Probing radical kinetics in the afterglow of pulsed discharges by absorption spectroscopy with light emitting diodes: Application to BCl radical

NASA Astrophysics Data System (ADS)

Vempaire, D.; Cunge, G.

2009-01-01

Measuring decay rates of radical densities in the afterglow of pulsed plasmas is a powerful approach to determine their gas phase and surface loss kinetics. We show that this measurement can be achieved by absorption spectroscopy with low cost and simple apparatus by using light emitting diodes as a light source. The feasibility is demonstrated by monitoring BCl radicals in pulsed low pressure high-density BCl3 plasmas. It is shown that BCl is lost both in the gas phase by reacting with Cl2 with a cross section of 9 Å2 and in the chamber walls with a sticking coefficient of about 0.3.

Carbon Nanotube Synthesis in a Flame with Independently Prepared Laser-Ablated Catalyst Particles

NASA Technical Reports Server (NTRS)

VanderWal, Randall L.; Berger, Gordon M.; Ticich, Thomas M.

2003-01-01

Laser ablation has been used ex situ to create metal nanoparticles for introduction into a reactive pyrolysis flame. By prior synthesis of the metal nanoparticles, the effects of the reactive gases can be clearly separated from the pyrolysis chemistry of a solvent carrier, as when nebulized solutions are used. Moreover, varying reactivity issues associated with particle growth and size are bypassed. Our results show that Fe selectively reacts with CO to produce nanotubes, whereas Ni selectively reacts with C2H2 to produce nanofibers. These observations are interpreted through the donation and withdrawal of electron density between the adsorbate's molecular orbitals and surface atoms of the metal nanoparticle. The rate of reaction of Ni with only C2H2 is found to be greater than the rate with C2H2 and CO. This suggests that CO inhibits the Ni-catalyzed reaction.

Insights into the mechanism of the capture of CO2 by K2CO3 sorbent: a DFT study.

PubMed

Liu, Hongyan; Qin, Qiaoyun; Zhang, Riguang; Ling, Lixia; Wang, Baojun

2017-09-13

The adsorption and reactions of CO 2 and H 2 O on both monoclinic and hexagonal crystal K 2 CO 3 were investigated using the density functional theory (DFT) approach. The calculated adsorption energies showed that adsorption of H 2 O molecules was clearly substantially stronger on the K 2 CO 3 surface than the adsorption of CO 2 , except on the (001)-1 surface of hexagonal K 2 CO 3 , where CO 2 is competitively adsorbed with H 2 O. Carbonation reactions easily occur on pure K 2 CO 3 and involve two parallel paths: one is where adsorbed H 2 O reacts with molecular CO 2 in gas to form the bicarbonate, while the other is where H 2 O dissociates into OH and H before bicarbonate formation, and then OH reacts with gaseous CO 2 to form a bicarbonate. Our results indicate that adding a support or promoter or using a special technique to expose more (001)-1 surfaces in hexagonal K 2 CO 3 may improve the conversion of CO 2 to the bicarbonate, which provides a theoretical direction for the experimental preparation of the K 2 CO 3 sorbent to capture CO 2 .

Methanol partial oxidation on Ag(111) from first principles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aljama, Hassan; Yoo, Jong Suk; Nørskov, Jens K.

In this work, we examine the thermochemistry and kinetics of the partial oxidation of methanol to formaldehyde on silver surfaces. Periodic density functional theory calculations employing the BEEF-vdW functional are used to identify the most stable phases of the silver surface under relevant reaction conditions and the reaction energetics are obtained on these surfaces. The calculated binding energies and transition state energies are used as input in a mean-field microkinetic model providing the reaction kinetics on silver surfaces under different reaction conditions. Our results show that, under conditions pertaining to methanol partial oxidation, oxygen is present at low concentrations andmore » it plays a critical role in the catalytic reaction. Surface oxygen promotes the reaction by activating the OH bond in methanol, thus forming a methoxy intermediate, which can react further to form formaldehyde. Finally, the dissociation of molecular oxygen is identified as the most critical step.« less

Methanol partial oxidation on Ag(111) from first principles

DOE PAGES

Aljama, Hassan; Yoo, Jong Suk; Nørskov, Jens K.; ...

2016-10-26

In this work, we examine the thermochemistry and kinetics of the partial oxidation of methanol to formaldehyde on silver surfaces. Periodic density functional theory calculations employing the BEEF-vdW functional are used to identify the most stable phases of the silver surface under relevant reaction conditions and the reaction energetics are obtained on these surfaces. The calculated binding energies and transition state energies are used as input in a mean-field microkinetic model providing the reaction kinetics on silver surfaces under different reaction conditions. Our results show that, under conditions pertaining to methanol partial oxidation, oxygen is present at low concentrations andmore » it plays a critical role in the catalytic reaction. Surface oxygen promotes the reaction by activating the OH bond in methanol, thus forming a methoxy intermediate, which can react further to form formaldehyde. Finally, the dissociation of molecular oxygen is identified as the most critical step.« less

Comparison of Mixing Calculations for Reacting and Non-Reacting Flows in a Cylindrical Duct

NASA Technical Reports Server (NTRS)

Oechsle, V. L.; Mongia, H. C.; Holdeman, J. D.

1994-01-01

A production 3-D elliptic flow code has been used to calculate non-reacting and reacting flow fields in an experimental mixing section relevant to a rich burn/quick mix/lean burn (RQL) combustion system. A number of test cases have been run to assess the effects of the variation in the number of orifices, mass flow ratio, and rich-zone equivalence ratio on the flow field and mixing rates. The calculated normalized temperature profiles for the non-reacting flow field agree qualitatively well with the normalized conserved variable isopleths for the reacting flow field indicating that non-reacting mixing experiments are appropriate for screening and ranking potential rapid mixing concepts. For a given set of jet momentum-flux ratio, mass flow ratio, and density ratio (J, MR, and DR), the reacting flow calculations show a reduced level of mixing compared to the non-reacting cases. In addition, the rich-zone equivalence ratio has noticeable effect on the mixing flow characteristics for reacting flows.

Conjugation of diisocyanate side chains to dimethacrylate reduces polymerization shrinkage and increases the hardness of composite resins.

PubMed

Jan, Yih-Dean; Lee, Bor-Shiunn; Lin, Chun-Pin; Tseng, Wan-Yu

2014-04-01

Polymerization shrinkage is one of the main causes of dental restoration failure. This study tried to conjugate two diisocyanate side chains to dimethacrylate resins in order to reduce polymerization shrinkage and increase the hardness of composite resins. Diisocyanate, 2-hydroxyethyl methacrylate, and bisphenol A dimethacrylate were reacted in different ratios to form urethane-modified new resin matrices, and then mixed with 50 wt.% silica fillers. The viscosities of matrices, polymerization shrinkage, surface hardness, and degrees of conversion of experimental composite resins were then evaluated and compared with a non-modified control group. The viscosities of resin matrices increased with increasing diisocyanate side chain density. Polymerization shrinkage and degree of conversion, however, decreased with increasing diisocyanate side chain density. The surface hardness of all diisocyanate-modified groups was equal to or significantly higher than that of the control group. Conjugation of diisocyanate side chains to dimethacrylate represents an effective means of reducing polymerization shrinkage and increasing the surface hardness of dental composite resins. Copyright © 2012. Published by Elsevier B.V.

DFT study of CO2 conversion on InZr3(110) surface.

PubMed

Zhang, Minhua; Dou, Maobin; Yu, Yingzhe

2017-11-01

Methanol and methane synthesis from CO 2 hydrogenation on a InZr 3 (110) surface has been studied using density functional theory calculations. The CO 2 can be chemically adsorbed via a polydentated configuration and the H 2 molecule can dissociate to H atoms spontaneously. The methanol is primarily formed via the HCOO route instead of the RWGS route, due to its higher activation barrier of 1.35 eV for HCO hydrogenation. In the HCOO route, the adsorbed CO 2 consecutively hydrogenates to form HCOO, H 2 COO and the H 3 CO species. The H 3 COH is produced via the reaction of H 3 CO with a surface OH group. Furthermore, the C-O bonds of CO, CHO, CH 2 O and CH 3 O species prefer to dissociate to C, CH, CH 2 CH 3 and surface O species. Methane is formed via the hydrogenation of CH x (x = 0-3) monomers with the highest activation barrier of 1.19 eV for CH 3 hydrogenation, which is higher than that of the hydrogenation of H 2 COO in methanol synthesis via the HCOO route. The surface O species formed during CO 2 hydrogenation reacts with the adsorbed H 2 molecule to produce an OH group which reacts with a surface H atom to form H 2 O with an activation barrier of 1.13 eV, which then desorbs to the gas phase. Our calculated results indicate that the InZr 3 alloy is a potential candidate catalyst for CO 2 utilization and conversion.

MPSalsa Version 1.5: A Finite Element Computer Program for Reacting Flow Problems: Part 1 - Theoretical Development

DOE Office of Scientific and Technical Information (OSTI.GOV)

Devine, K.D.; Hennigan, G.L.; Hutchinson, S.A.

1999-01-01

The theoretical background for the finite element computer program, MPSalsa Version 1.5, is presented in detail. MPSalsa is designed to solve laminar or turbulent low Mach number, two- or three-dimensional incompressible and variable density reacting fluid flows on massively parallel computers, using a Petrov-Galerkin finite element formulation. The code has the capability to solve coupled fluid flow (with auxiliary turbulence equations), heat transport, multicomponent species transport, and finite-rate chemical reactions, and to solve coupled multiple Poisson or advection-diffusion-reaction equations. The program employs the CHEMKIN library to provide a rigorous treatment of multicomponent ideal gas kinetics and transport. Chemical reactions occurringmore » in the gas phase and on surfaces are treated by calls to CHEMKIN and SURFACE CHEMK3N, respectively. The code employs unstructured meshes, using the EXODUS II finite element database suite of programs for its input and output files. MPSalsa solves both transient and steady flows by using fully implicit time integration, an inexact Newton method and iterative solvers based on preconditioned Krylov methods as implemented in the Aztec. solver library.« less

The sebaceous gland antigen defined by the OM-1 monoclonal antibody is expressed at high density on the surface of ovarian carcinoma cells.

PubMed

de Kretser, T A; Thorne, H J; Jacobs, D J; Jose, D G

1985-09-01

A monoclonal antibody, designated OM-1, was raised against ovarian serous papillary cystadenocarcinoma (stage IV) cells. This antibody was found to react strongly with primary and metastatic ovarian serous cystadenocarcinomas and endometrioid carcinomas but the antigen detected was either absent or at very low levels in ovarian mucinous adenocarcinomas, clear cell carcinomas, benign serous and mucinous cystadenomas and Brenner tumours. The OM-1 antibody gave no detectable reaction with 93 other human tumours, including examples of breast and colon adenocarcinomas. In normal tissues the OM-1 antibody reacted with normal sebaceous gland cells, lung type II pneumocytes and placental syncytial trophoblasts. In the normal ovary OM-1 reactivity was confined to extremely weak staining of the surface epithelium. No reaction with any other ovarian cell type could be detected. No evidence of reaction with other normal cell populations present in 24 adult and seven foetal tissues was found. The antigen detected is compared with other ovarian tumour-associated antigens. The OM-1 antibody is likely to prove of value in the detection and diagnosis of ovarian carcinoma.

Influence of Hydrogen Sulfide Exposure on the Transport and Structural Properties of the Metal–Organic Framework ZIF-8

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dutta, Akshita; Tymi?ska, Nina; Zhu, Guanghui

In this paper, the interaction between hydrogen sulfide and ZIF-8 was studied via structural characterizations and guest molecule diffusion measurements. It was found that hydrogen sulfide reacts with the ZIF-8 external particle surface to form a surface barrier that excludes the uptake of larger molecules (ethanol) and slows down the uptake of smaller molecules (carbon dioxide). Nonetheless, bulk transport properties were unaltered, as supported by pulsed field gradient nuclear magnetic resonance studies. Dispersion-corrected density functional theory calculations revealed that H 2S is consumed by reactions occurring at the ZIF external surface. These reactions result in water and defect formation, bothmore » of which were found to be exothermic and independent of both crystallographic facets ({001} and {110}) and surface termination. Finally, we concluded that these surface reactions lead to structural and chemical changes to the ZIF-8 external surface that generate surface barriers to molecular transport.« less

Influence of Hydrogen Sulfide Exposure on the Transport and Structural Properties of the Metal–Organic Framework ZIF-8

DOE PAGES

Dutta, Akshita; Tymi?ska, Nina; Zhu, Guanghui; ...

2018-03-09

In this paper, the interaction between hydrogen sulfide and ZIF-8 was studied via structural characterizations and guest molecule diffusion measurements. It was found that hydrogen sulfide reacts with the ZIF-8 external particle surface to form a surface barrier that excludes the uptake of larger molecules (ethanol) and slows down the uptake of smaller molecules (carbon dioxide). Nonetheless, bulk transport properties were unaltered, as supported by pulsed field gradient nuclear magnetic resonance studies. Dispersion-corrected density functional theory calculations revealed that H 2S is consumed by reactions occurring at the ZIF external surface. These reactions result in water and defect formation, bothmore » of which were found to be exothermic and independent of both crystallographic facets ({001} and {110}) and surface termination. Finally, we concluded that these surface reactions lead to structural and chemical changes to the ZIF-8 external surface that generate surface barriers to molecular transport.« less

Large Eddy Simulation of Spatially Developing Turbulent Reacting Shear Layers with the One-Dimensional Turbulence Model

NASA Astrophysics Data System (ADS)

Hoffie, Andreas Frank

Large eddy simulation (LES) combined with the one-dimensional turbulence (ODT) model is used to simulate spatially developing turbulent reacting shear layers with high heat release and high Reynolds numbers. The LES-ODT results are compared to results from direct numerical simulations (DNS), for model development and validation purposes. The LES-ODT approach is based on LES solutions for momentum and pressure on a coarse grid and solutions for momentum and reactive scalars on a fine, one-dimensional, but three-dimensionally coupled ODT subgrid, which is embedded into the LES computational domain. Although one-dimensional, all three velocity components are transported along the ODT domain. The low-dimensional spatial and temporal resolution of the subgrid scales describe a new modeling paradigm, referred to as autonomous microstructure evolution (AME) models, which resolve the multiscale nature of turbulence down to the Kolmogorv scales. While this new concept aims to mimic the turbulent cascade and to reduce the number of input parameters, AME enables also regime-independent combustion modeling, capable to simulate multiphysics problems simultaneously. The LES as well as the one-dimensional transport equations are solved using an incompressible, low Mach number approximation, however the effects of heat release are accounted for through variable density computed by the ideal gas equation of state, based on temperature variations. The computations are carried out on a three-dimensional structured mesh, which is stretched in the transverse direction. While the LES momentum equation is integrated with a third-order Runge-Kutta time-integration, the time integration at the ODT level is accomplished with an explicit Forward-Euler method. Spatial finite-difference schemes of third (LES) and first (ODT) order are utilized and a fully consistent fractional-step method at the LES level is used. Turbulence closure at the LES level is achieved by utilizing the Smagorinsky model. The chemical reaction is simulated with a global single-step, second-order equilibrium reaction with an Arrhenius reaction rate. The two benchmark cases of constant density reacting and variable density non-reacting shear layers used to determine ODT parameters yield perfect agreement with regards to first and second-order flow statistics as well as shear layer growth rate. The variable density non-reacting shear layer also serves as a testing case for the LES-ODT model to simulate passive scalar mixing. The variable density, reacting shear layer cases only agree reasonably well and indicate that more work is necessary to improve variable density coupling of ODT and LES. The disagreement is attributed to the fact that the ODT filtered density is kept constant across the Runge-Kutta steps. Furthermore, a more in-depth knowledge of large scale and subgrid turbulent kinetic energy (TKE) spectra at several downstream locations as well as TKE budgets need to be studied to obtain a better understanding about the model as well as about the flow under investigation. The local Reynolds number based on the one-percent thickness at the exit is Redelta ≈ 5300, for the constant density reacting and for the variable density non-reacting case. For the variable density reacting shear layer, the Reynolds number based on the 1% thickness is Redelta ≈ 2370. The variable density reacting shear layers show suppressed growth rates due to density variations caused by heat release. This has also been reported in literature. A Lewis number parameter study is performed to extract non-unity Lewis number effects. An increase in the Lewis number leads to a further suppression of the growth rate, however to an increase spread of second-order flow statistics. Major focus and challenge of this work is to improve and advance the three-dimensional coupling of the one-dimensional ODT domains while keeping the solution correct. This entails major restructuring of the model. The turbulent reacting shear layer poses a physical challenge to the model because of its nature being a statistically stationary, non-decaying inhomogeneous and anisotropic turbulent flow. This challenge also requires additions to the eddy sampling procedure. Besides physical advancements, the LES-ODT code is also improved regarding its ability to use general cuboid geometries, an array structure that allows to apply boundary conditions based on ghost-cells and non-uniform structured meshes. The use of transverse grid-stretching requires the implementation of the ODT triplet map on a stretched grid. Further, advancing subroutine structure handling with global variables that enable serial code speed-up and parallelization with OpenMP are undertaken. Porting the code to a higher-level language, object oriented, finite-volume based CFD platform, like OpenFoam for example that allows more advanced array and parallelization features with graphics processing units (GPUs) as well as parallelization with the message passing interface (MPI) to simulate complex geometries is recommended for future work.

Targeted Single-Site MOF Node Modification: Trivalent Metal Loading via Atomic Layer Deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, In Soo; Borycz, Joshua; Platero-Prats, Ana E.

Postsynthetic functionalization of metal organic frameworks (MOFs) enables the controlled, high-density incorporation of new atoms on a crystallographically precise framework. Leveraging the broad palette of known atomic layer deposition (ALD) chemistries, ALD in MOFs (AIM) is one such targeted approach to construct diverse, highly functional, few-atom clusters. We here demonstrate the saturating reaction of trimethylindium (InMe3) with the node hydroxyls and ligated water of NU-1000, which takes place without significant loss of MOF crystallinity or internal surface area. We computationally identify the elementary steps by which trimethylated trivalent metal compounds (ALD precursors) react with this Zr-based MOF node to generatemore » a uniform and well characterized new surface layer on the node itself, and we predict a final structure that is fully consistent with experimental X-ray pair distribution function (PDF) analysis. We further demonstrate tunable metal loading through controlled number density of the reactive handles (-OH and -OH2) achieved through node dehydration at elevated temperatures.« less

Grafting of polyethylenimine onto cellulose nanofibers for interfacial enhancement in their epoxy nanocomposites.

PubMed

Zhao, Jiangqi; Li, Qingye; Zhang, Xiaofang; Xiao, Meijie; Zhang, Wei; Lu, Canhui

2017-02-10

Cellulose nanofibers (CNFs) were surface-modified with polyethyleneimine (PEI), which brought plentiful amine groups on the surface of CNFs, leading to a reduced hydrogen bond density between CNFs and consequently less CNFs agglomerates. The amine groups could also react with the epoxy as an effective curing agent that could increase the interfacial crosslinking density and strengthen interfacial adhesion. The tensile strength and Young's modulus of CNFs-PEI/Epoxy nanocomposites were 88.1% and 237.6% higher than those of neat epoxy, respectively. The tensile storage modulus of the nanocomposites also increased significantly at the temperature either below or above the Tg. The coefficient of thermal expansion for the CNFs-PEI/Epoxy nanocomposites was 22.2ppmK -1 , much lower than that of the neat epoxy (88.6ppmK -1 ). In addition, the thermal conductivity of the nanocomposites was observed to increase as well. The exceptional and balanced properties may provide the nanocomposites promising applications in automotive, construction and electronic devices. Copyright © 2016 Elsevier Ltd. All rights reserved.

Analysis of density and epitopes of D antigen on the surface of erythrocytes from DEL phenotypic individuals carrying the RHD1227A allele.

PubMed

Gu, Juan; Sun, An-Yuan; Wang, Xue-Dong; Shao, Chao-Peng; Li, Zheng; Huang, Li-Hua; Pan, Zhao-Lin; Wang, Qing-Ping; Sun, Guang-Ming

2014-04-01

The characteristics of the D antigen are important as they influence the immunogenicity of D variant cells. Several studies on antigenic sites have been reported in normal D positive, weak D and partial D cases, including a comprehensive analysis of DEL types in Caucasians. The aim of this study was to assess D antigen density and epitopes on the erythrocyte surface of Asian type DEL phenotypic individuals carrying the RHD1227A allele in the Chinese population. A total of 154 DEL phenotypic individuals carrying the RHD1227A allele were identified through adsorption and elution tests and polymerase chain reaction analysis with sequence-specific primers in the Chinese population. D antigen density on the erythrocyte surface of these individuals was detected using a flow cytometric method. An erythrocyte sample with known D antigen density was used as a standard. Blood samples from D-negative and D-positive individuals were used as controls. In addition, D antigen epitopes on the erythrocyte surface of DEL individuals carrying the RHD1227A allele were investigated with 18 monoclonal anti-D antibodies specific for different D antigen epitopes. The means of the median fluorescence intensity of D antigen on the erythrocyte membrane surface of D-negative, D-positive and DEL individuals were 2.14±0.25, 193.61±11.43 and 2.45±0.82, respectively. The DEL samples were estimated to have approximately 22 D antigens per cell. The samples from all 154 DEL individuals reacted positively with 18 monoclonal anti-D antibodies specific for different D antigen epitopes. In this study, D antigen density on the erythrocyte surface of DEL individuals carrying the RHD1227A allele was extremely low, there being only very few antigenic molecules per cell, but the D antigen epitopes were grossly complete.

Evolution of Space Dependent Growth in the Teleost Astyanax mexicanus

PubMed Central

Gallo, Natalya D.; Jeffery, William R.

2012-01-01

The relationship between growth rate and environmental space is an unresolved issue in teleosts. While it is known from aquaculture studies that stocking density has a negative relationship to growth, the underlying mechanisms have not been elucidated, primarily because the growth rate of populations rather than individual fish were the subject of all previous studies. Here we investigate this problem in the teleost Astyanax mexicanus, which consists of a sighted surface-dwelling form (surface fish) and several blind cave-dwelling (cavefish) forms. Surface fish and cavefish are distinguished by living in spatially contrasting environments and therefore are excellent models to study the effects of environmental size on growth. Multiple controlled growth experiments with individual fish raised in confined or unconfined spaces showed that environmental size has a major impact on growth rate in surface fish, a trait we have termed space dependent growth (SDG). In contrast, SDG has regressed to different degrees in the Pachón and Tinaja populations of cavefish. Mating experiments between surface and Pachón cavefish show that SDG is inherited as a dominant trait and is controlled by multiple genetic factors. Despite its regression in blind cavefish, SDG is not affected when sighted surface fish are raised in darkness, indicating that vision is not required to perceive and react to environmental space. Analysis of plasma cortisol levels showed that an elevation above basal levels occurred soon after surface fish were exposed to confined space. This initial cortisol peak was absent in Pachón cavefish, suggesting that the effects of confined space on growth may be mediated partly through a stress response. We conclude that Astyanax reacts to confined spaces by exhibiting SDG, which has a genetic component and shows evolutionary regression during adaptation of cavefish to confined environments. PMID:22870223

LES, DNS and RANS for the analysis of high-speed turbulent reacting flows

NASA Technical Reports Server (NTRS)

Givi, Peyman

1994-01-01

The objective of this research is to continue our efforts in advancing the state of knowledge in Large Eddy Simulation (LES), Direct Numerical Simulation (DNS), and Reynolds Averaged Navier Stokes (RANS) methods for the analysis of high-speed reacting turbulent flows. In the first phase of this research, conducted within the past six months, focus was in three directions: RANS of turbulent reacting flows by Probability Density Function (PDF) methods, RANS of non-reacting turbulent flows by advanced turbulence closures, and LES of mixing dominated reacting flows by a dynamics subgrid closure. A summary of our efforts within the past six months of this research is provided in this semi-annual progress report.

Recent advances in PDF modeling of turbulent reacting flows

NASA Technical Reports Server (NTRS)

Leonard, Andrew D.; Dai, F.

1995-01-01

This viewgraph presentation concludes that a Monte Carlo probability density function (PDF) solution successfully couples with an existing finite volume code; PDF solution method applied to turbulent reacting flows shows good agreement with data; and PDF methods must be run on parallel machines for practical use.

Reactivation of dead sulfide species in lithium polysulfide flow battery for grid scale energy storage.

PubMed

Jin, Yang; Zhou, Guangmin; Shi, Feifei; Zhuo, Denys; Zhao, Jie; Liu, Kai; Liu, Yayuan; Zu, Chenxi; Chen, Wei; Zhang, Rufan; Huang, Xuanyi; Cui, Yi

2017-09-06

Lithium polysulfide batteries possess several favorable attributes including low cost and high energy density for grid energy storage. However, the precipitation of insoluble and irreversible sulfide species on the surface of carbon and lithium (called "dead" sulfide species) leads to continuous capacity degradation in high mass loading cells, which represents a great challenge. To address this problem, herein we propose a strategy to reactivate dead sulfide species by reacting them with sulfur powder with stirring and heating (70 °C) to recover the cell capacity, and further demonstrate a flow battery system based on the reactivation approach. As a result, ultrahigh mass loading (0.125 g cm -3 , 2 g sulfur in a single cell), high volumetric energy density (135 Wh L -1 ), good cycle life, and high single-cell capacity are achieved. The high volumetric energy density indicates its promising application for future grid energy storage.Lithium polysulfide batteries suffer from the precipitation of insoluble and irreversible sulfide species on the surface of carbon and lithium. Here the authors show a reactivation strategy by a reaction with cheap sulfur powder under stirring and heating to recover the cell capacity.

Phospholipid epitopes for mouse antibodies against bromelain-treated mouse erythrocytes.

PubMed Central

Kawaguchi, S

1987-01-01

The reactivity of mouse antibodies against bromelain-treated mouse erythrocytes (BrMRBC) with phospholipid epitopes was assessed by ELISA, using four clones of monoclonal anti-BrMRBC antibodies that had idiotypes distinct from one another. The four antibodies could bind to low-density lipoproteins (LDL) from human and chicken, but not to LDL from mouse and rat. As to liposomes of natural phospholipids, all the clones reacted with liposomes of phosphatidylcholine, and some of them could react with liposomes of sphingomyelin, phosphatidylglycerol, phosphatidylic acid or cardiolipin. For liposomes of synthetic phosphatidylcholine with different fatty acids, the length of carbon chains and the number of unsaturated carbon chains of the fatty acids markedly affected the binding of each monoclonal antibody to the liposomes. The addition of dicetyl phosphate or stearylamine to phosphatidylcholine liposomes changed the reactivity of the liposomes. These results support the view that mouse anti-BrMRBC antibodies can recognize appropriately spaced phosphorylcholine residues on the surface of phospholipid liposomes, LDL and cells. The four clones had similar capacities for binding to LDL as well as to BrMRBC, but they had obviously different capacities for binding to phospholipid liposomes; the epitopes on phospholipid liposomes used in the present study were not so perfect as to react well with every anti-BrMRBC antibody. PMID:2443446

Filtered Mass Density Function for Design Simulation of High Speed Airbreathing Propulsion Systems

NASA Technical Reports Server (NTRS)

Givi, P.; Madnia, C. K.; Gicquel, L. Y. M.; Sheikhi, M. R. H.; Drozda, T. G.

2002-01-01

The objective of this research is to improve and implement the filtered mass density function (FDF) methodology for large eddy simulation (LES) of high speed reacting turbulent flows. NASA is interested in the design of various components involved in air breathing propulsion systems such as the scramjet. There is a demand for development of robust tools that can aid in the design procedure. The physics of high speed reactive flows is rich with many complexities. LES is regarded as one of the most promising means of simulating turbulent reacting flows.

Enhancing Dissociative Adsorption of Water on Cu(111) via Chemisorbed Oxygen

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Qianqian; Li, Jonathan; Tong, Xiao

We have used X-ray photoelectron spectroscopy to study the dehydrogenation of H 2O molecules on the clean and oxygenated Cu(111) surfaces. The clean surface does not show reactivity toward H 2O dehydrogenation. By contrast, H 2O molecules on the oxygenated Cu(111) dissociate into OH species by reacting with chemisorbed oxygen until the complete consumption of the chemisorbed oxygen at which the surface loses its reactivity toward H 2O dehydrogenation. Increasing the temperature to 200 °C and above decreases molecularly adsorbed H 2O for dehydrogenation, thereby resulting in less loss of chemisorbed O. In conjunction with density-functional theory calculations, a three-stepmore » reaction pathway is proposed to account for the chemisorbed O assisted dehydrogenation of H 2O molecules and the net loss of surface oxygen. Finally, these results provide insight into understanding the elemental steps of the dehydrogenation of H 2O molecules and the controllable conditions for tuning H 2O dissociation on metal surfaces.« less

Enhancing Dissociative Adsorption of Water on Cu(111) via Chemisorbed Oxygen

DOE PAGES

Liu, Qianqian; Li, Jonathan; Tong, Xiao; ...

2017-05-16

We have used X-ray photoelectron spectroscopy to study the dehydrogenation of H 2O molecules on the clean and oxygenated Cu(111) surfaces. The clean surface does not show reactivity toward H 2O dehydrogenation. By contrast, H 2O molecules on the oxygenated Cu(111) dissociate into OH species by reacting with chemisorbed oxygen until the complete consumption of the chemisorbed oxygen at which the surface loses its reactivity toward H 2O dehydrogenation. Increasing the temperature to 200 °C and above decreases molecularly adsorbed H 2O for dehydrogenation, thereby resulting in less loss of chemisorbed O. In conjunction with density-functional theory calculations, a three-stepmore » reaction pathway is proposed to account for the chemisorbed O assisted dehydrogenation of H 2O molecules and the net loss of surface oxygen. Finally, these results provide insight into understanding the elemental steps of the dehydrogenation of H 2O molecules and the controllable conditions for tuning H 2O dissociation on metal surfaces.« less

Fictitious domain method for fully resolved reacting gas-solid flow simulation

NASA Astrophysics Data System (ADS)

Zhang, Longhui; Liu, Kai; You, Changfu

2015-10-01

Fully resolved simulation (FRS) for gas-solid multiphase flow considers solid objects as finite sized regions in flow fields and their behaviours are predicted by solving equations in both fluid and solid regions directly. Fixed mesh numerical methods, such as fictitious domain method, are preferred in solving FRS problems and have been widely researched. However, for reacting gas-solid flows no suitable fictitious domain numerical method has been developed. This work presents a new fictitious domain finite element method for FRS of reacting particulate flows. Low Mach number reacting flow governing equations are solved sequentially on a regular background mesh. Particles are immersed in the mesh and driven by their surface forces and torques integrated on immersed interfaces. Additional treatments on energy and surface reactions are developed. Several numerical test cases validated the method and a burning carbon particles array falling simulation proved the capability for solving moving reacting particle cluster problems.

Coadsorbed species explain the mechanism of methanol temperature-desorption on CeO 2(111)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sutton, Jonathan E.; Steven H. Overbury; Beste, Ariana

2016-03-24

Here, we have used density functional theory calculations to investigate the temperature-programmed desorption (TPD) of methanol from CeO 2(111). For the first time, low-temperature water formation and high-temperature methanol desorption are explained by our calculations. High coverages of methanol, which correspond to experimental conditions, are required to properly describe these features of the TPD spectrum. We identify a mechanism for the low-temperature formation of water involving the dissociation of two methanol molecules on the same surface O atom and filling of the resulting surface vacancy with one of the methoxy products. After water desorption, methoxy groups are stabilized on themore » surface and react at higher temperatures to form methanol and formaldehyde by a disproportionation mechanism. Alternatively, the stabilized methoxy groups undergo sequential C–H scission reactions to produce formaldehyde. Calculated energy requirements and methanol/formaldehyde selectivity agree with the experimental data.« less

Ensemble Averaged Probability Density Function (APDF) for Compressible Turbulent Reacting Flows

NASA Technical Reports Server (NTRS)

Shih, Tsan-Hsing; Liu, Nan-Suey

2012-01-01

In this paper, we present a concept of the averaged probability density function (APDF) for studying compressible turbulent reacting flows. The APDF is defined as an ensemble average of the fine grained probability density function (FG-PDF) with a mass density weighting. It can be used to exactly deduce the mass density weighted, ensemble averaged turbulent mean variables. The transport equation for APDF can be derived in two ways. One is the traditional way that starts from the transport equation of FG-PDF, in which the compressible Navier- Stokes equations are embedded. The resulting transport equation of APDF is then in a traditional form that contains conditional means of all terms from the right hand side of the Navier-Stokes equations except for the chemical reaction term. These conditional means are new unknown quantities that need to be modeled. Another way of deriving the transport equation of APDF is to start directly from the ensemble averaged Navier-Stokes equations. The resulting transport equation of APDF derived from this approach appears in a closed form without any need for additional modeling. The methodology of ensemble averaging presented in this paper can be extended to other averaging procedures: for example, the Reynolds time averaging for statistically steady flow and the Reynolds spatial averaging for statistically homogeneous flow. It can also be extended to a time or spatial filtering procedure to construct the filtered density function (FDF) for the large eddy simulation (LES) of compressible turbulent reacting flows.

Reactivation of dead sulfide species in lithium polysulfide flow battery for grid scale energy storage

DOE PAGES

Jin, Yang; Zhou, Guangmin; Shi, Feifei; ...

2017-09-06

Lithium polysulfide batteries possess several favorable attributes including low cost and high energy density for grid energy storage. However, the precipitation of insoluble and irreversible sulfide species on the surface of carbon and lithium (called “dead” sulfide species) leads to continuous capacity degradation in high mass loading cells, which represents a great challenge. To address this problem, herein we propose a strategy to reactivate dead sulfide species by reacting them with sulfur powder with stirring and heating (70 °C) to recover the cell capacity, and further demonstrate a flow battery system based on the reactivation approach. As a result, ultrahighmore » mass loading (0.125 g cm –3, 2g sulfur in a single cell), high volumetric energy density (135 Wh L –1), good cycle life, and high single-cell capacity are achieved. The high volumetric energy density indicates its promising application for future grid energy storage.« less

Reactivation of dead sulfide species in lithium polysulfide flow battery for grid scale energy storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin, Yang; Zhou, Guangmin; Shi, Feifei

Lithium polysulfide batteries possess several favorable attributes including low cost and high energy density for grid energy storage. However, the precipitation of insoluble and irreversible sulfide species on the surface of carbon and lithium (called “dead” sulfide species) leads to continuous capacity degradation in high mass loading cells, which represents a great challenge. To address this problem, herein we propose a strategy to reactivate dead sulfide species by reacting them with sulfur powder with stirring and heating (70 °C) to recover the cell capacity, and further demonstrate a flow battery system based on the reactivation approach. As a result, ultrahighmore » mass loading (0.125 g cm –3, 2g sulfur in a single cell), high volumetric energy density (135 Wh L –1), good cycle life, and high single-cell capacity are achieved. The high volumetric energy density indicates its promising application for future grid energy storage.« less

Simultaneous species concentration and temperature measurements using laser induced breakdown spectroscopy with direct spectrum matching

NASA Astrophysics Data System (ADS)

McGann, Brendan J.

Laser induced breakdown spectroscopy (LIBS) is used to simultaneously measure hydrocarbon fuel concentration and temperature in high temperature, high speed, compressible, and reacting flows, a regime in which LIBS has not been done previously. Emission spectra from the plasma produced from a focused laser pulse is correlated in the combustion region of a model scramjet operating in supersonic wind tunnel. A 532 nm Nd:YAG laser operating at 10 Hz is used to induce break-down. The emissions are captured during a 10 ns gate time approximately 75 ns after the first arrival of photons at the measurement location in order to minimize the measurement uncertainty in the turbulent, compressible, high-speed, and reacting environment. Three methods of emission detection are used and a new backward scattering direction method is developed that is beneficial in reducing the amount of optical access needed to perform LIBS measurements. Measurements are taken in the model supersonic combustion and the ignition process is shown to be highly dependent on fuel concentration and gas density as well as combustion surface temperature, concentration gradient, and flow field. Direct spectrum matching method is developed and used for quantitative measurements. In addition, a comprehensive database of spectra covering the fuel concentrations and gas densities found in the wind tunnel of Research Cell 19 at Wright Patterson Air Force Base is created which can be used for further work.

Targeted Single-Site MOF Node Modification: Trivalent Metal Loading via Atomic Layer Deposition

DOE PAGES

Kim, In Soo; Borycz, Joshua; Platero-Prats, Ana E.; ...

2015-07-02

Postsynthetic functionalization of metal organic frameworks (MOFs) enables the controlled, high-density incorporation of new atoms on a crystallographically precise framework. Leveraging the broad palette of known atomic layer deposition (ALD) chemistries, ALD in MOFs (AIM) is one such targeted approach to construct diverse, highly functional, few-atom clusters. In this paper, we demonstrate the saturating reaction of trimethylindium (InMe 3) with the node hydroxyls and ligated water of NU-1000, which takes place without significant loss of MOF crystallinity or internal surface area. We computationally identify the elementary steps by which trimethylated trivalent metal compounds (ALD precursors) react with this Zr-based MOFmore » node to generate a uniform and well characterized new surface layer on the node itself, and we predict a final structure that is fully consistent with experimental X-ray pair distribution function (PDF) analysis. Finally, we further demonstrate tunable metal loading through controlled number density of the reactive handles (–OH and –OH 2) achieved through node dehydration at elevated temperatures.« less

Targeted Single-Site MOF Node Modification: Trivalent Metal Loading via Atomic Layer Deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, In Soo; Borycz, Joshua; Platero-Prats, Ana E.

Postsynthetic functionalization of metal organic frameworks (MOFs) enables the controlled, high-density incorporation of new atoms on a crystallographically precise framework. Leveraging the broad palette of known atomic layer deposition (ALD) chemistries, ALD in MOFs (AIM) is one such targeted approach to construct diverse, highly functional, few-atom clusters. In this paper, we demonstrate the saturating reaction of trimethylindium (InMe 3) with the node hydroxyls and ligated water of NU-1000, which takes place without significant loss of MOF crystallinity or internal surface area. We computationally identify the elementary steps by which trimethylated trivalent metal compounds (ALD precursors) react with this Zr-based MOFmore » node to generate a uniform and well characterized new surface layer on the node itself, and we predict a final structure that is fully consistent with experimental X-ray pair distribution function (PDF) analysis. Finally, we further demonstrate tunable metal loading through controlled number density of the reactive handles (–OH and –OH 2) achieved through node dehydration at elevated temperatures.« less

Decomposition pathways of C2 oxygenates on Rh-modified tungsten carbide surfaces

DOE PAGES

Kelly, Thomas G.; Ren, Hui; Chen, Jingguang G.

2015-03-27

Ethanol decomposition on tungsten monocarbide (WC) and Rh-modified WC was investigated using ultrahigh vacuum (UHV) surface science experiments and density functional theory (DFT) calculations. DFT calculations indicated that the binding energies of ethanol and its decomposition intermediates on WC(0001) were modified by Rh, with Rh/WC(0001) showing similar values to those on Rh(111). Through temperature-programmed desorption (TPD) experiments on polycrystalline WC and Rh-modified WC, it was shown that the selectivity for ethanol decomposition was different on these surfaces. On WC, the C-O bond of ethanol was preferentially broken to produce ethylene; on Rh-modified WC, the C-C bond was broken to producemore » carbon monoxide and methane. In addition, high-resolution electron energy loss spectroscopy (HREELS) was used to determine likely surface intermediates. On Rh-modified WC, ethanol first formed ethoxy through O-H scission, then reacted through an aldehyde intermediate to form the C1 products.« less

Degradation of the chemotherapy drug 5-fluorouracil on medical-grade silver surfaces

NASA Astrophysics Data System (ADS)

Risinggård, Helene Kjær; Cooil, Simon; Mazzola, Federico; Hu, Di; Kjærvik, Marit; Østli, Elise Ramleth; Patil, Nilesh; Preobrajenski, Alexei; Andrew Evans, D.; Breiby, Dag W.; Trinh, Thuat T.; Wells, Justin W.

2018-03-01

The degradation of the chemotherapy drug 5-fluorouracil by a non-pristine metal surfaces is studied. Using density functional theory, X-ray photoelectron spectroscopy and X-ray absorption spectroscopy we show that the drug is entirely degraded by medical-grade silver surfaces, already at body temperature, and that all of the fluorine has left the molecule, presumably as HF. Remarkably, this degradation is even more severe than that reported previously for 5-fluorouracil on a pristine monocrystalline silver surface (in which case 80% of the drug reacted at body temperature) [1]. We conclude that the observed reaction is due to a reaction pathway, driven by H to F attraction between molecules on the surface, which results in the direct formation of HF; a pathway which is favoured when competing pathways involving reactive Ag surface sites are made unavailable by environmental contamination. Our measurements indicate that realistically cleaned, non-pristine silver alloys, which are typically used in medical applications, can result in severe degradation of 5-fluorouracil, with the release of HF - a finding which may have important implications for the handling of chemotherapy drugs.

In vitro production of beta-very low density lipoproteins and small, dense low density lipoproteins in mildly hypertriglyceridemic plasma: role of activities of lecithin:cholester acyltransferase, cholesterylester transfer proteins and lipoprotein lipase.

PubMed

Chung, B H; Segrest, J P; Franklin, F

1998-12-01

As a model for the formation of beta-very low density lipoproteins (VLDL) and small, dense LDL by the intraplasma metabolic activities in vivo, lipoproteins in fresh plasma were interacted in vitro with endogenous lecithin:cholesterol acyltransferase (LCAT) and cholesterylester transfer proteins (CETP) and subsequently with purified lipoprotein lipase (LpL). The LCAT and CETP reactions in a mildly hypertriglyceridemic (HTG) plasma at 37 degrees C for 18 h resulted in (1) esterification of about 45% plasma unesterified cholesterol (UC), (2) a marked increase in cholesterylester (CE) (+129%) and a decrease in triglyceride (TG) (-45%) in VLDL, and (3) a marked increase of TG (+ 341%) with a small net decrease of CE (-3.6%) in LDL, causing a significant alteration in the TG/CE of VLDL (from 8.0 to 1.9) and of LDL (from 0.20 to 0.93). The LDL in LCAT and CETP-reacted plasma is larger and more buoyant than that in control plasma. In vitro lipolysis of control and LCAT and CETP-reacted plasma by LpL, which hydrolyzed >90% of VLDL-TG and about 50-60% of LDL-TG, converted most of VLDL in control plasma (>85%) but less than half (40%) of VLDL in LCAT and CETP-reacted plasma into the IDL-LDL density fraction and transformed the large, buoyant LDL in the LCAT and CETP-reacted plasma into particles smaller and denser than those in the control plasma. The remnants that accumulated in the VLDL density region of the postlipolysis LCAT and CETP-reacted plasma contained apo B-100 and E but little or no detectable apo Cs and consisted of particles having pre-beta and beta-electrophoretic mobilities. The inhibition of LCAT during incubation of plasma, which lessened the extent of alteration in VLDL and LDL core lipids, increased the extent of lipolytic removal of VLDL from the VLDL density region but lowered the extent of alteration in the size and density of LDL. The LCAT, CETP and/or LpL-mediated alterations in the density of LDL in normolipidemic fasting plasma were less pronounced than that in mildly HTG plasma, but they became highly pronounced upon increase of its TG-rich lipoprotein level by the addition of preisolated VLDL or by the induction of postprandial lipemia. Although the effect of LCAT, CETP and LpL reactions in non-circulating plasma in vitro may be different from that in vivo, the above data suggests that the plasma TG-rich lipoprotein level and the extent of intraplasma LCAT, CETP, LpL and likely hepatic lipase (HL) reactions in vivo may play a role in determining the LDL phenotype.

[A surface reacted layer study of titanium-zirconium alloy after dental casting].

PubMed

Zhang, Y; Guo, T; Li, Z; Li, C

2000-10-01

To investigate the influence of the mold temperature on the surface reacted layer of Ti-Zr alloy castings. Ti-Zr alloy was casted into a mold which was made of a zircon (ZrO2.SiO2) for inner coating and a phosphate-bonded material for outer investing with a casting machine (China) designed as vacuum, pressure and centrifuge. At three mold temperatures (room temperature, 300 degrees C, 600 degrees C) the Ti-Zr alloy was casted separately. The surface roughness of the castings was calculated by instrument of smooth finish (China). From the surface to the inner part the Knoop hardness and thickness in reacted layer of Ti-Zr alloy casting was measured. The structure of the surface reacted layer was analysed by SEM. Elemental analyses of the interfacial zone of the casting was made by element line scanning observation. The surface roughness of the castings was increased significantly with the mold temperature increasing. At a higher mold temperature the Knoop hardness of the reactive layer was increased. At the three mold temperature the outmost surface was very hard, and microhardness data decreased rapidly where they reached constant values. The thickness was about 85 microns for castings at room temperature and 300 degrees C, 105 microns for castings at 600 degrees C. From the SEM micrograph of the Ti-Zr alloy casting, the surface reacted layer could be divided into three different layers. The first layer was called non-structure layer, which thickness was about 10 microns for room temperature group, 20 microns for 300 degrees C and 25 microns for 600 degrees C. The second layer was characterized by coarse-grained acicular crystal, which thickness was about 50 microns for three mold temperatures. The third layer was Ti-Zr alloy. The element line scanning showed non-structure layer with higher level of element of O, Al, Si and Zr, The higher the mold temperature during casting, the deeper the Si permeating and in the second layer the element Si could also be found. The mold temperature is one of the major factors influencing to casting quality. In order to reduce the surface reacted layer of Ti-Zr alloy castings, the lower mold temperature and the investment without Si should be chosen.

Probability density function approach for compressible turbulent reacting flows

NASA Technical Reports Server (NTRS)

Hsu, A. T.; Tsai, Y.-L. P.; Raju, M. S.

1994-01-01

The objective of the present work is to extend the probability density function (PDF) tubulence model to compressible reacting flows. The proability density function of the species mass fractions and enthalpy are obtained by solving a PDF evolution equation using a Monte Carlo scheme. The PDF solution procedure is coupled with a compression finite-volume flow solver which provides the velocity and pressure fields. A modeled PDF equation for compressible flows, capable of treating flows with shock waves and suitable to the present coupling scheme, is proposed and tested. Convergence of the combined finite-volume Monte Carlo solution procedure is discussed. Two super sonic diffusion flames are studied using the proposed PDF model and the results are compared with experimental data; marked improvements over solutions without PDF are observed.

Preparation and the Electrochemical Performance of MnO2/PANI@CNT Composite for Supercapacitors.

PubMed

Wang, Hongjuan; Wang, Xiaohui; Peng, Cheng; Peng, Feng; Yu, Hao

2015-01-01

Polyaniline (PANI) was settled on the surface of CNTs in advance and then used as self-sacrifice reducing agent that would react with KMnO4 to prepare MnO2/PANI@CNT supercapacitor material. With PANI substituting for CNTs to participant the redox reaction, CNTs was protected from being destroyed and could maintain its original morphology and conductivity. The results of cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) show that the optimal capacitive performance can be reached at the MnO2 loading of 64.4 wt% and the pH of 1 during the deposition of MnO2. With the protective PANI, MnO2/PANI@CNT composite exhibits the superior specific capacitance of 215.8 F/g at a current density of 200 mA/g and remains 86.5% of its maximal specific capacitance at a current density of 1000 mA/g.

Effect of nature of oxygen interactions on friction of titanium, aluminum, and molybdenum

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1976-01-01

Friction studies were conducted with a gold pin contacting titanium, aluminum, and molybdenum surfaces after exposure to oxygen with various methods. Oxygen was adsorbed on the surface, it reacted with the surface, and the surface was ion bombarded with oxygen. The presence of oxygen was monitored with Auger spectroscopy. Titanium friction varied with the mode of the metal-oxygen interaction. It was highest with the adsorbed oxygen and least with ion bombardment using oxygen. Aluminum exhibited lower friction values for the reacted and the ion bombarded surfaces than for the surface having the adsorbed layer. With molybdenum the friction coefficients were generally the same despite the nature of the surface treatment with oxygen.

Method for providing a low density high strength polyurethane foam

DOEpatents

Whinnery, Jr., Leroy L.; Goods, Steven H.; Skala, Dawn M.; Henderson, Craig C.; Keifer, Patrick N.

2013-06-18

Disclosed is a method for making a polyurethane closed-cell foam material exhibiting a bulk density below 4 lbs/ft.sup.3 and high strength. The present embodiment uses the reaction product of a modified MDI and a sucrose/glycerine based polyether polyol resin wherein a small measured quantity of the polyol resin is "pre-reacted" with a larger quantity of the isocyanate in a defined ratio such that when the necessary remaining quantity of the polyol resin is added to the "pre-reacted" resin together with a tertiary amine catalyst and water as a blowing agent, the polymerization proceeds slowly enough to provide a stable foam body.

Reactivity of dissolved- vs. supercritical-CO2 phase toward muscovite basal surfaces

NASA Astrophysics Data System (ADS)

Wan, J.; Tokunaga, T. K.; Kim, Y.; Wang, S.; Altoe, M. V. P.; Ashby, P. D.; DePaolo, D.

2015-12-01

The current understanding of geochemical reactions in reservoirs for geological carbon sequestration (GCS) is largely based on aqueous chemistry (CO2 dissolves in reservoir brine and brine reacts with rocks). However, only a portion of the injected supercritical (sc) CO2 dissolves before the buoyant plume contacts caprock, where it is expected to reside for a long time. Although numerous studies have addressed scCO2-mineral reactions occurring within adsorbed aqueous films, possible reactions resulting from direct CO2-rock contact remain less understood. Does CO2 as a supercritical phase react with reservoir rocks? Do mineral react differently with scCO2 than with dissolved CO2? We selected muscovite, one of the more stable and common rock-forming silicate minerals, to react with scCO2 phase (both water-saturated and water-free) and compared with CO2-saturated-brine. The reacted basal surfaces were analyzed using atomic force microscopy and X-ray photoelectron spectroscopy for examining the changes in surface morphology and chemistry. The results show that scCO2 (regardless of its water content) altered muscovite considerably more than CO2-saturated brine; suggest CO2 diffusion into mica interlayers and localized mica dissolution into scCO2 phase. The mechanisms underlying these observations and their implications for GCS need further exploration.

Evaluation of the new TAMZ titanium alloy for dental cast application.

PubMed

Zhang, Y M; Guo, T W; Li, Z C

2000-12-01

To reveal the potential of the new titanium alloy as dental prosthodontic materials. Dental castings of TAMZ alloy were investigated in the casting machine specially designed for titanium. A mesh pattern was used to count the castability value. The mechanical properties were measured by means of a universal testing machine. Optical micrography was done on the exposed cross-section of TAMZ alloy casting. From the surface to the inner part the Knoop hardness in reacted layer of TAMZ alloy casting was measured. The structure and elemental analyses of the reacted layer were made by SEM and element line scanning observation. The castability value (Cv = 98%) and the tensile test (sigma b = 850 Mpa, sigma 0.2 = 575 Mpa, delta = 7.33%) data were collected. The castings microstructure showed main alpha phase and small beta phase. Knoop hardness in the surface reacted layer was greater than that in the inner part. From the SEM and element line scanning observation, there are three different layers in the surface reacted layer of the TAMZ alloy castings, and higher level of element of O, Al, Si and Zr were found in the reacted layer while the Si permeated deeper than others. TAMZ alloy can be accepted as a material for dental alloy in prosthodontics.

Harnessing surface-bound enzymatic reactions to organize microcapsules in solution

PubMed Central

Shklyaev, Oleg E.; Shum, Henry; Sen, Ayusman; Balazs, Anna C.

2016-01-01

By developing new computational models, we examine how enzymatic reactions on an underlying surface can be harnessed to direct the motion and organization of reagent-laden microcapsules in a fluid-filled microchannel. In the presence of appropriate reagents, surface-bound enzymes can act as pumps, which drive large-scale fluid flows. When the reagents diffuse through the capsules’ porous shells, they can react with enzymatic sites on the bottom surface. The ensuing reaction generates fluid density variations, which result in fluid flows. These flows carry the suspended microcapsules and drive them to aggregate into “colonies” on and near the enzyme-covered sites. This aggregation continues until the reagent has been depleted and the convection stops. We show that the shape of the assembled colonies can be tailored by patterning the distribution of enzymes on the surface. This fundamental physicochemical mechanism could have played a role in the self-organization of early biological cells (protocells) and can be used to regulate the autonomous motion and targeted delivery of microcarriers in microfluidic devices. PMID:27034990

Experimental study of combustion in a turbulent free shear layer formed at a rearward facing step

NASA Technical Reports Server (NTRS)

Pitz, R. W.; Daily, J. W.

1981-01-01

A premixed propane-air flame is stabilized in a turbulent free shear layer formed at a rearward facing step. The mean and rms averages of the turbulent velocity flow field are determined by LDV for both reacting (equivalence ratio 0.57) and nonreacting flows (Reynolds number 15,000-37,000 based on step height). The effect of combustion is to shift the layer toward the recirculation zone and reduce the flame spread. For reacting flow, the growth rate is unchanged except very near the step. The probability density function of the velocity is bimodial near the origin of the reacting layer and single-peaked but often skewed elsewhere. Large-scale structures dominate the reacting shear layer. Measurements of their passing frequency from LDV are consistent with high-speed Schlieren movies of the reacting layer and indicate that the coalescence rate of the eddies in the shear layer is reduced by combustion.

Active site densities, oxygen activation and adsorbed reactive oxygen in alcohol activation on npAu catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Lu-Cun; Friend, C. M.; Fushimi, Rebecca

The activation of molecular O 2as well as the reactivity of adsorbed oxygen species is of central importance in aerobic selective oxidation chemistry on Au-based catalysts. Herein, we address the issue of O 2activation on unsupported nanoporous gold (npAu) catalysts by applying a transient pressure technique, a temporal analysis of products (TAP) reactor, to measure the saturation coverage of atomic oxygen, its collisional dissociation probability, the activation barrier for O 2dissociation, and the facility with which adsorbed O species activate methanol, the initial step in the catalytic cycle of esterification. The results from these experiments indicate that molecular O 2dissociationmore » is associated with surface silver, that the density of reactive sites is quite low, that adsorbed oxygen atoms do not spill over from the sites of activation onto the surrounding surface, and that methanol reacts quite facilely with the adsorbed oxygen atoms. In addition, the O species from O 2dissociation exhibits reactivity for the selective oxidation of methanol but not for CO. The TAP experiments also revealed that the surface of the npAu catalyst is saturated with adsorbed O under steady state reaction conditions, at least for the pulse reaction.« less

Active site densities, oxygen activation and adsorbed reactive oxygen in alcohol activation on npAu catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Lu-Cun; Friend, C. M.; Fushimi, Rebecca

2016-01-01

The activation of molecular O 2as well as the reactivity of adsorbed oxygen species is of central importance in aerobic selective oxidation chemistry on Au-based catalysts. Herein, we address the issue of O 2activation on unsupported nanoporous gold (npAu) catalysts by applying a transient pressure technique, a temporal analysis of products (TAP) reactor, to measure the saturation coverage of atomic oxygen, its collisional dissociation probability, the activation barrier for O 2dissociation, and the facility with which adsorbed O species activate methanol, the initial step in the catalytic cycle of esterification. The results from these experiments indicate that molecular O 2dissociationmore » is associated with surface silver, that the density of reactive sites is quite low, that adsorbed oxygen atoms do not spill over from the sites of activation onto the surrounding surface, and that methanol reacts quite facilely with the adsorbed oxygen atoms. In addition, the O species from O 2dissociation exhibits reactivity for the selective oxidation of methanol but not for CO. The TAP experiments also revealed that the surface of the npAu catalyst is saturated with adsorbed O under steady state reaction conditions, at least for the pulse reaction.« less

Role of CO2 in the oxy-dehydrogenation of ethylbenzene to styrene on the CeO2(111) surface

NASA Astrophysics Data System (ADS)

Fan, Hong-Xia; Feng, Jie; Li, Wen-Ying; Li, Xiao-Hong; Wiltowski, Tomasz; Ge, Qing-Feng

2018-01-01

The role of CO2 in the ethylbenzene oxy-dehydrogenation to styrene on the CeO2(111) surface was thoroughly investigated by the density functional theory (DFT) calculations. Results show that the first Csbnd H bond of ethylbenzene is activated via the oxo-insertion with a barrier of 1.70 eV, resulting in a 2-phenylethyl species and an H atom adsorbed on two-adjacent-lattice oxygen. The H adatom forms a hydroxyl-like species (denoted as O*H). The subsequent dehydrogenation to styrene can be assisted by either the next lattice oxygen (pathway R1) or the O*H species (pathway R2). The two pathways have almost the same activation energy (0.84 eV for R1 and 0.85 eV for R2), forming a new O*H and desorbing a H2O molecule while leaving an oxygen vacancy on the surface, respectively. In the presence of CO2, it will react with O*H through the reverse water gas shift reaction with an activation barrier of 0.98 eV and reaction energy of 0.30 eV. The reverse water gas shift reaction helps to clear the H adatoms from the lattice oxygen, thereby competing with styrene formation via pathway R2. However, the activation energy following the reverse water gas shift mechanism is 0.13 eV higher than that of styrene formation via pathway R2. Therefore, the formation of oxygen vacancy cannot be inhibited, while CO2 can react with the surface oxygen vacancy to produce CO with a high activation energy of 2.10 eV.

Methods of Attaching or Grafting Carbon Nanotubes to Silicon Surfaces and Composite Structures Derived Therefrom

NASA Technical Reports Server (NTRS)

Tour, James M. (Inventor); Chen, Bo (Inventor); Flatt, Austen K. (Inventor); Stewart, Michael P. (Inventor); Dyke, Christopher A. (Inventor); Maya, Francisco (Inventor)

2012-01-01

The present invention is directed toward methods of attaching or grafting carbon nanotubes (CNTs) to silicon surfaces. In some embodiments, such attaching or grafting occurs via functional groups on either or both of the CNTs and silicon surface. In some embodiments, the methods of the present invention include: (1) reacting a silicon surface with a functionalizing agent (such as oligo(phenylene ethynylene)) to form a functionalized silicon surface; (2) dispersing a quantity of CNTs in a solvent to form dispersed CNTs; and (3) reacting the functionalized silicon surface with the dispersed CNTs. The present invention is also directed to the novel compositions produced by such methods.

LES, DNS and RANS for the analysis of high-speed turbulent reacting flows

NASA Technical Reports Server (NTRS)

Givi, Peyman; Taulbee, Dale B.; Adumitroaie, Virgil; Sabini, George J.; Shieh, Geoffrey S.

1994-01-01

The purpose of this research is to continue our efforts in advancing the state of knowledge in large eddy simulation (LES), direct numerical simulation (DNS), and Reynolds averaged Navier Stokes (RANS) methods for the computational analysis of high-speed reacting turbulent flows. In the second phase of this work, covering the period 1 Sep. 1993 - 1 Sep. 1994, we have focused our efforts on two research problems: (1) developments of 'algebraic' moment closures for statistical descriptions of nonpremixed reacting systems, and (2) assessments of the Dirichlet frequency in presumed scalar probability density function (PDF) methods in stochastic description of turbulent reacting flows. This report provides a complete description of our efforts during this past year as supported by the NASA Langley Research Center under Grant NAG1-1122.

Harnessing catalytic pumps for directional delivery of microparticles in microchambers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, Sambeeta; Shklyaev, Oleg E.; Altemose, Alicia

The directed transport of microparticles in microfluidic devices is vital for efficient bioassays and fabrication of complex microstructures. There remains, but, a need for methods to propel and steer microscopic cargo that do not require modifying these particles. By using theory and experiments, we show that catalytic surface reactions can be used to deliver microparticle cargo to specified regions in microchambers. Here reagents diffuse from a gel reservoir and react with the catalyst-coated surface. Fluid density gradients due to the spatially varying reagent concentration induce a convective flow, which carries the suspended particles until the reagents are consumed. Consequently, themore » cargo is deposited around a specific position on the surface. The velocity and final peak location of the cargo can be tuned independently. And by increasing the local particle concentration, highly sensitive assays can be performed efficiently and rapidly. Moreover, the process can be repeated by introducing fresh reagent into the microchamber.« less

Harnessing catalytic pumps for directional delivery of microparticles in microchambers

DOE PAGES

Das, Sambeeta; Shklyaev, Oleg E.; Altemose, Alicia; ...

2017-02-17

The directed transport of microparticles in microfluidic devices is vital for efficient bioassays and fabrication of complex microstructures. There remains, but, a need for methods to propel and steer microscopic cargo that do not require modifying these particles. By using theory and experiments, we show that catalytic surface reactions can be used to deliver microparticle cargo to specified regions in microchambers. Here reagents diffuse from a gel reservoir and react with the catalyst-coated surface. Fluid density gradients due to the spatially varying reagent concentration induce a convective flow, which carries the suspended particles until the reagents are consumed. Consequently, themore » cargo is deposited around a specific position on the surface. The velocity and final peak location of the cargo can be tuned independently. And by increasing the local particle concentration, highly sensitive assays can be performed efficiently and rapidly. Moreover, the process can be repeated by introducing fresh reagent into the microchamber.« less

Comparison of polymer induced and solvent induced trypsin denaturation: the role of hydrophobicity.

PubMed

Jasti, Lakshmi S; Fadnavis, Nitin W; Addepally, Uma; Daniels, Siona; Deokar, Sarika; Ponrathnam, Surendra

2014-04-01

Trypsin adsorption from aqueous buffer by various copolymers of allyl glycidyl ether-ethylene glycol dimethacrylate (AGE-EGDM) copolymer with varying crosslink density increases with increasing crosslink density and the effect slowly wears off after reaching a plateau at 50% crosslink density. The copolymer with 25% crosslink density was reacted with different amines with alkyl/aryl side chains to obtain a series of copolymers with 1,2-amino alcohol functional groups and varying hydrophobicity. Trypsin binding capacity again increases with hydrophobicity of the reacting amine and a good correlation between logPoctanol of the amine and protein binding is observed. The bound trypsin is denatured to the extent of 90% in spite of the presence of hydrophilic hydroxyl and amino groups. The behavior was comparable to that in mixtures of aqueous buffer and water-miscible organic co-solvents where the solvent concentration required to deactivate 50% of the enzyme (C50) is dependent on logPoctanol of the co-solvent. Copyright © 2014 Elsevier B.V. All rights reserved.

Characterizing TPS Microstructure: A Review of Some techniques

NASA Technical Reports Server (NTRS)

Gasch, Matthew; Stackpole, Mairead; Agrawal, Parul; Chavez-Garcie, Jose

2011-01-01

I. When seeking to understand ablator microstructure and morphology there are several useful techniques A. SEM 1) Visual characteriza3on at various length scales. 2) Chemical mapping by backscatter or x-ray highlights areas of interest. 3) Combined with other techniques (density, weight change, chemical analysis) SEM is a powerful tool to aid in explaining thermo/structural data. B. ASAP. 1) Chemical characteriza3on at various length scales. 2) Chemical mapping of pore structure by gas adsorption. 3) Provides a map of pore size vs. pore volume. 4) Provided surface area of exposed TPS. II. Both methods help characterize and understand how ablators react with other chemical species and provides insight into how they oxidize.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garcia-Pintos, Delfina; Voss, Johannes; Jensen, Anker D.

Herein we describe the C–O cleavage of phenol and cyclohexanol over Rh(111) and Rh(211) surfaces using density functional theory calculations. Our analysis is complemented by a microkinetic model of the reactions, which indicates that the C–O bond cleavage of cyclohexanol is easier than that of phenol and that Rh(211) is more active than Rh(111) for both reactions. This indicates that phenol will react mainly following a pathway of initial hydrogenation to cyclohexanol followed by hydrodeoxygenation to cyclohexane. In conclusion, we show that there is a general relationship between the transition state and the final state of both C–O cleavage reactions,more » and that this relationship is the same for Rh(111) and Rh(211).« less

Numerical simulation of two-dimensional flow over a heated carbon surface with coupled heterogeneous and homogeneous reactions

NASA Astrophysics Data System (ADS)

Johnson, Ryan Federick; Chelliah, Harsha Kumar

2017-01-01

For a range of flow and chemical timescales, numerical simulations of two-dimensional laminar flow over a reacting carbon surface were performed to understand further the complex coupling between heterogeneous and homogeneous reactions. An open-source computational package (OpenFOAM®) was used with previously developed lumped heterogeneous reaction models for carbon surfaces and a detailed homogeneous reaction model for CO oxidation. The influence of finite-rate chemical kinetics was explored by varying the surface temperatures from 1800 to 2600 K, while flow residence time effects were explored by varying the free-stream velocity up to 50 m/s. The reacting boundary layer structure dependence on the residence time was analysed by extracting the ratio of chemical source and species diffusion terms. The important contributions of radical species reactions on overall carbon removal rate, which is often neglected in multi-dimensional simulations, are highlighted. The results provide a framework for future development and validation of lumped heterogeneous reaction models based on multi-dimensional reacting flow configurations.

Silica powders for powder evacuated thermal insulating panel and method

DOEpatents

Harris, Michael T.; Basaran, Osman A.; Kollie, Thomas G.; Weaver, Fred J.

1996-01-01

A powder evacuated thermal insulating panel using generally spherical and porous silica particles of a median size less than about 100 nanometers in diameter, a pour packing density of about 0.4 to 0.6 g/cm.sup.3 and an external surface area in the range of about 90 to 600 m.sup.2/ g is described. The silica powders are prepared by reacting a tetraakyl silicate with ammonia and water in an alcohol solvent, distilling the solution after the reaction to remove the ammonia and recover the alcohol. The resulting aqueous slurry was dried, ball-milled, and dried again to provide the silica particles with defined internal and external porosity. The nanometer size and the large external surface area of the silica particles along with the internal and external porosity of the silica particles provide powder evacuated thermal insulating panels with significantly higher R-values than obtainable using previously known silica powders.

Silica powders for powder evacuated thermal insulating panel and method

DOEpatents

Harris, Michael T.; Basaran, Osman A.; Kollie, Thomas G.; Weaver, Fred J.

1994-01-01

A powder evacuated thermal insulating panel using generally spherical and porous silica particles of a median size less than about 100 nanometers in diameter, a pour packing density of about 0.4 to 0.6 g/cm.sup.3 and an external surface area in the range of about 90 to 600 m.sup.2 /g is described. The silica powders are prepared by reacting a tetraakyl silicate with ammonia and water in an alcohol solvent, distilling the solution after the reaction to remove the ammonia and recover the alcohol. The resulting aqueous slurry was dried, ball-milled, and dried again to provide the silica particles with defined internal and external porosity. The nanometer size and the large external surface area of the silica particles along with the internal and external porosity of the silica particles provide powder evacuated thermal insulating panels with significantly higher R-values than obtainable using previously known silica powders.

Silica powders for powder evacuated thermal insulating panel and method

DOEpatents

Harris, Michael T.; Basaran, Osman A.; Kollie, Thomas G.; Weaver, Fred J.

