Effect of chemical and physical heterogeneities on colloid-facilitated cesium transport

Science.gov (United States)

Rod, Kenton; Um, Wooyong; Chun, Jaehun; Wu, Ning; Yin, Xialong; Wang, Guohui; Neeves, Keith

2018-06-01

A set of column experiments was conducted to investigate the chemical and physical heterogeneity effect on colloid facilitated transport under slow pore velocity conditions. Pore velocities were kept below 100 cm d-1 for all experiments. Glass beads were packed into columns establishing four different conditions: 1) homogeneous, 2) mixed physical heterogeneity, 3) sequentially layered physical heterogeneity, and 4) chemical heterogeneity. The homogeneous column was packed with glass beads (diameter 500-600 μm), and physical heterogeneities were created by sequential layering or mixing two sizes of glass bead (500-600 μm and 300-400 μm). A chemical heterogeneity was created using 25% of the glass beads coated with hydrophobic molecules (1H-1H-2H-2H-perfluorooctyltrichlorosilane) mixed with 75% pristine glass beads (all 500-600 μm). Input solution with 0.5 mM CsI and 50 mg L-1 colloids (1-μm diameter SiO2) was pulsed into columns under saturated conditions. The physical heterogeneity in the packed glass beads retarded the transport of colloids compared to homogeneous (R = 25.0), but showed only slight differences between sequentially layered (R = 60.7) and mixed heterogeneity(R = 62.4). The column with the chemical, hydrophobic/hydrophilic, heterogeneity removed most of the colloids from the input solution. All column conditions stripped Cs from colloids onto the column matrix of packed glass beads.

Atmosphere-surface interactions over polar oceans and heterogeneous surfaces

Energy Technology Data Exchange (ETDEWEB)

Vihma, T.

1995-12-31

Processes of interaction between the atmospheric boundary layer and the planetary surface have been studied with special emphasis on polar ocean surfaces: the open ocean, leads, polynyas and sea ice. The local exchange of momentum, heat and moisture has been studied experimentally both in the Weddell Sea and in the Greenland Sea. Exchange processes over heterogeneous surfaces are addressed by modelling studies. Over a homogeneous surface, the local turbulent fluxes can be reasonably well estimated using an iterative flux-profile scheme based on the Monin-Obukhov similarity theory. In the Greenland Sea, the near-surface air temperature and the generally small turbulent fluxes over the open ocean were affected by the sea surface temperature fronts. Over the sea ice cover in the Weddell Sea, the turbulent sensible heat flux was generally downwards, and together with an upward oceanic heat flux through the ice it compensated the heat loss from the surface via long-wave radiation. The wind dominated on time scales of days, while the current became important on longer time scales. The drift dynamics showed apparent spatial differences between the eastern and western regions, as well as between the Antarctic Circumpolar Current and the rest of the Weddell Sea. Inertial motion was present in regions of low ice concentration. The surface heterogeneity, arising e.g. from roughness or temperature distribution, poses a problem for the parameterization of surface exchange processes in large-scale models. In the case of neutral flow over a heterogeneous terrain, an effective roughness length can be used to parameterize the roughness effects

Atmosphere-surface interactions over polar oceans and heterogeneous surfaces

Energy Technology Data Exchange (ETDEWEB)

Vihma, T

1996-12-31

Processes of interaction between the atmospheric boundary layer and the planetary surface have been studied with special emphasis on polar ocean surfaces: the open ocean, leads, polynyas and sea ice. The local exchange of momentum, heat and moisture has been studied experimentally both in the Weddell Sea and in the Greenland Sea. Exchange processes over heterogeneous surfaces are addressed by modelling studies. Over a homogeneous surface, the local turbulent fluxes can be reasonably well estimated using an iterative flux-profile scheme based on the Monin-Obukhov similarity theory. In the Greenland Sea, the near-surface air temperature and the generally small turbulent fluxes over the open ocean were affected by the sea surface temperature fronts. Over the sea ice cover in the Weddell Sea, the turbulent sensible heat flux was generally downwards, and together with an upward oceanic heat flux through the ice it compensated the heat loss from the surface via long-wave radiation. The wind dominated on time scales of days, while the current became important on longer time scales. The drift dynamics showed apparent spatial differences between the eastern and western regions, as well as between the Antarctic Circumpolar Current and the rest of the Weddell Sea. Inertial motion was present in regions of low ice concentration. The surface heterogeneity, arising e.g. from roughness or temperature distribution, poses a problem for the parameterization of surface exchange processes in large-scale models. In the case of neutral flow over a heterogeneous terrain, an effective roughness length can be used to parameterize the roughness effects

Light-induced nitrous acid (HONO) production from NO2 heterogeneous reactions on household chemicals

Science.gov (United States)

Gómez Alvarez, Elena; Sörgel, Matthias; Gligorovski, Sasho; Bassil, Sabina; Bartolomei, Vincent; Coulomb, Bruno; Zetzsch, Cornelius; Wortham, Henri

2014-10-01

Nitrous acid (HONO) can be generated in various indoor environments directly during combustion processes or indirectly via heterogeneous NO2 reactions with water adsorbed layers on diverse surfaces. Indoors not only the concentrations of NO2 are higher but the surface to volume (S/V) ratios are larger and therefore the potential of HONO production is significantly elevated compared to outdoors. It has been claimed that the UV solar light is largely attenuated indoors. Here, we show that solar light (λ > 340 nm) penetrates indoors and can influence the heterogeneous reactions of gas-phase NO2 with various household surfaces. The NO2 to HONO conversion mediated by light on surfaces covered with domestic chemicals has been determined at atmospherically relevant conditions i.e. 50 ppb NO2 and 50% RH. The formation rates of HONO were enhanced in presence of light for all the studied surfaces and are determined in the following order: 1.3·109 molecules cm-2 s-1 for borosilicate glass, 1.7·109 molecules cm-2 s-1 for bathroom cleaner, 1.0·1010 molecules cm-2 s-1 on alkaline detergent (floor cleaner), 1.3·1010 molecules cm-2 s-1 for white wall paint and 2.7·1010 molecules cm-2 s-1 for lacquer. These results highlight the potential of household chemicals, used for cleaning purposes to generate HONO indoors through light-enhanced NO2 heterogeneous reactions. The results obtained have been applied to predict the timely evolution of HONO in a real indoor environment using a dynamic mass balance model. A steady state mixing ratio of HONO has been estimated at 1.6 ppb assuming a contribution from glass, paint and lacquer and considering the photolysis of HONO as the most important loss process.

