the shapes expected if the ordering occurred first at the surface. Disordering of Ge(111) surface 150 K below the bulk melting temperature - the intensities and profiles are inconsistent with surface melting or roughening, but a model based on molecular dynamics simulations is not ruled out. Order and disordering at decagonal quasicrystal Al 65 Cu 15 Co 20 surfaces - at room temperature the quasicrystalline order is well developed at both the 'ten-fold' surface (perpendicular to the ten-fold surface (perpendicular to the ten-fold periodic axis) and a 'two-fold' one (parallel to the ten-fold axis) as evidenced by narrow beam profiles. The ten-fold surface undergoes a disordering transition at 700 K, but the temperature dependence of the profiles is unlike that expected for the roughening transition anticipated theoretically. 57 refs., 15 figs

  8. Oxidation kinetics of corium pool

    International Nuclear Information System (INIS)

    Sulatsky, A.A.; Smirnov, S.A.; Granovsky, V.S.; Khabensky, V.B.; Krushinov, E.V.; Vitol, S.A.; Kotova, S.Yu.; Fischer, M.; Hellmann, S.; Tromm, W.; Miassoedov, A.; Bottomley, D.; Piluso, P.; Barrachin, M.

    2013-01-01

    Highlights: • The analysis of experimental data on molten corium oxidation was been carried out. • The analysis has revealed the main factors influencing the oxidation kinetics. • The analysis was used for developing a qualitative analytical model. • The numerical modeling has confirmed the results of experimental data analysis. -- Abstract: Experimental, theoretical and numerical studies of oxidation kinetics of an open surface corium pool have been reported. The experiments have been carried out within OECD MASCA program and ISTC METCOR, METCOR-P and EVAN projects. It has been shown that the melt oxidation is controlled by an oxidant supply to the melt free surface from the atmosphere, not by the reducer supply from the melt. The project experiments have not detected any input of the zirconium oxidation kinetics into the process chemistry. The completed analysis puts forward a simple analytical model, which gives an explanation of the main features of melt oxidation process. The numerical modeling results are in good agreement with experimental data and theoretical considerations

  9. Principles of chemical kinetics

    CERN Document Server

    House, James E

    2007-01-01

    James House's revised Principles of Chemical Kinetics provides a clear and logical description of chemical kinetics in a manner unlike any other book of its kind. Clearly written with detailed derivations, the text allows students to move rapidly from theoretical concepts of rates of reaction to concrete applications. Unlike other texts, House presents a balanced treatment of kinetic reactions in gas, solution, and solid states. The entire text has been revised and includes many new sections and an additional chapter on applications of kinetics. The topics covered include quantitative rela

  10. Introduction to chemical kinetics

    CERN Document Server

    Soustelle, Michel

    2013-01-01

    This book is a progressive presentation of kinetics of the chemical reactions. It provides complete coverage of the domain of chemical kinetics, which is necessary for the various future users in the fields of Chemistry, Physical Chemistry, Materials Science, Chemical Engineering, Macromolecular Chemistry and Combustion. It will help them to understand the most sophisticated knowledge of their future job area. Over 15 chapters, this book present the fundamentals of chemical kinetics, its relations with reaction mechanisms and kinetic properties. Two chapters are then devoted to experimental re

  11. LSM Microelectrodes: Kinetics and Surface Composition

    DEFF Research Database (Denmark)

    Hansen, Karin Vels; Norrman, Kion; Jacobsen, Torben

    2015-01-01

    Lanthanum strontium manganite microelectrodes with the nominal composition of (La0.75Sr0.25)0.95MnO3 and a thickness of ca 500 nm was electrochemically characterized in situ at temperatures from 660 to 850◦C using a controlled atmosphere high temperature scanning probe microscope. Impedance...... electron microscopy were performed to observe electrical, chemical and structural changes on the microelectrodes. © 2015 The Electrochemical Society....

  12. Kinetics of the electrochemical evolution of isotopically enriched gases

    International Nuclear Information System (INIS)

    Churchill, C.R.; Hibbert, D.B.

    1982-01-01

    A method is described which follows, by mass spectrometry, the kinetics of 18 O 16 O evolution from an electrode surface enriched with 18 O. The kinetics on a platinum surface in acid and alkaline electrolyte were consistent with a mechanism of oxygen evolution which involves successive oxidations on a single platinum atom. The total number of platinum sites responsible for oxygen evolution was less than the total number of atoms at the surface. (author)

  13. Electrode Kinetics and Gas Conversion in Solid Oxide Cells

    DEFF Research Database (Denmark)

    Njodzefon, Jean-Claude

    that the kinetics at the fuel electrode were exactly the same in both reformates. This means that chemical equilibrium reactions were much faster than the electrochemical reactions. The electrode displayed slightly faster kinetics in hydrogen/steam fuel than in the reformate fuels. To minimize the influence of (i...... slower reaction kinetics under cathodic mode operation at 50 mV overvoltage than in anodic mode. The trend was opposite for the lower performing La0.58Sr0.4Co0.2Fe0.8O3 (LSCF) oxygen electrode. However, with decreasing oxygen partial pressure both electrodes displayed increasing asymmetry between anodic...... and cathodic modes. It could be shown that surface exchange kinetics were the major cause of the decreasing kinetics with decreasing pO2 and that the cathodic mode kinetics were slowed down much more than the anodic branch kinetics thus increasing the asymmetry. Independent of operation mode, commercialization...

  14. Kinetics of oxidic phase dissolution in acids

    International Nuclear Information System (INIS)

    Gorichev, I.G.; Kipriyanov, N.A.

    1981-01-01

    The critical analysis of the experimental data on dissolution kinetics of metal oxides (BeO, V 2 O 5 , UO 2 , Nb 2 O 5 , Ta 2 O 5 etc.) in acid media is carried out. Kinetic peculiarities of oxide dissolution are explained on the basis of the notions of electron- proton theory. It is established that the surface nonstoichiometric ccomposition of oxide phase and potential jump, appearing on the interface of the oxide-electrolyte phase are the important factors, determining the dissolution rate of a solid phase. The dissolution rate of metal oxides is limited by the transition of protons into the solid oxide phase. Morphological models of heterogeneous kinetics are used when explaining kinetic regularities of oxide dissolution process [ru

  15. Kinetic equation solution by inverse kinetic method

    International Nuclear Information System (INIS)

    Salas, G.

    1983-01-01

    We propose a computer program (CAMU) which permits to solve the inverse kinetic equation. The CAMU code is written in HPL language for a HP 982 A microcomputer with a peripheral interface HP 9876 A ''thermal graphic printer''. The CAMU code solves the inverse kinetic equation by taking as data entry the output of the ionization chambers and integrating the equation with the help of the Simpson method. With this program we calculate the evolution of the reactivity in time for a given disturbance

  16. The role of surface morphology in nanocatalyst engineering

    Energy Technology Data Exchange (ETDEWEB)

    Stamenkovic, V. [Argonne National Laboratory, Argonne, IL (United States). Material Science Div.

    2008-07-01

    This study investigated extended polycrystalline platinum (Pt) alloys and PtNi(hkl) and Pt(hkl) single crystalline surfaces for various catalytic reactions. The surfaces were treated in an ultra-high vacuum by sputtering and annealing cycles. Auger electron spectroscopy (AES), low energy ion spectroscopy (LEIS), and ultraviolet photoelectron spectroscopy (UPS) techniques were used to characterize the alloys before they were transferred into an electrochemical environment. The study showed that electronic effect was caused by changes in the metallic d-band centre position. Structural effects were caused by surface roughening. The sputtered surfaces formed a Pt-skeleton on the outermost layers as a result of the dissolution of transition metal atoms. A modification of Pt electronic properties altered the adsorption and catalytic properties of the corresponding bimetallic alloy. The most active systems for the oxygen reduction reaction (ORR) were observed in the Pt-skin near-surface formation. 3 refs.

  17. Shear bond strength of composite resin bonded to preformed metal crowns for primary molars using a universal adhesive and two different surface treatments: an in vitro study.

    Science.gov (United States)

    Patil, S S; Kontham, U R; Kamath, A; Kontham, R

    2016-10-01

    This was to determine the shear bond strength of composite resin bonded to preformed metal crowns with a new adhesive. Buccal surfaces of the crowns were roughened by two different methods to increase retention. Typodont mandibular second primary molars (38) were divided into two groups (19 per group). Preformed metal crowns were cemented to the teeth with glass-ionomer cement. To enhance retention, buccal surfaces of the crowns in group I were roughened with cross-cut carbide burs (SS White #56); crowns in group II were sandblasted (aluminium oxide, 50 µm). Scotchbond Universal Adhesive (3 M-ESPE) was used to bond composite resin to the crowns. A universal testing machine tested the maximum shearing force withstood by the veneered composite surfaces. Sandblasted crowns demonstrated significantly higher resistance (p = 0.001) to shearing force (324.4 N) than did the crowns that were roughened with a bur (234.2 N). Chairside veneering of composite resin to pretreated crowns could be a feasible, aesthetically pleasing, and an economical option in paediatric dentistry.

  18. Kinetics of heterogeneous catalytic reactions

    CERN Document Server

    Boudart, Michel

    2014-01-01

    This book is a critical account of the principles of the kinetics of heterogeneous catalytic reactions in the light of recent developments in surface science and catalysis science. Originally published in 1984. The Princeton Legacy Library uses the latest print-on-demand technology to again make available previously out-of-print books from the distinguished backlist of Princeton University Press. These paperback editions preserve the original texts of these important books while presenting them in durable paperback editions. The goal of the Princeton Legacy Library is to vastly increase acc

  19. Non-kinetic capabilities: complementing the kinetic prevalence to targeting

    OpenAIRE

    Ducheine, P.

    2014-01-01

    Targeting is used in military doctrine to describe a military operational way, using (military) means to influence a target (or addressee) in order to achieve designated political and/or military goals. The four factors italicized are used to analyse non-kinetic targeting, complementing our knowledge and understanding of the kinetic prevalence. Paradoxically, non-kinetic targeting is not recognized as a separate concept: kinetic and non-kinetic are intertwined facets of targeting. Kinetic tar...

  20. Kinetics of hydrogen release from alloyed iron

    International Nuclear Information System (INIS)

    Gomozov, P.A.; Mogutnov, B.M.; Shvartsman, L.A.

    1977-01-01

    The kinetics of evolution of hydrogen from Armco-iron and alloys of iron with small amounts of carbon, phosphorus, sulfur, titanium, silicon and nickel was studied in the temperature range from 24 to 110 deg C. This process is described in terms of a kinetic equation which follows from the solution of the equation of diffusion with boundary conditions allowing for the rate of the chemical reaction on the surface of the specimen. A strong dependence is noted of the surface reaction on the presence of small amounts of alloying elements in the iron. The reaction of evolution of hydrogen from iron and its alloys in the temperature range from 24 to 110 deg C takes place in a combined diffusion-kinetic range

  1. 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.

  2. Thermochemical surface engineering of steels

    DEFF Research Database (Denmark)

    Thermochemical Surface Engineering of Steels provides a comprehensive scientific overview of the principles and different techniques involved in thermochemical surface engineering, including thermodynamics, kinetics principles, process technologies and techniques for enhanced performance of steels...

  3. Irreversible processes kinetic theory

    CERN Document Server

    Brush, Stephen G

    2013-01-01

    Kinetic Theory, Volume 2: Irreversible Processes deals with the kinetic theory of gases and the irreversible processes they undergo. It includes the two papers by James Clerk Maxwell and Ludwig Boltzmann in which the basic equations for transport processes in gases are formulated, together with the first derivation of Boltzmann's ""H-theorem"" and a discussion of this theorem, along with the problem of irreversibility.Comprised of 10 chapters, this volume begins with an introduction to the fundamental nature of heat and of gases, along with Boltzmann's work on the kinetic theory of gases and s

  4. Surface engineering with ion beams: from self-organized nanostructures to ultra-smooth surfaces

    International Nuclear Information System (INIS)

    Frost, F.; Ziberi, B.; Schindler, A.; Rauschenbach, B.

    2008-01-01

    Low-energy ion-beam sputtering, i.e. the removal of atoms from a surface due to the impact of energetic ions or atoms, is an inherent part of numerous surface processing techniques. Besides the actual removal of material, this surface erosion process often results in a pronounced alteration of the surface topography. Under certain conditions, sputtering results in the formation of well-ordered patterns. This self-organized pattern formation is related to a surface instability between curvature-dependent sputtering that roughens the surface and smoothing by different surface relaxation mechanisms. If the evolution of surface topography is dominated by relaxation mechanisms, surface smoothing can occur. In this presentation the current status of self-organized pattern formation and surface smoothing by low-energy ion-beam erosion of Si and Ge is summarized. In detail it will be shown that a multitude of patterns as well as ultra-smooth surfaces can develop, particularly on Si surfaces. Additionally, the most important experimental parameters that control these processes are discussed. Finally, examples are given for the application of low-energy ion beams as a novel approach for passive optical device engineering for many advanced optical applications. (orig.)

  5. Modeling the kinetics of the nitriding and nitrocarburizing of iron

    DEFF Research Database (Denmark)

    Somers, Marcel A. J.; Mittemeijer, Eric J.

    1998-01-01

    The growth kinetics of the iron-nitride compound layer during nitriding and nitrocarburizing of pure iron has been investigated for various temperatures and various combinations of imposed nitrogen and carbon activities. The results indicate that no local equilibrium occurs at the gas....../solid interface during nitriding/nitrocarburizing, due to the slow kinetics of ammonia dissociation, the development and subsequent desorption of molecular nitrogen gas at the surface and, for the case of nitrocarburizing, the fast initial carbon uptake. The kinetics of gaseous nitriding of pure iron can...... change with treatment time and the lack of accurate thermodynamic and kinetic data for Fe-N-C phases....

  6. Mechanism and kinetics of mineral weathering under acid conditions

    NARCIS (Netherlands)

    Anbeek, C.

    1994-01-01

    This study deals with the relationships between crystal structure, grain diameter, surface morphology and dissolution kinetics for feldspar and quartz under acid conditions.

    Intensively ground samples from large, naturally weathered mineral fragments are frequently used in

  7. Formulation and Permeation Kinetic Studies of Flurbiprofen Gel

    African Journals Online (AJOL)

    9-11]. The objective of this study was to investigate the permeation and drug release kinetics flurbiprofen gels using silicone membrane in modified Franz diffusion cells with the aid of surface response methodology. EXPERIMENTAL. Materials.

  8. Thermal kinetic inductance detector

    Science.gov (United States)

    Cecil, Thomas; Gades, Lisa; Miceli, Antonio; Quaranta, Orlando

    2016-12-20

    A microcalorimeter for radiation detection that uses superconducting kinetic inductance resonators as the thermometers. The detector is frequency-multiplexed which enables detector systems with a large number of pixels.

  9. Kinetic-energy absorber employs frictional force between mating cylinders

    Science.gov (United States)

    Conrad, E. W.

    1964-01-01

    A kinetic energy absorbing device uses a series of coaxial, mating cylindrical surfaces. These surfaces have high frictional resistance to relative motion when axial impact forces are applied. The device is designed for safe deceleration of vehicles impacting on landing surfaces.

  10. Pyrolysis of Sawdust, Rice Husk and Sugarcane Bagasse: Kinetic Modeling and Estimation of Kinetic Parameters using Different Optimization Tools

    Science.gov (United States)

    Khonde, Ruta Dhanram; Chaurasia, Ashish Subhash

    2015-04-01

    The present study provides the kinetic model to describe the pyrolysis of sawdust, rice-husk and sugarcane bagasse as biomass. The kinetic scheme used for modelling of primary pyrolysis consisting of the two parallel reactions giving gaseous volatiles and solid char. Estimation of kinetic parameters for pyrolysis process has been carried out for temperature range of 773-1,173 K. As there are serious issues regarding non-convergence of some of the methods or solutions converging to local-optima, the proposed kinetic model is optimized to predict the best values of kinetic parameters for the system using three approaches—Two-dimensional surface fitting non-linear regression technique, MS-Excel Solver Tool and COMSOL software. The model predictions are in agreement with experimental data over a wide range of pyrolysis conditions. The estimated value of kinetic parameters are compared with earlier researchers and found to be matching well.

  11. High-Fidelity Kinetics and Radiation Transport for NLTE Hypersonic Flows, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — The modeling of NLTE hypersonic flows combines several disciplines: chemistry, kinetics, radiation transport, fluid mechanics, and surface science. No single code or...