1995-01-01

A powder evacuated thermal insulating panel using generally spherical and porous silica particles of a median size less than about 100 nanometers in diameter, a pour packing density of about 0.4 to 0.6 g/cm.sup.3 and an external surface area in the range of about 90 to 600 m.sup.2/ g is described. The silica powders are prepared by reacting a tetraakyl silicate with ammonia and water in an alcohol solvent, distilling the solution after the reaction to remove the ammonia and recover the alcohol. The resulting aqueous slurry was dried, ball-milled, and dried again to provide the silica particles with defined internal and external porosity. The nanometer size and the large external surface area of the silica particles along with the internal and external porosity of the silica particles provide powder evacuated thermal insulating panels with significantly higher R-values than obtainable using previously known silica powders.

Silica powders for powder evacuated thermal insulating panel and method

DOEpatents

Harris, M.T.; Basaran, O.A.; Kollie, T.G.; Weaver, F.J.

1996-01-02

A powder evacuated thermal insulating panel using generally spherical and porous silica particles of a median size less than about 100 nanometers in diameter, a pour packing density of about 0.4 to 0.6 g/cm{sup 3} and an external surface area in the range of about 90 to 600 m{sup 2}/g is described. The silica powders are prepared by reacting a tetraalkyl silicate with ammonia and water in an alcohol solvent, distilling the solution after the reaction to remove the ammonia and recover the alcohol. The resulting aqueous slurry was dried, ball-milled, and dried again to provide the silica particles with defined internal and external porosity. The nanometer size and the large external surface area of the silica particles along with the internal and external porosity of the silica particles provide powder evacuated thermal insulating panels with significantly higher R-values than obtainable using previously known silica powders. 2 figs.

Studies on biodegradation of crosslinked hydroxy terminated-poly(proplyene fumarate) and formation of scaffold for orthopedic applications.

PubMed

Shalumon, K T; Jayabalan, M

2009-12-01

Biodegradation of crosslinked-hydroxy terminated-poly(proplyene fumarate) (X-HTPPF) has been studied in simulated physiological media to assess the formation of porous scaffold structure for bone growth and remodeling in load bearing orthopedic applications. Variation in crosslink density and surface hydrophilicity of X-HTPPF are observed due to non-stoichiometric mass of reacting partners. These variations influence absorption of the medium and biodegradation during aging. Though the initial absorption of medium is relatively higher with the crosslinked polymer (PNVP1) having 63.6% HT-PPF and 36.4% comonomer n-vinyl pyrrolidone (NVP) during the initial period of aging, the weight loss due to subsequent degradation with time is relatively lesser. PNVP1 undergo slow degradation with formation of fibril structure on the surface. The present crosslinked material PNVP1 is a candidate for the load bearing orthopedic applications.

Understanding the Mechanism of SiC Plasma-Enhanced Chemical Vapor Deposition (PECVD) and Developing Routes toward SiC Atomic Layer Deposition (ALD) with Density Functional Theory.

PubMed

Filatova, Ekaterina A; Hausmann, Dennis; Elliott, Simon D

2018-05-02

Understanding the mechanism of SiC chemical vapor deposition (CVD) is an important step in investigating the routes toward future atomic layer deposition (ALD) of SiC. The energetics of various silicon and carbon precursors reacting with bare and H-terminated 3C-SiC (011) are analyzed using ab initio density functional theory (DFT). Bare SiC is found to be reactive to silicon and carbon precursors, while H-terminated SiC is found to be not reactive with these precursors at 0 K. Furthermore, the reaction pathways of silane plasma fragments SiH 3 and SiH 2 are calculated along with the energetics for the methane plasma fragments CH 3 and CH 2 . SiH 3 and SiH 2 fragments follow different mechanisms toward Si growth, of which the SiH 3 mechanism is found to be more thermodynamically favorable. Moreover, both of the fragments were found to show selectivity toward the Si-H bond and not C-H bond of the surface. On the basis of this, a selective Si deposition process is suggested for silicon versus carbon-doped silicon oxide surfaces.

A PDF closure model for compressible turbulent chemically reacting flows

NASA Technical Reports Server (NTRS)

Kollmann, W.

1992-01-01

The objective of the proposed research project was the analysis of single point closures based on probability density function (pdf) and characteristic functions and the development of a prediction method for the joint velocity-scalar pdf in turbulent reacting flows. Turbulent flows of boundary layer type and stagnation point flows with and without chemical reactions were be calculated as principal applications. Pdf methods for compressible reacting flows were developed and tested in comparison with available experimental data. The research work carried in this project was concentrated on the closure of pdf equations for incompressible and compressible turbulent flows with and without chemical reactions.

A Novel Strategy for Numerical Simulation of High-speed Turbulent Reacting Flows

NASA Technical Reports Server (NTRS)

Sheikhi, M. R. H.; Drozda, T. G.; Givi, P.

2003-01-01

The objective of this research is to improve and implement the filtered mass density function (FDF) methodology for large eddy simulation (LES) of high-speed reacting turbulent flows. We have just completed Year 1 of this research. This is the Final Report on our activities during the period: January 1, 2003 to December 31, 2003. 2002. In the efforts during the past year, LES is conducted of the Sandia Flame D, which is a turbulent piloted nonpremixed methane jet flame. The subgrid scale (SGS) closure is based on the scalar filtered mass density function (SFMDF) methodology. The SFMDF is basically the mass weighted probability density function (PDF) of the SGS scalar quantities. For this flame (which exhibits little local extinction), a simple flamelet model is used to relate the instantaneous composition to the mixture fraction. The modelled SFMDF transport equation is solved by a hybrid finite-difference/Monte Carlo scheme.

Method for producing metal oxide aerogels

DOEpatents

Tillotson, Thomas M.; Poco, John F.; Hrubesh, Lawrence W.; Thomas, Ian M.

1995-01-01

A two-step hydrolysis-condensation method was developed to form metal oxide aerogels of any density, including densities of less than 0.003g/cm.sup.3 and greater than 0.27g/cm.sup.3. High purity metal alkoxide is reacted with water, alcohol solvent, and an additive to form a partially condensed metal intermediate. All solvent and reaction-generated alcohol is removed, and the intermediate is diluted with a nonalcoholic solvent. The intermediate can be stored for future use to make aerogels of any density. The aerogels are formed by reacting the intermediate with water, nonalcoholic solvent, and a catalyst, and extracting the nonalcoholic solvent directly. The resulting monolithic aerogels are hydrophobic and stable under atmospheric conditions, and exhibit good optical transparency, high clarity, and homogeneity. The aerogels have high thermal insulation capacity, high porosity, mechanical strength and stability, and require shorter gelation times than aerogels formed by conventional methods.

Method for producing metal oxide aerogels

DOEpatents

Tillotson, T.M.; Poco, J.F.; Hrubesh, L.W.; Thomas, I.M.

1995-04-25

A two-step hydrolysis-condensation method was developed to form metal oxide aerogels of any density, including densities of less than 0.003g/cm{sup 3} and greater than 0.27g/cm{sup 3}. High purity metal alkoxide is reacted with water, alcohol solvent, and an additive to form a partially condensed metal intermediate. All solvent and reaction-generated alcohol is removed, and the intermediate is diluted with a nonalcoholic solvent. The intermediate can be stored for future use to make aerogels of any density. The aerogels are formed by reacting the intermediate with water, nonalcoholic solvent, and a catalyst, and extracting the nonalcoholic solvent directly. The resulting monolithic aerogels are hydrophobic and stable under atmospheric conditions, and exhibit good optical transparency, high clarity, and homogeneity. The aerogels have high thermal insulation capacity, high porosity, mechanical strength and stability, and require shorter gelation times than aerogels formed by conventional methods. 8 figs.

Modeling of the reactant conversion rate in a turbulent shear flow

NASA Technical Reports Server (NTRS)

Frankel, S. H.; Madnia, C. K.; Givi, P.

1992-01-01

Results are presented of direct numerical simulations (DNS) of spatially developing shear flows under the influence of infinitely fast chemical reactions of the type A + B yields Products. The simulation results are used to construct the compositional structure of the scalar field in a statistical manner. The results of this statistical analysis indicate that the use of a Beta density for the probability density function (PDF) of an appropriate Shvab-Zeldovich mixture fraction provides a very good estimate of the limiting bounds of the reactant conversion rate within the shear layer. This provides a strong justification for the implementation of this density in practical modeling of non-homogeneous turbulent reacting flows. However, the validity of the model cannot be generalized for predictions of higher order statistical quantities. A closed form analytical expression is presented for predicting the maximum rate of reactant conversion in non-homogeneous reacting turbulence.

Large eddy simulations and direct numerical simulations of high speed turbulent reacting flows

NASA Technical Reports Server (NTRS)

Givi, P.; Madnia, C. K.; Steinberger, C. J.; Frankel, S. H.

1992-01-01

The basic objective of this research is to extend the capabilities of Large Eddy Simulations (LES) and Direct Numerical Simulations (DNS) for the computational analyses of high speed reacting flows. In the efforts related to LES, we were primarily involved with assessing the performance of the various modern methods based on the Probability Density Function (PDF) methods for providing closures for treating the subgrid fluctuation correlations of scalar quantities in reacting turbulent flows. In the work on DNS, we concentrated on understanding some of the relevant physics of compressible reacting flows by means of statistical analysis of the data generated by DNS of such flows. In the research conducted in the second year of this program, our efforts focused on the modeling of homogeneous compressible turbulent flows by PDF methods, and on DNS of non-equilibrium reacting high speed mixing layers. Some preliminary work is also in progress on PDF modeling of shear flows, and also on LES of such flows.

Understanding oxygen adsorption on 9.375 at. % Ga-stabilized δ-Pu (111) surface: A DFT study

DOE PAGES

Hernandez, Sarah C.; Wilkerson, Marianne P.; Huda, Muhammad N.

2015-08-30

Plutonium (Pu) metal reacts rapidly in the presence of oxygen (O), resulting in an oxide layer that will eventually have an olive green rust appearance over time. Recent experimental work suggested that the incorporation of gallium (Ga) as an alloying impurity to stabilize the highly symmetric high temperature δ-phase lattice may also provide resistance against corrosion/oxidation of plutonium. In this paper, we modeled a 9.375 at. % Ga stabilized δ-Pu (111) surface and investigated adsorption of atomic O using all-electron density functional theory. Key findings revealed that the O bonded strongly to a Pu-rich threefold hollow fcc site with amore » chemisorption energy of –5.06 eV. Migration of the O atom to a Pu-rich environment was also highly sensitive to the surface chemistry of the Pu–Ga surface; when the initial on-surface O adsorption site included a bond to a nearest neighboring Ga atom, the O atom relaxed to a Ga deficient environment, thus affirming the O preference for Pu. Only one calculated final on-surface O adsorption site included a Ga-O bond, but this chemisorption energy was energetically unfavorable. Chemisorption energies for interstitial adsorption sites that included a Pu or Pu-Ga environment suggested that over-coordination of the O atom was energetically unfavorable as well. Electronic structure properties of the on-surface sites, illustrated by the partial density of states, implied that the Ga 4p states indirectly but strongly influenced the Pu 6d states strongly to hybridize with the O 2p states, while also weakly influenced the Pu 5f states to hybridize with the O 2p states, even though Ga was not participating in bonding with O.« less

Understanding oxygen adsorption on 9.375 at. % Ga-stabilized δ-Pu (111) surface: A DFT study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hernandez, Sarah C.; Wilkerson, Marianne P.; Huda, Muhammad N.

Plutonium (Pu) metal reacts rapidly in the presence of oxygen (O), resulting in an oxide layer that will eventually have an olive green rust appearance over time. Recent experimental work suggested that the incorporation of gallium (Ga) as an alloying impurity to stabilize the highly symmetric high temperature δ-phase lattice may also provide resistance against corrosion/oxidation of plutonium. In this paper, we modeled a 9.375 at. % Ga stabilized δ-Pu (111) surface and investigated adsorption of atomic O using all-electron density functional theory. Key findings revealed that the O bonded strongly to a Pu-rich threefold hollow fcc site with amore » chemisorption energy of –5.06 eV. Migration of the O atom to a Pu-rich environment was also highly sensitive to the surface chemistry of the Pu–Ga surface; when the initial on-surface O adsorption site included a bond to a nearest neighboring Ga atom, the O atom relaxed to a Ga deficient environment, thus affirming the O preference for Pu. Only one calculated final on-surface O adsorption site included a Ga-O bond, but this chemisorption energy was energetically unfavorable. Chemisorption energies for interstitial adsorption sites that included a Pu or Pu-Ga environment suggested that over-coordination of the O atom was energetically unfavorable as well. Electronic structure properties of the on-surface sites, illustrated by the partial density of states, implied that the Ga 4p states indirectly but strongly influenced the Pu 6d states strongly to hybridize with the O 2p states, while also weakly influenced the Pu 5f states to hybridize with the O 2p states, even though Ga was not participating in bonding with O.« less

Reaction of methyl formate with VC(1 0 0) and TiC(1 0 0) surfaces

NASA Astrophysics Data System (ADS)

Frantz, Peter; Kim, Hyun I.; Didziulis, Stephen V.; Li, Shuang; Chen, Zhiying; Perry, Scott S.

2005-12-01

The chemistry of the (1 0 0) surface of the tribologically important materials vanadium carbide (VC) and titanium carbide (TiC) with methyl formate (CH 3OCHO) has been studied with X-ray photoelectron spectroscopy (XPS), high resolution electron energy loss spectroscopy (HREELS), and temperature programmed desorption (TPD). The molecule reacts with each surface at temperatures below 150 K, although the extent of reaction is greater on the TiC surface. XPS and HREELS results indicate that the first step in this chemistry is the cleavage of the CH 3O-CHO bond, generating surface methoxy groups (CH 3O-) and either carbon monoxide on VC or a formyl (CHO) group on TiC. The methoxy group reacts further on both surfaces via pathways expected based on previous methanol adsorption studies, primarily decomposing through a formyl intermediate on VC to generate formaldehyde and evolving methanol on TiC. The formyl group formed directly from methyl formate on TiC enables the production and evolution of formaldehyde, and also appears to break down further to the elements. These results indicate a propensity for these carbides to react with esters, leading potentially to the beneficial formation of friction lowering surface films or the deleterious degradation of ester-based lubricants.

Water vapor adsorption on goethite.

PubMed

Song, Xiaowei; Boily, Jean-François

2013-07-02

Goethite (α-FeOOH) is an important mineral contributing to processes of atmospheric and terrestrial importance. Their interactions with water vapor are particularly relevant in these contexts. In this work, molecular details of water vapor (0.0-19.0 Torr; 0-96% relative humidity at 25 °C) adsorption at surfaces of synthetic goethite nanoparticles reacted with and without HCl and NaCl were resolved using vibrational spectroscopy. This technique probed interactions between surface (hydr)oxo groups and liquid water-like films. Molecular dynamics showed that structures and orientations adopted by these waters are comparable to those adopted at the interface with liquid water. Particle surfaces reacted with HCl accumulated less water than acid-free surfaces due to disruptions in hydrogen bond networks by chemisorbed waters and chloride. Particles reacted with NaCl had lower loadings below ∼10 Torr water vapor but greater loadings above this value than salt-free surfaces. Water adsorption reactions were here affected by competitive hydration of coexisting salt-free surface regions, adsorbed chloride and sodium, as well as precipitated NaCl. Collectively, the findings presented in this study add further insight into the initial mechanisms of thin water film formation at goethite surfaces subjected to variations in water vapor pressure that are relevant to natural systems.

Effect of Reacting Surface Density on the Overall Graphite Oxidation Rate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chang H. Oh; Eung Kim; Jong Lim

2009-05-01

Graphite oxidation in an air-ingress accident is presently a very important issue for the reactor safety of the very high temperature gas cooled-reactor (VHTR), the concept of the next generation nuclear plant (NGNP) because of its potential problems such as mechanical degradation of the supporting graphite in the lower plenum of the VHTR might lead to core collapse if the countermeasure is taken carefully. The oxidation process of graphite has known to be affected by various factors, including temperature, pressure, oxygen concentration, types of graphite, graphite shape and size, flow distribution, etc. However, our recent study reveals that the internalmore » pore characteristics play very important roles in the overall graphite oxidation rate. One of the main issues regarding graphite oxidation is the potential core collapse problem that may occur following the degradation of graphite mechanical strength. In analyzing this phenomenon, it is very important to understand the relationship between the degree of oxidization and strength degradation. In addition, the change of oxidation rate by graphite oxidation degree characterization by burn-off (ratio of the oxidized graphite density to the original density) should be quantified because graphite strength degradation is followed by graphite density decrease, which highly affects oxidation rates and patterns. Because the density change is proportional to the internal pore surface area, they should be quantified in advance. In order to understand the above issues, the following experiments were performed: (1)Experiment on the fracture of the oxidized graphite and validation of the previous correlations, (2) Experiment on the change of oxidation rate using graphite density and data collection, (3) Measure the BET surface area of the graphite. The experiments were performed using H451 (Great Lakes Carbon Corporation) and IG-110 (Toyo Tanso Co., Ltd) graphite. The reason for the use of those graphite materials is because their chemical and mechanical characteristics are well identified by the previous investigations, and therefore it was convenient for us to access the published data, and to apply and validate our new methodologies. This paper presents preliminary results of compressive strength vs. burn-off and surface area density vs. burn-off, which can be used for the nuclear graphite selection for the NGNP.« less

Reactivity at the Lithium–Metal Anode Surface of Lithium–Sulfur Batteries

DOE PAGES

Camacho-Forero, Luis E.; Smith, Taylor W.; Bertolini, Samuel; ...

2015-11-11

Due to their high energy density and reduced cost, lithium–sulfur batteries are promising alternatives for applications such as electrical vehicles. However, a number of technical challenges need to be overcome in order to make them feasible for commercial uses. These challenges arise from the battery highly interconnected chemistry, which besides the electrochemical reactions includes side reactions at both electrodes and migration of soluble polysulfide (PS) species produced at the cathode to the anode side. The presence of such PS species alters the already complex reactivity of the Li anode. In this paper, interfacial reactions occurring at the surface of Limore » metal anodes due to electrochemical instability of the electrolyte components and PS species are investigated with density functional theory and ab initio molecular dynamics methods. It is found that the bis(trifluoromethane)sulfonimide lithium salt reacts very fast when in contact with the Li surface, and anion decomposition precedes salt dissociation. The anion decomposition mechanisms are fully elucidated. Two of the typical solvents used in Li–S technology, 1,3-dioxolane and 1,2-dimethoxyethane, are found stable during the entire simulation length, in contrast with the case of ethylene carbonate that is rapidly decomposed by sequential 2- or 4-electron mechanisms. Finally, on the other hand, the fast reactivity of the soluble PS species alters the side reactions because the PS totally decomposes before any of the electrolyte components forming Li 2S on the anode surface.« less

Chemical modification of TiO2 surfaces with methylsilanes and characterization by infrared absorption spectroscopy

NASA Technical Reports Server (NTRS)

Finklea, H. O.; Vithanage, R.

1982-01-01

Infrared absorption spectra of methylsilanes bonded to a TiO2 powder were obtained. The reacting silanes include Me sub (4-n)SiX sub n (n=1-4; X=Cl, OMe) and hexamethyldisilazane (HMDS). Reactions were performed on hydroxylated-but-anhydrous TiO2 surfaces in the gas phase. IR spectra confirm the presence of a bonded silane layer. Terminal surface OH groups are found to react more readily than bridging OH groups. By-products of the modification adsorp tenaciously to the surface. The various silanes show only small differences in their ability to sequester surface OH groups. Following hydrolysis in moist air, Si-OH groups are observed only for the tetrafunctional silanes.

Method of adhesion between an oxide layer and a metal layer

DOEpatents

Jennison, Dwight R.; Bogicevic, Alexander; Kelber, Jeffry A.; Chambers, Scott A.

2004-09-14

A method of controlling the wetting characteristics and increasing the adhesion between a metal and an oxide layer. By introducing a negatively-charged species to the surface of an oxide layer, layer-by-layer growth of metal deposited onto the oxide surface is promoted, increasing the adhesion strength of the metal-oxide interface. The negatively-charged species can either be deposited onto the oxide surface or a compound can be deposited that dissociates on, or reacts with, the surface to form the negatively-charged species. The deposited metal adatoms can thereby bond laterally to the negatively-charged species as well as vertically to the oxide surface as well as react with the negatively charged species, be oxidized, and incorporated on or into the surface of the oxide.

Effects of continuum breakdown on hypersonic aerothermodynamics for reacting flow

NASA Astrophysics Data System (ADS)

Holman, Timothy D.; Boyd, Iain D.

2011-02-01

This study investigates the effects of continuum breakdown on the surface aerothermodynamic properties (pressure, stress, and heat transfer rate) of a sphere in a Mach 25 flow of reacting air in regimes varying from continuum to a rarefied gas. Results are generated using both continuum [computational fluid dynamics (CFD)] and particle [direct simulation Monte Carlo (DSMC)] approaches. The DSMC method utilizes a chemistry model that calculates the backward rates from an equilibrium constant. A preferential dissociation model is modified in the CFD method to better compare with the vibrationally favored dissociation model that is utilized in the DSMC method. Tests of these models are performed to confirm their validity and to compare the chemistry models in both numerical methods. This study examines the effect of reacting air flow on continuum breakdown and the surface properties of the sphere. As the global Knudsen number increases, the amount of continuum breakdown in the flow and on the surface increases. This increase in continuum breakdown significantly affects the surface properties, causing an increase in the differences between CFD and DSMC. Explanations are provided for the trends observed.

Large eddy simulations and direct numerical simulations of high speed turbulent reacting flows

NASA Technical Reports Server (NTRS)

Givi, P.; Frankel, S. H.; Adumitroaie, V.; Sabini, G.; Madnia, C. K.

1993-01-01

The primary objective of this research is to extend current capabilities of Large Eddy Simulations (LES) and Direct Numerical Simulations (DNS) for the computational analyses of high speed reacting flows. Our efforts in the first two years of this research have been concentrated on a priori investigations of single-point Probability Density Function (PDF) methods for providing subgrid closures in reacting turbulent flows. In the efforts initiated in the third year, our primary focus has been on performing actual LES by means of PDF methods. The approach is based on assumed PDF methods and we have performed extensive analysis of turbulent reacting flows by means of LES. This includes simulations of both three-dimensional (3D) isotropic compressible flows and two-dimensional reacting planar mixing layers. In addition to these LES analyses, some work is in progress to assess the extent of validity of our assumed PDF methods. This assessment is done by making detailed companions with recent laboratory data in predicting the rate of reactant conversion in parallel reacting shear flows. This report provides a summary of our achievements for the first six months of the third year of this program.

Nuclear reactor fuel element

DOEpatents

Johnson, Carl E.; Crouthamel, Carl E.

1980-01-01

A nuclear reactor fuel element is described which has an outer cladding, a central core of fissionable or mixed fissionable and fertile fuel material and a layer of oxygen gettering material on the inner surface of the cladding. The gettering material reacts with oxygen released by the fissionable material during irradiation of the core thereby preventing the oxygen from reacting with and corroding the cladding. Also described is an improved method for coating the inner surface of the cladding with a layer of gettering material.

Chemically reacting supersonic flow calculation using an assumed PDF model

NASA Technical Reports Server (NTRS)

Farshchi, M.

1990-01-01

This work is motivated by the need to develop accurate models for chemically reacting compressible turbulent flow fields that are present in a typical supersonic combustion ramjet (SCRAMJET) engine. In this paper the development of a new assumed probability density function (PDF) reaction model for supersonic turbulent diffusion flames and its implementation into an efficient Navier-Stokes solver are discussed. The application of this model to a supersonic hydrogen-air flame will be considered.

Surface profile changes of scuffed bearing surfaces. [before and after acid treatment

NASA Technical Reports Server (NTRS)

Lauer, J. L.; Fung, S. S.; Jones, W. R., Jr.

1982-01-01

A phase locked interference microscope capable of resolving depth differences to 30 A and planar displacements of 6000 A was constructed for the examination of the profiles of bearing surfaces without physical contact. This instrument was used to determine surface chemical reactivity by applying a drop of dilute alcoholic hydrochloric acid and measuring the profile of the solid surface before and after application of this probe. Scuffed bearing surfaces reacted much faster than unscuffed ones, but bearing surfaces which had been previously exposed to lubricants containing an organic chloride reacted much more slowly. In a separate series of experiments, a number of stainless steel plates were heated in a nitrogen atmosphere to different temperatures and their reactivity examined later at room temperature. The change of surface contour as a result of the probe reaction followed an Arrhenius type relation with respect to heat treatment temperature. This result could have implications on the scuffing mechanism.

Simulations of Spray Reacting Flows in a Single Element LDI Injector With and Without Invoking an Eulerian Scalar PDF Method

NASA Technical Reports Server (NTRS)

Shih, Tsan-Hsing; Liu, Nan-Suey

2012-01-01

This paper presents the numerical simulations of the Jet-A spray reacting flow in a single element lean direct injection (LDI) injector by using the National Combustion Code (NCC) with and without invoking the Eulerian scalar probability density function (PDF) method. The flow field is calculated by using the Reynolds averaged Navier-Stokes equations (RANS and URANS) with nonlinear turbulence models, and when the scalar PDF method is invoked, the energy and compositions or species mass fractions are calculated by solving the equation of an ensemble averaged density-weighted fine-grained probability density function that is referred to here as the averaged probability density function (APDF). A nonlinear model for closing the convection term of the scalar APDF equation is used in the presented simulations and will be briefly described. Detailed comparisons between the results and available experimental data are carried out. Some positive findings of invoking the Eulerian scalar PDF method in both improving the simulation quality and reducing the computing cost are observed.

Flow Velocity Computation, from Temperature and Number Density Measurements using Spontaneous Raman Scattering, for Supersonic Chemically Reacting Flows.

NASA Astrophysics Data System (ADS)

Satish Jeyashekar, Nigil; Seiner, John

2006-11-01

The closure problem in chemically reacting turbulent flows would be solved when velocity, temperature and number density (transport variables) are known. The transport variables provide input to momentum, heat and mass transport equations leading to analysis of turbulence-chemistry interaction, providing a pathway to improve combustion efficiency. There are no measurement techniques to determine all three transport variables simultaneously. This paper shows the formulation to compute flow velocity from temperature and number density measurements, made from spontaneous Raman scattering, using kinetic theory of dilute gases coupled with Maxwell-Boltzmann velocity distribution. Temperature and number density measurements are made in a mach 1.5 supersonic air flow with subsonic hydrogen co-flow. Maxwell-Boltzmann distribution can be used to compute the average molecular velocity of each species, which in turn is used to compute the mass-averaged velocity or flow velocity. This formulation was validated by Raman measurements in a laminar adiabatic burner where the computed flow velocities were in good agreement with hot-wire velocity measurements.

Convection-driven aggregation of micron sized capsules

NASA Astrophysics Data System (ADS)

Shklyaev, Oleg; Shum, Henry; Balazs, Anna

Collective dynamics of microcapsules often serve as a model for understanding behavior observed in colonies of biological cells. Using computer simulations, we explore the capability of chemically generated convection to assemble microcapsules into a colony with neighbors close enough to facilitate chemical communication. The microcapsules are assumed to carry a supply of chemical fuel. When this fuel, leaking out of the capsules, reacts at enzyme-covered sites of the chamber, the reaction generates fluid density variations driving flows. These flows carry the microcapsules, which tend to aggregate into colonies on and near the enzyme-covered sites. This aggregation continues until the reagent has been depleted and convection stops. We show that capsule colonies of predesigned shapes can be assembled by patterning the enzyme-covered surface.

Sintering behavior of U 80 at.%Zr powder compacts in a vacuum environment

NASA Astrophysics Data System (ADS)

Kim, Tae-Kyu; Lee, Chong-Tak; Sohn, Dong-Seong

2008-01-01

Sintering behavior of U-80 at.%Zr powder compacts in a temperature range from 1100 to 1500 °C in a vacuum of 1 × 10 -4 Pa was evaluated. The sintered density depended more on the sintering temperature than on the sintering time. The sintered specimens consisted of the δ-UZr 2 matrix with acicular α-Zr precipitates, but it still had un-reacted zirconium when the sintering temperature was 1100 °C. The uranium depletion near the surface of the specimens sintered at temperatures above 1300 °C was detected. Massive Zr(O) grains in the sintered specimen were found, and their formation was restrained when the cooling rate from the sintering temperature was increased.

Surface passivation process of compound semiconductor material using UV photosulfidation

DOEpatents

Ashby, Carol I. H.

1995-01-01

A method for passivating compound semiconductor surfaces by photolytically disrupting molecular sulfur vapor with ultraviolet radiation to form reactive sulfur which then reacts with and passivates the surface of compound semiconductors.

Structure-Property Relationships in Porous 3-D Nanostructures as a Function of Preparation Conditions: Isocyanate Cross-Linked Silica Aerogels

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Capadona, Lynn A.; McCorkle, Linda; Padadopoulos, Demetrios S.; Leventis, Nicholas

2007-01-01

Sol-gel derived silica aerogels are attractive candidates for many unique thermal, optical, catalytic, and chemical applications because of their low density and high mesoporosity. However, their inherent fragility has restricted use of aerogel monoliths to applications where they are not subject to any load. We have previously reported cross-linking the mesoporous silica structure of aerogels with di-isocyanates, styrenes or epoxies reacting with amine decorated silica surfaces. These approaches have been shown to significantly increase the strength of aerogels with only a small effect on density or porosity. Though density is a prime predictor of properties such as strength and thermal conductivity for aerogels, it is becoming clear from previous studies that varying the silica backbone and size of the polymer cross-link independently can give rise to combinations of properties which cannot be predicted from density alone. Herein, we examine the effects of four processing parameters for producing this type of polymer cross-linked aerogel on properties of the resulting monoliths. We focus on the results of C-13 CP-MAS NMR which gives insight to the size and structure of polymer cross-link present in the monoliths, and relates the size of the cross-links to microstructure, mechanical properties and other characteristics of the materials obtained.

Structure-Property Relationships in Porous 3-D Nanostructures as a Function of Preparation Conditions: Isocyanate Cross-Linked Silica Aerogels

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Capadona, Lynn A.; McCorkle, Linda; Papadopoulos, Demetrios S.; Leventis, Nicholas

2007-01-01

Sol-gel derived silica aerogels are attractive candidates for many unique thermal, optical, catalytic, and chemical applications because of their low density and high mesoporosity. However, their inherent fragility has restricted use of aerogel monoliths to applications where they are not subject to any load. We have previously reported cross-linking the mesoporous silica structure of aerogels with di-isocyanates, styrenes or epoxies reacting with amine decorated silica surfaces. These approaches have been shown to significantly increase the strength of aerogels with only a small effect on density or porosity. Though density is a prime predictor of properties such as strength and thermal conductivity for aerogels, it is becoming clear from previous studies that varying the silica backbone and size of the polymer cross-link independently can give rise to combinations of properties which cannot be predicted from density alone. Herein, we examine the effects of four processing parameters for producing this type of polymer cross-linked aerogel on properties of the resulting monoliths. We focus on the results of 13C CP-MAS NMR which gives insight to the size and structure of polymer cross-link present in the monoliths, and relates the size of the cross-links to microstructure, mechanical properties and other characteristics of the materials obtained.

Monoclonal antibodies to the equine CD2 T lymphocyte marker, to a pan-granulocyte/monocyte marker and to a unique pan-B lymphocyte marker.

PubMed

Tumas, D B; Brassfield, A L; Travenor, A S; Hines, M T; Davis, W C; McGuire, T C

1994-12-01

Murine monoclonal antibodies, HB88A, B29A and DH59B separately identify the CD2 T lymphocyte molecule, a unique pan-B lymphocyte surface marker and a pan-granulocyte/monocyte surface molecule, respectively, in the horse. Specificity was shown by two-color immunofluorescent flow cytometry and immunofluorescent microscopy. MAb HB88A reacted with a 52 kDa pan-T lymphocyte molecule present on 75% +/- 7 of peripheral blood lymphocytes (PBL) (n = 15 horses). It also reacted with lymphocytes restricted to T lymphocyte dependent areas of lymph node and spleen. Specificity of mAb HB88A to CD2 was demonstrated by its reactivity to COS7 cells which expressed a transfected 1.5 kb equine lymphocyte c-DNA clone having 77.5% overall sequence homology with human CD2 c-DNA. MAb B29A reacted with a pan-B lymphocyte specific cell surface complex, 143, 72, 50, 40, 27 and 14.5 kDa, present on 19% +/- 7 of PBL (n = 15 horses). This complex has not been described in the horse or other species. MAb DH59B reacted with a 96 kDa pan-granulocyte/monocyte specific surface protein and identified macrophages and Kupffer cells in equine tissue sections. Together these mAbs can be used to identify and quantitate the major constituents of equine leukocytes.

Effect of calcium chloride solution immersion on surface hardness of restorative glass ionomer cements.

PubMed

Shiozawa, Maho; Takahashi, Hidekazu; Iwasaki, Naohiko; Uo, Motohiro

2013-01-01

The objective of this study was to evaluate the effect of the concentration of calcium chloride (CaCl2) solution on the surface hardness of restorative glass ionomer cements (GICs). Two high-viscosity GICs, Fuji IX GP and GlasIonomer FX-II, were immersed in several concentrations of CaCl2 solution for 1 day and 1 week. The immersed specimen surfaces were evaluated using microhardness testing, grazing incidence X-ray diffraction, and energy-dispersive X-ray spectroscopy. Immersion in a higher concentration of CaCl2 solution produced a greater increase in the surface hardness. No crystalline substance was observed on the immersed surface. Calcium ions were selectively absorbed in the matrix of the GIC surface after immersion. They reacted with the non-reacted carboxylic acid groups remaining in the cement matrix. These reactions were considered to cause an increase in the surface hardness of the GICs.

Trimethylaluminum and Oxygen Atomic Layer Deposition on Hydroxyl-Free Cu(111)

PubMed Central

2015-01-01

Atomic layer deposition (ALD) of alumina using trimethylaluminum (TMA) has technological importance in microelectronics. This process has demonstrated a high potential in applications of protective coatings on Cu surfaces for control of diffusion of Cu in Cu2S films in photovoltaic devices and sintering of Cu-based nanoparticles in liquid phase hydrogenation reactions. With this motivation in mind, the reaction between TMA and oxygen was investigated on Cu(111) and Cu2O/Cu(111) surfaces. TMA did not adsorb on the Cu(111) surface, a result consistent with density functional theory (DFT) calculations predicting that TMA adsorption and decomposition are thermodynamically unfavorable on pure Cu(111). On the other hand, TMA readily adsorbed on the Cu2O/Cu(111) surface at 473 K resulting in the reduction of some surface Cu1+ to metallic copper (Cu0) and the formation of a copper aluminate, most likely CuAlO2. The reaction is limited by the amount of surface oxygen. After the first TMA half-cycle on Cu2O/Cu(111), two-dimensional (2D) islands of the aluminate were observed on the surface by scanning tunneling microscopy (STM). According to DFT calculations, TMA decomposed completely on Cu2O/Cu(111). High-resolution electron energy loss spectroscopy (HREELS) was used to distinguish between tetrahedrally (Altet) and octahedrally (Aloct) coordinated Al3+ in surface adlayers. TMA dosing produced an aluminum oxide film, which contained more octahedrally coordinated Al3+ (Altet/Aloct HREELS peak area ratio ≈ 0.3) than did dosing O2 (Altet/Aloct HREELS peak area ratio ≈ 0.5). After the first ALD cycle, TMA reacted with both Cu2O and aluminum oxide surfaces in the absence of hydroxyl groups until film closure by the fourth ALD cycle. Then, TMA continued to react with surface Al–O, forming stoichiometric Al2O3. O2 half-cycles at 623 K were more effective for carbon removal than O2 half-cycles at 473 K or water half-cycles at 623 K. The growth rate was approximately 3–4 Å/cycle for TMA+O2 ALD (O2 half-cycles at 623 K). No preferential growth of Al2O3 on the steps of Cu(111) was observed. According to STM, Al2O3 grows homogeneously on Cu(111) terraces. PMID:26158796

Trimethylaluminum and Oxygen Atomic Layer Deposition on Hydroxyl-Free Cu(111).

PubMed

Gharachorlou, Amir; Detwiler, Michael D; Gu, Xiang-Kui; Mayr, Lukas; Klötzer, Bernhard; Greeley, Jeffrey; Reifenberger, Ronald G; Delgass, W Nicholas; Ribeiro, Fabio H; Zemlyanov, Dmitry Y

2015-08-05

Atomic layer deposition (ALD) of alumina using trimethylaluminum (TMA) has technological importance in microelectronics. This process has demonstrated a high potential in applications of protective coatings on Cu surfaces for control of diffusion of Cu in Cu2S films in photovoltaic devices and sintering of Cu-based nanoparticles in liquid phase hydrogenation reactions. With this motivation in mind, the reaction between TMA and oxygen was investigated on Cu(111) and Cu2O/Cu(111) surfaces. TMA did not adsorb on the Cu(111) surface, a result consistent with density functional theory (DFT) calculations predicting that TMA adsorption and decomposition are thermodynamically unfavorable on pure Cu(111). On the other hand, TMA readily adsorbed on the Cu2O/Cu(111) surface at 473 K resulting in the reduction of some surface Cu(1+) to metallic copper (Cu(0)) and the formation of a copper aluminate, most likely CuAlO2. The reaction is limited by the amount of surface oxygen. After the first TMA half-cycle on Cu2O/Cu(111), two-dimensional (2D) islands of the aluminate were observed on the surface by scanning tunneling microscopy (STM). According to DFT calculations, TMA decomposed completely on Cu2O/Cu(111). High-resolution electron energy loss spectroscopy (HREELS) was used to distinguish between tetrahedrally (Altet) and octahedrally (Aloct) coordinated Al(3+) in surface adlayers. TMA dosing produced an aluminum oxide film, which contained more octahedrally coordinated Al(3+) (Altet/Aloct HREELS peak area ratio ≈ 0.3) than did dosing O2 (Altet/Aloct HREELS peak area ratio ≈ 0.5). After the first ALD cycle, TMA reacted with both Cu2O and aluminum oxide surfaces in the absence of hydroxyl groups until film closure by the fourth ALD cycle. Then, TMA continued to react with surface Al-O, forming stoichiometric Al2O3. O2 half-cycles at 623 K were more effective for carbon removal than O2 half-cycles at 473 K or water half-cycles at 623 K. The growth rate was approximately 3-4 Å/cycle for TMA+O2 ALD (O2 half-cycles at 623 K). No preferential growth of Al2O3 on the steps of Cu(111) was observed. According to STM, Al2O3 grows homogeneously on Cu(111) terraces.

Discreteness effects in a reacting system of particles with finite interaction radius.

PubMed

Berti, S; López, C; Vergni, D; Vulpiani, A

2007-09-01

An autocatalytic reacting system with particles interacting at a finite distance is studied. We investigate the effects of the discrete-particle character of the model on properties like reaction rate, quenching phenomenon, and front propagation, focusing on differences with respect to the continuous case. We introduce a renormalized reaction rate depending both on the interaction radius and the particle density, and we relate it to macroscopic observables (e.g., front speed and front thickness) of the system.

Modeling of turbulent chemical reaction

NASA Technical Reports Server (NTRS)

Chen, J.-Y.

1995-01-01

Viewgraphs are presented on modeling turbulent reacting flows, regimes of turbulent combustion, regimes of premixed and regimes of non-premixed turbulent combustion, chemical closure models, flamelet model, conditional moment closure (CMC), NO(x) emissions from turbulent H2 jet flames, probability density function (PDF), departures from chemical equilibrium, mixing models for PDF methods, comparison of predicted and measured H2O mass fractions in turbulent nonpremixed jet flames, experimental evidence of preferential diffusion in turbulent jet flames, and computation of turbulent reacting flows.

Monolayer of Hydrazine Facilitates the Direct Covalent Attachment of C60 Fullerene to a Silicon Surface.

PubMed

Gao, Fei; Teplyakov, Andrew V

2017-09-05

The development of oxygen-free organic-inorganic interfaces has led to new schemes for the functionalization of silicon surfaces with nitrogen-based chemical groups. However, building layers of large structures directly on this functionalized surface has remained elusive. This work confirms the path to form a stable interface between silicon and buckminsterfullerene C 60 based on covalent chemical bonds. The starting point for this modification is the hydrazine-reacted Si(111) surface with the diamine functionality, which is further reacted directly with the C 60 molecules. The chemistry of this process is confirmed spectroscopically and microscopically and can be used to form organic-inorganic interfaces separated by a single layer of nitrogen.

Quantifying the density of surface capping ligands on semiconductor quantum dots

NASA Astrophysics Data System (ADS)

Zhan, Naiqian; Palui, Goutam; Merkl, Jan-Philip; Mattoussi, Hedi

2015-03-01

We have designed a new set of coordinating ligands made of a lipoic acid (LA) anchor and poly(ethylene glycol) (PEG) hydrophilic moiety appended with a terminal aldehyde for the surface functionalization of QDs. This ligand design was combined with a recently developed photoligation strategy to prepare hydrophilic CdSe-ZnS QDs with good control over the fraction of intact aldehyde (-CHO) groups per nanocrystal. We further applied the efficient hydrazone ligation to react aldehyde-QDs with 2-hydrazinopyridine (2-HP). This covalent modification produces QD-conjugates with a well-defined absorption feature at 350 nm ascribed to the hydrazone chromophore. We exploited this unique optical signature to accurately measure the number of aldehyde groups per QD when the fraction of LA-PEG-CHO per nanocrystal was varied. This allowed us to extract an estimate for the number of LA-PEG ligands per QD. These results suggest that hydrazone ligation has the potential to provide a simple and general analytical method to estimate the number of surface ligands for a variety of nanocrystals such as metal, metal oxide and semiconductor nanocrystals.

Understanding the role of Ti in reversible hydrogen storage as sodium alanate: a combined experimental and density functional theoretical approach.

PubMed

Chaudhuri, Santanu; Graetz, Jason; Ignatov, Alex; Reilly, James J; Muckerman, James T

2006-09-06

We report the results of an experimental and theoretical study of hydrogen storage in sodium alanate (NaAlH(4)). Reversible hydrogen storage in this material is dependent on the presence of 2-4% Ti dopant. Our combined study shows that the role of Ti may be linked entirely to Ti-containing active catalytic sites in the metallic Al phase present in the dehydrogenated NaAlH(4). The EXAFS data presented here show that dehydrogenated samples contain a highly disordered distribution of Ti-Al distances with no long-range order beyond the second coordination sphere. We have used density functional theory techniques to calculate the chemical potential of possible Ti arrangements on an Al(001) surface for Ti coverages ranging from 0.125 to 0.5 monolayer (ML) and have identified those that can chemisorb molecular hydrogen via spontaneous or only moderately activated pathways. The chemisorption process exhibits a characteristic nodal symmetry property for the low-barrier sites: the incipient doped surface-H(2) adduct's highest occupied molecular orbital (HOMO) incorporates the sigma antibonding molecular orbital of hydrogen, allowing the transfer of charge density from the surface to dissociate the molecular hydrogen. This work also proposes a plausible mechanism for the transport of an aluminum hydride species back into the NaH lattice that is supported by Car-Parrinello molecular dynamics (CPMD) simulations of the stability and mobility of aluminum clusters (alanes) on Al(001). As an experimental validation of the proposed role of titanium and the subsequent diffusion of alanes, we demonstrate experimentally that AlH(3) reacts with NaH to form NaAlH(4) without any requirement of a catalyst or hydrogen overpressure.

Tailoring the nickel nanoparticles anchored on the surface of Fe3O4@SiO2 spheres for nanocatalysis.

PubMed

Ding, Lei; Zhang, Min; Zhang, Yanwei; Yang, Jinbo; Zheng, Jing; Hayat, Tasawar; Alharbi, Njud S; Xu, Jingli

2017-08-25

Herein, we report an efficient and universal strategy for synthesizing a unique triple-shell structured Fe 3 O 4 @SiO 2 @C-Ni hybrid composite. Firstly, the Fe 3 O 4 cores were synthesized by hydrothermal reaction, and sequentially coated with SiO 2 and a thin layer of nickel-ion-doped resin-formaldehyde (RF-Ni 2+ ) using an extended Stöber method. This was followed by carbonization to produce the Fe 3 O 4 @SiO 2 @C-Ni nanocomposites with metallic nickel nanoparticles embedded in an RF-derived thin graphic carbon layer. Interestingly, the thin SiO 2 spacer layer between RF-Ni 2+ and Fe 3 O 4 plays a critical role on adjusting the size and density of the nickel nanoparticles on the surface of Fe 3 O 4 @SiO 2 nanospheres. The detailed tailoring mechanism is explicitly discussed, and it is shown that the iron oxide core can react with the nickel nanoparticles without the SiO 2 spacer layer, and the size and density of the nickel nanoparticles can be effectively controlled when the SiO 2 layer exits. The multifunctional composites exhibit a significantly enhanced catalytic performance in the reduction of 4-nitrophenol (4-NP).

Antigenic characterization of bovine ephemeral fever rhabdovirus G and GNS glycoproteins expressed from recombinant baculoviruses.

PubMed

Johal, Jasjit; Gresty, Karryn; Kongsuwan, Kritaya; Walker, Peter J

2008-01-01

Recombinant baculoviruses expressing the BEFV envelope glycoprotein G and non-structural glycoprotein G(NS) were constructed. The G protein expressed in insect cells was located on the cell surface and induced spontaneous cell fusion at mildly acidic pH. The expressed G protein reacted with MAbs to continuous and conformational neutralization sites (G1, G2, G3b and G4), but not to conformational site G3a. The expressed G(NS) protein was also located on the cell surface but did not exhibit fusogenic activity. The G(NS) protein reacted with polyclonal antiserum produced from vaccinia-virus-expressed recombinant G(NS) but did not react with G protein antibodies. A His(6)-tagged, soluble form of the G protein was expressed and purified by Ni(2+)-NTA chromatography. The purified G protein reacted with BEFV-neutralizing MAbs to all continuous and conformational antigenic sites. The highly protective characteristics of the native BEFV G protein suggest that the secreted, baculovirus-expressed product may be a useful vaccine antigen.

A scanning tunneling microscopy study of PH 3 adsorption on Si(1 1 1)-7 × 7 surfaces, P-segregation and thermal desorption

NASA Astrophysics Data System (ADS)

Ji, Jeong-Young; Shen, T.-C.

2007-04-01

PH 3 adsorption on Si(1 1 1)-7 × 7 was studied after various exposures between 0.3 and 60 L at room temperature by means of scanning tunneling microscopy (STM). PH 3-, PH 2-, H-reacted, and unreacted adatoms can be identified by analyzing empty-state STM images at different sample biases. PH x-reacted rest-atoms can be observed in empty-state STM images if neighboring adatoms are hydrogen terminated. Most of the PH 3 adsorbs dissociatively on the surface, generating H- and PH 2-adsorbed rest-atom and adatom sites. Dangling-bonds at rest-atom sites are more reactive than adatom sites and the faulted half of the 7 × 7 unit cell is more reactive than the unfaulted half. Center adatoms are overwhelmingly preferred over corner adatoms for PH 2 adsorption. The saturation P coverage is ˜0.18 ML. Annealing of PH 3-reacted 7 × 7 surfaces at 900 K generates disordered, partially P-covered surfaces, but dosing PH 3 at 900 K forms P/Si(1 1 1)- 6√{3} surfaces. Si deposition at 510 K leaves disordered clusters on the surface, which cannot be reordered by annealing up to 800 K. However, annealing above 900 K recreates P/Si(1 1 1)- 6√{3} surfaces. Surface morphologies formed by sequential rapid thermal annealing are also presented.

Nuclear reactor fuel element with vanadium getter on cladding

DOEpatents

Johnson, Carl E.; Carroll, Kenneth G.

1977-01-01

A nuclear reactor fuel element is described which has an outer cladding, a central core of fissionable or mixed fissionable and fertile fuel material and a layer of vanadium as an oxygen getter on the inner surface of the cladding. The vanadium reacts with oxygen released by the fissionable material during irradiation of the core to prevent the oxygen from reacting with and corroding the cladding. Also described is a method for coating the inner surface of small diameter tubes of cladding with a layer of vanadium.

One-pot reaction for the preparation of biofunctionalized self-assembled monolayers on gold surfaces

NASA Astrophysics Data System (ADS)

Raigoza, Annette F.; Fies, Whitney; Lim, Amber; Onyirioha, Kristeen; Webb, Lauren J.

2017-02-01

The Huisgen cycloaddition reaction (;click; chemistry) has been used extensively to functionalize surfaces with macromolecules in a straightforward manner. We have previously developed a procedure using the copper(I)-catalyzed click reaction to tether synthetic α-helical peptides carrying two alkyne groups to a well-ordered azide-terminated alkanethiol self-assembled monolayer (SAM) on a Au(111) surface. While convenient, click-based strategies potentially pose significant problems from reagents, solvents, and reaction temperatures that may irreversibly damage some molecules or substrates. Tuning click chemistry conditions would allow individual optimization of reaction conditions for a wide variety of biomolecules and substrate materials. Here, we explore the utility of simultaneous SAM formation and peptide-attachment chemistry in a one-pot reaction. We demonstrate that a formerly multistep reaction can be successfully carried out concurrently by mixing azide-terminated alkanethiols, CuCl, and a propargylglycine-containing peptide over a bare gold surface in ethanol and reacting at 70 °C. X-ray photoelectron spectroscopy (XPS), surface infrared spectroscopy, surface circular dichroic (CD) spectroscopy, and scanning tunneling microscopy (STM) were used to determine that this one-pot reaction strategy resulted in a high density of surface-bound α-helices without aggregation. This work demonstrates the simplicity and versatility of a SAM-plus-click chemistry strategy for functionalizing Au surfaces with structured biomolecules.

Thermal treatment to improve the hydrophobicity of ground CaCO3 particles modified with sodium stearate

NASA Astrophysics Data System (ADS)

Liang, Yong; Yu, Keyi; Zheng, Qinzhong; Xie, Jiuren; Wang, Ting-Jie

2018-04-01

The surface modification of calcium carbonate (CaCO3) particles, which is used as a filler, significantly affects the properties of the composed materials. The effects of thermal treatment on ground calcium carbonate (GCC) particles subjected to hydrophobic modification using sodium stearate (RCOONa) were studied. The contact angle of the modified GCC particles increased from 24.7° to 118.9° when the amount of RCOONa added was increased from 0% to 5% and then decreased to 97.5° when the RCOONa content was further increased to 10%. When a large amount of RCOONa was added, RCOO- reacts with Ca2+ and generates (RCOO)2Ca nuclei, which are adsorbed on the surface of the GCC particles, forming a discontinuous (RCOO)2Ca modified layer. After thermal treatment under sealed conditions, the contact angle of the GCC particles modified using 1.5% RCOONa/GCC increased from 112.8° to 139.6°. The thermal stability of the (RCOO)2Ca modified layer was increased, with the temperature increase of the mass-loss peak from 358.0 to 463.0 °C. It is confirmed that the spreading of melted (RCOO)2Ca nuclei on the surface of the GCC particles during the thermal treatment increased the continuity of the modified layer, converting the physical adsorption of the (RCOO)2Ca nuclei into chemisorption. The grafting density of RCOO- on the GCC particle surface after thermal treatment approximates to 5.00/nm2, which is close to the single-molecular-layer grafting density of RCOO-, indicating that excellent modification was achieved.

Superhydrophobic hybrid membranes by grafting arc-like macromolecular bridges on graphene sheets: Synthesis, characterization and properties

NASA Astrophysics Data System (ADS)

Mo, Zhao-Hua; Luo, Zheng; Huang, Qiang; Deng, Jian-Ping; Wu, Yi-Xian

2018-05-01

Grafting single end-tethered polymer chains on the surface of graphene is a conventional way to modify the surface properties of graphene oxide. However, grafting arc-like macromolecular bridges on graphene surfaces has been barely reported. Herein, a novel arc-like polydimethylsiloxane (PDMS) macromolecular bridges grafted graphene sheets (GO-g-Arc PDMS) was successfully synthesized via a confined interface reaction at 90 °C. Both the hydrophilic α- and ω-amino groups of linear hydrophobic NH2-PDMS-NH2 macromolecular chains rapidly reacted with epoxy and carboxyl groups on the surfaces of graphene oxide in water suspension to form arc-like PDMS macromolecular bridges on graphene sheets. The grafting density of arc-like PDMS bridges on graphene sheets can reach up to 0.80 mmol g-1 or 1.32 arc-like bridges per nm2 by this confined interface reaction. The water contact angle (WCA) of the hybrid membrane could be increased with increasing both the grafting density and content of covalent arc-like bridges architecture. The superhydrophobic hybrid membrane with a WCA of 153.4° was prepared by grinding of the above arc-like PDMS bridges grafted graphene hybrid, dispersing in ethanol and filtrating by organic filter membrane. This superhydrophobic hybrid membrane shows good self-cleaning and complete oil-water separation properties, which provides potential applications in anticontamination coating and oil-water separation. To the best of our knowledge, this is the first report on the synthesis of functional hybrid membranes by grafting arc-like PDMS macromolecular bridges on graphene sheets via a confined interface reaction.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andersson, Gunther G., E-mail: gunther.andersson@flinders.edu.au, E-mail: vladimir.golovko@canterbury.ac.nz, E-mail: greg.metha@adelaide.edu.au; Al Qahtani, Hassan S.; Golovko, Vladimir B., E-mail: gunther.andersson@flinders.edu.au, E-mail: vladimir.golovko@canterbury.ac.nz, E-mail: greg.metha@adelaide.edu.au

Chemically made, atomically precise phosphine-stabilized clusters Au{sub 9}(PPh{sub 3}){sub 8}(NO{sub 3}){sub 3} were deposited on titania and silica from solutions at various concentrations and the samples heated under vacuum to remove the ligands. Metastable induced electron spectroscopy was used to determine the density of states at the surface, and X-ray photoelectron spectroscopy for analysing the composition of the surface. It was found for the Au{sub 9} cluster deposited on titania that the ligands react with the titania substrate. Based on analysis using the singular value decomposition algorithm, the series of MIE spectra can be described as a linear combination ofmore » 3 base spectra that are assigned to the spectra of the substrate, the phosphine ligands on the substrate, and the Au clusters anchored to titania after removal of the ligands. On silica, the Au clusters show significant agglomeration after heat treatment and no interaction of the ligands with the substrate can be identified.« less

Density functional theory study the effects of oxygen-containing functional groups on oxygen molecules and oxygen atoms adsorbed on carbonaceous materials.

PubMed

Qi, Xuejun; Song, Wenwu; Shi, Jianwei

2017-01-01

Density functional theory was used to study the effects of different types of oxygen-containing functional groups on the adsorption of oxygen molecules and single active oxygen atoms on carbonaceous materials. During gasification or combustion reactions of carbonaceous materials, oxygen-containing functional groups such as hydroxyl(-OH), carbonyl(-CO), quinone(-O), and carboxyl(-COOH) are often present on the edge of graphite and can affect graphite's chemical properties. When oxygen-containing functional groups appear on a graphite surface, the oxygen molecules are strongly adsorbed onto the surface to form a four-member ring structure. At the same time, the O-O bond is greatly weakened and easily broken. The adsorption energy value indicates that the adsorption of oxygen molecules changes from physisorption to chemisorption for oxygen-containing functional groups on the edge of a graphite surface. In addition, our results indicate that the adsorption energy depends on the type of oxygen-containing functional group. When a single active oxygen atom is adsorbed on the bridge site of graphite, it gives rise to a stable epoxy structure. Epoxy can cause deformation of the graphite lattice due to the transition of graphite from sp2 to sp3 after the addition of an oxygen atom. For quinone group on the edge of graphite, oxygen atoms react with carbon atoms to form the precursor of CO2. Similarly, the single active oxygen atoms of carbonyl groups can interact with edge carbon atoms to form the precursor of CO2. The results show that oxygen-containing functional groups on graphite surfaces enhance the activity of graphite, which promotes adsorption on the graphite surface.

Density functional theory study the effects of oxygen-containing functional groups on oxygen molecules and oxygen atoms adsorbed on carbonaceous materials

PubMed Central

Song, Wenwu; Shi, Jianwei

2017-01-01

Density functional theory was used to study the effects of different types of oxygen-containing functional groups on the adsorption of oxygen molecules and single active oxygen atoms on carbonaceous materials. During gasification or combustion reactions of carbonaceous materials, oxygen-containing functional groups such as hydroxyl(-OH), carbonyl(-CO), quinone(-O), and carboxyl(-COOH) are often present on the edge of graphite and can affect graphite’s chemical properties. When oxygen-containing functional groups appear on a graphite surface, the oxygen molecules are strongly adsorbed onto the surface to form a four-member ring structure. At the same time, the O-O bond is greatly weakened and easily broken. The adsorption energy value indicates that the adsorption of oxygen molecules changes from physisorption to chemisorption for oxygen-containing functional groups on the edge of a graphite surface. In addition, our results indicate that the adsorption energy depends on the type of oxygen-containing functional group. When a single active oxygen atom is adsorbed on the bridge site of graphite, it gives rise to a stable epoxy structure. Epoxy can cause deformation of the graphite lattice due to the transition of graphite from sp2 to sp3 after the addition of an oxygen atom. For quinone group on the edge of graphite, oxygen atoms react with carbon atoms to form the precursor of CO2. Similarly, the single active oxygen atoms of carbonyl groups can interact with edge carbon atoms to form the precursor of CO2. The results show that oxygen-containing functional groups on graphite surfaces enhance the activity of graphite, which promotes adsorption on the graphite surface. PMID:28301544

Large eddy simulations of a bluff-body stabilized hydrogen-methane jet flame

NASA Astrophysics Data System (ADS)

Drozda, Tomasz; Pope, Stephen

2005-11-01

Large eddy simulation (LES) is conducted of the turbulent bluff-body stabilized hydrogen-methane flame as considered in the experiments of the Combustion Research Facility at the Sandia National Laboratories and of the Thermal Research Group at the University of Sydney [1]. Both, reacting and non-reacting flows are considered. The subgrid scale (SGS) closure in LES is based on the scalar filtered mass density function (SFMDF) methodology [2]. A flamelet model is used to relate the chemical composition to the mixture fraction. The modeled SFMDF transport equation is solved by a hybrid finite-difference (FD) / Monte Carlo (MC) scheme. The FD component of the hybrid solver is validated by comparisons of the experimentally available flow statistics with those predicted by LES. The results via this method capture important features of the flames as observed experimentally.[1] A. R. Masri, R. W. Dibble, and R. S. Barlow. The structure of turbulent nonpremixed flames revealed by Raman-Rayleigh-LIF measurements. Prog. Energy Combust. Sci., 22:307--362, 1996. [2] F. A. Jaberi, P. J. Colucci, S. James, P. Givi, and S. B. Pope. Filtered mass density function for large eddy simulation of turbulent reacting flows. J. Fluid Mech., 401:85--121, 1999.

Assessing Jet-Induced Spatial Mixing in a Rich, Reacting Crossflow

NASA Technical Reports Server (NTRS)

Demayo, T. N.; Leong, M. Y.; Samuelsen, G. S.

2004-01-01

In many advanced low NOx gas turbine combustion techniques, such as rich-burn/quick-mix/lean-burn (RQL), jet mixing in a reacting, hot, fuel-rich crossflow plays an important role in minimizing all pollutant emissions and maximizing combustion efficiency. Assessing the degree of mixing and predicting jet penetration is critical to the optimization of the jet injection design strategy. Different passive scalar quantities, including carbon, oxygen, and helium are compared to quantify mixing in an atmospheric RQL combustion rig under reacting conditions. The results show that the O2-based jet mixture fraction underpredicts the C-based mixture fraction due to jet dilution and combustion, whereas the He tracer overpredicts it possibly due to differences in density and diffusivity. The He-method also exhibits significant scatter in the mixture fraction data that can most likely be attributed to differences in gas density and turbulent diffusivity. The jet mixture fraction data were used to evaluate planar spatial unmixedness, which showed good agreement for all three scalars. This investigation suggests that, with further technique refinement, O2 or a He tracer could be used instead of C to determine the extent of reaction and mixing in an RQL combustor.

Specific surface area of a crushed welded tuff before and after aqueous dissolution

USGS Publications Warehouse

Reddy, M.M.; Claassen, H.C.

1994-01-01

Specific surface areas were measured for several reference minerals (anorthoclase, labradorite and augite), welded tuff and stream sediments from Snowshoe Mountain, near Creede, Colorado. Crushed and sieved tuff had an unexpectedly small variation in specific surface area over a range of size fractions. Replicate surface area measurements of the largest and smallest tuff particle size fractions examined (1-0.3 mm and <0.212 mm) were 2.3 ?? 0.2 m2/g for each size fraction. Reference minerals prepared in the same way as the tuff had smaller specific surface areas than that of the tuff of the same size fraction. Higher than expected tuff specific surface areas appear to be due to porous matrix. Tuff, reacted in solutions with pH values from 2 to 6, had little change in specific surface area in comparison with unreacted tuff. Tuff, reacted with solutions having high acid concentrations (0.1 M hydrochloric acid or sulfuric-hydrofluoric acid), exhibited a marked increase in specific surface area compared to unreacted tuff. ?? 1994.

Sensing mechanism of SnO2/ZnO nanofibers for CH3OH sensors: heterojunction effects

NASA Astrophysics Data System (ADS)

Tang, Wei

2017-11-01

SnO2/ZnO composite nanofibers were synthesized by a simple electrospinning method. The prepared SnO2/ZnO gas sensors exhibited good linear and high response to methanol. The enhanced sensing behavior of SnO2/ZnO might be associated with the homotypic heterojunction effects formed in n-SnO2/n-ZnO nanograins boundaries. In addition, the possible sensing mechanisms of methanol on SnO2/ZnO surface were investigated by density functional theory in order to make the methanol adsorption and desorption process clear. Zn doped SnO2 model was adopted to approximate the SnO2/ZnO structure because of the calculation power limitations. Calculation results showed that when exposed to methanol, the methanol would react with bridge oxygen O2c , planar O3c and pre adsorbed oxygen vacancy on the lattice surface. The -CH3 and -OH of methanol molecule would both lose one H atom. The lost H atoms bonded with oxygen at the adsorption sites. The final products were HCHO and H2O. Electrons were transferred from methanol to the lattice surface to reduce the resistance of semiconductor gas sensitive materials, which is in agreement with the experimental phenomena. More adsorption models of other interfering gases, such as ethanol, formaldehyde and acetone will be built and calculated to explain the selectivity issue from the perspective of adsorption energy, transferred charge and density of states in the future work.

Computation of turbulent reacting flow in a solid-propellant ducted rocket

NASA Astrophysics Data System (ADS)

Chao, Yei-Chin; Chou, Wen-Fuh; Liu, Sheng-Shyang

1995-05-01

A mathematical model for computation of turbulent reacting flows is developed under general curvilinear coordinate systems. An adaptive, streamline grid system is generated to deal with the complex flow structures in a multiple-inlet solid-propellant ducted rocket (SDR) combustor. General tensor representations of the k-epsilon and algebraic stress (ASM) turbulence models are derived in terms of contravariant velocity components, and modification caused by the effects of compressible turbulence is also included in the modeling. The clipped Gaussian probability density function is incorporated in the combustion model to account for fluctuations of properties. Validation of the above modeling is first examined by studying mixing and reacting characteristics in a confined coaxial-jet problem. This is followed by study of nonreacting and reacting SDR combustor flows. The results show that Gibson and Launder's ASM incorporated with Sarkar's modification for compressible turbulence effects based on the general curvilinear coordinate systems yields the most satisfactory prediction for this complicated SDR flowfield.

Computation of turbulent reacting flow in a solid-propellant ducted rocket

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chao, Y.; Chou, W.; Liu, S.

1995-05-01

A mathematical model for computation of turbulent reacting flows is developed under general curvilinear coordinate systems. An adaptive, streamline grid system is generated to deal with the complex flow structures in a multiple-inlet solid-propellant ducted rocket (SDR) combustor. General tensor representations of the k-epsilon and algebraic stress (ASM) turbulence models are derived in terms of contravariant velocity components, and modification caused by the effects of compressible turbulence is also included in the modeling. The clipped Gaussian probability density function is incorporated in the combustion model to account for fluctuations of properties. Validation of the above modeling is first examined bymore » studying mixing and reacting characteristics in a confined coaxial-jet problem. This is followed by study of nonreacting and reacting SDR combustor flows. The results show that Gibson and Launder`s ASM incorporated with Sarkar`s modification for compressible turbulence effects based on the general curvilinear coordinate systems yields the most satisfactory prediction for this complicated SDR flowfield. 36 refs.« less

Covalent surface modification of gallium arsenide photocathodes for water splitting in highly acidic electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garner, Logan E.; Steirer, K. Xerxes; Young, James L.

Efficient water splitting using light as the only energy input requires stable semiconductor electrodes with favorable energetics for the water-oxidation and proton-reduction reactions. Strategies to tune electrode potentials using molecular dipoles adsorbed to the semiconductor surface have been pursued for decades but are often based on weak interactions and quickly react to desorb the molecule under conditions relevant to sustained photoelectrolysis. Here, we show that covalent attachment of fluorinated, aromatic molecules to p-GaAs(1 0 0) surfaces can be employed to tune the photocurrent onset potentials of p-GaAs(1 0 0) photocathodes and reduce the external energy required for water splitting. Resultsmore » indicate that initial photocurrent onset potentials can be shifted by nearly 150 mV in pH -0.5 electrolyte under 1 Sun (1000 W m -2) illumination resulting from the covalently bound surface dipole. Furthermore, X-ray photoelectron spectroscopy analysis reveals that the covalent molecular dipole attachment is not robust under extended 50 h photoelectrolysis, the modified surface delays arsenic oxide formation that results in a p-GaAs(1 0 0) photoelectrode operating at a sustained photocurrent density of -20.5 mA cm -2 within -0.5 V of the reversible hydrogen electrode.« less

Covalent surface modification of gallium arsenide photocathodes for water splitting in highly acidic electrolyte

DOE PAGES

Garner, Logan E.; Steirer, K. Xerxes; Young, James L.; ...