Applications of micro-spectroscopy and chemical imaging to delineate contaminant associations in heterogeneous mineral environments

International Nuclear Information System (INIS)

Hunter, D.

1998-01-01

Full text: Chemical speciation of a contaminant in the environment controls its mobility, bioavailability and ultimately its toxicity to organisms, including man. Transport models for environmental contaminants have continually failed because of an incomplete understanding of the physicochemical controls regulating the chemical speciation of both inorganic and organic contaminants. One of the greatest analytical difficulties to studying contaminant behavior in the subsurface is the inherent heterogeneity of mineral and organic constituents. Added to the multiplicity, of geological component surfaces that contaminants can interact with is the synergistic (both positive and negative) effects that occur due to non-conservative interactions between these components. Modern spectroscopic techniques can provide detailed quantitative and qualitative information on how contaminants behave within a specific mineral's surface-water interface. In general, the information is so rich as to be un interpretable in heterogeneous systems where multiple binding environments exist on competing multi-mineralic surfaces. None-the-less, it is the behaviour of contaminants in complex heterogeneous environments that is tantamount to understanding and predicting transport behaviour under field conditions. One solution is micro-spot spectroscopy. In micro-spot spectroscopy, chemical composition is determined by dispersing light absorbed or emitted from a highly localized spatial position within a heterogeneous sample. Such examples include FT-IR, Raman, fluorescence, and X-Ray absorption spectroscopies where spatial resolutions of 1 to 10 μm can be achieved. This scale can be still far too large to fully spectroscopically probe binding behaviour that is heterogeneous on colloidal scales ranging down to nanometers. However, it can provide a bridge to established characterization techniques such as optical petrography, since the challenge lies not only in identifying the speciation and

Characterizing heterogeneous dynamics at hydrated electrode surfaces

Science.gov (United States)

Willard, Adam P.; Limmer, David T.; Madden, Paul A.; Chandler, David

2013-05-01

In models of Pt 111 and Pt 100 surfaces in water, motions of molecules in the first hydration layer are spatially and temporally correlated. To interpret these collective motions, we apply quantitative measures of dynamic heterogeneity that are standard tools for considering glassy systems. Specifically, we carry out an analysis in terms of mobility fields and distributions of persistence times and exchange times. In so doing, we show that dynamics in these systems is facilitated by transient disorder in frustrated two-dimensional hydrogen bonding networks. The frustration is the result of unfavorable geometry imposed by strong metal-water bonding. The geometry depends upon the structure of the underlying metal surface. Dynamic heterogeneity of water on the Pt 111 surface is therefore qualitatively different than that for water on the Pt 100 surface. In both cases, statistics of this ad-layer dynamic heterogeneity responds asymmetrically to applied voltage.

Characterizing heterogeneous dynamics at hydrated electrode surfaces.

Science.gov (United States)

Willard, Adam P; Limmer, David T; Madden, Paul A; Chandler, David

2013-05-14

In models of Pt 111 and Pt 100 surfaces in water, motions of molecules in the first hydration layer are spatially and temporally correlated. To interpret these collective motions, we apply quantitative measures of dynamic heterogeneity that are standard tools for considering glassy systems. Specifically, we carry out an analysis in terms of mobility fields and distributions of persistence times and exchange times. In so doing, we show that dynamics in these systems is facilitated by transient disorder in frustrated two-dimensional hydrogen bonding networks. The frustration is the result of unfavorable geometry imposed by strong metal-water bonding. The geometry depends upon the structure of the underlying metal surface. Dynamic heterogeneity of water on the Pt 111 surface is therefore qualitatively different than that for water on the Pt 100 surface. In both cases, statistics of this ad-layer dynamic heterogeneity responds asymmetrically to applied voltage.

Imaging near-surface heterogeneities by natural migration of surface waves

KAUST Repository

Liu, Zhaolun; AlTheyab, Abdullah; Hanafy, Sherif M.; Schuster, Gerard T.

2016-01-01

We demonstrate that near-surface heterogeneities can be imaged by natural migration of backscattered surface waves in common shot gathers. No velocity model is required because the data are migrated onto surface points with the virtual Green

Using subdivision surfaces and adaptive surface simplification algorithms for modeling chemical heterogeneities in geophysical flows

Science.gov (United States)

Schmalzl, JöRg; Loddoch, Alexander

2003-09-01

We present a new method for investigating the transport of an active chemical component in a convective flow. We apply a three-dimensional front tracking method using a triangular mesh. For the refinement of the mesh we use subdivision surfaces which have been developed over the last decade primarily in the field of computer graphics. We present two different subdivision schemes and discuss their applicability to problems related to fluid dynamics. For adaptive refinement we propose a weight function based on the length of triangle edge and the sum of the angles of the triangle formed with neighboring triangles. In order to remove excess triangles we apply an adaptive surface simplification method based on quadric error metrics. We test these schemes by advecting a blob of passive material in a steady state flow in which the total volume is well preserved over a long time. Since for time-dependent flows the number of triangles may increase exponentially in time we propose the use of a subdivision scheme with diffusive properties in order to remove the small scale features of the chemical field. By doing so we are able to follow the evolution of a heavy chemical component in a vigorously convecting field. This calculation is aimed at the fate of a heavy layer at the Earth's core-mantle boundary. Since the viscosity variation with temperature is of key importance we also present a calculation with a strongly temperature-dependent viscosity.