  12. Thermodynamic and structural study of two-dimensional phase transitions within films of molecules physi-sorbed on graphite; the role of orientational order in wetting and roughening phenomena

    International Nuclear Information System (INIS)

    Angerand, Francois

    1987-01-01

    Two-dimensional phase transitions within films physi-sorbed upon the basal face of graphite have been investigated using two experimental methods: volumetric measurements of adsorption isotherms and neutron diffraction. Our main objective was to study the role played by orientational order in these films, its influence on their thermodynamic and structural properties, and its significance in wetting and roughening phenomena, which are indirectly accessible from adsorption studies. A comparative study of the adsorption isotherms of two molecules having comparable dipole moments, NH 3 and C 2 H 3 F, discloses very dissimilar behaviours, due to the fact that hydrogen bonding is involved in the interaction between NH 3 , but not C 2 H 3 F, molecules. The impossibility of such a bond for the interaction of the adsorbate with the substrate results in a poor cohesion energy of the NH 3 ad-film in comparison with those of its bulk condensed phases. The situation is opposite for the film of C 2 H 3 F which behaves almost as a rare gas film. From multilayer adsorption isotherms of CO it is shown that graphite (0001) is perfectly wet by the plastic (orientationally disordered) crystal phase, β-CO, whereas it is incompletely wet by the low-temperature crystal phase α-CO, in which the molecules are orientationally ordered. The critical temperatures of two-dimensional condensation have been measured for the successive ad-layers, up to the fifth. They seem to converge towards a value of 65 K, which we consider as representing the temperature of the roughening transition of the (0001) face of β-CO. A neutron diffraction study of the monolayers of N 2 O and C(CD 3 ) 4 adsorbed on graphite has been carried out. For N 2 O our results suggest a structure more involved than conjectured. For C(CD 3 ) 4 we have evidence for a triple point at 178 K. The crystal monolayer has a compact hexagonal structure. (author) [fr

  13. Thermodynamics, kinetics and process control of nitriding

    DEFF Research Database (Denmark)

    Mittemeijer, Eric J.; Somers, Marcel A. J.

    1997-01-01

    As a prerequisite for the predictability of properties obtained by a nitriding treatment of iron based workpieces, the relation between the process parameters and the composition and structure of the surface layer produced must be known. At present, even the description of thermodynamic equilibrium...... of the International Federation for Heat Treatment and Surface Engineering held in Brighton, UK on 1-5 September 1996. (C) 1997 The Institute of Materials......., the nitriding result is determined largely by kinetics. Nitriding kinetics are shown to be characterised by local near equilibria and stationary states at surfaces and interfaces, and the diffusion coefficient of nitrogen in the various phases, for which new data are presented. The necessary background...

  14. Nonlocal kinetic-energy-density functionals

    International Nuclear Information System (INIS)

    Garcia-Gonzalez, P.; Alvarellos, J.E.; Chacon, E.

    1996-01-01

    In this paper we present nonlocal kinetic-energy functionals T[n] within the average density approximation (ADA) framework, which do not require any extra input when applied to any electron system and recover the exact kinetic energy and the linear response function of a homogeneous system. In contrast with previous ADA functionals, these present good behavior of the long-range tail of the exact weight function. The averaging procedure for the kinetic functional (averaging the Fermi momentum of the electron gas, instead of averaging the electron density) leads to a functional without numerical difficulties in the calculation of extended systems, and it gives excellent results when applied to atoms and jellium surfaces. copyright 1996 The American Physical Society

  15. Self-avoiding and planar random surfaces on the lattice

    International Nuclear Information System (INIS)

    Durhuus, B.; Froehlich, J.

    1983-01-01

    We study models of self-avoiding (SARS) and of planar (PRS) random surfaces on a (hyper-) cubic lattice. If Nsub(γ)(A) is the number of such surfaces with given boundary γ and area A, then Nsub(γ)(A)=exp(β 0 A+o(A)), where β 0 is independent of γ. We prove that, for β>β 0 , the string tension is finite for the SARS model and strictly positive for the PRS model and that in both models the correlation length (inverse mass) is positive and finite. We discuss the possibility of the existence of a critical point and of a roughening transition. Estimates on intersection proabilities for random surfaces and connections with lattice gauge theories are sketched. (orig.)

  16. The historical development of heat transfer surfaces for gas-cooled reactors analysed with a simple criterion

    International Nuclear Information System (INIS)

    Leslie, D.C.

    1980-01-01

    The evolution of finned heat transfer surfaces for gas-cooled reactors, from longitudinal through transverse to the sophisticated helical polyzonal and herring-bone fins, is described, and their merits are compared using a simple criterion of heat transfer efficiency. These fins cannot be used in AGR's because of the high neutron absorption and low thermal conductivity of stainless steel, and artificial roughening in the form of ribbing is used instead; the same criterion can be applied to this type of surface. The interest of the material is largely historical. (author)

  17. Multiple alternative substrate kinetics.

    Science.gov (United States)

    Anderson, Vernon E

    2015-11-01

    The specificity of enzymes for their respective substrates has been a focal point of enzyme kinetics since the initial characterization of metabolic chemistry. Various processes to quantify an enzyme's specificity using kinetics have been utilized over the decades. Fersht's definition of the ratio kcat/Km for two different substrates as the "specificity constant" (ref [7]), based on the premise that the important specificity existed when the substrates were competing in the same reaction, has become a consensus standard for enzymes obeying Michaelis-Menten kinetics. The expansion of the theory for the determination of the relative specificity constants for a very large number of competing substrates, e.g. those present in a combinatorial library, in a single reaction mixture has been developed in this contribution. The ratio of kcat/Km for isotopologs has also become a standard in mechanistic enzymology where kinetic isotope effects have been measured by the development of internal competition experiments with extreme precision. This contribution extends the theory of kinetic isotope effects to internal competition between three isotopologs present at non-tracer concentrations in the same reaction mix. This article is part of a special issue titled: Enzyme Transition States from Theory and Experiment. Published by Elsevier B.V.

  18. The effects of surface roughness on the scattering properties of hexagonal columns with sizes from the Rayleigh to the geometric optics regimes

    International Nuclear Information System (INIS)

    Liu, Chao; Lee Panetta, R.; Yang, Ping

    2013-01-01

    Effects of surface roughness on the optical scattering properties of ice crystals are investigated using a random wave superposition model of roughness that is a simplification of models used in studies of scattering by surface water waves. Unlike previous work with models of rough surfaces applicable only in limited size ranges, such as surface perturbation methods in the small particle regime or the tilted-facet (TF) method in the large particle regime, ours uses a single roughness model to cover a range in sizes extending from the Rayleigh to the geometric optics regimes. The basic crystal shape we examine is the hexagonal column but our roughening model can be used for a wide variety of particle geometries. To compute scattering properties over the range of sizes we use the pseudo-spectral time domain method (PSTD) for small to moderate sized particles and the improved geometric optics method (IGOM) for large ones. Use of the PSTD with our roughness model is straightforward. By discretizing the roughened surface with triangular sub-elements, we adapt the IGOM to give full consideration of shadow effects, multiple reflections/refractions at the surface, and possible reentrance of the scattered beams. We measure the degree of roughness of a surface by the variance (σ 2 ) of surface slopes occurring on the surfaces. For moderately roughened surfaces (σ 2 ≤0.1) in the large particle regime, the scattering properties given by the TF and IGOM agree well, but differences in results obtained with the two methods become noticeable as the surface becomes increasingly roughened. Having a definite, albeit idealized, roughness model we are able to use the combination of the PSTD and IGOM to examine how a fixed degree of surface roughness affects the scattering properties of a particle as the size parameter of the particle changes. We find that for moderately rough surfaces in our model, as particle size parameter increases beyond about 20 the influence of surface

  19. Effect of operational and water quality parameters on conventional ozonation and the advanced oxidation process O3/H2O2: Kinetics of micropollutant abatement, transformation product and bromate formation in a surface water.

    Science.gov (United States)

    Bourgin, Marc; Borowska, Ewa; Helbing, Jakob; Hollender, Juliane; Kaiser, Hans-Peter; Kienle, Cornelia; McArdell, Christa S; Simon, Eszter; von Gunten, Urs

    2017-10-01

    The efficiency of ozone-based processes under various conditions was studied for the treatment of a surface water (Lake Zürich water, Switzerland) spiked with 19 micropollutants (pharmaceuticals, pesticides, industrial chemical, X-ray contrast medium, sweetener) each at 1 μg L -1 . Two pilot-scale ozonation reactors (4-5 m 3  h -1 ), a 4-chamber reactor and a tubular reactor, were investigated by either conventional ozonation and/or the advanced oxidation process (AOP) O 3 /H 2 O 2 . The effects of selected operational parameters, such as ozone dose (0.5-3 mg L -1 ) and H 2 O 2 dose (O 3 :H 2 O 2  = 1:3-3:1 (mass ratio)), and selected water quality parameters, such as pH (6.5-8.5) and initial bromide concentration (15-200 μg L -1 ), on micropollutant abatement and bromate formation were investigated. Under the studied conditions, compounds with high second-order rate constants k O3 >10 4  M -1  s -1 for their reaction with ozone were well abated (>90%) even for the lowest ozone dose of 0.5 mg L -1 . Conversely, the abatement efficiency of sucralose, which only reacts with hydroxyl radicals (OH), varied between 19 and 90%. Generally, the abatement efficiency increased with higher ozone doses and higher pH and lower bromide concentrations. H 2 O 2 addition accelerated the ozone conversion to OH, which enables a faster abatement of ozone-resistant micropollutants. Interestingly, the abatement of micropollutants decreased with higher bromide concentrations during conventional ozonation due to competitive ozone-consuming reactions, except for lamotrigine, due to the suspected reaction of HOBr/OBr - with the primary amine moieties. In addition to the abatement of micropollutants, the evolution of the two main transformation products (TPs) of hydrochlorothiazide (HCTZ) and tramadol (TRA), chlorothiazide (CTZ) and tramadol N-oxide (TRA-NOX), respectively, was assessed by chemical analysis and kinetic modeling. Both selected TPs were quickly formed initially

  20. Erbium hydride decomposition kinetics.

    Energy Technology Data Exchange (ETDEWEB)

    Ferrizz, Robert Matthew

    2006-11-01

    Thermal desorption spectroscopy (TDS) is used to study the decomposition kinetics of erbium hydride thin films. The TDS results presented in this report are analyzed quantitatively using Redhead's method to yield kinetic parameters (E{sub A} {approx} 54.2 kcal/mol), which are then utilized to predict hydrogen outgassing in vacuum for a variety of thermal treatments. Interestingly, it was found that the activation energy for desorption can vary by more than 7 kcal/mol (0.30 eV) for seemingly similar samples. In addition, small amounts of less-stable hydrogen were observed for all erbium dihydride films. A detailed explanation of several approaches for analyzing thermal desorption spectra to obtain kinetic information is included as an appendix.

  1. Effect of surface morphology on the sputtering yields. II. Ion sputtering from rippled surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Makeev, Maxim A. E-mail: makeev@usc.edu; Barabasi, Albert-Laszlo E-mail: alb@nd.edu

    2004-08-01

    Off-normal ion bombardment of solid targets with energetic particles often leads to development of periodically modulated structures on the surfaces of eroded materials. Ion-induced surface roughening, in its turn, causes sputtering yield changes. We report on a comprehensive theoretical study of the effect of rippled surface morphology on the sputtering yields. The yield is computed as a function of the parameters characterizing the surface morphology and the incident ion beam, using the Sigmund's theory of ion sputtering. We find that the surface morphology development may cause substantial variations in the sputter yields, depending on a complex interplay between the parameters characterizing the ripple structure and the incident ion beam. For certain realizations of the ripple structure, the surface morphology is found to induce enhanced, relative to the flat surface value, sputtering yields. On the other hand, there exist regimes in which the sputtering yield is suppressed by the surface roughness below the flat surface result. We confront the obtained theoretical results with available experimental data and find that our model provides an excellent qualitative and, in some cases, quantitative agreement with the results of experimental studies.

  2. Quantum kinetic theory

    CERN Document Server

    Bonitz, Michael

    2016-01-01

    This book presents quantum kinetic theory in a comprehensive way. The focus is on density operator methods and on non-equilibrium Green functions. The theory allows to rigorously treat nonequilibrium dynamics in quantum many-body systems. Of particular interest are ultrafast processes in plasmas, condensed matter and trapped atoms that are stimulated by rapidly developing experiments with short pulse lasers and free electron lasers. To describe these experiments theoretically, the most powerful approach is given by non-Markovian quantum kinetic equations that are discussed in detail, including computational aspects.

  3. Relativistic Kinetic Theory

    Science.gov (United States)

    Vereshchagin, Gregory V.; Aksenov, Alexey G.

    2017-02-01

    Preface; Acknowledgements; Acronyms and definitions; Introduction; Part I. Theoretical Foundations: 1. Basic concepts; 2. Kinetic equation; 3. Averaging; 4. Conservation laws and equilibrium; 5. Relativistic BBGKY hierarchy; 6. Basic parameters in gases and plasmas; Part II. Numerical Methods: 7. The basics of computational physics; 8. Direct integration of Boltzmann equations; 9. Multidimensional hydrodynamics; Part III. Applications: 10. Wave dispersion in relativistic plasma; 11. Thermalization in relativistic plasma; 12. Kinetics of particles in strong fields; 13. Compton scattering in astrophysics and cosmology; 14. Self-gravitating systems; 15. Neutrinos, gravitational collapse and supernovae; Appendices; Bibliography; Index.

  4. Posture and theophylline kinetics.

    OpenAIRE

    Warren, J B; Cuss, F; Barnes, P J

    1985-01-01

    The effect of posture on theophylline kinetics was examined in six healthy men who took 450 mg slow-release aminophylline orally at the same time of day on two separate occasions. On one day they remained standing and on the other supine throughout. Plasma theophylline was measured hourly for 6 h from ingestion. Mean theophylline levels were significantly higher in the standing position at all times (P less than 0.01). We conclude that diurnal variation in theophylline kinetics can be explain...

  5. Tebuconazole photocatalytic degradation kinetics

    OpenAIRE

    Prestes, Thiago de Hermann; Gibbon, Danielle de Oliveira; Lansarin, Marla Azário; Moro, Celso Camilo

    2010-01-01

    The tebuconazole photocatalytic degradation kinetics was studied in a batch reactor using TiO2 (P25-Degussa) as catalyst and a high pressure mercury lamp. The photolysis, adsorption and irradiation effects in the reaction rate were evaluated. Afterward, the suspension catalyst concentration and initial pH to the maximum reaction rate was determined. It was observed that the reaction rate can be approached by a pseudo-first order, with a maximum kinetics constant at 260 mg L-1catalyst concentr...

  6. A Simple "Boxed Molecular Kinetics" Approach To Accelerate Rare Events in the Stochastic Kinetic Master Equation.

    Science.gov (United States)

    Shannon, Robin; Glowacki, David R

    2018-02-15

    The chemical master equation is a powerful theoretical tool for analyzing the kinetics of complex multiwell potential energy surfaces in a wide range of different domains of chemical kinetics spanning combustion, atmospheric chemistry, gas-surface chemistry, solution phase chemistry, and biochemistry. There are two well-established methodologies for solving the chemical master equation: a stochastic "kinetic Monte Carlo" approach and a matrix-based approach. In principle, the results yielded by both approaches are identical; the decision of which approach is better suited to a particular study depends on the details of the specific system under investigation. In this Article, we present a rigorous method for accelerating stochastic approaches by several orders of magnitude, along with a method for unbiasing the accelerated results to recover the "true" value. The approach we take in this paper is inspired by the so-called "boxed molecular dynamics" (BXD) method, which has previously only been applied to accelerate rare events in molecular dynamics simulations. Here we extend BXD to design a simple algorithmic strategy for accelerating rare events in stochastic kinetic simulations. Tests on a number of systems show that the results obtained using the BXD rare event strategy are in good agreement with unbiased results. To carry out these tests, we have implemented a kinetic Monte Carlo approach in MESMER, which is a cross-platform, open-source, and freely available master equation solver.

  7. Ag nanostructures on a poly(3,4-ethylenedioxythiophene) film prepared with electrochemical route: A controllable roughened SERS substrate with high repeatability and stability

    International Nuclear Information System (INIS)

    Dogan, Üzeyir; Kaya, Murat; Cihaner, Atilla; Volkan, Mürvet

    2012-01-01

    A simple, reliable and reproducible one-step electrochemical method for the preparation of surface-enhanced Raman-active polymer-mediated silver nanoparticles (Ag NPs) on planar indium tin oxide (ITO) coated glass substrates was reported. Poly(3,4-ethylenedioxythiophene) (PEDOT) film was used as a support material for dispersing nanostructured silver nanostructures on the surface homogeneously, since 3,4-ethylenedioxythiophene (EDOT) monomer polymerizes regioregularly. The optical properties and morphologies of the silver substrates have been investigated by ultraviolet–visible (UV–vis) spectroscopy and field emission scanning electron microscopy (FE-SEM). The UV–vis and FE-SEM results revealed that the Ag nanostructures separately appeared on the PEDOT coated ITO after reduction. The effect of the thickness of PEDOT polymer film, reduction potential of silver, the concentration of silver ion solution and the amount of silver particle on the polymer film on the SERS response were studied as well as repeatability and temporal stability of prepared substrates. Brilliant cresyl blue (BCB) has been used as Raman probes to evaluate the properties of the new SERS substrates. Signals collected over multiple spots within the same substrate resulted in a relative standard deviation (RSD) of 9.34%, while an RSD of 11.05% was measured in signals collected from different substrates. The SERS-active substrates were robust and stable which lost only 5.71% of initial intensity after 1 month.