2016-12-12

Efficient water splitting using light as the only energy input requires stable semiconductor electrodes with favorable energetics for the water-oxidation and proton-reduction reactions. Strategies to tune electrode potentials using molecular dipoles adsorbed to the semiconductor surface have been pursued for decades but are often based on weak interactions and quickly react to desorb the molecule under conditions relevant to sustained photoelectrolysis. Here, we show that covalent attachment of fluorinated, aromatic molecules to p-GaAs(1 0 0) surfaces can be employed to tune the photocurrent onset potentials of p-GaAs(1 0 0) photocathodes and reduce the external energy required for water splitting. Resultsmore » indicate that initial photocurrent onset potentials can be shifted by nearly 150 mV in pH -0.5 electrolyte under 1 Sun (1000 W m -2) illumination resulting from the covalently bound surface dipole. Furthermore, X-ray photoelectron spectroscopy analysis reveals that the covalent molecular dipole attachment is not robust under extended 50 h photoelectrolysis, the modified surface delays arsenic oxide formation that results in a p-GaAs(1 0 0) photoelectrode operating at a sustained photocurrent density of -20.5 mA cm -2 within -0.5 V of the reversible hydrogen electrode.« less

Interface architecture between TiO2/perovskite, perovskite/hole transport layer, and perovskite grain boundary(Conference Presentation)

NASA Astrophysics Data System (ADS)

Hayase, Shuzi; Hirotani, Daisuke; Moriya, Masahiro; Ogomi, Yuhei; Shen, Qing; Yoshino, Kenji; Toyoda, Taro

2016-09-01

In order to examine the interface structure of TiO2/perovskite layer, quartz crystal microbalance sensor (QCM) was used. On the QCM sensor, TiO2 layer was fabricated and the PbI2 solution in Dimethylformamide (DMF) was passed on the QCM sensor to estimate the adsorption density of the PbI2 on the titania2. The amount of PbI2 adsorption on TiO2 surface increased as the adsorption time and leveled off at a certain time. PbI2 still remained even after the solvent only (DMF) was passed on the TiO2 layer on QCM (namely rinsing with DMF), suggesting that the PbI2 was tightly bonded on the TiO2 surface. The bonding structure was found to be Ti-O-Pb linkage by XPS analysis. We concluded that the Ti-OH on the surface of TiO2 reacts with I-Pb-I to form Ti-O-Pb-I and HI (Fig.1 B). The surface trap density was measured by thermally stimulated current (TSC) method. Before the PbI2 passivation, the trap density of TiO2 was 1019 cm3. The trap density decreased to 1016/cm3 after the PbI2 passivation, suggesting that the TiO2 surface trap was passivated with I-Pb-I. The passivation density was tuned by the concentration of PbI2 in DMF, by which TiO2 layer was passivated. Perovskite solar cells were fabricated on the passivated TiO2 layer with various PbI2 passivation densities by one step process (mixture of PbI2 + MAI in DMF). It was found that Jsc increased with an increase in the Ti-O-Pb density. We concluded that the interface between TiO2 and perovskite layer has passivation structure consisting of Ti-O-Pb-I which decreases the trap density of the interfaces and supresses charge recombination. The effect of Cl anion on high efficiency is still controversial when perovskite layer is prepared by one step method from the mixture of MAI and PbCl2. It was found that adsorption density of PbCl2 on TiO2 surface was much higher than that of PbI2 from the experiment using QCM sensor. After the surface was washed with DMF, Cl and Pb were detected. These results suggest that the TiO2 surface was much more passivated by PbCl2 than by PbI2. This may explain partially the high efficiency when the perovskite layer was fabricated by one step process consisting of MAI and PbCl2 solution. We also observed that the crystal size increased with an increase in the amount of Cl anion which of course one of the explanation of the high efficiency. The interface of hole transport layer/perovskite layer, and between perovskite layer /perovskite layer (grain boundary) was passivated with organic amines. The passivation was also effective for increasing Voc and Jsc. This was explained by the results of transient absorption spectroscopy that the charge recombination time between hole transport payer/perovskite layer increased from 0.3 μsec to 60 μsec.

Primordial clays on Mars formed beneath a steam or supercritical atmosphere.

PubMed

Cannon, Kevin M; Parman, Stephen W; Mustard, John F

2017-12-06

On Mars, clay minerals are widespread in terrains that date back to the Noachian period (4.1 billion to 3.7 billion years ago). It is thought that the Martian basaltic crust reacted with liquid water during this time to form hydrated clay minerals. Here we propose, however, that a substantial proportion of these clays was formed when Mars' primary crust reacted with a dense steam or supercritical atmosphere of water and carbon dioxide that was outgassed during magma ocean cooling. We present experimental evidence that shows rapid clay formation under conditions that would have been present at the base of such an atmosphere and also deeper in the porous crust. Furthermore, we explore the fate of a primordial clay-rich layer with the help of a parameterized crustal evolution model; we find that the primordial clay is locally disrupted by impacts and buried by impact-ejected material and by erupted volcanic material, but that it survives as a mostly coherent layer at depth, with limited surface exposures. These exposures are similar to those observed in remotely sensed orbital data from Mars. Our results can explain the present distribution of many clays on Mars, and the anomalously low density of the Martian crust in comparison with expectations.

Primordial clays on Mars formed beneath a steam or supercritical atmosphere

NASA Astrophysics Data System (ADS)

Cannon, Kevin M.; Parman, Stephen W.; Mustard, John F.

2017-12-01

On Mars, clay minerals are widespread in terrains that date back to the Noachian period (4.1 billion to 3.7 billion years ago). It is thought that the Martian basaltic crust reacted with liquid water during this time to form hydrated clay minerals. Here we propose, however, that a substantial proportion of these clays was formed when Mars’ primary crust reacted with a dense steam or supercritical atmosphere of water and carbon dioxide that was outgassed during magma ocean cooling. We present experimental evidence that shows rapid clay formation under conditions that would have been present at the base of such an atmosphere and also deeper in the porous crust. Furthermore, we explore the fate of a primordial clay-rich layer with the help of a parameterized crustal evolution model; we find that the primordial clay is locally disrupted by impacts and buried by impact-ejected material and by erupted volcanic material, but that it survives as a mostly coherent layer at depth, with limited surface exposures. These exposures are similar to those observed in remotely sensed orbital data from Mars. Our results can explain the present distribution of many clays on Mars, and the anomalously low density of the Martian crust in comparison with expectations.

Blunt-Body Aerothermodynamic Database from High-Enthalpy CO2 Testing in an Expansion Tunnel

NASA Technical Reports Server (NTRS)

Hollis, Brian R.; Prabhu, Dinesh K.; Maclean, Matthew; Dufrene, Aaron

2016-01-01

An extensive database of heating, pressure, and flow field measurements on a 70-deg sphere-cone blunt body geometry in high-enthalpy, CO2 flow has been generated through testing in an expansion tunnel. This database is intended to support development and validation of computational tools and methods to be employed in the design of future Mars missions. The test was conducted in an expansion tunnel in order to avoid uncertainties in the definition of free stream conditions noted in previous studies performed in reflected shock tunnels. Data were obtained across a wide range of test velocity/density conditions that produced various physical phenomena of interest, including laminar and transitional/turbulent boundary layers, non-reacting to completely dissociated post-shock gas composition and shock-layer radiation. Flow field computations were performed at the test conditions and comparisons were made with the experimental data. Based on these comparisons, it is recommended that computational uncertainties on surface heating and pressure, for laminar, reacting-gas environments can be reduced to +/-10% and +/-5%, respectively. However, for flows with turbulence and shock-layer radiation, there were not sufficient validation-quality data obtained in this study to make any conclusions with respect to uncertainties, which highlights the need for further research in these areas.

Computer program to solve two-dimensional shock-wave interference problems with an equilibrium chemically reacting air model

NASA Technical Reports Server (NTRS)

Glass, Christopher E.

1990-01-01

The computer program EASI, an acronym for Equilibrium Air Shock Interference, was developed to calculate the inviscid flowfield, the maximum surface pressure, and the maximum heat flux produced by six shock wave interference patterns on a 2-D, cylindrical configuration. Thermodynamic properties of the inviscid flowfield are determined using either an 11-specie, 7-reaction equilibrium chemically reacting air model or a calorically perfect air model. The inviscid flowfield is solved using the integral form of the conservation equations. Surface heating calculations at the impingement point for the equilibrium chemically reacting air model use variable transport properties and specific heat. However, for the calorically perfect air model, heating rate calculations use a constant Prandtl number. Sample calculations of the six shock wave interference patterns, a listing of the computer program, and flowcharts of the programming logic are included.

Computer program to solve two-dimensional shock-wave interference problems with an equilibrium chemically reacting air model

NASA Astrophysics Data System (ADS)

Glass, Christopher E.

1990-08-01

The computer program EASI, an acronym for Equilibrium Air Shock Interference, was developed to calculate the inviscid flowfield, the maximum surface pressure, and the maximum heat flux produced by six shock wave interference patterns on a 2-D, cylindrical configuration. Thermodynamic properties of the inviscid flowfield are determined using either an 11-specie, 7-reaction equilibrium chemically reacting air model or a calorically perfect air model. The inviscid flowfield is solved using the integral form of the conservation equations. Surface heating calculations at the impingement point for the equilibrium chemically reacting air model use variable transport properties and specific heat. However, for the calorically perfect air model, heating rate calculations use a constant Prandtl number. Sample calculations of the six shock wave interference patterns, a listing of the computer program, and flowcharts of the programming logic are included.

OpenGeoSys: An Open-Source Initiative for Numerical Simulation of Thermo-Hydro-Mechanical/Chemical (THM/C) Processes in Porous Media

NASA Astrophysics Data System (ADS)

Watanabe, N.; Bilke, L.; Fischer, T.; Kalbacher, T.; Nagel, T.; Naumov, D.; Rink, K.; Shao, H.; Wang, W.; Kolditz, O.

2014-12-01

The current understanding of geochemical reactions in reservoirs for geological carbon sequestration (GCS) is largely based on aqueous chemistry (CO2 dissolves in reservoir brine and brine reacts with rocks). However, only a portion of the injected supercritical (sc) CO2 dissolves before the buoyant plume contacts caprock, where it is expected to reside for a long time. Although numerous studies have addressed scCO2-mineral reactions occurring within adsorbed aqueous films, possible reactions resulting from direct CO2-rock contact remain less understood. Does CO2 as a supercritical phase react with reservoir rocks? Do mineral react differently with scCO2 than with dissolved CO2? We selected muscovite, one of the more stable and common rock-forming silicate minerals, to react with scCO2 phase (both water-saturated and water-free) and compared with CO2-saturated-brine. The reacted basal surfaces were analyzed using atomic force microscopy and X-ray photoelectron spectroscopy for examining the changes in surface morphology and chemistry. The results show that scCO2 (regardless of its water content) altered muscovite considerably more than CO2-saturated brine; suggest CO2 diffusion into mica interlayers and localized mica dissolution into scCO2 phase. The mechanisms underlying these observations and their implications for GCS need further exploration.

Method of coating metal surfaces to form protective metal coating thereon

DOEpatents

Krikorian, Oscar H.; Curtis, Paul G.

1992-01-01

A process is disclosed for forming a protective metal coating on a metal surface using a flux consisting of an alkali metal fluoride, an alkaline earth metal fluoride, an alkali metal fluoaluminate, an alkali metal fluosilicate, and mixtures thereof. The flux, in particulate form, is mixed with particles of a metal coating material which may comprise aluminum, chromium, mixtures thereof, and alloys containing at least 50 wt. % aluminum and the particulate mixture is applied to the metal surface in a single step, followed by heating the coated metal surface to a temperature sufficient to cause the metal coating material to react with the metal surface to form a protective reaction product in the form of a metal coating bonded to the metal surface. The metal surface which reacts with the metal coating material to form the protective coating may comprise Fe, Co, Ni, Ti, V, Cr, Mn, Zr, Nb, Mo, Tc, Hf, Ta, W, Re and alloys thereof.

Microscopic contour changes of tribological surfaces by chemical and mechanical action

NASA Technical Reports Server (NTRS)

Lauer, J. L.; Fung, S. S.

1982-01-01

An electronic optical laser interferometer capable of resolving depth differences of as low as 30 A and planar displacements of 6000 A was constructed for the examination of surface profiles of bearing surfaces without physical contact. This instrument was used to determine topological chemical reactivity by applying a drop of dilute alcoholic hydrochloric acid and measuring the profile of the solid surface before and after application of this probe. It was found that scuffed bearing surfaces reacted much faster than virgin ones but that bearing surfaces exposed to lubricants containing an organic chloride reacted much more slowly. In a separate series of experiments, a number of stainless steel plates were heated in a nitrogen atmosphere to different temperatures and their reactivity examined later at ambient temperature. The change of surface contour as a result of the probe reaction was found to follow an Arrhenius-type relation with respect to heat treatment temperature. This result could have implications on the scuffing mechanism.

Method of coating metal surfaces to form protective metal coating thereon

DOEpatents

Krikorian, O.H.; Curtis, P.G.

1992-03-31

A process is disclosed for forming a protective metal coating on a metal surface using a flux consisting of an alkali metal fluoride, an alkaline earth metal fluoride, an alkali metal fluoaluminate, an alkali metal fluosilicate, and mixtures thereof. The flux, in particulate form, is mixed with particles of a metal coating material which may comprise aluminum, chromium, mixtures thereof, and alloys containing at least 50 wt. % aluminum and the particulate mixture is applied to the metal surface in a single step, followed by heating the coated metal surface to a temperature sufficient to cause the metal coating material to react with the metal surface to form a protective reaction product in the form of a metal coating bonded to the metal surface. The metal surface which reacts with the metal coating material to form the protective coating may comprise Fe, Co, Ni, Ti, V, Cr, Mn, Zr, Nb, Mo, Tc, Hf, Ta, W, Re and alloys thereof. 1 figure.

Heterogeneous interactions of chlorine nitrate, hydrogen chloride, and nitric acid with sulfuric acid surfaces at stratospheric temperatures

NASA Technical Reports Server (NTRS)

Tolbert, Margaret A.; Rossi, Michel J.; Golden, David M.

1988-01-01

The heterogeneous interactions of ClONO2, HCl, and HNO3 with sulfuric acid surfaces were studied using a Knudsen cell flow reactor. The surfaces studied, chosen to simulate global stratospheric particulate, were composed of 65-75 percent H2SO4 solutions at temperatures in the range -63 to -43 C. Heterogeneous loss, but not reaction, of HNO3 and HCl occurred on these surfaces; the measured sticking coefficients are reported. Chlorine nitrate reacted on the cold sulfuric acid surfaces, producing gas-phase HOCl and condensed HNO3. CLONO2 also reacted with HCl dissolved in the 65-percent H2SO4 solution at -63 C, forming gaseous Cl2. In all cases studied, the sticking and/or reaction coefficients were much larger for the 65-percent H2SO4 solution at -63 C than for the 75-percent solution at -43 C.

Acetaldehyde Adsorption and Reaction onCeO2(100) Thin Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mullins, David R; Albrecht, Peter M

2013-01-01

This study reports and compares the adsorption and dissociation of acetaldehyde on oxidized and reduced CeOX(100) thin films. Acetaldehyde reacts and decomposes on fully oxidized CeO2(100) whereas it desorbs molecularly at low temperature on CeO2(111). The primary products are CO, CO2 and water along with trace amounts of crotonaldehyde and acetylene. The acetaldehyde adsorbs as the 2-acetaldehyde species, dioxyethylene. Decomposition proceeds by dehydrogenation through acetate and enolate intermediates. The reaction pathway is similar on the reduced CeO2-X(100) surface however the inability to react with surface O on the reduced surface results in H2 rather than H2O desorption and C ismore » left on the surface rather than producing CO and CO2. C-O bond cleavage in the enolate intermediate followed by reaction with surface H results in ethylene desorption.« less

Increased level of antibodies cross-reacting with Ves v 5 and CRISP-2 in MAR-positive patients.

PubMed

Brunner-Agten, S; Pavlovic, R; Müller, L; Horn, M P; Huber, A R; Stadler, B M; Vogel, M

2013-01-01

Anti-sperm antibodies (ASA) have been described to be involved in immunological infertility. A possible antigen for ASA is the human cysteine-rich secretory protein 2 (CRISP-2), a sperm surface protein important in sperm-oocyte interaction. Furthermore, anti-CRISP-2 antibodies were shown to decrease fertility rates in vitro. Recently, we have reported cross-reacting antibodies recognizing CRISP-2 and antigen 5 from yellow jacket venom (Ves v 5) in human serum. Here, we investigated anti-Ves v 5 and CRISP-2 antibodies in sera from two groups of donors: MAR+ and MAR- patients. A higher incidence of allergy against hymenoptera venom was found in MAR+ patients. Interestingly, affinity-purified ASA from MAR+ patients' sera reacted against both Ves v 5 and CRISP-2, leading to sperm immobilization. Immunofluorescence analysis showed that ASA bound to the sperm surface, including the head part where CRISP-2 is localized. Taken together, these results showed a higher incidence of antibodies cross-reacting with Ves v 5 and CRISP-2 in MAR+ patients. This leads to the hypothesis that MAR+ patients may have a higher risk to develop wasp allergy. Copyright © 2012 S. Karger AG, Basel.

Density functional theory study of acetaldehyde hydrodeoxygenation on MoO3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mei, Donghai; Karim, Ayman M.; Wang, Yong

2011-04-06

Periodic spin-polarized density functional theory calculations were performed to investigate acetaldehyde (CH3CHO) hydrodeoxygenation on the reduced molybdenum trioxide (MoO3) surface. The perfect O-terminated α-MoO3(010) surface is reduced to generate an oxygen defect site in the presence of H2. H2 dissociatively adsorbs at the surface oxygen sites forming two surface hydroxyls, which can recombine into a water molecule weakly bound at the Mo site. A terminal oxygen (Ot) defect site thus forms after water desorption. CH3CHO adsorbs at the O-deficient Mo site via either the sole O-Mo bond or the O-Mo and the C-O double bonds. The possible reaction pathways ofmore » the adsorbed CH3CHO with these two configurations were thoroughly examined using the dimer searching method. Our results show that the ideal deoxygenation of CH3CHO leading to ethylene (C2H4) on the reduced MoO3(010) surface is feasible. The adsorbed CH3CHO first dehydrogenate into CH2CHO by reacting with a neighboring terminal Ot. The hydroxyl (OtH) then hydrogenates CH2CHO into CH2CH2O to complete the hydrogen transfer cycle with an activation barrier of 1.39 eV. The direct hydrogen transfer from CH3CHO to CH2CH2O is unlikely due to the high barrier of 2.00 eV. The produced CH2CH2O readily decomposes into C2H4 that directly releases to the gas phase, and regenerates the Ot atom on the Mo site. As a result, the reduced MoO3(010) surface is reoxidized to the perfect MoO3(010) surface after CH3CHO deoxygenation. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less

Energy efficient synthesis of boranes

DOEpatents

Thorn, David L [Los Alamos, NM; Tumas, William [Los Alamos, NM; Schwarz, Daniel E [Los Alamos, NM; Burrell, Anthony K [Los Alamos, NM

2012-01-24

The reaction of halo-boron compounds (B--X compounds, compounds having one or more boron-halogen bonds) with silanes provides boranes (B--H compounds, compounds having one or more B--H bonds) and halosilanes. Inorganic hydrides, such as surface-bound silane hydrides (Si--H) react with B--X compounds to form B--H compounds and surface-bound halosilanes. The surface bound halosilanes are converted back to surface-bound silanes electrochemically. Halo-boron compounds react with stannanes (tin compounds having a Sn--H bond) to form boranes and halostannanes (tin compounds having a Sn--X bond). The halostannanes are converted back to stannanes electrochemically or by the thermolysis of Sn-formate compounds. When the halo-boron compound is BCl.sub.3, the B--H compound is B.sub.2H.sub.6, and where the reducing potential is provided electrochemically or by the thermolysis of formate.

Energy efficient synthesis of boranes

DOEpatents

Thorn, David L.; Tumas, William; Schwarz, Daniel E.; Burrell, Anthony K.

2010-11-23

The reaction of halo-boron compounds (B--X compounds, compounds having one or more boron-halogen bonds) with silanes provides boranes (B--H compounds, compounds having one or more B--H bonds) and halosilanes. Inorganic hydrides, such as surface-bound silane hydrides (Si--H) react with B--X compounds to form B--H compounds and surface-bound halosilanes. The surface bound halosilanes are converted back to surface-bound silanes electrochemically. Halo-boron compounds react with stannanes (tin compounds having a Sn--H bond) to form boranes and halostannanes (tin compounds having a Sn--X bond). The halostannanes are converted back to stannanes electrochemically or by the thermolysis of Sn-formate compounds. When the halo-boron compound is BCl.sub.3, the B--H compound is B.sub.2H.sub.6, and where the reducing potential is provided electrochemically or by the thermolysis of formate.

Promotion of water-mediated carbon removal by nanostructured barium oxide/nickel interfaces in solid oxide fuel cells.

PubMed

Yang, Lei; Choi, YongMan; Qin, Wentao; Chen, Haiyan; Blinn, Kevin; Liu, Mingfei; Liu, Ping; Bai, Jianming; Tyson, Trevor A; Liu, Meilin

2011-06-21

The existing Ni-yttria-stabilized zirconia anodes in solid oxide fuel cells (SOFCs) perform poorly in carbon-containing fuels because of coking and deactivation at desired operating temperatures. Here we report a new anode with nanostructured barium oxide/nickel (BaO/Ni) interfaces for low-cost SOFCs, demonstrating high power density and stability in C(3)H(8), CO and gasified carbon fuels at 750°C. Synchrotron-based X-ray analyses and microscopy reveal that nanosized BaO islands grow on the Ni surface, creating numerous nanostructured BaO/Ni interfaces that readily adsorb water and facilitate water-mediated carbon removal reactions. Density functional theory calculations predict that the dissociated OH from H(2)O on BaO reacts with C on Ni near the BaO/Ni interface to produce CO and H species, which are then electrochemically oxidized at the triple-phase boundaries of the anode. This anode offers potential for ushering in a new generation of SOFCs for efficient, low-emission conversion of readily available fuels to electricity.

Natural Tissue Microenvironmental Conditions Modulate Adhesive Material Performance

PubMed Central

Oliva, Nuria; Shitreet, Sagi; Abraham, Eytan; Stanley, Butch; Edelman, Elazer R.; Artzi, Natalie

2015-01-01

We designed and optimized tissue-responsive adhesive materials by matching material and tissue properties. A two-component material based on dextran aldehyde and dendrimer amine provides a cohesive gel through aldehyde–amine cross-linking and an adhesive interface created by a dextran aldehyde-selective reaction with tissue amines. By altering aldehyde–amine chemistry, we examined how variations in tissue surfaces (serosal amine density in the duodenum, jejunum, and ileum) affect interactions with adhesive materials of varied compositions (aldehyde content). Interestingly, the same adhesive formulation reacts differentially with the three regions of the small intestine as a result of variation in the tissue amine density along the intestinal tract, affecting the tissue–material interfacial morphology, adhesion strength, and adhesive mechanical properties. Whereas tissues provide chemical anchors for interaction with materials, we were able to tune the adhesion strength for each section of the small intestine tissue by altering the adhesive formulation using a two-component material with flexible variables aimed at controlling the aldehyde/amine ratio. This tissue-specific approach should be applied to the broad spectrum of biomaterials, taking into account specific microenvironmental conditions in material design. PMID:23046479

Promotion of water-mediated carbon removal by nanostructured barium oxide/nickel interfaces in solid oxide fuel cells

PubMed Central

Yang, Lei; Choi, YongMan; Qin, Wentao; Chen, Haiyan; Blinn, Kevin; Liu, Mingfei; Liu, Ping; Bai, Jianming; Tyson, Trevor A.; Liu, Meilin

2011-01-01

The existing Ni-yttria-stabilized zirconia anodes in solid oxide fuel cells (SOFCs) perform poorly in carbon-containing fuels because of coking and deactivation at desired operating temperatures. Here we report a new anode with nanostructured barium oxide/nickel (BaO/Ni) interfaces for low-cost SOFCs, demonstrating high power density and stability in C3H8, CO and gasified carbon fuels at 750°C. Synchrotron-based X-ray analyses and microscopy reveal that nanosized BaO islands grow on the Ni surface, creating numerous nanostructured BaO/Ni interfaces that readily adsorb water and facilitate water-mediated carbon removal reactions. Density functional theory calculations predict that the dissociated OH from H2O on BaO reacts with C on Ni near the BaO/Ni interface to produce CO and H species, which are then electrochemically oxidized at the triple-phase boundaries of the anode. This anode offers potential for ushering in a new generation of SOFCs for efficient, low-emission conversion of readily available fuels to electricity. PMID:21694705

Real-time {sup 90}Sr Counter

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaneko, Naomi; Kawai, Hideyuki; Kodama, Satoshi

2015-07-01

Radioisotopes have been emitted around Japan due to a nuclear accident at the Fukushima Daiichi nuclear power station in March 2011. A problem is the contaminated water including the atomic nucleus which relatively has a long half- life time and soluble such as {sup 90}Sr, {sup 137}Cs. Internal exposures by {sup 90}Sr are more dangerous than {sup 137}Cs's because Sr has effective half-life time of 18 years and property of accumulation in a born. We have developed real-time {sup 90}Sr counter which is sensitive beta-ray of maximum kinematic energy of 2.28 MeV from {sup 90}Sr and insensitive of beta-ray ofmore » maximum kinematic energy of 1.17 MeV and gamma-ray from {sup 90}Sr by Cherenkov detection. This counter composes of Cerenkov counter, trigger scintillation counter and veto counter. Silica aerogel for Cherenkov counter can obtain refractive index between 1.017 and 1.049 easily. And wavelength shifting fiber (WLSF) is used as a light guide for extending effective area and producing lower cost. A mechanism of the identification of {sup 90}Sr is explained in following. In case of {sup 90}Sr, when the trigger counter reacts on the beta-ray from {sup 90}Sr, aerogel emits the Cherenkov light and WLSF reacts and read the Cherenkov light. On the other hand, in case of {sup 137}Cs, the trigger counter reacts on the beta-ray, aerogel stops the beta- ray and Cherenkov light is not emitted. Therefore, aerogel has a function as a radiator and shielding material. the gamma-ray is not reacted on the lower density detector. Cosmic rays would be also reacted by the veto counter. A prototype counter whose the effective area is 30 cm x 10 cm was obtained (2.0±1.2){sup 3} of mis-identification as {sup 137}Cs/{sup 90}Sr. Detection limit in the surface contamination inspection depends on measurement time and effective area mainly. The sensitivity of wide range, 10{sup -2} - 10{sup 4} Bq/cm{sup 2}, is obtained by adjustment of detection level in circuit of this counter. A lower radioactive sample (< 10{sup -2} Bq/cm{sup 2}) allows be detected significantly by heating treatment to evaporate water shielding the beta-rays. (authors)« less

Amino-functionalized surface modification of polyacrylonitrile hollow fiber-supported polydimethylsiloxane membranes

NASA Astrophysics Data System (ADS)

Hu, Leiqing; Cheng, Jun; Li, Yannan; Liu, Jianzhong; Zhou, Junhu; Cen, Kefa

2017-08-01

This study aimed to improve surface polarity of polydimethylsiloxane (PDMS) membranes and provide surface active sites which were easy to react with other chemicals. 3-Aminopropyltriethoxysilane (APTES) containing an amino group was introduced into a PDMS membrane by crosslinking to prepare polyacrylonitrile hollow fiber-supported PDMS membranes with an amino-functionalized surface. Fourier transform infrared and X-ray photoelectron spectroscopic analyses proved the existence of APTES and its amino group in the PDMS membrane. The concentration of N atoms on the PDMS membrane surface reached ∼6% when the mass ratio of APTES/PDMS oligomer in the PDMS coating solution was increased to 4/3. The water contact angle decreased from ∼114° to ∼87.5°, indicating the improved surface polarization of the PDMS membrane. The density and swelling degree of the PDMS membrane decreased and increased, respectively, with increasing APTES content in PDMS. This phenomenon increased CO2 permeability and decreased CO2/H2 selectivity, CO2/CH4 selectivity, and CO2/N2 selectivity. When the mass ratio of APTES/PDMS oligomer was increased from 0 to 4/3, the CO2 permeation rate of the hollow fiber-supported PDMS membranes initially decreased from ∼2370 GPU to ∼860 GPU and then increased to ∼2000 GPU due to the change in coating solution viscosity.

Structure formation and surface chemistry of ionic liquids on model electrode surfaces—Model studies for the electrode | electrolyte interface in Li-ion batteries

NASA Astrophysics Data System (ADS)

Buchner, Florian; Uhl, Benedikt; Forster-Tonigold, Katrin; Bansmann, Joachim; Groß, Axel; Behm, R. Jürgen

2018-05-01

Ionic liquids (ILs) are considered as attractive electrolyte solvents in modern battery concepts such as Li-ion batteries. Here we present a comprehensive review of the results of previous model studies on the interaction of the battery relevant IL 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([BMP]+[TFSI]-) with a series of structurally and chemically well-defined model electrode surfaces, which are increasingly complex and relevant for battery applications [Ag(111), Au(111), Cu(111), pristine and lithiated highly oriented pyrolytic graphite (HOPG), and rutile TiO2(110)]. Combining surface science techniques such as high resolution scanning tunneling microscopy and X-ray photoelectron spectroscopy for characterizing surface structure and chemical composition in deposited (sub-)monolayer adlayers with dispersion corrected density functional theory based calculations, this work aims at a molecular scale understanding of the fundamental processes at the electrode | electrolyte interface, which are crucial for the development of the so-called solid electrolyte interphase (SEI) layer in batteries. Performed under idealized conditions, in an ultrahigh vacuum environment, these model studies provide detailed insights on the structure formation in the adlayer, the substrate-adsorbate and adsorbate-adsorbate interactions responsible for this, and the tendency for chemically induced decomposition of the IL. To mimic the situation in an electrolyte, we also investigated the interaction of adsorbed IL (sub-)monolayers with coadsorbed lithium. Even at 80 K, postdeposited Li is found to react with the IL, leading to decomposition products such as LiF, Li3N, Li2S, LixSOy, and Li2O. In the absence of a [BMP]+[TFSI]- adlayer, it tends to adsorb, dissolve, or intercalate into the substrate (metals, HOPG) or to react with the substrate (TiO2) above a critical temperature, forming LiOx and Ti3+ species in the latter case. Finally, the formation of stable decomposition products was found to sensitively change the equilibrium between surface Li and Li+ intercalated in the bulk, leading to a deintercalation from lithiated HOPG in the presence of an adsorbed IL adlayer at >230 K. Overall, these results provide detailed insights into the surface chemistry at the solid | electrolyte interface and the initial stages of SEI formation at electrode surfaces in the absence of an applied potential, which is essential for the further improvement of future Li-ion batteries.

PDF approach for compressible turbulent reacting flows

NASA Technical Reports Server (NTRS)

Hsu, A. T.; Tsai, Y.-L. P.; Raju, M. S.

1993-01-01

The objective of the present work is to develop a probability density function (pdf) turbulence model for compressible reacting flows for use with a CFD flow solver. The probability density function of the species mass fraction and enthalpy are obtained by solving a pdf evolution equation using a Monte Carlo scheme. The pdf solution procedure is coupled with a compressible CFD flow solver which provides the velocity and pressure fields. A modeled pdf equation for compressible flows, capable of capturing shock waves and suitable to the present coupling scheme, is proposed and tested. Convergence of the combined finite-volume Monte Carlo solution procedure is discussed, and an averaging procedure is developed to provide smooth Monte-Carlo solutions to ensure convergence. Two supersonic diffusion flames are studied using the proposed pdf model and the results are compared with experimental data; marked improvements over CFD solutions without pdf are observed. Preliminary applications of pdf to 3D flows are also reported.

A study of the formation of amorphous calcium phosphate and hydroxyapatite on melt quenched Bioglass using surface sensitive shallow angle X-ray diffraction.

PubMed

Martin, R A; Twyman, H; Qiu, D; Knowles, J C; Newport, R J

2009-04-01

Melt quenched silicate glasses containing calcium, phosphorous and alkali metals have the ability to promote bone regeneration and to fuse to living bone. These glasses, including 45S5 Bioglass((R)) [(CaO)(26.9)(Na(2)O)(24.4)(SiO(2))(46.1)(P(2)O(5))(2.6)], are routinely used as clinical implants. Consequently there have been numerous studies on the structure of these glasses using conventional diffraction techniques. These studies have provided important information on the atomic structure of Bioglass((R)) but are of course intrinsically limited in the sense that they probe the bulk material and cannot be as sensitive to thin layers of near-surface dissolution/growth. The present study therefore uses surface sensitive shallow angle X-ray diffraction to study the formation of amorphous calcium phosphate and hydroxyapatite on Bioglass((R)) samples, pre-reacted in simulated body fluid (SBF). Unreacted Bioglass((R)) is dominated by a broad amorphous feature around 2.2 A(-1) which is characteristic of sodium calcium silicate glass. After reacting Bioglass((R)) in SBF a second broad amorphous feature evolves ~1.6 A(-1) which is attributed to amorphous calcium phosphate. This feature is evident for samples after only 4 h reacting in SBF and by 8 h the amorphous feature becomes comparable in magnitude to the background signal of the bulk Bioglass((R)). Bragg peaks characteristic of hydroxyapatite form after 1-3 days of reacting in SBF.

A second-order closure analysis of turbulent diffusion flames. [combustion physics

NASA Technical Reports Server (NTRS)

Varma, A. K.; Fishburne, E. S.; Beddini, R. A.

1977-01-01

A complete second-order closure computer program for the investigation of compressible, turbulent, reacting shear layers was developed. The equations for the means and the second order correlations were derived from the time-averaged Navier-Stokes equations and contain third order and higher order correlations, which have to be modeled in terms of the lower-order correlations to close the system of equations. In addition to fluid mechanical turbulence models and parameters used in previous studies of a variety of incompressible and compressible shear flows, a number of additional scalar correlations were modeled for chemically reacting flows, and a typical eddy model developed for the joint probability density function for all the scalars. The program which is capable of handling multi-species, multistep chemical reactions, was used to calculate nonreacting and reacting flows in a hydrogen-air diffusion flame.

Investigation of Grid Adaptation to Reduce Computational Efforts for a 2-D Hydrogen-Fueled Dual-Mode Scramjet

NASA Astrophysics Data System (ADS)

Foo, Kam Keong

A two-dimensional dual-mode scramjet flowpath is developed and evaluated using the ANSYS Fluent density-based flow solver with various computational grids. Results are obtained for fuel-off, fuel-on non-reacting, and fuel-on reacting cases at different equivalence ratios. A one-step global chemical kinetics hydrogen-air model is used in conjunction with the eddy-dissipation model. Coarse, medium and fine computational grids are used to evaluate grid sensitivity and to investigate a lack of grid independence. Different grid adaptation strategies are performed on the coarse grid in an attempt to emulate the solutions obtained from the finer grids. The goal of this study is to investigate the feasibility of using various mesh adaptation criteria to significantly decrease computational efforts for high-speed reacting flows.

Recent advances in ultrafast-laser-based spectroscopy and imaging for reacting plasmas and flames

NASA Astrophysics Data System (ADS)

Patnaik, Anil K.; Adamovich, Igor; Gord, James R.; Roy, Sukesh

2017-10-01

Reacting flows and plasmas are prevalent in a wide array of systems involving defense, commercial, space, energy, medical, and consumer products. Understanding the complex physical and chemical processes involving reacting flows and plasmas requires measurements of key parameters, such as temperature, pressure, electric field, velocity, and number densities of chemical species. Time-resolved measurements of key chemical species and temperature are required to determine kinetics related to the chemical reactions and transient phenomena. Laser-based, noninvasive linear and nonlinear spectroscopic approaches have proved to be very valuable in providing key insights into the physico-chemical processes governing reacting flows and plasmas as well as validating numerical models. The advent of kilohertz rate amplified femtosecond lasers has expanded the multidimensional imaging of key atomic species such as H, O, and N in a significant way, providing unprecedented insight into preferential diffusion and production of these species under chemical reactions or electric-field driven processes. These lasers not only provide 2D imaging of chemical species but have the ability to perform measurements free of various interferences. Moreover, these lasers allow 1D and 2D temperature-field measurements, which were quite unimaginable only a few years ago. The rapid growth of the ultrafast-laser-based spectroscopic measurements has been fueled by the need to achieve the following when measurements are performed in reacting flows and plasmas. They are: (1) interference-free measurements (collision broadening, photolytic dissociation, Stark broadening, etc), (2) time-resolved single-shot measurements at a rate of 1-10 kHz, (3) spatially-resolved measurements, (4) higher dimensionality (line, planar, or volumetric), and (5) simultaneous detection of multiple species. The overarching goal of this article is to review the current state-of-the-art ultrafast-laser-based spectroscopic techniques and their remarkable development in the past two decades in meeting one or all of the above five goals for the spectroscopic measurement of temperature, number density of the atomic and molecular species, and electric field.

Effects of Reduced Terrestrial LiDAR Point Density on High-Resolution Grain Crop Surface Models in Precision Agriculture

PubMed Central

Hämmerle, Martin; Höfle, Bernhard

2014-01-01

3D geodata play an increasingly important role in precision agriculture, e.g., for modeling in-field variations of grain crop features such as height or biomass. A common data capturing method is LiDAR, which often requires expensive equipment and produces large datasets. This study contributes to the improvement of 3D geodata capturing efficiency by assessing the effect of reduced scanning resolution on crop surface models (CSMs). The analysis is based on high-end LiDAR point clouds of grain crop fields of different varieties (rye and wheat) and nitrogen fertilization stages (100%, 50%, 10%). Lower scanning resolutions are simulated by keeping every n-th laser beam with increasing step widths n. For each iteration step, high-resolution CSMs (0.01 m2 cells) are derived and assessed regarding their coverage relative to a seamless CSM derived from the original point cloud, standard deviation of elevation and mean elevation. Reducing the resolution to, e.g., 25% still leads to a coverage of >90% and a mean CSM elevation of >96% of measured crop height. CSM types (maximum elevation or 90th-percentile elevation) react differently to reduced scanning resolutions in different crops (variety, density). The results can help to assess the trade-off between CSM quality and minimum requirements regarding equipment and capturing set-up. PMID:25521383

Nanoparticle Treated Stainless Steel Filters for Metal Vapor Sequestration

NASA Astrophysics Data System (ADS)

Murph, Simona E. Hunyadi; Larsen, George K.; Korinko, Paul; Coopersmith, Kaitlin J.; Summer, Ansley J.; Lewis, Rebecca

2017-02-01

The ability to sequester vapor phase radioactive compounds during industrial processes reduces the exposure of workers and the environment to dangerous radioactive materials. Nanomaterials have a lot of potential in this area because they typically demonstrate size- and shape-dependent properties with higher reactivity than bulk. This is due to the increased surface area-to-volume ratio and quantum size effects. In this report, we developed a gold nanomaterial-treated stainless steel filter, namely wools and coupons, that can be efficiently used for zinc vapor sequestration. Without nanoparticle modification, stainless steel coupons do not react or alloy with Zn. Gold nanomaterials were grown onto various stainless steel filters using solution chemistry that is amenable to scaling up. Materials were characterized by electron microscopy, inductively coupled plasma mass spectroscopy and dynamic light scattering before and after exposure to zinc vapors. X-ray diffraction, high-resolution transmission electron microscopy, energy dispersive x-ray spectroscopy mapping and ultraviolet-visible spectroscopy confirm the formation of gold-zinc alloys after Zn vapor exposure. The effect of surface topography on nanoparticle morphology, size and loading density were also investigated, and stainless steel surface defects were found to have an impact on the Au NP growth and subsequently Zn sequestration.

Self-catalyzed carbon plasma-assisted growth of tin-doped indium oxide nanostructures by the sputtering method

NASA Astrophysics Data System (ADS)

Setti, Grazielle O.; de Jesus, Dosil P.; Joanni, Ednan

2016-10-01

In this work a new strategy for growth of nanostructured indium tin oxide (ITO) by RF sputtering is presented. ITO is deposited in the presence of a carbon plasma which reacts with the free oxygen atoms during the deposition, forming species like CO x . These species are removed from the chamber by the pumping system, and one-dimensional ITO nanostructures are formed without the need for a seed layer. Different values of substrate temperature and power applied to the gun containing the carbon target were investigated, resulting in different nanostructure morphologies. The samples containing a higher density of nanowires were covered with gold and evaluated as surface-enhanced Raman scattering substrates for detection of dye solutions. The concept might be applied to other oxides, providing a simple method for unidimensional nanostructural synthesis.

Sulfur hexafluoride plasma surface modification of Gly-Ala and Ala-Gly as Bombyx mori silk model compounds: Mechanism investigations

NASA Astrophysics Data System (ADS)

Sangprasert, W.; Lee, V. S.; Boonyawan, D.; Tashiro, K.; Nimmanpipug, P.

2010-01-01

Low-pressure plasma has been used to improve the hydrophobicity of Thai silk. In this study, Glycine-Alanine (GA) and Alanine-Glycine (AG) were chosen to represent model compounds of Bombyx mori silk. Single crystals of the simplified model compounds were characterized by polarizing microscopy and X-ray diffraction. The space groups of P2 12 12 1 and P2 1 were found for AG and GA, respectively. The initial structures for calculation were obtained from the experimental crystal structures. Density functional theory at the BHandHLYP levels was used to investigate possible mechanisms of fluorine radicals reacting with AG and GA in the SF 6 plasma treatment. The results indicate that hydrogen atoms of silk model compounds were most likely to be abstracted from the alanine residue.

Monte Carlo PDF method for turbulent reacting flow in a jet-stirred reactor

NASA Astrophysics Data System (ADS)

Roekaerts, D.

1992-01-01

A stochastic algorithm for the solution of the modeled scalar probability density function (PDF) transport equation for single-phase turbulent reacting flow is described. Cylindrical symmetry is assumed. The PDF is represented by ensembles of N representative values of the thermochemical variables in each cell of a nonuniform finite-difference grid and operations on these elements representing convection, diffusion, mixing and reaction are derived. A simplified model and solution algorithm which neglects the influence of turbulent fluctuations on mean reaction rates is also described. Both algorithms are applied to a selectivity problem in a real reactor.

A two-phase restricted equilibrium model for combustion of metalized solid propellants

NASA Technical Reports Server (NTRS)

Sabnis, J. S.; Dejong, F. J.; Gibeling, H. J.

1992-01-01

An Eulerian-Lagrangian two-phase approach was adopted to model the multi-phase reacting internal flow in a solid rocket with a metalized propellant. An Eulerian description was used to analyze the motion of the continuous phase which includes the gas as well as the small (micron-sized) particulates, while a Lagrangian description is used for the analysis of the discrete phase which consists of the larger particulates in the motor chamber. The particulates consist of Al and Al2O3 such that the particulate composition is 100 percent Al at injection from the propellant surface with Al2O3 fraction increasing due to combustion along the particle trajectory. An empirical model is used to compute the combustion rate for agglomerates while the continuous phase chemistry is treated using chemical equilibrium. The computer code was used to simulate the reacting flow in a solid rocket motor with an AP/HTPB/Al propellant. The computed results show the existence of an extended combustion zone in the chamber rather than a thin reaction region. The presence of the extended combustion zone results in the chamber flow field and chemical being far from isothermal (as would be predicted by a surface combustion assumption). The temperature in the chamber increases from about 2600 K at the propellant surface to about 3350 K in the core. Similarly the chemical composition and the density of the propellant gas also show spatially non-uniform distribution in the chamber. The analysis developed under the present effort provides a more sophisticated tool for solid rocket internal flow predictions than is presently available, and can be useful in studying apparent anomalies and improving the simple correlations currently in use. The code can be used in the analysis of combustion efficiency, thermal load in the internal insulation, plume radiation, etc.

Carbide and carbonitride surface treatment method for refractory metals

DOEpatents

Meyer, G.A.; Schildbach, M.A.

1996-12-03

A carbide and carbonitride surface treatment method for refractory metals is provided, in steps including, heating a part formed of boron, chromium, hafnium, molybdenum, niobium, tantalum, titanium, tungsten or zirconium, or alloys thereof, in an evacuated chamber and then introducing reaction gases including nitrogen and hydrogen, either in elemental or water vapor form, which react with a source of elemental carbon to form carbon-containing gaseous reactants which then react with the metal part to form the desired surface layer. Apparatus for practicing the method is also provided, in the form of a carbide and carbonitride surface treatment system including a reaction chamber, a source of elemental carbon, a heating subassembly and a source of reaction gases. Alternative methods of providing the elemental carbon and the reaction gases are provided, as well as methods of supporting the metal part, evacuating the chamber with a vacuum subassembly and heating all of the components to the desired temperature. 5 figs.

Laser Ablation Cleaning of Self-Reacting Friction Stir Weld Seam Surfaces: A Preliminary Evaluation

NASA Technical Reports Server (NTRS)

Nunes, A. C., Jr.; Russell, C. K.; Brooke, S. A.; Parry, Q.; Lowrey, N. M.

2014-01-01

Anodized aluminum panels were cleaned by three lasers at three separate sites with a view to determining whether more economical laser cleaning might supplant current manual cleaning methods for preparation of surfaces to be welded by the self-reacting friction stir process. Uncleaned panels yielded welds exhibiting residual oxide defect (ROD) and failing at very low stresses along the trace of the weld seam. Manually cleaned panels yielded welds without ROD; these welds failed at nominal stress levels along an angled fracture surface not following the weld seam trace. Laser cleaned panels yielded welds failing at intermediate stress levels. The inadequacy of the laser cleaning processes leaves questions: Was the anodized aluminum test too stringent to represent actual cleaning requirements? Were the wrong laser cleaning techniques/parameters used for the study? Is the laser cleaning mechanism inadequate for effective preweld surface cleaning?

Group IV nanocrystals with ion-exchangeable surface ligands and methods of making the same

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.

Methods are described that include reacting a starting nanocrystal that includes a starting nanocrystal core and a covalently bound surface species to create an ion-exchangeable (IE) nanocrystal that includes a surface charge and a first ion-exchangeable (IE) surface ligand ionically bound to the surface charge, where the starting nanocrystal core includes a group IV element.

Method for lubricating contacting surfaces

DOEpatents

Dugger, Michael T [Tijeras, NM; Ohlhausen, James A [Albuquerque, NM; Asay, David B [Boalsburg, PA; Kim, Seong H [State College, PA

2011-12-06

A method is provided for tribological lubrication of sliding contact surfaces, where two surfaces are in contact and in motion relative to each other, operating in a vapor-phase environment containing at least one alcohol compound at a concentration sufficiently high to provide one monolayer of coverage on at least one of the surfaces, where the alcohol compound continuously reacts at the surface to provide lubrication.

Covalent Surface Modification of Gallium Arsenide Photocathodes for Water Splitting in Highly Acidic Electrolyte.

PubMed

Garner, Logan E; Steirer, K Xerxes; Young, James L; Anderson, Nicholas C; Miller, Elisa M; Tinkham, Jonathan S; Deutsch, Todd G; Sellinger, Alan; Turner, John A; Neale, Nathan R

2017-02-22

Efficient water splitting using light as the only energy input requires stable semiconductor electrodes with favorable energetics for the water-oxidation and proton-reduction reactions. Strategies to tune electrode potentials using molecular dipoles adsorbed to the semiconductor surface have been pursued for decades but are often based on weak interactions and quickly react to desorb the molecule under conditions relevant to sustained photoelectrolysis. Here, we show that covalent attachment of fluorinated, aromatic molecules to p-GaAs(1 0 0) surfaces can be employed to tune the photocurrent onset potentials of p-GaAs(1 0 0) photocathodes and reduce the external energy required for water splitting. Results indicate that initial photocurrent onset potentials can be shifted by nearly 150 mV in pH -0.5 electrolyte under 1 Sun (1000 W m -2 ) illumination resulting from the covalently bound surface dipole. Though X-ray photoelectron spectroscopy analysis reveals that the covalent molecular dipole attachment is not robust under extended 50 h photoelectrolysis, the modified surface delays arsenic oxide formation that results in a p-GaAs(1 0 0) photoelectrode operating at a sustained photocurrent density of -20.5 mA cm -2 within -0.5 V of the reversible hydrogen electrode. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Standing and sitting adlayers in atomic layer deposition of ZnO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Zhengning; Banerjee, Parag, E-mail: parag.banerjee@wustl.edu; Wu, Fei

The extent of reactivity of diethyl zinc (DEZ) with a hydroxylated surface during atomic layer deposition (ALD) of ZnO using DEZ and water is measured. Two adlayer configurations of DEZ are possible. The “standing” adlayer releases one ethyl group from DEZ. The “sitting” adlayer releases both ethyl groups, thus forming a Zn bridge between two O anions. Density functional theory calculations suggest the sitting configuration is more stable than the standing configuration by 790 meV. In situ quadrupole mass spectroscopy of by-product ethane generated in ALD half cycles indicate that ∼1.56 OH sites react with a DEZ molecule resulting in 71.6%more » of sitting sites. A simple simulation of a “ball-and-stick” DEZ molecule randomly collapsing on a neighboring site remarkably captures this adlayer behavior. It is concluded that DEZ fraction sitting is a competitive process of a standing DEZ molecule collapsing onto an available neighboring hydroxyl site, as sites vie for occupancy via adsorption and surface diffusion.« less

X-ray photoelectron spectroscopic and morphologic studies of Ru nanoparticles deposited onto highly oriented pyrolytic graphite

NASA Astrophysics Data System (ADS)

Bavand, R.; Yelon, A.; Sacher, E.

2015-11-01

Ruthenium nanoparticles (Ru NPs) function as effective catalysts in specific reactions, such as methanation and Fischer-Tropsch syntheses. It is our purpose to physicochemically characterize their surfaces, at which catalysis occurs, by surface-sensitive X-ray photoelectron spectroscopy (XPS), using the symmetric peak component anaylsis technique developed in our laboratory to reveal previously hidden components. Ru NPs were deposited by evaporation (0.25-1.5 nm nominal deposition range) onto highly oriented pyrolytic graphite (HOPG). In addition to their surfaces being characterized by XPS, an indication of morphology was obtained from transmission electron microscopy (TEM). Our use of symmetric peak component XPS analysis has revealed detailed information on a previously unidentified surface oxide initially formed, as well as on the valence electronic structure and its variation with NP size, information that is of potential importance in the use of these NPs in catalysis. Each of the several Ru core XPS spectra characterized (3d, 3p and 3s) was found to be composed of three symmetric components. Together with two metal oxide O1s components, these give evidence of a rather complex, previously unidentified oxide that is initially formed. The Ru valence band (4d and 5s) spectra clearly demonstrate a loss of metallicity, a simultaneous increase of the Kubo gap, and an abrupt transfer in valence electron density from the 4d to the 5s orbitals (known as electron spill-over), as the NP size decreases below 0.5 nm. TEM photomicrographs, as a function of deposition rate, show that, at a rate that gives insufficient time for the NP condensation energy to dissipate, the initially well-separated NPs are capable of diffusing laterally and aggregating. This indicates weak NP bonding to the HOPG substrate. Carbide is formed, at both high and low deposition rates, at Ru deposition thicknesses greater than 0.25 nm, its formation explained by Ru NPs reacting with residual hydrocarbon vapor, under the influence of the heat of condensation released on Ru deposition, and not by Ru reacting with the HOPG substrate.

Fast Reacting Nano Composite Energetic Materials: Synthesis and Combustion Characterization

DTIC Science & Technology

2015-08-24

mg of composite resulting in a loose powder fill estimated to be 7% of the theoretical maximum density. Once prepared, the tube was placed in a steel ...theoretical maximum density. Once prepared, the tube was placed in a steel combustion chamber and the experimental setup is schematically represented... Valery Levitas. "Effect of oxide shell growth on ano- aluminum thermite propagation rates." Combustion and Flame 159 (2012): 3448-3453. I. Liakosa

A relativistic density functional study of the role of 5f electrons in atomic and molecular adsorptions on actinide surfaces

NASA Astrophysics Data System (ADS)

Huda, Muhammad Nurul

Atomic and molecular adsorptions of oxygen and hydrogen on actinide surfaces have been studied within the generalized gradient approximations to density functional theory (GGA-DFT). The primary goal of this work is to understand the details of the adsorption processes, such as chemisorption sites, energies, adsorption configurations and activation energies for dissociation of molecules; and the signature role of the plutonium 5f electrons. The localization of the 5f electrons remains one of central questions in actinides and one objective here is to understand the extent to which localizations plays a role in adsorption on actinide surfaces. We also investigated the magnetism of the plutonium surfaces, given the fact that magnetism in bulk plutonium is a highly controversial issue, and the surface magnetism of it is not a well explored territory. Both the non-spin-polarized and spin-polarized calculations have been performed to arrive at our conclusions. We have studied both the atomic and molecular hydrogen and oxygen adsorptions on plutonium (100) and (111) surfaces. We have also investigated the oxygen molecule adsorptions on uranium (100) surface. Comparing the adsorption on uranium and plutonium (100) surfaces, we have seen that O2 chemisorption energy for the most favorable adsorption site on uranium surface has higher chemisorption energy, 9.492 eV, than the corresponding plutonium site, 8.787 eV. Also degree of localization of 5f electrons is less for uranium surface. In almost all of the cases, the most favorable adsorption sites are found where the coordination numbers are higher. For example, we found center sites are the most favorable sites for atomic adsorptions. In general oxygen reacts more strongly with plutonium surface than hydrogen. We found that atomic oxygen adsorption energy on (100) surface is 3.613 eV more than that of the hydrogen adsorptions, considering only the most favorable site. This is also true for molecular adsorptions, as the oxygen molecules on both (100) and (111) plutonium surfaces dissociate almost spontaneously, whereas hydrogen needs some activation energy to dissociate. From spin-polarized calculations we found both (100) and (111) surfaces have the layer by layer alternating spin-magnetic behavior. In general adsorption of H2 and O2 do not change this behavior.

Evolution of the Copper Surface in the Course of Oxidation by CCl4-L (L=THF, Dmf, Dmso): Scanning Probe Microscope Study

NASA Astrophysics Data System (ADS)

Panteleev, S. V.; Maslennikov, S. V.; Ignatov, S. K.; Spirina, I. V.; Kruglova, M. V.; Gribkov, B. A.; Vdovichev, S. N.

2013-04-01

The evolution of compact surface of the 100 nm copper film deposited on the glass-ceramics doped with vanadium coating in the course of the oxidation by the CCl4-L (L = dimethylformamide (DMF), tetrahydrofuran (THF), dimethylsulfoxide (DMSO), CCl4 concentration ≈ 1 mol/L) was studied by atomic force microscopy (AFM) in contact mode. The dynamics of active centers formation and destruction was investigated in the course of the oxidation process. The metallic sample dissolution rate was estimated as a function of the coordinating solvent nature. The development of the metal surface oxidation was established to lead to a significant increase of surface roughness. This phenomenon can be explained by the fact that different parts of the surface react at different rates. Further course of the reaction leads to a significant decrease of the surface roughness of copper films. The amount of the metal reacted has an almost linear dependence on the reaction time. AFM scans indicate that there is the same mechanism of the reaction between copper and carbon tetrachloride for all solvents.

VAR2CSA domains expressed in Escherichia coli induce cross-reactive antibodies to native protein.

PubMed

Oleinikov, Andrew V; Francis, Susan E; Dorfman, Jeffrey R; Rossnagle, Eddie; Balcaitis, Stephanie; Getz, Tony; Avril, Marion; Gose, Severin; Smith, Joseph D; Fried, Michal; Duffy, Patrick E

2008-04-15

The variant surface antigen VAR2CSA is a pregnancy malaria vaccine candidate, but its size and polymorphism are obstacles to development. We expressed 3D7-type VAR2CSA domains in Escherichia coli as insoluble His-tagged proteins (Duffy binding-like [DBL] domains DBL1, DBL3, DBL4, and DBL5) that were denatured and refolded or as soluble glutathione S-transferase-tagged protein (DBL6). Anti-DBL5 antiserum cross-reacted with surface proteins of chondroitin sulfate A (CSA)-binding laboratory strains (3D7-CSA and FCR3-CSA) and a clinical pregnancy malaria isolate, whereas anti-DBL6 antiserum reacted only to 3D7 surface protein. This is the first report that E. coli-expressed VAR2CSA domains induce antibody to native VAR2CSA.

Covalent immobilisation of antibodies in Teflon-FEP microfluidic devices for the sensitive quantification of clinically relevant protein biomarkers.

PubMed

Pivetal, Jeremy; Pereira, Filipa M; Barbosa, Ana I; Castanheira, Ana P; Reis, Nuno M; Edwards, Alexander D

2017-03-13

This study reports for the first time the sensitive colorimetric and fluorescence detection of clinically relevant protein biomarkers by sandwich immunoassays using the covalent immobilisation of antibodies onto the fluoropolymer surface inside Teflon®-FEP microfluidic devices. Teflon®-FEP has outstanding optical transparency ideal for high-sensitivity colorimetric and fluorescence bioassays, however this thermoplastic is regarded as chemically inert and very hydrophobic. Covalent immobilisation can offer benefits over passive adsorption to plastic surfaces by allowing better control over antibody density, orientation and analyte binding capacity, and so we tested a range of different and novel covalent immobilisation strategies. We first functionalised the inner surface of a 10-bore, 200 μm internal diameter FEP microcapillary film with high-molecular weight polyvinyl alcohol (PVOH) without changing the outstanding optical transparency of the device delivered by the matched refractive index of FEP and water. Glutaraldehyde immobilisation was compared with the use of photoactivated linkers and NHS-ester crosslinkers for covalently immobilising capture antibodies onto PVOH. Three clinically relevant sandwich ELISAs were tested against the cytokine IL-1β, the myocardial infarct marker cardiac troponin I (cTnI), and the chronic heart failure marker brain natriuretic peptide (BNP). Overall, glutaraldehyde immobilisation was effective for BNP assays, but yielded unacceptable background for IL-1β and cTnI assays caused by direct binding of the biotinylated detection antibody to the modified PVOH surface. We found NHS-ester groups reacted with APTES-treated PVOH coated fluoropolymers. This facilitated a novel method for capture antibody immobilisation onto fluoropolymer devices using a bifunctional NHS-maleimide crosslinker. The density of covalently immobilised capture antibodies achieved using PVOH/APTES/NHS/maleimide approached levels seen with passive adsorption, and sensitive and quantitative assay performance was achieved using this method. Overall, the PVOH coating provided an excellent surface for controlled covalent antibody immobilisation onto Teflon®-FEP for performing high-sensitivity immunoassays.

Computer Animation of a Chemical Reaction.

ERIC Educational Resources Information Center

Eaker, Charles W.; Jacobs, Edwin L.

1982-01-01

Taking a prototype chemical reaction (molecular hydrogen plus hydrogen atom), constructs an accurate semiempirical, generalized diatomics-in-molecules potential energy surface, calculates motions of these atoms on this surface using REACTS trajectory program, and presents results as moving picture on a microcomputer graphics system. Provides…

Simulating the fate and transport of nanomaterials in surface waters

EPA Science Inventory

The unique properties of nanomaterials have resulted in their increased production. However, it is unclear how nanomaterials will move and react once released to the environment One approach for addressing possible exposure of nanomaterials in surface waters is by using numerical...

2D and 3D surface photopatterning via laser-promoted homopolymerization of a perfluorophenyl azide-substituted BODIPY.

PubMed

Raffy, Guillaume; Bofinger, Robin; Tron, Arnaud; Guerzo, André Del; McClenaghan, Nathan D; Vincent, Jean-Marc

2017-11-09

An innovative photopatterning process is described that allows, in a single laser-promoted operation, the covalent attachment of a molecule on a surface (2D patterning - xy dimensions) and its photopolymerization to grow micro-/nanostructures with spatial control in a third z-dimension. The surface patterning process, based on nitrene reactivity, was harnessed using the highly fluorescent azide-substituted boron difluoride dipyrromethene (BODIPY) 1 that was prepared in a single synthetic step from the parent pentafluorophenyl BODIPY on reacting with NaN 3 . Using the laser of a fluorescence microscope (375 nm or 532 nm) 1 could be grafted on adapted surfaces and then homopolymerised. In this study we show that using glass coverslips coated with PEG/high density alkyne groups (density of ∼1 × 10 14 per cm 2 ), the patterning process was much more spatially confined than when using PEG only coating. Varying the irradiation time (1 to 15 s) or laser power (0.14-3.53 μW) allowed variation of the amount of deposited BODIPY to afford, in the extreme case, pillars of a height up to 800 nm. AFM and MS studies revealed that the nano/microstructures were formed of particles of photopolymerized 1 having a mean diameter of ca. 30 nm. The emission spectra and fluorescence lifetimes for the patterned structures were measured, revealing a red-shift (from ∼560 nm up to 620 nm) of the maximum emission and a shortening (from ∼6 ns to 0.8 ns) of the fluorescence lifetimes in areas where the density of BODIPY is high. As an application of the patterning process, a figure formed of 136 dots/pillars was prepared. The confocal hyperspectral fluorescence image revealed that the figure is clearly resolved and constituted by highly photoluminescent red dots whose fluorescence intensities and emission color proved to be highly reproducible. SEM and AFM studies showed that the luminescent dots were pillars with a conical shape, an average height of 710 ± 28 nm and a FWHM of 400 ± 20 nm.

Fuel Effects on Nozzle Flow and Spray Using Fully Coupled Eulerian Simulations

DTIC Science & Technology

2015-09-01

Density of liquid fuel, kg/m 3 = Density of ambient gas , kg/m 3 VOF = Volume of Fluid model = Volume of Fluid Scalar ROI = Rate of...have been reported arising from individual refinery processes, crude oil source, and also varying with season, year and age of the fuel. This myriad...configurations. Under reacting conditions, Violi et al. (6) presented a surrogate mixture of six pure hydrocarbon ( Utah surrogate) and found that it

Composite materials and bodies including silicon carbide and titanium diboride and methods of forming same

DOEpatents

Lillo, Thomas M.; Chu, Henry S.; Harrison, William M.; Bailey, Derek

2013-01-22

Methods of forming composite materials include coating particles of titanium dioxide with a substance including boron (e.g., boron carbide) and a substance including carbon, and reacting the titanium dioxide with the substance including boron and the substance including carbon to form titanium diboride. The methods may be used to form ceramic composite bodies and materials, such as, for example, a ceramic composite body or material including silicon carbide and titanium diboride. Such bodies and materials may be used as armor bodies and armor materials. Such methods may include forming a green body and sintering the green body to a desirable final density. Green bodies formed in accordance with such methods may include particles comprising titanium dioxide and a coating at least partially covering exterior surfaces thereof, the coating comprising a substance including boron (e.g., boron carbide) and a substance including carbon.

Excess charge driven dissociative hydrogen adsorption on Ti2O4.

PubMed

Song, Xiaowei; Fagiani, Matias R; Debnath, Sreekanta; Gao, Min; Maeda, Satoshi; Taketsugu, Tetsuya; Gewinner, Sandy; Schöllkopf, Wieland; Asmis, Knut R; Lyalin, Andrey

2017-08-30

The mechanism of dissociative D 2 adsorption on Ti 2 O 4 - , which serves as a model for an oxygen vacancy on a titania surface, is studied using infrared photodissociation spectroscopy in combination with density functional theory calculations and a recently developed single-component artificial force induced reaction method. Ti 2 O 4 - readily reacts with D 2 under multiple collision conditions in a gas-filled ion trap held at 16 K forming a global minimum-energy structure (DO-Ti-(O) 2 -Ti(D)-O) - . The highly exergonic reaction proceeds quasi barrier-free via several intermediate species, involving heterolytic D 2 -bond cleavage followed by D-atom migration. We show that, compared to neutral Ti 2 O 4 , the excess negative charge in Ti 2 O 4 - is responsible for the substantial lowering of the D 2 dissociation barrier, but does not affect the molecular D 2 adsorption energy in the initial physisorption step.

Fabrication of solid oxide fuel cell by electrochemical vapor deposition

DOEpatents

Brian, Riley; Szreders, Bernard E.

1989-01-01

In a high temperature solid oxide fuel cell (SOFC), the deposition of an impervious high density thin layer of electrically conductive interconnector material, such as magnesium doped lanthanum chromite, and of an electrolyte material, such as yttria stabilized zirconia, onto a porous support/air electrode substrate surface is carried out at high temperatures (approximately 1100.degree.-1300.degree. C.) by a process of electrochemical vapor deposition. In this process, the mixed chlorides of the specific metals involved react in the gaseous state with water vapor resulting in the deposit of an impervious thin oxide layer on the support tube/air electrode substrate of between 20-50 microns in thickness. An internal heater, such as a heat pipe, is placed within the support tube/air electrode substrate and induces a uniform temperature profile therein so as to afford precise and uniform oxide deposition kinetics in an arrangement which is particularly adapted for large scale, commercial fabrication of SOFCs.

Manganese-calcium intermixing facilitates heteroepitaxial growth at the (1014) calcite-water interface

DOE PAGES

Xu, Man; Riechers, Shawn L.; Ilton, Eugene S.; ...

2017-09-05

For this research, in situ atomic force microscopy (AFM) measurements were performed to probe surface precipitates that formed on the (10more » $$\\bar{1}$$4) surface of calcite (CaCO 3) single crystals following reaction with Mn2 +-bearing aqueous solutions. Three-dimensional epitaxial islands were observed to precipitate and grow on the surfaces. In situ time-sequenced measurements demonstrated that the growth rates were commensurate with those obtained for epitaxial islands formed on calcite crystals reacted with Cd2 +-bearing aqueous solutions of the same range in supersaturation with respect to the pure metal carbonate phase. This finding was unexpected as rhodochrosite (MnCO 3) and calcite display a 10% lattice mismatch, based on the area of their (10$$\\bar{1}$$4) surface unit cells, whereas the lattice mismatch is only 4% for otavite (CdCO 3) and calcite. Coatings of varying thicknesses were therefore synthesized by reacting calcite single crystals in calcite-equilibrated aqueous solutions with up to 250 μM MnCl 2. Ex situ X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), X-ray reflectivity (XRR), and AFM measurements of the reacted crystals demonstrated the formation of an epitaxial (Mn,Ca)CO 3 solid solution. The epitaxial solid solution had a spatially complex composition, whereby the first few nanometers were rich in Ca and the Mn content increased with distance from the original calcite surface, culminating in a topmost region of almost pure MnCO 3 for the thickest coatings. The effective lattice mismatch was therefore much smaller than the nominal mismatch thus explaining the measured growth rates. Lastly, these findings highlight the strong influence played by the substrate on the composition of surface precipitates in aqueous conditions.« less

Functionalization of poly(methyl methacrylate) (PMMA) as a substrate for DNA microarrays

PubMed Central

Fixe, F.; Dufva, M.; Telleman, P.; Christensen, C. B. V.

2004-01-01

A chemical procedure was developed to functionalize poly(methyl methacrylate) (PMMA) substrates. PMMA is reacted with hexamethylene diamine to yield an aminated surface for immobilizing DNA in microarrays. The density of primary NH2 groups was 0.29 nmol/cm2. The availability of these primary amines was confirmed by the immobilization of DNA probes and hybridization with a complementary DNA strand. The hybridization signal and the hybridization efficiency of the chemically aminated PMMA slides were comparable to the hybridization signal and the hybridization efficiency obtained from differently chemically modified PMMA slides, silanized glass, commercial silylated glass and commercial plastic Euray™ slides. Immobilized and hybridized densities of 10 and 0.75 pmol/cm2, respectively, were observed for microarrays on chemically aminated PMMA. The immobilized probes were heat stable since the hybridization performance of microarrays subjected to 20 PCR heat cycles was only reduced by 4%. In conclusion, this new strategy to modify PMMA provides a robust procedure to immobilize DNA, which is a very useful substrate for fabricating single use diagnostics devices with integrated functions, like sample preparation, treatment and detection using microfabrication and microelectronic techniques. PMID:14718554

PERFORMANCE EVALUATION OF AN AIR COUPLED PHASED ARRAY RADAR FOR NEAR FIELD DETECTION OF STEEL

DTIC Science & Technology

2015-04-24

sulfur dioxide reacts with the hydrated cement, the surface of the concrete starts to dissolve because it does not diffuse into concrete as quickly...Carbon dioxide begins to diffuse into the concrete and reacts with the hydrated cement to produce calcium carbonate. The presence of sulfur ...its design life. The health and state of the concrete roadways and bridge decks that commuters rely on a daily basis can be efficiently examined and

Surface topographical changes measured by phase-locked interferometry

NASA Technical Reports Server (NTRS)

Lauer, J. L.; Fung, S. S.