Surface current double-heterogeneous multilayer multicell methodology

International Nuclear Information System (INIS)

Stepanek, J.; Segev, M.

1991-01-01

A surface current methodology is developed to respond to the need for treating the various levels of material heterogeneity in a double-heterogeneous multilayer multicell in processing neutron multigroup cross sections in the resonance as well as thermal energy range. First, the basic surface cosine current transport equations to calculate the energy-dependent neutron flux spatial distribution in the multilayered multicell are formulated. Slab, spherical and cylindrical geometries, as well as square and hexagonal lattices and pebble-bed configurations with white or reflective cell boundary conditions, are considered. Second, starting from the surface cosine-current formulation, a two-zone three-layer multicell formalism for reduction of heterogeneous flux expressions to equivalent homogeneous flux expression for table method was developed. This formalism allows an infinite, as well as a limited, number of second-heterogeneity cells within a partial first-heterogeneity cell layer to be considered. Also, the number of the first-and second-heterogeneity cell types is quite general. The 'outer' (right side) as well as 'inner' (left side) Dancoff probabilities can be calculated for any particular layer. An accurate, efficient, and compact interpolation procedure is developed to calculate the basic collision probabilities. These are transmission and escape probabilities for shells in slab, cylindrical, and spherical geometries, as well as Dancoff probabilities for cylinders in square and hexagonal lattices. The use of the interpolation procedure is exemplified in a multilayer multicell approximation for the Dancoff probability, enabling a routine evaluation of the equivalence-based shielded resonance integral in highly complex lattices of slab, cylindrical, or spherical cells. (author) 1 fig., 2 tabs., 10 refs

Communicating why land surface heterogeneity matters

Science.gov (United States)

Tague, C.; Burke, W.; Bart, R. R.; Turpin, E.; Wood, T.; Gordon, D.

2017-12-01

As hydrologic scientists, we know that land surface heterogeneity can have nuanced and sometimes dramatic impacts on the water cycle. Land surface characteristics, including the structure and composition of vegetation and soil storage and drainage properties, alter how incoming precipitation is translated into streamflow and evapotranspiration. Land surface heterogeneity can explain why this partitioning of incoming precipitation cannot always be computed by a simple water budget calculation. We also know that land surface characteristics are dynamic - vegetation grows and changes with fire, disease and human actions and these changes will alter the partitioning of water - how much so, however depends itself on other site characteristics - soil water storage and the timing and magnitude of precipitation. This complex impact of space-time dynamics on the water cycle is something we need to effectively communicate to non-experts. For example, we may want to explain why sometimes forest management practices increase water availability but sometimes they don't - or why the impacts of urbanization or fire are location specific. If we do not communicate these dependencies we risk over-simplifying and eroding scientific credibility when observed effects don't match simple generalizations. On the other hand excessive detail can overwhelm and disengage audiences. So how do we help different communities public, private landowners, other scientists, NGOs, governments to better understand the role of space-time heterogeneity. To address this issue, we present some results from ongoing work that looks at the impact of fuel treatment of forest ecohydrology. This work stem from a collaboration between an ecohydrologic modeling team, social-scientists, a visual artist and compute graphics students. We use a coupled model, validated with field measurements, to show why spatial heterogeneity matters for understanding the impact of fuel treatments on the water cycle for the Sierra

Kinetics of heterogeneous chemical reactions: a theoretical model for the accumulation of pesticides in soil.

Science.gov (United States)

Lin, S H; Sahai, R; Eyring, H

1971-04-01

A theoretical model for the accumulation of pesticides in soil has been proposed and discussed from the viewpoint of heterogeneous reaction kinetics with a basic aim to understand the complex nature of soil processes relating to the environmental pollution. In the bulk of soil, the pesticide disappears by diffusion and a chemical reaction; the rate processes considered on the surface of soil are diffusion, chemical reaction, vaporization, and regular pesticide application. The differential equations involved have been solved analytically by the Laplace-transform method.

Substrate Vibrations as Promoters of Chemical Reactivity on Metal Surfaces.

Science.gov (United States)

Campbell, Victoria L; Chen, Nan; Guo, Han; Jackson, Bret; Utz, Arthur L

2015-12-17

Studies exploring how vibrational energy (Evib) promotes chemical reactivity most often focus on molecular reagents, leaving the role of substrate atom motion in heterogeneous interfacial chemistry underexplored. This combined theoretical and experimental study of methane dissociation on Ni(111) shows that lattice atom motion modulates the reaction barrier height during each surface atom's vibrational period, which leads to a strong variation in the reaction probability (S0) with surface temperature (Tsurf). State-resolved beam-surface scattering studies at Tsurf = 90 K show a sharp threshold in S0 at translational energy (Etrans) = 42 kJ/mol. When Etrans decreases from 42 kJ/mol to 34 kJ/mol, S0 decreases 1000-fold at Tsurf = 90 K, but only 2-fold at Tsurf = 475 K. Results highlight the mechanism for this effect, provide benchmarks for DFT calculations, and suggest the potential importance of surface atom induced barrier height modulation in heterogeneously catalyzed reactions, particularly on structurally labile nanoscale particles and defect sites.