  8. Modeling chemical kinetics graphically

    NARCIS (Netherlands)

    Heck, A.

    2012-01-01

    In literature on chemistry education it has often been suggested that students, at high school level and beyond, can benefit in their studies of chemical kinetics from computer supported activities. Use of system dynamics modeling software is one of the suggested quantitative approaches that could

  9. CATALYTIC KINETIC SPECTROPHOTOMETRIC DETERMINATION ...

    African Journals Online (AJOL)

    Preferred Customer

    acetylchlorophosphonazo(CPApA) by hydrogen peroxide in 0.10 M phosphoric acid. A novel catalytic kinetic-spectrophotometric method is proposed for the determination of copper based on this principle. Copper(II) can be determined spectrophotometrically ...

  10. Kinetics and Catalysis Demonstrations.

    Science.gov (United States)

    Falconer, John L.; Britten, Jerald A.

    1984-01-01

    Eleven videotaped kinetics and catalysis demonstrations are described. Demonstrations include the clock reaction, oscillating reaction, hydrogen oxidation in air, hydrogen-oxygen explosion, acid-base properties of solids, high- and low-temperature zeolite reactivity, copper catalysis of ammonia oxidation and sodium peroxide decomposition, ammonia…

  11. SHORT COMMUNICATION KINETIC SPECTROPHOTOMETRIC ...

    African Journals Online (AJOL)

    Preferred Customer

    gingili paste, oat slice, sleeve-fish silk food samples. The determined results were in agreement with those by atomic absorption spectrometry. KEY WORDS: KEY WORDS: Iron, Catalytic kinetic spectrophotometry, p–Acetylarsenazo, Potassium periodate. INTRODUCTION. Iron is an important component for the human body.

  12. Point kinetics modeling

    International Nuclear Information System (INIS)

    Kimpland, R.H.

    1996-01-01

    A normalized form of the point kinetics equations, a prompt jump approximation, and the Nordheim-Fuchs model are used to model nuclear systems. Reactivity feedback mechanisms considered include volumetric expansion, thermal neutron temperature effect, Doppler effect and void formation. A sample problem of an excursion occurring in a plutonium solution accidentally formed in a glovebox is presented

  13. CATALYTIC KINETIC SPECTROPHOTOMETRIC DETERMINATION ...

    African Journals Online (AJOL)

    Based on the property that in 0.12 M sulfuric acid medium titanium(IV) catalyzes the discoloring reaction of DBS-arsenazo oxidized by potassium bromate, a new catalytic kinetic spectrophotometric method for the determination of trace titanium (IV) was developed. The linear range of the determination of titanium is

  14. Kinetic modelization of water-rock interaction processes

    International Nuclear Information System (INIS)

    Pena, J.; Gimeno, M.J.

    1994-01-01

    A review of basic concepts in kinetics of low temperature natural systems is given: elementary and overall reactions, steady state and reaction mechanism, sequential reactions, parallel reactions and rate-determining step, temperature dependence of rate constant and principle of detailed balancing. The current status of kinetics modeling of water/rock interaction is treated. The comparison of the mean life of the processes with the residence time of the water in the system is very useful to decide the application or not of the kinetics treatment to the water/rock interaction processes. The right application of the kinetics treatment to the water/rock interaction needs the knowledge of the magnitude of the surface through which the water/rock reaction take place and its variation with time. Two ways to treat kinetically the water/rock interaction are the Mass Transfer method and the quasi-stationary state method

  15. Energy Conservation Tests of a Coupled Kinetic-kinetic Plasma-neutral Transport Code

    Energy Technology Data Exchange (ETDEWEB)

    Stotler, D. P.; Chang, C. S.; Ku, S. H.; Lang, J.; Park, G.

    2012-08-29

    A Monte Carlo neutral transport routine, based on DEGAS2, has been coupled to the guiding center ion-electron-neutral neoclassical PIC code XGC0 to provide a realistic treatment of neutral atoms and molecules in the tokamak edge plasma. The DEGAS2 routine allows detailed atomic physics and plasma-material interaction processes to be incorporated into these simulations. The spatial pro le of the neutral particle source used in the DEGAS2 routine is determined from the uxes of XGC0 ions to the material surfaces. The kinetic-kinetic plasma-neutral transport capability is demonstrated with example pedestal fueling simulations.

  16. Comparison of Flow Characteristics of Different Sphere Geometries Under the Free Surface Effect

    Directory of Open Access Journals (Sweden)

    Sahin B.

    2013-04-01

    Full Text Available Comparison of the experimental results of turbulent flow structures between a smooth sphere and a sphere with a vent hole, roughened, and o-ring is presented in the presence of a free-surface. Dye visualization and particle image velocimetry (PIV techniques were performed to examine effects of passive control methods on the sphere wake for Reynolds number Re = 5000 based on the sphere diameter with a 42.5mm in an open water channel. Instantaneous and time-averaged flow patterns in the wake region of the sphere were examined from point of flow physics for the different sphere locations in the range of 0≤h/D≤2.0 where h was the space between the top point of the sphere and the free surface. The ratio of ventilation hole to sphere diameter was 0.15, o-ring was located at 55° with a 2 mm from front stagnation point of the sphere and roughened surface was formed by means of totally 410 circular holes with a 3 mm diameter and around 2 mm depth in an equilateral triangle arrangement. The flow characteristics of instantaneous velocity vectors, vorticity contours, time-averaged streamline patterns, Reynolds stress correlations and streamwise and cross-stream velocity fluctuations for both the smooth and passively controlled sphere were interpreted.

  17. Bond strength of resin cement to dentin and to surface-treated posts of titanium alloy, glass fiber, and zirconia.

    Science.gov (United States)

    Sahafi, Alireza; Peutzfeldt, Anne; Asmussen, Erik; Gotfredsen, Klaus

    2003-01-01

    To determine the effect of surface treatments on bond strength of two resin cements (ParaPost Cement and Panavia F) to posts of titanium alloy (ParaPost XH), glass fiber (ParaPost Fiber White), and zirconia (Cerapost), and to dentin. After embedding, planar surfaces of posts (n = 9 to 14) and human dentin (n = 10) were obtained by grinding. The posts received one of three surface treatments: 1. roughening (sandblasting, hydrofluoric acid etching), 2. application of primer (Alloy Primer, Metalprimer II, silane), or 3. roughening followed by application of primer (sandblasting or etching followed by primer, Cojet treatment). ParaPost Cement and Panavia F were bonded to the post and dentin specimens, and the bonded specimens were placed in water at 37 degrees C for 7 days. The specimens were debonded in shear. Panavia F had significantly higher bond strength to ground ParaPost XH, Cerapost, and dentin than did ParaPost Cement. Most surface treatments resulted in an improved bond strength of resin cements to the posts. Compared to the ground control, Cojet treatment and sandblasting were the most effective treatments. Etching of Cerapost with hydrofluoric acid with and without silane treatment significantly decreased the bond strength of Panavia F to the post. The bond strength of resin cements to the posts was affected by the material of the post, the surface treatment of the post, and by the type of resin cement. The bond strength of resin cement to dentin was influenced by the type of resin cement.

  18. Light-responsive smart surface with controllable wettability and excellent stability.

    Science.gov (United States)

    Zhou, Yin-Ning; Li, Jin-Jin; Zhang, Qing; Luo, Zheng-Hong

    2014-10-21

    Novel fluorinated gradient copolymer was designed for smart surface with light-responsive controllable wettability and excellent stability. The switchable mechanism and physicochemical characteristics of the as-prepared surface decorated by designed polymeric material were investigated by ultraviolet-visible (UV-vis) spectrum, scanning electron microscope (SEM), atomic force microscope (AFM), and X-ray photoelectron spectroscopy (XPS). Thanks to the functional film and surface roughening, etched silicon surface fabricated by copolymer involving spiropyran (Sp) moieties possesses a fairly large variation range of WCA (28.1°) and achieves the transformation between hydrophilicity (95.2° 109.2°) relative to blank sample (109.2°). The synthetic strategy and developed smart surface offer a promising application in coating with controllable wettability, which bridge the gap between chemical structure and material properties.

  19. Plasma Surface Modification of Glass-Fibre-Reinforced Polyester Enhanced by Ultrasonic Irradiation

    DEFF Research Database (Denmark)

    Kusano, Yukihiro; Singh, Shailendra Vikram; Bardenshtein, Alexander

    2010-01-01

    .295, 0.385 and 0.447, respectively. This indicated that the plasma treatment oxidized and roughened the GFRP surface, and the ultrasonic irradiation further enhanced the oxidation. It is concluded that plasma treatment efficiency for adhesion improvement of GFRPs is enhanced by the ultrasonic irradiation.......During atmospheric pressure plasma treatment, reactive species generated in the plasma diffuse through a boundary gas layer which is adsorbed at the material surface. Many of the reactive species become inactivated before reaching the surface due to their short lifetime. The efficiency of plasma....... The surface characterizations were performed using contact angle measurements, X-ray photoelectron spectroscopy (XPS) and atomic force mictroscopy (AFM). O/C ratios at the GFRP surfaces before the treatments, after 30-s plasma treatment, and after 30-s plasma treatment with ultrasonic irradiation were 0...

  20. A novel and inexpensive technique for creating superhydrophobic surfaces using Teflon and sandpaper

    Science.gov (United States)

    Nilsson, Michael A.; Daniello, Robert J.; Rothstein, Jonathan P.

    2010-02-01

    Considerable efforts have been spent over the last decade developing hydrophobic surfaces exhibiting very large contact angles with water. Many of these methods require complex and expensive fabrication techniques. We demonstrate that sanding Teflon can produce superhydrophobic surfaces with advancing contact angles of up to 151° and contact angle hysteresis of less than 4°. Furthermore, we show that a wide range of both advancing contact angles and contact angle hysteresis can be achieved by varying the grit size of the sandpaper, allowing for future hysteresis and contact angle studies. Scanning electron microscopy images of the roughened surfaces depict the range and amplitude of length scales imparted on the surface by the sandpaper, which leads to deeper understanding of the state of wetting on the surface.

  1. Oxide driven strength evolution of silicon surfaces

    Science.gov (United States)

    Grutzik, Scott J.; Milosevic, Erik; Boyce, Brad L.; Zehnder, Alan T.

    2015-11-01

    Previous experiments have shown a link between oxidation and strength changes in single crystal silicon nanostructures but provided no clues as to the mechanisms leading to this relationship. Using atomic force microscope-based fracture strength experiments, molecular dynamics modeling, and measurement of oxide development with angle resolved x-ray spectroscopy we study the evolution of strength of silicon (111) surfaces as they oxidize and with fully developed oxide layers. We find that strength drops with partial oxidation but recovers when a fully developed oxide is formed and that surfaces intentionally oxidized from the start maintain their high initial strengths. MD simulations show that strength decreases with the height of atomic layer steps on the surface. These results are corroborated by a completely separate line of testing using micro-scale, polysilicon devices, and the slack chain method in which strength recovers over a long period of exposure to the atmosphere. Combining our results with insights from prior experiments we conclude that previously described strength decrease is a result of oxidation induced roughening of an initially flat silicon (1 1 1) surface and that this effect is transient, a result consistent with the observation that surfaces flatten upon full oxidation.

  2. Kinetic energy absorbing pad

    International Nuclear Information System (INIS)

    Bricmont, R.J.; Hamilton, P.A.; Ming Long Ting, R.

    1981-01-01

    Reactors, fuel processing plants etc incorporate pipes and conduits for fluids under high pressure. Fractures, particularly adjacent to conduit elbows, produce a jet of liquid which whips the broken conduit at an extremely high velocity. An enormous impact load would be applied to any stationary object in the conduit's path. The design of cellular, corrugated metal impact pads to absorb the kinetic energy of the high velocity conduits is given. (U.K.)

  3. Kinetic transport in crystals

    OpenAIRE

    Marklof, Jens

    2009-01-01

    One of the central challenges in kinetic theory is the derivation of macroscopic evolution equations--describing, for example, the dynamics of an electron gas--from the underlying fundamental microscopic laws of classical or quantum mechanics. An iconic mathematical model in this research area is the Lorentz gas, which describes an ensemble of non-interacting point particles in an infinite array of spherical scatterers. In the case of a disordered scatterer configuration, the classical result...

  4. The Effect of Abutment Surface Roughness on the Retention of Implant-Supported Crowns Cemented with Provisional

    Directory of Open Access Journals (Sweden)

    Seyyed Mohammad Abrisham

    2012-09-01

    Full Text Available Introduction: Surface roughness can increase the retention of castings by ridges and grooves that are microretentive. This study compared the retention of implant-supported crowns when used with 3 different surface roughness abutments and one temporary cement. Methods: Thirty solid abutments (ITI, 4 mm high, were divided into three groups randomly. In the first group, 10 abutments were roughened with sandblast (50-µm aluminum oxide and in the second group, 10 abutments were roughened with diamond bur. The third group had no surface treatment. Then, thirty implant fixture analogs (ITI were placed in the center of acrylic cylinders. After that a solid abutment was tightened on the each fixture analog with 35 N/cm force. Thirty base metal crowns were made on the 4 mm ITI abutment analogs using plastic coping. The prepared copings were cemented on the abutments by TempBond temporary cement and finally, crowns were pulled from the abutment in a universal test machine at a cross speed of 0.5cm/min. Results: The mean tensile strength in sandblasted, bur treated, and control group were 64.38±8, 91.37±7.19, and 58.61±1.93, respectively. Bur treated group showed higher tensile strength in comparison with two other groups. Conclusion: Surface modification of implant abutment by diamond bur may be an effective method to increase retention of crown when TempBond is used.

  5. The Effect of Abutment Surface Roughness on the Retention of Implant-Supported Crowns Cemented with Provisional Luting Cement

    Directory of Open Access Journals (Sweden)

    Jalil Ganbarzadeh

    2013-01-01

    Full Text Available Introduction: Surface roughness can increase the retention of castings by ridges and grooves that are microretentive. This study compared the retention of implant-supported crowns when used with 3 different surface roughness abutments and one temporary cement. Methods: Thirty solid abutments (ITI, 4 mm high, were divided into three groups randomly. In the first group, 10 abutments were roughened with sandblast (50-µm aluminum oxide and in the second group, 10 abutments were roughened with diamond bur. The third group had no surface treatment. Then, thirty implant fixture analogs (ITI were placed in the center of acrylic cylinders. After that a solid abutment was tightened on the each fixture analog with 35 N/cm force. Thirty base metal crowns were made on the 4 mm ITI abutment analogs using plastic coping. The prepared copings were cemented on the abutments by TempBond temporary cement and finally, crowns were pulled from the abutment in a universal test machine at a cross speed of 0.5cm/min. Results: The mean tensile strength in sandblasted, bur treated, and control group were 64.38±8, 91.37±7.19, and 58.61±1.93, respectively. Bur treated group showed higher tensile strength in comparison with two other groups. Conclusion: Surface modification of implant abutment by diamond bur may be an effective method to increase retention of crown when TempBond is used.

  6. Influence of Sea Surface Roughness on the Electromagnetic Wave Propagation in the Duct Environment

    Directory of Open Access Journals (Sweden)

    X. Zhao

    2010-12-01

    Full Text Available This paper deals with a study of the influence of sea surface roughness on the electromagnetic wave propagation in the duct environment. The problem of electromagnetic wave propagation is modeled by using the parabolic equation method. The roughness of the sea surface is computed by modifying the smooth surface Fresnel reflection coefficient to account for the reduction in the specular reflection due to the roughness resulting from sea wind speed. The propagation model is solved by the mixed Fourier split-step algorithm. Numerical experiments indicate that wind-driven roughened sea surface has an impact on the electromagnetic wave propagation in the duct environment, and the strength is intensified along with the increment of sea wind speeds and/or the operating frequencies. In a fixed duct environment, however, proper disposition of the transmitter could reduce these impacts.

  7. On the spectrum of facet crystallization waves at the smooth 4He crystal surface

    International Nuclear Information System (INIS)

    Burmistrov, S.N.