1984-01-01

An electronic optical laser interferometer capable of resolving depth differences of as low as 30 A and planar displacements of 6000 A was constructed to examine surface profiles of bearing surfaces without physical contact. Topological chemical reactivity was determined by applying a drop of dilute alcoholic hydrochloric acid and measuring the profile of the solid surface before and after application of this probe. Scuffed bearing surfaces reacted much faster than virgin ones but that bearing surfaces exposed to lubricants containing an organic chloride reacted much more slowly. The reactivity of stainless steel plates, heated in a nitrogen atmosphere to different temperatures, were examined later at ambient temperature. The change of surface contour as a result of the probe reaction followed Arrhenius-type relation with respect to heat treatment temperature. The contact area of the plate of a ball/plate sliding elastohydrodynamic contact run on trimethylopropane triheptanoate with or without additives was optically profiled periodically. As scuffing was approached, the change of profile within the contact region changed much more rapidly by the acid probe and assumed a constant high value after scuffing. A nonetching metallurgical phase was found in the scuff mark, which was apparently responsible for the high reactivity.

Carbide and carbonitride surface treatment method for refractory metals

DOEpatents

Meyer, Glenn A.; Schildbach, Marcus A.

1996-01-01

A carbide and carbonitride surface treatment method for refractory metals is provided, in steps including, heating a part formed of boron, chromium, hafnium, molybdenum, niobium, tantalum, titanium, tungsten or zirconium, or alloys thereof, in an evacuated chamber and then introducing reaction gases including nitrogen and hydrogen, either in elemental or water vapor form, which react with a source of elemental carbon to form carbon-containing gaseous reactants which then react with the metal part to form the desired surface layer. Apparatus for practicing the method is also provided, in the form of a carbide and carbonitride surface treatment system (10) including a reaction chamber (14), a source of elemental carbon (17), a heating subassembly (20) and a source of reaction gases (23). Alternative methods of providing the elemental carbon (17) and the reaction gases (23) are provided, as well as methods of supporting the metal part (12), evacuating the chamber (14) with a vacuum subassembly (18) and heating all of the components to the desired temperature.

The PDF method for turbulent combustion

NASA Technical Reports Server (NTRS)

Pope, S. B.

1991-01-01

Probability Density Function (PDF) methods provide a means of calculating the properties of turbulent reacting flows. They have been successfully applied to many turbulent flames, including some with finite rate kinetic effects. Here the methods are reviewed with an emphasis on computational issues and their application to turbulent combustion.

Equation of state, initiation, and detonation of pure ammonium nitrate

NASA Astrophysics Data System (ADS)

Robbins, D. L.; Sheffield, S. A.; Dattelbaum, D. M.; Velisavljevic, N.; Stahl, D. B.

2009-06-01

Ammonium nitrate (AN) is a widely used fertilizer and mining explosive throughout the world. One of the more common explosives using AN is called ANFO, a mixture of AN prills and fuel oil in a 94:6 ratio by weight. The AN prills are specially made to absorb the fuel oil, forming a mixture that reacts under shock loading through a diffusion-controlled process, resulting in a non-ideal explosive with detonation velocities around 4 km/s. While there are a number of studies on ANFO, there are only a few studies relating to the equation of state (EOS) and detonation properties of pure AN - resulting mainly from studies of accidents that have occurred during transportation of large quantities of AN. We present the results of a series of gas gun-driven plate impact experiments on pressed AN ranging in density from 1.72 to 0.9 g/cm^3. Several of the high density experiments were performed in front surface impact geometry, in which pressed AN disks were built into the projectile front and impacted onto LiF windows. Additional experiments at low density have been done in ``half cell'' multiple magnetic gauge gun experiments. From this work a complete unreacted EOS has been developed, as well as some initiation and detonation information. Additional high pressure x-ray diffraction experiments in diamond anvil cells have provided a static isotherm for AN.

Cross-immunoreactivity between the LH1 antibody and cytokeratin epitopes in the differentiating epidermis of embryos of the grass snake Natrix natrix L. during the end stages of embryogenesis.

PubMed

Swadźba, Elwira; Rupik, Weronika

2012-01-01

The monoclonal anti-cytokeratin 1/10 (LH1) antibody recognizing K1/K10 keratin epitopes that characterizes a keratinized epidermis of mammals cross-reacts with the beta and Oberhäutchen layers covering the scales and gastrosteges of grass snake embryos during the final period of epidermis differentiation. The immunolocalization of the anti-cytokeratin 1/10 (LH1) antibody appears in the beta layer of the epidermis, covering the outer surface of the gastrosteges at the beginning of developmental stage XI, and in the beta layer of the epidermis, covering the outer surface of the scales at the end of developmental stage XI. This antibody cross-reacts with the Oberhäutchen layers in the epidermis covering the outer surface of both scales and gastrosteges at developmental stages XI and XII just before its fusion with the beta layers. After fusion of the Oberhäutchen and beta layers, LH1 immunolabeling is weaker than before. This might suggest that alpha-keratins in these layers of the epidermis are masked by beta-keratins, modified, or degraded. The anti-cytokeratin 1/10 (LH1) antibody stains the Oberhäutchen layer in the epidermis covering the inner surface of the gastrosteges and the hinge regions between gastrosteges at the end of developmental stage XI. However, the Oberhäutchen of the epidermis covering the inner surfaces of the scales and the hinge regions between scales does not show cytokeratin 1/10 (LH1) immunolabeling until hatching. This cross-reactivity suggests that the beta and Oberhäutchen layers probably contain some alpha-keratins that react with the LH1 antibody. It is possible that these alpha-keratins create specific scaffolding for the latest beta-keratin deposition. It is also possible that the LH1 antibody cross-reacts with other epidermal proteins such as filament-associated proteins, i.e., filaggrin-like. The anti-cytokeratin 1/10 (LH1) antibody does not stain the alpha and mesos layers until hatching. We suppose that the differentiation of these layers will begin just after the first postnatal sloughing.

Manganese-calcium intermixing facilitates heteroepitaxial growth at the 10 1 ¯ 4 calcite-water interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Man; Riechers, Shawn L.; Ilton, Eugene S.

2017-10-01

In situ atomic force microscopy (AFM) measurements were performed to probe surface precipitates that formed on the (10-14) surface of calcite (CaCO3) single crystals following reaction with Mn2+-bearing aqueous solutions with a range of initial concentrations. Three-dimensional epitaxial islands were observed to precipitate and grow on the surfaces and in situ time-sequenced measurements demonstrated that their growth rates were commensurate with those obtained for epitaxial islands formed on calcite crystals reacted with Cd2+-bearing aqueous solutions of the same range in supersaturation with respect to the pure metal carbonate phase. This finding was unexpected as rhodochrosite (MnCO3) and calcite display amore » 10% lattice mismatch, based on the area of their (10-14) surface unit cells, whereas the lattice mismatch is only 4% for otavite (CdCO3) and calcite. Coatings of varying thicknesses were therefore synthesized by reacting calcite single crystals with calcite-equilibrated aqueous solutions with concentrations of up to 250 µM MnCl2 and analyzed to determine the composition of the surface precipitates. Ex situ X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), X-ray reflectivity (XRR), and AFM measurements of the reacted crystals demonstrated the formation of an epitaxial (Mn,Ca)CO3 solid solution with a spatially complex composition atop the calcite surface, whereby the first few nanometers were rich in Ca and the Mn content increased with distance from the original calcite surface, culminating in a topmost region of almost pure MnCO3 for the thickest coatings. These findings explain the measured growth rates (the effective lattice mismatch was much smaller than nominal mismatch) and highlight the strong influence played by the substrate on the composition of surface precipitates in aqueous conditions.« less

Hydrogen isotopic substitution of solid methylamine through atomic surface reactions at low temperatures: A potential contribution to the D/H ratio of methylamine in molecular clouds

NASA Astrophysics Data System (ADS)

Oba, Yasuhiro; Chigai, Takeshi; Osamura, Yoshihiro; Watanabe, Naoki; Kouchi, Akira

2014-01-01

We experimentally studied hydrogen (H)-deuterium (D) substitution reactions of solid methylamine (CH3NH2) under astrophysically relevant conditions. We also calculated the potential energy surface for the H-D substitution reactions of methylamine isotopologues using quantum chemical methods. Despite the relatively large energy barrier of more than 18 kJ mol-1, CH3NH2 reacted with D atoms to yield deuterated methylamines at 10 K, suggesting that the H-D substitution reaction proceeds through quantum tunneling. Deuterated methylamines reacted with H atoms as well. On the basis of present results, we propose that methylamine has potential for D enrichment through atomic surface reactions on interstellar grains at very low temperatures in molecular clouds. D enrichment would occur in particular in the methyl group of methylamine.

Photoluminescent silicon nanocrystals with chlorosilane surfaces - synthesis and reactivity

NASA Astrophysics Data System (ADS)

Höhlein, Ignaz M. D.; Kehrle, Julian; Purkait, Tapas K.; Veinot, Jonathan G. C.; Rieger, Bernhard

2014-12-01

We present a new efficient two-step method to covalently functionalize hydride terminated silicon nanocrystals with nucleophiles. First a reactive chlorosilane layer was formed via diazonium salt initiated hydrosilylation of chlorodimethyl(vinyl)silane which was then reacted with alcohols, silanols and organolithium reagents. With organolithium compounds a side reaction is observed in which a direct functionalization of the silicon surface takes place.We present a new efficient two-step method to covalently functionalize hydride terminated silicon nanocrystals with nucleophiles. First a reactive chlorosilane layer was formed via diazonium salt initiated hydrosilylation of chlorodimethyl(vinyl)silane which was then reacted with alcohols, silanols and organolithium reagents. With organolithium compounds a side reaction is observed in which a direct functionalization of the silicon surface takes place. Electronic supplementary information (ESI) available: Detailed experimental procedures and additional NMR, PL, EDX, DLS and TEM data. See DOI: 10.1039/C4NR05888G

Surface Fluorination of Reactive Battery Anode Materials for Enhanced Stability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Jie; Liao, Lei; Shi, Feifei

Significant increases in the energy density of batteries must be achieved by exploring new materials and cell configurations. Lithium metal and lithiated silicon are two promising high-capacity anode materials. Unfortunately, both of these anodes require a reliable passivating layer to survive the serious environmental corrosion during handling and cycling. Here we developed a surface fluorination process to form a homogeneous and dense LiF coating on reactive anode materials, with in situ generated fluorine gas, by using a fluoropolymer, CYTOP, as the precursor. The process is effectively a “reaction in the beaker”, avoiding direct handling of highly toxic fluorine gas. Formore » lithium metal, this LiF coating serves as a chemically stable and mechanically strong interphase, which minimizes the corrosion reaction with carbonate electrolytes and suppresses dendrite formation, enabling dendrite-free and stable cycling over 300 cycles with current densities up to 5 mA/cm 2. Lithiated silicon can serve as either a pre-lithiation additive for existing lithium-ion batteries or a replacement for lithium metal in Li–O 2 and Li–S batteries. However, lithiated silicon reacts vigorously with the standard slurry solvent N-methyl-2-pyrrolidinone (NMP), indicating it is not compatible with the real battery fabrication process. With the protection of crystalline and dense LiF coating, Li xSi can be processed in anhydrous NMP with a high capacity of 2504 mAh/g. With low solubility of LiF in water, this protection layer also allows Li xSi to be stable in humid air (~40% relative humidity). Furthermore, this facile surface fluorination process brings huge benefit to both the existing lithium-ion batteries and next-generation lithium metal batteries.« less

Surface Fluorination of Reactive Battery Anode Materials for Enhanced Stability

DOE PAGES

Zhao, Jie; Liao, Lei; Shi, Feifei; ...

2017-07-26

Significant increases in the energy density of batteries must be achieved by exploring new materials and cell configurations. Lithium metal and lithiated silicon are two promising high-capacity anode materials. Unfortunately, both of these anodes require a reliable passivating layer to survive the serious environmental corrosion during handling and cycling. Here we developed a surface fluorination process to form a homogeneous and dense LiF coating on reactive anode materials, with in situ generated fluorine gas, by using a fluoropolymer, CYTOP, as the precursor. The process is effectively a “reaction in the beaker”, avoiding direct handling of highly toxic fluorine gas. Formore » lithium metal, this LiF coating serves as a chemically stable and mechanically strong interphase, which minimizes the corrosion reaction with carbonate electrolytes and suppresses dendrite formation, enabling dendrite-free and stable cycling over 300 cycles with current densities up to 5 mA/cm 2. Lithiated silicon can serve as either a pre-lithiation additive for existing lithium-ion batteries or a replacement for lithium metal in Li–O 2 and Li–S batteries. However, lithiated silicon reacts vigorously with the standard slurry solvent N-methyl-2-pyrrolidinone (NMP), indicating it is not compatible with the real battery fabrication process. With the protection of crystalline and dense LiF coating, Li xSi can be processed in anhydrous NMP with a high capacity of 2504 mAh/g. With low solubility of LiF in water, this protection layer also allows Li xSi to be stable in humid air (~40% relative humidity). Furthermore, this facile surface fluorination process brings huge benefit to both the existing lithium-ion batteries and next-generation lithium metal batteries.« less

Nanoparticle treated stainless steel filters for metal vapor sequestration

DOE PAGES

Murph, Simona E. Hunyadi; Larsen, George K.; Korinko, Paul; ...

2016-12-07

The ability to sequester vapor phase radioactive compounds during industrial processes reduces the exposure of workers and the environment to dangerous radioactive materials. Nanomaterials have a lot of potential in this area because they typically demonstrate size- and shape-dependent properties with higher reactivity than bulk. This is due to the increased surface area-to-volume ratio and quantum size effects. In this report, we developed a gold nanomaterial-treated stainless steel filter, namely wools and coupons, that can be efficiently used for zinc vapor sequestration. Without nanoparticle modification, stainless steel coupons do not react or alloy with Zn. Gold nanomaterials were grown ontomore » various stainless steel filters using solution chemistry that is amenable to scaling up. Materials were characterized by electron microscopy, inductively coupled plasma mass spectroscopy and dynamic light scattering before and after exposure to zinc vapors. X-ray diffraction, high-resolution transmission electron microscopy, energy dispersive x-ray spectroscopy mapping and ultraviolet-visible spectroscopy confirm the formation of gold-zinc alloys after Zn vapor exposure. Furthermore, the effect of surface topography on nanoparticle morphology, size and loading density were also investigated, and stainless steel surface defects were found to have an impact on the Au NP growth and subsequently Zn sequestration.« less

Nanoparticle treated stainless steel filters for metal vapor sequestration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Murph, Simona E. Hunyadi; Larsen, George K.; Korinko, Paul

The ability to sequester vapor phase radioactive compounds during industrial processes reduces the exposure of workers and the environment to dangerous radioactive materials. Nanomaterials have a lot of potential in this area because they typically demonstrate size- and shape-dependent properties with higher reactivity than bulk. This is due to the increased surface area-to-volume ratio and quantum size effects. In this report, we developed a gold nanomaterial-treated stainless steel filter, namely wools and coupons, that can be efficiently used for zinc vapor sequestration. Without nanoparticle modification, stainless steel coupons do not react or alloy with Zn. Gold nanomaterials were grown ontomore » various stainless steel filters using solution chemistry that is amenable to scaling up. Materials were characterized by electron microscopy, inductively coupled plasma mass spectroscopy and dynamic light scattering before and after exposure to zinc vapors. X-ray diffraction, high-resolution transmission electron microscopy, energy dispersive x-ray spectroscopy mapping and ultraviolet-visible spectroscopy confirm the formation of gold-zinc alloys after Zn vapor exposure. Furthermore, the effect of surface topography on nanoparticle morphology, size and loading density were also investigated, and stainless steel surface defects were found to have an impact on the Au NP growth and subsequently Zn sequestration.« less

Keratin, luminal epithelial antigen and carcinoembryonic antigen in human urinary bladder carcinomas. An immunohistochemical study.

PubMed

Nathrath, W B; Arnholdt, H; Wilson, P D

1982-01-01

14 urinary bladder carcinomas of all main types were investigated with antisera to "broad spectrum keratin" (aK), "luminal epithelial antigen" (aLEA) and carcinoembryonic antigen (aCEA), using an indirect immunoperoxidase method on formalin fixed paraffin embedded sections. Keratin and LEA were both present in normal transitional epithelium, papilloma and carcinoma in situ whereas CEA was absent. Transitional cell carcinomas reacted with both aK and aLEA whereas CEA was seen only in a few foci. In squamous metaplasia and squamous carcinoma reaction with aK was particularly strong, while LEA was almost lacking and CEA was present in necrotic centres. In adenocarcinomas aK and aLEA reacted equally while aCEA reacted only on the surface.

Three-dimensional computer simulation of non-reacting jet-gas flow mixing in an MHD second stage combustor

NASA Astrophysics Data System (ADS)

Chang, S. L.; Lottes, S. A.; Berry, G. F.

Argonne National Laboratory is investigating the non-reacting jet-gas mixing patterns in a magnetohydrodynamics (MHD) second stage combustor by using a three-dimensional single-phase hydrodynamics computer program. The computer simulation is intended to enhance the understanding of flow and mixing patterns in the combustor, which in turn may improve downstream MHD channel performance. The code is used to examine the three-dimensional effects of the side walls and the distributed jet flows on the non-reacting jet-gas mixing patterns. The code solves the conservation equations of mass, momentum, and energy, and a transport equation of a turbulence parameter and allows permeable surfaces to be specified for any computational cell.

DFT study on dry reforming of methane over Ni2Fe overlayer of Ni(1 1 1) surface

NASA Astrophysics Data System (ADS)

Xu, Li-li; Wen, Hong; Jin, Xin; Bing, Qi-ming; Liu, Jing-yao

2018-06-01

We reported the complete catalytic cycle of dry reforming of methane (DRM) on Ni2Fe overlayer of Ni(1 1 1) surface by periodic density functional theory (DFT) calculations. The pathways for dehydrogenation of CH4 and CO2 activation were located. Our results demonstrate that compared with pure Ni(1 1 1) surface, the introduction Fe into Ni increases the energy barrier of CH dissociation to carbon and hydrogen atoms, thereby suppressing coke deposition on the surface, while it promotes the H-induced CO2 activation pathway to form OH radical, and thus not only the surface oxygen but also OH are responsible for the oxidation of CHx (x = 0,1) on the Ni2Fe overlayer. The most favorable pathway of CH/C oxidation is found to be CH∗ + OH∗ → CHOH∗ → CHO∗ + H∗ → CO∗ + 2H∗, with the rate-limiting energy barrier of 1.12 eV. Furthermore, since Fe is oxidized partially to FeO leading to a partial dealloying under DRM conditions, we also studied the surface-carbon removal and the activity for the reforming of methane on the FeO ribbon supported Ni(1 1 1) (FeO/Ni) interface by DFT+U method. The surface C reacts with lattice oxygen of FeO to produce CO via a Mars-van Krevelen (MvK) mechanism, with a very lower energy barrier of 0.16 eV. The present results show that the introduction of Fe into Ni has a positive effect on the activity toward DRM and has an improved coke resistance.

Monte Carlo Computational Modeling of Atomic Oxygen Interactions

NASA Technical Reports Server (NTRS)

Banks, Bruce A.; Stueber, Thomas J.; Miller, Sharon K.; De Groh, Kim K.

2017-01-01

Computational modeling of the erosion of polymers caused by atomic oxygen in low Earth orbit (LEO) is useful for determining areas of concern for spacecraft environment durability. Successful modeling requires that the characteristics of the environment such as atomic oxygen energy distribution, flux, and angular distribution be properly represented in the model. Thus whether the atomic oxygen is arriving normal to or inclined to a surface and whether it arrives in a consistent direction or is sweeping across the surface such as in the case of polymeric solar array blankets is important to determine durability. When atomic oxygen impacts a polymer surface it can react removing a certain volume per incident atom (called the erosion yield), recombine, or be ejected as an active oxygen atom to potentially either react with other polymer atoms or exit into space. Scattered atoms can also have a lower energy as a result of partial or total thermal accommodation. Many solutions to polymer durability in LEO involve protective thin films of metal oxides such as SiO2 to prevent atomic oxygen erosion. Such protective films also have their own interaction characteristics. A Monte Carlo computational model has been developed which takes into account the various types of atomic oxygen arrival and how it reacts with a representative polymer (polyimide Kapton H) and how it reacts at defect sites in an oxide protective coating, such as SiO2 on that polymer. Although this model was initially intended to determine atomic oxygen erosion behavior at defect sites for the International Space Station solar arrays, it has been used to predict atomic oxygen erosion or oxidation behavior on many other spacecraft components including erosion of polymeric joints, durability of solar array blanket box covers, and scattering of atomic oxygen into telescopes and microwave cavities where oxidation of critical component surfaces can take place. The computational model is a two dimensional model which has the capability to tune the interactions of how the atomic oxygen reacts, scatters, or recombines on polymer or nonreactive surfaces. In addition to the specification of atomic oxygen arrival details, a total of 15 atomic oxygen interaction parameters have been identified as necessary to properly simulate observed interactions and resulting polymer erosion that have been observed in LEO. The tuning of the Monte Carlo model has been accomplished by adjusting interaction parameters so the erosion patterns produced by the model match those from several actual LEO space experiments. Surface texturing in LEO can also be predicted by the model. Such comparison of space tests with ground laboratory experiments have enabled confidence in ground laboratory lifetime prediction of protected polymers. Results of Monte Carlo tuning, examples of surface texturing and undercutting erosion prediction, and several examples of how the model can be used to predict other LEO and Mars orbital space results are presented.

Block copolymer adhesion promoters via ring-opening metathesis polymerization

DOEpatents

Kent, M.S.; Saunders, R.

1997-02-18

Coupling agents are disclosed based on functionalized block copolymers for bonding thermoset polymers to solid materials. These are polymers which possess at least two types of functional groups, one which is able to attach to and react with solid surfaces, and another which can react with a thermoset resin, which are incorporated as pendant groups in monomers distributed in blocks (typically two) along the backbone of the chain. The block copolymers in this invention are synthesized by living ring-opening metathesis polymerization. 18 figs.

Block copolymer adhesion promoters via ring-opening metathesis polymerization

DOEpatents

Kent, Michael S.; Saunders, Randall

1997-01-01

Coupling agents based on functionalized block copolymers for bonding thermoset polymers to solid materials. These are polymers which possess at least two types of functional groups, one which is able to attach to and react with solid surfaces, and another which can react with a thermoset resin, which are incorporated as pendant groups in monomers distributed in blocks (typically two) along the backbone of the chain. The block copolymers in this invention are synthesized by living ring-opening metathesis polymerization.

46 CFR 151.25-1 - Cargo tank.

Code of Federal Regulations, 2014 CFR

2014-10-01

... not react with the cargo. (c) Ventilated (forced). Vapor space above the liquid surface in the tank is... (natural). Vapor space above the liquid surface in the tank is continuously swept with atmospheric air... LIQUID HAZARDOUS MATERIAL CARGOES Environmental Control § 151.25-1 Cargo tank. When carrying certain...

46 CFR 151.25-1 - Cargo tank.

Code of Federal Regulations, 2012 CFR

2012-10-01

... not react with the cargo. (c) Ventilated (forced). Vapor space above the liquid surface in the tank is... (natural). Vapor space above the liquid surface in the tank is continuously swept with atmospheric air... LIQUID HAZARDOUS MATERIAL CARGOES Environmental Control § 151.25-1 Cargo tank. When carrying certain...

46 CFR 151.25-1 - Cargo tank.

Code of Federal Regulations, 2011 CFR

2011-10-01

... not react with the cargo. (c) Ventilated (forced). Vapor space above the liquid surface in the tank is... (natural). Vapor space above the liquid surface in the tank is continuously swept with atmospheric air... LIQUID HAZARDOUS MATERIAL CARGOES Environmental Control § 151.25-1 Cargo tank. When carrying certain...

46 CFR 151.25-1 - Cargo tank.

Code of Federal Regulations, 2013 CFR

2013-10-01

... not react with the cargo. (c) Ventilated (forced). Vapor space above the liquid surface in the tank is... (natural). Vapor space above the liquid surface in the tank is continuously swept with atmospheric air... LIQUID HAZARDOUS MATERIAL CARGOES Environmental Control § 151.25-1 Cargo tank. When carrying certain...

46 CFR 151.25-1 - Cargo tank.

Code of Federal Regulations, 2010 CFR

2010-10-01

... not react with the cargo. (c) Ventilated (forced). Vapor space above the liquid surface in the tank is... (natural). Vapor space above the liquid surface in the tank is continuously swept with atmospheric air... LIQUID HAZARDOUS MATERIAL CARGOES Environmental Control § 151.25-1 Cargo tank. When carrying certain...

METHOD OF FORMING A PROTECTIVE COATING ON FERROUS METAL SURFACES

DOEpatents

Schweitzer, D.G.; Weeks, J.R.; Kammerer, O.F.; Gurinsky, D.H.

1960-02-23

A method is described of protecting ferrous metal surfaces from corrosive attack by liquid metals, such as liquid bismuth or lead-bismuth alloys. The nitrogen content of the ferrous metal surface is first reduced by reacting the metal surface with a metal which forms a stable nitride. Thereafter, the surface is contacted with liquid metal containing at least 2 ppm zirconium at a temperature in the range of 550 to 1100 deg C to form an adherent zirconium carbide layer on the ferrous surface.

The combustion program at CTR

NASA Technical Reports Server (NTRS)

Poinsot, Thierry J.

1993-01-01

Understanding and modeling of turbulent combustion are key problems in the computation of numerous practical systems. Because of the lack of analytical theories in this field and of the difficulty of performing precise experiments, direct numerical simulation (DNS) appears to be one of the most attractive tools to use in addressing this problem. The general objective of DNS of reacting flows is to improve our knowledge of turbulent combustion but also to use this information for turbulent combustion models. For the foreseeable future, numerical simulation of the full three-dimensional governing partial differential equations with variable density and transport properties as well as complex chemistry will remain intractable; thus, various levels of simplification will remain necessary. On one hand, the requirement to simplify is not necessarily a handicap: numerical simulations allow the researcher a degree of control in isolating specific physical phenomena that is inaccessible in experiments. CTR has pursued an intensive research program in the field of DNS for turbulent reacting flows since 1987. DNS of reacting flows is quite different from DNS of non-reacting flows: without reaction, the equations to solve are clearly the five conservation equations of the Navier Stokes system for compressible situations (four for incompressible cases), and the limitation of the approach is the Reynolds number (or in other words the number of points in the computation). For reacting flows, the choice of the equations, the species (each species will require one additional conservation equation), the chemical scheme, and the configuration itself is more complex.

Chemical characterization of diesel and hydrotreated vegetable oil (HVO) soot after reactive gas probing using diffuse reflectance FTIR spectroscopy (DRIFTS).

PubMed

Tapia, A; Salgado, M S; Martín, M P; Rodríguez-Fernández, J; Rossi, M J; Cabañas, B

2017-03-01

A chemical characterization of diesel and hydrotreated vegetable oil (HVO) soot has been developed using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) before and after the reaction with different probe gases. Samples were generated under combustion conditions corresponding to an urban operation mode of a diesel engine and were reacted with probe gas-phase molecules in a Knudsen flow reactor. Specifically, NH 2 OH, O 3 and NO 2 were used as reactants (probes) and selected according to their reactivities towards specific functional groups on the sample surface. Samples of previously ground soot were diluted with KBr and were introduced in a DRIFTS accessory. A comparison between unreacted and reacted soot samples was made in order to establish chemical changes on the soot surface upon reaction. It was concluded that the interface of diesel and HVO soot before reaction mainly consists polycyclic aromatic hydrocarbons, nitro and carbonyl compounds, as well as ether functionalities. The main difference between both soot samples was observed in the band of the C=O groups that in diesel soot was observed at 1719 cm -1 but not in HVO soot. After reaction with probe gases, it was found that nitro compounds remain on the soot surface, that the degree of unsaturation decreases for reacted samples, and that new spectral bands such as hydroxyl groups are observed.

The study of PDF turbulence models in combustion

NASA Technical Reports Server (NTRS)

Hsu, Andrew T.

1991-01-01

The accurate prediction of turbulent combustion is still beyond reach for today's computation techniques. It is the consensus of the combustion profession that the predictions of chemically reacting flow were poor if conventional turbulence models were used. The main difficulty lies in the fact that the reaction rate is highly nonlinear, and the use of averaged temperature, pressure, and density produces excessively large errors. The probability density function (PDF) method is the only alternative at the present time that uses local instant values of the temperature, density, etc. in predicting chemical reaction rate, and thus it is the only viable approach for turbulent combustion calculations.

GAS COOLED NUCLEAR REACTORS

DOEpatents

Long, E.; Rodwell, W.

1958-06-10

A gas-cooled nuclear reactor consisting of a graphite reacting core and reflector structure supported in a containing vessel is described. A gas sealing means is included for sealing between the walls of the graphite structure and containing vessel to prevent the gas coolant by-passing the reacting core. The reacting core is a multi-sided right prismatic structure having a pair of parallel slots around its periphery. The containing vessel is cylindrical and has a rib on its internal surface which supports two continuous ring shaped flexible web members with their radially innermost ends in sealing engagement within the radially outermost portion of the slots. The core structure is supported on ball bearings. This design permits thermal expansion of the core stracture and vessel while maintainirg a peripheral seal between the tvo elements.

Computation of H2/air reacting flowfields in drag-reduction external combustion

NASA Technical Reports Server (NTRS)

Lai, H. T.

1992-01-01

Numerical simulation and analysis of the solution are presented for a laminar reacting flowfield of air and hydrogen in the case of external combustion employed to reduce base drag in hypersonic vehicles operating at transonic speeds. The flowfield consists of a transonic air stream at a Mach number of 1.26 and a sonic transverse hydrogen injection along a row of 26 orifices. Self-sustained combustion is computed over an expansion ramp downstream of the injection and a flameholder, using the recently developed RPLUS code. Measured data is available only for surface pressure distributions and is used for validation of the code in practical 3D reacting flowfields. Pressure comparison shows generally good agreements, and the main effects of combustion are also qualitatively consistent with experiment.

Analysis of Fc(epsilon)RI-mediated mast cell stimulation by surface-carried antigens.

PubMed Central

Schweitzer-Stenner, R; Tamir, I; Pecht, I

1997-01-01

Clustering of the type I receptor for IgE (Fc[epsilon]RI) on mast cells initiates a cascade of biochemical processes that result in secretion of inflammatory mediators. To determine the Fc(epsilon)RI proximity, cluster size, and mobility requirements for initiating the Fc(epsilon)RI cascade, a novel experimental protocol has been developed in which mast cells are reacted with glass surfaces carrying different densities of both antigen and bound IgE, and the cell's secretory response to these stimuli is measured. The results have been analyzed in terms of a model based on the following assumptions: 1) the glass surface antigen distribution and consequently that of the bound IgE are random; 2) Fc(epsilon)RI binding to these surface-bound IgEs immobilizes the former and saturates the latter; 3) the cell surface is formally divided into small elements, which function as a secretory stimulus unit when occupied by two or more immobilized IgE-Fc(epsilon)RI complexes; 4) alternatively, similar stimulatory units can be formed by binding of surface-carried IgE dimers to two Fc(epsilon)RI. This model yielded a satisfactory and self-consistent fitting of all of the different experimental data sets. Hence the present results establish the essential role of Fc(epsilon)RI immobilization for initiating its signaling cascade. Moreover, it provides independent support for the notion that as few as two Fc(epsilon)RIs immobilized at van der Waals contact constitute an "elementary stimulatory unit" leading to mast cell (RBL-2H3 line) secretory response. PMID:9168023

Investigation of Atomization and Combustion Performance of Renewable Biofuels and the Effects of Ethanol Blending in Biodiesel

NASA Astrophysics Data System (ADS)

Silver, Adam Gregory

This thesis presents results from an experimental investigation of the macroscopic and microscopic atomization and combustion behavior of B99 biodiesel, ethanol, B99-ethanol blends, methanol, and an F-76-Algae biodiesel blend. In addition, conventional F-76 and Diesel #2 sprays were characterized as a base case to compare with. The physical properties and chemical composition of each fuel were measured in order to characterize and predict atomization performance. A variety of B99-ethanol fuel blends were used which demonstrate a tradeoff between lower density, surface tension, and viscosity with a decrease in the air to liquid ratio. A plain jet air-blast atomizer was used for both non-reacting and reacting tests. The flow rates for the alternative fuels were set by matching the power input provided by the baseline fossil fuels in order to simulate use as a drop in replacement. For this study, phase Doppler interferometry is employed to gain information on drop size, SMD, velocity, and volume flux distribution across the spray plume. A high speed camera is used to gather high speed cinematography of the sprays for observing breakup characteristics and providing additional insight. Reacting flow tests captured NOx, CO, and UHC emissions along with high speed footage used to predict soot levels based on flame luminosity. The results illustrate how the fuel type impacts the atomization and spray characteristics. The air-blast atomizer resulted in similar atomization performance among the DF2, F-76, and the F-76/Algae blend. While methanol and ethanol are not suitable candidates for this air-blast configuration and B99 produces significantly larger droplets, the addition of ethanol decreased drop sizes for all B99-ethanol blends by approximately 5 microns. In regards to reacting conditions, increased ethanol blending to B99 consistently lowered NOx emissions while decreasing combustion efficiency. Overall, lower NOx and CO emissions were achieved with the fuel blends than for conventional diesels, while the neat biofuels emitted overall less NOx per CO than the baseline fuels. This research clearly demonstrated that blends of two renewable fuels (B99 and ethanol improved (1) atomization and (2) emissions performance for the burner studied when compared to the baseline fossil fuels DF2 and F-76.

Measurements of non-reacting and reacting flow fields of a liquid swirl flame burner

NASA Astrophysics Data System (ADS)

Chong, Cheng Tung; Hochgreb, Simone

2015-03-01

The understanding of the liquid fuel spray and flow field characteristics inside a combustor is crucial for designing a fuel efficient and low emission device. Characterisation of the flow field of a model gas turbine liquid swirl burner is performed by using a 2-D particle imaging velocimetry(PIV) system. The flow field pattern of an axial flow burner with a fixed swirl intensity is compared under confined and unconfined conditions, i.e., with and without the combustor wall. The effect of temperature on the main swirling air flow is investigated under open and non-reacting conditions. The result shows that axial and radial velocities increase as a result of decreased flow density and increased flow volume. The flow field of the main swirling flow with liquid fuel spray injection is compared to non-spray swirling flow. Introduction of liquid fuel spray changes the swirl air flow field at the burner outlet, where the radial velocity components increase for both open and confined environment. Under reacting condition, the enclosure generates a corner recirculation zone that intensifies the strength of radial velocity. The reverse flow and corner recirculation zone assists in stabilizing the flame by preheating the reactants. The flow field data can be used as validation target for swirl combustion modelling.

Fermi Level Unpinning of GaSb (100) using Plasma Enhanced Atomic Layer Deposition of Al2O3

DTIC Science & Technology

2010-01-01

of high-/GaSb semiconductor interface. GaSb has a highly reactive surface and on exposure to air it will form a native oxide layer composed of Ga2O3 ...and Sb2O3 2GaSb+3O2→ Ga2O3 +Sb2O3. The Sb2O3 can fur- ther react with the GaSb surface forming elemental Sb and Ga2O3 Sb2O3+2GaSb→ Ga2O3 +4Sb.5,6...rights_and_permissions mentioned before, Sb2O3 reacts with GaSb forming Ga2O3 and elemental Sb.6 The kinetics of this reaction is enhanced at higher temperatures200 °C.14

Apparatus for making environmentally stable reactive alloy powders

DOEpatents

Anderson, I.E.; Lograsso, B.K.; Terpstra, R.L.

1996-12-31

Apparatus and method are disclosed for making powder from a metallic melt by atomizing the melt to form droplets and reacting the droplets downstream of the atomizing location with a reactive gas. The droplets are reacted with the gas at a temperature where a solidified exterior surface is formed thereon and where a protective refractory barrier layer (reaction layer) is formed whose penetration into the droplets is limited by the presence of the solidified surface so as to avoid selective reduction of key reactive alloyants needed to achieve desired powder end use properties. The barrier layer protects the reactive powder particles from environmental constituents such as air and water in the liquid or vapor form during subsequent fabrication of the powder to end-use shapes and during use in the intended service environment. 7 figs.

Assembly of Oriented Virus Arrays by Chemo-Selective Ligation Methods and Nanolithography Techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Camarero, J A; Cheung, C L; Lin, T

2002-12-02

The present work describes our ongoing efforts towards the creation of nano-scaled ordered arrays of protein/virus covalently attached to site-specific chemical linkers patterned by different nanolithograpy techniques. We will present a new and efficient solid-phase approach for the synthesis of chemically modified long alkyl-thiols. These compounds can be used to introduce chemoselective reacting groups onto gold and silicon-based surfaces. Furthermore, these modified thiols have been used to create nanometric patterns by using different nanolithography techniques. We will show that these patterns can react chemoselectively with proteins and/or virus which have been chemically or recombinantly modified to contain complementary chemical groupsmore » at specific positions thus resulting in the oriented attachment of the protein or virus to the surface.« less

Linking molecular level chemistry to macroscopic combustion behavior for nano-energetic materials with halogen containing oxides.

PubMed

Farley, Cory W; Pantoya, Michelle L; Losada, Martin; Chaudhuri, Santanu

2013-08-21

Coupling molecular scale reaction kinetics with macroscopic combustion behavior is critical to understanding the influences of intermediate chemistry on energy propagation, yet bridging this multi-scale gap is challenging. This study integrates ab initio quantum chemical calculations and condensed phase density functional theory to elucidate factors contributing to experimentally measured high flame speeds (i.e., >900 m∕s) associated with halogen based energetic composites, such as aluminum (Al) and iodine pentoxide (I2O5). Experiments show a direct correlation between apparent activation energy and flame speed suggesting that flame speed is directly influenced by chemical kinetics. Toward this end, the first principle simulations resolve key exothermic surface and intermediate chemistries contributing toward the kinetics that promote high flame speeds. Linking molecular level exothermicity to macroscopic experimental investigations provides insight into the unique role of the alumina oxide shell passivating aluminum particles. In the case of Al reacting with I2O5, the alumina shell promotes exothermic surface chemistries that reduce activation energy and increase flame speed. This finding is in contrast to Al reaction with metal oxides that show the alumina shell does not participate exothermically in the reaction.

Very Large Eddy Simulations of a Jet-A Spray Reacting Flow in a Single Element LDI Injector With and Without Invoking an Eulerian Scalar DWFDF Method

NASA Technical Reports Server (NTRS)

Shih, Tsan-Hsing; Liu, Nan-Suey

2013-01-01

This paper presents the very large eddy simulations (VLES) of a Jet-A spray reacting flow in a single element lean direct injection (LDI) injector by using the National Combustion Code (NCC) with and without invoking the Eulerian scalar DWFDF method, in which DWFDF is defined as the density weighted time filtered fine grained probability density function. The flow field is calculated by using the time filtered compressible Navier-Stokes equations (TFNS) with nonlinear subscale turbulence models, and when the Eulerian scalar DWFDF method is invoked, the energy and species mass fractions are calculated by solving the equation of DWFDF. A nonlinear subscale model for closing the convection term of the Eulerian scalar DWFDF equation is used and will be briefly described in this paper. Detailed comparisons between the results and available experimental data are carried out. Some positive findings of invoking the Eulerian scalar DWFDF method in both improving the simulation quality and maintaining economic computing cost are observed.

Method for providing adhesion to a metal surface

DOEpatents

Harrah, L.A.; Allred, R.E.; Wilson, K.V. Jr.

1992-02-18

A process for treating metal surfaces to obtain improved susceptibility to bonding with adhesive compositions is disclosed. A metal surface is oxidized with a halogen to form a monolayer of halide ions on the surface. The halide ions are then exchanged with azide ions to form an azide monolayer on the metal surface. Upon contact of the treated surface with an adhesive composition, the azide layer may be thermally or photochemically decomposed to form active nitrene species, which react to bond the adhesive composition to the metal surface.

Method for providing adhesion to a metal surface

DOEpatents

Harrah, Larry A.; Allred, Ronald E.; Wilson, Jr., Kennard V.

1992-01-01

A process for treating metal surfaces to obtain improved susceptibility to bonding with adhesive compositions is disclosed. A metal surface is oxidized with a halogen to form a monolayer of halide ions on the surface. The halide ions are then exchanged with azide ions to form an azide monolayer on the metal surface. Upon contact of the treated surface with an adhesive composition, the azide layer may be thermally or photochemically decomposed to form active nitrene species, which react to bond the adhesive composition to the metal surface.

Evaluation of Recombinant Plasmodium knowlesi Merozoite Surface Protein-133 for Detection of Human Malaria

PubMed Central

Cheong, Fei Wen; Lau, Yee Ling; Fong, Mun Yik; Mahmud, Rohela

2013-01-01

Plasmodium knowlesi is now known as the fifth Plasmodium species that can cause human malaria. The Plasmodium merozoite surface protein (MSP) has been reported to be potential target for vaccination and diagnosis of malaria. MSP-133 has been shown to be immunogenic and its T cell epitopes could mediate cellular immune protection. However, limited studies have focused on P. knowlesi MSP-133. In this study, an approximately 28-kDa recombinant P. knowlesi MSP-133 (pkMSP-133) was expressed by using an Escherichia coli system. The purified pkMSP-133 reacted with serum samples of patients infected with P. knowlesi (31 of 31, 100%) and non-P. knowlesi malaria (27 of 28, 96.43%) by Western blotting. The pkMSP-133 also reacted with P. knowlesi (25 of 31, 80.65%) and non-P. knowlesi malaria sera (20 of 28, 71.43%) in an enzyme-linked immunosorbent assay (ELISA). Most of the non-malarial infection (49 of 52 in by Western blotting and 46 of 52 in the ELISA) and healthy donor serum samples (65 of 65 by Western blotting and ELISA) did not react with recombinant pkMSP-133. PMID:23509118

Arsenic transformation and adsorption by iron hydroxide/manganese dioxide doped straw activated carbon

NASA Astrophysics Data System (ADS)

Xiong, Ying; Tong, Qiang; Shan, Weijun; Xing, Zhiqiang; Wang, Yuejiao; Wen, Siqi; Lou, Zhenning

2017-09-01

Iron hydroxide/manganese dioxide doped straw activated carbon was synthesized for As(III) adsorption. The Fe-Mn-SAc adsorbent has two advantages, on the one hand, the straw active carbon has a large surface area (1360.99 m2 g-1) for FeOOH and MnO2 deposition, on the other hand, the manganese dioxide has oxidative property as a redox potential of (MnO2 + H+)/Mn2+, which could convert As(III) into As(V). Combined with the arsenic species after reacting with Fe-Mn-SAc, the As(III) transformation and adsorption mechanism was discussed. H2AsO4-oxidized from As(III) reacts with the Fe-Mn-SAc by electrostatic interaction, and unoxidized As(III) as H3AsO3 reacts with SAc and/or iron oxide surface by chelation effect. The adsorption was well-described by Langmuir isotherms model, and the adsorption capacity of As(III) was 75.82 mg g-1 at pH 3. Therefore, considering the straw as waste biomass material, the biosorbent (Fe-Mn-SAc) is promising to be exploited for applications in the treatment of industrial wastewaters containing a certain ratio of arsenic and germanium.

Reactant conversion in homogeneous turbulence: Mathematical modeling, computational validations and practical applications

NASA Technical Reports Server (NTRS)

Madnia, C. K.; Frankel, S. H.; Givi, P.

1992-01-01

Closed form analytical expressions are obtained for predicting the limited rate of reactant conversion in a binary reaction of the type F + rO yields (1 + r) Product in unpremixed homogeneous turbulence. These relations are obtained by means of a single point Probability Density Function (PDF) method based on the Amplitude Mapping Closure. It is demonstrated that with this model, the maximum rate of the reactants' decay can be conveniently expressed in terms of definite integrals of the Parabolic Cylinder Functions. For the cases with complete initial segregation, it is shown that the results agree very closely with those predicted by employing a Beta density of the first kind for an appropriately defined Shvab-Zeldovich scalar variable. With this assumption, the final results can also be expressed in terms of closed form analytical expressions which are based on the Incomplete Beta Functions. With both models, the dependence of the results on the stoichiometric coefficient and the equivalence ratio can be expressed in an explicit manner. For a stoichiometric mixture, the analytical results simplify significantly. In the mapping closure, these results are expressed in terms of simple trigonometric functions. For the Beta density model, they are in the form of Gamma Functions. In all the cases considered, the results are shown to agree well with data generated by Direct Numerical Simulations (DNS). Due to the simplicity of these expressions and because of nice mathematical features of the Parabolic Cylinder and the Incomplete Beta Functions, these models are recommended for estimating the limiting rate of reactant conversion in homogeneous reacting flows. These results also provide useful insights in assessing the extent of validity of turbulence closures in the modeling of unpremixed reacting flows. Some discussions are provided on the extension of the model for treating more complicated reacting systems including realistic kinetics schemes and multi-scalar mixing with finite rate chemical reactions in more complex configurations.

Non-equilibrium radiation from viscous chemically reacting two-phase exhaust plumes

NASA Technical Reports Server (NTRS)

Penny, M. M.; Smith, S. D.; Mikatarian, R. R.; Ring, L. R.; Anderson, P. G.

1976-01-01

A knowledge of the structure of the rocket exhaust plumes is necessary to solve problems involving plume signatures, base heating, plume/surface interactions, etc. An algorithm is presented which treats the viscous flow of multiphase chemically reacting fluids in a two-dimensional or axisymmetric supersonic flow field. The gas-particle flow solution is fully coupled with the chemical kinetics calculated using an implicit scheme to calculate chemical production rates. Viscous effects include chemical species diffusion with the viscosity coefficient calculated using a two-equation turbulent kinetic energy model.

Method and apparatus for producing high purity silicon

DOEpatents

Olson, Jerry M.

1984-01-01

A method for producing high purity silicon includes forming a copper silie alloy and positioning the alloy within an enclosure. A filament member is also placed within the enclosure opposite the alloy. The enclosure is then filled with a chemical vapor transport gas adapted for transporting silicon. Finally, both the filament member and the alloy are heated to temperatures sufficient to cause the gas to react with silicon at the alloy surface and deposit the reacted silicon on the filament member. In addition, an apparatus for carrying out this method is also disclosed.

Method and apparatus for producing high purity silicon

DOEpatents

Olson, J.M.

1983-05-27

A method for producing high purity silicon includes forming a copper silicide alloy and positioning the alloy within an enclosure. A filament member is also placed within the enclosure opposite the alloy. The enclosure is then filled with a chemical vapor transport gas adapted for transporting silicon. Finally, both the filament member and the alloy are heated to temperatures sufficient to cause the gas to react with silicon at the alloy surface and deposit the reacted silicon on the filament member. In addition, an apparatus for carrying out this method is also disclosed.

Ignition and structure of a laminar diffusion flame in the field of a vortex

NASA Technical Reports Server (NTRS)

Macaraeg, Michele G.; Jackson, T. L.; Hussaini, M. Y.

1991-01-01

The distortion of flames in flows with vortical motion is examined via asymptotic analysis and numerical simulation. The model consists of a constant density, one step, irreversible Arrhenius reaction between initially unmixed species occupying adjacent half-planes which are then allowed to mix and react in the presence of a vortex. The evolution in time of the temperature and mass fraction fields is followed. Emphasis is placed on the ignition time and location as a function of vortex Reynolds number and initial temperature differences of the reacting species. The study brings out the influence of the vortex on the chemical reaction. In all phases, good agreement is observed between asymptotic analysis and the full numerical solution of the model equations.

A comprehensive model to determine the effects of temperature and species fluctuations on reaction rates in turbulent reacting flows

NASA Technical Reports Server (NTRS)

Foy, E.; Ronan, G.; Chinitz, W.

1982-01-01

A principal element to be derived from modeling turbulent reacting flows is an expression for the reaction rates of the various species involved in any particular combustion process under consideration. A temperature-derived most-likely probability density function (pdf) was used to describe the effects of temperature fluctuations on the Arrhenius reaction rate constant. A most-likely bivariate pdf described the effects of temperature and species concentrations fluctuations on the reaction rate. A criterion is developed for the use of an "appropriate" temperature pdf. The formulation of models to calculate the mean turbulent Arrhenius reaction rate constant and the mean turbulent reaction rate is considered and the results of calculations using these models are presented.

Density functional theory simulation of titanium migration and reaction with oxygen in the early stages of oxidation of equiatomic NiTi alloy.

PubMed

Nolan, Michael; Tofail, Syed A M

2010-05-01

The biocompatibility of NiTi shape memory alloys (SMA) has made possible applications in self-expandable cardio-vascular stents, stone extraction baskets, catheter guide wires and other invasive and minimally invasive biomedical devices. The NiTi intermetallic alloy spontaneously forms a thin passive layer of TiO(2), which provides its biocompatibility. The oxide layer is thought to form as the Ti in the alloy surface reacts with oxygen, resulting in a depletion of Ti in the subsurface region - experimental evidence indicates formation of a Ni-rich layer below the oxide film. In this paper, we study the initial stages of oxide growth on the (110) surface of the NiTi alloy to understand the formation of alloy/oxide interface. We initially adsorb atomic and molecular oxygen on the (110) surface and then successively add O(2) molecules, up to 2 monolayer of O(2). Oxygen adsorption always results in a large energy gain. With atomic oxygen, Ti is pulled out of the surface layer leaving behind a Ni-rich subsurface region. Molecular O(2), on the other hand adsorbs dissociatively and pulls a Ti atom farther out of the surface layer. The addition of further O(2) up to 1 monolayer is also dissociative and results in complete removal of Ti from the initial surface layer. When further O(2) is added up to 2 monolayer, Ti is pulled even further out of the surface and a single thin layer of composition O-Ti-O is formed. The electronic structure shows that the metallic character of the alloy is unaffected by interaction with oxygen and formation of the oxide layer, consistent with the oxide layer being a passivant. Copyright 2010 Elsevier Ltd. All rights reserved.

New insights into the adsorption of 3-(trimethoxysilyl)propylmethacrylate on hydroxylated ZnO nanopowders.

PubMed

Bressy, Christine; Ngo, Van Giang; Ziarelli, Fabio; Margaillan, André

2012-02-14

Functionalization of zinc oxide (ZnO) nano-objects by silane grafting is an attractive method to provide nanostructured materials with a variety of surface properties. Active hydroxyl groups on the oxide surface are one of the causes governing the interfacial bond strength in nanohybrid particles. Here, "as-prepared" and commercially available zinc oxide nanopowders with a wide range of surface hydroxyl density were functionalized by a well-known polymerizable silane coupling agent, i.e., 3-(trimethoxysilyl)propylmethacrylate (MPS). Fourier transform infrared (FTIR) and solid-state (13)C and (29)Si nuclear magnetic resonance (NMR) spectroscopic investigations demonstrated that the silane coupling agent was fully hydrolyzed and linked to the hydroxyl groups already present on the particle surface through covalent and hydrogen bonds. Due to a basic catalyzed condensation of MPS with water, a siloxane layer was shown to be anchored to the nanoparticles through mono- and tridentate structures. Quantitative investigations were performed by thermogravimetric (TGA) and elemental analyses. The amount of silane linked to ZnO particles was shown to be affected by the amount of isolated hydroxyl groups available to react on the particle surface. For as-prepared ZnO nanoparticles, the number of isolated and available hydroxyl groups per square nanometer was up to 3 times higher than the one found on commercially available ZnO nanoparticles, leading to higher amounts of polymerizable silane agent linked to the surface. The MPS molecules were shown to be mainly oriented perpendicular to the oxide surface for all the as-prepared ZnO nanoparticles, whereas a parallel orientation was found for the preheated commercially ZnO nanopowders. In addition, ZnO nanoparticles were shown to be hydrophobized by the MPS treatment with water contact angles higher than 60°.

Adsorption of acrylonitrile on diamond and silicon (001)-(2 x 1) surfaces: effects of dimer structure on reaction pathways and product distributions.

PubMed

Schwartz, Michael P; Barlow, Daniel E; Russell, John N; Butler, James E; D'Evelyn, Mark P; Hamers, Robert J

2005-06-15

Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) are used to compare the reaction of acrylonitrile with Si(001) and C(001) (diamond) surfaces. Our results show that reaction with Si(001) and C(001) yield very different product distributions that result from fundamental differences in the ionic character of these surfaces. While acrylonitrile reacts with the C(001) surface via a [2 + 2] cycloaddition reaction in a manner similar to nonpolar molecules such as alkenes and disilenes, reaction with the Si(001) surface occurs largely through the nitrile group. This work represents the first experimental example of how differences in dimer structure lead to very different chemistry for C(001) compared to that for Si(001). The fact that Si(001) reacts with the strongly polar nitrile group of acrylonitrile indicates that the zwitterionic character of this surface controls its reactivity. C(001) dimers, on the other hand, behave more like a true molecular double bond, albeit a highly strained one. Consequently, while alternative strategies will be necessary for chemical modification of Si(001), traditional schemes from organic chemistry for functionalization of alkenes and disilenes may be available for building molecular layers on C(001).

Effects of polishing on surface roughness, gloss and color of surface reaction type pre-reacted glass-ionomer filled resin composite.

PubMed

Hosoya, Yumiko; Shiraishi, Takanobu; Odatsu, Tetsuro; Miyazaki, Masashi; García-Godoy, Franklin

2011-06-01

To evaluate the effects of polishing on surface roughness, gloss and color of different shades of surface reaction type pre-reacted glass-ionomer (S-PRG) filled nano-hybrid resin composite. Resin disks of 15 mm diameter and 2 mm thickness and final polish with 1000-grit SiC paper, super fine cut diamond (FG) point, silicon (MFR) point and Super-Snap mini-disk red (SNAP) were made with Beautifil II shades: A2, A20, Inc). One week after curing, the surface roughness, gloss and color were measured. Data was analyzed with ANOVA and Fisher's PLSD with alpha= 0.05 For all shades, the order of roughness (Ra) ranked according to groups of 1000-grit SiC > FG > MFR > SNAP with significant differences among all groups. For all shades, the order of gloss ranked according to groups of SNAP > MFR > FG > 1000-grit SiC with significant differences among the groups except for between MFR and FG without significant difference. The influence of the surface roughness on color differed among the polishing groups and shades. However, the values of the color differences (deltaE*ab) between the polishing groups of all shades were imperceptible to the naked eye.

Caries-preventive effect of fissure sealant containing surface reaction-type pre-reacted glass ionomer filler and bonded by self-etching primer.

PubMed

Shimazu, Kisaki; Ogata, Kiyokazu; Karibe, Hiroyuki

2012-01-01

We aimed to evaluate the caries-preventive effect of a fissure sealant containing surface reaction-type pre-reacted glass ionomer (S-PRG) filler and bonded by self-etching primer versus those of 2 conventional resin-based sealants bonded by acid etching in terms of its impact on enamel demineralization and remineralization, enamel bond strength, and integrity of debonded enamel surfaces. Demineralization, remineralization, and bond strength on untreated enamel and enamel subsurface lesions of bovine incisors were assessed among the sealants by polarizing microscopy and microradiography; debonded enamel surfaces were examined by scanning electron microscopy. The conventional resin-based sealants bonded by acid etching caused surface defects on the enamel subsurface lesions and significantly increased the lesion depth (p = 0.014), indicative of enamel demineralization. However the S-PRG filler-containing sealant bonded by self-etching primer maintained the enamel surface integrity and inhibited enamel demineralization. No difference in bond strength on both untreated enamel and enamel subsurface lesions was noted among the sealants. An S-PRG filler-containing fissure sealant bonded by self-etching primer can prevent enamel demineralization, microleakage, and gaps without the tags created by acid etching regardless of the enamel condition. Such sealants are suitable for protecting the pits and fissures of immature permanent teeth.

Rapid Aluminum Nanoparticle Production by Milling in NH₃ and CH₃NH₂ Atmospheres: An Experimental and Theoretical Study.

PubMed

McMahon, Brandon W; Yu, Jiang; Boatz, Jerry A; Anderson, Scott L

2015-07-29

Ball milling of aluminum in gaseous atmospheres of ammonia and monomethylamine (MMA) was found to produce particles in the 100 nm size range with high efficiency. A combination of mass spectrometry, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis with mass spectrometric product analysis (TGA-MS), scanning electron microscopy (SEM), infrared spectroscopy, and dynamic light scattering (DLS) was used to study the particles and the chemical interactions responsible for particle production. To help understand the nature of the surface chemistry, high level quantum chemical calculations were performed to predict the structures and energetics for binding and reactions of NH3 and MMA on aluminum surfaces. Both NH3 and MMA react with aluminum under milling conditions, producing H2 and other gaseous products, and leaving the surfaces functionalized. The surface functionalization enhances size reduction by reducing the surface free energy and the tendency toward mechanochemical welding. For both NH3 and MMA, the particle cores are metallic aluminum, but the surface chemical properties are quite different. The ammonia-milled particles are capped by an AlNxOyHz layer ∼10 nm thick, which passivates the particles. The MMA-milled particles are capped with a thinner passivating layer, such that they are pyrophoric in air and react with N2 at elevated temperatures.

Boosting immunity to small tumor-associated carbohydrates with bacteriophage qβ capsids.

PubMed

Yin, Zhaojun; Comellas-Aragones, Marta; Chowdhury, Sudipa; Bentley, Philip; Kaczanowska, Katarzyna; Benmohamed, Lbachir; Gildersleeve, Jeffrey C; Finn, M G; Huang, Xuefei

2013-01-01

The development of an effective immunotherapy is an attractive strategy toward cancer treatment. Tumor associated carbohydrate antigens (TACAs) are overexpressed on a variety of cancer cell surfaces, which present tempting targets for anticancer vaccine development. However, such carbohydrates are often poorly immunogenic. To overcome this challenge, we show here that the display of a very weak TACA, the monomeric Tn antigen, on bacteriophage Qβ virus-like particles elicits powerful humoral responses to the carbohydrate. The effects of adjuvants, antigen display pattern, and vaccine dose on the strength and subclasses of antibody responses were established. The local density of antigen rather than the total amount of antigen administered was found to be crucial for induction of high Tn-specific IgG titers. The ability to display antigens in an organized and high density manner is a key advantage of virus-like particles such as Qβ as vaccine carriers. Glycan microarray analysis showed that the antibodies generated were highly selective toward Tn antigens. Furthermore, Qβ elicited much higher levels of IgG antibodies than other types of virus-like particles, and the IgG antibodies produced reacted strongly with the native Tn antigens on human leukemia cells. Thus, Qβ presents a highly attractive platform for the development of carbohydrate-based anticancer vaccines.

Preparation of High Density Polyethylene/Waste Polyurethane Blends Compatibilized with Polyethylene-Graft-Maleic Anhydride by Radiation

PubMed Central

Park, Jong-Seok; Lim, Youn-Mook; Nho, Young-Chang

2015-01-01

Polyurethane (PU) is a very popular polymer that is used in a variety of applications due to its good mechanical, thermal, and chemical properties. However, PU recycling has received significant attention due to environmental issues. In this study, we developed a recycling method for waste PU that utilizes the radiation grafting technique. Grafting of waste PU was carried out using a radiation technique with polyethylene-graft-maleic anhydride (PE-g-MA). The PE-g-MA-grafted PU/high density polyethylene (HDPE) composite was prepared by melt-blending at various concentrations (0–10 phr) of PE-g-MA-grafted PU. The composites were characterized using fourier transform infrared spectroscopy (FT-IR), and their surface morphology and thermal/mechanical properties are reported. For 1 phr PU, the PU could be easily introduced to the HDPE during the melt processing in the blender after the radiation-induced grafting of PU with PE-g-MA. PE-g-MA was easily reacted with PU according to the increasing radiation dose and was located at the interface between the PU and the HDPE during the melt processing in the blender, which improved the interfacial interactions and the mechanical properties of the resultant composites. However, the elongation at break for a PU content >2 phr was drastically decreased. PMID:28788022

Protein labelling: Playing tag with proteins

NASA Astrophysics Data System (ADS)

Romanini, Dante W.; Cornish, Virginia W.

2012-04-01

Fluorescent labels can now be attached to a specific protein on the surface of live cells using a two-step method that reacts a norbornene -- introduced using genetic encoding -- with a variety of dyes.

Attrition reactor system

DOEpatents

Scott, Charles D.; Davison, Brian H.

1993-01-01

A reactor vessel for reacting a solid particulate with a liquid reactant has a centrifugal pump in circulatory flow communication with the reactor vessel for providing particulate attrition, resulting in additional fresh surface where the reaction can occur.

Identification of Surface Protein Biomarkers of Listeria monocytogenes via Bioinformatics and Antibody-Based Protein Detection Tools

PubMed Central

Zhang, Cathy X. Y.; Brooks, Brian W.; Huang, Hongsheng; Pagotto, Franco

2016-01-01

ABSTRACT The Gram-positive bacterium Listeria monocytogenes causes a significant percentage of the fatalities among foodborne illnesses in humans. Surface proteins specifically expressed in a wide range of L. monocytogenes serotypes under selective enrichment culture conditions could serve as potential biomarkers for detection and isolation of this pathogen via antibody-based methods. Our study aimed to identify such biomarkers. Interrogation of the L. monocytogenes serotype 4b strain F2365 genome identified 130 putative or known surface proteins. The homologues of four surface proteins, LMOf2365_0578, LMOf2365_0581, LMOf2365_0639, and LMOf2365_2117, were assessed as biomarkers due to the presence of conserved regions among strains of L. monocytogenes which are variable among other Listeria species. Rabbit polyclonal antibodies against the four recombinant proteins revealed the expression of only LMOf2365_0639 on the surface of serotype 4b strain LI0521 cells despite PCR detection of mRNA transcripts for all four proteins in the organism. Three of 35 monoclonal antibodies (MAbs) to LMOf2365_0639, MAbs M3643, M3644, and M3651, specifically recognized 42 (91.3%) of 46 L. monocytogenes lineage I and II isolates grown in nonselective brain heart infusion medium. While M3644 and M3651 reacted with 14 to 15 (82.4 to 88.2%) of 17 L. monocytogenes lineage I and II isolates, M3643 reacted with 22 (91.7%) of 24 lineage I, II, and III isolates grown in selective enrichment media (UVM1, modified Fraser, Palcam, and UVM2 media). The three MAbs exhibited only weak reactivities (the optical densities at 414 nm were close to the cutoff value) to some other Listeria species grown in selective enrichment media. Collectively, the data indicate the potential of LMOf2365_0639 as a surface biomarker of L. monocytogenes, with the aid of specific MAbs, for pathogen detection, identification, and isolation in clinical, environmental, and food samples. IMPORTANCE L. monocytogenes is traditionally divided into at least 12 serotypes. Currently, there are no monoclonal antibodies (MAbs) available that are capable of binding to the surface of L. monocytogenes strains representing all 12 serotypes. Such antibodies would be useful and are needed for the development of methods to detect and isolate L. monocytogenes from food samples. In our study, we aimed to identify surface proteins that possess regions of well-conserved amino acid sequences among various serotypes and then to employ them as antigen targets (biomarkers) for the development of MAbs. Through bioinformatics and protein expression analysis, we identified one of the four putative surface protein candidates, LMOf2365_0639, encoded by the genome of the L. monocytogenes serotype 4b strain F2365, as a useful surface biomarker. Extensive assessment of 35 MAbs raised against LMOf2365_0639 in our study revealed three MAbs (M3643, M3644, and M3651) that recognized a wide range of L. monocytogenes isolates. PMID:27342549

Environmentally stable reactive alloy powders and method of making same

DOEpatents

Anderson, I.E.; Lograsso, B.K.; Terpstra, R.L.

1998-09-22

Apparatus and method are disclosed for making powder from a metallic melt by atomizing the melt to form droplets and reacting the droplets downstream of the atomizing location with a reactive gas. The droplets are reacted with the gas at a temperature where a solidified exterior surface is formed thereon and where a protective refractory barrier layer (reaction layer) is formed whose penetration into the droplets is limited by the presence of the solidified surface so as to avoid selective reduction of key reactive alloys needed to achieve desired powder end use properties. The barrier layer protects the reactive powder particles from environmental constituents such as air and water in the liquid or vapor form during subsequent fabrication of the powder to end-use shapes and during use in the intended service environment. 7 figs.

Instrumentation development for study of Reynolds Analogy in reacting flows

NASA Technical Reports Server (NTRS)

Deturris, Dianne J.

1995-01-01

Boundary layers in supersonic reacting flows are not well understood. Recently a technique has been developed which makes more extensive surface measurements practical, increasing the capability to understand the turbulent boundary layer. A significant advance in this understanding would be the formulation of an analytic relation between the transfer of momentum and the transfer of heat for this flow, similar to the Reynolds Analogy that exists for laminar flow. A gauge has been designed and built which allows a thorough experimental investigation of the relative effects of heat transfer and skin friction in the presence of combustion. Direct concurrent measurements made at the same location, combined with local flow conditions, enable a quantitative analysis to obtain a relation between the surface drag and wall heating, as well as identifying possible ways of reducing both.

Combined LAURA-UPS solution procedure for chemically-reacting flows. M.S. Thesis

NASA Technical Reports Server (NTRS)

Wood, William A.

1994-01-01

A new procedure seeks to combine the thin-layer Navier-Stokes solver LAURA with the parabolized Navier-Stokes solver UPS for the aerothermodynamic solution of chemically-reacting air flowfields. The interface protocol is presented and the method is applied to two slender, blunted shapes. Both axisymmetric and three dimensional solutions are included with surface pressure and heat transfer comparisons between the present method and previously published results. The case of Mach 25 flow over an axisymmetric six degree sphere-cone with a noncatalytic wall is considered to 100 nose radii. A stability bound on the marching step size was observed with this case and is attributed to chemistry effects resulting from the noncatalytic wall boundary condition. A second case with Mach 28 flow over a sphere-cone-cylinder-flare configuration is computed at both two and five degree angles of attack with a fully-catalytic wall. Surface pressures are seen to be within five percent with the present method compared to the baseline LAURA solution and heat transfers are within 10 percent. The effect of grid resolution is investigated and the nonequilibrium results are compared with a perfect gas solution, showing that while the surface pressure is relatively unchanged by the inclusion of reacting chemistry the nonequilibrium heating is 25 percent higher. The procedure demonstrates significant, order of magnitude reductions in solution time and required memory for the three dimensional case over an all thin-layer Navier-Stokes solution.