Analysis of heterogeneous oxygen exchange and fuel oxidation on the catalytic surface of perovskite membranes

KAUST Repository

Hong, Jongsup

2013-10-01

The catalytic kinetics of oxygen surface exchange and fuel oxidation for a perovskite membrane is investigated in terms of the thermodynamic state in the immediate vicinity of or on the membrane surface. Perovskite membranes have been shown to exhibit both oxygen perm-selectivity and catalytic activity for hydrocarbon conversion. A fundamental description of their catalytic surface reactions is needed. In this study, we infer the kinetic parameters for heterogeneous oxygen surface exchange and catalytic fuel conversion reactions, based on permeation rate measurements and a spatially resolved physical model that incorporates detailed chemical kinetics and transport in the gas-phase. The conservation equations for surface and bulk species are coupled with those of the gas-phase species through the species production rates from surface reactions. It is shown that oxygen surface exchange is limited by dissociative/associative adsorption/desorption of oxygen molecules onto/from the membrane surface. On the sweep side, while the catalytic conversion of methane to methyl radical governs the overall surface reactions at high temperature, carbon monoxide oxidation on the membrane surface is dominant at low temperature. Given the sweep side conditions considered in ITM reactor experiments, gas-phase reactions also play an important role, indicating the significance of investigating both homogeneous and heterogeneous chemistry and their coupling when examining the results. We show that the local thermodynamic state at the membrane surface should be considered when constructing and examining models of oxygen permeation and heterogeneous chemistry. © 2013 Elsevier B.V.

Analysis of heterogeneous oxygen exchange and fuel oxidation on the catalytic surface of perovskite membranes

KAUST Repository

Hong, Jongsup; Kirchen, Patrick; Ghoniem, Ahmed F.

2013-01-01

The catalytic kinetics of oxygen surface exchange and fuel oxidation for a perovskite membrane is investigated in terms of the thermodynamic state in the immediate vicinity of or on the membrane surface. Perovskite membranes have been shown to exhibit both oxygen perm-selectivity and catalytic activity for hydrocarbon conversion. A fundamental description of their catalytic surface reactions is needed. In this study, we infer the kinetic parameters for heterogeneous oxygen surface exchange and catalytic fuel conversion reactions, based on permeation rate measurements and a spatially resolved physical model that incorporates detailed chemical kinetics and transport in the gas-phase. The conservation equations for surface and bulk species are coupled with those of the gas-phase species through the species production rates from surface reactions. It is shown that oxygen surface exchange is limited by dissociative/associative adsorption/desorption of oxygen molecules onto/from the membrane surface. On the sweep side, while the catalytic conversion of methane to methyl radical governs the overall surface reactions at high temperature, carbon monoxide oxidation on the membrane surface is dominant at low temperature. Given the sweep side conditions considered in ITM reactor experiments, gas-phase reactions also play an important role, indicating the significance of investigating both homogeneous and heterogeneous chemistry and their coupling when examining the results. We show that the local thermodynamic state at the membrane surface should be considered when constructing and examining models of oxygen permeation and heterogeneous chemistry. © 2013 Elsevier B.V.

Surface-Enhanced Raman Spectroscopy for Heterogeneous Catalysis Research

NARCIS (Netherlands)

Harvey, C.E.

2013-01-01

Raman spectroscopy is valuable characterization technique for the chemical analysis of heterogeneous catalysts, both under ex-situ and in-situ conditions. The potential for Raman to shine light on the chemical bonds present in a sample makes the method highly desirable for detailed catalyst

The Theory of Thermodynamics for Chemical Reactions in Dispersed Heterogeneous Systems

Science.gov (United States)

Yongqiang; Baojiao; Jianfeng

1997-07-01

In this paper, the expressions of Gibbs energy change, enthalpy change, entropy change, and equilibrium constant for chemical reactions in dispersed heterogeneous systems are derived using classical thermodynamics theory. The thermodynamical relations for the same reaction system between the dispersed and the block state are also derived. The effects of degree of dispersion on thermodynamical properties, reaction directions, and chemical equilibria are discussed. The results show that the present equation of thermodynamics for chemical reactions is only a special case of the above-mentioned formulas and that the effect of the dispersity of a heterogeneous system on the chemical reaction obeys the Le Chatelier principle of movement of equilibria.

Surface science and heterogeneous catalysis

International Nuclear Information System (INIS)

Somorjai, G.A.

1980-05-01

The catalytic reactions studied include hydrocarbon conversion over platinum, the transition metal-catalyzed hydrogenation of carbon monoxide, and the photocatalyzed dissociation of water over oxide surfaces. The method of combined surface science and catalytic studies is similar to those used in synthetic organic chemistry. The single-crystal models for the working catalyst are compared with real catalysts by comparing the rates of cyclopropane ring opening on platinum and the hydrogenation of carbon monoxide on rhodium single crystal surface with those on practical commercial catalyst systems. Excellent agreement was obtained for these reactions. This document reviews what was learned about heterogeneous catalysis from these surface science approaches over the past 15 years and present models of the active catalyst surface

Influence of chemical heterogeneity of solid solutions on brittleness in chromium steels

International Nuclear Information System (INIS)

Madyanov, S.A.; Sedov, V.K.; Apaev, B.A.

1985-01-01

The role of chemical heterogeneity of solid solutions in formation of mechanical properties of Kh09, Kh15, Kh20, Kh19N2G5T chromium steels has been investigated. It is established that besides the known regioA of chemical heterogeneity in the vicinity of 475 deg C exists a high-temperature region (1000-1050 deg C), where maximum heteroge=- neity of chromium distribution in solid solution, is observed. Both types of chemical heterogeneity cause essential hardening of alloys, which becomes apparent in abrupt change of capability to microplastic deformation The mechanism of occurrence of the given temper brittleness consists in carbon diffusion into microvolunes enriched in carbide-forming elements

Do goethite surfaces really control the transport and retention of multi-walled carbon nanotubes in chemically heterogeneous porous media?