    2011-01-01

    The wavelike processes of crystallization and melting or crystallization waves are well known to exist at the 4 He crystal surface in the rough state. Much less is known about crystallization waves for the 4 He crystal surface in the smooth well-faceted state below the roughening transition temperature. To meet the lack, we analyze here the spectrum of facet crystallization waves and its dependence upon the wavelength, perturbation amplitude, and the number of possible facet steps distributed somehow over the wavelength. All the distinctive features of facet crystallization waves from conventional waves at the rough surface result from a nonanalytic cusplike behavior in the angle dependence for the surface tension of smooth crystal facets.

  8. Stretched versus compressed exponential kinetics in α-helix folding

    International Nuclear Information System (INIS)

    Hamm, Peter; Helbing, Jan; Bredenbeck, Jens

    2006-01-01

    In a recent paper (J. Bredenbeck, J. Helbing, J.R. Kumita, G.A. Woolley, P. Hamm, α-helix formation in a photoswitchable peptide tracked from picoseconds to microseconds by time resolved IR spectroscopy, Proc. Natl. Acad. Sci USA 102 (2005) 2379), we have investigated the folding of a photo-switchable α-helix with a kinetics that could be fit by a stretched exponential function exp(-(t/τ) β ). The stretching factor β became smaller as the temperature was lowered, a result which has been interpreted in terms of activated diffusion on a rugged energy surface. In the present paper, we discuss under which conditions diffusion problems occur with stretched exponential kinetics (β 1). We show that diffusion problems do have a strong tendency to yield stretched exponential kinetics, yet, that there are conditions (strong perturbation from equilibrium, performing the experiment in the folding direction) under which compressed exponential kinetics would be expected instead. We discuss the kinetics on free energy surfaces predicted by simple initiation-propagation models (zipper models) of α-helix folding, as well as by folding funnel models. We show that our recent experiment has been performed under condition for which models with strong downhill driving force, such as the zipper model, would predict compressed, rather than stretched exponential kinetics, in disagreement with the experimental observation. We therefore propose that the free energy surface along a reaction coordinate that governs the folding kinetics must be relatively flat and has a shape similar to a 1D golf course. We discuss how this conclusion can be unified with the thermodynamically well established zipper model by introducing an additional kinetic reaction coordinate

  9. Kinetics of tetrataenite disordering

    International Nuclear Information System (INIS)

    Dos Santos, E.; Gattacceca, J.; Rochette, P.; Fillion, G.; Scorzelli, R.B.

    2015-01-01

    Tetrataenite is a chemically ordered L1 0 -type Fe 50 Ni 50 alloy detected for the first time in 1977 by 57 Fe Mössbauer spectroscopy studies in iron meteorites. The thermal history of meteorites, in particular short thermal events like those associated to hypervelocity impacts, can be constrained by tracing the presence of tetrataenite or its disordering into taenite. The knowledge of the disordering kinetics of tetrataenite, that is associated with changes in its magnetic properties, is still very fragmentary so that the time–temperature history of these meteorites cannot be constrained in details. Furthermore, knowledge of disordering kinetics is important due to potential technological application of tetrataenite as a rare-earth free strong magnet. Thus, this work provides the first time–temperature data for disordering reaction of tetrataenite. We have shown that disordering is not an instantaneous process but is a kinetic limited reaction. It was shown that disordering may take place at any temperature above the order–disorder transition for L 10 superstructure phase (∼320 °C) when the appropriate time-scale is considered. This result means that the apparent Curie point for tetrataenite is not an absolute property in the sense that any estimate of this parameter should be referred to a given time-scale. - Highlights: • The first time–temperature data for tetrataenite disordering reaction is provided. • Previous works does not give a complete picture of tetrataenite disordering. • Apparent Curie temperature of tetrataenite should be referred to a time-scale. • Tetrataenite can be used as a probe to detect thermal/shock events recorded in meteorites

  10. Kinetics of tetrataenite disordering

    Energy Technology Data Exchange (ETDEWEB)

    Dos Santos, E., E-mail: edisanfi@cbpf.br [Centro Brasileiro de Pesquisas Físicas, Rio de Janeiro (Brazil); Gattacceca, J.; Rochette, P. [Centre Européen de Recherche et d’Enseignement des Géosciences de l’Environnement, UM34, CNRS/Aix-Marseille University, Aix-en-Provence (France); Fillion, G. [Laboratoire National des Champs Magnétiques Intenses (LNCMI), CNRS, UJF, 38042 Grenoble (France); Scorzelli, R.B. [Centro Brasileiro de Pesquisas Físicas, Rio de Janeiro (Brazil)

    2015-02-01

    Tetrataenite is a chemically ordered L1{sub 0}-type Fe{sub 50}Ni{sub 50} alloy detected for the first time in 1977 by {sup 57}Fe Mössbauer spectroscopy studies in iron meteorites. The thermal history of meteorites, in particular short thermal events like those associated to hypervelocity impacts, can be constrained by tracing the presence of tetrataenite or its disordering into taenite. The knowledge of the disordering kinetics of tetrataenite, that is associated with changes in its magnetic properties, is still very fragmentary so that the time–temperature history of these meteorites cannot be constrained in details. Furthermore, knowledge of disordering kinetics is important due to potential technological application of tetrataenite as a rare-earth free strong magnet. Thus, this work provides the first time–temperature data for disordering reaction of tetrataenite. We have shown that disordering is not an instantaneous process but is a kinetic limited reaction. It was shown that disordering may take place at any temperature above the order–disorder transition for L{sub 10} superstructure phase (∼320 °C) when the appropriate time-scale is considered. This result means that the apparent Curie point for tetrataenite is not an absolute property in the sense that any estimate of this parameter should be referred to a given time-scale. - Highlights: • The first time–temperature data for tetrataenite disordering reaction is provided. • Previous works does not give a complete picture of tetrataenite disordering. • Apparent Curie temperature of tetrataenite should be referred to a time-scale. • Tetrataenite can be used as a probe to detect thermal/shock events recorded in meteorites.

  11. Kinetics of stress fibers

    International Nuclear Information System (INIS)

    Stachowiak, Matthew R; O'Shaughnessy, Ben

    2008-01-01

    Stress fibers are contractile cytoskeletal structures, tensile actomyosin bundles which allow sensing and production of force, provide cells with adjustable rigidity and participate in various processes such as wound healing. The stress fiber is possibly the best characterized and most accessible multiprotein cellular contractile machine. Here we develop a quantitative model of the structure and relaxation kinetics of stress fibers. The principal experimentally known features are incorporated. The fiber has a periodic sarcomeric structure similar to muscle fibers with myosin motor proteins exerting contractile force by pulling on actin filaments. In addition the fiber contains the giant spring-like protein titin. Actin is continuously renewed by exchange with the cytosol leading to a turnover time of several minutes. In order that steady state be possible, turnover must be regulated. Our model invokes simple turnover and regulation mechanisms: actin association and dissociation occur at filament ends, while actin filament overlap above a certain threshold in the myosin-containing regions augments depolymerization rates. We use the model to study stress fiber relaxation kinetics after stimulation, as observed in a recent experimental study where some fiber regions were contractile and others expansive. We find that two distinct episodes ensue after stimulation: the turnover-overlap system relaxes rapidly in seconds, followed by the slow relaxation of sarcomere lengths in minutes. For parameter values as they have been characterized experimentally, we find the long time relaxation of sarcomere length is set by the rate at which actin filaments can grow or shrink in response to the forces exerted by the elastic and contractile elements. Consequently, the stress fiber relaxation time scales inversely with both titin spring constant and the intrinsic actin turnover rate. The model's predicted sarcomere velocities and contraction-expansion kinetics are in good

  12. Kinetics of stress fibers

    Energy Technology Data Exchange (ETDEWEB)

    Stachowiak, Matthew R; O' Shaughnessy, Ben [Department of Chemical Engineering, Columbia University, New York, NY 10027 (United States)], E-mail: bo8@columbia.edu

    2008-02-15

    Stress fibers are contractile cytoskeletal structures, tensile actomyosin bundles which allow sensing and production of force, provide cells with adjustable rigidity and participate in various processes such as wound healing. The stress fiber is possibly the best characterized and most accessible multiprotein cellular contractile machine. Here we develop a quantitative model of the structure and relaxation kinetics of stress fibers. The principal experimentally known features are incorporated. The fiber has a periodic sarcomeric structure similar to muscle fibers with myosin motor proteins exerting contractile force by pulling on actin filaments. In addition the fiber contains the giant spring-like protein titin. Actin is continuously renewed by exchange with the cytosol leading to a turnover time of several minutes. In order that steady state be possible, turnover must be regulated. Our model invokes simple turnover and regulation mechanisms: actin association and dissociation occur at filament ends, while actin filament overlap above a certain threshold in the myosin-containing regions augments depolymerization rates. We use the model to study stress fiber relaxation kinetics after stimulation, as observed in a recent experimental study where some fiber regions were contractile and others expansive. We find that two distinct episodes ensue after stimulation: the turnover-overlap system relaxes rapidly in seconds, followed by the slow relaxation of sarcomere lengths in minutes. For parameter values as they have been characterized experimentally, we find the long time relaxation of sarcomere length is set by the rate at which actin filaments can grow or shrink in response to the forces exerted by the elastic and contractile elements. Consequently, the stress fiber relaxation time scales inversely with both titin spring constant and the intrinsic actin turnover rate. The model's predicted sarcomere velocities and contraction-expansion kinetics are in good

  13. Uniform superhydrophobic surfaces using micro/nano complex structures formed spontaneously by a simple and cost-effective nonlithographic process based on anodic aluminum oxide technology

    International Nuclear Information System (INIS)

    Kim, Dae-Ho; Cho, Chae-Ryong; Kim, Jong-Man; Kim, Yongsung; Kim, Byung Min; Ko, Jong Soo

    2011-01-01

    This paper presents a uniform micro/nano double-roughened superhydrophobic surface with a high static contact angle (CA) and low contact angle hysteresis (CAH). The proposed micro/nano complex structured surfaces were self-fabricated simply and efficiently using a very simple and low-cost nonlithographic sequential process, which consists of aluminum (Al) sputtering, anodization of the Al layer and pore widening, without specific equipment and additional subsequent processes. The wetting properties of the fabricated surfaces were characterized by measuring the static CAs and the CAHs after plasma polymerized fluorocarbon coating with a low surface energy. The measured static CA and CAH were 154 ± 2.3° and 5.7 ± 0.8°, respectively, showing that the fabricated double-roughened surfaces exhibit superhydrophobic behaviors clearly. In addition, the proposed double-scaled surfaces at a wafer-level exhibited uniform superhydrophobic behaviors across the wafer with an apparent CA and CAH of 153.9 ± 0.8° and 4.9 ± 1.3°, respectively.

  14. Chemical kinetics modeling

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C.K.; Pitz, W.J. [Lawrence Livermore National Laboratory, CA (United States)

    1993-12-01

    This project emphasizes numerical modeling of chemical kinetics of combustion, including applications in both practical combustion systems and in controlled laboratory experiments. Elementary reaction rate parameters are combined into mechanisms which then describe the overall reaction of the fuels being studied. Detailed sensitivity analyses are used to identify those reaction rates and product species distributions to which the results are most sensitive and therefore warrant the greatest attention from other experimental and theoretical research programs. Experimental data from a variety of environments are combined together to validate the reaction mechanisms, including results from laminar flames, shock tubes, flow systems, detonations, and even internal combustion engines.

  15. Kinetics of Peptide Folding in Lipid Membranes

    Science.gov (United States)

    Oh, Kwang-Im; Smith-Dupont, Kathryn B.; Markiewicz, Beatrice N.; Gai, Feng

    2015-01-01

    Despite our extensive understanding of water-soluble protein folding kinetics, much less is known about the folding dynamics and mechanisms of membrane proteins. However, recent studies have shown that for relatively simple systems, such as peptides that form a transmembrane α-helix, helical dimer, or helix-turn-helix, it is possible to assess the kinetics of several important steps, including peptide binding to the membrane from aqueous solution, peptide folding on the membrane surface, helix insertion into the membrane, and helix-helix association inside the membrane. Herein, we provide a brief review of these studies and also suggest new initiation and probing methods that could lead to improved temporal and structural resolution in future experiments. PMID:25808575

  16. Kinetic Titration Series with Biolayer Interferometry

    Science.gov (United States)

    Frenzel, Daniel; Willbold, Dieter

    2014-01-01

    Biolayer interferometry is a method to analyze protein interactions in real-time. In this study, we illustrate the usefulness to quantitatively analyze high affinity protein ligand interactions employing a kinetic titration series for characterizing the interactions between two pairs of interaction patterns, in particular immunoglobulin G and protein G B1 as well as scFv IC16 and amyloid beta (1–42). Kinetic titration series are commonly used in surface plasmon resonance and involve sequential injections of analyte over a desired concentration range on a single ligand coated sensor chip without waiting for complete dissociation between the injections. We show that applying this method to biolayer interferometry is straightforward and i) circumvents problems in data evaluation caused by unavoidable sensor differences, ii) saves resources and iii) increases throughput if screening a multitude of different analyte/ligand combinations. PMID:25229647

  17. Thermodynamics, Kinetics and Microstructural Evolution during Nitrocarburising

    DEFF Research Database (Denmark)

    Somers, Marcel A.J.; Du, Hong

    2000-01-01

    The evolution of the phase distribution, the composition and the growth kinetics of the compound layer is described for nitrocarburising experiments at well defined combinations of nitriding and carburising potentials in the gaseous environment. Initially, the compound layer development is associ......The evolution of the phase distribution, the composition and the growth kinetics of the compound layer is described for nitrocarburising experiments at well defined combinations of nitriding and carburising potentials in the gaseous environment. Initially, the compound layer development...... for compound layers where epsilon carbonitride phase is the dominant phase and extends from the surface to the interface with the substrate. Both cementite and gamma' phase, with narrow composition ranges, reduce the growth rate. Modelling of the microstructure evolution during nitrocarburising is hindered...

  18. The Effect of Ytterbium-Doped Fiber Laser with Different Parameters on Physical Properties of Zirconia Surface.

    Science.gov (United States)

    Mutluay Unal, Server; Ozkir, Serhat Emre; Seyfioglu Polat, Zelal; Guven, Sedat; Asutay, Hilal

    2017-03-01

    Laser irradiation is an alternative surface treatment method for roughening zirconia surfaces. The aim of this study was to evaluate the effects of ytterbium-doped fiber laser (YbPL) on zirconia. Zirconia surfaces are resistant to many surface treatment methods, but surface roughness is crucial for adhesion of veneering materials and cements to zirconia. The zirconia discs were prepared and divided into four groups according to the power of the laser irradiation (5, 12, 17, and 20 W). These groups were divided into five subgroups according to the frequency (25, 40, 60, 80, and 100 kHz). Surface roughness values were measured with a noncontact profilometer, and the mean Ra values were calculated. Wettability was measured with a goniometer. The surface morphology was observed with a scanning electron microscope (SEM). The changes in the surface crystalline structure were analyzed with X-ray diffractometry. Ra values of all groups were higher than the control group. The highest surface roughness value was at 20 W and 100 kHz. Best wettability characteristic was observed at 5 W and 60 kHz. The correlations between Ra and wettability were low but significant. SEM examination of 5 W with different frequencies showed no microcracks, however, melted areas were observed. Remaining groups had microcracks and melted layers. A significantly lower T/M-phase transformation was observed in some groups. YbPL irradiation was effective at roughening the zirconia surface. Although laser treatment affected zirconia surfaces and provided surface roughness, the power and frequency should be adjusted to achieve optimum results.

  19. Chemical kinetics of gas reactions

    CERN Document Server

    Kondrat'Ev, V N

    2013-01-01

    Chemical Kinetics of Gas Reactions explores the advances in gas kinetics and thermal, photochemical, electrical discharge, and radiation chemical reactions. This book is composed of 10 chapters, and begins with the presentation of general kinetic rules for simple and complex chemical reactions. The next chapters deal with the experimental methods for evaluating chemical reaction mechanisms and some theories of elementary chemical processes. These topics are followed by discussions on certain class of chemical reactions, including unimolecular, bimolecular, and termolecular reactions. The rema

  20. Kinetics of coal pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Seery, D.J.; Freihaut, J.D.; Proscia, W.M. (United Technologies Research Center, East Hartford, CT (USA)); Howard, J.B.; Peters, W.; Hsu, J.; Hajaligol, M.; Sarofim, A. (Massachusetts Inst. of Tech., Cambridge, MA (USA)); Jenkins, R.; Mallin, J.; Espindola-Merin, B. (Pennsylvania State Univ., University Park, PA (USA)); Essenhigh, R.; Misra, M.K. (Ohio State Univ., Columbus, OH (USA))

    1989-07-01

    This report contains results of a coordinated, multi-laboratory investigation of coal devolatilization. Data is reported pertaining to the devolatilization for bituminous coals over three orders of magnitude in apparent heating rate (100 to 100,000 + {degree}C/sec), over two orders of magnitude in particle size (20 to 700 microns), final particle temperatures from 400 to 1600{degree}C, heat transfer modes ranging from convection to radiative, ambient pressure ranging from near vacuum to one atmosphere pressure. The heat transfer characteristics of the reactors are reported in detail. It is assumed the experimental results are to form the basis of a devolatilization data base. Empirical rate expressions are developed for each phase of devolatilization which, when coupled to an awareness of the heat transfer rate potential of a particular devolatilization reactor, indicate the kinetics emphasized by a particular system reactor plus coal sample. The analysis indicates the particular phase of devolatilization that will be emphasized by a particular reactor type and, thereby, the kinetic expressions appropriate to that devolatilization system. Engineering rate expressions are developed from the empirical rate expressions in the context of a fundamental understanding of coal devolatilization developed in the course of the investigation. 164 refs., 223 figs., 44 tabs.