Investigations of turbulent scalar fields using probability density function approach

NASA Technical Reports Server (NTRS)

Gao, Feng

1991-01-01

Scalar fields undergoing random advection have attracted much attention from researchers in both the theoretical and practical sectors. Research interest spans from the study of the small scale structures of turbulent scalar fields to the modeling and simulations of turbulent reacting flows. The probability density function (PDF) method is an effective tool in the study of turbulent scalar fields, especially for those which involve chemical reactions. It has been argued that a one-point, joint PDF approach is the one to choose from among many simulation and closure methods for turbulent combustion and chemically reacting flows based on its practical feasibility in the foreseeable future for multiple reactants. Instead of the multi-point PDF, the joint PDF of a scalar and its gradient which represents the roles of both scalar and scalar diffusion is introduced. A proper closure model for the molecular diffusion term in the PDF equation is investigated. Another direction in this research is to study the mapping closure method that has been recently proposed to deal with the PDF's in turbulent fields. This method seems to have captured the physics correctly when applied to diffusion problems. However, if the turbulent stretching is included, the amplitude mapping has to be supplemented by either adjusting the parameters representing turbulent stretching at each time step or by introducing the coordinate mapping. This technique is still under development and seems to be quite promising. The final objective of this project is to understand some fundamental properties of the turbulent scalar fields and to develop practical numerical schemes that are capable of handling turbulent reacting flows.

First principles study of the atomic layer deposition of alumina by TMA-H2O-process.

PubMed

Weckman, Timo; Laasonen, Kari

2015-07-14

Atomic layer deposition (ALD) is a coating technology used to produce highly uniform thin films. Aluminiumoxide, Al2O3, is mainly deposited using trimethylaluminium (TMA) and water as precursors and is the most studied ALD-process to date. However, only few theoretical studies have been reported in the literature. The surface reaction mechanisms and energetics previously reported focus on a gibbsite-like surface model but a more realistic description of the surface can be achieved when the hydroxylation of the surface is taken into account using dissociatively adsorbed water molecules. The adsorbed water changes the structure of the surface and reaction energetics change considerably when compared to previously studied surface model. Here we have studied the TMA-H2O process using density functional theory on a hydroxylated alumina surface and reproduced the previous results for comparison. Mechanisms and energetics during both the TMA and the subsequent water pulse are presented. TMA is found to adsorb exothermically onto the surface. The reaction barriers for the ligand-exchange reactions between the TMA and the surface hydroxyl groups were found to be much lower compared to previously presented results. TMA dissociation on the surface is predicted to saturate at monomethylaluminium. Barriers for proton diffusion between surface sites are observed to be low. TMA adsorption was also found to be cooperative with the formation of methyl bridges between the adsorbants. The water pulse was studied using single water molecules reacting with the DMA and MMA surface species. Barriers for these reactions were found to reasonable in the process conditions. However, stabilizing interactions amongst water molecules were found to lower the reaction barriers and the dynamical nature of water is predicted to be of importance. It is expected that these calculations can only set an upper limit for the barriers during the water pulse.

A DFT Investigation of the Mechanism of Propene Ammoxidation over α-Bismuth Molybdate

DOE PAGES

Licht, Rachel B.; Bell, Alexis T.

2016-11-17

We investigated the mechanisms and energetics for the propene oxidation and ammoxidation occurring on the (010) surface of Bi 2 Mo 3 O 12 using density functional theory (DFT). An energetically feasible sequence of elementary steps for propene oxidation to acrolein, propene ammoxidation to acrylonitrile, and acrolein ammoxidation to acrylonitrile is proposed. Consistent with experimental findings, the rate-limiting step for both propene oxidation and ammoxidation is the initial hydrogen abstraction from the methyl group of propene, which is calculated to have an apparent activation energy of 27.3 kcal/mol. The allyl species produced in this reaction is stabilized as an allylmore » alkoxide, which can then undergo hydrogen abstraction to form acrolein or react with ammonia adsorbed on under-coordinated surface Bi 3+ cations to form allylamine. Dehydrogenation of allylamine is shown to produce acrylonitrile, whereas reaction with additional adsorbed ammonia leads to the formation of acetonitrile and hydrogen cyanide. The dehydrogenation of allyalkoxide species is found to have a significantly higher activation barrier than reaction with adsorbed ammonia, consistent with the observation that very little acrolein is produced when ammonia is present. Finally, we found that rapid reoxidation of the catalyst surface to release wate the driving force for all reactions involving the cleavage of C-H or N-H bonds, because practically all of these steps are endothermic. (Chemical Equation Presented).« less

Characterization of an immunogenic glycocalyx on the surfaces of Cryptosporidium parvum oocysts and sporozoites.

PubMed

Nanduri, J; Williams, S; Aji, T; Flanigan, T P

1999-04-01

Ruthenium red staining of Cryptosporidium parvum oocysts revealed the presence of a carbohydrate matrix on their outer bilayers that is characteristic of a glycocalyx. Surface labeling of intact oocysts identified material of high molecular weight (>10(6)) that reacted positively with sera from cryptosporidium-infected patients and with immunoglobulin A monoclonal antibodies.

Characterization of an Immunogenic Glycocalyx on the Surfaces of Cryptosporidium parvum Oocysts and Sporozoites

PubMed Central

Nanduri, Jayasri; Williams, Selvi; Aji, Toshiki; Flanigan, Timothy P.

1999-01-01

Ruthenium red staining of Cryptosporidium parvum oocysts revealed the presence of a carbohydrate matrix on their outer bilayers that is characteristic of a glycocalyx. Surface labeling of intact oocysts identified material of high molecular weight (>106) that reacted positively with sera from cryptosporidium-infected patients and with immunoglobulin A monoclonal antibodies. PMID:10085053

Numerical simulation of electromagnetic wave attenuation in a nonequilibrium chemically reacting hypervelocity flow

NASA Astrophysics Data System (ADS)

Nusca, Michael Joseph, Jr.

The effects of various gasdynamic phenomena on the attenuation of an electromagnetic wave propagating through the nonequilibrium chemically reacting air flow field generated by an aerodynamic body travelling at high velocity is investigated. The nonequilibrium flow field is assumed to consist of seven species including nitric oxide ions and free electrons. The ionization of oxygen and nitrogen atoms is ignored. The aerodynamic body considered is a blunt wedge. The nonequilibrium chemically reacting flow field around this body is numerically simulated using a computer code based on computational fluid dynamics. The computer code solves the Navier-Stokes equations including mass diffusion and heat transfer, using a time-marching, explicit Runge-Kutta scheme. A nonequilibrium air kinetics model consisting of seven species and twenty-eight reactions as well as an equilibrium air model consisting of the same seven species are used. The body surface boundaries are considered as adiabatic or isothermal walls, as well as fully-catalytic and non-catalytic surfaces. Both laminar and turbulent flows are considered; wall generated flow turbulence is simulated using an algebraic mixing length model. An electromagnetic wave is considered as originating from an antenna within the body and is effected by the free electrons in the chemically reacting flow. Analysis of the electromagnetics is performed separately from the fluid dynamic analysis using a series solution of Maxwell's equations valid for the propagation of a long-wavelength plane electromagnetic wave through a thin (i.e., in comparison to wavelength) inhomogeneous plasma layer. The plasma layer is the chemically reacting shock layer around the body. The Navier-Stokes equations are uncoupled from Maxwell's equations. The results of this computational study demonstrate for the first time and in a systematic fashion, the importance of several parameters including equilibrium chemistry, nonequilibrium chemical kinetics, the reaction mechanism, flow viscosity, mass diffusion, and wall boundary conditions on modeling wave attenuation resulting from the interaction of an electromagnetic wave with an aerodynamic plasma. Comparison is made with experimental data.

Mechanism of atomic layer deposition of SiO2 on the silicon (100)-2×1 surface using SiCl4 and H2O as precursors

NASA Astrophysics Data System (ADS)

Kang, Jeung Ku; Musgrave, Charles B.

2002-03-01

We use density functional theory to investigate atomic layer deposition (ALD) mechanism of silicon dioxide on the Si(100)-2×1 surface from the precursors SiCl4 and H2O. First, we explore the reaction mechanism of water with the bare Si(100)-2×1 surface to produce surface hydroxyl groups. We find that this reaction proceeds through a two-step pathway with an overall barrier of 33.3 kcal/mol. Next, we investigate the ALD mechanism for the binary reaction sequence: the SiCl4 half reaction and the H2O half reaction. For the SiCl4 half reaction, SiCl4 first forms a σ-bond with the oxygen of the surface OH group and then releases an HCl molecule. The predicted barrier for this process is 15.8 kcal/mol. Next, adsorbed SiCl3 reacts with a neighboring OH group to form bridged SiCl2 with a barrier of 22.6 kcal/mol. The H2O half reaction also proceeds through two sequential steps with an overall barrier of 19.1 kcal/mol for the reaction of H2O with bridged SiCl2 to form bridged Si(OH)2. The predicted barrier of 22.6 kcal/mol for the rate-limiting step of the ALD binary reaction mechanism is consistent with the experimental value of 22.0 kcal/mol. In addition, we find that the calculated frequencies are in good agreement with the experimentally measured IR spectra.

Effect of hydration on the stability of fullerene-like silica molecules

NASA Astrophysics Data System (ADS)

Filonenko, O. V.; Lobanov, V. V.

2011-05-01

The hydration of fullerene-like silica molecules was studied by the density functional method (exchange-correlation functional B3LYP, basis set 6-31G**). It was demonstrated that completely coordinated structures transform to more stable hydroxylated ones during hydrolysis. These in turn react with H2O molecules with the formation of hydrogen bonds.

Human monoclonal antibodies reactive with human myelomonocytic leukemia cells.

PubMed

Posner, M R; Santos, D J; Elboim, H S; Tumber, M B; Frackelton, A R

1989-04-01

Peripheral blood mononuclear cells from a patient with chronic myelogenous leukemia (CML), in remission, were depleted of CD8-positive T-cells and cultured with Epstein-Barr virus. Four of 20 cultures (20%) secreted human IgG antibodies selectively reactive with the cell surfaces of certain human leukemia cell lines. Three polyclonal, Epstein-Barr virus-transformed, B-cell lines were expanded and fused with the human-mouse myeloma analogue HMMA2.11TG/O. Antibody from secreting clones HL 1.2 (IgG1), HL 2.1 (IgG3), and HL 3.1 (IgG1) have been characterized. All three react with HL-60 (promyelocytic), RWLeu4 (CML promyelocytic), and U937 (monocytic), but not with KG-1 (myeloblastic) or K562 (CML erythroid). There is no reactivity with T-cell lines, Burkitt's cell lines, pre-B-leukemia cell lines, or an undifferentiated CML cell line, BV173. Leukemic cells from two of seven patients with acute myelogenous leukemia and one of five with acute lymphocytic leukemia react with all three antibodies. Normal lymphocytes, monocytes, polymorphonuclear cells, red blood cells, bone marrow cells, and platelets do not react. Samples from patients with other diverse hematopoietic malignancies showed no reactivity. Immunoprecipitations suggest that the reactive antigen(s) is a lactoperoxidase iodinatable series of cell surface proteins with molecular weights of 42,000-54,000 and a noniodinatable protein with a molecular weight of 82,000. Based on these data these human monoclonal antibodies appear to react with myelomonocytic leukemic cells and may detect a leukemia-specific antigen or a highly restricted differentiation antigen.

Flame-conditioned turbulence modeling for reacting flows

NASA Astrophysics Data System (ADS)

Macart, Jonathan F.; Mueller, Michael E.

2017-11-01

Conventional approaches to turbulence modeling in reacting flows rely on unconditional averaging or filtering, that is, consideration of the momentum equations only in physical space, implicitly assuming that the flame only weakly affects the turbulence, aside from a variation in density. Conversely, for scalars, which are strongly coupled to the flame structure, their evolution equations are often projected onto a reduced-order manifold, that is, conditionally averaged or filtered, on a flame variable such as a mixture fraction or progress variable. Such approaches include Conditional Moment Closure (CMC) and related variants. However, recent observations from Direct Numerical Simulation (DNS) have indicated that the flame can strongly affect turbulence in premixed combustion at low Karlovitz number. In this work, a new approach to turbulence modeling for reacting flows is investigated in which conditionally averaged or filtered equations are evolved for the momentum. The conditionally-averaged equations for the velocity and its covariances are derived, and budgets are evaluated from DNS databases of turbulent premixed planar jet flames. The most important terms in these equations are identified, and preliminary closure models are proposed.

A highly efficient polysulfide mediator for lithium-sulfur batteries

NASA Astrophysics Data System (ADS)

Liang, Xiao; Hart, Connor; Pang, Quan; Garsuch, Arnd; Weiss, Thomas; Nazar, Linda F.

2015-01-01

The lithium-sulfur battery is receiving intense interest because its theoretical energy density exceeds that of lithium-ion batteries at much lower cost, but practical applications are still hindered by capacity decay caused by the polysulfide shuttle. Here we report a strategy to entrap polysulfides in the cathode that relies on a chemical process, whereby a host—manganese dioxide nanosheets serve as the prototype—reacts with initially formed lithium polysulfides to form surface-bound intermediates. These function as a redox shuttle to catenate and bind ‘higher’ polysulfides, and convert them on reduction to insoluble lithium sulfide via disproportionation. The sulfur/manganese dioxide nanosheet composite with 75 wt% sulfur exhibits a reversible capacity of 1,300 mA h g-1 at moderate rates and a fade rate over 2,000 cycles of 0.036%/cycle, among the best reported to date. We furthermore show that this mechanism extends to graphene oxide and suggest it can be employed more widely.

Porous mesocarbon microbeads with graphitic shells: constructing a high-rate, high-capacity cathode for hybrid supercapacitor

PubMed Central

Lei, Yu; Huang, Zheng-Hong; Yang, Ying; Shen, Wanci; Zheng, Yongping; Sun, Hongyu; Kang, Feiyu

2013-01-01

Li4Ti5O12/activated carbon hybrid supercapacitor can combine the advantages of both lithium-ion battery and supercapacitor, which may meet the requirements for developing high-performance hybrid electric vehicles. Here we proposed a novel “core-shell” porous graphitic carbon (PGC) to replace conventional activated carbon for achieving excellent cell performance. In this PGC structure made from mesocarbon microbead (MCMB), the inner core is composed of porous amorphous carbon, while the outer shell is graphitic carbon. The abundant porosity and the high surface area not only offer sufficient reaction sites to store electrical charge physically, but also can accelerate the liquid electrolyte to penetrate the electrode and the ions to reach the reacting sites. Meanwhile, the outer graphitic shells of the porous carbon microbeads contribute to a conductive network which will remarkably facilitate the electron transportation, and thus can be used to construct a high-rate, high-capacity cathode for hybrid supercapacitor, especially at high current densities. PMID:23963328

Rebound and jet formation of a fluid-filled sphere

NASA Astrophysics Data System (ADS)

Killian, Taylor W.; Klaus, Robert A.; Truscott, Tadd T.

2012-12-01

This study investigates the impact dynamics of hollow elastic spheres partially filled with fluid. Unlike an empty sphere, the internal fluid mitigates some of the rebound through an impulse driven exchange of energy wherein the fluid forms a jet inside the sphere. Surprisingly, this occurs on the second rebound or when the free surface is initially perturbed. Images gathered through experimentation show that the fluid reacts more quickly to the impact than the sphere, which decouples the two masses (fluid and sphere), imparts energy to the fluid, and removes rebound energy from the sphere. The experimental results are analyzed in terms of acceleration, momentum and an energy method suggesting an optimal fill volume in the neighborhood of 30%. While the characteristics of the fluid (i.e., density, viscosity, etc.) affect the fluid motion (i.e., type and size of jet formation), the rebound characteristics remain similar for a given fluid volume independent of fluid type. Implications of this work are a potential use of similar passive damping systems in sports technology and marine engineering.

Isothermal absorption of soluble gases by atmospheric nanoaerosols

NASA Astrophysics Data System (ADS)

Elperin, T.; Fominykh, A.; Krasovitov, B.; Lushnikov, A.

2013-01-01

We investigate mass transfer during the isothermal absorption of atmospheric trace soluble gases by a single droplet whose size is comparable to the molecular mean free path in air at normal conditions. It is assumed that the trace reactant diffuses to the droplet surface and then reacts with the substances inside the droplet according to the first-order rate law. Our analysis applies a flux-matching theory of transport processes in gases and assumes constant thermophysical properties of the gases and liquids. We derive an integral equation of Volterra type for the transient molecular flux density to a liquid droplet and solve it numerically. Numerical calculations are performed for absorption of sulfur dioxide (SO2), dinitrogen trioxide (N2O3), and chlorine (Cl2) by liquid nanoaerosols accompanied by chemical dissociation reaction. It is shown that during gas absorption by nanoaerosols, the kinetic effects play a significant role, and neglecting kinetic effects leads to a significant overestimation of the soluble gas flux into a droplet during the entire period of gas absorption.

Fabrication of solid oxide fuel cell by electrochemical vapor deposition

DOEpatents

Riley, B.; Szreders, B.E.

1988-04-26

In a high temperature solid oxide fuel cell (SOFC), the deposition of an impervious high density thin layer of electrically conductive interconnector material, such as magnesium doped lanthanum chromite, and of an electrolyte material, such as yttria stabilized zirconia, onto a porous support/air electrode substrate surface is carried out at high temperatures (/approximately/1100/degree/ /minus/ 1300/degree/C) by a process of electrochemical vapor deposition. In this process, the mixed chlorides of the specific metals involved react in the gaseous state with water vapor resulting in the deposit of an impervious thin oxide layer on the support tube/air electrode substrate of between 20--50 microns in thickness. An internal heater, such as a heat pipe, is placed within the support tube/air electrode substrate and induces a uniform temperature profile therein so as to afford precise and uniform oxide deposition kinetics in an arrangement which is particularly adapted for large scale, commercial fabrication of SOFCs.

Views supporting the Window Experiment (WINDEX) of shuttle environment

NASA Image and Video Library

1995-08-03

STS070-386-027 (13-22 JULY 1995) --- High-speed film provided this close-up view of the Space Shuttle Discovery’s aft, featuring the ignition of one of the primary thrusters. Note the impact of the firing on the starboard side of the vertical stabilizer. Crew members told a August 11, 1995, gathering of Johnson Space Center (JSC) employees that the Window Experiment (WINDEX) paid close attention to surface glow, jet plumes, water dumps, aurora and airglow. The data collection is part of an effort to avoid misinterpretation of measurements of Earth, the solar system and starts taken from satellites in low Earth-orbits and prevent damage to sensitive systems and solar arrays during rendezvous and docking. Such firings of the thrusters increase local densities of gases in the atmosphere dramatically and introduce non-natural elements that react with the atmosphere dramatically and spacecraft systems enveloped by the thruster plume. WINDEX recorded phenomena associated with thruster start-up and shut-down transients and observed the effect of the transients on Shuttle glow phenomenon.

Isothermal absorption of soluble gases by atmospheric nanoaerosols.

PubMed

Elperin, T; Fominykh, A; Krasovitov, B; Lushnikov, A

2013-01-01

We investigate mass transfer during the isothermal absorption of atmospheric trace soluble gases by a single droplet whose size is comparable to the molecular mean free path in air at normal conditions. It is assumed that the trace reactant diffuses to the droplet surface and then reacts with the substances inside the droplet according to the first-order rate law. Our analysis applies a flux-matching theory of transport processes in gases and assumes constant thermophysical properties of the gases and liquids. We derive an integral equation of Volterra type for the transient molecular flux density to a liquid droplet and solve it numerically. Numerical calculations are performed for absorption of sulfur dioxide (SO(2)), dinitrogen trioxide (N(2)O(3)), and chlorine (Cl(2)) by liquid nanoaerosols accompanied by chemical dissociation reaction. It is shown that during gas absorption by nanoaerosols, the kinetic effects play a significant role, and neglecting kinetic effects leads to a significant overestimation of the soluble gas flux into a droplet during the entire period of gas absorption.

Method for producing high quality thin layer films on substrates

DOEpatents

Strongin, Myron; Ruckman, Mark; Strongin, Daniel

1994-01-01

A method for producing high quality, thin layer films of inorganic compounds upon the surface of a substrate is disclosed. The method involves condensing a mixture of preselected molecular precursors on the surface of a substrate and subsequently inducing the formation of reactive species using high energy photon or charged particle irradiation. The reactive species react with one another to produce a film of the desired compound upon the surface of the substrate.

Attrition reactor system

DOEpatents

Scott, C.D.; Davison, B.H.

1993-09-28

A reactor vessel for reacting a solid particulate with a liquid reactant has a centrifugal pump in circulatory flow communication with the reactor vessel for providing particulate attrition, resulting in additional fresh surface where the reaction can occur. 2 figures.

Spatiotemporal temperature and density characterization of high-power atmospheric flashover discharges over inert poly(methyl methacrylate) and energetic pentaerythritol tetranitrate dielectric surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, V.; Grant, C. D.; McCarrick, J. F.

2012-03-01

A flashover arc source that delivered up to 200 mJ on the 100s-of-ns time-scale to the arc and a user-selected dielectric surface was characterized for studying high-explosive kinetics under plasma conditions. The flashover was driven over thin pentaerythritol tetranitrate (PETN) and poly(methyl methacrylate) (PMMA) dielectric films and the resultant plasma was characterized in detail. Time- and space-resolved temperatures and electron densities of the plasma were obtained using atomic emission spectroscopy. The hydrodynamics of the plasma was captured through fast, visible imaging. Fourier transform infrared spectroscopy (FTIR) was used to characterize the films pre- and post-shot for any chemical alterations. Time-resolvedmore » infrared spectroscopy (TRIR) provided PETN depletion data during the plasma discharge. For both types of films, temperatures of 1.6-1.7 eV and electron densities of {approx}7-8 x 10{sup 17}/cm{sup 3}{approx}570 ns after the start of the discharge were observed with temperatures of 0.6-0.7 eV persisting out to 15 {mu}s. At 1.2 {mu}s, spatial characterization showed flat temperature and density profiles of 1.1-1.3 eV and 2-2.8 x 10{sup 17}/cm{sup 3} for PETN and PMMA films, respectively. Images of the plasma showed an expanding hot kernel starting from radii of {approx}0.2 mm at {approx}50 ns and reaching {approx}1.1 mm at {approx}600 ns. The thin films ablated or reacted several hundred nm of material in response to the discharge. First TRIR data showing the in situ reaction or depletion of PETN in response to the flashover arc were successfully obtained, and a 2-{mu}s, 1/e decay constant was measured. Preliminary 1 D simulations compared reasonably well with the experimentally determined plasma radii and temperatures. These results complete the first steps to resolving arc-driven PETN reaction pathways and their associated kinetic rates using in situ spectroscopy techniques.« less

Long-Chain Polysulfide Retention at the Cathode of Li–S Batteries

DOE PAGES

Kamphaus, Ethan P.; Balbuena, Perla B.

2016-02-10

Lithium–sulfur batteries present a complex interconnected chemistry where the three components—anode, electrolyte, and cathode—strongly interact with each other. One of the main issues associated with these interactions is the dissolution in the electrolyte solution of part of the sulfur reduction products (mainly long-chain polysulfides) during the discharge reactions at the cathode. These dissolved species can migrate and react at the anode surface producing undesired insulating films. A potential solution to mitigate this problem is to resort to additional materials which can act as anchors of the soluble species thus avoiding their migration. Density functional theory and ab initio molecular dynamicsmore » simulations are employed to investigate the ability of certain substrates to retain long-chain polysulfides (Li 2S 6 and Li 2S 8) at their surfaces in the presence of a pure solvent or a lithiated solution. Nanopores of graphene are first tested because the cathode is usually a mix of sulfur and carbon. Then, MoS 2 and Mo-doped graphene are evaluated because of the well-known Mo–S affinity. Finally, a material which has been reported successful in experimental studies, MnO 2, is analyzed and compared with another oxide surface, Fe 2O 3. Adsorption energies of the polysulfides to the surfaces and the detailed interactions of the Li ions and S atoms with the substrate are characterized via charge and geometric analyses. Both the Mo-containing materials and the oxides adsorb the polysulfides much more strongly than graphene nanopores do. However, some of these surfaces are found to be excessively reactive. Thus, a balance between affinity for S and moderate surface reactivity is found as a promising guideline for designing these materials.« less

Water and Carbon Dioxide Adsorption at Olivine Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kerisit, Sebastien N.; Bylaska, Eric J.; Felmy, Andrew R.

2013-11-14

Plane-wave density functional theory (DFT) calculations were performed to simulate water and carbon dioxide adsorption at the (010) surface of five olivine minerals, namely, forsterite (Mg2SiO4), calcio-olivine (Ca2SiO4), tephroite (Mn2SiO4), fayalite (Fe2SiO4), and Co-olivine (Co2SiO4). Adsorption energies per water molecule obtained from energy minimizations varied from -78 kJ mol-1 for fayalite to -128 kJ mol-1 for calcio-olivine at sub-monolayer coverage and became less exothermic as coverage increased. In contrast, carbon dioxide adsorption energies at sub-monolayer coverage ranged from -20 kJ mol-1 for fayalite to -59 kJ mol-1 for calcio-olivine. Therefore, the DFT calculations show a strong driving force for carbonmore » dioxide displacement by water at the surface of all olivine minerals in a competitive adsorption scenario. Additionally, adsorption energies for both water and carbon dioxide were found to be more exothermic for the alkaline-earth (AE) olivines than for the transition-metal (TM) olivines and to not correlate with the solvation enthalpies of the corresponding divalent cations. However, a correlation was obtained with the charge of the surface divalent cation indicating that the more ionic character of the AE cations in the olivine structure relative to the TM cations leads to greater interactions with adsorbed water and carbon dioxide molecules at the surface and thus more exothermic adsorption energies for the AE olivines. For calcio-olivine, which exhibits the highest divalent cation charge of the five olivines, ab initio molecular dynamics simulations showed that this effect leads both water and carbon dioxide to react with the surface and form hydroxyl groups and a carbonate-like species, respectively.« less

A comprehensive model to determine the effects of temperature and species fluctuations on reaction rates in turbulent reacting flows

NASA Technical Reports Server (NTRS)

Goldstein, D.; Magnotti, F.; Chinitz, W.

1983-01-01

Reaction rates in turbulent, reacting flows are reviewed. Assumed probability density functions (pdf) modeling of reaction rates is being investigated in relation to a three variable pdf employing a 'most likely pdf' model. Chemical kinetic mechanisms treating hydrogen air combustion is studied. Perfectly stirred reactor modeling of flame stabilizing recirculation regions was used to investigate the stable flame regions for silane, hydrogen, methane, and propane, and for certain mixtures thereof. It is concluded that in general, silane can be counted upon to stabilize flames only when the overall fuel air ratio is close to or greater than unity. For lean flames, silane may tend to destabilize the flame. Other factors favoring stable flames are high initial reactant temperatures and system pressure.

Cascade redox flow battery systems

DOEpatents

Horne, Craig R.; Kinoshita, Kim; Hickey, Darren B.; Sha, Jay E.; Bose, Deepak

2014-07-22

A reduction/oxidation ("redox") flow battery system includes a series of electrochemical cells arranged in a cascade, whereby liquid electrolyte reacts in a first electrochemical cell (or group of cells) before being directed into a second cell (or group of cells) where it reacts before being directed to subsequent cells. The cascade includes 2 to n stages, each stage having one or more electrochemical cells. During a charge reaction, electrolyte entering a first stage will have a lower state-of-charge than electrolyte entering the nth stage. In some embodiments, cell components and/or characteristics may be configured based on a state-of-charge of electrolytes expected at each cascade stage. Such engineered cascades provide redox flow battery systems with higher energy efficiency over a broader range of current density than prior art arrangements.

The Behavior and Acrosomal Status of Mouse Spermatozoa In Vitro, and Within the Oviduct During Fertilization after Natural Mating.

PubMed

Hino, Toshiaki; Muro, Yuko; Tamura-Nakano, Miwa; Okabe, Masaru; Tateno, Hiroyuki; Yanagimachi, Ryuzo

2016-09-01

Although 90%-100% of mouse oocytes can be fertilized in vitro with capacitated spermatozoa within 1 h after insemination, oocytes within the oviduct are fertilized one by one over a period of several hours. In vitro experiments showed that both acrosome-intact and acrosome-reacted spermatozoa entered the cumulus oophorus, but that acrosome-reacted spermatozoa reached the surface of oocytes more readily than acrosome-intact spermatozoa. During the period of fertilization within the oviduct, acrosome-reacted spermatozoa were seen throughout the isthmus, but with higher incidence in the upper than in the mid- and lower segments of the isthmus. Very few spermatozoa were present in the ampulla, and almost all were acrosome reacted. Although the cumulus oophorus and zona pellucida are known to be able to induce or facilitate the acrosome reaction of spermatozoa, this picture makes it likely that almost all fertilizing mouse spermatozoa within the oviduct begin to react before ascending from the isthmus to the ampulla. We witnessed a reacted spermatozoon that stayed on the zona pellucida of a fertilized oocyte for a while; it then moved out of the cumulus before reaching the zona pellucida of the nearby unfertilized oocyte. We noted that only a few spermatozoa migrate from the isthmus to the ampulla during the progression of fertilization, and this must be one of the reasons why we do not see many spermatozoa swarming around a single oocyte during in vivo fertilization. © 2016 by the Society for the Study of Reproduction, Inc.

Incompletely-Condensed Fluoroalkyl Silsesquioxanes and Derivatives: Precursors for Low Surface Energy Materials (Preprint)

DTIC Science & Technology

2011-09-13

superhydrophobic and oleophobic materials. Utilizing triflic acid, open-cage compounds were created and then reacted with a variety of dichlorosilanes...fluorinated nanobuilding blocks with a controlled level of reactive functionality for the development of new superhydrophobic and oleophobic...F-POSS), which are useful as low surface energy materials for superhydrophobic and oleophobic materials. Utilizing triflic acid, open-cage

Sonogashira cross-coupling over Au(1 1 1): from UHV to ambient pressure

NASA Astrophysics Data System (ADS)

Johansson, N.; Sisodiya, S.; Shayesteh, P.; Chaudhary, S.; Andersen, J. N.; Knudsen, J.; Wendt, O. F.; Schnadt, J.

2017-11-01

We have studied the reaction of phenylacetylene (PA) with chloro-, bromo-, and iodobenzene on the Au(1 1 1) surface as a model system for the gold-catalysed Sonogashira cross-coupling. Both ultrahigh vacuum-based and ambient pressure x-ray photoelectron spectroscopy show that iodo- and chlorobenzene (IB and CB) undergo the cross-coupling reaction towards diphenylacetylene. Bromobenzene (BB), in contrast, does not react in the UHV experiments. Further, at ambient pressure signs are found for poisoning of the Au(1 1 1) surface by a carbon species formed in the reaction. The understanding obtained in the reaction experiments are based on a thorough investigation of the adsorption of PA, IB, CB, and BB on the Au(1 1 1) surface by soft x-ray absorption spectroscopy and temperature-dependent x-ray photoelectron spectroscopy. In particular, the experiments provide the orientation of the intact adsorbates with respect to the surfaces at liquid nitrogen temperature. Dissociation in the temperature regime between  -80 and  -15 °C is observed for iodo- and chlorobenzene, but not for BB, in agreement with that only IB and CB, but not BB, react with PA to form diphenylacetylene. The difference is tentatively attributed to a difference in surface orientation of the different halobenzenes.

Protective conversion coating on mixed-metal substrates and methods thereof

DOEpatents

O'Keefe, Matthew J.; Maddela, Surender

2016-09-06

Mixed-metal automotive vehicle bodies-in-white comprising ferrous metal surfaces, zinc surfaces, aluminum alloy surfaces, and magnesium alloy surfaces are cleaned and immersed in an aqueous bath comprising an adhesion promoter and an aqueous electrocoat bath (the adhesion promoter may be in the electrocoat bath. The adhesion promoter, which may be a cerium salt, is selected to react with each metal in the body surfaces to form an oxide layer that provides corrosion resistance for the surface and adherence for the deposited polymeric paint coating. The body is cathodic in the electrocoat deposition.

Diffusion with chemical reaction: An attempt to explain number density anomalies in experiments involving alkali vapor

NASA Technical Reports Server (NTRS)

Snow, W. L.

1974-01-01

The mutual diffusion of two reacting gases is examined which takes place in a bath of inert gas atoms. Solutions are obtained between concentric spheres, each sphere acting as a source for one of the reactants. The calculational model is used to illustrate severe number density gradients observed in absorption experiments with alkali vapor. Severe gradients result when sq root k/D R is approximately 5 where k, D, and R are respectively the second order rate constant, the multicomponent diffusion constant, and the geometrical dimension of the experiment.

Characterizing Variability In Ohio River Natural Organic Matter

EPA Science Inventory

Surface water contains natural organic matter (NOM) which reacts with disinfectants creating disinfection byproducts (DBPs), some of which are USEPA regulated contaminants. Characterizing NOM can provide important insight on DBP formation and water treatment process adaptation t...

South Pole

NASA Image and Video Library

2012-11-02

As spring progresses at the south pole, the surface reacts to the change of season. This image from NASA 2001 Mars Odyssey spacecraft shows a region of the south pole that is monitored throughout spring, summer, and fall at the south pole.

Dispersoid reinforced alloy powder and method of making

DOEpatents

Anderson, Iver E; Terpstra, Robert L

2014-10-21

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with a reactive species acquired from an atomizing gas than does the alloying element. The melted alloy is atomized with the atomizing gas including the reactive species to form atomized particles so that the reactive species is (a) dissolved in solid solution to a depth below the surface of atomized particles and/or (b) reacted with the dispersoid-forming element to form dispersoids in the atomized particles to a depth below the surface of said atomized particles. Bodies made from the dispersion strengthened solidified particles exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures.

Dissolution-Assisted Pattern Formation During Olivine Carbonation

NASA Astrophysics Data System (ADS)

Lisabeth, Harrison; Zhu, Wenlu; Xing, Tiange; De Andrade, Vincent

2017-10-01

Olivine and pyroxene-bearing rocks in the oceanic crust react with hydrothermal fluids producing changes in the physical characteristics and behaviors of the altered rocks. Notably, these reactions tend to increase solid volume, reducing pore volume, permeability, and available reactive surface area, yet entirely hydrated and/or carbonated rocks are commonly observed in the field. We investigate the evolution of porosity and permeability of fractured dunites reacted with CO2-rich solutions in laboratory experiments. The alteration of crack surfaces changes the mechanical and transport properties of the bulk samples. Analysis of three-dimensional microstructural data shows that although precipitation of secondary minerals causes the total porosity of the sample to decrease, an interconnected network of porosity is maintained through channelized dissolution and coupled carbonate precipitation. The observed microstructure appears to be the result of chemo-mechanical coupling, which may provide a mechanism of porosity maintenance without the need to invoke reaction-driven cracking.

A reentrant loop domain in the glutamate carrier EAAT1 participates in substrate binding and translocation.

PubMed

Seal, R P; Amara, S G

1998-12-01

To investigate the structural determinants underlying transport by the glutamate transporter EAAT1, we mutated each of 24 highly conserved residues (P392 to Q415) to cysteine. A majority of these substituted cysteines react with the sulfhydryl-modifying reagent MTSEA, suggesting that they reside in an aqueous environment. The impermeant reagents MTSES and MTSET react with residues at each end of the domain (A395C and A414C), supporting a model that places these residues near the extracellular surface. Substrates and inhibitors block the reaction between MTS derivatives and A395C, and the cosubstrate, sodium, slows reaction of MTSEA with Y405C and E406C. From these results, we propose that this domain forms a reentrant membrane loop at the cell surface and may comprise part of the translocation pore for substrates and cotransported ions.

Onboard hydrogen generation for automobiles

NASA Technical Reports Server (NTRS)

Houseman, J.; Cerini, D. J.

1976-01-01

Problems concerning the use of hydrogen as a fuel for motor vehicles are related to the storage of the hydrogen onboard a vehicle. The feasibility is investigated to use an approach based on onboard hydrogen generation as a means to avoid these storage difficulties. Two major chemical processes can be used to produce hydrogen from liquid hydrocarbons and methanol. In steam reforming, the fuel reacts with water on a catalytic surface to produce a mixture of hydrogen and carbon monoxide. In partial oxidation, the fuel reacts with air, either on a catalytic surface or in a flame front, to yield a mixture of hydrogen and carbon monoxide. There are many trade-offs in onboard hydrogen generation, both in the choice of fuels as well as in the choice of a chemical process. Attention is given to these alternatives, the results of some experimental work in this area, and the combustion of various hydrogen-rich gases in an internal combustion engine.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lisabeth, Harrison; Zhu, Wenlu; Xing, Tiange

Olivine and pyroxene bearing rocks in the oceanic crust react with hydrothermal fluids producing changes in the physical characteristics and behaviors of the altered rocks. Notably, these reactions tend to increase solid volume, reducing pore volume, permeability and available reactive surface area; yet, entirely hydrated and/or carbonated rocks are commonly observed in the field. We investigate the evolution of porosity and permeability of fractured dunites reacted with CO 2-rich solutions in laboratory experiments. The alteration of crack surfaces changes the mechanical and transport properties of the bulk samples. Analysis of three-dimensional microstructural data shows that although precipitation of secondary mineralsmore » causes the total porosity of the sample to decrease, an interconnected network of porosity is maintained through channelized dissolution and coupled carbonate precipitation. Lastly, the observed microstructure appears to be the result of chemo-mechanical coupling, which may provide a mechanism of porosity maintenance without the need to invoke reaction-driven cracking.« less

Dissolution-Assisted Pattern Formation During Olivine Carbonation

DOE PAGES

Lisabeth, Harrison; Zhu, Wenlu; Xing, Tiange; ...

2017-08-31

Olivine and pyroxene bearing rocks in the oceanic crust react with hydrothermal fluids producing changes in the physical characteristics and behaviors of the altered rocks. Notably, these reactions tend to increase solid volume, reducing pore volume, permeability and available reactive surface area; yet, entirely hydrated and/or carbonated rocks are commonly observed in the field. We investigate the evolution of porosity and permeability of fractured dunites reacted with CO 2-rich solutions in laboratory experiments. The alteration of crack surfaces changes the mechanical and transport properties of the bulk samples. Analysis of three-dimensional microstructural data shows that although precipitation of secondary mineralsmore » causes the total porosity of the sample to decrease, an interconnected network of porosity is maintained through channelized dissolution and coupled carbonate precipitation. Lastly, the observed microstructure appears to be the result of chemo-mechanical coupling, which may provide a mechanism of porosity maintenance without the need to invoke reaction-driven cracking.« less

Structural analysis of strontium in human teeth treated with surface pre-reacted glass-ionomer filler eluate by using extended X-ray absorption fine structure analysis.

PubMed

Uo, Motohiro; Wada, Takahiro; Asakura, Kiyotaka

2017-03-31

The bioactive effects of strontium released from surface pre-reacted glass-ionomer (S-PRG) fillers may aid in caries prevention. In this study, the local structure of strontium taken up by teeth was estimated by extended X-ray absorption fine structure analysis. Immersing teeth into S-PRG filler eluate increased the strontium content in enamel and dentin by more than 100 times. The local structure of strontium in enamel and dentin stored in distilled water was the same as that in synthetic strontium-containing hydroxyapatite (SrHAP). Moreover, the local structure of strontium in enamel and dentin after immersion in the S-PRG filler eluate was also similar to that of SrHAP. After immersion in the S-PRG filler eluate, strontium was suggested to be incorporated into the hydroxyapatite (HAP) of enamel and dentin at the calcium site in HAP.

Method for producing high quality thin layer films on substrates

DOEpatents

Strongin, M.; Ruckman, M.; Strongin, D.

1994-04-26

A method for producing high quality, thin layer films of inorganic compounds upon the surface of a substrate is disclosed. The method involves condensing a mixture of preselected molecular precursors on the surface of a substrate and subsequently inducing the formation of reactive species using high energy photon or charged particle irradiation. The reactive species react with one another to produce a film of the desired compound upon the surface of the substrate. 4 figures.

Tryptophan 334 Oxidation in Bovine Cytochrome c Oxidase Subunit I Involves Free Radical Migration

PubMed Central

Lemma-Gray, Patrizia; Weintraub, Susan T.; Carroll, Christopher A.; Musatov, Andrej; Robinson, Neal C.

2007-01-01

A single tryptophan (W334(I)) within the mitochondrial-encoded core subunits of cytochrome c oxidase (CcO) is selectively oxidized when hydrogen peroxide reacts with the binuclear center. W334(I) is converted to hydroxytryptophan as identified by HPLC-ESI/MS/MS analysis of peptides derived from the three SDS-PAGE purified subunits (total sequence coverage of subunits I, II and III was limited to 84%, 66% and 54%, respectively). W334(I) is located on the surface of CcO at the membrane interface. Two other surface tryptophans within nuclear-encoded subunits, W48(IV) and W19(VIIc), are also oxidized when hydrogen peroxide reacts with the binuclear center (Musatov et. al., 2004, Biochemistry 43, 1003–1009). Two aromatic-rich networks of amino acids were identified that link the binuclear center to the three oxidized tryptophans. We propose the following mechanism to explain these results. Electron transfer through the aromatic networks moves the free radicals generated at the binuclear center to the surface-exposed tryptophans, where they produce hydroxytryptophan. PMID:17239857

Chemical deposition methods using supercritical fluid solutions

DOEpatents

Sievers, Robert E.; Hansen, Brian N.

1990-01-01

A method for depositing a film of a desired material on a substrate comprises dissolving at least one reagent in a supercritical fluid comprising at least one solvent. Either the reagent is capable of reacting with or is a precursor of a compound capable of reacting with the solvent to form the desired product, or at least one additional reagent is included in the supercritical solution and is capable of reacting with or is a precursor of a compound capable of reacting with the first reagent or with a compound derived from the first reagent to form the desired material. The supercritical solution is expanded to produce a vapor or aerosol and a chemical reaction is induced in the vapor or aerosol so that a film of the desired material resulting from the chemical reaction is deposited on the substrate surface. In an alternate embodiment, the supercritical solution containing at least one reagent is expanded to produce a vapor or aerosol which is then mixed with a gas containing at least one additional reagent. A chemical reaction is induced in the resulting mixture so that a film of the desired material is deposited.

Novel 2D RuPt core-edge nanocluster catalyst for CO electro-oxidation

NASA Astrophysics Data System (ADS)

Grabow, Lars C.; Yuan, Qiuyi; Doan, Hieu A.; Brankovic, Stanko R.

2015-10-01

A single layer, bi-metallic RuPt catalyst on Au(111) is synthesized using surface limited red-ox replacement of underpotentially deposited Cu and Pb monolayers though a two-step process. The resulting 2D RuPt monolayer nanoclusters have a unique core-edge structure with a Ru core and Pt at the edge along the perimeter. The activity of this catalyst is evaluated using CO monolayer oxidation as the probe reaction. Cyclic voltammetry demonstrates that the 2D RuPt core-edge catalyst morphology is significantly more active than either Pt or Ru monolayer catalysts. Density functional theory calculations in combination with infra-red spectroscopy data point towards oscillating variations (ripples) in the adsorption energy landscape along the radial direction of the Ru core as the origin of the observed behavior. Both, CO and OH experience a thermodynamic driving force for surface migration towards the Ru-Pt interface, where they adsorb most strongly and react rapidly. We propose that the complex interplay between epitaxial strain, ligand and finite size effects is responsible for the formation of the rippled RuPt monolayer cluster, which provides optimal conditions for a quasi-ideal bi-functional mechanism for CO oxidation, in which CO is adsorbed mainly on Pt, and Ru provides OH to the active Pt-Ru interface.

Detailed Studies on Flame Extinction by Inert Particles in Normal- and Micro-gravity

NASA Technical Reports Server (NTRS)

Andac, M. G.; Egolfopoulos, F. N.; Campbell, C. S.

2001-01-01

The combustion of dusty flows has been studied to lesser extent than pure gas phase flows and sprays. Particles can have a strong effect by modifying the dynamic response and detailed structure of flames through the dynamic, thermal, and chemical couplings between the two phases. A rigorous understanding of the dynamics and structure of two-phase flows can be attained in stagnation flow configurations, which have been used by others to study spray combustion as well as reacting dusty flows. In earlier studies on reacting dusty flows, the thermal coupling between the two phases as well as the effect of gravity on the flame response were not considered. However, in Ref. 6, the thermal coupling between chemically inert particles and the gas was addressed in premixed flames. The effects of gravity was also studied showing that it can substantially affect the profiles of the particle velocity, number density, mass flux, and temperature. The results showed a strong dynamic and thermal dependence of reacting dusty flows to particle number density. However, the work was only numerical and limited to twin-flames, stagnation, premixed flames. In Ref. 7 the effects of chemically inert particle clouds on the extinction of strained premixed and non-premixed flames were studied both experimentally and numerically at 1-g. It was shown and explained that large particles can cause more effective flame cooling compared to smaller particles. The effects of flame configuration and particle injection orientation were also addressed. The complexity of the coupling between the various parameters in such flows was demonstrated and it was shown that it was impossible to obtain a simple and still meaningful scaling that captured all the pertinent physics.

Interface Reaction of Nickel-Oxide on Steel.

DTIC Science & Technology

In vacuum or an argon atmosphere, nickel oxide reacts with steel at 600 to 750C to form a surface layer of gamma- NiFe which affords corrosion protection to the steel in air and warm humid conditions. (Author)

Chemical modification of nanocrystal surfaces

DOEpatents

Alivisatos, A. Paul; Owen, Jonathan

2013-05-07

A method is disclosed. The method includes obtaining a precursor nanoparticle comprising a base material and a first ligand attached to the base material, and reacting the precursor nanoparticle with a reactant comprising a silicon bond, thereby removing the first ligand.

Nanolaminate Mirrors With "Piston" Figure-Control Actuators

NASA Technical Reports Server (NTRS)

Lowman, Andrew; Redding, David; Hickey, Gregory; Knight, Jennifer; Moynihan, Philip; Lih, Shyh0Shiuh; Barbee, Troy

2003-01-01

Efforts are under way to develop a special class of thin-shell curved mirrors for high-resolution imaging in visible and infrared light in a variety of terrestrial or extraterrestrial applications. These mirrors can have diameters of the order of a meter and include metallic film reflectors on nanolaminate substrates supported by multiple distributed piezoceramic gpiston h-type actuators for micron-level figure control. Whereas conventional glass mirrors of equivalent size and precision have areal mass densities between 50 and 150 kg/sq m, the nanolaminate mirrors, including not only the reflector/ shell portions but also the actuators and the backing structures needed to react the actuation forces, would have areal mass densities that may approach .5 kg/m2. Moreover, whereas fabrication of a conventional glass mirror of equivalent precision takes several years, the reflector/shell portion of a nanolaminate mirror can be fabricated in less than a week, and its actuation system can be fabricated in 1 to 2 months. The engineering of these mirrors involves a fusion of the technological heritage of multisegmented adaptive optics and deformable mirrors with more recent advances in metallic nanolaminates and in mathematical modeling of the deflections of thin, curved shells in response to displacements by multiple, distributed actuators. Because a nanolaminate shell is of the order of 10 times as strong as an otherwise identical shell made of a single, high-strength, non-nanolaminate metal suitable for mirror use, a nanolaminate mirror can be made very thin (typically between 100 and 150 m from the back of the nanolaminate substrate to the front reflecting surface). The thinness and strength of the nanolaminate are what make it possible to use distributed gpiston h-type actuators for surface figure control with minimal local concentrated distortion (called print-through in the art) at the actuation points.

Analyzing the influence of PEG molecular weight on the separation of PEGylated gold nanoparticles by asymmetric-flow field-flow fractionation.

PubMed

Hansen, Matthew; Smith, Mackensie C; Crist, Rachael M; Clogston, Jeffrey D; McNeil, Scott E

2015-11-01

Polyethylene glycol (PEG) is an important tool for increasing the biocompatibility of nanoparticle therapeutics. Understanding how these potential nanomedicines will react after they have been introduced into the bloodstream is a critical component of the preclinical evaluation process. Hence, it is paramount that better methods for separating, characterizing, and analyzing these complex and polydisperse formulations are developed. We present a method for separating nominal 30-nm gold nanoparticles coated with various molecular weight PEG moieties that uses only phosphate-buffered saline as the mobile phase, without the need for stabilizing surfactants. The optimized asymmetric-flow field-flow fractionation technique using in-line multiangle light scattering, dynamic light scattering, refractive index, and UV-vis detectors allowed successful separation and detection of a mixture of nanoparticles coated with 2-, 5-, 10-, and 20-kDa PEG. The particles coated with the larger PEG species (10 and 20 kDa) were eluted at times significantly earlier than predicted by field-flow fractionation theory. This was attributed to a lower-density PEG shell for the higher molecular weight PEGylated nanoparticles, which allows a more fluid PEG surface that can be greater influenced by external forces. Hence, the apparent particle hydrodynamic size may fluctuate significantly depending on the overall density of the stabilizing surface coating when an external force is applied. This has considerable implications for PEGylated nanoparticles intended for in vivo application, as nanoparticle size is important for determining circulation times, accumulation sites, and routes of excretion, and highlights the importance and value of the use of secondary size detectors when one is working with complex samples in asymmetric-flow field-flow fractionation.

METHOD OF FORMING TANTALUM SILICIDE ON TANTALUM SURFACES

DOEpatents

Bowman, M.G.; Krikorian, N.H.

1961-10-01

A method is described for forming a non-corrosive silicide coating on tantalum. The coating is made through the heating of trirhenium silicides in contact with the tantalum object to approximately 1400 deg C at which temperature trirhenium silicide decomposes into rhenium and gaseous silicons. The silicon vapor reacts with the tantalum surface to form a tantalum silicide layer approximately 10 microns thick. (AEC)

Method for preparing hydride configurations and reactive metal surfaces

DOEpatents

Silver, Gary L.

1988-08-16

A method for preparing highly hydrogen-reactive surfaces on metals which normally require substantial heating, high pressures, or an extended induction period, which involves pretreatment of said surfaces with either a non-oxidizing acid or hydrogen gas to form a hydrogen-bearing coating on said surfaces, and subsequently heating said coated metal in the absence of moisture and oxygen for a period sufficient to decompose said coating and cooling said metal to room temperature. Surfaces so treated will react almost instantaneously with hydrogen gas at room temperature and low pressure. The method is particularly applicable to uranium, thorium, and lanthanide metals.

Engineering surfaces for bioconjugation: developing strategies and quantifying the extent of the reactions.

PubMed

Gauvreau, Virginie; Chevallier, Pascale; Vallières, Karine; Petitclerc, Eric; Gaudreault, René C; Laroche, Gaétan

2004-01-01

This study presents two-step and multistep reactions for modifying the surface of plasma-functionalized poly(tetrafluoroethylene) (PTFE) surfaces for subsequent conjugation of biologically relevant molecules. First, PTFE films were treated by a radiofrequency glow discharge (RFGD) ammonia plasma to introduce amino groups on the fluoropolymer surface. This plasma treatment is well optimized and allows the incorporation of a relative surface concentration of approximately 2-3.5% of amino groups, as assessed by chemical derivatization followed by X-ray photoelectron spectroscopy (XPS). In a second step, these amino groups were further reacted with various chemical reagents to provide the surface with chemical functionalities such as maleimides, carboxylic acids, acetals, aldehydes, and thiols, that could be used later on to conjugate a wide variety of biologically relevant molecules such as proteins, DNA, drugs, etc. In the present study, glutaric and cis-aconitic anhydrides were evaluated for their capability to provide carboxylic functions to the PTFE plasma-treated surface. Bromoacetaldehyde diethylacetal was reacted with the aminated PTFE surface, providing a diethylacetal function, which is a latent form of aldehyde functionality. Reactions with cross-linkers such as sulfo-succinimidyl derivatives (sulfo-SMCC, sulfo-SMPB) were evaluated to provide a highly reactive maleimide function suitable for further chemical reactions with thiolated molecules. Traut reagent (2-iminothiolane) was also conjugated to introduce a thiol group onto the fluoropolymer surface. PTFE-modified surfaces were analyzed by XPS with a particular attention to quantify the extent of the reactions that occurred on the polymer. Finally, surface immobilization of fibronectin performed using either glutaric anhydride or sulfo-SMPB activators demonstrated the importance of selecting the appropriate conjugation strategy to retain the protein biological activity.

Interrelationships among Grain Size, Surface Composition, Air Stability, and Interfacial Resistance of Al-Substituted Li7La3Zr2O12 Solid Electrolytes.

PubMed

Cheng, Lei; Wu, Cheng Hao; Jarry, Angelique; Chen, Wei; Ye, Yifan; Zhu, Junfa; Kostecki, Robert; Persson, Kristin; Guo, Jinghua; Salmeron, Miquel; Chen, Guoying; Doeff, Marca

2015-08-19

The interfacial resistances of symmetrical lithium cells containing Al-substituted Li7La3Zr2O12 (LLZO) solid electrolytes are sensitive to their microstructures and histories of exposure to air. Air exposure of LLZO samples with large grain sizes (∼150 μm) results in dramatically increased interfacial impedances in cells containing them, compared to those with pristine large-grained samples. In contrast, a much smaller difference is seen between cells with small-grained (∼20 μm) pristine and air-exposed LLZO samples. A combination of soft X-ray absorption (sXAS) and Raman spectroscopy, with probing depths ranging from nanometer to micrometer scales, revealed that the small-grained LLZO pellets are more air-stable than large-grained ones, forming far less surface Li2CO3 under both short- and long-term exposure conditions. Surface sensitive X-ray photoelectron spectroscopy (XPS) indicates that the better chemical stability of the small-grained LLZO is related to differences in the distribution of Al and Li at sample surfaces. Density functional theory calculations show that LLZO can react via two different pathways to form Li2CO3. The first, more rapid, pathway involves a reaction with moisture in air to form LiOH, which subsequently absorbs CO2 to form Li2CO3. The second, slower, pathway involves direct reaction with CO2 and is favored when surface lithium contents are lower, as with the small-grained samples. These observations have important implications for the operation of solid-state lithium batteries containing LLZO because the results suggest that the interfacial impedances of these devices is critically dependent upon specific characteristics of the solid electrolyte and how it is prepared.

Chemical, corrosion and topographical analysis of stainless steel implants after different implantation periods.

PubMed

Chrzanowski, Wojciech; Armitage, David Andrew; Knowles, Jonathan Campbell; Szade, Jacek; Korlacki, Wojciech; Marciniak, Jan

2008-07-01

The aim of this work is to examine the corrosion properties, chemical composition, and material-implant interaction after different periods of implantation of plates used to correct funnel chest. The implants are made of 316L stainless steel. Examinations are carried out on three implants: new (nonimplanted) and two implanted for 29 and 35 months. The corrosion study reveals that in the potential range that could occur in the physiological condition the new bar has the lowest current density and the highest corrosion potential. This indicates that the new plate has the highest corrosion resistance and the corrosion resistance could be reduced during implantation by the instruments used during the operation. XPS analysis reveals changes in the surface chemistry. The longer the implantation time the more carbon and oxygen are observed and only trace of elements such as Cr, Mo are detected indicating that surface is covered by an organic layer. On some parts of the implants whitish tissue is observed: the thickness of which increased with the time of implantation. This tissue was identified as an organic layer; mainly attached to the surface on the areas close to where the implant was bent to attain anatomical fit and thus where the implant has higher surface roughness. The study indicates that the chest plates are impaired by the implantation procedure and contact with biological environment. The organic layer on the surface shows that the implant did not stay passive but some reactions at the tissue-implant interface occurred. These reactions should be seen as positive, as it indicates that the implants were accepted by the tissues. Nevertheless, if the implants react, they may continue to release chromium, nickel, and other harmful ions long term as indicated by lower corrosion resistance of the implants following implantation.

Effects of radiative heat transfer on the turbulence structure in inert and reacting mixing layers

NASA Astrophysics Data System (ADS)

Ghosh, Somnath; Friedrich, Rainer

2015-05-01

We use large-eddy simulation to study the interaction between turbulence and radiative heat transfer in low-speed inert and reacting plane temporal mixing layers. An explicit filtering scheme based on approximate deconvolution is applied to treat the closure problem arising from quadratic nonlinearities of the filtered transport equations. In the reacting case, the working fluid is a mixture of ideal gases where the low-speed stream consists of hydrogen and nitrogen and the high-speed stream consists of oxygen and nitrogen. Both streams are premixed in a way that the free-stream densities are the same and the stoichiometric mixture fraction is 0.3. The filtered heat release term is modelled using equilibrium chemistry. In the inert case, the low-speed stream consists of nitrogen at a temperature of 1000 K and the highspeed stream is pure water vapour of 2000 K, when radiation is turned off. Simulations assuming the gas mixtures as gray gases with artificially increased Planck mean absorption coefficients are performed in which the large-eddy simulation code and the radiation code PRISSMA are fully coupled. In both cases, radiative heat transfer is found to clearly affect fluctuations of thermodynamic variables, Reynolds stresses, and Reynolds stress budget terms like pressure-strain correlations. Source terms in the transport equation for the variance of temperature are used to explain the decrease of this variance in the reacting case and its increase in the inert case.

Effects of radiative heat transfer on the turbulence structure in inert and reacting mixing layers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghosh, Somnath, E-mail: sghosh@aero.iitkgp.ernet.in; Friedrich, Rainer

2015-05-15

We use large-eddy simulation to study the interaction between turbulence and radiative heat transfer in low-speed inert and reacting plane temporal mixing layers. An explicit filtering scheme based on approximate deconvolution is applied to treat the closure problem arising from quadratic nonlinearities of the filtered transport equations. In the reacting case, the working fluid is a mixture of ideal gases where the low-speed stream consists of hydrogen and nitrogen and the high-speed stream consists of oxygen and nitrogen. Both streams are premixed in a way that the free-stream densities are the same and the stoichiometric mixture fraction is 0.3. Themore » filtered heat release term is modelled using equilibrium chemistry. In the inert case, the low-speed stream consists of nitrogen at a temperature of 1000 K and the highspeed stream is pure water vapour of 2000 K, when radiation is turned off. Simulations assuming the gas mixtures as gray gases with artificially increased Planck mean absorption coefficients are performed in which the large-eddy simulation code and the radiation code PRISSMA are fully coupled. In both cases, radiative heat transfer is found to clearly affect fluctuations of thermodynamic variables, Reynolds stresses, and Reynolds stress budget terms like pressure-strain correlations. Source terms in the transport equation for the variance of temperature are used to explain the decrease of this variance in the reacting case and its increase in the inert case.« less

Effects of observers using different methods upon the total population estimates of two resident island birds

Treesearch

Sheila Conant; Mark S. Collins; C. John Ralph

1981-01-01

During a 5-week study of the Nihoa Millerbird and Nihoa Finch, we censused birds using these techniques: two line transect methods, a variable-distance circular plot method, and spot-mapping of territories (millerbirds only). Densities derived from these methods varied greatly. Due to differences in behavior, it appeared that the two species reacted differently to the...

CONTINUOUS PROCESS FOR THE CONVERSION OF UF$sub 6$ TO UF$sub 4$

DOEpatents

Smiley, S.H.; Brater, D.C.; Nimmo, R.H.

1959-10-01

A method is presented for reducing UF/sub 6/ to UF/sub 6/ with hydrogen. A preheated mixture of UF/sub 6/ and fluorine is contacted with a stoichiometric excess of preheated hydrogen in a reaction chamber thereby producing UF/sub 6/. The UF/sub 6/ reacts quantitatively and the UF/sub 6/ produced is of high purity and high density.

4D XMT of Reaction in Carbonates: Reactive Transport Dynamics at Multiples Scales

NASA Astrophysics Data System (ADS)

Menke, H. P.; Reynolds, C. A.; Andrew, M. G.; Nunes, J. P. P.; Bijeljic, B.; Blunt, M. J.

2016-12-01

Upscaling pore scale rock-fluid interaction processes for predictive modelling poses a challenge to underground carbon storage. We have completed experiments and flow modelling to investigate the impact of pore-space heterogeneity and scale on the dissolution of two limestones at both the mm and cm scales. Two samples were reacted with reservoir condition CO2-saturated brine at both scales and scanned dynamically as dissolution took place. First, 1-cm long 4-mm diameter micro cores were scanned during reactive flow at a 4-μm resolution between 4 and 40 times using 4D X-ray micro-tomography over the course of 1.5 hours using a laboratory μ-CT. Second, 3.8-cm diameter, 8-cm long macro cores were reacted at the same conditions inside a reservoir condition flow rig and imaged using a medical CT scanner. Each sample was imaged 10 times over the course of 1.5 hours at a 250 x 250 x 500-μm resolution. The reacted macro cores were then scanned inside a μ-CT at a 27-μm resolution to assess the alteration in pore-scale reaction-induced heterogeneity. It was found that both limestones showed channel formation at the pore-scale and progressive high porosity pathway dissolution at the core-scale with the more heterogeneous rock having dissolution progressing along direction of flow more quickly. Additionally, upon analysis of the high-resolution macro core images it was found that the dissolution pathways contained a distinct microstructure that was not visible at the resolution of the medical CT, where the reactive fluid had not completely dissolved the internal pore-structure. Flow was modelled in connected pathways, the flow streamlines were traced and streamline density for each voxel was calculated. It was found that the streamline density was highest in the most well-connected pathways and that density increased with increasing heterogeneity as the number of connected pathways decreased and flow was consolidated along fewer pathways. This work represents the first study of scale dependency using reservoir condition 4D X-ray tomography and provides insight into the mechanisms that control local reaction rates at multiple scales.

A computer model for one-dimensional mass and energy transport in and around chemically reacting particles, including complex gas-phase chemistry, multicomponent molecular diffusion, surface evaporation, and heterogeneous reaction

NASA Technical Reports Server (NTRS)

Cho, S. Y.; Yetter, R. A.; Dryer, F. L.

1992-01-01

Various chemically reacting flow problems highlighting chemical and physical fundamentals rather than flow geometry are presently investigated by means of a comprehensive mathematical model that incorporates multicomponent molecular diffusion, complex chemistry, and heterogeneous processes, in the interest of obtaining sensitivity-related information. The sensitivity equations were decoupled from those of the model, and then integrated one time-step behind the integration of the model equations, and analytical Jacobian matrices were applied to improve the accuracy of sensitivity coefficients that are calculated together with model solutions.

Calculation of three-dimensional compressible laminar and turbulent boundary flows. Three-dimensional compressible boundary layers of reacting gases over realistic configurations

NASA Technical Reports Server (NTRS)

Kendall, R. M.; Bonnett, W. S.; Nardo, C. T.; Abbett, M. J.

1975-01-01

A three-dimensional boundary-layer code was developed for particular application to realistic hypersonic aircraft. It is very general and can be applied to a wide variety of boundary-layer flows. Laminar, transitional, and fully turbulent flows of compressible, reacting gases are efficiently calculated by use of the code. A body-oriented orthogonal coordinate system is used for the calculation and the user has complete freedom in specifying the coordinate system within the restrictions that one coordinate must be normal to the surface and the three coordinates must be mutually orthogonal.

Evaluation of Ohio River NOM Variability and NOM Concentration vs. Reconstitution

EPA Science Inventory

Surface water contains natural organic matter (NOM) which reacts with disinfectants creating disinfection byproducts (DBPs), some of which are USEPA regulated contaminants. Characterizing NOM can provide important insight on DBP formation and water treatment process adaptation t...

Bank accretion and the development of vegetated depositional surfaces along modified alluvial channels

USGS Publications Warehouse

Hupp, C.R.; Simon, A.

1991-01-01

This paper describes the recovery of stable bank form and development of vegetated depositional surfaces along the banks of channelized West Tennessee streams. Most perennial streams in West Tennessee were straightened and dredged since the turn of the century. Patterns of fluvial ecological responses to channelization have previously been described by a six-stage model. Dendrogeomorphic (tree-ring) techniques allowed the determination of location, timing, amount, and rate of bank-sediment deposition. Channel cross sections and ecological analyses made at 101 locations along 12 streams, encompassing bends and straight reaches, show that channel and bank processes initially react vertically to channelization through downcutting. A depositional surface forms on banks once bed-degradation and heightened bank mass wasting processes have eased or slowed. The formation of this depositional surface marks the beginning of bank recovery from channelization. Dominating lateral processes, characteristic of stable or natural channels, return during the formation and expansion of the depositional surface, suggesting a relation with thalweg deflection, point-bar development, and meanderloop extension. Characteristic woody riparian vegetation begins to grow as this depositional surface develops and becomes part of the process and form of restabilizing banks. The depositional surface initially forms low on the bank and tends to maintain a slope of about 24??. Mean accretion rates ranges from 5.9 cm/yr on inside bends to 0 cm/yr on most outside bends; straight reaches have a mean-accretion rate of 4.2 cm/yr. The relatively stable, convex upward, depositional surface expands and ultimately attaches to the flood plain. The time required for the recovery process to reach equilibrium averaged about 50 years. Indicative pioneer speccies of woody riparian vegetation include black willow, river birch, silver maple, and boxelder. Stem densities generally decrease with time after and initial flush of about 160 stems per 100 m2. Together bank accretion and vegetative regrowth appear to be the most important environmental processes involved in channel bank recovery from channelization or rejuvenation. ?? 1991.

Study on improvement of durability for reinforced concrete by surface-painting migrating corrosion inhibitor and engineering application

NASA Astrophysics Data System (ADS)

Song, Ning; WANG, Zixiao; LIU, Zhiyong; Zhou, Jiyuan; Zheng, Duo

2017-01-01

The corrosion currents of steel bar in concrete with three W/B and four chloride contents after surface-painting two migrating corrosion inhibitors (PCI-2015 and MCI-A) 14d to 150d in atmospheric condition were measured. The results showed that the corrosion current density (I corr) of steel bar reduced to 0.1 μA.cm-2 from the initial highest 3.833 μA.cm-2 (W/B=0.65, NaCl-1%) after surface-painting PCI-2015 14 d, and the I corr was still lower than 0.1 μA.cm-2 until 150d. The compressive strength and chloride migration coefficient of concrete specimens were tested. The possible reasons of the mechanisms of durability improvement for reinforced concrete by applying PCI-2015 inhibitor were PCI-2015 may be reacted with calcium hydroxide in cement concrete and lots of inhibitor particles may be adsorbed on the active sites first and then a stable protective layer may be formed. The I corr of steel bars in a hydraulic aqueduct concrete structure after painting PCI-2015, MCI-A (the United States) and MCI-B (Europe) during 6 months was monitored by Gecor 8 tester. The results showed that the average values of I corr of steel bars after painting the PCI-2015 150d fulfilled the specification requirements in “Design code for concrete structure strengthening (E.3) ”(GB 50367-2013).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aden, Bethany; Kite, Camille M.; Hopkins, Benjamin W.