Science.gov (United States)

Transport and retention behavior of multiwalled carbon nanotubes (MWCNTs) was studied in mixtures of negatively charged quartz sand (QS) and positively charged goethite-coated sand (GQS) to assess the role of chemical heterogeneity. The linear equilibrium sorption model provided a good description o...

Practical chemical analysis of Pt and Pd based heterogeneous catalysts with hard X-ray photoelectron spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Yoshikawa, H., E-mail: YOSHIKAWA.Hideki@nims.go.jp [National Institute for Materials Science, 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047 (Japan); Matolínová, I.; Matolín, V. [Charles University in Prague, Faculty of Mathematics and Physics, V Holešovičkách 2, 18000 Prague 8 (Czech Republic)

2013-10-15

Highlights: •Hard X-ray photoelectron spectroscopy (HAXPES) enables interface analysis of catalyst. •HAXPES enables overall analysis of porous film of Pt-doped CeO{sub 2} and related catalyst. •HAXPES enables analysis of trace elements for Pd and Pt{sub 3}Ni nanoparticle catalysts. -- Abstract: Interfacial properties including configuration, porosity, chemical states, and atomic diffusion greatly affect the performance of supported heterogeneous catalysts. Hard X-ray photoelectron spectroscopy (HAXPES) can be used to analyze the interfaces of heterogeneous catalysts because of its large information depth of more than 20 nm. We use HAXPES to examine Pt-doped CeO{sub 2} and related thin film catalysts evaporated on Si, carbon, and carbon nanotube substrates, because Pt-doped CeO{sub 2} has great potential as a noble metal-based heterogeneous catalyst for fuel cells. The HAXPES measurements clarify that the dopant material, substrate material, and surface pretreatment of substrate are important parameters that affect the interfacial properties of Pt-doped CeO{sub 2} and related thin film catalysts. Another advantage of HAXPES measurement of heterogeneous catalysts is that it can be used for chemical analysis of trace elements by detecting photoelectrons from deep core levels, which have large photoionization cross-sections in the hard X-ray region. We use HAXPES for chemical analysis of trace elements in Pd nanoparticle catalysts immobilized on sulfur-terminated substrates and Pt{sub 3}Ni nanoparticle catalysts enveloped by dendrimer molecules.

Interaction of 3D dewetting nanodroplets on homogeneous and chemically heterogeneous substrates

International Nuclear Information System (INIS)

Asgari, M; Moosavi, A

2014-01-01

Long-time interaction of dewetting nanodroplets is investigated using a long-wave approximation method. Although three-dimensional (3D) droplets evolution dynamics exhibits qualitative behavior analogous to two-dimensional (2D) dynamics, there is an extensive quantitative difference between them. 3D dynamics is substantially faster than 2D dynamics. This can be related to the larger curvature and, as a consequence, the larger Laplace pressure difference between the droplets in 3D systems. The influence of various chemical heterogeneities on the behavior of droplets has also been studied. In the case of gradient surfaces, it is shown how the gradient direction could change the dynamics. For a chemical step located between the droplets, the dynamics is enhanced or weakened depending on the initial configuration of the system. (paper)

Surface engineering of one-dimensional tin oxide nanostructures for chemical sensors

International Nuclear Information System (INIS)

Ma, Yuanyuan; Qu, Yongquan; Zhou, Wei

2013-01-01

Nanostructured materials are promising candidates for chemical sensors due to their fascinating physicochemical properties. Among various candidates, tin oxide (SnO 2 ) has been widely explored in gas sensing elements due to its excellent chemical stability, low cost, ease of fabrication and remarkable reproducibility. We are presenting an overview on recent investigations on 1-dimensional (1D) SnO 2 nanostructures for chemical sensing. In particular, we focus on the performance of devices based on surface engineered SnO 2 nanostructures, and on aspects of morphology, size, and functionality. The synthesis and sensing mechanism of highly selective, sensitive and stable 1D nanostructures for use in chemical sensing are discussed first. This is followed by a discussion of the relationship between the surface properties of the SnO 2 layer and the sensor performance from a thermodynamic point of view. Then, the opportunities and recent progress of chemical sensors fabricated from 1D SnO 2 heterogeneous nanostructures are discussed. Finally, we summarize current challenges in terms of improving the performance of chemical (gas) sensors using such nanostructures and suggest potential applications. (author)

Heterogeneous nucleation of calcium oxalate on native oxide surfaces

International Nuclear Information System (INIS)

Song, L.; Pattillo, M.J.; Graff, G.L.; Campbell, A.A.; Bunker, B.C.

1994-04-01

The aqueous deposition of calcium oxalate onto colloidal oxides has been studied as a model system for understanding heterogeneous nucleation processes of importance in biomimetic synthesis of ceramic thin films. Calcium oxalate nucleation has been monitored by measuring induction times for nucleation using Constant Composition techniques and by measuring nucleation densities on extended oxide surfaces using an atomic force microscope. Results show that the dependence of calcium oxalate nucleation on solution supersaturation fits the functional form predicted by classical nucleation theories. Anionic surfaces appear to promote nucleation better than cationic surfaces, lowering the effective energy barrier to heterogeneous nucleation

Adsorption of gas mixtures on heterogeneous solid surfaces

Energy Technology Data Exchange (ETDEWEB)

Jaroniec, M; Rudzinski, W

1977-01-01

A review of theoretical studies on the physical adsorption from gas mixtures on heterogeneous solid surfaces, mainly by Jaroniec and coworkers, covers the vector notation used in the calculations; adsorption isotherms for multicomponent gases; the generalized integral equation for adsorption of gas mixtures, its numerical and analytical solutions, applied, (e.g., to interpret the experimental adsorption isotherms of ethane/ethylene on Nuxit-AL); thermodynamic relations, applied, (e.g., to calculating isosteric adsorption heats from experimental parameters for the adsorption of propylene from propane/propylene mixtures on Nuxit-AL); and the derivation and use of a simplified integral equation for describing the adsorption from gas mixtures on heterogeneous surfaces. 75 references.