  1. SURFACE PREPARATION OF STEEL SUBSTRATES USING GRIT-BLASTING

    Energy Technology Data Exchange (ETDEWEB)

    Donna Post Guillen; D. J. Varacalle, Jr.; D. Deason; W. Rhodaberger; E. Sampson

    2005-05-01

    The primary purpose of grit blasting for thermal spray applications is to ensure a strong mechanical bond between the substrate and the coating by the enhanced roughening of the substrate material. This study presents statistically designed experiments that were accomplished to investigate the effect of abrasives on roughness for A36/1020 steel. The experiments were conducted using a Box statistical design of experiment (SDE) approach. Three grit blasting parameters and their effect on the resultant substrate roughness were investigated. These include blast media, blast pressure, and working distance. The substrates were characterized for roughness using surface profilometry. These attributes were correlated with the changes in operating parameters. Twin-Wire Electric Arc (TWEA) coatings of aluminum and zinc/aluminum were deposited on the grit-blasted substrates. These coatings were then tested for bond strength. Bond strength studies were conducted utilizing a portable adhesion tester following ASTM standard D4541.

  2. Recent advances in the kinetics of oxygen reduction

    Energy Technology Data Exchange (ETDEWEB)

    Adzic, R.

    1996-07-01

    Oxygen reduction is considered an important electrocatalytic reaction; the most notable need remains improvement of the catalytic activity of existing metal electrocatalysts and development of new ones. A review is given of new advances in the understanding of reaction kinetics and improvements of the electrocatalytic properties of some surfaces, with focus on recent studies of relationship of the surface properties to its activity and reaction kinetics. The urgent need is to improve catalytic activity of Pt and synthesize new, possibly non- noble metal catalysts. New experimental techniques for obtaining new level of information include various {ital in situ} spectroscopies and scanning probes, some involving synchrotron radiation. 138 refs, 18 figs, 2 tabs.

  3. Adsorption analysis equilibria and kinetics

    CERN Document Server

    Do, Duong D

    1998-01-01

    This book covers topics of equilibria and kinetics of adsorption in porous media. Fundamental equilibria and kinetics are dealt with for homogeneous as well as heterogeneous particles. Five chapters of the book deal with equilibria and eight chapters deal with kinetics. Single component as well as multicomponent systems are discussed. In kinetics analysis, we deal with the various mass transport processes and their interactions inside a porous particle. Conventional approaches as well as the new approach using Maxwell-Stefan equations are presented. Various methods to measure diffusivity, such

  4. Kinetic behaviour of the adsorption and desorption of phosphorus-32 on aluminium hydroxide

    International Nuclear Information System (INIS)

    Ribeiro, E.M.G.

    1993-01-01

    Great amount of phosphate fertilizers are used in agriculture. Soil fertility have been studied using fertilizer labelled with phosphorus 32 to improve agronomic practices by increasing the efficient use of phosphate fertilizer. Previous research work have been published suggesting the potential use of kinetics parameters to characterize phosphorus in soil and to diagnosis the phosphate level. In this work the kinetic behaviour of the absorption and desorption of phosphorus-32 on a synthetic aluminium hydroxide was studied attempting to detect the formation of a precipitated phase on the hydroxide surface. The kinetic data for adsorption was adjusted with the Elovich and Fardeau equations for isotopic exchange. It was verified a change in the kinetic behaviour when the surface was approximately 80% saturated. This change suggested the formation of a precipitate. The kinetic data for desorption was fitted with the Fardeau equation, and it was verified the desorption kinetics slower than the desorption. (B.C.A.). 40 refs, 17 figs, 5 tabs

  5. Effect of surface roughness, chemical composition, and native oxide crystallinity on the orientation of self-assembled GaN nanowires on Ti foils

    Science.gov (United States)

    Calabrese, G.; Pettersen, S. V.; Pfüller, C.; Ramsteiner, M.; Grepstad, J. K.; Brandt, O.; Geelhaar, L.; Fernández-Garrido, S.

    2017-10-01

    We report on plasma-assisted molecular beam epitaxial growth of almost randomly oriented, uniformly tilted, and vertically aligned self-assembled GaN nanowires (NWs), respectively, on different types of polycrystalline Ti foils. The NW orientation with respect to the substrate normal, which is affected by an in situ treatment of the foil surface before NW growth, depends on the crystallinity of the native oxide. Direct growth on the as-received foils results in the formation of ensembles of nearly randomly oriented NWs due to the strong roughening of the surface induced by chemical reactions between the impinging elements and Ti. Surface nitridation preceding the NW growth is found to reduce this roughening by transformation of the uppermost layers into TiN and TiO x N y species. These compounds are more stable against chemical reactions and facilitate the growth of uniformly oriented GaN NW ensembles on the surface of the individual grains of the polycrystalline Ti foils. If an amorphous oxide layer is present at the foil surface, vertically oriented NWs are obtained all across the substrate because this layer blocks the transfering of the epitaxial information from the underlying grains. The control of NW orientation and the understanding behind the achievement of vertically oriented NWs obtained in this study represent an important step towards the realization of GaN NW-based bendable devices on polycrystalline metal foils.

  6. Kinetics of Social Contagion

    Science.gov (United States)

    Ruan, Zhongyuan; Iñiguez, Gerardo; Karsai, Márton; Kertész, János

    2015-11-01

    Diffusion of information, behavioral patterns or innovations follows diverse pathways depending on a number of conditions, including the structure of the underlying social network, the sensitivity to peer pressure and the influence of media. Here we study analytically and by simulations a general model that incorporates threshold mechanism capturing sensitivity to peer pressure, the effect of "immune" nodes who never adopt, and a perpetual flow of external information. While any constant, nonzero rate of dynamically introduced spontaneous adopters leads to global spreading, the kinetics by which the asymptotic state is approached shows rich behavior. In particular, we find that, as a function of the immune node density, there is a transition from fast to slow spreading governed by entirely different mechanisms. This transition happens below the percolation threshold of network fragmentation, and has its origin in the competition between cascading behavior induced by adopters and blocking due to immune nodes. This change is accompanied by a percolation transition of the induced clusters.

  7. Fabrication of hierarchically structured superhydrophobic PDMS surfaces by Cu and CuO casting

    Science.gov (United States)

    Migliaccio, Christopher P.; Lazarus, Nathan

    2015-10-01

    Poly(dimethylsiloxane) (PDMS) films decorated with hierarchically structured pillars are cast from large area copper and copper oxide negative molds. The molds are fabricated using a single patterning step and electroplating. The process of casting structured PDMS films is simpler and cheaper than alternatives based on deep reactive ion etching or laser roughening of bulk silicone. Texture imparted to the pillars from the mold walls renders the PDMS films superhydrophobic, with the contact angle/hysteresis of the most non-wetting surfaces measuring 164°/9° and 158°/10° for surfaces with and without application of a low surface energy coating. The usefulness of patterned PDMS films as a "self-cleaning" solar cell module covering is demonstrated and other applications are discussed.

  8. Thermodynamics, kinetics and process control of nitriding

    DEFF Research Database (Denmark)

    Mittemeijer, Eric J.; Somers, Marcel A. J.

    1999-01-01

    As a prerequisite for predictability of properties obtained by a nitriding treatment of iron-based workpieces, the relation between the process parameters and the composition and structure of the surface layer produced must be known. At present (even) the description of thermodynamic equilibrium ...... been presented. The necessary background has been given for process control of gaseous nitriding, by monitoring the partial pressure of oxygen in the furnace, utilising a solid state electrolyte.......As a prerequisite for predictability of properties obtained by a nitriding treatment of iron-based workpieces, the relation between the process parameters and the composition and structure of the surface layer produced must be known. At present (even) the description of thermodynamic equilibrium......, the nitriding result is determined largely by the kinetics of the process. The nitriding kinetics have been shown to be characterised by the occurring local near-equilibria and stationary states at surfaces and interfaces, and the diffusion coefficient of nitrogen in the various phases, for which new data have...

  9. Surface science an introduction

    CERN Document Server

    Hudson, John

    1991-01-01

    The whole field of surface science is covered in this work. Starting with a description of the structure and thermodynamics of clean surfaces, the book goes on to discuss kinetic theory of gases and molecular beam formation. This is followed by a largesection on gas-surface interactions, and another major section on energetic particle-surface interactions. The final chapter provides the background to crystal nucleation and growth. The approach adopted is interdisciplinary and slanted towards theexperimental side, with practical analytical techniques being used to illustrate general princi

  10. Dimensional enhancement of kinetic energies

    DEFF Research Database (Denmark)

    Schleich, W.P.; Dahl, Jens Peder

    2002-01-01

    Simple thermodynamics considers kinetic energy to be an extensive variable which is proportional to the number N of particles. We present a quantum state of N noninteracting particles for which the kinetic energy increases quadratically with N. This enhancement effect is tied to the quantum...

  11. Evolution of Enzyme Kinetic Mechanisms.

    Science.gov (United States)

    Ulusu, Nuriye Nuray

    2015-06-01

    This review paper discusses the reciprocal kinetic behaviours of enzymes and the evolution of structure-function dichotomy. Kinetic mechanisms have evolved in response to alterations in ecological and metabolic conditions. The kinetic mechanisms of single-substrate mono-substrate enzyme reactions are easier to understand and much simpler than those of bi-bi substrate enzyme reactions. The increasing complexities of kinetic mechanisms, as well as the increasing number of enzyme subunits, can be used to shed light on the evolution of kinetic mechanisms. Enzymes with heterogeneous kinetic mechanisms attempt to achieve specific products to subsist. In many organisms, kinetic mechanisms have evolved to aid survival in response to changing environmental factors. Enzyme promiscuity is defined as adaptation to changing environmental conditions, such as the introduction of a toxin or a new carbon source. Enzyme promiscuity is defined as adaptation to changing environmental conditions, such as the introduction of a toxin or a new carbon source. Enzymes with broad substrate specificity and promiscuous properties are believed to be more evolved than single-substrate enzymes. This group of enzymes can adapt to changing environmental substrate conditions and adjust catalysing mechanisms according to the substrate's properties, and their kinetic mechanisms have evolved in response to substrate variability.

  12. Calcium kinetics in parathyroid disease

    International Nuclear Information System (INIS)

    Dymling, J.F.

    1964-01-01

    This paper reports a study of calcium kinetics in twelve cases of parathyroid disease. The data suggest that hyperparathyroidism usually causes increased bone turnover. The study of calcium kinetics may be a valuable tool in the differential diagnosis of primary hyperparathyroidism and in evaluating treatment of secondary hyperparathyroidism. The bone turnover in one case of hypoparathyroidism was extremely low. 1 fig., 1 tab

  13. Effects of Surface Roughness, Oxidation, and Temperature on the Emissivity of Reactor Pressure Vessel Alloys

    Energy Technology Data Exchange (ETDEWEB)

    King, J. L. [University of Wisconsin–Madison, Department of Engineering Physics, Madison, Wisconsin; Jo, H. [University of Wisconsin–Madison, Department of Engineering Physics, Madison, Wisconsin; Tirawat, R. [National Renewable Energy Laboratory, Concentrating Solar Power Group, Golden, Colorado; Blomstrand, K. [University of Wisconsin–Madison, Department of Engineering Physics, Madison, Wisconsin; Sridharan, K. [University of Wisconsin–Madison, Department of Engineering Physics, Madison, Wisconsin

    2017-08-31

    Thermal radiation will be an important mode of heat transfer in future high-temperature reactors and in off-normal high-temperature scenarios in present reactors. In this work, spectral directional emissivities of two reactor pressure vessel (RPV) candidate materials were measured at room temperature after exposure to high-temperature air. In the case of SA508 steel, significant increases in emissivity were observed due to oxidation. In the case of Grade 91 steel, only very small increases were observed under the tested conditions. Effects of roughness were also investigated. To study the effects of roughening, unexposed samples of SA508 and Grade 91 steel were roughened via one of either grinding or shot-peening before being measured. Significant increases were observed only in samples having roughness exceeding the roughness expected of RPV surfaces. While the emissivity increases for SA508 from oxidation were indeed significant, the measured emissivity coefficients were below that of values commonly used in heat transfer models. Based on the observed experimental data, recommendations for emissivity inputs for heat transfer simulations are provided.

  14. Kinetics of Bio-Reactions

    DEFF Research Database (Denmark)

    Villadsen, John

    2015-01-01

    . The models can be used in mass balances for design of processes under process conditions not yet studied experimentally. The value of the predictive kinetic model depends on the quality of the experimental data on which the model is based, and well-founded kinetic models for enzyme reactions have...... a considerable predictive power. This is also true for cell reaction models, when the model is used in its proper context. The chapter first discusses the kinetics for enzymatically catalyzed reactions (“enzyme reactions”). The kinetics can be derived from a mechanistic model. Then, the chapter derives empirical......his chapter predicts the specific rates of reaction by means of a mathematical expression, the kinetics of the reaction. This expression can be derived through a mechanistic interpretation of an enzymatically catalyzed reaction, but it is essentially of empirical nature for cell reactions...

  15. Evaluation of kinetic energy in flowing rivers

    Energy Technology Data Exchange (ETDEWEB)

    Faure, T. [National Research Council of Canada, Ottawa, ON (Canada). Canadian Hydraulics Centre

    2008-07-01

    New methods of evaluating the kinetic energy in rivers were discussed. Developed by the National Research Council's Canadian Hydraulics Centre, the numerical models were designed to generate hydrographs of river flow from dams; accommodate power density anomalies caused by the presence of islands in a river; and assess mean kinetic power rates. This presentation provided details of a simulation of 6 turbines located in close proximity to each other. The model was used to calculate velocity fields downstream of the turbines as well as changes in water surface elevation due to power production by the 6 75 kW turbines. Turbine power extraction and kinetic power in the upstream cross-section was assessed. The model showed that the turbines extracted 9 per cent of the river's 17,000 kW of estimated energy potential. The turbines were modelled by considering the porosity of the numerical elements at the location of the turbine and extracting known quantities of energy from the flow. The model was also used to calculate new hydrodynamics of the whole region with the turbines in place by assuming that energy was extracted over the entire depth of the location. The presentation included detailed charts of rivers modelled during the study. tabs., figs.

  16. Kinetic distance and kinetic maps from molecular dynamics simulation.

    Science.gov (United States)

    Noé, Frank; Clementi, Cecilia

    2015-10-13

    Characterizing macromolecular kinetics from molecular dynamics (MD) simulations requires a distance metric that can distinguish slowly interconverting states. Here, we build upon diffusion map theory and define a kinetic distance metric for irreducible Markov processes that quantifies how slowly molecular conformations interconvert. The kinetic distance can be computed given a model that approximates the eigenvalues and eigenvectors (reaction coordinates) of the MD Markov operator. Here, we employ the time-lagged independent component analysis (TICA). The TICA components can be scaled to provide a kinetic map in which the Euclidean distance corresponds to the kinetic distance. As a result, the question of how many TICA dimensions should be kept in a dimensionality reduction approach becomes obsolete, and one parameter less needs to be specified in the kinetic model construction. We demonstrate the approach using TICA and Markov state model (MSM) analyses for illustrative models, protein conformation dynamics in bovine pancreatic trypsin inhibitor and protein-inhibitor association in trypsin and benzamidine. We find that the total kinetic variance (TKV) is an excellent indicator of model quality and can be used to rank different input feature sets.