Designing thin films or surface scaffolds with an appropriate display of chemical functionality is useful for biomedical applications, sensing platforms, adhesives, and barrier coatings. Relationships between the structural characteristics of model thin films based on reactive poly(2-vinyl-4,4-dimethyl azlactone) (PVDMA) brushes and the amount and distribution of primary amines used to chemically functionalize these layers in situ are quantitatively detailed via neutron reflectometry and compared with results from ellipsometry. After functionalization, the PVDMA brush thickness increases as a result of the primary amines reacting with the azlactone rings. Both techniques show that the extent of functionalization by small-molecule amines depends onmore » the size of the amine, the grafting density of brush chains, and their molecular weight. However, constrained analysis of neutron reflectivity data predicated on that technique’s sensitivity to isotopic substitution and its ability to resolve structure at the nanoscale shows that the extent of functionalization is not accurately represented by the average extent of functionalization determined from ellipsometric thickness: reactive modification is not uniform, even in modestly dense brushes, except when the penetrant is small. In addition, there appears to be a loss of PVDMA chains during functionalization, attributed to chain scission resulting from additional stretching brought about by functionalization. In conclusion, these findings provide unprecedented insight into the alteration of surface properties by reactive modification and broadly support efforts to produce tailored surfaces in which properties such as friction, colloidal stability, adhesion, wettability, and biocompatibility can be modulated in situ by chemical modification.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aden, Bethany; Kite, Camille M.; Hopkins, Benjamin W.

Designing thin films or surface scaffolds with an appropriate display of chemical functionality is useful for biomedical applications, sensing platforms, adhesives, and barrier coatings. Relationships between the structural characteristics of model thin films based on reactive poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) brushes and the amount and distribution of primary amines used to chemically functionalize the layer in situ are quantitatively detailed via neutron reflectometry and compared with results from ellipsometry. After functionalization, the PVDMA brush thickness increases as a result of the primary amines reacting with the azlactone rings. Both techniques show that the extent of functionalization by small-molecule amines depends on themore » size of the amine, the grafting density of brush chains and their molecular weight. However, constrained analysis of neutron reflectivity data predicated on that technique’s sensitivity to isotopic substitution and its ability to resolve structure at the nanoscale, shows that the extent of functionalization is not accurately represented by the average extent of functionalization determined from ellipsometric thickness: reactive modification is not uniform, even in modestly dense brushes, except when the penetrant is small. Additionally, there appears to be a loss of PVDMA chains during functionalization, attributed to chain scission resulting from additional stretching brought about by functionalization. These findings provide unprecedented insight into the alteration of surface properties by reactive modification and broadly support efforts to produce tailored surfaces in which properties such as friction, colloidal stability, adhesion, wettability, and biocompatibility can be modulated in situ by chemical modification.« less

Internal density waves of shock type induced by chemoconvection in miscible reacting liquids

NASA Astrophysics Data System (ADS)

Bratsun, D. A.

2017-10-01

A theoretical explanation of the phenomenon of spontaneous emergence of density waves experimentally observed recently in bilayered systems of miscible liquids placed in a narrow vertical gap of the Hele-Shaw cell in the gravitational field is provided. Upper and lower layers represent aqueous solutions of acids and bases, respectively, whose contact leads to the beginning of a neutralization reaction. The process is accompanied by a strong dependence of the reagent's diffusion coefficients on their concentrations, giving rise to the generation of local density pockets, in which convection develops. The cavities collapse under certain conditions, causing a density jump, which moves faster than typical perturbations in a medium and takes the form of a shock wave. A mathematical model of the phenomenon is proposed, which can be formally reduced to equations of motion of a compressible gas under certain assumptions. Numerical calculations are given and compared with the experimental data.

Candida krusei form mycelia along agar surfaces towards each other and other Candida species.

PubMed

Fleischmann, Jacob; Broeckling, Corey D; Lyons, Sarah

2017-03-11

Candida krusei has been known to exhibit communal interactions such as pellicle formation and crawling out of nutritional broth. We noticed another possible interaction on agar surfaces, where C. krusei yeast cells formed mycelia along agar surfaces toward each other. We report here the results of experiments to study this interaction. When C.krusei yeast cells are plated in parallel streaks, they form mycelia along agar surfaces toward other yeasts. They also detect the presence of Candida albicans and Candida glabrata across agar surfaces, while the latter two react neither to their own kind, nor to C. krusei. Secreted molecule(s) are likely involved as C.krusei does not react to heat killed C. krusei. Timing and rate of mycelia formation across distances suggests that mycelia start forming when a secreted molecule(s) on agar surface reaches a certain concentration. We detected farnesol, tyrosol and tryptophol molecules that may be involved with mycelial formation, on the agar surfaces between yeast streaks. Unexpectedly the amounts detected between streaks were significantly higher than would have expected from additive amounts of two streaks. All three Candida species secreted these molecules. When tested on agar surface however, none of these molecules individually or combined induced mycelia formation by C. krusei. Our data confirms another communal interaction by C. krusei, manifested by formation of mycelia by yeast cells toward their own kind and other yeasts on agar surfaces. We detected secretion of farnesol, tyrosol and tryptophol by C. krusei but none of these molecules induced this activity on agar surface making it unlikely that they are the ones utilized by this yeast for this activity.

Preparation and properties of porous microspheres made from borate glass.

PubMed

Conzone, Samuel D; Day, Delbert E

2009-02-01

Dysprosium lithium-borate glass microspheres and particles, ranging from 45 to 150 microm in diameter, were reacted with a 0.25 M phosphate solution at 37 degrees C, whose pH was either 3 or 8.8. The glass reacted nonuniformly and was converted into a porous, amorphous, hydrated, dysprosium phosphate reaction product. The amorphous product had the same volume and shape (pseudomorphic) as the unreacted glass, and could be dried without cracking. After heating at 300 degrees C for 1 h, the amorphous reaction product had a specific surface area of approximately 200 m(2)/g, a pore size of approximately 30 nm, and nominal crushing strength of approximately 10 MPa. When the reaction product was heated to 600 degrees C for 15 min, the specific surface area decreased to approximately 90 m(2)/g and the nominal crushing strength increased to 35 MPa. Heating above 615 degrees C converted the amorphous dysprosium phosphate product into crystalline DyPO(4), which contained open porosity until heated above 800 degrees C for 15 min. Highly porous materials of different chemical composition can be prepared by chemically reacting a borate-based glass with an aqueous solution at low-temperature (<100 degrees C). These highly porous materials are easy to process, and are considered candidates for controlled drug delivery, catalysis, chromatographic separation, filtration, and as bioactive materials.

V/sub 3/Ga wire fabricated by the modified jelly roll technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gubser, D.U.; Francavilla, T.L.; Pande, C.S.

V/sub 3/Ga wire has been fabricated by the modified jelly roll technique for the first time. Critical current densities in magnetic fields to 22 T, critical magnetic fields, and superconducting transition temperatures are reported for this wire as a function of reaction temperature for forming the interfacial V/sub 3/Ga layer. Superconducting properties of the reacted wire are optimized for reaction temperatures between 550--580 /sup 0/C. With a reaction temperature of 580 /sup 0/C, the overall (noncopper) current density of the wire is over 10/sup 4/ amp/cm/sup 2/ at 19 T.

Prediction of heat release effects on a mixing layer

NASA Technical Reports Server (NTRS)

Farshchi, M.

1986-01-01

A fully second-order closure model for turbulent reacting flows is suggested based on Favre statistics. For diffusion flames the local thermodynamic state is related to single conserved scalar. The properties of pressure fluctuations are analyzed for turbulent flows with fluctuating density. Closure models for pressure correlations are discussed and modeled transport equations for Reynolds stresses, turbulent kinetic energy dissipation, density-velocity correlations, scalar moments and dissipation are presented and solved, together with the mean equations for momentum and mixture fraction. Solutions of these equations are compared with the experimental data for high heat release free mixing layers of fluorine and hydrogen in a nitrogen diluent.

EEG sleep activities react topographically different to GABAergic sleep modulation by flunitrazepam: relationship to regional distribution of benzodiazepine receptor subtypes?

PubMed

Scheuler, W

Spectral analysis was performed to study the response of various EEG sleep activities to a modification of GABAergic sleep regulation by flunitrazepam. We observed sleep stage- and sleep cycle-dependent differences in the topographic distribution of the reactions. An increase in power density was found in the frontal regions for the alpha 2 and sigma 1 frequency band whereas a decrease in power density was emphasized in the posterior regions for the delta and alpha 1 frequency band. These topographic differences might be related to the regional distribution of benzodiazepine receptor subtypes.

Enhanced carbon monoxide utilization in methanation process

DOEpatents

Elek, Louis F.; Frost, Albert C.

1984-01-01

Carbon monoxide - containing gas streams are passed over a catalyst to deposit a surface layer of active surface carbon thereon essentially without the formation of inactive coke. The active carbon is subsequently reacted with steam or hydrogen to form methane. Surprisingly, hydrogen and water vapor present in the feed gas do not adversely affect CO utilization significantly, and such hydrogen actually results in a significant increase in CO utilization.

Influence of Surface Coating on Metal Ion Release: Evaluation in Patients With Metal Allergy.

PubMed

Thomas, Peter; Weik, Thomas; Roider, Gabriele; Summer, Burkhard; Thomsen, Marc

2016-05-01

Nickel, chromium, and cobalt in stainless steel and Cobalt-chrome-molybdenum (CoCrMo) alloys may induce allergy. The objectives of this study were to evaluate surface coating regarding ion release, patch test reactivity, and arthroplasty performance. Materials and methods included patch test in 31 patients with metal allergy and 30 patients with no allergy to stainless steel and CoCrMo disks that are uncoated or coated by titanium nitride/zirconium nitride (TiN/ZrN). Assessment include atomic absorption spectrometry of released nickel, cobalt, and chromium from the disks after exposure to distilled water, artificial sweat and culture medium. Results showed that both coatings reduced the nickel and chromium release from stainless steel and CoCrMo disks and mostly the cobalt release from the disks (maximally 11.755 µg/cm(2)/5 d to 1.624 by Ti-N and to 0.442 by ZrN). Six of the 31 patients with metal allergy reacted to uncoated disks, but none reacted to the coated disks. The current authors report on exemplary patients with metal allergy who had symptom relief by revision with surface-coated arthroplasty. The authors concluded that the surface coating may prevent cutaneous and peri-implant allergic reactions. [Orthopedics. 2016; 39(3):S24-S30.]. Copyright 2016, SLACK Incorporated.

Reacting Flow in the Entrance to a Channel with Surface and Gas-Phase Kinetics

NASA Astrophysics Data System (ADS)

Mikolaitis, David; Griffen, Patrick

2006-11-01

In many catalytic reactors the conversion process is most intense at the very beginning of the channel where the flow is not yet fully developed; hence there will be important interactions between the developing flow field and reaction. To study this problem we have written an object-oriented code for the analysis of reacting flow in the entrance of a channel where both surface reaction and gas-phase reaction are modeled with detailed kinetics. Fluid mechanical momentum and energy equations are modeled by parabolic ``boundary layer''-type equations where streamwise gradient terms are small and the pressure is constant in the transverse direction. Transport properties are modeled with mixture-averaging and the chemical kinetic sources terms are evaluated using Cantera. Numerical integration is done with Matlab using the function pdepe. Calculations were completed using mixtures of methane and air flowing through a channel with platinum walls held at a fixed temperature. GRI-Mech 3.0 was used to describe the gas-phase chemistry and Deutchmann's methane-air-platinum model was used for the surface chemistry. Ignition in the gas phase is predicted for high enough wall temperatures. A hot spot forms away from the walls just before ignition that is fed by radicals produced at the surface.

Effect of Pb2+ ions on ilmenite flotation and adsorption of benzohydroxamic acid as a collector

NASA Astrophysics Data System (ADS)

Xu, Longhua; Tian, Jia; Wu, Houqin; Lu, Zhongyuan; Yang, Yaohui; Sun, Wei; Hu, Yuehua

2017-12-01

The effects of Pb2+ ions on ilmenite flotation and adsorption of benzohydroxamic acid (BHA) as a collector were investigated using microflotation tests, zeta potential measurements, adsorption analysis, Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The microflotation results indicate that the addition of Pb2+ significantly improves the recovery of ilmenite using BHA as a collector. A maximum recovery of 88.46% is obtained at pH 8.12 in the presence of Pb2+; a maximum recovery of 45% is obtained at the same pH using BHA alone. At pHs below 8.0, lead nitrate are mainly present in the solution as Pb2+ and PbOH+, while at pHs above 8.0, the predominant components are Pb(OH)2(s) and Pb(OH)3-. The adsorption of these lead species influences the zeta potential of ilmenite and the number of activated sites on the ilmenite surface. FTIR and XPS analyses reveal that lead species and BHA react with the metal sites on the ilmenite surface. The lead species in solution are either adsorbed onto the ilmenite surface, which increases the surface activity of ilmenite, or react with BHA in solution to form complexes of lead and BHA.

Composite sensor membrane

DOEpatents

Majumdar, Arun [Orinda, CA; Satyanarayana, Srinath [Berkeley, CA; Yue, Min [Albany, CA

2008-03-18

A sensor may include a membrane to deflect in response to a change in surface stress, where a layer on the membrane is to couple one or more probe molecules with the membrane. The membrane may deflect when a target molecule reacts with one or more probe molecules.

Characterizing Ohio River NOM Variability and Reconstituted-Lyophilized NOM as a Source Surrogate

EPA Science Inventory

Surface water contains natural organic matter (NOM) that reacts with disinfectants creating disinfection byproducts (DBPs), some of which are USEPA regulated contaminants. Characterizing NOM can provide insight with respect to DBP formation and water treatment process adaptation...

Direct formation of (CH sub 3 ) sub 2 HSiCl from silicon and CH sub 3 Cl

DOE Office of Scientific and Technical Information (OSTI.GOV)

Magrini, K.A.; Falconer, J.L.; Koel, B.E.

1989-07-13

A Cu-catalyzed reaction procedure was found for the selective formation of dimethylchlorosilane ((CH{sub 3}){sub 2}HSiCl) from the direct reaction of CH{sub 3}Cl with solid Si. The new procedure is a two-step process. A Cu/Si sample is prepared by evaporating Cu onto clean polycrystalline Si under ultrahigh vacuum, and the Cu/Si surface is first activated by exposure to 10% HSiCl{sub 3}/CH{sub 3}Cl at 598 K. After the HSiCl{sub 3}CH{sub 3}Cl mixture is evacuated from the reactor, the activated Cu/Si surface is reacted in fresh CH{sub 3}Cl. For low surface concentrations of Cu, the partially hydrogenated silane, (CH{sub 3}){sub 2}HSiCl, is selectivelymore » produced. Trichlorosilane was also found to activate polycrystalline Si (in the absence of Cu) for production of highly chlorinated methylchlorosilanes at a much higher rate than on the Cu/Si surface but with poor selectively to (CH{sub 3}){sub 2}HSiCl. All reactions are carried out at atmospheric pressure in a reactor that is attached to an ultrahigh-vacuum chamber. This allows surface analysis of Auger electron spectroscopy, which detected SiCl{sub x} on reacted surfaces. These SiCl{sub x} sites, which appear necessary for methylchlorosilane formation, are apparently formed during activation by HSiCl{sub 3}.« less

Plasmodium vivax: a monoclonal antibody recognizes a circumsporozoite protein precursor on the sporozoite surface.

PubMed

Gonzalez-Ceron, L; Rodriguez, M H; Wirtz, R A; Sina, B J; Palomeque, O L; Nettel, J A; Tsutsumi, V

1998-11-01

The major surface circumsporozoite (CS) proteins are known to play a role in malaria sporozoite development and invasion of invertebrate and vertebrate host cells. Plasmodium vivax CS protein processing during mosquito midgut oocyst and salivary gland sporozoite development was studied using monoclonal antibodies which recognize different CS protein epitopes. Monoclonal antibodies which react with the CS amino acid repeat sequences by ELISA recognized a 50-kDa precursor protein in immature oocyst and additional 47- and 42-kDa proteins in older oocysts. A 42-kDa CS protein was detected after initial sporozoite invasion of mosquito salivary glands and an additional 50-kDa precursor CS protein observed later in infected salivary glands. These data confirm previous results with other Plasmodium species, in which more CS protein precursors were detected in oocysts than in salivary gland sporozoites. A monoclonal antibody (PvPCS) was characterized which reacts with an epitope found only in the 50-kDa precursor CS protein. PvPCS reacted with all P. vivax sporozoite strains tested by indirect immunofluorescent assay, homogeneously staining the sporozoite periphery with much lower intensity than that produced by anti-CS repeat antibodies. Immunoelectron microscopy using PvPCS showed that the CS protein precursor was associated with peripheral cytoplasmic vacuoles and membranes of sporoblast and budding sporozoites in development oocysts. In salivary gland sporozoites, the CS protein precursor was primarily associated with micronemes and sporozoite membranes. Our results suggest that the 50-kDa CS protein precursor is synthesized intracellularly and secreted on the membrane surface, where it is proteolytically processed to form the 42-kDa mature CS protein. These data indicate that differences in CS protein processing in oocyst and salivary gland sporozoites development may occur. Copyright 1998 Academic Press.

Surface Structure Dependence of SO 2 Interaction with Ceria Nanocrystals with Well-defined Surface Facets

DOE PAGES

Tumuluri, Uma; Li, Meijun; Cook, Brandon G.; ...

2015-12-02

The effects of the surface structure of ceria (CeO 2) on the nature, strength, and amount of species resulting from SO 2 adsorption were studied using in situ IR and Raman spectroscopies coupled with mass spectrometry, along with first-principles calculations based on density functional theory (DFT). CeO 2 nanocrystals with different morphologies, namely, rods (representing a defective structure), cubes (100 facet), and octahedra (111 facet), were used to represent different CeO 2 surface structures. IR and Raman spectroscopic studies showed that the structure and binding strength of adsorbed species from SO 2 depend on the shape of the CeO 2more » nanocrystals. SO 2 adsorbs mainly as surface sulfites and sulfates at room temperature on CeO 2 rods, cubes, and octahedra that were either oxidatively or reductively pretreated. The formation of sulfites is more evident on CeO 2 octahedra, whereas surface sulfates are more prominent on CeO 2 rods and cubes. This is explained by the increasing reducibility of the surface oxygen in the order octahedra < cubes < rods. Bulk sulfites are also formed during SO 2 adsorption on reduced CeO 2 rods. The formation of surface sulfites and sulfates on CeO 2 cubes is in good agreement with our DFT results of SO 2 interactions with the CeO 2(100) surface. CeO 2 rods desorb SO2 at higher temperatures than cubes and octahedra nanocrystals, but bulk sulfates are formed on CeO 2 rods and cubes after high-temperature desorption whereas only some surface sulfates/sulfites are left on octahedra. This difference is rationalized by the fact that CeO 2 rods have the highest surface basicity and largest amount of defects among the three nanocrystals, so they bind and react with SO 2 strongly and are the most degraded after SO 2 adsorption cycles. The fundamental understanding obtained in this work on the effects of the surface structure and defects on the interaction of SO 2 with CeO 2 provides insights for the design of more sulfur-resistant CeO 2-based catalysts.« less

Conditional Moment Closure of Mixing and Reaction in Turbulent Nonpremixed Combustion

NASA Technical Reports Server (NTRS)

Smith, Nigel S. A.

1996-01-01

Nonpremixed combustion is the process whereby fuel and oxidizer species, which are each nonflammable in isolation, concurrently mix to burn a flammable mixture, and chemically react in the flammable mixture. In cases of practical industrial interest, the bulk of nonpremixed combustion occurs in a turbulent mixing regime where enhanced mass transfer rates flow the maximum power density to be achieved in any given thermochemical device.

Optimisation of micro-perforated cylindrical silencers in linear and nonlinear regimes

NASA Astrophysics Data System (ADS)

Bravo, Teresa; Maury, Cédric; Pinhède, Cédric

2016-02-01

This paper describes analytical and experimental studies conducted to understand the potential of lightweight non-fibrous alternatives to dissipative mufflers for in-duct noise control problems, especially under high sound pressure levels (SPLs) and in the low frequency domain. The cost-efficient multi-modal propagation method has been extended to predict nonlinear effects in the dissipation and the transmission loss (TL) of micro-perforated cylindrical liners with sub-millimetric holes diameter. A validation experiment was performed in a standing wave tube to measure the power dissipated and transmitted by a nonlocally reacting liner under moderate and high SPLs. Although nonlinear effects significantly reduce the dissipation and TL around the liner maximum damping frequency, these power quantities may be enhanced below the half-bandwidth resonance. An optimal value of the in-hole peak particle velocity has been found that maximizes the TL of locally reacting liners at low frequencies. Optimisation studies based on dissipation or TL maximization showed the sensitivity of the liner constituting parameters to variations in the design target range such as the center frequency, the levels of acoustic excitation and the nature of the surface impedance (locally or nonlocally reacting). An analysis is proposed of the deviation observed at low frequencies between the optimum impedance of the locally reacting liner under moderate SPLs and Cremer's optimum impedances.

Apparatus and process for the surface treatment of carbon fibers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paulauskas, Felix Leonard; Ozcan, Soydan; Naskar, Amit K.

A method for surface treating a carbon-containing material in which carbon-containing material is reacted with decomposing ozone in a reactor (e.g., a hollow tube reactor), wherein a concentration of ozone is maintained throughout the reactor by appropriate selection of at least processing temperature, gas stream flow rate, reactor dimensions, ozone concentration entering the reactor, and position of one or more ozone inlets (ports) in the reactor, wherein the method produces a surface-oxidized carbon or carbon-containing material, preferably having a surface atomic oxygen content of at least 15%. The resulting surface-oxidized carbon material and solid composites made therefrom are also described.

Microcontact Printing Patterning of an HOPG Surface by an Inverse Electron Demand Diels-Alder Reaction.

PubMed

Zhu, Jun; Hiltz, Jonathan; Tefashe, Ushula M; Mauzeroll, Janine; Lennox, R Bruce

2018-06-21

The chemical modification of an sp 2 hybridized carbon surface in a controllable manner is very challenging but also crucial for many applications. An inverse electron demand Diels-Alder (IEDDA) reaction using microcontact printing technique is introduced to spatially control the modification of a highly ordered pyrolytic graphite (HOPG) surface under ambient conditions. The covalent modification was characterized by Raman spectroscopy, XPS, and SECM. Tetrazine derivatives can effectively react with an HOPG surface and with microcontact printing methods resulting in spatially patterned surfaces being produced with micrometer-scale resolution. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure and chemistry of model catalysts in ultrahigh vacuum

NASA Astrophysics Data System (ADS)

Walker, Joshua D.

The study of catalysis is a key area of focus not only in the industrial sector but also in the nature and biological systems. The market for catalysis is a multi-billion dollar industry. Many of the materials and products we use on a daily basis are formed through a catalytic process. The quest to understanding and improving catalytic mechanisms is ongoing. Many model catalysts use transition metals as a support for chemical reactions to take place due to their selectivity and activity. Palladium, gold, and copper metals are studied in this work and show the ability to be catalytically reactive. It is important to understand the characteristics and properties of these surfaces. A well-known example of catalysis is the conversion of carbon monoxide (CO), a very harmful gas to carbon dioxide (CO2) which is less harmful. This reaction is mainly seen in the automotive industry. This reaction is investigated in this work on a Au(111) single crystal, which is normally inert but becomes reactivity with the adsorption of oxygen on the surface. Temperature Programmed Desorption (TPD) is used to understand some of the chemistry and effects with and without the addition of H2O. The oxidation of CO is shown to be enhanced by the addition of water, but warrants further analysis too fully understand the different mechanisms and reaction pathways existing. The field of nano-electronics is rapidly growing as technology continues to challenge scientists to create innovative ideas. The trend to produce smaller electronic products is increasing as consumer demands persist. It has been shown previously that 1,4-phenlyene diisocyanobenzene (1,4-PDI) on Au(111) react to form one-dimensional oligomer chains comprising alternating gold and 1,4-PDI units on the Au(111) surface. A similar compound 1,3-phenlyene diisocyanobenzene (1,3-PDI) was studied in order to investigate whether the oligomerization found for 1,4-PDI is a general phenomenon and to ultimately explore the effect of molecular geometry on electron transport using a range of surface-sensitive techniques. Sulfur-containing molecules, in particular those with sulfur-sulfur linkages, are used as lubricant additives for ferrous surfaces [1-14] so that dialkyl disulfides have been used as simple model compounds to explore the surface and tribological chemistry on iron [15,16] where they react at the high temperatures attained at the interface during rubbing to deposit a ferrous sulfide film. However, the tribological chemistry can depend critically on the nature of the substrate so that a good lubricant additive for one type of surface may not be applicable to another. In particular, the lubrication of sliding copper-copper interfaces in electrical motors [17-20] provides a particular challenge. To study this system surface sensitive techniques Low energy electron diffraction (LEED) and TPD surface analysis was employed. LEED experiments suggest that tribological experiments can be conducted on copper foils rather than copper single crystals and produce comparable results. The ability to produce ideal model catalysts is very important in the Surface science field. To enhance catalytic performance of these catalysts, various strategies can be used in the preparation process. One approach in this quest is to produce an alloy surface that increases the activity of the surface. The process of developing and understanding the chemistry of AuPd alloys was probed in detail using TPD, LEED and Density Functional Theory (DFT).

Effect of grafting RGD and BMP-2 protein-derived peptides to a hydrogel substrate on osteogenic differentiation of marrow stromal cells.

PubMed

He, Xuezhong; Ma, Junyu; Jabbari, Esmaiel

2008-11-04

Osteogenic differentiation and mineralization of bone marrow stromal (BMS) cells depends on the cells' interactions with bioactive peptides associated with the matrix proteins. The RGD peptides of ECM proteins interact with BMS cells through integrin surface receptors to facilitate cell spreading and adhesion. The BMP peptide corresponding to residues 73-92 of bone morphogenetic protein-2 promotes differentiation and mineralization of BMS cells. The objective of this work was to investigate the effects of RGD and BMP peptides, grafted to a hydrogel substrate, on osteogenic differentiation and mineralization of BMS cells. RGD peptide was acrylamide-terminated by reacting acrylic acid with the N-terminal amine group of the peptide to produce the functionalized Ac-GRGD peptide. The PEGylated BMP peptide was reacted with 4-carboxybenzenesulfonazide to produce an azide functionalized Az-mPEG-BMP peptide. Poly (lactide-co-ethylene oxide- co-fumarate) (PLEOF) macromer was cross-linked with Ac-GRGD peptide and propargyl acrylate to produce an RGD conjugated hydrogel. Az-mPEG-BMP peptide was grafted to the hydrogel by "click chemistry". The RGD and BMP peptide density on the hydrogel surface was 1.62+/-0.37 and 5.2+/-0.6 pmol/cm2, respectively. BMS cells were seeded on the hydrogels and the effect of RGD and BMP peptides on osteogenesis was evaluated by measuring ALPase activity and calcium content with incubation time. BMS cells cultured on RGD conjugated, BMP peptide grafted, and RGD+BMP peptide modified hydrogels showed 3, 2.5, and 5-fold increase in ALPase activity after 14 days incubation. BMS cells seeded on RGD+BMP peptides modified hydrogel showed 4.9- and 11.8-fold increase in calcium content after 14 and 21 days, respectively, which was significantly higher than RGD conjugated or BMP grafted hydrogels. These results demonstrate that RGD and BMP peptides, grafted to a hydrogel substrate, act synergistically to enhance osteogenic differentiation and mineralization of BMS cells. These findings are potentially useful in developing engineered scaffolds for bone regeneration.

Molecular printboards: monolayers of beta-cyclodextrins on silicon oxide surfaces.

PubMed

Onclin, Steffen; Mulder, Alart; Huskens, Jurriaan; Ravoo, Bart Jan; Reinhoudt, David N

2004-06-22

Monolayers of beta-cyclodextrin host molecules have been prepared on SiO2 surfaces. An ordered and stable cyano-terminated monolayer was modified in three consecutive surface reactions. First, the cyanide groups were reduced to their corresponding free amines using Red Al as a reducing agent. Second, 1,4-phenylene diisothiocyanate was used to react with the amine monolayer where it acts as a linking molecule, exposing isothiocyanates that can be derivatized further. Finally, per-6-amino beta-cyclodextrin was reacted with these isothiocyanate functions to yield a monolayer exposing beta-cyclodextrin. All monolayers were characterized by contact angle measurements, ellipsometric thickness measurements, Brewster angle Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry, which indicate the formation of a densely packed cyclodextrin surface. It was demonstrated that the beta-cyclodextrin monolayer could bind suitable guest molecules in a reversible manner. A fluorescent molecule (1), equipped with two adamantyl groups for complexation, was adsorbed onto the host monolayer from solution to form a monolayer of guest molecules. Subsequently, the guest molecules were desorbed from the surface by competition with increasing beta-cyclodextrin concentration in solution. The data were fitted using a model. An intrinsic binding constant of 3.3 +/- 1 x 10(5) M(-1) was obtained, which corresponds well to previously obtained results with a divalent guest molecule on beta-cyclodextrin monolayers on gold. In addition, the number of guest molecules bound to the host surface was determined, and a surface coverage of ca. 30% was found.

Single Crystal Substrates for Surface Acoustic Wave Devices.

DTIC Science & Technology

1981-01-01

Research Laboratory 2W 5 University Park PA 16802____________ 1 1. CONTROLLING OFFICE NAME ANO ADDRESS Deputy for Electronic Technology (RADC/ EEA )// Janu...avoid contamination during the preparation of the reacted starting powders. Mixina was performed in plastic hall mills with teflon rollers, and sinterinq

Split Space-Marching Finite-Volume Method for Chemically Reacting Supersonic Flow

NASA Technical Reports Server (NTRS)

Rizzi, Arthur W.; Bailey, Harry E.

1976-01-01

A space-marching finite-volume method employing a nonorthogonal coordinate system and using a split differencing scheme for calculating steady supersonic flow over aerodynamic shapes is presented. It is a second-order-accurate mixed explicit-implicit procedure that solves the inviscid adiabatic and nondiffusive equations for chemically reacting flow in integral conservation-law form. The relationship between the finite-volume and differential forms of the equations is examined and the relative merits of each discussed. The method admits initial Cauchy data situated on any arbitrary surface and integrates them forward along a general curvilinear coordinate, distorting and deforming the surface as it advances. The chemical kinetics term is split from the convective terms which are themselves dimensionally split, thereby freeing the fluid operators from the restricted step size imposed by the chemical reactions and increasing the computational efficiency. The accuracy of this splitting technique is analyzed, a sufficient stability criterion is established, a representative flow computation is discussed, and some comparisons are made with another method.

Mitigation of radiation induced surface contamination

DOEpatents

Klebanoff, Leonard E.; Stulen, Richard H.

2003-01-01

A process for mitigating or eliminating contamination and/or degradation of surfaces having common, adventitious atmospheric contaminants adsorbed thereon and exposed to radiation. A gas or a mixture of gases is introduced into the environment of a surface(s) to be protected. The choice of the gaseous species to be introduced (typically a hydrocarbon gas, water vapor, or oxygen or mixtures thereof) is dependent upon the contaminant as well as the ability of the gaseous species to bind to the surface to be protected. When the surface and associated bound species are exposed to radiation reactive species are formed that react with surface contaminants such as carbon or oxide films to form volatile products (e.g., CO, CO.sub.2) which desorb from the surface.

Chemical composition and heterogeneous reactivity of soot generated in the combustion of diesel and GTL (Gas-to-Liquid) fuels and amorphous carbon Printex U with NO2 and CF3COOH gases

NASA Astrophysics Data System (ADS)

Tapia, A.; Salgado, S.; Martín, P.; Villanueva, F.; García-Contreras, R.; Cabañas, B.

2018-03-01

The heterogeneous reactions of nitrogen dioxide (NO2) and trifluoroacetic acid (CF3COOH) with soot produced by diesel and GTL (gas-to-liquid) fuels were investigated using a Knudsen flow reactor with mass spectrometry as a detection system for gas phase species. Soot was generated with a 4 cylinder diesel engine working under steady-state like urban operation mode. Heterogeneous reaction of the mentioned gases with a commercial carbon, Printex U, used as reference, was also analyzed. The initial and the steady-state uptake coefficients, γ0 and γss, respectively, were measured indicating that GTL soot reacts faster than diesel soot and Printex U carbon for NO2 gas reactant. According to the number of reacted molecules on the surface, Printex U soot presents more reducing sites than diesel and GTL soot. Initial uptake coefficients for GTL and diesel soot for the reaction with CF3COOH gas reactant are very similar and no clear conclusions can be obtained related to the initial reactivity. The number of reacted molecules calculated for CF3COOH reactions shows values two orders of magnitude higher than the corresponding to NO2 reactions, indicating a greater presence of basic functionalities in the soot surfaces. More information of the surface composition has been obtained using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) before and after the reaction of soot samples with gas reactants. As conclusion, the interface of diesel and GTL soot before reaction mainly consists of polycyclic aromatic hydrocarbons (PAHs), nitro-compounds as well as ether functionalities. After reaction with gas reactant, it was observed that PAHs and nitro-compounds remain on the soot surface and new spectral bands such as carbonyl groups (carboxylic acids, aldehydes, esters and ketones) are observed. Physical properties of soot from both fuels studied such as BET surface isotherm and SEM analysis were also developed and related to the observed reactivity.

Transverse liquid fuel jet breakup, burning, and ignition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Hsi-shang

1990-01-01

An analytical/numerical study of the breakup, burning, and ignition of liquid fuels injected transversely into a hot air stream is conducted. The non-reacting liquid jet breakup location is determined by the local sonic point criterion first proposed by Schetz, et al. (1980). Two models, one employing analysis of an elliptical jet cross-section and the other employing a two-dimensional blunt body to represent the transverse jet, have been used for sonic point calculations. An auxiliary criterion based on surface tension stability is used as a separate means of determining the breakup location. For the reacting liquid jet problem, a diffusion flamemore » supported by a one-step chemical reaction within the gaseous boundary layer is solved along the ellipse surface in subsonic crossflow. Typical flame structures and concentration profiles have been calculated for various locations along the jet cross-section as a function of upstream Mach numbers. The integrated reaction rate along the jet cross-section is used to predict ignition position, which is found to be situated near the stagnation point. While a multi-step reaction is needed to represent the ignition process more accurately, the present calculation does yield reasonable predictions concerning ignition along a curved surface.« less

Transverse liquid fuel jet breakup, burning, and ignition. M.S. Thesis

NASA Technical Reports Server (NTRS)

Li, Hsi-Shang

1990-01-01

An analytical study of the breakup, burning, and ignition of liquid fuels injected transversely into a hot air stream is conducted. The non-reacting liquid jet breakup location is determined by the local sonic point criterion. Two models, one employing analysis of an elliptical jet cross-section and the other employing a two-dimensional blunt body to represent the transverse jet, were used for sonic point calculations. An auxiliary criterion based on surface tension stability is used as a separate means of determining the breakup location. For the reacting liquid jet problem, a diffusion flame supported by a one-step chemical reaction within the gaseous boundary layer is solved along the ellipse surface in subsonic cross flow. Typical flame structures and concentration profiles were calculated for various locations along the jet cross-section as a function of upstream Mach numbers. The integration reaction rate along the jet cross-section is used to predict ignition position, which is found to be situated near the stagnation point. While a multi-step reaction is needed to represent the ignition process more accurately, the present calculation does yield reasonable predictions concerning ignition along a curved surface.

Difference of EGCg adhesion on cell surface between Staphylococcus aureus and Escherichia coli visualized by electron microscopy after novel indirect staining with cerium chloride.

PubMed

Nakayama, Motokazu; Shigemune, Naofumi; Tsugukuni, Takashi; Tokuda, Hajime; Miyamoto, Takahisa

2011-07-01

We developed a novel method using indirect staining with cerium chloride for visualization of the catechin derivative epigallocatechin gallate (EGCg) on the surface of particles, i.e., polystyrene beads and bacterial cells, by electron microscopy. The staining method is based on the fact that in an alkaline environment, EGCg produces hydrogen peroxide, and then hydrogen peroxide reacts with cerium, resulting in a cerium hydroperoxide precipitate. This precipitate subsequently reacts with EGCg to produce larger deposits. The amount of precipitate is proportional to the amount of EGCg. Highly EGCg-sensitive Staphylococcus aureus and EGCg-resistant Escherichia coli were treated with EGCg under various pH conditions. Transmission electron microscopy observation showed that the amount of deposits on S. aureus increased with an increase in EGCg concentration. After treating bacterial cells with 0.5mg/mL EGCg (pH 6.0), attachment of EGCg was significantly lower to E. coli than to S. aureus. This is the first report that shows differences in affinity of EGCg to the cell surfaces of Gram-positive and -negative bacteria by electron microscopy. Copyright © 2011 Elsevier B.V. All rights reserved.

Porous aluminum room temperature anodizing process in a fluorinated-oxalic acid solution

NASA Astrophysics Data System (ADS)

Dhahri, S.; Fazio, E.; Barreca, F.; Neri, F.; Ezzaouia, H.

2016-08-01

Anodizing of aluminum is used for producing porous insulating films suitable for different applications in electronics and microelectronics. Porous-type aluminum films are most simply realized by galvanostatic anodizing in aqueous acidic solutions. The improvement in application of anodizing technique is associated with a substantial reduction of the anodizing voltage at appropriate current densities as well as to the possibility to carry out the synthesis process at room temperature in order to obtain a self-planarizing dielectric material incorporated in array of super-narrow metal lines. In this work, the anodizing of aluminum to obtain porous oxide was carried out, at room temperature, on three different substrates (glass, stainless steel and aluminum), using an oxalic acid-based electrolyte with the addition of a relatively low amount of 0.4 % of HF. Different surface morphologies, from nearly spherical to larger porous nanostructures with smooth edges, were observed by means of scanning electron microscopy. These evidences are explained by considering the formation, transport and adsorption of the fluorine species which react with the Al3+ ions. The behavior is also influenced by the nature of the original substrate.

VARIATION IN ACCESSIBLE CELL SURFACE IMMUNOGLOBULIN AMONG ANTIBODY-FORMING CELLS

PubMed Central

Nossal, G. J. V.; Lewis, Heather

1972-01-01

Spleen cells from CBA mice that had been primarily or secondarily immunized with sheep red blood cells were reacted at 0°C with a 125I-labeled polyvalent rabbit anti-mouse globulin reagent. After suitable washing, the cells were placed in a plaque-revealing monolayer and warmed to 37°C. Plaques appeared within 10–20 min. Single plaque-forming cells (PFC) were taken from the middle of plaques, were washed by micromanipulation, and were singly dried on glass slides. The amount of attached antireceptor was assessed by quantitative radioautography. Great variation in "receptor density" was encountered among the 258 single cells studied. However, early, immature PFC in both primary and secondary responses had statistically significantly more receptors than late, mature PFC. On any given day point, no difference was found between IgM- and IgG-forming cells. The results were consistent with the view that cells still able to be driven to further proliferation by antigen retain receptors, and conversely that cells, as they mature, lose both receptors and ability to be influenced by antigen. PMID:4554455

Tungsten Hydride Phosphorus- and Arsenic-Bearing Molecules with Double and Triple W-P and W-As Bonds.

PubMed

Andrews, Lester; Cho, Han-Gook; Fang, Zongtang; Vasiliu, Monica; Dixon, David A

2018-05-07

Laser ablation of tungsten metal provides W atoms which react with phosphine and arsine during condensation in excess argon and neon, leading to major new infrared (IR) absorptions. Annealing, UV irradiation, and deuterium substitution experiments coupled with electronic structure calculations at the density functional theory level led to the assignment of the observed IR absorptions to the E≡WH 3 and HE═WH 2 molecules for E = P and As. The potential energy surfaces for hydrogen transfer from PH 3 to the W were calculated at the coupled-cluster CCSD(T)/complete basis set level. Additional weak bands in the phosphide and arsenide W-H stretching region are assigned to the molecules with loss of H from W, E≡WH 2 . The electronic structure calculations show that the E≡WH 3 molecules have a W-E triple bond, the HE═WH 2 molecules have a W-E double bond, and the H 2 E-WH molecules have a W-E single bond. The formation of multiple E-W bonds leads to increasing stability for the isomers.

Impacts of Geomagnetic Storms on the Terrestrial H-Exosphere Using Twins-Lyman Stereo Data

NASA Astrophysics Data System (ADS)

Nass, U.; Zoennchen, J.; Fahr, H. J.; Goldstein, J.

2015-12-01

Based on continuously monitored Lyman-alpha data registered by the TWINS1/2-LAD instruments we have studied the impact of a weaker and a stronger geomagnetic storm on the exospheric H-density distribution between heights of 3--8 Earth-radii. As is well known, solar Lyman-alpha radiation is resonantly backscattered from geocoronal neutral hydrogen (H). The resulting resonance glow intensity in the optically thin regime is proportional to H column density along the line of sight (LOS). Here we present the terrestrial exospheric response to geomagnetic storms. We quantify the reaction to geomagnetic activity in form of amplitude and temporal response of the H-density, sampled at different geocentric distances. We find that even in case of a weak storm, the exospheric H-density in regions above the exobase reacts with a suprisingly large increase in a remarkably short time period of less than half a day. Careful analysis of this geomagnetic density effect indicates that it is an expansion in the radial scale height of the exospheric H-density, developing from exobasic heights.

Production of light elements and 98Tc through the ν-process with the neutrino oscillation in supernova explosion

NASA Astrophysics Data System (ADS)

Ko, Heamin; Kusakabe, Motohiko; Cheoun, Myung-Ki; Kwak, Kyujin; Kim, Kyungsik

2018-04-01

Stars ending with core collapse supernovae (SNe) emit a tremendous number of neutrinos during their explosions. While these neutrinos pass through each layer of the stars, they react with the nuclides in the progenitor. Although the neutrino cross sections are very small, its huge flux is high enough to react with nuclides to change their abundances. We consider this ν-process, by which abundances of some elements may be explained exclusively by this neutrino process. One of the candidates is 98Tc. In this study, we check the ν-process contributions due to the neutrino reactions. In this calculation we also include the neutrino oscillation effect in the matter with varying density, so called MSW effect, not only for 98Tc production but also 4He and 12C destruction, which occurs at first in the He/C layer in the present model.

A consistent transported PDF model for treating differential molecular diffusion

NASA Astrophysics Data System (ADS)

Wang, Haifeng; Zhang, Pei

2016-11-01

Differential molecular diffusion is a fundamentally significant phenomenon in all multi-component turbulent reacting or non-reacting flows caused by the different rates of molecular diffusion of energy and species concentrations. In the transported probability density function (PDF) method, the differential molecular diffusion can be treated by using a mean drift model developed by McDermott and Pope. This model correctly accounts for the differential molecular diffusion in the scalar mean transport and yields a correct DNS limit of the scalar variance production. The model, however, misses the molecular diffusion term in the scalar variance transport equation, which yields an inconsistent prediction of the scalar variance in the transported PDF method. In this work, a new model is introduced to remedy this problem that can yield a consistent scalar variance prediction. The model formulation along with its numerical implementation is discussed, and the model validation is conducted in a turbulent mixing layer problem.

Numerical Simulations of Two-Phase Reacting Flow in a Single-Element Lean Direct Injection (LDI) Combustor Using NCC

NASA Technical Reports Server (NTRS)

Liu, Nan-Suey; Shih, Tsan-Hsing; Wey, C. Thomas

2011-01-01

A series of numerical simulations of Jet-A spray reacting flow in a single-element lean direct injection (LDI) combustor have been conducted by using the National Combustion Code (NCC). The simulations have been carried out using the time filtered Navier-Stokes (TFNS) approach ranging from the steady Reynolds-averaged Navier-Stokes (RANS), unsteady RANS (URANS), to the dynamic flow structure simulation (DFS). The sub-grid model employed for turbulent mixing and combustion includes the well-mixed model, the linear eddy mixing (LEM) model, and the filtered mass density function (FDF/PDF) model. The starting condition of the injected liquid spray is specified via empirical droplet size correlation, and a five-species single-step global reduced mechanism is employed for fuel chemistry. All the calculations use the same grid whose resolution is of the RANS type. Comparisons of results from various models are presented.

DNS of High Pressure Supercritical Combustion

NASA Astrophysics Data System (ADS)

Chong, Shao Teng; Raman, Venkatramanan

2016-11-01

Supercritical flows have always been important to rocket motors, and more recently to aircraft engines and stationary gas turbines. The purpose of the present study is to understand effects of differential diffusion on reacting scalars using supercritical isotropic turbulence. Focus is on fuel and oxidant reacting in the transcritical region where density, heat capacity and transport properties are highly sensitive to variations in temperature and pressure. Reynolds and Damkohler number vary as a result and although it is common to neglect differential diffusion effects if Re is sufficiently large, this large variation in temperature with heat release can accentuate molecular transport differences. Direct numerical simulations (DNS) for one step chemistry reaction between fuel and oxidizer are used to examine the differential diffusion effects. A key issue investigated in this paper is if the flamelet progress variable approach, where the Lewis number is usually assumed to be unity and constant for all species, can be accurately applied to simulate supercritical combustion.

The calculation of a turbulent diffusion flame in a free shear flow with a statistical turbulence model

NASA Astrophysics Data System (ADS)

Bywater, R. J.

1980-01-01

Solutions are presented for the turbulent diffusion flame in a two-dimensional shear layer based upon a kinetic theory of turbulence (KTT). The fuel and oxidizer comprising the two streams are considered to react infinitely fast according to a one-step, irreversible kinetic mechanism. The solutions are obtained by direct numerical calculation of the transverse velocity probability density function (PDF) and the associated species distributions. The mean reactant profiles calculated from the solutions display the characteristic thick, turbulent flame zone. The phenomena result from the fact that in the context of the KTT, species react only when in the same velocity cell. This coincides with the known physical requirement that molecular mixing precedes reaction. The solutions demonstrate this behavior by showing how reactants can coexist in the mean, even when infinite reaction rates are enforced at each point (t,x,u) of velocity space.

Standard Gibbs free energies of reactions of ozone with free radicals in aqueous solution: quantum-chemical calculations.

PubMed

Naumov, Sergej; von Sonntag, Clemens

2011-11-01

Free radicals are common intermediates in the chemistry of ozone in aqueous solution. Their reactions with ozone have been probed by calculating the standard Gibbs free energies of such reactions using density functional theory (Jaguar 7.6 program). O(2) reacts fast and irreversibly only with simple carbon-centered radicals. In contrast, ozone also reacts irreversibly with conjugated carbon-centered radicals such as bisallylic (hydroxycylohexadienyl) radicals, with conjugated carbon/oxygen-centered radicals such as phenoxyl radicals, and even with nitrogen- oxygen-, sulfur-, and halogen-centered radicals. In these reactions, further ozone-reactive radicals are generated. Chain reactions may destroy ozone without giving rise to products other than O(2). This may be of importance when ozonation is used in pollution control, and reactions of free radicals with ozone have to be taken into account in modeling such processes.

Insulator coating for high temperature alloys method for producing insulator coating for high temperature alloys

DOEpatents

Park, J.H.

1998-06-23

A method for fabricating an electrically insulating coating on a surface is disclosed comprising coating the surface with a metal, and reacting the metal coated surface with a nonmetal so as to create a film on the metal-coated surface. Alternatively, the invention provides for a method for producing a noncorrosive, electrically insulating coating on a surface saturated with a nonmetal comprising supplying a molten fluid, dissolving a metal in the molten fluid to create a mixture, and contacting the mixture with the saturated surface. Lastly, the invention provides an electrically insulative coating comprising an underlying structural substrate coated with an oxide or nitride compound. 2 figs.

Processing of Novel Nanoparticle Dispersion Strengthened Ceramics for Improved Mechanical Performance

DTIC Science & Technology

1992-12-14

the composite . The top and bottom surfaces of each disc were removed to eliminate any reaction layer, and the discs were machined ’ to produce bars...l.It is postulated that during grinding of the composite , compressive stresses and machining flaws are introduced into the surface. The compressive...two materials considered would react differently to the annealing step. It can be expected that machining flaws will heal in the composite samples

Remote Sensing and Monitoring of Earthen Flood-Control Structures

DTIC Science & Technology

2017-07-01

The source of energy in passive techniques is derived from incident solar radiation or sunlight that reacts with the atmosphere, hydrosphere, and...the energy reflected or emitted from the earth’s surface. The source of energy in passive techniques involves incident solar radiation or sunlight... solar radiation is reflected back into the atmosphere, or where heat energy is emitted from the earth’s surface. As shown by Figure 2-3, certain regions

Enhanced catalyst stability for cyclic co methanation operations

DOEpatents

Risch, Alan P.; Rabo, Jule A.

1983-01-01

Carbon monoxide-containing gas streams are passed over a catalyst to deposit a surface layer of active surface carbon thereon essentially without the formation of inactive coke. The active carbon is thereafter reacted with steam or hydrogen to form methane. Enhanced catalyst stability for long term, cyclic operation is obtained by the incorporation of an alkali or alkaline earth dopant in a silica binding agent added to the catalyst-support additive composition.

Design and Construction of a High Vacuum Surface Analysis Instrument to Study Chemistry at Nanoparticulate Surfaces

DTIC Science & Technology

2011-04-21

various paints , metals, and polymers.2, 11 Furthermore, some CWAs are resistant to a certain decontamination formula or react with the decontamination...The use of solid-state decontaminants increases portability, decreases weight, and could potentially be incorporated into coatings or paints and...enclosure with weather stripping . Figure 2.8: Front and top views of the focusing optics enclosure. The dashed line indicates IR beam path. A

Atomic Oxygen Effects

NASA Technical Reports Server (NTRS)

Miller, Sharon K. R.

2014-01-01

Atomic oxygen, which is the most predominant species in low Earth orbit, is highly reactive and can break chemical bonds on the surface of a wide variety of materials leading to volatilization or surface oxidation which can result in failure of spacecraft materials and components. This presentation will give an overview of how atomic oxygen reacts with spacecraft materials, results of space exposure testing of a variety of materials, and examples of failures caused by atomic oxygen.

Tin soldering of aluminum and its alloys

NASA Technical Reports Server (NTRS)

Gallo, Gino

1921-01-01

A method is presented for soldering aluminum to other metals. The method adopted consists of a galvanic application to the surface of the light-metal parts to be soldered, of a layer of another metal, which, without reacting electrolytically on the aluminum, adheres strongly to the surface to which it is applied, and is, on the other hand, adapted to receive the soft solder. The metal found to meet the criteria best was iron.

Sulfur dioxide reactions on ice surfaces: Implications for dry deposition to snow

Treesearch

Martha H. Conklin; Richard A. Sommerfeld; S. Kay Laird; John E. Villinski

1993-01-01

Controlled exposure of ice to a reactive gas, SO2, demonstrated the importance of the chemical composition of the ice surface on the accumulation of acidity in snow. In a series of bench-scale continuous-flow column experiments run at four temperatures (-1, -8, -30 and -60°C), SO2 was shown to dissolve and to react with other species in the ice-air interfacial region...

Corrosion protection

DOEpatents

Brown, Donald W.; Wagh, Arun S.

2003-05-27

There has been invented a chemically bonded phosphate corrosion protection material and process for application of the corrosion protection material for corrosion prevention. A slurry of iron oxide and phosphoric acid is used to contact a warm surface of iron, steel or other metal to be treated. In the presence of ferrous ions from the iron, steel or other metal, the slurry reacts to form iron phosphates which form grains chemically bonded onto the surface of the steel.

Passivation of high temperature superconductors

NASA Technical Reports Server (NTRS)

Vasquez, Richard P. (Inventor)

1991-01-01

The surface of high temperature superconductors such as YBa2Cu3O(7-x) are passivated by reacting the native Y, Ba and Cu metal ions with an anion such as sulfate or oxalate to form a surface film that is impervious to water and has a solubility in water of no more than 10(exp -3) M. The passivating treatment is preferably conducted by immersing the surface in dilute aqueous acid solution since more soluble species dissolve into the solution. The treatment does not degrade the superconducting properties of the bulk material.

Effect of non-equilibrium flow chemistry on the heating distribution over the MESUR forebody during a Martian entry

NASA Technical Reports Server (NTRS)

Chen, Yih-Kang

1992-01-01

Effect of flow field properties on the heating distribution over a 140 deg blunt cone was determined for a Martian atmosphere using Euler, Navier-Stokes (NS), viscous shock layer (VSL), and reacting boundary layer (BLIMPK) equations. The effect of gas kinetics on the flow field and the surface heating distribution were investigated. Gas models with nine species and nine reactions were implemented into the codes. Effects of surface catalysis on the heating distribution were studied using a surface kinetics model having five reactions.

Topology of Surface Ligands on Liposomes: Characterization Based on the Terms, Incorporation Ratio, Surface Anchor Density, and Reaction Yield.

PubMed

Lee, Shang-Hsuan; Sato, Yusuke; Hyodo, Mamoru; Harashima, Hideyoshi

2016-01-01

The surface topology of ligands on liposomes is an important factor in active targeting in drug delivery systems. Accurately evaluating the density of anchors and bioactive functional ligands on a liposomal surface is critical for ensuring the efficient delivery of liposomes. For evaluating surface ligand density, it is necessary to clarify that on the ligand-modified liposomal surfaces, some anchors are attached to ligands but some are not. To distinguish between these situations, a key parameter, surface anchor density, was introduced to specify amount of total anchors on the liposomal surface. Second, the parameter reaction yield was introduced to identify the amount of ligand-attached anchors among total anchors, since the conjugation efficiency is not always the same nor 100%. Combining these independent parameters, we derived: incorporation ratio=surface anchor density×reaction yield. The term incorporation ratio defines the surface ligand density. Since the surface anchor density represents the density of polyethylene glycol (PEG) on the surfaces in most cases, it also determines liposomal function. It is possible to accurately characterize various PEG and ligand densities and to define the surface topologies. In conclusion, this quantitative methodology can standardize the liposome preparation process and qualify the modified liposomal surfaces.

Surface Structure Dependence of SO 2 Interaction with Ceria Nanocrystals with Well-Defined Surface Facets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tumuluri, Uma; Li, Meijun; Cook, Brandon G.

2015-12-31

The effects of the surface structure of ceria (CeO2) on the nature, strength, and amount of species resulting from SO2 adsorption were studied using in situ IR and Raman spectroscopies coupled with mass spectrometry, along with first-principles calculations based on density functional theory (DFT). CeO2 nanocrystals with different morphologies, namely, rods (representing a defective structure), cubes (100 facet), and octahedra (111 facet), were used to represent different CeO2 surface structures. IR and Raman spectroscopic studies showed that the structure and binding strength of adsorbed species from SO2 depend on the shape of the CeO2 nanocrystals. SO2 adsorbs mainly as surfacemore » sulfites and sulfates at room temperature on CeO2 rods, cubes, and octahedra that were either oxidatively or reductively pretreated. The formation of sulfites is more evident on CeO2 octahedra, whereas surface sulfates are more prominent on CeO2 rods and cubes. This is explained by the increasing reducibility of the surface oxygen in the order octahedra < cubes < rods. Bulk sulfites are also formed during SO2 adsorption on reduced CeO2 rods. The formation of surface sulfites and sulfates on CeO2 cubes is in good agreement with our DFT results of SO2 interactions with the CeO2(100) surface. CeO2 rods desorb SO2 at higher temperatures than cubes and octahedra nanocrystals, but bulk sulfates are formed on CeO2 rods and cubes after high-temperature desorption whereas only some surface sulfates/sulfites are left on octahedra. This difference is rationalized by the fact that CeO2 rods have the highest surface basicity and largest amount of defects among the three nanocrystals, so they bind and react with SO2 strongly and are the most degraded after SO2 adsorption cycles. The fundamental understanding obtained in this work on the effects of the surface structure and defects on the interaction of SO2 with CeO2 provides insights for the design of more sulfur-resistant CeO2-based catalysts.« less

Low-Friction, Low-Profile, High-Moment Two-Axis Joint

NASA Technical Reports Server (NTRS)

Lewis, James L.; Le, Thang; Carroll, Monty B.

2010-01-01

The two-axis joint is a mechanical device that provides two-degrees-of-freedom motion between connected components. A compact, moment-resistant, two-axis joint is used to connect an electromechanical actuator to its driven structural members. Due to the requirements of the overall mechanism, the joint has a low profile to fit within the allowable space, low friction, and high moment-reacting capability. The mechanical arrangement of this joint can withstand high moments when loads are applied. These features allow the joint to be used in tight spaces where a high load capability is required, as well as in applications where penetrating the mounting surface is not an option or where surface mounting is required. The joint consists of one base, one clevis, one cap, two needle bearings, and a circular shim. The base of the joint is the housing (the base and the cap together), and is connected to the grounding structure via fasteners and a bolt pattern. Captive within the housing, between the base and the cap, are the rotating clevis and the needle bearings. The clevis is attached to the mechanical system (linear actuator) via a pin. This pin, and the rotational movement of the clevis with respect to the housing, provides two rotational degrees of freedom. The larger diameter flange of the clevis is sandwiched between a pair of needle bearings, one on each side of the flange. During the assembly of the two-axis joint, the circular shims are used to adjust the amount of preload that is applied to the needle bearings. The above arrangement enables the joint to handle high moments with minimal friction. To achieve the high-moment capability within a low-profile joint, the use of depth of engagement (like that of a conventional rotating shaft) to react moment is replaced with planar engagement parallel to the mounting surface. The needle bearings with the clevis flange provide the surface area to react the clevis loads/moments into the joint housing while providing minimal friction during rotation. The diameter of the flange and the bearings can be increased to react higher loads and still maintain a compact surface mounting capability. This type of joint can be used in a wide variety of mechanisms and mechanical systems. It is especially effective where precise, smooth, continuous motion is required. For example, the joint can be used at the end of a linear actuator that is required to extend and rotate simultaneously. The current design application is for use in a spacecraft docking-system capture mechanism. Other applications might include industrial robotic or assembly line apparatuses, positioning systems, or in the motion-based simulator industry that employs complex, multi-axis manipulators for various types of motions.

The effects of oil-in-water nanoemulsion polyethylene glycol surface density on intracellular stability, pharmacokinetics, and biodistribution in tumor bearing mice.

PubMed

Hak, Sjoerd; Garaiova, Zuzana; Olsen, Linda Therese; Nilsen, Asbjørn Magne; de Lange Davies, Catharina

2015-04-01

Lipid-based nanoparticles are extensively studied for drug delivery. These nanoparticles are often surface-coated with polyethylene glycol (PEG) to improve their biodistribution. Until now, the effects of varying PEG surface density have been studied in a narrow and low range. Here, the effects of high and a broad range of PEG surface densities on the in vivo performance of lipid-based nanoparticles were studied. Oil-in-water nanoemulsions were prepared with PEG surface densities of 5-50 mol%. Confocal microscopy was used to assess intracellular disintegration in vitro. In vivo pharmacokinetics and biodistribution in tumor bearing mice were studied using a small animal optical imager. PEG surface density did not affect intracellular nanoemulsion stability. Surprisingly, circulation half-lives decreased with increasing PEG surface density. A plausible explanation was that nanoemulsion with high (50 mol%) PEG surface density activated the complement in a whole blood assay, whereas nanoemulsion with low (5 mol%) PEG density did not. In vivo, nanoemulsion with low PEG surface density was mostly confined to the tumor and organs of the mononuclear phagocyte system, whereas nanoemulsion with high PEG density accumulated throughout the mouse. Optimal PEG surface density of lipid-based nanoparticles for tumor targeting was found to be below 10 mol%.

Assembly, Structure, and Functionality of Metal-Organic Networks and Organic Semiconductor Layers at Surfaces

NASA Astrophysics Data System (ADS)

Tempas, Christopher D.

Self-assembled nanostructures at surfaces show promise for the development of next generation technologies including organic electronic devices and heterogeneous catalysis. In many cases, the functionality of these nanostructures is not well understood. This thesis presents strategies for the structural design of new on-surface metal-organic networks and probes their chemical reactivity. It is shown that creating uniform metal sites greatly increases selectivity when compared to ligand-free metal islands. When O2 reacts with single-site vanadium centers, in redox-active self-assembled coordination networks on the Au(100) surface, it forms one product. When O2 reacts with vanadium metal islands on the same surface, multiple products are formed. Other metal-organic networks described in this thesis include a mixed valence network containing Pt0 and PtII and a network where two Fe centers reside in close proximity. This structure is stable to temperatures >450 °C. These new on-surface assemblies may offer the ability to perform reactions of increasing complexity as future heterogeneous catalysts. The functionalization of organic semiconductor molecules is also shown. When a few molecular layers are grown on the surface, it is seen that the addition of functional groups changes both the film's structure and charge transport properties. This is due to changes in both first layer packing structure and the pi-electron distribution in the functionalized molecules compared to the original molecule. The systems described in this thesis were studied using high-resolution scanning tunneling microscopy, non-contact atomic force microscopy, and X-ray photoelectron spectroscopy. Overall, this work provides strategies for the creation of new, well-defined on-surface nanostructures and adds additional chemical insight into their properties.

NON-CORROSIVE REACTOR FUEL SYSTEM

DOEpatents

Herrick, C.C.

1962-08-14

A non-corrosive nuclear reactor fuel system was developed utilizing a molten plutonium-- iron alloy fuel having about 2 at.% carbon and contained in a tantalum vessel. This carbon reacts with the interior surface of the tantalum vessel to form a plutonium resistant self-healing tantalum carbide film. (AEC)

A Validation Summary of the NCC Turbulent Reacting/non-reacting Spray Computations

NASA Technical Reports Server (NTRS)

Raju, M. S.; Liu, N.-S. (Technical Monitor)

2000-01-01

This pper provides a validation summary of the spray computations performed as a part of the NCC (National Combustion Code) development activity. NCC is being developed with the aim of advancing the current prediction tools used in the design of advanced technology combustors based on the multidimensional computational methods. The solution procedure combines the novelty of the application of the scalar Monte Carlo PDF (Probability Density Function) method to the modeling of turbulent spray flames with the ability to perform the computations on unstructured grids with parallel computing. The calculation procedure was applied to predict the flow properties of three different spray cases. One is a nonswirling unconfined reacting spray, the second is a nonswirling unconfined nonreacting spray, and the third is a confined swirl-stabilized spray flame. The comparisons involving both gas-phase and droplet velocities, droplet size distributions, and gas-phase temperatures show reasonable agreement with the available experimental data. The comparisons involve both the results obtained from the use of the Monte Carlo PDF method as well as those obtained from the conventional computational fluid dynamics (CFD) solution. Detailed comparisons in the case of a reacting nonswirling spray clearly highlight the importance of chemistry/turbulence interactions in the modeling of reacting sprays. The results from the PDF and non-PDF methods were found to be markedly different and the PDF solution is closer to the reported experimental data. The PDF computations predict that most of the combustion occurs in a predominantly diffusion-flame environment. However, the non-PDF solution predicts incorrectly that the combustion occurs in a predominantly vaporization-controlled regime. The Monte Carlo temperature distribution shows that the functional form of the PDF for the temperature fluctuations varies substantially from point to point. The results also bring to the fore some of the deficiencies associated with the use of assumed-shape PDF methods in spray computations.

Evidence for Particle Inward Transport, Theoretical prediction and Importance for Reacting Plasmas

NASA Astrophysics Data System (ADS)

Sharky, N.; Coppi, B.; Mazzotta, C.

2017-10-01

The fact that particle transport cannot be described by a diffusion equation but by one that would include an inflow term, involving transport in the direction of the density gradient, was evidenced by experiments on magnetically confined plasmas in which the central plasma density was observed to increase as a result of gas injection at the edge of the plasma column. The validity of the proposed equation has been repeatedly confirmed over the years and limitations for the occurrence of particle inflow in a variety of experimental conditions have been uncovered. The direct experimental observation of the inward propagating particle cloud leading to a profile peaking is described and the effects of different degrees of density peaking in fusion burning plasmas are analyzed. Sponsored in part by the U.S. DoE.

Preparation of superhydrophobic glass fiber and interfacially reinforced glass fiber/epoxy composites by grafting polysiloxane nanowires

NASA Astrophysics Data System (ADS)

Lv, Junwei; Wang, Bin; Ma, Qi; Li, Mengyao; Wang, Wenjing; Lu, Gaotaihang; Li, Hui; Zhao, Chunxia

2018-04-01

Ethyltrichlorosilane used as precursor reacted with glass fiber (GF) surface. Then polysiloxane was functionalized onto GF surface to improve GF’s hydrophobicity and interfacial properties of GF reinforced composites. Fourier transform infrared spectroscopy (FTIR) confirmed the successful grafting of polysiloxane onto GF’s surface. Energy dispersive spectroscopy (EDS) characterized the variation of chemical composition of GF surface. Scanning electron microscopy (SEM) images showed that the polysiloxane was grafted onto GF’s surface uniformly and the surface roughness of GF was enhanced obviously. Static contact angle analysis (SCA) revealed the significant improvement of surface hydrophobicity. Compared with the original GF composites, the interfacial shear strength (IFSS) increased by 36.52%. Meanwhile, we discovered a facile way to accomplish the experiment.

High speed turbulent reacting flows: DNS and LES

NASA Technical Reports Server (NTRS)

Givi, Peyman

1990-01-01

Work on understanding the mechanisms of mixing and reaction in high speed turbulent reacting flows was continued. Efforts, in particular, were concentrated on taking advantage of modern computational methods to simulate high speed turbulent flows. In doing so, two methodologies were used: large eddy simulations (LES) and direct numerical simulations (DNS). In the work related with LES the objective is to study the behavior of the probability density functions (pdfs) of scalar properties within the subgrid in reacting turbulent flows. The data base obtained by DNS for a detailed study of the pdf characteristics within the subgrid was used. Simulations are performed for flows under various initializations to include the effects of compressibility on mixing and chemical reactions. In the work related with DNS, a two-dimensional temporally developing high speed mixing layer under the influence of a second-order non-equilibrium chemical reaction of the type A + B yields products + heat was considered. Simulations were performed with different magnitudes of the convective Mach numbers and with different chemical kinetic parameters for the purpose of examining the isolated effects of the compressibility and the heat released by the chemical reactions on the structure of the layer. A full compressible code was developed and utilized, so that the coupling between mixing and chemical reactions is captured in a realistic manner.

Investigation on interfacial and electrical properties of Ge MOS capacitor with different NH3-plasma treatment procedure

NASA Astrophysics Data System (ADS)

Liu, Xiaoyu; Xu, Jingping; Liu, Lu; Cheng, Zhixiang; Huang, Yong; Gong, Jingkang

2017-08-01

The effects of different NH3-plasma treatment procedures on interfacial and electrical properties of Ge MOS capacitors with stacked gate dielectric of HfTiON/TaON were investigated. The NH3-plasma treatment was performed at different steps during fabrication of the stacked gate dielectric, i.e. before or after interlayer (TaON) deposition, or after deposition of high-k dielectric (HfTiON). It was found that the excellent interface quality with an interface-state density of 4.79 × 1011 eV-1 cm-2 and low gate leakage current (3.43 × 10-5 A/cm2 at {V}{{g}}=1 {{V}}) could be achieved for the sample with NH3-plasma treatment directly on the Ge surface before TaON deposition. The involved mechanisms are attributed to the fact that the NH3-plasma can directly react with the Ge surface to form more Ge-N bonds, i.e. more GeO x Ny, which effectively blocks the inter-diffusion of elements and suppresses the formation of unstable GeO x interfacial layer, and also passivates oxygen vacancies and dangling bonds near/at the interface due to more N incorporation and decomposed H atoms from the NH3-plasma. Project supported by the National Natural Science Foundation of China (Nos. 61176100, 61274112).

Comments on PDF methods

NASA Technical Reports Server (NTRS)

Chen, J.-Y.