Evaporation rates and surface profiles on heterogeneous surfaces with mass transfer and surface reaction

Energy Technology Data Exchange (ETDEWEB)

Flytzani-Stephanopoulos, M; Schmidt, L D

1979-01-01

Simple models incorporating surface reaction and diffusion of volatile products through a boundary layer are developed to calculate effective rates of evaporation and local surface profiles on surfaces having active and inactive regions. The coupling between surface heterogeneities with respect to a particular reaction and external mass transfer may provide a mechanism for the surface rearrangement and metal loss encountered in several catalytic systems of practical interest. Calculated transport rates for the volatilization of platinum in oxidizing environments and the rearrangement of this metal during the ammonia oxidation reaction agree well with published experimental data.

Resolving the chemical nature of nanodesigned silica surface obtained via a bottom-up approach.

Science.gov (United States)

Rahma, Hakim; Buffeteau, Thierry; Belin, Colette; Le Bourdon, Gwenaëlle; Degueil, Marie; Bennetau, Bernard; Vellutini, Luc; Heuzé, Karine

2013-08-14

The covalent grafting on silica surfaces of a functional dendritic organosilane coupling agent inserted, in a long alkyl chain monolayer, is described. In this paper, we show that depending on experimental parameters, particularly the solvent, it is possible to obtain a nanodesigned surface via a bottom-up approach. Thus, we succeed in the formation of both homogeneous dense monolayer and a heterogeneous dense monolayer, the latter being characterized by a nanosized volcano-type pattern (4-6 nm of height, 100 nm of width, and around 3 volcanos/μm(2)) randomly distributed over the surface. The dendritic attribute of the grafted silylated coupling agent affords enough anchoring sites to immobilize covalently functional gold nanoparticles (GNPs), coated with amino PEG polymer to resolve the chemical nature of the surfaces and especially the volcano type nanopattern structures of the heterogeneous monolayer. Thus, the versatile surface chemistry developed herein is particularly challenging as the nanodesign is straightforward achieved in a bottom-up approach without any specific lithography device.

Quantifying seismic anisotropy induced by small-scale chemical heterogeneities

Science.gov (United States)

Alder, C.; Bodin, T.; Ricard, Y.; Capdeville, Y.; Debayle, E.; Montagner, J. P.

2017-12-01

Observations of seismic anisotropy are usually used as a proxy for lattice-preferred orientation (LPO) of anisotropic minerals in the Earth's mantle. In this way, seismic anisotropy observed in tomographic models provides important constraints on the geometry of mantle deformation associated with thermal convection and plate tectonics. However, in addition to LPO, small-scale heterogeneities that cannot be resolved by long-period seismic waves may also produce anisotropy. The observed (i.e. apparent) anisotropy is then a combination of an intrinsic and an extrinsic component. Assuming the Earth's mantle exhibits petrological inhomogeneities at all scales, tomographic models built from long-period seismic waves may thus display extrinsic anisotropy. In this paper, we investigate the relation between the amplitude of seismic heterogeneities and the level of induced S-wave radial anisotropy as seen by long-period seismic waves. We generate some simple 1-D and 2-D isotropic models that exhibit a power spectrum of heterogeneities as what is expected for the Earth's mantle, that is, varying as 1/k, with k the wavenumber of these heterogeneities. The 1-D toy models correspond to simple layered media. In the 2-D case, our models depict marble-cake patterns in which an anomaly in shear wave velocity has been advected within convective cells. The long-wavelength equivalents of these models are computed using upscaling relations that link properties of a rapidly varying elastic medium to properties of the effective, that is, apparent, medium as seen by long-period waves. The resulting homogenized media exhibit extrinsic anisotropy and represent what would be observed in tomography. In the 1-D case, we analytically show that the level of anisotropy increases with the square of the amplitude of heterogeneities. This relation is numerically verified for both 1-D and 2-D media. In addition, we predict that 10 per cent of chemical heterogeneities in 2-D marble-cake models can

Irreversible adsorption of particles on heterogeneous surfaces.

Science.gov (United States)

Adamczyk, Zbigniew; Jaszczółt, Katarzyna; Michna, Aneta; Siwek, Barbara; Szyk-Warszyńska, Lilianna; Zembala, Maria

2005-12-30

Methods of theoretical and experimental evaluation of irreversible adsorption of particles, e.g., colloids and globular proteins at heterogeneous surfaces were reviewed. The theoretical models were based on the generalized random sequential adsorption (RSA) approach. Within the scope of these models, localized adsorption of particles occurring as a result of short-ranged attractive interactions with discrete adsorption sites was analyzed. Monte-Carlo type simulations performed according to this model enabled one to determine the initial flux, adsorption kinetics, jamming coverage and the structure of the particle monolayer as a function of the site coverage and the particle/site size ratio, denoted by lambda. It was revealed that the initial flux increased significantly with the site coverage theta(s) and the lambda parameter. This behavior was quantitatively interpreted in terms of the scaled particle theory. It also was demonstrated that particle adsorption kinetics and the jamming coverage increased significantly, at fixed site coverage, when the lambda parameter increased. Practically, for alpha = lambda2theta(s) > 1 the jamming coverage at the heterogeneous surfaces attained the value pertinent to continuous surfaces. The results obtained prove unequivocally that spherically shaped sites were more efficient in binding particles in comparison with disk-shaped sites. It also was predicted that for particle size ratio lambda charge. Particle deposition occurred under diffusion-controlled transport conditions and their coverage was evaluated by direct particle counting using the optical and electron microscopy. Adsorption kinetics was quantitatively interpreted in terms of numerical solutions of the governing diffusion equation with the non-linear boundary condition derived from Monte-Carlo simulations. It was proven that for site coverage as low as a few percent the initial flux at heterogeneous surfaces attained the maximum value pertinent to homogeneous

Effect of surface physical and chemical properties on interaction and annihilation mechanisms of positrons

International Nuclear Information System (INIS)

Gol'danskij, V.I.; Levin, B.M.; Shantarovich, V.P.