  17. Extending the throughput of Biacore 4000 biosensor to accelerate kinetic analysis of antibody-antigen interaction.

    Science.gov (United States)

    Kamat, Vishal; Rafique, Ashique

    2017-08-01

    The surface plasmon resonance (SPR) biosensors are being routinely used in different stages of drug discovery and development. However, the lack of high throughput SPR biosensors continues to be a primary bottleneck for the rapid kinetic screening of large panels of monoclonal antibodies (mAbs). To further increase the throughput of the Biacore 4000 biosensor, we have developed three kinetic screening assays to characterize mAb-antigen interactions - (i) 16-mAb capture kinetic, (ii) single cycle kinetic (SCK), and (iii) parallel kinetic (PK). The performance of all three kinetic assays was evaluated by characterizing the binding of kinetically diverse human mAbs to four antigens with molecular weights of 14kD, 29kD, 38kD, and 48kD and binding affinities ranging from 130pM to 200 nM. The binding rate constants measured using all three kinetic assays were reproducible across multiple experiments and correlated with the values generated using the conventional 8-mAb capture kinetic assay on the Biacore 4000 (R 2  > 0.94). Moreover, the 16-mAb capture assay decreased experiment time and analyte consumption by 35% and 50%, respectively. This work illustrates the significance of the 16-mAb capture kinetic, SCK, and PK assays to increase the throughput of Biacore 4000 and to support rapid kinetic screening of mAbs. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

  18. Size dependence of adsorption kinetics of nano-MgO: a theoretical and experimental study

    International Nuclear Information System (INIS)

    Wang, Shuting; Wen, Yanzhen; Cui, Zixiang; Xue, Yongqiang

    2016-01-01

    Nanoparticles present tremendous differences in adsorption kinetics compared with corresponding bulk particles which have great influences on the applications of nanoparticles. A size-dependent adsorption kinetic theory was proposed, the relations between adsorption kinetic parameters, respectively, and particle size of nano-adsorbent were derived theoretically, and the influence mechanism of particle size on the adsorption kinetic parameters was discussed. In experiment, nanoscale magnesium oxide (nano-MgO) with different diameters between 11.5 and 41.4 nm with narrow size distribution and low agglomeration were prepared, and the kinetic parameters of adsorption of benzene on nano-MgO in aqueous solution were obtained. Then the influence regularities of the particle size on the adsorption kinetic parameters were obtained. The experimental results are consistent with the nano-adsorption kinetic theory. With particle size decreasing, the adsorption rate constant increases; the adsorption activation energy and the adsorption pre-exponential factor decrease. Furthermore, the logarithm of adsorption rate constant, the adsorption activation energy, and the logarithm of adsorption pre-exponential factor are linearly related to the reciprocal of particle diameter, respectively. The mechanism of particle size influence on the kinetic parameters is that the activation energy is influenced by the molar surface enthalpy of nano-adsorbent, the pre-exponential factor by the molar surface entropy, and the rate constant by both the molar surface enthalpy and the molar surface entropy

  19. Simplified kinetic models of methanol oxidation on silver

    DEFF Research Database (Denmark)

    Andreasen, A.; Lynggaard, H.; Stegelmann, C.

    2005-01-01

    Recently the authors developed a microkinetic model of methanol oxidation on silver [A. Andreasen, H. Lynggaard, C. Stegelmann, P. Stoltze, Surf. Sci. 544 (2003) 5-23]. The model successfully explains both surface science experiments and kinetic experiments at industrial conditions applying...

  20. Kinetics and mechanism of soot formation in hydrocarbon combustion

    Science.gov (United States)

    Frenklach, Michael

    1990-01-01

    The focus of this work was on kinetic modeling. The specific objectives were: detailed modeling of soot formation in premixed flames, elucidation of the effects of fuel structure on the pathway to soot, and the development of a numerical technique for accurate modeling of soot particle coagulation and surface growth. Those tasks were successfully completed and are briefly summarized.

  1. On grain growth kinetics in two-phase polycrystalline materials ...

    Indian Academy of Sciences (India)

    Monte Carlo Potts model simulation was carried out on a 2D square lattice for various surface fractions of second phase particles for over 50,000 iterations. The observations are in good agreement with known theoretical and experimental results with respect to both growth kinetics as well as grain size distribution. Further ...

  2. Simplified kinetic models of methanol oxidation on silver

    DEFF Research Database (Denmark)

    Andreasen, Anders; Lynggaard, Hasse Harloff; Stegelmann, Carsten

    2005-01-01

    Recently the authors developed a microkinetic model of methanol oxidation on silver [A. Andreasen, H. Lynggaard, C. Stegelmann, P. Stoltze, Surf. Sci. 544 (2003) 5–23]. The model successfully explains both surface science experiments and kinetic experiments at industrial conditions applying...

  3. Catalyst dynamics: consequences for classical kinetic descriptions of reactors

    DEFF Research Database (Denmark)

    Johannessen, Tue; Larsen, Jane Hvolbæk; Chorkendorff, Ib

    2001-01-01

    in situ studies and surface science investigations has brought added attention to the fact that catalysts may behave in a dynamic manner and reconstruct depending on the reaction conditions. This feature severely limits traditional kinetic descriptions. In the present paper, we present examples...

  4. Energetic Mapping of Ni Catalysts by Detailed Kinetic Modeling

    DEFF Research Database (Denmark)

    Bjørgum, Erlend; Chen, De; Bakken, Mari G.

    2005-01-01

    precursor seems to result in more steplike sites, kinks, and defects for carbon monoxide dissociation. A detailed kinetic modeling of the TPO results based on elementary reaction steps has been conducted to give an energetic map of supported Ni catalysts. Experimental results from the ideal Ni surface fit...

  5. Reconstruction of Cell Surface Densities of Ion Pumps, Exchangers, and Channels from mRNA Expression, Conductance Kinetics, Whole-Cell Calcium, and Current-Clamp Voltage Recordings, with an Application to Human Uterine Smooth Muscle Cells.

    Directory of Open Access Journals (Sweden)

    Jolene Atia

    2016-04-01

    Full Text Available Uterine smooth muscle cells remain quiescent throughout most of gestation, only generating spontaneous action potentials immediately prior to, and during, labor. This study presents a method that combines transcriptomics with biophysical recordings to characterise the conductance repertoire of these cells, the 'conductance repertoire' being the total complement of ion channels and transporters expressed by an electrically active cell. Transcriptomic analysis provides a set of potential electrogenic entities, of which the conductance repertoire is a subset. Each entity within the conductance repertoire was modeled independently and its gating parameter values were fixed using the available biophysical data. The only remaining free parameters were the surface densities for each entity. We characterise the space of combinations of surface densities (density vectors consistent with experimentally observed membrane potential and calcium waveforms. This yields insights on the functional redundancy of the system as well as its behavioral versatility. Our approach couples high-throughput transcriptomic data with physiological behaviors in health and disease, and provides a formal method to link genotype to phenotype in excitable systems. We accurately predict current densities and chart functional redundancy. For example, we find that to evoke the observed voltage waveform, the BK channel is functionally redundant whereas hERG is essential. Furthermore, our analysis suggests that activation of calcium-activated chloride conductances by intracellular calcium release is the key factor underlying spontaneous depolarisations.

  6. Kinetics of Levoglucosenone Isomerization.

    Science.gov (United States)

    Krishna, Siddarth H; Walker, Theodore W; Dumesic, James A; Huber, George W

    2017-01-10

    We studied the acid-catalyzed isomerization of levoglucosenone (LGO) to 5-hydroxymethylfurfural (HMF) and developed a reaction kinetics model that describes the experimental data across a range of conditions (100-150 °C, 50-100 mm H 2 SO 4 , 50-150 mm LGO). LGO and its hydrated derivative exist in equilibrium under these reaction conditions. Thermal and catalytic degradation of HMF are the major sources of carbon loss. Within the range of conditions studied, higher temperatures and shorter reaction times favor the production of HMF. The yields of HMF and levulinic acid decrease monotonically as tetrahydrofuran is added to the aqueous solvent system, indicating that water plays a role in the LGO isomerization reaction. Initial-rate analyses show that HMF is produced solely from LGO rather than from the hydrated derivative of LGO. The results of this study are consistent with a mechanism for LGO isomerization that proceeds through hydration of the anhydro bridge, followed by ring rearrangement analogous to the isomerization of glucose to fructose. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Kinetics of thyroid hormones

    International Nuclear Information System (INIS)

    Inada, Mitsuo; Nishikawa, Mitsushige; Naito, Kimikazu; Ishii, Hitoshi; Tanaka, Kiyoshi

    1980-01-01

    Kinetics of thyroid hormones were outlined, and recent progress in metabolism of these hormones was also described. Recently, not only T 4 and T 3 but also rT 3 , 3,3'-T 2 , 3',5'-T 2 , and 3,5-T 2 can be measured by RIA. To clarify metabolic pathways of these hormones, metabolic clearance rate and production rate of these hormones were calculated. As single-compartment analysis was insufficient to clarify disappearance curves of thyroid hormones in blood such as T 3 and T 2 of which metabolic speed was so fast, multi-compartment analysis or non-compartment analysis were also performed. Thyroid hormones seemed to be measured more precisely by constant infusion method. At the first step of T 4 metabolism, T 3 was formed by 5'-monodeiodination of T 4 , and rT 3 was formed by 5-monodeiodination of T 4 . As metabolic pathways of T 3 and rT 3 , conversion of them to 3,3'-T 2 or to 3',5'-T 2 and 3,5-T 2 was supposed. This subject will be an interesting research theme in future. (Tsunoda, M.)

  8. Kinetics of the sorption of triterpene saponin by hypercrosslinked polystyrene

    Science.gov (United States)

    Mironenko, N. V.; Brezhneva, T. A.; Selemenev, V. F.

    2013-03-01

    The kinetics of sorption of triterpene saponin by the polymer sorbent NM-200 is considered. The influence of the surface activity of glycoside on the rate of formation and structure of the adsorption layer on the sorbent's surface is established. The rate-determining step of sorption is found to be diffusion into the sorbent grain. The value of the activation energy demonstrates the determining role of dispersion forces in the interaction between triterpene saponin and the polymer sorbent MN-200.

  9. High-temperature spreading kinetics of metals

    Energy Technology Data Exchange (ETDEWEB)

    Rauch, N.

    2005-05-15

    In this PhD work a drop transfer setup combined with high speed photography has been used to analyze the spreading of Ag on polished polycrystalline Mo and single crystalline Mo (110) and (100) substrates. The objective of this work was to unveil the basic phenomena controlling spreading in metal-metal systems. The observed spreading kinetics were compared with current theories of low and high temperature spreading such as a molecular kinetic model and a fluid flow model. Analyses of the data reveal that the molecular model does describe the fastest velocity data well for all the investigated systems. Therefore, the energy which is dissipated during the spreading process is a dissipation at the triple line rather than dissipation due to the viscosity in the liquid. A comparison of the determined free activation energy for wetting of {delta}G95{approx}145kJ/mol with literature values allows the statement that the rate determining step seems to be a surface diffusion of the Ag atoms along the triple line. In order to investigate possible ridge formation, due to local atomic diffusion of atoms of the substrate at the triple during the spreading process, grooving experiments of the polycrystalline Mo were performed to calculate the surface diffusities that will control ridge evolution. The analyses of this work showed that a ridge formation at the fastest reported wetting velocities was not possible if there is no initial perturbation for a ridge. If there was an initial perturbation for a ridge the ridge had to be much smaller than 1 nm in order to be able to move with the liquid font. Therefore ridge formation does not influence the spreading kinetics for the studied system and the chosen conditions. SEM, AFM and TEM investigations of the triple line showed that ridge formation does also not occur at the end of the wetting experiment when the drop is close to equilibrium and the wetting velocity is slow. (orig.)

  10. On the relationships between Michaelis-Menten kinetics, reverse Michaelis-Menten kinetics, Equilibrium Chemistry Approximation kinetics and quadratic kinetics

    Science.gov (United States)

    Tang, J. Y.

    2015-09-01

    The Michaelis-Menten kinetics and the reverse Michaelis-Menten kinetics are two popular mathematical formulations used in many land biogeochemical models to describe how microbes and plants would respond to changes in substrate abundance. However, the criteria of when to use which of the two are often ambiguous. Here I show that these two kinetics are special approximations to the Equilibrium Chemistry Approximation kinetics, which is the first order approximation to the quadratic kinetics that solves the equation of enzyme-substrate complex exactly for a single enzyme single substrate biogeochemical reaction with the law of mass action and the assumption of quasi-steady-state for the enzyme-substrate complex and that the product genesis from enzyme-substrate complex is much slower than the equilibration between enzyme-substrate complexes, substrates and enzymes. In particular, I showed that the derivation of the Michaelis-Menten kinetics does not consider the mass balance constraint of the substrate, and the reverse Michaelis-Menten kinetics does not consider the mass balance constraint of the enzyme, whereas both of these constraints are taken into account in the Equilibrium Chemistry Approximation kinetics. By benchmarking against predictions from the quadratic kinetics for a wide range of substrate and enzyme concentrations, the Michaelis-Menten kinetics was found to persistently under-predict the normalized sensitivity ∂ ln v / ∂ ln k2+ of the reaction velocity v with respect to the maximum product genesis rate k2+, persistently over-predict the normalized sensitivity ∂ ln v / ∂ ln k1+ of v with respect to the intrinsic substrate affinity k1+, persistently over-predict the normalized sensitivity ∂ ln v / ∂ ln [ E ]T of v with respect the total enzyme concentration [ E ]T and persistently under-predict the normalized sensitivity ∂ ln v / ∂ ln [ S ]T of v with respect to the total substrate concentration [ S ]T. Meanwhile, the reverse Michaelis

  11. Effect of surfactant on kinetics of thinning of capillary bridges

    Science.gov (United States)

    Nowak, Emilia; Kovalchuk, Nina; Simmons, Mark

    2015-11-01

    Kinetics of thinning of capillary bridges is of great scientific and industrial interest being of vital importance for example in various emulsification and microfluidic processes. It is well known that the rate of bridge thinning is proportional to the interfacial tension. Therefore it is expected that the process should slow down by addition of surfactant. The kinetics of capillary bridges in the presence of surfactant was studied by the dripping of liquid from a capillary tip under conditions of nearly zero flow rate (We personal care products. The viscosity, surfactant activity and adsorption kinetics have been controlled by addition of glycerol and sodium chloride. The study has shown that the kinetics of capillary bridges are determined by dynamic surface tension rather than by its equilibrium value. In particular, the kinetics of the bridge thinning for the 0.1 g L-1 aqueous SLES solution is practically the same as that of pure water despite twice lower equilibrium surface tension. EPSRC Programme Grant, MEMPHIS, EP/K0039761/1.

  12. Effect of system variables involved in packed column SFC of nevirapine as model analyte using response surface methodology: application to retention thermodynamics, solute transfer kinetic study and binary diffusion coefficient determination.

    Science.gov (United States)

    Kaul, Neerej; Agrawal, Himani; Paradkar, A R; Mahadik, K R

    2005-08-31

    A multifactor optimization technique is successfully applied to study the effect of simultaneously varying the system variables on feasibility of nevirapine analysis by packed column supercritical fluid chromatography (PC-SFC). The optimal conditions were determined with the aid of the response surface methodology using 3(3) factorial designs. The method is based on methanol-modified carbon dioxide as the mobile phase at flow rate of 3.0 ml/min with elution through a JASCO Finepak SIL-5, [C18 (5-micron, 25 cm x 4.6 mm, i.d.)] column using photodiode array detection. The method has been successfully used to analyze commercial solid dosage form to assess the chromatographic performance of SFC system. The present work briefs the thermodynamic applications of PC-SFC with an emphasis on the results of nevirapine. The foremost of such applications is the determination of solute diffusion coefficient in supercritical mobile phase by Taylor-Aris peak broadening technique.

  13. Toluene and benzyl decomposition mechanisms: elementary reactions and kinetic simulations.

    Science.gov (United States)

    Derudi, Marco; Polino, Daniela; Cavallotti, Carlo

    2011-12-28

    The high temperature decomposition kinetics of toluene and benzyl were investigated by combining a kinetic analysis with the ab initio/master equation study of new reaction channels. It was found that similarly to toluene, which decomposes to benzyl and phenyl losing atomic hydrogen and methyl, also benzyl decomposition proceeds through two channels with similar products. The first leads to the formation of fulvenallene and hydrogen and has already been investigated in detail in recent publications. In this work it is proposed that benzyl can decompose also through a second decomposition channel to form benzyne and methyl. The channel specific kinetic constants of benzyl decomposition were determined by integrating the RRKM/master equation over the C(7)H(7) potential energy surface. The energies of wells and saddle points were determined at the CCSD(T) level on B3LYP/6-31+G(d,p) structures. A kinetic mechanism was then formulated, which comprises the benzyl and toluene decomposition reactions together with a recently proposed fulvenallene decomposition mechanism, the decomposition kinetics of the fulvenallenyl radical, and some reactions describing the secondary chemistry originated by the decomposition products. The kinetic mechanism so obtained was used to simulate the production of H atoms measured in a wide pressure and temperature range using different experimental setups. The calculated and experimental data are in good agreement. Kinetic constants of the new reaction channels here examined are reported as a function of temperature at different pressures. The mechanism here proposed is not compatible with the assumption often used in literature kinetic mechanisms that benzyl decomposition can be effectively described through a lumped reaction whose products are the cyclopentadienyl radical and acetylene.