1992-01-01

Viewgraphs are presented on the following topics: the grand challenge of combustion engineering; research of probability density function (PDF) methods at Sandia; experiments of turbulent jet flames (Masri and Dibble, 1988); departures from chemical equilibrium; modeling turbulent reacting flows; superequilibrium OH radical; pdf modeling of turbulent jet flames; scatter plot for CH4 (methane) and O2 (oxygen); methanol turbulent jet flames; comparisons between predictions and experimental data; and turbulent C2H4 jet flames.

Ab initio molecular dynamics simulation study of successive hydrogenation reactions of carbon monoxide producing methanol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pham, Thi Nu; Ono, Shota; Ohno, Kaoru, E-mail: ohno@ynu.ac.jp

Doing ab initio molecular dynamics simulations, we demonstrate a possibility of hydrogenation of carbon monoxide producing methanol step by step. At first, the hydrogen atom reacts with the carbon monoxide molecule at the excited state forming the formyl radical. Formaldehyde was formed after adding one more hydrogen atom to the system. Finally, absorption of two hydrogen atoms to formaldehyde produces methanol molecule. This study is performed by using the all-electron mixed basis approach based on the time dependent density functional theory within the adiabatic local density approximation for an electronic ground-state configuration and the one-shot GW approximation for an electronicmore » excited state configuration.« less

Modeling of turbulent supersonic H2-air combustion with a multivariate beta PDF

NASA Technical Reports Server (NTRS)

Baurle, R. A.; Hassan, H. A.

1993-01-01

Recent calculations of turbulent supersonic reacting shear flows using an assumed multivariate beta PDF (probability density function) resulted in reduced production rates and a delay in the onset of combustion. This result is not consistent with available measurements. The present research explores two possible reasons for this behavior: use of PDF's that do not yield Favre averaged quantities, and the gradient diffusion assumption. A new multivariate beta PDF involving species densities is introduced which makes it possible to compute Favre averaged mass fractions. However, using this PDF did not improve comparisons with experiment. A countergradient diffusion model is then introduced. Preliminary calculations suggest this to be the cause of the discrepancy.

Pressure balanced drag turbine mass flow meter

DOEpatents

Dacus, M.W.; Cole, J.H.

1980-04-23

The density of the fluid flowing through a tubular member may be measured by a device comprising a rotor assembly suspended within the tubular member, a fluid bearing medium for the rotor assembly shaft, independent fluid flow lines to each bearing chamber, and a scheme for detection of any difference between the upstream and downstream bearing fluid pressures. The rotor assembly reacts to fluid flow both by rotation and axial displacement; therefore concurrent measurements may be made of the velocity of blade rotation and also bearing pressure changes, where the pressure changes may be equated to the fluid momentum flux imparted to the rotor blades. From these parameters the flow velocity and density of the fluid may be deduced.

Pressure balanced drag turbine mass flow meter

DOEpatents

Dacus, Michael W.; Cole, Jack H.

1982-01-01

The density of the fluid flowing through a tubular member may be measured by a device comprising a rotor assembly suspended within the tubular member, a fluid bearing medium for the rotor assembly shaft, independent fluid flow lines to each bearing chamber, and a scheme for detection of any difference between the upstream and downstream bearing fluid pressures. The rotor assembly reacts to fluid flow both by rotation and axial displacement; therefore concurrent measurements may be made of the velocity of blade rotation and also bearing pressure changes, where the pressure changes may be equated to the fluid momentum flux imparted to the rotor blades. From these parameters the flow velocity and density of the fluid may be deduced.

Intumescent Coatings as Fire Retardants

NASA Technical Reports Server (NTRS)

Parker, J. A.; Fohlen, G. M.; Sawko, P. M.; Fish, R. H.

1970-01-01

The development of fire-retardant coatings to protect surfaces which may be exposed to fire or extreme heat is a subject of intense interest to many industries. A fire-retardant paint has been developed which represents a new chemical approach for preparing intumescent coatings, and potentially, is very important to fire-prevention authorities. The requirements for a superior coating include ease of application, suitability to a wide variety of surfaces and finishes, and stability over an extended period of time within a broad range of ambient temperature and humidity conditions. These innovative coatings, when activated by the heat of a fire, react to form a thick, low-density, polymeric coating or char layer. Water vapor and sulphur dioxide are released during the intumescent reaction. Two fire-protection mechanisms thus become available: (1) the char layer retards the flow of heat, due to the extremely low thermal conductivity; and (2) water vapor and sulfur dioxide are released, providing fire quenching properties. Still another mechanism functions in cases where the char, by virtue of its high oxidation resistance and low thermal conductivity, reaches a sufficiently high temperature to re-radiate much of the incident heat load. The coatings consist of dispersions of selective salts of a nitro-amino-arornatic compound. Specifically, para-nitroaniline bisulfate and the ammonium salt of para-nitroaniline-ortho sulphuric acid (2-amino-5-nitrobenzenesulphuric acid) are used. Suitable vehicles are cellulose nitrate of lacquer grade, a nitrite-phenolic modified rubber, or epoxy-polysulfide copolymer. Three separate formulations have been developed. A solvent is usually employed, such as methylethyl ketone, butyl acetate, or toluene, which renders the coatings suitably thin and which evaporates after the coatings are applied. Generally, the intumescent material is treated as insoluble in the vehicle, and is ground and dispersed in the vehicle and solvent like an ordinary coating pigment. The char found on intumescence is better in terms of yield and physical properties than chars obtained from many previously known intumescent materials. Prior to intumescence, the coating has a density of 85 pounds per cubic foot. After intumescence, the density is approximately 0.3 pounds per cubic loot. The linear expansion of the coatings ranges from 70 to 200 times the applied coating thickness.

Adhesion inhibition of Mycoplasma iowae to chicken lymphoma DT40 cells by monoclonal antibodies reacting with a 65-kD polypeptide.

PubMed

Fiorentin, L; Panangala, V S; Zhang, Y; Toivio-Kinnucan, M

1998-01-01

Tissue- and cell-specific attachment of mycoplasmas is a key aspect of the host-parasite relationship. In this study, monoclonal antibodies (MAbs) recognizing surface membrane polypeptides with molecular masses of 46 kD (p46) and 65 kD (p65), respectively, were examined in a microtiter cell attachment (agglutination) inhibition assay. MAbs MI3, MI6, and MI12 reacting with p65 polypeptide of Mycoplasma iowae inhibited attachment of the organisms to chicken lymphoma (DT 40) cells. One MAb (MI2) that reacted with p65 in immunoblots did not inhibit cell attachment, possibly because of the intrinsic native conformation of the epitope(s) in intact mycoplasmas as opposed to the linear state (sodium dodecyl sulfate denatured) in immunoblots. More pronounced M. iowae adherence inhibition was demonstrated by polyclonal turkey and mouse anti-M. iowae antisera compared with MAbs. Immunogold labelling followed by electron microscopy allowed us to localize the MAb-recognized epitopes on the membrane surface of M. iowae. On the basis of the cell attachment inhibition of M. iowae by specific MAbs (MI3, MI6, and MI12), we propose that the p65 polypeptide plays a role in cytadherence. The ability of polyclonal antisera to inhibit attachment of M. iowae more efficiently than the MAbs suggests that additional epitopes within p65 and/or other proteins are involved in cell attachment.

Mapping epitopes and antigenicity by site-directed masking

NASA Astrophysics Data System (ADS)

Paus, Didrik; Winter, Greg

2006-06-01

Here we describe a method for mapping the binding of antibodies to the surface of a folded antigen. We first created a panel of mutant antigens (-lactamase) in which single surface-exposed residues were mutated to cysteine. We then chemically tethered the cysteine residues to a solid phase, thereby masking a surface patch centered on each cysteine residue and blocking the binding of antibodies to this region of the surface. By these means we mapped the epitopes of several mAbs directed to -lactamase. Furthermore, by depleting samples of polyclonal antisera to the masked antigens and measuring the binding of each depleted sample of antisera to unmasked antigen, we mapped the antigenicity of 23 different epitopes. After immunization of mice and rabbits with -lactamase in Freund's adjuvant, we found that the antisera reacted with both native and denatured antigen and that the antibody response was mainly directed to an exposed and flexible loop region of the native antigen. By contrast, after immunization in PBS, we found that the antisera reacted only weakly with denatured antigen and that the antibody response was more evenly distributed over the antigenic surface. We suggest that denatured antigen (created during emulsification in Freund's adjuvant) elicits antibodies that bind mainly to the flexible regions of the native protein and that this explains the correlation between antigenicity and backbone flexibility. Denaturation of antigen during vaccination or natural infections would therefore be expected to focus the antibody response to the flexible loops. backbone flexibility | Freund's adjuvant | conformational epitope | antisera

Superhydrophobic photosensitizers. Mechanistic studies of (1)O2 generation in the plastron and solid/liquid droplet interface.

PubMed

Aebisher, David; Bartusik, Dorota; Liu, Yang; Zhao, Yuanyuan; Barahman, Mark; Xu, QianFeng; Lyons, Alan M; Greer, Alexander

2013-12-18

We describe here a physical-organic study of the first triphasic superhydrophobic sensitizer for photooxidations in water droplets. Control of synthetic parameters enables the mechanistic study of "borderline" two- and three-phase superhydrophobic sensitizer surfaces where (1)O2 is generated in compartments that are wetted, partially wetted, or remain dry in the plastron (i.e., air layer beneath the droplet). The superhydrophobic surface is synthesized by partially embedding silicon phthalocyanine (Pc) sensitizing particles to specific locations on polydimethylsiloxane (PDMS) posts printed in a square array (1 mm tall posts on 0.5 mm pitch). In the presence of red light and oxygen, singlet oxygen is formed on the superhydrophobic surface and reacts with 9,10-anthracene dipropionate dianion (1) within a freestanding water droplet to produce an endoperoxide in 54-72% yields. Control of the (1)O2 chemistry was achieved by the synthesis of superhydrophobic surfaces enriched with Pc particles either at the PDMS end-tips or at PDMS post bases. Much of the (1)O2 that reacts with anthracene 1 in the droplets was generated by the sensitizer "wetted" at the Pc particle/water droplet interface and gave the highest endoperoxide yields. About 20% of the (1)O2 can be introduced into the droplet from the plastron. The results indicate that the superhydrophobic sensitizer surface offers a unique system to study (1)O2 transfer routes where a balance of gas and liquid contributions of (1)O2 is tunable within the same superhydrophobic surface.

Forensic Chemistry: The Revelation of Latent Fingerprints

ERIC Educational Resources Information Center

Friesen, J. Brent

2015-01-01

The visualization of latent fingerprints often involves the use of a chemical substance that creates a contrast between the fingerprint residues and the surface on which the print was deposited. The chemical-aided visualization techniques can be divided into two main categories: those that chemically react with the fingerprint residue and those…

High-resolution single-molecule recognition imaging of the molecular details of ricin-aptamer interaction

USDA-ARS?s Scientific Manuscript database

The molecular details of DNA aptamer-ricin interactions were investigated. The toxic protein ricin molecules were immobilized on Au(111) surface using N-hydroxysuccinimide (NHS) ester to specifically react with lysine residues located on the ricin B chains. A single ricin molecule was visualized in ...

Idea Project Final Report, Engineered Visibility Warning Signals: Tests Of Time To React, Detectability, Identifiability And Salience

DOT National Transportation Integrated Search

1996-05-01

THIS INVESTIGATION WAS COMPLETED AS PART OF THE ITS-IDEA PROGRAM WHICH IS ONE OF THREE IDEA PROGRAMS MANAGED BY THE TRANSPORTATION RESEARCH BOARD (TRB) TO FOSTER INNOVATIONS IN SURFACE TRANSPORTATION. IT FOCUSES ON PRODUCTS AND RESULT FOR THE DEVELOP...

Wet-on-Wet: Wow!

ERIC Educational Resources Information Center

Guhin, Paula

1985-01-01

Seventh graders reacted enthusiastically to this watercolor art activity. A blank piece of white drawing paper was soaked in water and then removed to a newspaper-covered table. Students held a brush full of watercolor above the paper and squeezed the bristles. When the droplets hit the surface, they spread beautifully. (RM)

Characterizing Variability in Ohio River NOM and Validating Reconstituted Freeze-Dried NOM as a Surrogate for its Aqueous Source

EPA Science Inventory

Surface water contains natural organic matter (NOM) which reacts with disinfectants creating disinfection byproducts (DBPs), some of which are USEPA regulated contaminants. Characterizing NOM can provide important insight on DBP formation and water treatment process adaptation t...

Coupled Diffusion and Reaction Processes in Rock Matrices: Impact on Dilute Groundwater Plumes

DTIC Science & Technology

2015-12-28

28 Figure 3.5.6 Plastic dish used for permanganate diffusion experiment ........................................ 32 Figure 3.6.5...Manganese profiles following permanganate experiments ................................... 78 Figure 4.4.4.3 Carbon profiles...Figure A.3 SEM images and EDS spectra of permanganate -reacted surfaces ........................... 107

When Diagnostic Labels Mask Trauma

ERIC Educational Resources Information Center

Foltz, Robert; Dang, Sidney; Daniels, Brian; Doyle, Hillary; McFee, Scott; Quisenberry, Carolyn

2013-01-01

A growing body of research shows that many seriously troubled children and adolescents are reacting to adverse life experiences. Yet traditional diagnostic labels are based on checklists of surface symptoms. Distracted by disruptive behavior, the common response is to medicate, punish, or exclude rather than respond to needs of youth who have…

APOPTOSIS AND PROLIFERATION DURING DICHLOROACETIC ACID (DCA) INDUCED HEPTACELLULAR CARCINOGENESIS IN THE F344 MALE RAT

EPA Science Inventory

Apoptosis and Proliferation During DicWoroacetic Acid (DCA) Induced Hepatocellular
Carcinogenesis in the F344 Male Rat

Chlorine, introduced into public drinking \\\\'ater supplies for disinfection, can react with organic compounds in surface waters to form toxic by-prod...

Carbonate-mediated Mars-van Krevelen mechanism for CO oxidation on cobalt-doped ceria catalysts: facet-dependence and coordination-dependence.

PubMed

Liu, Bing; Li, Wenping; Song, Weiyu; Liu, Jian

2018-06-13

Carbonate intermediates have been reported to play an active role in CO oxidation over ceria-based catalysts in recent experimental studies. However, the detailed CO oxidation mechanism involving carbonate intermediates over ceria-based catalysts remains obscure. In this work, we carried out systematic density functional theory calculations corrected by on-site Coulomb interactions (DFT+U) to investigate the complete CO oxidation mechanism involving carbonate intermediates over cobalt-doped CeO2 catalysts, aiming to unravel how the carbonate participates in CO oxidation and shed light on the underlying factors that control the carbonate-mediated reaction mechanism. A novel carbonate-mediated Mars-van Krevelen (M-vK) mechanism was proposed, in which the carbonate acts as an active intermediate rather than a spectator and can react with CO to form CO2. This carbonate-mediated M-vK mechanism is facet-dependent because it is predominant on the (110) surface whereas the conventional M-vK mechanism is more favorable on (111) and (100) surfaces. The origin of facet-dependence was discussed by analyzing the geometric and electronic structures. It is found that the negatively charged bent CO2- intermediate formed on the (110) surface plays a critical role in the carbonate-mediated M-vK mechanism, whereas the formation of a neutral linear CO2 intermediate on (111) and (100) surfaces hinders the carbonate-mediated M-vK mechanism. The surface oxygen vacancy hinders the formation of carbonate intermediates, indicating that the carbonate-mediated M-vK mechanism is also vacancy-dependent. The formation of carbonate intermediates on different metal (Ti, V, W, Mo and Re) doped CeO2(110) surfaces was studied and the results indicate that the coordination environment of the dopant species is a key factor that determines the carbonate-mediated M-vK mechanism. This study provides atomic-scale insights into the reaction mechanism involving carbonate intermediates and the structure-mechanism relationship for CO oxidation over cobalt-ceria catalysts.

An Integrated Tool for the Coupled Thermal and Mechanical Analysis of Pyrolyzing Heatshield Materials

NASA Technical Reports Server (NTRS)

Pronchick, Stephen W.

1998-01-01

Materials that pyrolyze at elevated temperature have been commonly used as thermal protection materials in hypersonic flight, and advanced pyrolyzing materials for this purpose continue to be developed. Because of the large temperature gradients that can arise in thermal protection materials, significant thermal stresses can develop. Advanced applications of pyrolytic materials are calling for more complex heatshield configurations, making accurate thermal stress analysis more important, and more challenging. For non-pyrolyzing materials, many finite element codes are available and capable of performing coupled thermal-mechanical analyses. These codes do not, however, have a built-in capability to perform analyses that include pyrolysis effects. When a pyrolyzing material is heated, one or more components of the original virgin material pyrolyze and create a gas. This gas flows away from the pyrolysis zone to the surface, resulting in a reduction in surface heating. A porous residue, referred to as char, remains in place of the virgin material. While the processes involved can be complex, it has been found that a simple physical model in which virgin material reacts to form char and pyrolysis gas, will yield satisfactory analytical results. Specifically, the effects that must be modeled include: (1) Variation of thermal properties (density, specific heat, thermal conductivity) as the material composition changes; (2) Energy released or absorbed by the pyrolysis reactions; (3) Energy convected by the flow of pyrolysis gas from the interior to the surface; (4) The reduction in surface heating due to surface blowing; and (5) Chemical and mass diffusion effects at the surface between the pyrolysis gas and edge gas Computational tools for the one-dimensional thermal analysis these materials exist and have proven to be reliable design tools. The objective of the present work is to extend the analysis capabilities of pyrolyzing materials to axisymmetric configurations, and to couple thermal and mechanical analyses so that thermal stresses may be efficiently and accurately calculated.

Oxidation of boron nitride in an arc heated jet.

NASA Technical Reports Server (NTRS)

Buckley, J. D.

1971-01-01

Two grades of hot pressed boron nitride and a boron nitride composite were subjected to oxidation tests in a 2.5 megawatt atmospheric arc jet. The results showed that fabrication and/or composition influenced thermal shock and oxidation resistance. Changes in surface structure and recession due to oxidation suggest correlation with specimen composition. The boron nitride composite reacted with the oxygen in the hot subsonic airstream to produce a glassy coating on the hot face surface.

Copper Benzenetricarboxylate Metal-Organic Framework Nucleation Mechanisms on Metal Oxide Powders and Thin Films formed by Atomic Layer Deposition.

PubMed

Lemaire, Paul C; Zhao, Junjie; Williams, Philip S; Walls, Howard J; Shepherd, Sarah D; Losego, Mark D; Peterson, Gregory W; Parsons, Gregory N

2016-04-13

Chemically functional microporous metal-organic framework (MOF) crystals are attractive for filtration and gas storage applications, and recent results show that they can be immobilized on high surface area substrates, such as fiber mats. However, fundamental knowledge is still lacking regarding initial key reaction steps in thin film MOF nucleation and growth. We find that thin inorganic nucleation layers formed by atomic layer deposition (ALD) can promote solvothermal growth of copper benzenetricarboxylate MOF (Cu-BTC) on various substrate surfaces. The nature of the ALD material affects the MOF nucleation time, crystal size and morphology, and the resulting MOF surface area per unit mass. To understand MOF nucleation mechanisms, we investigate detailed Cu-BTC MOF nucleation behavior on metal oxide powders and Al2O3, ZnO, and TiO2 layers formed by ALD on polypropylene substrates. Studying both combined and sequential MOF reactant exposure conditions, we find that during solvothermal synthesis ALD metal oxides can react with the MOF metal precursor to form double hydroxy salts that can further convert to Cu-BTC MOF. The acidic organic linker can also etch or react with the surface to form MOF from an oxide metal source, which can also function as a nucleation agent for Cu-BTC in the mixed solvothermal solution. We discuss the implications of these results for better controlled thin film MOF nucleation and growth.

The role of mineral surface chemistry in modified dextrin adsorption.

PubMed

Beaussart, Audrey; Mierczynska-Vasilev, Agnieszka M; Harmer, Sarah L; Beattie, David A

2011-05-15

The adsorption of two modified dextrins (phenyl succinate dextrin--PS Dextrin; styrene oxide dextrin--SO Dextrin) on four different mineral surfaces has been studied using X-ray photoelectron spectroscopy (XPS), in situ atomic force microscopy (AFM) imaging, and captive bubble contact angle measurements. The four surfaces include highly orientated pyrolytic graphite (HOPG), freshly cleaved synthetic sphalerite (ZnS), and two surfaces produced through surface reactions of sphalerite: one oxidized in alkaline solution (pH 9, 1 h immersion); and one subjected to metal ion exchange between copper and zinc (i.e. copper activation: exposed to 1×10(-3) M CuSO(4) solution for 1 h). XPS measurements indicate that the different sphalerite surfaces contain varying amounts of sulfur, zinc, oxygen, and copper, producing substrates for polymer adsorption with a range of possible binding sites. AFM imaging has shown that the two polymers adsorb to a similar extent on HOPG, and that the two polymers display very different propensities for adsorption on the three sphalerite surface types, with freshly cleaved sphalerite encouraging the least adsorption, and copper activated and oxidized sphalerite encouraging significantly more adsorption. Contact angle measurements of the four surfaces indicate that synthetic sphalerite has a low contact angle upon fracture, and that oxidation on the timescale of one hour substantially alters the hydrophobicity. HOPG and copper-activated sphalerite were the most hydrophobic, as expected due to the carbon and di/poly-sulfide rich surfaces of the two samples, respectively. SO Dextrin is seen to have a significant impact on the wettability of HOPG and the surface reacted sphalerite samples, highlighting the difficulty in selectively separating sphalerite from carbonaceous unwanted minerals in flotation. PS Dextrin has the least effect on the hydrophobicity of the reacted sphalerite surfaces, whilst still significantly increasing the wettability of graphite, and thus has more potential for use as a polymer depressant in this separation. Copyright © 2011 Elsevier Inc. All rights reserved.

Assessing Chemical Transformation of Reactive, Interfacial Thin Films Made of End-Tethered Poly(2-vinyl-4,4-dimethyl azlactone) (PVDMA) Chains

DOE PAGES

Aden, Bethany; Kite, Camille M.; Hopkins, Benjamin W.; ...

2017-01-24

Designing thin films or surface scaffolds with an appropriate display of chemical functionality is useful for biomedical applications, sensing platforms, adhesives, and barrier coatings. Relationships between the structural characteristics of model thin films based on reactive poly(2-vinyl-4,4-dimethyl azlactone) (PVDMA) brushes and the amount and distribution of primary amines used to chemically functionalize these layers in situ are quantitatively detailed via neutron reflectometry and compared with results from ellipsometry. After functionalization, the PVDMA brush thickness increases as a result of the primary amines reacting with the azlactone rings. Both techniques show that the extent of functionalization by small-molecule amines depends onmore » the size of the amine, the grafting density of brush chains, and their molecular weight. However, constrained analysis of neutron reflectivity data predicated on that technique’s sensitivity to isotopic substitution and its ability to resolve structure at the nanoscale shows that the extent of functionalization is not accurately represented by the average extent of functionalization determined from ellipsometric thickness: reactive modification is not uniform, even in modestly dense brushes, except when the penetrant is small. In addition, there appears to be a loss of PVDMA chains during functionalization, attributed to chain scission resulting from additional stretching brought about by functionalization. In conclusion, these findings provide unprecedented insight into the alteration of surface properties by reactive modification and broadly support efforts to produce tailored surfaces in which properties such as friction, colloidal stability, adhesion, wettability, and biocompatibility can be modulated in situ by chemical modification.« less

Correction of localized shape errors on optical surfaces by altering the localized density of surface or near-surface layers

DOEpatents

Taylor, John S.; Folta, James A.; Montcalm, Claude

2005-01-18

Figure errors are corrected on optical or other precision surfaces by changing the local density of material in a zone at or near the surface. Optical surface height is correlated with the localized density of the material within the same region. A change in the height of the optical surface can then be caused by a change in the localized density of the material at or near the surface.

Isocyanate Cross-Linked Silica: Structurally Strong Aerogels

NASA Technical Reports Server (NTRS)

Leventis, Nicholas; Sotiriou-Leventis, Chariklia; Zhang, Guo-Hui; Rawashdeh, Abdel-Monem M.

2002-01-01

Molecular-level synergism between the silica nanoparticles of pre-formed monoliths and molecular cross-linkers inverts the relative host-guest roles in glass-polymer composites, leading to new strong low-density materials. Attempts to load gels with variable amounts of polyurethane precursors such as di-ISO and diol end-capped polybutylene adipate followed by heat treatment, washing, and supercritical drying led to opaque materials, somewhat stronger than silica but still quite brittle and much inferior to the materials described above. Direct mixing of a diisocyanate and an alcohol-free sol has been attempted recently by Yim et al. Reportedly, that procedure leads to week-long gelation times and requires an at least equally long aging period. In our attempt to add various amounts of di-ISO in a base-catalyzed sol in PC, we also noticed a week-long gelation time. The resulting aerogels were translucent but no less brittle than native silica. According to more recent studies, if propylene carbonate is replaced with acetone, it leads not only to shorter processing times, but also to much stronger gels that can tolerate loads in excess of 40 kg in the arrangement presented. We attribute that behavior to the lower viscosity of acetone, that allows faster diffusion of the di-ISO solution within the pores before di-ISO has time to react with the surface of silica. Further studies are underway to vary the chemical identity of the diisocyanate, as well as the composition and density of silica.

Recovery of valuable metals from cathodic active material of spent lithium ion batteries: Leaching and kinetic aspects.

PubMed

Meshram, Pratima; Pandey, B D; Mankhand, T R

2015-11-01

This work is focussed on the processing of cathodic active material of spent lithium ion batteries (LIBs) to ensure resource recovery and minimize environmental degradation. The sulfuric acid leaching of metals was carried out for the recovery of all the valuable metals including nickel and manganese along with the frequently targeted metals like lithium and cobalt. The process parameters such as acid concentration, pulp density, time and temperature for the leaching of metals from the cathode powder containing 35.8% Co, 6.5% Li, 11.6% Mn and 10.06% Ni, were optimized. Results show the optimized leach recovery of 93.4% Li, 66.2% Co, 96.3% Ni and 50.2% Mn when the material was leached in 1M H2SO4 at 368 K and 50 g/L pulp density for 240 min. The need of a reductant for improved recovery of cobalt and manganese has been explained by the thermodynamic analysis (Eh-pH diagram) for these metals. Leaching of the valuable metals was found to follow the logarithmic rate law controlled by surface layer diffusion of the lixiviant reacting with the particles. The mode of leaching of the metals from the spent LIBs was further examined by chemical analysis of the samples at various stage of processing which was further corroborated by characterizing the untreated sample and the leach residues by XRD phase identification and the SEM-EDS studies. Copyright © 2015 Elsevier Ltd. All rights reserved.

High strength kiloampere Bi 2Sr 2CaCu 2O x cables for high-field magnet applications

DOE PAGES

Shen, Tengming; Li, Pei; Jiang, Jianyi; ...

2015-04-17

Multifilamentary Ag-sheathed Bi 2Sr 2CaCu 2O x (Bi-2212) wire can carry sufficient critical current density J c for the development of powerful superconducting magnets. But, the range of its applications is limited by the low mechanical strength of the Ag/Bi-2212 strand. A potential solution is to cable Ag/Bi-2212 wire with high-strength materials that are compatible with the Bi-2212 heat treatment in an oxygen atmosphere. Past attempts have not always been successful, because the high-strength materials reacted with Bi-2212 wires, significantly reducing their J c. We examined the nature of reactions occurring when Ag/Bi-2212 wires are heat-treated in direct contact withmore » several commonly used high-strength alloys and a new Fe-Cr-Al alloy. INCONEL X750 and INCONEL 600 resulted in significant J c loss, whereas Ni80-Cr caused little or no J c loss; however, all of them formed chromium oxide that subsequently reacted with silver, creating cracks in the silver sheath. We found that Fe-Cr-Al did not show significant reactions with Ag/Bi-2212 strands. Scanning electron microscopy (SEM) and energy dispersive x-ray (EDS) examinations revealed that the Fe-Cr-Al alloy benefits from the formation of a uniform, crack-free, continuous alumina layer on its surface that does not react with Ag and that helps minimize the Cu loss found with INCONEL X750 and INCONEL 600. We then fabricated prototype 6-around-1 cables with six Bi-2212 strands twisted and transposed around an Fe-Cr-Al alloy core coated with TiO 2. After standard 1 bar melt processing, the cable retained 100% of the total current-carrying capability of its strands, and, after a 10 bar overpressure processing, the cable reached a total current of 1025 A at 4.2 K and 10 T. Tensile tests showed that Fe-Cr-Al becomes brittle after being cooled to 4.2 K, whereas INCONEL X750 remains ductile and retains a modulus of 183 GPa. Finally. we proposed new cable designs that take advantage of the chemical compatibility of Fe-Cr-Al and high strength of INCONEL X750 for various high-field magnet applications.« less

An LES-PBE-PDF approach for modeling particle formation in turbulent reacting flows

NASA Astrophysics Data System (ADS)

Sewerin, Fabian; Rigopoulos, Stelios

2017-10-01

Many chemical and environmental processes involve the formation of a polydispersed particulate phase in a turbulent carrier flow. Frequently, the immersed particles are characterized by an intrinsic property such as the particle size, and the distribution of this property across a sample population is taken as an indicator for the quality of the particulate product or its environmental impact. In the present article, we propose a comprehensive model and an efficient numerical solution scheme for predicting the evolution of the property distribution associated with a polydispersed particulate phase forming in a turbulent reacting flow. Here, the particulate phase is described in terms of the particle number density whose evolution in both physical and particle property space is governed by the population balance equation (PBE). Based on the concept of large eddy simulation (LES), we augment the existing LES-transported probability density function (PDF) approach for fluid phase scalars by the particle number density and obtain a modeled evolution equation for the filtered PDF associated with the instantaneous fluid composition and particle property distribution. This LES-PBE-PDF approach allows us to predict the LES-filtered fluid composition and particle property distribution at each spatial location and point in time without any restriction on the chemical or particle formation kinetics. In view of a numerical solution, we apply the method of Eulerian stochastic fields, invoking an explicit adaptive grid technique in order to discretize the stochastic field equation for the number density in particle property space. In this way, sharp moving features of the particle property distribution can be accurately resolved at a significantly reduced computational cost. As a test case, we consider the condensation of an aerosol in a developed turbulent mixing layer. Our investigation not only demonstrates the predictive capabilities of the LES-PBE-PDF model but also indicates the computational efficiency of the numerical solution scheme.

Current-voltage characteristics influenced by the nanochannel diameter and surface charge density in a fluidic field-effect-transistor.

PubMed

Singh, Kunwar Pal; Guo, Chunlei

2017-06-21

The nanochannel diameter and surface charge density have a significant impact on current-voltage characteristics in a nanofluidic transistor. We have simulated the effect of the channel diameter and surface charge density on current-voltage characteristics of a fluidic nanochannel with positive surface charge on its walls and a gate electrode on its surface. Anion depletion/enrichment leads to a decrease/increase in ion current with gate potential. The ion current tends to increase linearly with gate potential for narrow channels at high surface charge densities and narrow channels are more effective to control the ion current at high surface charge densities. The current-voltage characteristics are highly nonlinear for wide channels at low surface charge densities and they show different regions of current change with gate potential. The ion current decreases with gate potential after attaining a peak value for wide channels at low values of surface charge densities. At low surface charge densities, the ion current can be controlled by a narrow range of gate potentials for wide channels. The current change with source drain voltage shows ohmic, limiting and overlimiting regions.

A model of Martian surface chemistry

NASA Technical Reports Server (NTRS)

Oyama, V. I.; Berdahl, B. J.

1979-01-01

Alkaline earth and alkali metal superoxides and peroxides, gamma-Fe2O3 and carbon suboxide polymer, are proposed to be constituents of the Martian surface material. These reactive substances explain the water modified reactions and thermal behaviors of the Martian samples demonstrated by all of the Viking Biology Experiments. It is also proposed that the syntheses of these substances result mainly from electrical discharges between wind-mobilized particles at Martian pressures; plasmas are initiated and maintained by these discharges. Active species in the plasma either combine to form or react with inorganic surfaces to create the reactive constituents.

STM observation of the chemical reaction of atomic hydrogen on the N-adsorbed Cu(001) surface

NASA Astrophysics Data System (ADS)

Hattori, Takuma; Yamada, Masamichi; Komori, Fumio

2017-01-01

Chemical reaction of atomic hydrogen with the N-adsorbed Cu(001) surfaces was investigated at room temperature by scanning tunnel microscopy. At the low exposure of atomic hydrogen, it reacted with the N atoms and turned to be the NH species on the surface. The reaction rate is proportional to the amount of the unreacted N atoms. By increasing the exposure of atomic hydrogen from this condition, the amount of nitrogen species on the surface decreased. This is attributed to the formation of ammonia and its desorption from the surface. The NH species on the surface turn to NH3 through the surface NH2 species by atomic hydrogen. Coexistence of the clean Cu surface enhances the rate of ammonia formation owing to atomic hydrogen migrating on the clean surface.

Method for making monolithic metal oxide aerogels

DOEpatents

Droege, M.W.; Coronado, P.R.; Hair, L.M.

1995-03-07

Transparent, monolithic metal oxide aerogels of varying densities are produced using a method in which a metal alkoxide solution and a catalyst solution are prepared separately and reacted. The resulting hydrolyzed-condensed colloidal solution is gelled, and the wet gel is contained within a sealed, but gas permeable, containment vessel during supercritical extraction of the solvent. The present invention is especially advantageous for making metal oxides other than silica that are prone to forming opaque, cracked aerogels. 6 figs.

Method for making monolithic metal oxide aerogels

DOEpatents

Droege, Michael W.; Coronado, Paul R.; Hair, Lucy M.

1995-01-01

Transparent, monolithic metal oxide aerogels of varying densities are produced using a method in which a metal alkoxide solution and a catalyst solution are prepared separately and reacted. The resulting hydrolyzed-condensed colloidal solution is gelled, and the wet gel is contained within a sealed, but gas permeable, containment vessel during supercritical extraction of the solvent. The present invention is especially advantageous for making metal oxides other than silica that are prone to forming opaque, cracked aerogels.

Phenylethynyl reactive diluents

NASA Technical Reports Server (NTRS)

Bryant, Robert G. (Inventor); Jensen, Brian J. (Inventor); Hergenrother, Paul M. (Inventor)

1995-01-01

A composition of matter having a specified general structure is employed to terminate a nucleophilic reagent, resulting in the exclusive production of phenylethynyl terminated reactive oligomers which display unique thermal characteristics. A reactive diluent having a specified general structure is employed to decrease the melt viscosity of a phenylethynyl terminated reactive oligomer and to subsequently react with to provide a thermosetting material of enhanced density. These materials have features which make them attractive candidates for use as composite matrices and adhesives.

Direct computation of thermodynamic properties of chemically reacting air with consideration to CFD

NASA Astrophysics Data System (ADS)

Iannelli, Joe

2003-10-01

This paper details a two-equation procedure to calculate exactly mass and mole fractions, pressure, temperature, specific heats, speed of sound and the thermodynamic and jacobian partial derivatives of pressure and temperature for a five-species chemically reacting equilibrium air. The procedure generates these thermodynamic properties using as independent variables either pressure and temperature or density and internal energy, for CFD applications. An original element in this procedure consists in the exact physically meaningful solution of the mass-fraction and mass-action equations. Air-equivalent molecular masses for oxygen and nitrogen are then developed to account, within a mixture of only oxygen and nitrogen, for the presence of carbon dioxide, argon and the other noble gases within atmospheric air. The mathematical formulation also introduces a versatile system non-dimensionalization that makes the procedure uniformly applicable to flows ranging from shock-tube flows with zero initial velocity to aerothermodynamic flows with supersonic/hypersonic free-stream Mach numbers. Over a temperature range of more than 10000 K and pressure and density ranges corresponding to an increase in altitude in standard atmosphere of 30000 m above sea level, the predicted distributions of mole fractions, constant-volume specific heat, and speed of sound for the model five species agree with independently published results, and all the calculated thermodynamic properties, including their partial derivatives, remain continuous, smooth, and physically meaningful.

Entropy Filtered Density Function for Large Eddy Simulation of Turbulent Reacting Flows

NASA Astrophysics Data System (ADS)

Safari, Mehdi

Analysis of local entropy generation is an effective means to optimize the performance of energy and combustion systems by minimizing the irreversibilities in transport processes. Large eddy simulation (LES) is employed to describe entropy transport and generation in turbulent reacting flows. The entropy transport equation in LES contains several unclosed terms. These are the subgrid scale (SGS) entropy flux and entropy generation caused by irreversible processes: heat conduction, mass diffusion, chemical reaction and viscous dissipation. The SGS effects are taken into account using a novel methodology based on the filtered density function (FDF). This methodology, entitled entropy FDF (En-FDF), is developed and utilized in the form of joint entropy-velocity-scalar-turbulent frequency FDF and the marginal scalar-entropy FDF, both of which contain the chemical reaction effects in a closed form. The former constitutes the most comprehensive form of the En-FDF and provides closure for all the unclosed filtered moments. This methodology is applied for LES of a turbulent shear layer involving transport of passive scalars. Predictions show favor- able agreements with the data generated by direct numerical simulation (DNS) of the same layer. The marginal En-FDF accounts for entropy generation effects as well as scalar and entropy statistics. This methodology is applied to a turbulent nonpremixed jet flame (Sandia Flame D) and predictions are validated against experimental data. In both flows, sources of irreversibility are predicted and analyzed.

Membrane-associated mucins in normal human conjunctiva.

PubMed

Berry, M; Ellingham, R B; Corfield, A P

2000-02-01

To examine the presence of specific membrane-associated mucins in normal human conjunctiva. Glycoconjugates were extracted from membranes with two detergents: octylglucoside and Triton X114. Mucins were separated by cesium chloride density gradient centrifugation. Size was assessed by gel filtration on Sepharose CL2B and charge by ion-exchange chromatography on MonoQ. Cross reaction with antibodies against mucin gene products was assessed in blots of electrophoresis gels. Extraction of total tissue membranes yielded material with a buoyant density typical of mucins. Gel filtration showed material reacting with antimucin antibodies in a range of molecular sizes. Agarose electrophoresis confirmed the presence of MUC1 and MUC4 and the absence of MUC2 or MUC5AC. Isolation of membrane mucins by sequential, exhaustive extraction with octylglucoside followed by Triton X114 suggested the existence of mucins in different membrane environments. Reagents to carbohydrate epitopes revealed high mobility material, comigrating with MUC1 and MUC4. Low mobility membrane-bound mucins did not cross-react with any antibodies to mucin genes known to be expressed in human conjunctiva. Membrane-associated mucins are distinct from secreted mucins in normal human conjunctiva. MUC1 and MUC4 mature products decorate the membranes of conjunctival epithelial cells. Their segregation between octyl glucoside and the detergent and aqueous phases of Triton X114 suggests a variety of membrane anchoring modes.

Chemical factors that control lignin polymerization.

PubMed

Sangha, Amandeep K; Davison, Brian H; Standaert, Robert F; Davis, Mark F; Smith, Jeremy C; Parks, Jerry M

2014-01-09

Lignin is a complex, branched polymer that reinforces plant tissue. Understanding the factors that govern lignin structure is of central importance to the development of technologies for converting lignocellulosic biomass into fuels because lignin imparts resistance to chemical, enzymatic, and mechanical deconstruction. Lignin is formed by enzymatic oxidation of phenolic monomers (monolignols) of three main types, guaiacyl (G), syringyl (S), and p-hydroxyphenyl (H) subunits. It is known that increasing the relative abundance of H subunits results in lower molecular weight lignin polymers and hence more easily deconstructed biomass, but it is not known why. Here, we report an analysis of frontier molecular orbitals in mono-, di-, and trilignols, calculated using density functional theory, which points to a requirement of strong p-electron density on the reacting phenolic oxygen atom of the neutral precursor for enzymatic oxidation to occur. This model is consistent with a proton-coupled electron transfer (PCET) mechanism and for the first time explains why H subunits in certain linkages (β-β or β-5) react poorly and tend to "cap" the polymer. In general, β-5 linkages with either a G or H terminus are predicted to inhibit elongation. More broadly, the model correctly accounts for the reactivity of the phenolic groups in a diverse set of dilignols comprising H and G subunits. Thus, we provide a coherent framework for understanding the propensity toward growth or termination of different terminal subunits in lignin.

Simulations of Turbulent Momentum and Scalar Transport in Non-Reacting Confined Swirling Coaxial Jets

NASA Technical Reports Server (NTRS)

Shih, Tsan-Hsing; Liu, Nan-Suey; Moder, Jeffrey P.

2015-01-01

This paper presents the numerical simulations of confined three-dimensional coaxial water jets. The objectives are to validate the newly proposed nonlinear turbulence models of momentum and scalar transport, and to evaluate the newly introduced scalar APDF and DWFDF equation along with its Eulerian implementation in the National Combustion Code (NCC). Simulations conducted include the steady RANS, the unsteady RANS (URANS), and the time-filtered Navier-Stokes (TFNS); both without and with invoking the APDF or DWFDF equation. When the APDF (ensemble averaged probability density function) or DWFDF (density weighted filtered density function) equation is invoked, the simulations are of a hybrid nature, i.e., the transport equations of energy and species are replaced by the APDF or DWFDF equation. Results of simulations are compared with the available experimental data. Some positive impacts of the nonlinear turbulence models and the Eulerian scalar APDF and DWFDF approach are observed.

Spheroidization of glass powders for glass ionomer cements.

PubMed

Gu, Y W; Yap, A U J; Cheang, P; Kumar, R

2004-08-01

Commercial angular glass powders were spheroidized using both the flame spraying and inductively coupled radio frequency plasma spraying techniques. Spherical powders with different particle size distributions were obtained after spheroidization. The effects of spherical glass powders on the mechanical properties of glass ionomer cements (GICs) were investigated. Results showed that the particle size distribution of the glass powders had a significant influence on the mechanical properties of GICs. Powders with a bimodal particle size distribution ensured a high packing density of glass ionomer cements, giving relatively high mechanical properties of GICs. GICs prepared by flame-spheroidized powders showed low strength values due to the loss of fine particles during flame spraying, leading to a low packing density and few metal ions reacting with polyacrylic acid to form cross-linking. GICs prepared by the nano-sized powders showed low strength because of the low bulk density of the nano-sized powders and hence low powder/liquid ratio of GICs.

A complex magma mixing origin for rocks erupted in 1915, Lassen Peak, California

USGS Publications Warehouse

Clynne, M.A.

1999-01-01

The eruption of Lassen Peak in May 1915 produced four volcanic rock types within 3 days, and in the following order: (1) hybrid black dacite lava containing (2) undercooled andesitic inclusions, (3) compositionally banded pumice with dark andesite and light dacite bands, and (4) unbanded light dacite. All types represent stages of a complex mixing process between basaltic andesite and dacite that was interrupted by the eruption. They contain disequilibrium phenocryst assemblages characterized by the co-existence of magnesian olivine and quartz and by reacted and unreacted phenocrysts derived from the dacite. The petrography and crystal chemistry of the phenocrysts and the variation in rock compositions indicate that basaltic andesite intruded dacite magma and partially hybridized with it. Phenocrysts from the dacite magma were reacted. Cooling, cyrstallization, and vesiculation of the hybrid andesite magma converted it to a layer of mafic foam. The decreased density of the andesite magma destabilized and disrupted the foam. Blobs of foam rose into and were further cooled by the overlying dacite magma, forming the andesitic inclusions. Disaggregation of andesitic inclusions in the host dacite produced the black dacite and light dacite magmas. Formation of foam was a dynamic process. Removal of foam propagated the foam layer downward into the hybrid andesite magma. Eventually the thermal and compositional contrasts between the hybrid andesite and black dacite magmas were reduced. Then, they mixed directly, forming the dark andesite magma. About 40-50% andesitic inclusions were disaggregated into the host dacite to produce the hybrid black dacite. Thus, disaggregation of inclusions into small fragments and individual crystals can be an efficient magma-mixing process. Disaggregation of undercooled inclusions carrying reacted host-magma phenocrysts produces co-existing reacted and unreacted phenocrysts populations.

Rotational and vibrational Raman spectroscopy for thermochemistry measurements in supersonic flames

NASA Astrophysics Data System (ADS)

Bayeh, Alexander Christian

High speed chemically reacting flows are important in a variety of aerospace applications, namely ramjets, scramjets, afterburners, and rocket exhausts. To study flame extinction under similar high Mach number conditions, we need access to thermochemistry measurements in supersonic environments. In the current work a two-stage miniaturized combustor has been designed that can produce open supersonic methane-air flames amenable to laser diagnostics. The first stage is a vitiation burner, and was inspired by well-known principles of jet combustors. We explored the salient parameters of operation experimentally, and verified flame holding computationally using a well-stirred reactor model. The second stage of the burner generates an external supersonic flame, operating in premixed and partially premixed modes. The very high Mach numbers present in the supersonic flames should provide a useful test bed for the examination of flame suppression and extinction using laser diagnostics. We also present the development of new line imaging diagnostics for thermochemistry measurements in high speed flows. A novel combination of vibrational and rotational Raman scattering is used to measure major species densities (O 2, N2, CH4, H2O,CO2, CO, & H2) and temperature. Temperature is determined by the rotational Raman technique by comparing measured rotational spectra to simulated spectra based on the measured chemical composition. Pressure is calculated from density and temperature measurements through the ideal gas law. The independent assessment of density and temperature allows for measurements in environments where the pressure is not known a priori. In the present study we applied the diagnostics to laboratory scale supersonic air and vitiation jets, and examine the feasibility of such measurements in reacting supersonic flames. Results of full thermochemistry were obtained for the air and vitiation jets that reveal the expected structure of an under-expanded jet. Centerline traces of density, temperature, and pressure of the air jet agree well with computations, while measurements of chemical composition for the vitiation flow also agree well with predicted equilibrium values. Finally, we apply the new diagnostics to the exhaust of the developed burner, and show the first ever results for density, temperature, and pressure, as well as chemical composition in a supersonic flame.

Controlled Interphases in Glass Fiber and Particulate Reinforced Polymers: Structure of Silane Coupling Agents in Solutions and On Substrates

DTIC Science & Technology

1993-01-01

to dissolve into water. Table 3. Typical industrially used silane coupling agents Organofunctional Chemical Formula Group Cationic styryl CH2...can also react with the surface as some unreacted silanol groups remain in the oligomers. The notion of physisorbed and chemisorbed silanes is used ...silanes use many silanol groups for covalent bonding with the substrate surface whereas the loosely chemisorbed silanes use only a few silanols to bond to

Deposition of Polymer Thin Films on ZnO Nanoparticles by a Plasma Treatment

DTIC Science & Technology

2001-11-01

exchange for removing metal ions frori water. If on the surface of these nanoparticles, an extremely thin layer of polyacrylic filr can be coated by a...plasma treatment. The polyacrylic film will react with metallic ions in water. As a result of the high surface-to-volume ratio of these narioparticles, the...experiments performed on a JEM 2010F. In FFIR experiment, potassium bromide(KBr) of 99%+ purity was obtained from Aldrich Chemical Company Inc

Evidence for glycosyl-phosphatidylinositol anchoring of Toxoplasma gondii major surface antigens

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tomavo, S.; Schwarz, R.T.; Dubremetz, J.F.

1989-10-01

The four major surface antigens of Toxoplasma gondii tachyzoites (P43, P35, P30, and P22) were made water soluble by phosphatidylinositol-specific phospholipase C (PI-PLC). These antigens were biosynthetically labeled with {sup 3}H-fatty acids, ({sup 3}H)ethanolamine, and ({sup 3}H)carbohydrates. Treatment of {sup 3}H-fatty-acid-labeled parasite lysates with PI-PLC removed the radioactive label from these antigens. A cross-reacting determinant was exposed on these antigens after PI-PLC treatment.

Surface Antigens Common to Mouse Cleavage Embryos and Primitive Teratocarcinoma Cells in Culture

PubMed Central

Artzt, Karen; Dubois, Philippe; Bennett, Dorothea; Condamine, Hubert; Babinet, Charles; Jacob, François

1973-01-01

Syngeneic antisera have been produced in mouse strain 129/Sv-CP males against the primitive cells of teratocarcinoma. These sera react specifically with the primitive cells and are negative on various types of differentiated teratoma cells derived from the same original tumor. They are negative on all other mouse cells tested, with the exception of male germ cells and cleavage-stage embryos. Thus, teratoma cells possess cell-surface antigens in common with normal cleavage-stage embryos. Images PMID:4355379

Ethylene Glycol Adsorption and Reaction over CeOX(111) Thin Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mullins, David R; Chen, Tsung-Liang

2011-01-01

This study reports the interaction of ethylene glycol with well-ordered CeO{sub x}(111) thin film surfaces. Ethylene glycol initially adsorbs on fully oxidized CeO{sub 2}(111) and reduced CeO{sub 2-x}(111) through the formation of one C-O-Ce bond and then forms a second alkoxy bond after annealing. On fully oxidized CeO{sub 2}(111) both recombination of ethylene glycol and water desorption occur at low temperature leaving stable -OCH{sub 2}CH{sub 2}O- (ethylenedioxy) intermediates and oxygen vacancies on the surface. This ethylenedioxy intermediate goes through C-C bond scission to produce formate species which then react to produce CO and CO{sub 2}. The formation of water resultsmore » in the reduction of the ceria. On a reduced CeO{sub 2-x}(111) surface the reaction selectivity shifts toward a dehydration process. The ethylenedioxy intermediate decomposes by breaking a C-O bond and converts into an enolate species. Similar to the reaction of acetaldehyde on reduced CeO{sub 2-x}(111), the enolate reacts to produce acetaldehyde, acetylene, and ethylene. The loss of O from ethylene glycol leads to a small amount of oxidation of the reduced ceria.« less

Ethylene Glycol Adsorption and Reaction over CeOX(111) Thin Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

T Chen; D Mullins

2011-12-31

This study reports the interaction of ethylene glycol with well-ordered CeO{sub x}(111) thin film surfaces. Ethylene glycol initially adsorbs on fully oxidized CeO{sub 2}(111) and reduced CeO{sub 2-x}(111) through the formation of one C-O-Ce bond and then forms a second alkoxy bond after annealing. On fully oxidized CeO{sub 2}(111) both recombination of ethylene glycol and water desorption occur at low temperature leaving stable -OCH{sub 2}CH{sub 2}O- (ethylenedioxy) intermediates and oxygen vacancies on the surface. This ethylenedioxy intermediate goes through C-C bond scission to produce formate species which then react to produce CO and CO{sub 2}. The formation of water resultsmore » in the reduction of the ceria. On a reduced CeO{sub 2-x}(111) surface the reaction selectivity shifts toward a dehydration process. The ethylenedioxy intermediate decomposes by breaking a C-O bond and converts into an enolate species. Similar to the reaction of acetaldehyde on reduced CeO{sub 2-x}(111), the enolate reacts to produce acetaldehyde, acetylene, and ethylene. The loss of O from ethylene glycol leads to a small amount of oxidation of the reduced ceria.« less

Polyelectrolyte coating on superparamagnetic iron oxide nanoparticles as interface between magnetic core and biorelevant media

PubMed Central

Farkas, Katalin; Földesi, Imre; Szekeres, Márta; Illés, Erzsébet; Tóth, Ildikó Y.; Nesztor, Daniel; Szabó, Tamás

2016-01-01

Nanoparticles do not exist in thermodynamical equilibrium because of high surface free energy, thus they have only kinetic stability. Spontaneous changes can be delayed by designed surface coating. In biomedical applications, superparamagnetic iron oxide nanoparticles (SPIONs) require an optimized coating in order to fulfil the expectation of medicine regulatory agencies and ultimately that of biocompatibility. In this work, we show the high surface reactivity of naked SPIONs due to ≡Fe–OH sites, which can react with H+/OH− to form pH- and ionic strength-dependent charges. We explain the post-coating of naked SPIONs with organic polyacids via multi-site complex bonds formed spontaneously. The excess polyacids can be removed from the medium. The free COOH groups in coating are prone to react with active biomolecules like proteins. Charging and pH- and salt-dependent behaviour of carboxylated SPIONs were characterized quantitatively. The interrelation between the coating quality and colloidal stability measured under biorelevant conditions is discussed. Our coagulation kinetics results allow us to predict colloidal stability both on storage and in use; however, a simpler method would be required to test SPION preparations. Haemocompatibility tests (smears) support our qualification for good and bad SPION manufacturing; the latter ‘promises’ fatal outcome in vivo. PMID:27920900

Heterogeneous Atmospheric Chemistry of Lead Oxide Particles with Nitrogen Dioxide Increases Lead Solubility: Environmental and Health Implications

PubMed Central

Baltrusaitis, Jonas; Chen, Haihan; Rubasinghege, Gayan

2012-01-01

Heterogeneous chemistry of nitrogen dioxide with lead-containing particles is investigated to better understand lead metal mobilization in the environment. In particular, PbO particles, a model lead-containing compound due to its wide spread presence as a component of lead paint and as naturally occurring minerals, massicot and litharge, are exposed to nitrogen dioxide at different relative humidity. X-ray photoelectron spectroscopy (XPS) shows that upon exposure to nitrogen dioxide the surface of PbO particles react to form adsorbed nitrates and lead nitrate thin films with the extent of formation of nitrate relative humidity dependent. Surface adsorbed nitrate increases the amount of dissolved lead. These reacted particles are found to have an increase in the amount of lead that dissolves in aqueous suspensions at circumneutral pH compared to unreacted particles. These results point to the potential importance and impact that heterogeneous chemistry with trace atmospheric gases can have on increasing solubility and therefore the mobilization of heavy metals, such as lead, in the environment. This study also show that surface intermediates, such as adsorbed nitrates, that form can yield higher concentrations of lead in water systems. In the environment, these water systems can include drinking water, ground water, estuaries and lakes. PMID:23057678

A stochastic particle method for the investigation of turbulence/chemistry interactions in large-eddy simulations of turbulent reacting flows

NASA Astrophysics Data System (ADS)

Ferrero, Pietro

The main objective of this work is to investigate the effects of the coupling between the turbulent fluctuations and the highly non-linear chemical source terms in the context of large-eddy simulations of turbulent reacting flows. To this aim we implement the filtered mass density function (FMDF) methodology on an existing finite volume (FV) fluid dynamics solver. The FMDF provides additional statistical sub-grid scale (SGS) information about the thermochemical state of the flow - species mass fractions and enthalpy - which would not be available otherwise. The core of the methodology involves solving a transport equation for the FMDF by means of a stochastic, grid-free, Lagrangian particle procedure. Any moments of the distribution can be obtained by taking ensemble averages of the particles. The main advantage of this strategy is that the chemical source terms appear in closed form so that the effects of turbulent fluctuations on these terms are already accounted for and do not need to be modeled. We first validate and demonstrate the consistency of our implementation by comparing the results of the hybrid FV/FMDF procedure against model-free LES for temporally developing, non-reacting mixing layers. Consistency requires that, for non-reacting cases, the two solvers should yield identical solutions. We investigate the sensitivity of the FMDF solution on the most relevant numerical parameters, such as the number of particles per cell and the size of the ensemble domain. Next, we apply the FMDF modeling strategy to the simulation of chemically reacting, two- and three-dimensional temporally developing mixing layers and compare the results against both DNS and model-free LES. We clearly show that, when the turbulence/chemistry interaction is accounted for with the FMDF methodology, the results are in much better agreement to the DNS data. Finally, we perform two- and three-dimensional simulations of high Reynolds number, spatially developing, chemically reacting mixing layers, with the intent of reproducing a set of experimental results obtained at the California Institute of Technology. The mean temperature rise calculated by the hybrid FV/FMDF solver, which is associated with the amount of product formed, lies very close to the experimental profile. Conversely, when the effects of turbulence/chemistry coupling are ignored, the simulations clearly over predict the amount of product that is formed.

Textured-surface quartz resonator fluid density and viscosity monitor

DOEpatents

Martin, Stephen J.; Wiczer, James J.; Cernosek, Richard W.; Frye, Gregory C.; Gebert, Charles T.; Casaus, Leonard; Mitchell, Mary A.

1998-08-25

A pair of thickness-shear mode resonators, one smooth and one with a textured surface, allows fluid density and viscosity to be independently resolved. A textured surface, either randomly rough or regularly patterned, leads to trapping of liquid at the device surface. The synchronous motion of this trapped liquid with the oscillating device surface allows the device to weigh the liquid; this leads to an additional response that depends on liquid density. This additional response enables a pair of devices, one smooth and one textured, to independently resolve liquid density and viscosity; the difference in responses determines the density while the smooth device determines the density-viscosity product, and thus, the pair determines both density and viscosity.

p-Nitrophenol and glutathione response in medaka (Oryzias latipes)exposed to MX, a drinking water carcinogen

EPA Science Inventory

When chlorine is introduced into public drinking water for disinfection, it can react with organic compounds in surface waters to form toxic by-products such as 3-chloro-4-(dichloromethyl)-5-hydroxy-2[5H]-furanone (MX). We investigated the effect of exposure to MX on cytochrome ...

P-NITROPHENOL AND GLUTATHIONE RESPONSE IN MEDAKA (ORYZIAS LATIPES) EXPOSED TO MX, A DRINKING WATER CARCINOGEN.

EPA Science Inventory

When chlorine is introduced into public drinking water for disinfection, it can react with organic compounds in surface waters to form toxic by-products such as 3-chloro-4- (dichloromethyl)-5-hydroxy-2[5H]-furanone (MX). We investigated the effect of exposure to MX on cytochr...

Health Wise: March 2010

ERIC Educational Resources Information Center

Streker, Meg

2010-01-01

In this article, the author discusses how to tell the difference between a cold and airborne allergy symptoms. A cold is caused by a viral infection. Viruses spread through an infected person's cough, sneeze, handshake, or contact with a contaminated surface. When a virus enters one's body, his/her immune system reacts. This produces the symptoms…

Method of Obtaining Uniform Coatings on Graphite

DOEpatents

Campbell, I. E.

1961-04-01

A method is given for obtaining uniform carbide coatings on graphite bodies. According to the invention a metallic halide in vapor form is passed over the graphite body under such conditions of temperature and pressure that the halide reacts with the graphite to form a coating of the metal carbide on the surface of the graphite.

METHOD OF OBTAINING UNIFORM COATINGS ON GRAPHITE

DOEpatents

Campbell, I.E.

1961-04-01

A method is given for obtaining uniform carbide coatings on graphite bodies. According to the invention a metallic halide in vapor form is passed over the graphite body under such conditions of temperature and pressure that the halide reacts with the graphite to form a coating of the metal carbide on the surface of the graphite.

Dispersoid reinforced alloy powder and method of making

DOEpatents

Anderson, Iver E [Ames, IA; Terpstra, Robert L [Ames, IA

2012-06-12

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with a reactive species acquired from an atomizing gas than does the alloying element. The melted alloy is atomized with the atomizing gas including the reactive species to form atomized particles so that the reactive species is (a) dissolved in solid solution to a depth below the surface of atomized particles and/or (b) reacted with the dispersoid-forming element to form dispersoids in the atomized particles to a depth below the surface of said atomized particles. The atomized alloy particles are solidified as solidified alloy particles or as a solidified deposit of alloy particles. Bodies made from the dispersion strengthened alloy particles, deposit thereof, exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures by virtue of the presence of the corrosion and/or oxidation resistance imparting alloying element in solid solution in the particle alloy matrix.

Dispersoid reinforced alloy powder and method of making

DOEpatents

Anderson, Iver E.; Terpstra, Robert L.

2010-04-20

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with a reactive species acquired from an atomizing gas than does the alloying element. The melted alloy is atomized with the atomizing gas including the reactive species to form atomized particles so that the reactive species is (a) dissolved in solid solution to a depth below the surface of atomized particles and/or (b) reacted with the dispersoid-forming element to form dispersoids in the atomized particles to a depth below the surface of said atomized particles. The atomized alloy particles are solidified as solidified alloy particles or as a solidified deposit of alloy particles. Bodies made from the dispersion strengthened alloy particles, deposit thereof, exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures by virtue of the presence of the corrosion and/or oxidation resistance imparting alloying element in solid solution in the particle alloy matrix.

The Role of Lewis and Brønsted Acid Sites in NO Reduction with NH3 on Sulfur Modified TiO2-Supported V2O5 Catalyst

NASA Astrophysics Data System (ADS)

Zhao, Wei; Dou, Shengping; Zhong, Qin; Wu, Licheng; Wang, Qian; Wang, Aijian

2017-12-01

V2O5/S-doped TiO2 was prepared by the sol-gel and impregnation methods. The adsorption of NO, NH3, and O2 over the catalyst was studied by in situ DRIFTS spectroscopy to elucidate the reaction mechanism of the low-temperature selective catalytic reduction of NO with NH3. Exposing the catalyst to O2 and NO, three types of nitrates species appeared on the surface. The introduction of S to TiO2 could generate large amounts of acid sites for ammonia adsorption on the catalyst, which was believed to be an important role in the SCR reaction and hereby improved the catalytic activity. The results indicated two possible SCR reaction pathways for catalyst. One was that NO was absorbed to form nitrite species, which could react with NH3 on Lewis acid sites, producing N2 and H2O. Another way was that NH3 was adsorbed, then reacted with gas phase NO (E-R) and nitrite intermediates on the surface (L-H).

Polystyrene Foam EOS as a Function of Porosity and Fill Gas

NASA Astrophysics Data System (ADS)

Mulford, Roberta; Swift, Damian

2009-06-01

An accurate EOS for polystyrene foam is necessary for analysis of numerous experiments in shock compression, inertial confinement fusion, and astrophysics. Plastic to gas ratios vary between various samples of foam, according to the density and cell-size of the foam. A matrix of compositions has been investigated, allowing prediction of foam response as a function of the plastic-to-air ratio. The EOS code CHEETAH allows participation of the air in the decomposition reaction of the foam, Differences between air-filled, nitrogen-blown, and CO2-blown foams are investigated, to estimate the importance of allowing air to react with plastic products during decomposition. Results differ somewhat from the conventional EOS, which are generated from values for plastic extrapolated to low densities.

Modeling turbulent/chemistry interactions using assumed pdf methods

NASA Technical Reports Server (NTRS)

Gaffney, R. L, Jr.; White, J. A.; Girimaji, S. S.; Drummond, J. P.

1992-01-01

Two assumed probability density functions (pdfs) are employed for computing the effect of temperature fluctuations on chemical reaction. The pdfs assumed for this purpose are the Gaussian and the beta densities of the first kind. The pdfs are first used in a parametric study to determine the influence of temperature fluctuations on the mean reaction-rate coefficients. Results indicate that temperature fluctuations significantly affect the magnitude of the mean reaction-rate coefficients of some reactions depending on the mean temperature and the intensity of the fluctuations. The pdfs are then tested on a high-speed turbulent reacting mixing layer. Results clearly show a decrease in the ignition delay time due to increases in the magnitude of most of the mean reaction rate coefficients.

Surface Modified Particles By Multi-Step Michael-Type Addition And Process For The Preparation Thereof

DOEpatents

Cook, Ronald Lee; Elliott, Brian John; Luebben, Silvia DeVito; Myers, Andrew William; Smith, Bryan Matthew

2005-05-03

A new class of surface modified particles and a multi-step Michael-type addition surface modification process for the preparation of the same is provided. The multi-step Michael-type addition surface modification process involves two or more reactions to compatibilize particles with various host systems and/or to provide the particles with particular chemical reactivities. The initial step comprises the attachment of a small organic compound to the surface of the inorganic particle. The subsequent steps attach additional compounds to the previously attached organic compounds through reactive organic linking groups. Specifically, these reactive groups are activated carbon—carbon pi bonds and carbon and non-carbon nucleophiles that react via Michael or Michael-type additions.

Quantitative X-ray photoelectron spectroscopy-based depth profiling of bioleached arsenopyrite surface by Acidithiobacillus ferrooxidans

NASA Astrophysics Data System (ADS)

Zhu, Tingting; Lu, Xiancai; Liu, Huan; Li, Juan; Zhu, Xiangyu; Lu, Jianjun; Wang, Rucheng

2014-02-01

In supergene environments, microbial activities significantly enhance sulfide oxidation and result in the release of heavy metals, causing serious contamination of soils and waters. As the most commonly encountered arsenic mineral in nature, arsenopyrite (FeAsS) accounts for arsenic contaminants in various environments. In order to investigate the geochemical behavior of arsenic during microbial oxidation of arsenopyrite, (2 3 0) surfaces of arsenopyrite slices were characterized after acidic (pH 2.00) and oxidative decomposition with or without an acidophilic microorganism Acidithiobacillus ferrooxidans. The morphology as well as chemical and elemental depth profiles of the oxidized arsenopyrite surface were investigated by scanning electron microscopy and X-ray photoelectron spectroscopy. With the mediation of bacteria, cell-shaped and acicular pits were observed on the reacted arsenopyrite surface, and the concentration of released arsenic species in solution was 50 times as high as that of the abiotic reaction after 10 days reaction. Fine-scale XPS depth profiles of the reacted arsenopyrite surfaces after both microbial and abiotic oxidation provided insights into the changes in chemical states of the elements in arsenopyrite surface layers. Within the 450 nm surface layer of abiotically oxidized arsenopyrite, Fe(III)-oxides appeared and gradually increased towards the surface, and detectable sulfite and monovalent arsenic appeared above 50 nm. In comparison, higher contents of ferric sulfate, sulfite, and arsenite were found in the surface layer of approximately 3 μm of the microbially oxidized arsenopyrite. Intermediates, such as Fe(III)-AsS and S0, were detectable in the presence of bacteria. Changes of oxidative species derived from XPS depth profiles show the oxidation sequence is Fe > As = S in abiotic oxidation, and Fe > S > As in microbial oxidation. Based on these results, a possible reaction path of microbial oxidation was proposed in a concept model.

Damage-free polymer surface modification employing inward-type plasma

NASA Astrophysics Data System (ADS)

Kanou, Ryo; Suga, Hiroshi; Utsumi, Hideyuki; Takahashi, Satoshi; Shirayama, Yuya; Watanabe, Norimichi; Petit, Stèphane; Shimizu, Tetsuo

2017-08-01

Inward-type plasmas, which spread upstream against the gas flow in the capillary tube where the gas is discharged, can react with samples placed near the entrance of such a capillary tube. In this study, surface modification of polymer surfaces is conducted using inward plasma. The modification is also done by conventional microplasma jet, and the modified surfaces with two plasma techniques are characterized by contact angle measurement, X-ray photoemission spectroscopy (XPS), and atomic force microscopy (AFM). Although inward-plasma-treated surfaces are less hydrophilic than conventional plasma-treated ones, they are still sufficiently hydrophilic for surface coatings. In addition, it turns out that the polymer surfaces irradiated with the inward plasma yield much smoother surfaces than those treated with the conventional plasma jet. Thus, the inward plasma treatment is a viable technique when the surface flatness is crucial, such as for the surface coating of plastic lenses.

Differential reactivity of maleimide and bromoacetyl functions with thiols: application to the preparation of liposomal diepitope constructs.