1982-01-01

The possibility of positron use is illustrated, to investigate physical and chemical properties of the surface, by a number of effects found by the authors while studying the interaction and annihilation of β + -decay positrons in highly-dispersed heterogeneous systems positronium formation and ortho-para conversion close to the surface of metal particles in a dielectric matrix, postronium oxidation by proton centers on the surface of an aluminosilicate catalyst). The ways, new in the main, are revealed to study the properties of the surface by the technique of monochromatic positron beams of low energy

Understanding and exploiting nanoscale surface heterogeneity for particle and cell manipulation

Science.gov (United States)

Kalasin, Surachate

This thesis explores the impact of surface heterogeneities on colloidal interactions and translates concepts to biointerfacial systems, for instance, microfluidic and biomedical devices. The thesis advances a model system, originally put forth by Kozlova: Tunable electrostatic surface heterogeneity is produced by adsorbing small amounts of cationic polyelectrolyte on a silica flat. The resulting positive electrostatic patches possess a density that is tuned from a saturated carpet down to average spacings on the order of a few hundred nanometers. At these length-scales, multiple adhesive elements (from tens to thousands) are present in the area of contact between a particle and a surface, a distinguishing feature of the thesis. Much of the literature addressing surface "heterogeneity" engineers surfaces with micron-scale features, almost always larger than the contact area between a particle and a second surface. With a nanoscale heterogeneity model, this thesis reports and quantitatively explains particle interaction behavior not typical of homogeneous interfaces. This includes (1) an adhesion threshold, a minimum average surface density of cationic patches needed for particle capture, (previously observed by Kozlova); (2) a crossover, from salt-destabilized to salt-stabilized interactions between heterogeneous surfaces with net-negative charge; (3) a shift of the adhesion threshold with shear, reducing adhesion; (4) a crossover from shear-enhanced to shear-hindered particle adhesion; (5) a range of surface compositions and processing parameters that sustain particle rolling; and (6) conditions where particles arrest immediately on contact. Through variations in ionic strength and particle size, the particle-surface contact area is systematically varied relative to the heterogeneity lengthscale. This provides a semi-quantitative explanation for the shifting of the adhesion threshold, in terms of the statistical probability of a particle being able to find a

Effect of Heterogeneous Chemical Reactions on the Köhler Activation of Aqueous Organic Aerosols.

Science.gov (United States)

Djikaev, Yuri S; Ruckenstein, Eli

2018-05-03

We study some thermodynamic aspects of the activation of aqueous organic aerosols into cloud droplets considering the aerosols to consist of liquid solution of water and hydrophilic and hydrophobic organic compounds, taking into account the presence of reactive species in the air. The hydrophobic (surfactant) organic molecules on the surface of such an aerosol can be processed by chemical reactions with some atmospheric species; this affects the hygroscopicity of the aerosol and hence its ability to become a cloud droplet either via nucleation or via Köhler activation. The most probable pathway of such processing involves atmospheric hydroxyl radicals that abstract hydrogen atoms from hydrophobic organic molecules located on the aerosol surface (first step), the resulting radicals being quickly oxidized by ubiquitous atmospheric oxygen molecules to produce surface-bound peroxyl radicals (second step). These two reactions play a crucial role in the enhancement of the Köhler activation of the aerosol and its evolution into a cloud droplet. Taking them and a third reaction (next in the multistep chain of relevant heterogeneous reactions) into account, one can derive an explicit expression for the free energy of formation of a four-component aqueous droplet on a ternary aqueous organic aerosol as a function of four independent variables of state of a droplet. The results of numerical calculations suggest that the formation of cloud droplets on such (aqueous hydrophilic/hydrophobic organic) aerosols is most likely to occur as a Köhler activation-like process rather than via nucleation. The model allows one to determine the threshold parameters of the system necessary for the Köhler activation of such aerosols, which are predicted to be very sensitive to the equilibrium constant of the chain of three heterogeneous reactions involved in the chemical aging of aerosols.

The kinetics of nonequilibrium chain plasma-chemical oxidation in heterogeneous media

International Nuclear Information System (INIS)

Deminskii, M.A.; Potapkin, B.V.; Rusanov, V.D.

1994-01-01

The kinetics of oxidation of low-impurity components in air mixtures under heterogeneous conditions was studied. The principal kinetic features of the process were determined on the basis of theoretical analysis of plasma-chemical oxidation in heterogeneous media. The analysis also showed that low concentrations of impurities in liquid aerosol particles can be efficiently oxidized via a chain process induced by reactive species formed in the gas

Continuous-Flow Processes in Heterogeneously Catalyzed Transformations of Biomass Derivatives into Fuels and Chemicals

Directory of Open Access Journals (Sweden)

Antonio A. Romero

2012-07-01

Full Text Available Continuous flow chemical processes offer several advantages as compared to batch chemistries. These are particularly relevant in the case of heterogeneously catalyzed transformations of biomass-derived platform molecules into valuable chemicals and fuels. This work is aimed to provide an overview of key continuous flow processes developed to date dealing with a series of transformations of platform chemicals including alcohols, furanics, organic acids and polyols using a wide range of heterogeneous catalysts based on supported metals, solid acids and bifunctional (metal + acidic materials.

Facile spray-coating process for the fabrication of tunable adhesive superhydrophobic surfaces with heterogeneous chemical compositions used for selective transportation of microdroplets with different volumes.