  14. Kinetics of laser irradiated nanoparticles cloud

    Science.gov (United States)

    Mishra, S. K.; Upadhyay Kahaly, M.; Misra, Shikha

    2018-02-01

    A comprehensive kinetic model describing the complex kinetics of a laser irradiated nanoparticle ensemble has been developed. The absorbed laser radiation here serves dual purpose, viz., photoenhanced thermionic emission via rise in its temperature and direct photoemission of electrons. On the basis of mean charge theory along with the equations for particle (electron) and energy flux balance over the nanoparticles, the transient processes of charge/temperature evolution over its surface and mass diminution on account of the sublimation (phase change) process have been elucidated. Using this formulation phenomenon of nanoparticle charging, its temperature rise to the sublimation point, mass ablation, and cloud disintegration have been investigated; afterwards, typical timescales of disintegration, sublimation and complete evaporation in reference to a graphite nanoparticle cloud (as an illustrative case) have been parametrically investigated. Based on a numerical analysis, an adequate parameter space describing the nanoparticle operation below the sublimation temperature, in terms of laser intensity, wavelength and nanoparticle material work function, has been identified. The cloud disintegration is found to be sensitive to the nanoparticle charging through photoemission; as a consequence, it illustrates that radiation operating below the photoemission threshold causes disintegration in the phase change state, while above the threshold, it occurs with the onset of surface heating.

  15. Gas Kinetics of Traffic Jam

    Science.gov (United States)

    Nagatani, Takashi

    1997-04-01

    The kinetics of one-dimensional traffic flow is descibed in terms of Boltzmann-like gas kinetic equation. Paveri-Fontana's gas kinetic equation is modified to take into account the desired velocity depending on the car density. A discrete version of the gas kinetic equation is derived to numerically solve the equation. The velocity distributions are calculated by a numerical method. It is found that the traffic jam is formed in the congested traffic flow when the car density is higher than the critical value. The traffic jam propagates backward, its propagation velocity increases with the accerelation and the density within the jam decreases with increasing accerelation. It is shown that the velocity distributions change significantly before and after the traffic jam.

  16. Cell kinetics and therapeutic efficiency

    International Nuclear Information System (INIS)

    Andreeff, M.; Abenhardt, W.; Gruner, B.; Stoffner, D.; Mainz Univ.

    1976-01-01

    The study shows that cell kinetics effects correlate with the effects of cytostatic drugs in the tumour model investigated here. It should, however, be noted that even genetically related tumour cell types may react differently to the same cytostatic drug, and that the cell kinetics effects, due to the changes in the cell cycle, cannot be predicted but should be followed with a very fast method, e.g. sequential flan fluorescence cytophotometry, for optimal therapeutic results. (orig./GSE) [de

  17. Hydrophobic and hydrophilic surface nano-modification of PET fabric by plasma process.

    Science.gov (United States)

    Paosawatyanyong, B; Kamlangkla, K; Hodak, S K

    2010-11-01

    Polyethylene terephthalate (PET) fabrics were treated by radio frequency inductively coupled plasma (RF-ICP) to modify their hydrophobic and hydrophilic properties. Types of gases which were SF6, O2, N2 and Ar, treatment time, pressure and RF power were varied systematically. The water droplet contact angle measurements showed that, treating with SF6 plasma would result in the increase of hydrophobicity of PET samples while treating with O2, N2 and Ar plasmas would yield hydrophilic properties. In both hydrophobic and hydrophilic cases, the surface morphology of PET fibers was roughened after exposed to plasma. Hence, it is not obvious that these surface roughness induced by plasma is sufficient to yield the increase in hydrophobicity by the well known lotus effect.

  18. Surface exchange kinetics and chemical diffusivities of BaZr{sub 0.2}Ce{sub 0.65}Y{sub 0.15}O{sub 3−δ} by electrical conductivity relaxation

    Energy Technology Data Exchange (ETDEWEB)

    Lim, Dae-Kwang; Jeon, Sang-Yun; Singh, Bhupendra [Ionics Lab, School of Materials Science and Engineering, Chonnam National University, 77 Yongbong-ro, Buk-gu, Gwang-Ju 500-757 (Korea, Republic of); Park, Jun-Young [Department of Advanced Materials Engineering, Sejong University, Seoul 143-747 (Korea, Republic of); Song, Sun-Ju, E-mail: song@chonnam.ac.kr [Ionics Lab, School of Materials Science and Engineering, Chonnam National University, 77 Yongbong-ro, Buk-gu, Gwang-Ju 500-757 (Korea, Republic of)

    2014-10-15

    Highlights: • Electrical conductivity relaxation in BaCe{sub 0.65}Zr{sub 0.2}Y{sub 0.15}O{sub 3−δ} was monitored. • Monotonic relaxation behavior was observed during oxidation/reduction. • Nonmonotonic twofold relaxation behavior was observed during hydration/dehydration. • Surface exchange coefficients and diffusivities of O and H were calculated. - Abstract: Perovskite-type oxide BaCe{sub 0.65}Zr{sub 0.2}Y{sub 0.15}O{sub 3−δ} (BCZY2015) was synthesized by a solid state reaction method. BCZY2015 samples were characterized by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). The time dependent variation in electrical conductivity of BCZY2015 was monitored during the oxidation/reduction in oxygen partial pressure (pO{sub 2}) range of −2.28 ⩽ log (pO{sub 2}/atm) ⩽ −0.68 at a fixed water vapor pressure (pH{sub 2}O), and during the hydration/dehydration in −3.15 ⩽ log (pH{sub 2}O/atm) ⩽ −2.35 range in air. The electrical conductivity showed a monotonic relaxation behavior by the ambipolar diffusion of V{sub o}{sup ··} and OH{sub o}{sup ·} during the oxidation/reduction and the relaxation process was governed by the diffusivity of oxygen (D-tilde{sub vO}). On the other hand, during the hydration/dehydration process, a non-monotonic twofold relaxation behavior was observed due to the decoupled diffusion of H and O components with the mediation of holes, and the conductivity relaxation process was governed by the diffusivities of both H (D-tilde{sub iH}) and O (D-tlde{sub vH}). The values of surface exchange coefficients and diffusivities of oxygen and hydrogen were calculated from Fick’s second law by the nonlinear least squares fitting of the conductivity data, as proposed by Yoo et al. (2008)

  19. Bioaccumulation of the synthetic dye Basic Violet 3 and heavy metals in single and binary systems by Candida tropicalis grown in a sugarcane bagasse extract medium: Modelling optimal conditions using response surface methodology (RSM) and inhibition kinetics

    International Nuclear Information System (INIS)

    Das, Devlina; Charumathi, D.; Das, Nilanjana

    2011-01-01

    Single and binary effects of dye Basic Violet 3 and heavy metals, 'namely', Pb(II) and Cd(II), were investigated for their role in dye and heavy metal bioaccumulation by Candida tropicalis that was grown in a sugarcane bagasse extract medium containing 8 g/L, 16 g/L or 24 g/L of sugar. The optimum pH was found to be 4.0 in the single system and 5.0 in the binary system. A central composite design was successfully used to analyse the experimental results. Four numerical correlations that were fitted to a second order quadratic equation were used to estimate optimum combinations predicted by response surface methodology. In the dye-Pb(II) binary system, C. tropicalis was capable of bioaccumulating 49.5% of the dye and 49.6% of the Pb(II), in comparison to 15.9% of the dye and 55.5% of the Cd(II) in the dye-Cd(II) binary system. In these two systems, the pollutants were dispersed at minimum working concentration levels. Competitive inhibition was observed in both the single and binary systems, which was suggested by an increase in the saturation constant, K s , and a simultaneous decrease in the specific growth rate that was calculated from Lineweaver-Burk plots. Atomic force microscopy images demonstrated changes in yeast cell morphology by exposure to these contaminants in the dye-Pb(II) binary system grown in a bioaccumulation medium.

  20. Kinetics of biofilm formation and desiccation survival of Listeria monocytogenes in single and dual species biofilms with Pseudomonas fluorescens, Serratia proteamaculans or Shewanella baltica on food-grade stainless steel surfaces.

    Science.gov (United States)

    Daneshvar Alavi, Hessam Edin; Truelstrup Hansen, Lisbeth

    2013-01-01

    This study investigated the dynamics of static biofilm formation (100% RH, 15 °C, 48-72 h) and desiccation survival (43% RH, 15 °C, 21 days) of Listeria monocytogenes, in dual species biofilms with the common spoilage bacteria, Pseudomonas fluorescens, Serratia proteamaculans and Shewanella baltica, on the surface of food grade stainless steel. The Gram-negative bacteria reduced the maximum biofilm population of L. monocytogenes in dual species biofilms and increased its inactivation during desiccation. However, due to the higher desiccation resistance of Listeria relative to P. fluorescens and S. baltica, the pathogen survived in greater final numbers. In contrast, S. proteamaculans outcompeted the pathogen during the biofilm formation and exhibited similar desiccation survival, causing the N21 days of Serratia to be ca 3 Log10(CFU cm(-2)) greater than that of Listeria in the dual species biofilm. Microscopy revealed biofilm morphologies with variable amounts of exopolymeric substance and the presence of separate microcolonies. Under these simulated food plant conditions, the fate of L. monocytogenes during formation of mixed biofilms and desiccation depended on the implicit characteristics of the co-cultured bacterium.

  1. Response surface methodology approach for optimization of adsorption of Janus Green B from aqueous solution onto ZnO/Zn(OH)2-NP-AC: Kinetic and isotherm study

    Science.gov (United States)

    Ghaedi, M.; Khafri, H. Zare; Asfaram, A.; Goudarzi, A.

    2016-01-01

    The Janus Green B (JGB) adsorption onto homemade ZnO/Zn(OH)2 nanoparticles loaded on activated carbon (AC) which characterized by FESEM and XRD analysis has been reported. Combination of response surface methodology (RSM) and central composite design (CCD) has been employed to model and optimize variables using STATISTICA 10.0 software. The influence of parameters over pH (2.0-8.0), adsorbent (0.004-0.012 g), sonication time (4-8 min) and JGB concentration (3-21 mg L-1) on JGB removal percentage was investigated and their main and interaction contribution was examined. It was revealed that 21 mg L-1 JGB, 0.012 g ZnO/Zn(OH)2-NP-AC at pH 7.0 and 7 min sonication time permit to achieve removal percentage more than 99%. Finally, a good agreement between experimental and predicted values after 7 min was achieved using pseudo-second-order rate equation. The Langmuir adsorption is appropriate for correlation of equilibrium data. The small amount of adsorbent (0.008-0.015 g) is applicable for successful removal of JGB (RE > 99%) in short time (7 min) with high adsorption capacity (81.3-98.03 mg g-1).

  2. Growth kinetics of step edges on celestite (0 0 1) surfaces as a function of temperature, saturation state, ionic strength, and aqueous strontium:sulfate ratio: An in-situ atomic force microscopy study

    Science.gov (United States)

    Bracco, Jacquelyn N.; Gooijer, Yiscka; Higgins, Steven R.

    2016-02-01

    Step velocities on the celestite (0 0 1) surface have been measured as a function of temperature (23-45 °C), saturation state (S = 1.1-2.2), ionic strength (I = 0.01, 0.06, and 0.1 M), and aqueous strontium:sulfate ratio (r = 0.01-100) using atomic force microscopy (AFM). Celestite growth hillocks were flanked by [0 1 0]-aligned step edges, which are polar, and step edges vicinal to , which are non-polar. [0 1 0] step velocities increased with temperature and saturation state, however step velocities did not vary significantly with ionic strength. Step velocities were non-linear with saturation state, suggesting a change in mechanism at high S as compared with low S. At constant S, the step velocities were maximized at r = 1 and decreased significantly at extreme r, demonstrating the governing role of solute stoichiometry. We successfully fit the step velocity data as a function of r using the Stack and Grantham (2010) nucleation and propagation model. Based on the results as a function of ionic strength and r, the mechanism at low S is likely ion-by-ion attachment to the step with an activation energy of 75 (±10) kJ mol-1. At high S the mechanism is a combination of the one at low S and possibly attachment of a neutral species such as an ion pair with an activation energy of 43 (±9) kJ mol-1.

  3. The kinetics of fossil resin extraction from a flotation concentrate

    Energy Technology Data Exchange (ETDEWEB)

    Li, L.; Yu, Q.; Miller, J.D. [Univ. of Utah, Salt Lake City, UT (United States)

    1995-11-01

    The kinetics of fossil resin extraction from a flotation concentrate by heptane were investigated as a function of process variables using monosize particles. Experimental results provide for a better understanding of the refining process and the basis for subsequent design and construction of a continuous resin refining circuit. Based on the effect of process variables (particle size, stirring speed, and temperature) the resin extraction rate appears to be controlled by surface solvation phenomena. The initial extraction rate was found to be inversely proportional to the initial particle size and a kinetic model is being developed to describe the experimental results.

  4. Effect of surface condition and storage time on the repairability of temporary crown and fixed partial denture materials.

    Science.gov (United States)

    Balkenhol, Markus; Meyer, Manuela; Michel, Karin; Ferger, Paul; Wöstmann, Bernd

    2008-11-01

    The aim of the present study was to investigate which parameters (chemical nature, time after mixing, surface characteristics) might affect the repair strength of temporary crown and bridge materials (t-c&b). Four different t-c&bs (Cool Temp Natural, Protemp 3 Garant, Structur Premium, Trim) were investigated using a shear-bond strength (SBS) setup. A cylinder (2 mm x 2.37 mm) of identical t-c&b (n=10) was bonded onto a specimen surface of either freshly set t-c&b (10 min after mixing) or onto specimens that were stored for 24h (37 degrees C, distilled water) and 7 days (thermocycling x 5,000, 5-55 degrees C=TC), respectively. The specimen surface was roughened with SiC paper (grit size 320) or left as it was (specimens stored for 10 min) prior to repair to retain the oxygen-inhibition layer. In addition, mono-block specimens were fabricated as control. The thickness of the oxygen-inhibition layer and the surface morphology was determined. Statistical analysis was carried out with an ANOVA followed by parametric tests (p=0.05). SBS values ranged from 10 to 40 MPa. Trim showed lowest SBS values for most storage conditions. Material, surface characteristics and time after mixing significantly affected the SBS (ANOVA p0.05). In case of monomethacrylates, storage and surface condition do not affect the repair strength. In contrast, the repair quality of dimethacrylates greatly depends on the material. In any case, roughening the surface is recommended, even if an oxygen-inhibition layer is present.

  5. Effect of the plate surface characteristics and gap height on yield stresses of a magnetorheological fluid

    International Nuclear Information System (INIS)

    Jonkkari, I; Syrjala, S; Kostamo, E; Kostamo, J; Pietola, M

    2012-01-01

    Effects of the plate material, surface roughness and measuring gap height on static and dynamic yield stresses of a magnetorheological (MR) fluid were investigated with a commercial plate–plate magnetorheometer. Magnetic and non-magnetic plates with smooth (Ra ∼ 0.3 μm) and rough (Ra ∼ 10 μm) surface finishes were used. It was shown by Hall probe measurements and finite element simulations that the use of magnetic plates or higher gap heights increases the level of magnetic flux density and changes the shape of the radial flux density profile. The yield stress increase caused by these factors was determined and subtracted from the measured values in order to examine only the effect of the wall characteristics or the gap height. Roughening of the surfaces offered a significant increase in the yield stresses for non-magnetic plates. With magnetic plates the yield stresses were higher to start with, but roughening did not increase them further. A significant part of the difference in measured stresses between rough non-magnetic and magnetic plates was caused by changes in magnetic flux density rather than by better contact of the particles to the plate surfaces. In a similar manner, an increase in gap height from 0.25 to 1.00 mm can lead to over 20% increase in measured stresses due to changes in the flux density profile. When these changes were compensated the dynamic yield stresses generally remained independent of the gap height, even in the cases where it was obvious that the wall slip was present. This suggests that with MR fluids the wall slip cannot be reliably detected by comparison of flow curves measured at different gap heights. (paper)

  6. Gyrocenter-gauge kinetic theory

    International Nuclear Information System (INIS)

    Qin, H.; Tang, W.M.; Lee, W.W.