PubMed

Schelté, P; Boeckler, C; Frisch, B; Schuber, F

2000-01-01

The comparative reactivity of maleimide and bromoacetyl groups with thiols (2-mercaptoethanol, free cysteine, and cysteine residues present at the N-terminus of peptides) was investigated in aqueous media. These studies were performed (i) with water-soluble functionalized model molecules, i.e., polyoxyethylene-based spacer arms that could also be coupled to lipophilic anchors destined to be incorporated into liposomes, and (ii) with small unilamellar liposomes carrying at their surface these thiol-reactive functions. Our results indicate that an important kinetic discrimination (2-3 orders of magnitude in terms of rate constants) can be achieved between the maleimide and bromoacetyl functions when the reactions with thiols are performed at pH 6.5. The bromoacetyl function which reacts at higher pH values (e.g., pH 9.0) retained a high chemoselectivity; i.e., under conditions where it reacted appreciably with the thiols of, e.g., HS-peptides, it did react with other nucleophilic functions such as alpha- and epsilon-amino groups or imidazole, which could also be present in peptides. This differential reactivity was applied to design chemically defined and highly immunogenic liposomal diepitope constructs as synthetic vaccines, i.e., vesicles carrying at their surface two different peptides conjugated each to a specific amphiphilic anchor. This was realized by coupling sequentially at pH 6.5 and 9.0 two HS-peptides to preformed vesicles containing lipophilic anchors functionalized with maleimide and bromoacetyl groups [Boeckler, C., et al. (1999) Eur. J. Immunol. 29, 2297-2308].

Tin-decorated ruthenium nanoparticles: a way to tune selectivity in hydrogenation reaction

NASA Astrophysics Data System (ADS)

Bonnefille, Eric; Novio, Fernando; Gutmann, Torsten; Poteau, Romuald; Lecante, Pierre; Jumas, Jean-Claude; Philippot, Karine; Chaudret, Bruno

2014-07-01

Two series of ruthenium nanoparticles stabilized either by a polymer (polyvinylpyrrolidone; Ru/PVP) or a ligand (bisdiphenylphosphinobutane; Ru/dppb) were reacted with tributyltin hydride [(n-C4H9)3SnH] leading to tin-decorated ruthenium nanoparticles, Ru/PVP/Sn and Ru/dppb/Sn. The Sn/Ru molar ratio was varied in order to study the influence of the surface tin content on the properties of these new nanoparticles, by comparison with Ru/PVP and Ru/dppb. Besides HRTEM and WAXS analyses, spectroscopic techniques (IR, NMR and Mössbauer) combined with theoretical calculations and a simple catalytic test (styrene hydrogenation) allowed us to evidence the formation of μ3-bridging ``SnR'' groups on the ruthenium surface as well as to rationalize their influence on surface chemistry and catalytic activity.Two series of ruthenium nanoparticles stabilized either by a polymer (polyvinylpyrrolidone; Ru/PVP) or a ligand (bisdiphenylphosphinobutane; Ru/dppb) were reacted with tributyltin hydride [(n-C4H9)3SnH] leading to tin-decorated ruthenium nanoparticles, Ru/PVP/Sn and Ru/dppb/Sn. The Sn/Ru molar ratio was varied in order to study the influence of the surface tin content on the properties of these new nanoparticles, by comparison with Ru/PVP and Ru/dppb. Besides HRTEM and WAXS analyses, spectroscopic techniques (IR, NMR and Mössbauer) combined with theoretical calculations and a simple catalytic test (styrene hydrogenation) allowed us to evidence the formation of μ3-bridging ``SnR'' groups on the ruthenium surface as well as to rationalize their influence on surface chemistry and catalytic activity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr00791c

Engineering design of sub-micron topographies for simultaneously adherent and reflective metal-polymer interfaces

NASA Technical Reports Server (NTRS)

Brown, Christopher A.

1993-01-01

The approach of the project is to base the design of multi-function, reflective topographies on the theory that topographically dependent phenomena react with surfaces and interfaces at certain scales. The first phase of the project emphasizes the development of methods for understanding the sizes of topographic features which influence reflectivity. Subsequent phases, if necessary, will address the scales of interaction for adhesion and manufacturing processes. A simulation of the interaction of electromagnetic radiation, or light, with a reflective surface is performed using specialized software. Reflectivity of the surface as a function of scale is evaluated and the results from the simulation are compared with reflectivity measurements made on multi-function, reflective surfaces.

Atmospheric-Pressure Plasma Jet Surface Treatment for Use in Improving Adhesion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuettner, Lindsey Ann

Atmospheric-pressure plasma jets (APPJs) are a method of plasma treatment that plays an important role in material processing and modifying surface properties of materials, especially polymers. Gas plasmas react with polymer surfaces in numerous ways such as oxidation, radical formation, degradation, and promotion of cross-linking. Because of this, gas and plasma conditions can be explored for chosen processes to maximize desired properties. The purpose of this study is to investigate plasma parameters in order to modify surface properties for improved adhesion between aluminum and epoxy substrates using two types of adhesives. The background, results to date, and future work willmore » be discussed.« less

Land Use and Land Cover Change, Urban Heat Island Phenomenon, and Health Implications: A Remote Sensing Approach

NASA Technical Reports Server (NTRS)

Lo, C. P.; Quattrochi, Dale A.

2003-01-01

Land use and land cover maps of Atlanta Metropolitan Area in Georgia were produced from Landsat MSS and TM images for 1973,1979,1983,1987,1992, and 1997, spanning a period of 25 years. Dramatic changes in land use and land cover have occurred with loss of forest and cropland to urban use. In particular, low-density urban use, which includes largely residential use, has increased by over 119% between 1973 and 1997. These land use and land cover changes have drastically altered the land surface characteristics. An analysis of Landsat images revealed an increase in surface temperature and a decline in NDVI from 1973 to 1997. These changes have forced the development of a significant urban heat island effect and an increase in ground level ozone production to such an extent, that Atlanta has violated EPA's ozone level standard in recent years. The urban heat island initiated precipitation events that were identified between 1996 and 2000 tended to occur near high-density urban areas but outside the I-285 loop that traverses around the Central Business District, i.e. not in the inner city area, but some in close proximity to the highways. The health implications were investigated by comparing the spatial patterns of volatile organic compounds (VOC) and nitrogen oxides (NOx) emissions, the two ingredients that form ozone by reacting with sunlight, with those of rates of cardiovascular and chronic lower respiratory diseases. A clear core-periphery pattern was revealed for both VOC and NOx emissions, but the spatial pattern was more random in the cases of rates of cardiovascular and chronic lower respiratory diseases. Clearly, factors other than ozone pollution were involved in explaining the rates of these diseases. Further research is therefore needed to understand the health geography and its relationship to land use and land cover change as well as urban heat island effect. This paper illustrates the usefulness of a remote sensing approach for this purpose.

A large eddy simulation scheme for turbulent reacting flows

NASA Technical Reports Server (NTRS)

Gao, Feng

1993-01-01

The recent development of the dynamic subgrid-scale (SGS) model has provided a consistent method for generating localized turbulent mixing models and has opened up great possibilities for applying the large eddy simulation (LES) technique to real world problems. Given the fact that the direct numerical simulation (DNS) can not solve for engineering flow problems in the foreseeable future (Reynolds 1989), the LES is certainly an attractive alternative. It seems only natural to bring this new development in SGS modeling to bear on the reacting flows. The major stumbling block for introducing LES to reacting flow problems has been the proper modeling of the reaction source terms. Various models have been proposed, but none of them has a wide range of applicability. For example, some of the models in combustion have been based on the flamelet assumption which is only valid for relatively fast reactions. Some other models have neglected the effects of chemical reactions on the turbulent mixing time scale, which is certainly not valid for fast and non-isothermal reactions. The probability density function (PDF) method can be usefully employed to deal with the modeling of the reaction source terms. In order to fit into the framework of LES, a new PDF, the large eddy PDF (LEPDF), is introduced. This PDF provides an accurate representation for the filtered chemical source terms and can be readily calculated in the simulations. The details of this scheme are described.

A novel technique using potassium permanganate and reflectance confocal microscopy to image biofilm extracellular polymeric matrix reveals non-eDNA networks in Pseudomonas aeruginosa biofilms

PubMed Central

Swearingen, Matthew C.; Mehta, Ajeet; Mehta, Amar; Nistico, Laura; Hill, Preston J.; Falzarano, Anthony R.; Wozniak, Daniel J.; Hall-Stoodley, Luanne; Stoodley, Paul

2015-01-01

Biofilms are etiologically important in the development of chronic medical and dental infections. The biofilm extracellular polymeric substance (EPS) determines biofilm structure and allows bacteria in biofilms to adapt to changes in mechanical loads such as fluid shear. However, EPS components are difficult to visualize microscopically because of their low density and molecular complexity. Here, we tested potassium permanganate, KMnO4, for use as a non-specific EPS contrast-enhancing stain using confocal laser scanning microscopy in reflectance mode. We demonstrate that KMnO4 reacted with EPS components of various strains of Pseudomonas, Staphylococcus and Streptococcus, yielding brown MnO2 precipitate deposition on the EPS, which was quantifiable using data from the laser reflection detector. Furthermore, the MnO2 signal could be quantified in combination with fluorescent nucleic acid staining. COMSTAT image analysis indicated that KMnO4 staining increased the estimated biovolume over that determined by nucleic acid staining alone for all strains tested, and revealed non-eDNA EPS networks in Pseudomonas aeruginosa biofilm. In vitro and in vivo testing indicated that KMnO4 reacted with poly-N-acetylglucosamine and Pseudomonas Pel polysaccharide, but did not react strongly with DNA or alginate. KMnO4 staining may have application as a research tool and for diagnostic potential for biofilms in clinical samples. PMID:26536894

Statistical analysis of the velocity and scalar fields in reacting turbulent wall-jets

NASA Astrophysics Data System (ADS)

Pouransari, Z.; Biferale, L.; Johansson, A. V.

2015-02-01

The concept of local isotropy in a chemically reacting turbulent wall-jet flow is addressed using direct numerical simulation (DNS) data. Different DNS databases with isothermal and exothermic reactions are examined. The chemical reaction and heat release effects on the turbulent velocity, passive scalar, and reactive species fields are studied using their probability density functions (PDFs) and higher order moments for velocities and scalar fields, as well as their gradients. With the aid of the anisotropy invariant maps for the Reynolds stress tensor, the heat release effects on the anisotropy level at different wall-normal locations are evaluated and found to be most accentuated in the near-wall region. It is observed that the small-scale anisotropies are persistent both in the near-wall region and inside the jet flame. Two exothermic cases with different Damköhler numbers are examined and the comparison revealed that the Damköhler number effects are most dominant in the near-wall region, where the wall cooling effects are influential. In addition, with the aid of PDFs conditioned on the mixture fraction, the significance of the reactive scalar characteristics in the reaction zone is illustrated. We argue that the combined effects of strong intermittency and strong persistency of anisotropy at the small scales in the entire domain can affect mixing and ultimately the combustion characteristics of the reacting flow.

Multi-GPU unsteady 2D flow simulation coupled with a state-to-state chemical kinetics

NASA Astrophysics Data System (ADS)

Tuttafesta, Michele; Pascazio, Giuseppe; Colonna, Gianpiero

2016-10-01

In this work we are presenting a GPU version of a CFD code for high enthalpy reacting flow, using the state-to-state approach. In supersonic and hypersonic flows, thermal and chemical non-equilibrium is one of the fundamental aspects that must be taken into account for the accurate characterization of the plasma and state-to-state kinetics is the most accurate approach used for this kind of problems. This model consists in writing a continuity equation for the population of each vibrational level of the molecules in the mixture, determining at the same time the species densities and the distribution of the population in internal levels. An explicit scheme is employed here to integrate the governing equations, so as to exploit the GPU structure and obtain an efficient algorithm. The best performances are obtained for reacting flows in state-to-state approach, reaching speedups of the order of 100, thanks to the use of an operator splitting scheme for the kinetics equations.

A comprehensive model to determine the effects of temperature and species fluctuations on reaction rates in turbulent reacting flows

NASA Technical Reports Server (NTRS)

Chinitz, W.; Foy, E.; Rowan, G.; Goldstein, D.

1982-01-01

The use of probability theory to determine the effects of turbulent fluctuations on reaction rates in turbulent combustion systems is briefly reviewed. Results are presented for the effect of species fluctuations in particular. It is found that turbulent fluctuations of species act to reduce the reaction rates, in contrast with the temperature fluctuations previously determined to increase Arrhenius reaction rate constants. For the temperature fluctuations, a criterion is set forth for determining if, in a given region of a turbulent flow field, the temperature can be expected to exhibit ramp like fluctuations. Using the above results, along with results previously obtained, a model is described for testing the effects of turbulent fluctuations of temperature and species on reaction rates in computer programs dealing with turbulent reacting flows. An alternative model which employs three variable probability density functions (temperature and two species) and is currently being formulated is discussed as well.

Germ tube-specific antigens of Candida albicans cell walls

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sundstrom, P.R.

1986-01-01

Studies were performed to characterize the surface differences between blastospores and germ tubes of the pathogenic, dimorphic yeast, Candida albicans, and to identify components of yeast cells responsible for these differences. Investigation of surfaces differences of the two growth forms was facilitated by the production of rabbit antiserum prepared against Formalin-treated yeast possessing germ tubes. To prepare antiserum specific for germ tubes, this serum was adsorbed with stationary phase blastospores. Whereas the unadsorbed antiserum reacted with both blastospore and germ tube forms by immunofluorescence and Enzyme-Linked Immunosorbent Assay, the adsorbed antiserum did not react with blastospores but detected germ tube-specificmore » antigens in hyphal forms. The differences between blastospores and germ tubes of Candida albicans, were further studied by comparing enzymatic digests of cell walls of both growth forms in radiolabeled organisms. Organisms were labeled either on the surface with /sup 125/I, or metabolically with (/sup 35/S) methionine or (/sup 3/H) mannose. Three-surface-located components (as shown by antibody adsorption and elution experiments) were precipitated from Zymolase digests. All three components were mannoproteins as shown by their ability to bind Concanavalin A, and to be labeled in protein labeling procedures, and two of these (200,000 and 155,000 molecular weight) were germ tube specific, as shown by their ability to be precipitated by germ tube-specific antiserum. Monoclonal antibodies were prepared to C. albicans, using blastospores bearing germ tubes as immunogen.« less

Synergistic effect among Cl2, SO2 and NO2 in their heterogeneous reactions on gamma-alumina

NASA Astrophysics Data System (ADS)

Huang, Zhenling; Zhang, Zhaohui; Kong, Weiheng; Feng, Shuo; Qiu, Ye; Tang, Siqun; Xia, Chuanqin; Ma, Lingling; Luo, Min; Xu, Diandou

2017-10-01

Severe haze in China has been a global concern in recent years. Most studies about the mechanism of haze formation mare only focused on the heterogeneous reactions of SO2 and NO2 on mineral aerosols. However, little is known about the role of molecular chlorine (Cl2) in those reactions. Here, we investigated the heterogeneous uptake of Cl2, SO2 and NO2 on γ-Al2O3 particles under different conditions using a quartz-based flow reactor. We found that the existence of γ-Al2O3 seed aerosols significantly promotes the formation of secondary chloride, sulfate and nitrate aerosols, and Cl2, NO2 and SO2 have synergistic effects when they react on γ-Al2O3 surface under humid condition. The results also shows that Cl2 can promote the formation of secondary sulfate and nitrate aerosols on γ-Al2O3 surface. Moreover, Cl2 is much easier to react with the surface of γ-Al2O3 and form secondary Cl- aerosol when comparing with NO2 and SO2, suggesting that Cl2 is of great importance in atmospheric chemistry, it has the potential to alter the surface properties (e.g., chemical composition and fraction) of mineral aerosol, enhance the production of secondary inorganic aerosols in the troposphere, and thus cause adverse effects on the climate and human health.

A local leaky-box model for the local stellar surface density-gas surface density-gas phase metallicity relation

NASA Astrophysics Data System (ADS)

Zhu, Guangtun Ben; Barrera-Ballesteros, Jorge K.; Heckman, Timothy M.; Zakamska, Nadia L.; Sánchez, Sebastian F.; Yan, Renbin; Brinkmann, Jonathan

2017-07-01

We revisit the relation between the stellar surface density, the gas surface density and the gas-phase metallicity of typical disc galaxies in the local Universe with the SDSS-IV/MaNGA survey, using the star formation rate surface density as an indicator for the gas surface density. We show that these three local parameters form a tight relationship, confirming previous works (e.g. by the PINGS and CALIFA surveys), but with a larger sample. We present a new local leaky-box model, assuming star-formation history and chemical evolution is localized except for outflowing materials. We derive closed-form solutions for the evolution of stellar surface density, gas surface density and gas-phase metallicity, and show that these parameters form a tight relation independent of initial gas density and time. We show that, with canonical values of model parameters, this predicted relation match the observed one well. In addition, we briefly describe a pathway to improving the current semi-analytic models of galaxy formation by incorporating the local leaky-box model in the cosmological context, which can potentially explain simultaneously multiple properties of Milky Way-type disc galaxies, such as the size growth and the global stellar mass-gas metallicity relation.

The frequency-domain approach for apparent density mapping

NASA Astrophysics Data System (ADS)

Tong, T.; Guo, L.

2017-12-01

Apparent density mapping is a technique to estimate density distribution in the subsurface layer from the observed gravity data. It has been widely applied for geologic mapping, tectonic study and mineral exploration for decades. Apparent density mapping usually models the density layer as a collection of vertical, juxtaposed prisms in both horizontal directions, whose top and bottom surfaces are assumed to be horizontal or variable-depth, and then inverts or deconvolves the gravity anomalies to determine the density of each prism. Conventionally, the frequency-domain approach, which assumes that both top and bottom surfaces of the layer are horizontal, is usually utilized for fast density mapping. However, such assumption is not always valid in the real world, since either the top surface or the bottom surface may be variable-depth. Here, we presented a frequency-domain approach for apparent density mapping, which permits both the top and bottom surfaces of the layer to be variable-depth. We first derived the formula for forward calculation of gravity anomalies caused by the density layer, whose top and bottom surfaces are variable-depth, and the formula for inversion of gravity anomalies for the density distribution. Then we proposed the procedure for density mapping based on both the formulas of inversion and forward calculation. We tested the approach on the synthetic data, which verified its effectiveness. We also tested the approach on the real Bouguer gravity anomalies data from the central South China. The top surface was assumed to be flat and was on the sea level, and the bottom surface was considered as the Moho surface. The result presented the crustal density distribution, which was coinciding well with the basic tectonic features in the study area.

Method for making monolithic metal oxide aerogels

DOEpatents

Coronado, Paul R.

1999-01-01

Transparent, monolithic metal oxide aerogels of varying densities are produced using a method in which a metal alkoxide solution and a catalyst solution are prepared separately and reacted. The resulting hydrolyzed-condensed colloidal solution is gelled, and the wet gel is contained within a sealed, but gas permeable, containment vessel during supercritical extraction of the solvent. The containment vessel is enclosed within an aqueous atmosphere that is above the supercritical temperature and pressure of the solvent of the metal alkoxide solution.

Maximizing Immune Response to Carbohydrate Antigens on Breast Tumors

DTIC Science & Technology

2004-08-01

selectin binding. In vitro phenotyping of the tumor cells suggests that both KM93-Neg and Pos cells grow at the same rate; however, KM-93Neg cells are...and Figure 2. ABL ( Agaricus bisporus, mushroom, lectin) and ACA (Amaranthus caudatus, lectin) do not react with either the KM93-Pos or KM93-Neg...is different (Figure 6B). The KM93-Pos variant, which is similar to the original 4T1, tends to grow in clusters with high densities. While clusters are

Observation of the adsorption and desorption of vibrationally excited molecules on a metal surface

NASA Astrophysics Data System (ADS)

Shirhatti, Pranav R.; Rahinov, Igor; Golibrzuch, Kai; Werdecker, Jörn; Geweke, Jan; Altschäffel, Jan; Kumar, Sumit; Auerbach, Daniel J.; Bartels, Christof; Wodtke, Alec M.

2018-06-01

The most common mechanism of catalytic surface chemistry is that of Langmuir and Hinshelwood (LH). In the LH mechanism, reactants adsorb, become thermalized with the surface, and subsequently react. The measured vibrational (relaxation) lifetimes of molecules adsorbed at metal surfaces are in the range of a few picoseconds. As a consequence, vibrational promotion of LH chemistry is rarely observed, with the exception of LH reactions occurring via a molecular physisorbed intermediate. Here, we directly detect adsorption and subsequent desorption of vibrationally excited CO molecules from a Au(111) surface. Our results show that CO (v = 1) survives on a Au(111) surface for 1 × 10-10 s. Such long vibrational lifetimes for adsorbates on metal surfaces are unexpected and pose an interesting challenge to the current understanding of vibrational energy dissipation on metal surfaces. They also suggest that vibrational promotion of surface chemistry might be more common than is generally believed.

Identification of Pyruvate Kinase as an Antigen Associated with Tourette Syndrome

PubMed Central

Kansy, Janice W.; Katsovich, Liliya; McIver, Kevin S.; Pick, Jennifer; Zabriskie, John B.; Lombroso, Paul J.; Leckman, James F.; Bibb, James A.

2007-01-01

Immune responses to β-hemolytic streptococcal infections are hypothesized to trigger tic disorders and early-onset obsessive-compulsive disorder (OCD) in some pediatric populations. Here we identify the M1 isoform of the glycolytic enzyme, pyruvate kinase (PK) as an autoimmune target in Tourette syndrome and associated disorders. Antibodies to PK reacted strongly with surface antigens of infectious strains of streptococcus, and antibodies to streptococcal M proteins reacted with PK. Moreover, immunoreactivity to PK in patients with exacerbated symptoms who had recently acquired a streptococcal infection was 7-fold higher compared to patients with exacerbated symptoms and no evidence of a streptococcal infection. These data suggest that PK can function as an autoimmune target and that this immunoreactivity may be associated with Tourette syndrome, OCD, and associated disorders. PMID:17011640

Method for Estimating the Charge Density Distribution on a Dielectric Surface.

PubMed

Nakashima, Takuya; Suhara, Hiroyuki; Murata, Hidekazu; Shimoyama, Hiroshi

2017-06-01

High-quality color output from digital photocopiers and laser printers is in strong demand, motivating attempts to achieve fine dot reproducibility and stability. The resolution of a digital photocopier depends on the charge density distribution on the organic photoconductor surface; however, directly measuring the charge density distribution is impossible. In this study, we propose a new electron optical instrument that can rapidly measure the electrostatic latent image on an organic photoconductor surface, which is a dielectric surface, as well as a novel method to quantitatively estimate the charge density distribution on a dielectric surface by combining experimental data obtained from the apparatus via a computer simulation. In the computer simulation, an improved three-dimensional boundary charge density method (BCM) is used for electric field analysis in the vicinity of the dielectric material with a charge density distribution. This method enables us to estimate the profile and quantity of the charge density distribution on a dielectric surface with a resolution of the order of microns. Furthermore, the surface potential on the dielectric surface can be immediately calculated using the obtained charge density. This method enables the relation between the charge pattern on the organic photoconductor surface and toner particle behavior to be studied; an understanding regarding the same may lead to the development of a new generation of higher resolution photocopiers.

Supported metallocene catalysts by surface organometallic chemistry. Synthesis, characterization, and reactivity in ethylene polymerization of oxide-supported mono- and biscyclopentadienyl zirconium alkyl complexes: establishment of structure/reactivity relationships.

PubMed

Jezequel, M; Dufaud, V; Ruiz-Garcia, M J; Carrillo-Hermosilla, F; Neugebauer, U; Niccolai, G P; Lefebvre, F; Bayard, F; Corker, J; Fiddy, S; Evans, J; Broyer, J P; Malinge, J; Basset, J M

2001-04-18

The reactions of CpZr(CH(3))(3), 1, and Cp(2)Zr(CH(3))(2), 2, with partially dehydroxylated silica, silica-alumina, and alumina surfaces have been carried out with careful identification of the resulting surface organometallic complexes in order to probe the relationship between catalyst structure and polymerization activity. The characterization of the supported complexes has been achieved in most cases by in situ infrared spectroscopy, surface microanalysis, qualitative and quantitative analysis of evolved gases during surface reactions with labeled surface, solid state (1)H and (13)C NMR using (13)C-enriched compounds, and EXAFS. 1 and 2 react with silica(500) and silica-alumina(500) by simple protonolysis of one Zr-Me bond by surface silanols with formation of a single well-defined neutral compound. In the case of silica-alumina, a fraction of the supported complexes exhibits some interactions with electronically unsaturated surface aluminum sites. 1 and 2 also react with the hydroxyl groups of gamma-alumina(500), leading to several surface structures. Correlation between EXAFS and (13)C NMR data suggests, in short, two main surface structures having different environments for the methyl group: [Al](3)-OZrCp(CH(3))(2) and [Al](2)-OZrCp(CH(3))(mu-CH(3))-[Al] for the monoCp series and [Al](2)-OZrCp(2)(CH(3)) and [Al]-OZrCp(2)(mu-CH(3))-[Al] for the bisCp series. Ethylene polymerization has been carried out with all the supported complexes under various reaction conditions. Silica-supported catalysts in the absence of any cocatalyst exhibited no activity whatsoever for ethylene polymerization. When the oxide contained Lewis acidic sites, the resulting surface species were active. The activity, although improved by the presence of additional cocatalysts, remained very low by comparison with that of the homogeneous metallocene systems. This trend has been interpreted on the basis of various possible parameters, including the (p-pi)-(d-pi) back-donation of surface oxygen atoms to the zirconium center.

Conduction below 100 °C in nominal Li 6ZnNb 4O 14

DOE PAGES

Li, Yunchao; Paranthaman, Mariappan Parans; Gill, Lance W.; ...

2015-09-15

The increasing demand for a safe rechargeable battery with a high energy density per cell is driving a search for a novel solid electrolyte with a high Li + or Na + conductivity that is chemically stable in a working Li-ion or Na-ion battery. Li 6ZnNb 4O 14 has been reported to exhibit a σ Li > 10 -2 S cm -1 at 250 °C, but to disproportionate into multiple phases on cooling from 850 °C to room temperature. An investigation of the room-temperature Li-ion conductivity in a porous pellet of a multiphase product of a nominal Li 6ZnNb 4Omore » 14 composition is shown to have bulk σ Li 3.3 x 10 -5 S cm -1 at room temperature that increases to 1.4 x 10 -4 S cm -1 by 50 °C. 7Li MAS NMR spectra were fitted to two Lorentzian lines, one of which showed a dramatic increase with increasing temperature. As a result, a test for water stability indicates that Li + may move to the particle and grain surfaces to react with adsorbed water as occurs in the garnet Li + conductors.« less

Applying high-emittance and solar-absorptance coating to aluminum

NASA Technical Reports Server (NTRS)

Progar, D. J.

1973-01-01

Coated surface withstands space environment with negilgible change in radiation characteristics and physical properties. Process can be used with any porous substance, as long as pores are large enough to allow molecules of reacting solutions to enter and yet not so large as to allow nickel sulfide to be leached out of pores before sealing.

Controllable Biotinylated Poly(Ethylene-co-Glycidyl Methacrylate) (PE-co-GMA) Nanofibers to Bind Streptavidin-Horseradish Peroxidase (HRP) for Potential Biosensor Applications

USDA-ARS?s Scientific Manuscript database

Poly(ethylene-co-glycidyl methacrylate) (PE-co-GMA) nanofibers with abundant active epoxy groups on surfaces were fabricated through a novel manufacturing process. The prepared PE-co-GMA nanofibers with different average diameters ranging from 100 to 400 nm were aminated by reacting the epoxy groups...

CARCINOGENICITY OF BROMODICHLOROMETHANE ADMINISTERED IN DRINKING WATER TO THE MALE F344/N RAT AND B6C3F1 MOUSE

EPA Science Inventory

Chlorine added to surface waters for the purposes of disinfection, reacts with humic material in the water to produce a variety of compounds collectively known as disinfection by-product (DBPs). The trihalomethanes (THM), the class of DBPs that occur at the highest concentrations...

Same-Side Platinum Electrodes for Metal Assisted Etching of Porous Silicon

DTIC Science & Technology

2015-11-01

hydrogen peroxide (H2O2), and ethanol etch solution. The H2O2 reacts with hydrogen ions from the HF at the catalytic metal surface to become water...order to measure the combustion rates of the PSi, bridge wires were photolithographically deposited onto the wafers, prior to PSi etching, using a...

Effects of chemically modified wood on bond durability

Treesearch

Rishawn Brandon; Rebecca E. Ibach; Charles R. Frihart

2005-01-01

Chemical modification of wood can improve its dimensional stability and resistance to biological degradation and moisture, but modification can also create a new surface for bonding. Acetylation of wood results in the loss of hydroxyl groups, making the wood more hydrophobic and reduces its ability to hydrogen-bond with the adhesive. In contrast, reacting wood with...

A Technique for the Microstructural Examination of Polycrystalline Graphites

DTIC Science & Technology

1959-02-01

dichromate in concentrated phosphoric acid . This etchsnt reacted quite readily with the graphite surface, yet at a rate that was...formation of lamellar compounds, and carbide formation at high temperatues . Of the three classes of reaction, oxidation seems to...reagents and conditions were directed toward preliminary studies of such chemical oxidants as potassium dichromate-phosphoric acid mixtures

CO2-Water-Rock Wettability: Variability, Influencing Factors, and Implications for CO2 Geostorage.

PubMed

Iglauer, Stefan

2017-05-16

Carbon geosequestration (CGS) has been identified as a key technology to reduce anthropogenic greenhouse gas emissions and thus significantly mitigate climate change. In CGS, CO 2 is captured from large point-source emitters (e.g., coal fired power stations), purified, and injected deep underground into geological formations for disposal. However, the CO 2 has a lower density than the resident formation brine and thus migrates upward due to buoyancy forces. To prevent the CO 2 from leaking back to the surface, four trapping mechanisms are used: (1) structural trapping (where a tight caprock acts as a seal barrier through which the CO 2 cannot percolate), (2) residual trapping (where the CO 2 plume is split into many micrometer-sized bubbles, which are immobilized by capillary forces in the pore network of the rock), (3) dissolution trapping (where CO 2 dissolves in the formation brine and sinks deep into the reservoir due to a slight increase in brine density), and (4) mineral trapping (where the CO 2 introduced into the subsurface chemically reacts with the formation brine or reservoir rock or both to form solid precipitates). The efficiency of these trapping mechanisms and the movement of CO 2 through the rock are strongly influenced by the CO 2 -brine-rock wettability (mainly due to the small capillary-like pores in the rock which form a complex network), and it is thus of key importance to rigorously understand CO 2 -wettability. In this context, a substantial number of experiments have been conducted from which several conclusions can be drawn: of prime importance is the rock surface chemistry, and hydrophilic surfaces are water-wet while hydrophobic surfaces are CO 2 -wet. Note that CO 2 -wet surfaces dramatically reduce CO 2 storage capacities. Furthermore, increasing pressure, salinity, or dissolved ion valency increases CO 2 -wettability, while the effect of temperature is not well understood. Indeed theoretical understanding of CO 2 -wettability and the ability to quantitatively predict it are currently limited although recent advances have been made. Moreover, data for real storage rock and real injection gas (which contains impurities) is scarce and it is an open question how realistic subsurface conditions can be reproduced in laboratory experiments. In conclusion, however, it is clear that in principal CO 2 -wettability can vary drastically from completely water-wet to almost completely CO 2 -wet, and this possible variation introduces a large uncertainty into trapping capacity and containment security predictions.

Fluorescence-Based Sensor for Monitoring Activation of Lunar Dust

NASA Technical Reports Server (NTRS)

Wallace, William T.; Jeevarajan, Antony S.

2012-01-01

This sensor unit is designed to determine the level of activation of lunar dust or simulant particles using a fluorescent technique. Activation of the surface of a lunar soil sample (for instance, through grinding) should produce a freshly fractured surface. When these reactive surfaces interact with oxygen and water, they produce hydroxyl radicals. These radicals will react with a terephthalate diluted in the aqueous medium to form 2-hydroxyterephthalate. The fluorescence produced by 2-hydroxyterephthalate provides qualitative proof of the activation of the sample. Using a calibration curve produced by synthesized 2-hydroxyterephthalate, the amount of hydroxyl radicals produced as a function of sample concentration can also be determined.

Use of Atmospheric-Pressure Plasma Jet for Polymer Surface Modification: An Overview

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuettner, Lindsey A.

Atmospheric-pressure plasma jets (APPJs) are playing an increasingly important role in materials processing procedures. Plasma treatment is a useful tool to modify surface properties of materials, especially polymers. Plasma reacts with polymer surfaces in numerous ways thus the type of process gas and plasma conditions must be explored for chosen substrates and materials to maximize desired properties. This report discusses plasma treatments and looks further into atmospheric-pressure plasma jets and the effects of gases and plasma conditions. Following the short literature review, a general overview of the future work and research at Los Alamos National Laboratory (LANL) is discussed.

Effect of surface charge density on the affinity of oxide nanoparticles for the vapor-water interface.

PubMed

Brown, Matthew A; Duyckaerts, Nicolas; Redondo, Amaia Beloqui; Jordan, Inga; Nolting, Frithjof; Kleibert, Armin; Ammann, Markus; Wörner, Hans Jakob; van Bokhoven, Jeroen A; Abbas, Zareen

2013-04-23

Using in-situ X-ray photoelectron spectroscopy at the vapor-water interface, the affinity of nanometer-sized silica colloids to adsorb at the interface is shown to depend on colloid surface charge density. In aqueous suspensions at pH 10 corrected Debye-Hückel theory for surface complexation calculations predict that smaller silica colloids have increased negative surface charge density that originates from enhanced screening of deprotonated silanol groups (≡Si-O(-)) by counterions in the condensed ion layer. The increased negative surface charge density results in an electrostatic repulsion from the vapor-water interface that is seen to a lesser extent for larger particles that have a reduced charge density in the XPS measurements. We compare the results and interpretation of the in-situ XPS and corrected Debye-Hückel theory for surface complexation calculations with traditional surface tension measurements. Our results show that controlling the surface charge density of colloid particles can regulate their adsorption to the interface between two dielectrics.

Promotional effect of surface hydroxyls on electrochemical reduction of CO 2 over SnO x/Sn electrode

DOE PAGES

Cui, Chaonan; Han, Jinyu; Zhu, Xinli; ...

2016-01-16

In this study, tin oxide (SnO x) formation on tin-based electrode surfaces during CO 2 electrochemical reduction can have a significant impact on the activity and selectivity of the reaction. In the present study, density functional theory (DFT) calculations have been performed to understand the role of SnO x in CO 2 reduction using a SnO monolayer on the Sn(112) surface as a model for SnO x. Water molecules have been treated explicitly and considered actively participating in the reaction. The results showed that H 2O dissociates on the perfect SnO monolayer into two hydroxyl groups symmetrically on the surface.more » CO 2 energetically prefers to react with the hydroxyl, forming a bicarbonate (HCO 3(t)*) intermediate, which can then be reduced to either formate (HCOO*) by hydrogenating the carbon atom or carboxyl (COOH*) by protonating the oxygen atom. Both steps involve a simultaneous Csingle bondO bond breaking. Further reduction of HCOO* species leads to the formation of formic acid in the acidic solution at pH < 4, while the COOH* will decompose to CO and H 2O via protonation. Whereas the oxygen vacancy (VO) in the oxide monolayer maybe formed by the reduction, it can be recovered by H 2O dissociation, resulting in two embedded hydroxyl groups. The results show that the hydroxylated surface with two symmetric hydroxyls is energetically more favorable for CO 2 reduction than the hydroxylated VO surface with two embedded hydroxyls. The reduction potential for the former has a limiting-potential of –0.20 V (RHE), lower than that for the latter (–0.74 V (RHE)). Compared to the pure Sn electrode, the formation of SnO x monolayer on the electrode under the operating conditions promotes CO 2 reduction more effectively by forming surface hydroxyls, thereby providing a new channel via COOH* to the CO formation, although formic acid is still the major reduction product.« less

Surface modification of active material structures in battery electrodes

DOEpatents

Erickson, Michael; Tikhonov, Konstantin

2016-02-02

Provided herein are methods of processing electrode active material structures for use in electrochemical cells or, more specifically, methods of forming surface layers on these structures. The structures are combined with a liquid to form a mixture. The mixture includes a surface reagent that chemically reacts and forms a surface layer covalently bound to the structures. The surface reagent may be a part of the initial liquid or added to the mixture after the liquid is combined with the structures. In some embodiments, the mixture may be processed to form a powder containing the structures with the surface layer thereon. Alternatively, the mixture may be deposited onto a current collecting substrate and dried to form an electrode layer. Furthermore, the liquid may be an electrolyte containing the surface reagent and a salt. The liquid soaks the previously arranged electrodes in order to contact the structures with the surface reagent.

Production of the virus-like particles of nipah virus matrix protein in Pichia pastoris as diagnostic reagents.

PubMed

Joseph, Narcisse Ms; Ho, Kok Lian; Tey, Beng Ti; Tan, Chon Seng; Shafee, Norazizah; Tan, Wen Siang

2016-07-08

The matrix (M) protein of Nipah virus (NiV) is a peripheral protein that plays a vital role in the envelopment of nucleocapsid protein and acts as a bridge between the viral surface and the nucleocapsid proteins. The M protein is also proven to play an important role in production of virus-like particles (VLPs) and is essential for assembly and budding of NiV particles. The recombinant M protein produced in Escherichia coli assembled into VLPs in the absence of the viral surface proteins. However, the E. coli produced VLPs are smaller than the native virus particles. Therefore, the aims of this study were to produce NiV M protein in Pichia pastoris, to examine the structure of the VLPs formed, and to assess the potential of the VLPs as a diagnostic reagent. The M protein was successfully expressed in P. pastoris and was detected with anti-myc antibody using Western blotting. The VLPs formed by the recombinant M protein were purified with sucrose density gradient ultracentrifugation, high-performance liquid chromatography (HPLC), and Immobilized Metal Affinity Chromatography (IMAC). Immunogold staining and transmission electron microscopy confirmed that the M protein assembled into VLPs as large as 200 nm. ELISA revealed that the NiV M protein produced in P. pastoris reacted strongly with positive NiV sera demonstrating its potential as a diagnostic reagent. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:1038-1045, 2016. © 2016 American Institute of Chemical Engineers.

A transport equation for the scalar dissipation in reacting flows with variable density: First results

NASA Technical Reports Server (NTRS)

Mantel, T.

1993-01-01

Although the different regimes of premixed combustion are not well defined, most of the recent developments in turbulent combustion modeling are led in the so-called flamelet regime. The goal of these models is to give a realistic expression to the mean reaction rate (w). Several methods can be used to estimate (w). Bray and coworkers (Libby & Bray 1980, Bray 1985, Bray & Libby 1986) express the instantaneous reaction rate by means of a flamelet library and a frequency which describes the local interaction between the laminar flamelets and the turbulent flowfield. In another way, the mean reaction rate can be directly connected to the flame surface density (Sigma). This quantity can be given by the transport equation of the coherent flame model initially proposed by Marble & Broadwell 1977 and developed elsewhere. The mean reaction rate, (w), can also be estimated thanks to the evolution of an arbitrary scalar field G(x, t) = G(sub O) which represents the flame sheet. G(x, t) is obtained from the G-equation proposed by Williams 1985, Kerstein et al. 1988 and Peters 1993. Another possibility proposed in a recent study by Mantel & Borghi 1991, where a transport equation for the mean dissipation rate (epsilon(sub c)) of the progress variable c is used to determine (w). In their model, Mantel & Borghi 1991 considered a medium with constant density and constant diffusivity in the determination of the transport equation for (epsilon(sub c)). A comparison of different flamelet models made by Duclos et al. 1993 shows the realistic behavior of this model even in the case of constant density. Our objective in this present report is to present preliminary results on the study of this equation in the case of variable density and variable diffusivity. Assumptions of constant pressure and a Lewis number equal to unity allow us to significantly simplify the equation. A systematic order of magnitude analysis based on adequate scale relations is performed on each term of the equation. As in the case of constant density and constant diffusivity, the effects of stretching of the scalar field by the turbulent strain field, of local curvature, and of chemical reactions are predominant. In this preliminary work, we suggest closure models for certain terms, which will be validated after comparisons with DNS data.

Volatile Reaction Products From Silicon-Based Ceramics in Combustion Environments Identified

NASA Technical Reports Server (NTRS)

Opila, Elizabeth J.

1997-01-01

Silicon-based ceramics and composites are prime candidates for use as components in the hot sections of advanced aircraft engines. These materials must have long-term durability in the combustion environment. Because water vapor is always present as a major product of combustion in the engine environment, its effect on the durability of silicon-based ceramics must be understood. In combustion environments, silicon-based ceramics react with water vapor to form a surface silica (SiO2) scale. This SiO2 scale, in turn, has been found to react with water vapor to form volatile hydroxides. Studies to date have focused on how water vapor reacts with high-purity silicon carbide (SiC) and SiO2 in model combustion environments. Because the combustion environment in advanced aircraft engines is expected to contain about 10-percent water vapor at 10-atm total pressure, the durability of SiC and SiO2 in gas mixtures containing 0.1- to 1-atm water vapor is of interest. The reactions of SiC and SiO2 with water vapor were monitored by measuring weight changes of sample coupons in a 0.5-atm water vapor/0.5-atm oxygen gas mixture with thermogravimetric analysis.

Adsorption of Bromine on Gold Nanoclusters

NASA Astrophysics Data System (ADS)

Salvo, Christopher; Keagy, Josiah; Yarmoff, Jory

Small metal nanoclusters are extremely effective as catalysts, with rates that rival those of enzymes in biological systems. The first step in a catalytic reaction is the adsorption of a precursor molecule. The neutralization of alkali projectiles during low energy ion scattering (LEIS), which is acutely sensitive to the local electrostatic potential a few Å's above the surface, is used here to probe Au nanoclusters grown on SiO2 as they are reacted with Br2. Previous work had demonstrated very efficient neutralization in scattering from small catalytically active Au clusters, which was interpreted as an indication that the bare clusters are negatively charged. X-ray photoelectron spectroscopy and LEIS show little or no Br signal after exposing SiO2 and Au foil to Br2, suggesting that adsorption does not occur because the Br-Br bond does not break. Dissociative adsorption occurs rapidly, however, when small Au nanoclusters are reacted with Br2. 1.5 keV Na+ ions scattered from the Au clusters show a decrease in the neutralization probability as Br is reacted, indicating that adsorption results in charge being transferred from the cluster to the Br adatom. This material is based upon work supported by the National Science Foundation under CHE - 1611563.

Quartz resonator fluid density and viscosity monitor

DOEpatents

Martin, Stephen J.; Wiczer, James J.; Cernosek, Richard W.; Frye, Gregory C.; Gebert, Charles T.; Casaus, Leonard; Mitchell, Mary A.

1998-01-01

A pair of thickness-shear mode resonators, one smooth and one with a textured surface, allows fluid density and viscosity to be independently resolved. A textured surface, either randomly rough or regularly patterned, leads to trapping of liquid at the device surface. The synchronous motion of this trapped liquid with the oscillating device surface allows the device to weigh the liquid; this leads to an additional response that depends on liquid density. This additional response enables a pair of devices, one smooth and one textured, to independently resolve liquid density and viscosity; the difference in responses determines the density while the smooth device determines the density-viscosity product, and thus, the pair determines both density and viscosity.

Isotopic tracing for calculating the surface density of arginine-glycine-aspartic acid-containing peptide on allogeneic bone.

PubMed

Hou, Xiao-bin; Hu, Yong-cheng; He, Jin-quan

2013-02-01

To investigate the feasibility of determining the surface density of arginine-glycine-aspartic acid (RGD) peptides grafted onto allogeneic bone by an isotopic tracing method involving labeling these peptides with (125) I, evaluating the impact of the input concentration of RGD peptides on surface density and establishing the correlation between surface density and their input concentration. A synthetic RGD-containing polypeptide (EPRGDNYR) was labeled with (125) I and its specific radioactivity calculated. Reactive solutions of RGD peptide with radioactive (125) I-RGD as probe with input concentrations of 0.01 mg/mL, 0.10 mg/mL, 0.50 mg/mL, 1.00 mg/mL, 2.00 mg/mL and 4.00 mg/mL were prepared. Using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide as a cross-linking agent, reactions were induced by placing allogeneic bone fragments into reactive solutions of RGD peptide of different input concentrations. On completion of the reactions, the surface densities of RGD peptides grafted onto the allogeneic bone fragments were calculated by evaluating the radioactivity and surface areas of the bone fragments. The impact of input concentration of RGD peptides on surface density was measured and a curve constructed. Measurements by a radiodensity γ-counter showed that the RGD peptides had been labeled successfully with (125) I. The allogeneic bone fragments were radioactive after the reaction, demonstrating that the RGD peptides had been successfully grafted onto their surfaces. It was also found that with increasing input concentration, the surface density increased. It was concluded that the surface density of RGD peptides is quantitatively related to their input concentration. With increasing input concentration, the surface density gradually increases to saturation value. © 2013 Chinese Orthopaedic Association and Wiley Publishing Asia Pty Ltd.

Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

Monoclonal Antibody Binding to a Surface-Exposed Epitope on Cowdria ruminantium That Is Conserved among Eight Strains

PubMed Central

Shompole, Sankale; Rurangirwa, Fred R.; Wambugu, Anderson; Sitienei, John; Mwangi, Duncan M.; Musoke, Anthony J.; Mahan, Suman; Wells, Clive W.; McGuire, Travis C.

2000-01-01

Monoclonal antibodies (MAb) binding to Cowdria ruminantium elementary bodies (EB) were identified by enzyme-linked immunosorbent assay, and surface binding of one MAb (446.15) to intact EB was determined by immunofluorescence, immunogold labeling, and transmission electron microscopy. MAb 446.15 bound an antigen of approximately 43 kDa in immunoblots of eight geographically distinct strains. The MAb did not react with Ehrlichia canis antigens or uninfected bovine endothelial cell lysate and may be useful in diagnostic assays and vaccine development. PMID:11063511

Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

DOEpatents

Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

2017-01-24

The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

Binding of methane to activated mineral surfaces - a methane sink on Mars?

NASA Astrophysics Data System (ADS)

Nørnberg, P.; Knak Jensen, S. J.; Skibsted, J.; Jakobsen, H. J.; ten Kate, I. L.; Gunnlaugsson, H. P.; Merrison, J. P.; Finster, K.; Bak, Ebbe; Iversen, J. J.; Kondrup, J. C.

2015-10-01

Tumbling experiments that simulate the wind erosion of quartz grains in an atmosphere of 13 C-enriched methane are reported. The eroded grains are analyzed by 13C and 29 Si solid-state NMR techniques after several months of tumbling. The analysis shows that methane has reacted with the eroded surface to form covalent Si-CH3 bonds, which stay intact for temperatures up to at least 250oC. These findings offer a model for a methane sink that might explain the fast disappearance of methane on Mars.

Characterisation of monoclonal antibodies to common protein epitopes on the cell surface of Streptococcus mutans and Streptococcus sobrinus.

PubMed

Smith, R; Lehner, T

1989-09-01

Three monoclonal antibodies (MAb) were prepared against a cell surface antigen which cross-react between Streptococcus mutans (serotypes c, e and f) and Streptococcus sobrinus (serotypes d and g). Two of the MAb also recognise a determinant on the surface of Streptococcus cricetus (serotype a). The common antigen shared between S. mutans and S. sobrinus was demonstrated by Western blotting to be about 200 kD in size. This antigen is shared not only by the cell surfaces of serotypes a, c, d, e, f and g, but also by the major cell surface antigen of S. mutans of 185 kD and another of 150 kD. These MAb identify all but one mutans type of streptococci and can be utilised as analytical reagents.

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

NASA Technical Reports Server (NTRS)

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

1991-01-01

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

Quantification of surface charge density and its effect on boundary slip.

PubMed

Jing, Dalei; Bhushan, Bharat

2013-06-11

Reduction of fluid drag is important in the micro-/nanofluidic systems. Surface charge and boundary slip can affect the fluid drag, and surface charge is also believed to affect boundary slip. The quantification of surface charge and boundary slip at a solid-liquid interface has been widely studied, but there is a lack of understanding of the effect of surface charge on boundary slip. In this paper, the surface charge density of borosilicate glass and octadecyltrichlorosilane (OTS) surfaces immersed in saline solutions with two ionic concentrations and deionized (DI) water with different pH values and electric field values is quantified by fitting experimental atomic force microscopy (AFM) electrostatic force data using a theoretical model relating the surface charge density and electrostatic force. Results show that pH and electric field can affect the surface charge density of glass and OTS surfaces immersed in saline solutions and DI water. The mechanisms of the effect of pH and electric field on the surface charge density are discussed. The slip length of the OTS surface immersed in saline solutions with two ionic concentrations and DI water with different pH values and electric field values is measured, and their effects on the slip length are analyzed from the point of surface charge. Results show that a larger absolute value of surface charge density leads to a smaller slip length for the OTS surface.

Observation of local cloud and moisture feedbacks over high ocean and desert surface temperatures

NASA Technical Reports Server (NTRS)

Chahine, Moustafa T.

1995-01-01

New data on clouds and moisture, made possible by reanalysis of weather satellite observations, show that the atmosphere reacts to warm clusters of very high sea surface temperatures in the western Pacific Ocean with increased moisture, cloudiness, and convection, suggesting a negative feedback limiting the sea surface temperature rise. The reverse was observed over dry and hot deserts where both moisture and cloudiness decrease, suggesting a positive feedback perpetuating existing desert conditions. In addition, the observations show a common critical surface temperature for both oceans and land; the distribution of atmospheric moisture is observed to reach a maximum value when the daily surface temperatures approach 304 +/- 1 K. These observations reveal complex dynamic-radiative interactions where multiple processes act simultaneously at the surface as well as in the atmosphere to regulate the feedback processes.

Medical implants and methods of making medical implants

DOEpatents

Shaw, Wendy J; Yonker, Clement R; Fulton, John L; Tarasevich, Barbara J; McClain, James B; Taylor, Doug

2014-09-16

A medical implant device having a substrate with an oxidized surface and a silane derivative coating covalently bonded to the oxidized surface. A bioactive agent is covalently bonded to the silane derivative coating. An implantable stent device including a stent core having an oxidized surface with a layer of silane derivative covalently bonded thereto. A spacer layer comprising polyethylene glycol (PEG) is covalently bonded to the layer of silane derivative and a protein is covalently bonded to the PEG. A method of making a medical implant device including providing a substrate having a surface, oxidizing the surface and reacting with derivitized silane to form a silane coating covalently bonded to the surface. A bioactive agent is then covalently bonded to the silane coating. In particular instances, an additional coating of bio-absorbable polymer and/or pharmaceutical agent is deposited over the bioactive agent.

Influence of Laser Shock Texturing on W9 Steel Surface Friction Property

NASA Astrophysics Data System (ADS)

Fan, Yujie; Cui, Pengfei; Zhou, Jianzhong; Dai, Yibin; Guo, Erbin; Tang, Deye

2017-09-01

To improve surface friction property of high speed steel, micro-dent arrays on W9Mo3Cr4V surface were produced by laser shock processing. Friction test was conducted on smooth surface and texturing surface and effect of surface texturing density on friction property was studied. The results show that, under the same condition, friction coefficient of textured surface is lower than smooth surface with dent area density less than 6%, wear mass loss, width and depth of wear scar are smaller; Wear resistance of the surface is the best and the friction coefficient is the smallest when dent area density is 2.2%; Friction coefficient, wear mass loss, width and depth of wear scar increase correspondingly as density of dent area increases when dent area density is more than 2.2%. Abrasive wear and adhesive wear, oxidative wear appear in the wear process. Reasonable control of geometric parameters of surface texturing induced by laser shock processing is helpful to improve friction performance.

An Overview of the NCC Spray/Monte-Carlo-PDF Computations

NASA Technical Reports Server (NTRS)

Raju, M. S.; Liu, Nan-Suey (Technical Monitor)

2000-01-01

This paper advances the state-of-the-art in spray computations with some of our recent contributions involving scalar Monte Carlo PDF (Probability Density Function), unstructured grids and parallel computing. It provides a complete overview of the scalar Monte Carlo PDF and Lagrangian spray computer codes developed for application with unstructured grids and parallel computing. Detailed comparisons for the case of a reacting non-swirling spray clearly highlight the important role that chemistry/turbulence interactions play in the modeling of reacting sprays. The results from the PDF and non-PDF methods were found to be markedly different and the PDF solution is closer to the reported experimental data. The PDF computations predict that some of the combustion occurs in a predominantly premixed-flame environment and the rest in a predominantly diffusion-flame environment. However, the non-PDF solution predicts wrongly for the combustion to occur in a vaporization-controlled regime. Near the premixed flame, the Monte Carlo particle temperature distribution shows two distinct peaks: one centered around the flame temperature and the other around the surrounding-gas temperature. Near the diffusion flame, the Monte Carlo particle temperature distribution shows a single peak. In both cases, the computed PDF's shape and strength are found to vary substantially depending upon the proximity to the flame surface. The results bring to the fore some of the deficiencies associated with the use of assumed-shape PDF methods in spray computations. Finally, we end the paper by demonstrating the computational viability of the present solution procedure for its use in 3D combustor calculations by summarizing the results of a 3D test case with periodic boundary conditions. For the 3D case, the parallel performance of all the three solvers (CFD, PDF, and spray) has been found to be good when the computations were performed on a 24-processor SGI Origin work-station.

Spatial and temporal effects of drought on soil CO2 efflux in a cacao agroforestry system in Sulawesi, Indonesia

NASA Astrophysics Data System (ADS)

van Straaten, O.; Veldkamp, E.; Köhler, M.; Anas, I.

2010-04-01

Climate change induced droughts pose a serious threat to ecosystems across the tropics and sub-tropics, particularly to those areas not adapted to natural dry periods. In order to study the vulnerability of cacao (Theobroma cacao) - Gliricidia sepium agroforestry plantations to droughts a large scale throughfall displacement roof was built in Central Sulawesi, Indonesia. In this 19-month experiment, we compared soil surface CO2 efflux (soil respiration) from three roof plots with three adjacent control plots. Soil respiration rates peaked at intermediate soil moisture conditions and decreased under increasingly dry conditions (drought induced), or increasingly wet conditions (as evidenced in control plots). The roof plots exhibited a slight decrease in soil respiration compared to the control plots (average 13% decrease). The strength of the drought effect was spatially variable - while some measurement chamber sites reacted strongly (responsive) to the decrease in soil water content (up to R2=0.70) (n=11), others did not react at all (non-responsive) (n=7). A significant correlation was measured between responsive soil respiration chamber sites and sap flux density ratios of cacao (R=0.61) and Gliricidia (R=0.65). Leaf litter CO2 respiration decreased as conditions became drier. The litter layer contributed approximately 3-4% of the total CO2 efflux during dry periods and up to 40% during wet periods. Within days of roof opening soil CO2 efflux rose to control plot levels. Thereafter, CO2 efflux remained comparable between roof and control plots. The cumulative effect on soil CO2 emissions over the duration of the experiment was not significantly different: the control plots respired 11.1±0.5 Mg C ha-1 yr-1, while roof plots respired 10.5±0.5 Mg C ha-1 yr-1. The relatively mild decrease measured in soil CO2 efflux indicates that this agroforestry ecosystem is capable of mitigating droughts with only minor stress symptoms.

Drought effects on soil CO

NASA Astrophysics Data System (ADS)

van Straaten, O.; Veldkamp, E.; Köhler, M.; Anas, I.

2009-12-01

Climate change induced droughts pose a serious threat to ecosystems across the tropics and sub-tropics, particularly to those areas not adapted to natural dry periods. In order to study the vulnerability of cacao (Theobroma cacao) - Gliricidia sepium agroforestry plantations to droughts a large scale throughfall displacement roof was built in Central Sulawesi, Indonesia. In this 19-month replicated experiment, we measured soil surface CO2 efflux (soil respiration) in three simulated drought plots compared with three adjacent control plots. Soil respiration rates peaked at intermediate soil moisture and decreased under increasingly dry conditions (drought induced), but also decreased when soils became water saturated, as evidenced in control plots. The simulated drought plots exhibited a slight decrease in soil respiration compared to the control plots (average 13% decrease). The strength of the drought effect was spatially variable - while some measurement chamber sites reacted strongly ("responsive") to the decrease in soil water content (up to R2=0.70) (n=11), others did not react at all ("non-responsive") (n=7). The degree of soil CO2 respiration drought response was highest around cacao tree stems and decreased with distance from the stem (R2=0.22). A significant correlation was measured between "responsive" soil respiration chamber sites and sap flux density ratios of cacao (R=0.61) and Gliricidia (R=0.65). Leaf litter CO2 respiration decreased as conditions became drier. During dry periods the litter layer contributed approximately 3-4% of the total CO2 efflux and up to 40% during wet periods. A CO2 flush was recorded during the rewetting phase that lasted for approximately two weeks, during which time accumulated labile carbon stocks mineralized. The net effect on soil CO2 emissions over the duration of the experiment was neutral, control plots respired 11.1±0.5 Mg C ha-1 yr-1, while roof plots respired 10.5±0.5 Mg C ha-1 yr-1.

Direct catalytic conversion of methane and light hydrocarbon gases. Quarterly report No. 10, January 1--March 31, 1989

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilson, R.B. Jr.; Posin, B.M.; Chan, Yee Wai

The goal of this research is to develop catalysts that directly convert methane and light hydrocarbons to intermediates that later can be converted to either liquid fuels or value-added chemicals, as economics dictate. In this reporting period, we have utilized samples of magnesia differing in their pretreatment temperature. Both the hydrido-ruthenium complex H{sub 4}Ru{sub 4}(CO){sub 12} and its reaction product with triethyl aluminum were reacted with these samples. The two ruthenium clusters are expected to react with the magnesia surface in different ways: by deprotonation of the hydride through an acid-base reaction with the basic surface, or by hydrolysis ofmore » the aluminum-carbon bond of the triethyl aluminum adduct. The concentration of hydroxyl groups on the magnesia surface able to hydrolyze the aluminum-carbon bond for immobilation should vary depending on the temperature of the pretreatment; the concentration of basic sites which can deprotonate the cluster should also vary with temperature. These differences were borne out by the experiment. We also compared the activity of two batches of AlRu{sub 4}/MgO which had been synthesized at different times in the project. Both batches had approximately the same activity, but the newer batch had greater selectivity for C{sub 6+} hydrocarbons.« less

Multifrequency electron paramagnetic resonance and electron-nuclear double-resonance studies of photo-hole processes in AgBr and AgCl emulsion grains

NASA Astrophysics Data System (ADS)

Eachus, R. S.; Pawlik, Th D.; Baetzold, R. C.

2000-10-01

By using a combination of multifrequency EPR spectroscopy, ENDOR spectroscopy and calculations of structure and energy, the reactivities of photo-generated holes in microcrystalline AgBr and AgCl dispersions (photographic emulsions) have been followed in detail. Progress has been facilitated by the use of both gelatin and polyvinyl alcohol (PVA) as peptizers. The initial trapped hole centres produced by band-gap excitation have been identified. In AgBr, this species is [(Br4)3-.V], a neutral complex formed from hole trapping by the four nearest neighbours of a surface Ag+ vacancy (=V). [(Br4)3-.V] reacts with gelatin to produce a transient organic radical at the grain's surface. It does not, however, react with PVA. The formation of the oxidized gelatin radical might involve atomic bromine as an intermediate. In AgCl, the well-known self-trapped hole centre (AgCl6)4- is the initial hole species. The hole diffuses by an electron exchange process until it is trapped by a silver ion on the grain's surface or within its penultimate layer of lattice ions. It is subsequently released from this Ag2+ site to be retrapped at a centre containing four equivalent Cl- ions. The precise identity of this defect has yet to be determined, but its decay also results in the oxidation of gelatin.

A PDF projection method: A pressure algorithm for stand-alone transported PDFs

NASA Astrophysics Data System (ADS)

Ghorbani, Asghar; Steinhilber, Gerd; Markus, Detlev; Maas, Ulrich

2015-03-01

In this paper, a new formulation of the projection approach is introduced for stand-alone probability density function (PDF) methods. The method is suitable for applications in low-Mach number transient turbulent reacting flows. The method is based on a fractional step method in which first the advection-diffusion-reaction equations are modelled and solved within a particle-based PDF method to predict an intermediate velocity field. Then the mean velocity field is projected onto a space where the continuity for the mean velocity is satisfied. In this approach, a Poisson equation is solved on the Eulerian grid to obtain the mean pressure field. Then the mean pressure is interpolated at the location of each stochastic Lagrangian particle. The formulation of the Poisson equation avoids the time derivatives of the density (due to convection) as well as second-order spatial derivatives. This in turn eliminates the major sources of instability in the presence of stochastic noise that are inherent in particle-based PDF methods. The convergence of the algorithm (in the non-turbulent case) is investigated first by the method of manufactured solutions. Then the algorithm is applied to a one-dimensional turbulent premixed flame in order to assess the accuracy and convergence of the method in the case of turbulent combustion. As a part of this work, we also apply the algorithm to a more realistic flow, namely a transient turbulent reacting jet, in order to assess the performance of the method.

Characterization of outer membranes isolated from Treponema pallidum, the syphilis spirochete.

PubMed

Radolf, J D; Robinson, E J; Bourell, K W; Akins, D R; Porcella, S F; Weigel, L M; Jones, J D; Norgard, M V

1995-11-01

Previous freeze-fracture electron microscopy (EM) studies have shown that the outer membrane (OM) of Treponema pallidum contains sparse transmembrane proteins. One strategy for molecular characterization of these rare OM proteins involves isolation of T. pallidum OMs. Here we describe a simple and extremely gentle method for OM isolation based upon isopycnic sucrose density gradient ultracentrifugation of treponemes following plasmolysis in 20% sucrose. Evidence that T. pallidum OMs were isolated included (i) the extremely low protein/lipid ratio of the putative OM fraction, (ii) a paucity of antigenic and/or biochemical markers for periplasmic, cytoplasmic membrane, and cytosolic compartments, and (iii) freeze-fracture EM demonstrating that the putative OMs contained intramembranous particles highly similar in size and density to those in native T. pallidum OMs. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis analysis revealed that the OMs contained a relatively small number of treponemal proteins, including several which did not appear to correspond to previously characterized T. pallidum antigens. Interestingly, these candidate rare OM proteins reacted poorly with syphilitic sera as determined by both conventional immunoblotting and enhanced chemiluminescence. Compared with whole cells, T. pallidum OMs were deficient in cardiolipin, the major lipoidal antigen reactive with antibodies in syphilitic sera. Also noteworthy was that other lipoidal constituents of OMs, including the recently discovered glycolipids, did not react with human syphilitic sera. These latter observations suggest that the poor antigenicity of virulent T. pallidum is a function of both the lipid composition and the low protein content of its OM.

Protein quantification on dendrimer-activated surfaces by using time-of-flight secondary ion mass spectrometry and principal component regression

NASA Astrophysics Data System (ADS)

Kim, Young-Pil; Hong, Mi-Young; Shon, Hyun Kyong; Chegal, Won; Cho, Hyun Mo; Moon, Dae Won; Kim, Hak-Sung; Lee, Tae Geol

2008-12-01

Interaction between streptavidin and biotin on poly(amidoamine) (PAMAM) dendrimer-activated surfaces and on self-assembled monolayers (SAMs) was quantitatively studied by using time-of-flight secondary ion mass spectrometry (ToF-SIMS). The surface protein density was systematically varied as a function of protein concentration and independently quantified using the ellipsometry technique. Principal component analysis (PCA) and principal component regression (PCR) were used to identify a correlation between the intensities of the secondary ion peaks and the surface protein densities. From the ToF-SIMS and ellipsometry results, a good linear correlation of protein density was found. Our study shows that surface protein densities are higher on dendrimer-activated surfaces than on SAMs surfaces due to the spherical property of the dendrimer, and that these surface protein densities can be easily quantified with high sensitivity in a label-free manner by ToF-SIMS.

Mapping surface charge density of lipid bilayers by quantitative surface conductivity microscopy

PubMed Central

Klausen, Lasse Hyldgaard; Fuhs, Thomas; Dong, Mingdong

2016-01-01

Local surface charge density of lipid membranes influences membrane–protein interactions leading to distinct functions in all living cells, and it is a vital parameter in understanding membrane-binding mechanisms, liposome design and drug delivery. Despite the significance, no method has so far been capable of mapping surface charge densities under physiologically relevant conditions. Here, we use a scanning nanopipette setup (scanning ion-conductance microscope) combined with a novel algorithm to investigate the surface conductivity near supported lipid bilayers, and we present a new approach, quantitative surface conductivity microscopy (QSCM), capable of mapping surface charge density with high-quantitative precision and nanoscale resolution. The method is validated through an extensive theoretical analysis of the ionic current at the nanopipette tip, and we demonstrate the capacity of QSCM by mapping the surface charge density of model cationic, anionic and zwitterionic lipids with results accurately matching theoretical values. PMID:27561322

Mapping surface charge density of lipid bilayers by quantitative surface conductivity microscopy

NASA Astrophysics Data System (ADS)

Klausen, Lasse Hyldgaard; Fuhs, Thomas; Dong, Mingdong

2016-08-01

Local surface charge density of lipid membranes influences membrane-protein interactions leading to distinct functions in all living cells, and it is a vital parameter in understanding membrane-binding mechanisms, liposome design and drug delivery. Despite the significance, no method has so far been capable of mapping surface charge densities under physiologically relevant conditions. Here, we use a scanning nanopipette setup (scanning ion-conductance microscope) combined with a novel algorithm to investigate the surface conductivity near supported lipid bilayers, and we present a new approach, quantitative surface conductivity microscopy (QSCM), capable of mapping surface charge density with high-quantitative precision and nanoscale resolution. The method is validated through an extensive theoretical analysis of the ionic current at the nanopipette tip, and we demonstrate the capacity of QSCM by mapping the surface charge density of model cationic, anionic and zwitterionic lipids with results accurately matching theoretical values.

Mapping surface charge density of lipid bilayers by quantitative surface conductivity microscopy.

PubMed

Klausen, Lasse Hyldgaard; Fuhs, Thomas; Dong, Mingdong

2016-08-26

Local surface charge density of lipid membranes influences membrane-protein interactions leading to distinct functions in all living cells, and it is a vital parameter in understanding membrane-binding mechanisms, liposome design and drug delivery. Despite the significance, no method has so far been capable of mapping surface charge densities under physiologically relevant conditions. Here, we use a scanning nanopipette setup (scanning ion-conductance microscope) combined with a novel algorithm to investigate the surface conductivity near supported lipid bilayers, and we present a new approach, quantitative surface conductivity microscopy (QSCM), capable of mapping surface charge density with high-quantitative precision and nanoscale resolution. The method is validated through an extensive theoretical analysis of the ionic current at the nanopipette tip, and we demonstrate the capacity of QSCM by mapping the surface charge density of model cationic, anionic and zwitterionic lipids with results accurately matching theoretical values.