    2000-01-01

    Gyrocenter-gauge kinetic theory is developed as an extension of the existing gyrokinetic theories. In essence, the formalism introduced here is a kinetic description of magnetized plasmas in the gyrocenter coordinates which is fully equivalent to the Vlasov-Maxwell system in the particle coordinates. In particular, provided the gyroradius is smaller than the scale-length of the magnetic field, it can treat high frequency range as well as the usual low frequency range normally associated with gyrokinetic approaches. A significant advantage of this formalism is that it enables the direct particle-in-cell simulations of compressional Alfven waves for MHD applications and of RF waves relevant to plasma heating in space and laboratory plasmas. The gyrocenter-gauge kinetic susceptibility for arbitrary wavelength and arbitrary frequency electromagnetic perturbations in a homogeneous magnetized plasma is shown to recover exactly the classical result obtained by integrating the Vlasov-Maxwell system in the particle coordinates. This demonstrates that all the waves supported by the Vlasov-Maxwell system can be studied using the gyrocenter-gauge kinetic model in the gyrocenter coordinates. This theoretical approach is so named to distinguish it from the existing gyrokinetic theory, which has been successfully developed and applied to many important low-frequency and long parallel wavelength problems, where the conventional meaning of gyrokinetic has been standardized. Besides the usual gyrokinetic distribution function, the gyrocenter-gauge kinetic theory emphasizes as well the gyrocenter-gauge distribution function, which sometimes contains all the physics of the problems being studied, and whose importance has not been realized previously. The gyrocenter-gauge distribution function enters Maxwell's equations through the pull-back transformation of the gyrocenter transformation, which depends on the perturbed fields. The efficacy of the gyrocenter-gauge kinetic approach is

  7. Comparison of peri-implant bone formation around injection-molded and machined surface zirconia implants in rabbit tibiae

    Science.gov (United States)

    Kim, Hong-Kyun; Woo, Kyung mi; Shon, Won-Jun; Ahn, Jin-Soo; Cha, Seunghee; Park, Young-Seok

    2017-01-01

    The aim of this study was to compare osseointegration and surface characteristics of zirconia implants made by the powder injection molding (PIM) technique and made by the conventional milling procedure in rabbit tibiae. Surface characteristics of 2 types of implant were evaluated. Sixteeen rabbits received 2 types of external hex implants with similar geometry, machined zirconia implants and PIM zirconia implants, in the tibiae. Removal torque tests and histomorphometric analyses were performed. The roughness of PIM zirconia implants was higher than that of machined zirconia implants. The PIM zirconia implants exhibited significantly higher bone-implant contact and removal torque values than the machined zirconia implants (P zirconia implant is promising, and PIM, using the roughened mold etching technique, can produce substantially rough surfaces on zirconia implants. PMID:26235717

  8. Morphological stability of 4H-SiC crystals in solution growth on {0001} and {1 1 ̅0m } surfaces

    Science.gov (United States)

    Mitani, Takeshi; Komatsu, Naoyoshi; Hayashi, Yuichiro; Kato, Tomohisa; Okumura, Hajime

    2017-06-01

    For solution growth of 4H-SiC, the surface morphology of the crystals grown on {0001 } and {1 1 ̅0m } (m=0‒4, 10 and 20) surfaces was systematically investigated. For short-term growth for 30 min on {0001 } and {1 1 ̅0m } (m=0 and 2) seeds, the height of the macrosteps was less than 400 nm, and terraces having the same crystallographic orientation as the seeds were formed. In contrast, the growth surfaces on {1 1 ̅0m } (m=4, 10 and 20) seeds became rough owing to the surface reconstruction with the {1 1 ̅02 } and {0001} planes, suggesting the morphological stability of the {1 1 ̅0m } (m=0 and 2) planes. Long-term morphological stability was examined by bulk growth experiments for 24 h. A smooth growth surface was obtained on both (1 ̅10 1 ̅) and (1 ̅10 2 ̅) seeds. Surface roughening owing to the macrostep faceting was observed for the long-term growth on (000 1 ̅) and (1 1 ̅00) seeds, whereas smooth step-terrace surfaces were obtained for the short-term growth on these planes. We also found that surface roughening tended to increase in the step-flow directions in which the angle formed by the original growth surface and a faceted slope of large macrosteps is large. Among the (1 ̅10 m ̅) (m=1 and 2) planes, growth on a (1 ̅10 1 ̅) plane exhibited the smoothest surface even after long-term growth with several millimeters in thickness.

  9. ASTER L2 Surface Temperature V003

    Data.gov (United States)

    National Aeronautics and Space Administration — The ASTER L2 Surface Kinetic Temperature is an on-demand product generated using the five thermal infrared (TIR) bands (acquired either during the day or night time)...

  10. Amyloid protein unfolding and insertion kinetics on neuronal membrane mimics

    Science.gov (United States)

    Qiu, Liming; Buie, Creighton; Vaughn, Mark; Cheng, Kwan

    2010-03-01

    Atomistic details of beta-amyloid (Aβ ) protein unfolding and lipid interaction kinetics mediated by the neuronal membrane surface are important for developing new therapeutic strategies to prevent and cure Alzheimer's disease. Using all-atom MD simulations, we explored the early unfolding and insertion kinetics of 40 and 42 residue long Aβ in binary lipid mixtures with and without cholesterol that mimic the cholesterol-depleted and cholesterol-enriched lipid nanodomains of neurons. The protein conformational transition kinetics was evaluated from the secondary structure profile versus simulation time plot. The extent of membrane disruption was examined by the calculated order parameters of lipid acyl chains and cholesterol fused rings as well as the density profiles of water and lipid headgroups at defined regions across the lipid bilayer from our simulations. Our results revealed that both the cholesterol content and the length of the protein affect the protein-insertion and membrane stability in our model lipid bilayer systems.

  11. ANALYTICAL METHODS FOR KINETIC STUDIES OF BIOLOGICAL INTERACTIONS: A REVIEW

    Science.gov (United States)

    Zheng, Xiwei; Bi, Cong; Li, Zhao; Podariu, Maria; Hage, David S.

    2015-01-01

    The rates at which biological interactions occur can provide important information concerning the mechanism and behavior of these processes in living systems. This review discusses several analytical methods that can be used to examine the kinetics of biological interactions. These techniques include common or traditional methods such as stopped-flow analysis and surface plasmon resonance spectroscopy, as well as alternative methods based on affinity chromatography and capillary electrophoresis. The general principles and theory behind these approaches are examined, and it is shown how each technique can be utilized to provide information on the kinetics of biological interactions. Examples of applications are also given for each method. In addition, a discussion is provided on the relative advantages or potential limitations of each technique regarding its use in kinetic studies. PMID:25700721

  12. Internal Diffusion-Controlled Enzyme Reaction: The Acetylcholinesterase Kinetics.

    Science.gov (United States)

    Lee, Sangyun; Kim, Ji-Hyun; Lee, Sangyoub

    2012-02-14

    Acetylcholinesterase is an enzyme with a very high turnover rate; it quenches the neurotransmitter, acetylcholine, at the synapse. We have investigated the kinetics of the enzyme reaction by calculating the diffusion rate of the substrate molecule along an active site channel inside the enzyme from atomic-level molecular dynamics simulations. In contrast to the previous works, we have found that the internal substrate diffusion is the determinant of the acetylcholinesterase kinetics in the low substrate concentration limit. Our estimate of the overall bimolecular reaction rate constant for the enzyme is in good agreement with the experimental data. In addition, the present calculation provides a reasonable explanation for the effects of the ionic strength of solution and the mutation of surface residues of the enzyme. The study suggests that internal diffusion of the substrate could be a key factor in understanding the kinetics of enzymes of similar characteristics.

  13. Kinetics of alkali-based photocathode degradation

    Directory of Open Access Journals (Sweden)

    Vitaly Pavlenko

    2016-11-01

    Full Text Available We report on a kinetic model that describes the degradation of the quantum efficiency (QE of Cs3Sb and negative electron affinity (NEA GaAs photocathodes under UHV conditions. In addition to the generally accepted irreversible chemical change of a photocathode’s surface due to reactions with residual gases, such as O2, CO2, and H2O, the model incorporates an intermediate reversible physisorption step, similar to Langmuir adsorption. This intermediate step is needed to satisfactorily describe the strongly non-exponential QE degradation curves for two distinctly different classes of photocathodes –surface-activated and “bulk,” indicating that in both systems the QE degradation results from surface damage. The recovery of the QE upon improvement of vacuum conditions is also accurately predicted by this model with three parameters (rates of gas adsorption, desorption, and irreversible chemical reaction with the surface comprising metrics to better characterize the lifetime of the cathodes, instead of time-pressure exposure expressed in Langmuir units.

  14. First principles Tafel kinetics of methanol oxidation on Pt(111)

    Science.gov (United States)

    Fang, Ya-Hui; Liu, Zhi-Pan

    2015-01-01

    Electrocatalytic methanol oxidation is of fundamental importance in electrochemistry and also a key reaction in direct methanol fuel cell. To resolve the kinetics at the atomic level, this work investigates the potential-dependent reaction kinetics of methanol oxidation on Pt(111) using the first principles periodic continuum solvation model based on modified-Poisson-Boltzmann equation (CM-MPB), focusing on the initial dehydrogenation elementary steps. A theoretical model to predict Tafel kinetics (current vs potential) is established by considering that the rate-determining step of methanol oxidation (to CO) is the first Csbnd H bond breaking (CH3OH(aq) → CH2OH* + H*) according to the computed free energy profile. The first Csbnd H bond breaking reaction needs to overcome a large entropy loss during methanol approaching to the surface and replacing the adsorbed water molecules. While no apparent charge transfer is involved in this elementary step, the charge transfer coefficient of the reaction is calculated to be 0.36, an unconventional value for charge transfer reactions, and the Tafel slope is deduced to be 166 mV. The results show that the metal/adsorbate interaction and the solvation environment play important roles on influencing the Tafel kinetics. The knowledge learned from the potential-dependent kinetics of methanol oxidation can be applied in general for understanding the electrocatalytic reactions of organic molecules at the solid-liquid interface.

  15. Transformation kinetics for nucleus clusters

    International Nuclear Information System (INIS)

    Villa, Elena; Rios, Paulo R.

    2009-01-01

    A rigorous mathematical approach based on stochastic geometry concepts is presented to extend previous Johnson-Mehl, Avrami, Kolmogorov treatment of transformation kinetics to situations in which nuclei are not homogeneously located in space but are located in clusters. An exact analytical solution is presented here for the first time assuming that nucleation sites follow a Matern cluster process. The influence of Matern cluster process parameters on subsequent growth kinetics and the microstructural path are illustrated by means of numerical examples. Moreover, using the superposition principle, exact analytical solutions are also obtained when nucleation takes place by a combination of a Matern cluster process and an inhomogeneous Poisson point process. The new solutions presented here significantly increase the number of exactly solvable cases available to formal kinetics.

  16. Robustness Analysis of Kinetic Structures

    DEFF Research Database (Denmark)

    Kirkegaard, Poul Henning; Sørensen, John Dalsgaard

    2009-01-01

    The present paper considers robustness of kinetic structures. Robustness of structures has obtained a renewed interest due to a much more frequent use of advanced types of structures with limited redundancy and serious consequences in case of failure. Especially for these types of structural syst...... systems, it is of interest to investigate how robust the structures are, or what happens if a structural element is added to or removed from the original structure. The present paper discusses this issue for kinetic structures in architecture.......The present paper considers robustness of kinetic structures. Robustness of structures has obtained a renewed interest due to a much more frequent use of advanced types of structures with limited redundancy and serious consequences in case of failure. Especially for these types of structural...

  17. Kinetic theory and transport phenomena

    CERN Document Server

    Soto, Rodrigo

    2016-01-01

    This textbook presents kinetic theory, which is a systematic approach to describing nonequilibrium systems. The text is balanced between the fundamental concepts of kinetic theory (irreversibility, transport processes, separation of time scales, conservations, coarse graining, distribution functions, etc.) and the results and predictions of the theory, where the relevant properties of different systems are computed. The book is organised in thematic chapters where different paradigmatic systems are studied. The specific features of these systems are described, building and analysing the appropriate kinetic equations. Specifically, the book considers the classical transport of charges, the dynamics of classical gases, Brownian motion, plasmas, and self-gravitating systems, quantum gases, the electronic transport in solids and, finally, semiconductors. Besides these systems that are studied in detail, concepts are applied to some modern examples including the quark–gluon plasma, the motion of bacterial suspen...

  18. Surface morphology of silicone soft relining material after mechanical and chemical cleaning.

    Science.gov (United States)

    Ueda, Takayuki; Kubo, Keitaro; Saito, Takeshi; Obata, Tomokuni; Wada, Takeshi; Yanagisawa, Koichiro; Sakurai, Kaoru

    2018-04-07

    The objective was to investigate the influence of chemical and mechanical cleaning on the surface morphology of a silicone soft relining material. Three plate-shaped specimens were prepared for each group (Control, Hard and Soft) by laminating a 1.5-mm-thick silicone soft relining material. The Control group specimens were stored in water, and the Hard and Soft group specimens were cleaned with hard and soft bristle denture brushes, respectively. Abrasion testing with a toothbrush and immersion testing with an enzyme-containing peroxide denture cleanser were performed, simulating a period of approximately 4 months. The arithmetic mean roughness (Sa) and maximum height of the cross-section (Sz) were measured before and after abrasion and immersion testing. Sa was 4.9±0.9, 22.1±4.2 and 44.2±4.0μm in the Control, Soft and Hard groups, respectively. Sz was 257.5±31.7, 392.0±23.8 and 452.2±41.9μm in the Control, Soft and Hard groups, respectively. After abrasion testing, Sa and Sz differed significantly between the Soft and Control groups and between the Hard and Control groups. Sa was 2.2±1.2μm before and after immersion, and Sz was 142.1±81.4μm before and after immersion. No significant difference was noted in either Sa or Sz in the Control specimens before or after immersion. Surfaces cleaned using a soft bristle brush were less likely to roughen than those cleaned with a hard bristle brush under the conditions of this study. Additionally, chemical cleaning using the enzyme+neutral peroxide denture cleanser did not roughen the surface of the silicone soft relining material. Copyright © 2018 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

  19. Influence of roughness of machined surface on adhesion of anticorrosion system

    Directory of Open Access Journals (Sweden)

    Jiří Votava

    2013-01-01

    Full Text Available The goal of this experiment is to analyse dependence of roughness of machined surface on adhesion performance of various anticorrosion systems. In order to prepare samples for the experiment, samples were milled on a knee and column type of a horizontal milling machine. Depending on cutting conditions and machining tool, there were set intervals of roughness of machined surface which are commonly achievable on this type of machine. It is a roughness in the interval of 0.4–1.6 µm (finishing, 1.6–6.3 µm (standard milling a 6.3–12.5 µm (roughening. Removable cutting tips were used as a machining tool and for roughening, a shell end milling cutter NAREX 63x40 HSS 90 was used. Three types of anticorrosion systems were used in order to analyse the adhesion, that is a water-thinnable system Eternal, synthetic single layer coating Hostagrund and a duplex system, whose first layer is formed by dipped zinc and a top layer by a single-layer acrylate system Zinorex. Testing of the influence of surface roughness (anchoring system on adhesion of the individual anticorrosion systems were processed in compliance with the norm ČSN EN ISO 4624, a tearing test. The main criterion of adhesion of anticorrosion system is defined as a power which needed for tear-off testing object stuck to a tested sample. This analysis was processed also during the corrosion test in the salt spray environment according to the norm ČSN EN ISO 9227. In order to better identify the adhesion of the individual anticorrosion systems, the analysis of undercorrosion according to the norm ISO 4628-8 was processed.

  20. Quantum kinetic theory of the chiral anomaly

    Science.gov (United States)

    Sekine, Akihiko; Culcer, Dimitrie; MacDonald, Allan H.

    2017-12-01

    We present a general quantum kinetic theory of low-field magnetotransport in weakly disordered crystals that accounts fully for the interplay between electric-field-induced interband coherence, Bloch-state scattering, and an external magnetic field. The quantum kinetic equation we derive for the Bloch-state density matrix naturally incorporates the momentum-space Berry phase effects whose influence on Bloch-state wave-packet dynamics is normally incorporated into transport theory in an ad hoc manner. The Berry phase correction to the momentum-space density of states in the presence of an external magnetic field implied by semiclassical wave-packet dynamics is captured by our theory as an intrinsic density-matrix response to a magnetic field. We propose a simple and general procedure for expanding the linear response of the Bloch-state density matrix to an electric field in powers of magnetic field. As an illustration, we apply our theory to magnetotransport in Weyl semimetals. We show that the chiral anomaly (positive magnetoconductivity quadratic in magnetic field) that appears when separate Fermi surface pockets surround distinct Weyl points survives only when intervalley scattering is very weak compared to intravalley scattering.