Science.gov (United States)

Li, Jian; Jing, Zhijiao; Zha, Fei; Yang, Yaoxia; Wang, Qingtao; Lei, Ziqiang

2014-06-11

In this paper, tunable adhesive superhydrophobic ZnO surfaces have been fabricated successfully by spraying ZnO nanoparticle (NP) suspensions onto desired substrates. We regulate the spray-coating process by changing the mass percentage of hydrophobic ZnO NPs (which were achieved by modifying hydrophilic ZnO NPs with stearic acid) in the hydrophobic/hydrophilic ZnO NP mixtures to control heterogeneous chemical composition of the ZnO surfaces. Thus, the water adhesion on the same superhydrophobic ZnO surface could be effectively tuned by controlling the surface chemical composition without altering the surface morphology. Compared with the conventional tunable adhesive superhydrophobic surfaces, on which there were only three different water sliding angle values: lower than 10°, 90° (the water droplet is firmly pinned on the surface at any tilted angles), and the value between the two ones, the water adhesion on the superhydrophobic ZnO surfaces has been tuned effectively, on which the sliding angle is controlled from 2 ± 1° to 9 ± 1°, 21 ± 2°, 39 ± 3°, and 90°. Accordingly, the adhesive force can be adjusted from extremely low (∼2.5 μN) to very high (∼111.6 μN). On the basis of the different adhesive forces of the tunable adhesive superhydrophobic surfaces, the selective transportation of microdroplets with different volumes was achieved, which has never been reported before. In addition, we demonstrated a proof of selective transportation of microdroplets with different volumes for application in the droplet-based microreactors via our tunable adhesive superhydrophobic surfaces for the quantitative detection of AgNO3 and NaOH. The results reported herein realize the selective transportation of microdroplets with different volumes and we believe that this method would potentially be used in many important applications, such as selective water droplet transportation, biomolecular quantitative detection and droplet-based biodetection.

Surface fluxes in heterogeneous landscape

Energy Technology Data Exchange (ETDEWEB)

Bay Hasager, C

1997-01-01

The surface fluxes in homogeneous landscapes are calculated by similarity scaling principles. The methodology is well establish. In heterogeneous landscapes with spatial changes in the micro scale range, i e from 100 m to 10 km, advective effects are significant. The present work focus on these effects in an agricultural countryside typical for the midlatitudes. Meteorological and satellite data from a highly heterogeneous landscape in the Rhine Valley, Germany was collected in the large-scale field experiment TRACT (Transport of pollutants over complex terrain) in 1992. Classified satellite images, Landsat TM and ERS SAR, are used as basis for roughness maps. The roughnesses were measured at meteorological masts in the various cover classes and assigned pixel by pixel to the images. The roughness maps are aggregated, i e spatially averaged, into so-called effective roughness lengths. This calculation is performed by a micro scale aggregation model. The model solves the linearized atmospheric flow equations by a numerical (Fast Fourier Transform) method. This model also calculate maps of friction velocity and momentum flux pixel wise in heterogeneous landscapes. It is indicated how the aggregation methodology can be used to calculate the heat fluxes based on the relevant satellite data i e temperature and soil moisture information. (au) 10 tabs., 49 ills., 223 refs.

Chemical Gel for Surface Decontamination

International Nuclear Information System (INIS)

Jung, Chong Hun; Moon, J. K.; Won, H. J.; Lee, K. W.; Kim, C. K.

2010-01-01

Many chemical decontamination processes operate by immersing components in aggressive chemical solutions. In these applications chemical decontamination technique produce large amounts of radioactive liquid waste. Therefore it is necessary to develop processes using chemical gels instead of chemical solutions, to avoid the well-known disadvantages of chemical decontamination techniques while retaining their high efficiency. Chemical gels decontamination process consists of applying the gel by spraying it onto the surface of large area components (floors, walls, etc) to be decontaminated. The gel adheres to any vertical or complex surface due to their thixotropic properties and operates by dissolving the radioactive deposit, along with a thin layer of the gel support, so that the radioactivity trapped at the surface can be removed. Important aspects of the gels are that small quantities can be used and they show thixitropic properties : liquid during spraying, and solid when stationary, allowing for strong adherence to surfaces. This work investigates the decontamination behaviors of organic-based chemical gel for SS 304 metallic surfaces contaminated with radioactive materials

The influence of idealized surface heterogeneity on virtual turbulent flux measurements

Science.gov (United States)

De Roo, Frederik; Mauder, Matthias

2018-04-01

The imbalance of the surface energy budget in eddy-covariance measurements is still an unsolved problem. A possible cause is the presence of land surface heterogeneity, which affects the boundary-layer turbulence. To investigate the impact of surface variables on the partitioning of the energy budget of flux measurements in the surface layer under convective conditions, we set up a systematic parameter study by means of large-eddy simulation. For the study we use a virtual control volume approach, which allows the determination of advection by the mean flow, flux-divergence and storage terms of the energy budget at the virtual measurement site, in addition to the standard turbulent flux. We focus on the heterogeneity of the surface fluxes and keep the topography flat. The surface fluxes vary locally in intensity and these patches have different length scales. Intensity and length scales can vary for the two horizontal dimensions but follow an idealized chessboard pattern. Our main focus lies on surface heterogeneity of the kilometer scale, and one order of magnitude smaller. For these two length scales, we investigate the average response of the fluxes at a number of virtual towers, when varying the heterogeneity length within the length scale and when varying the contrast between the different patches. For each simulation, virtual measurement towers were positioned at functionally different positions (e.g., downdraft region, updraft region, at border between domains, etc.). As the storage term is always small, the non-closure is given by the sum of the advection by the mean flow and the flux-divergence. Remarkably, the missing flux can be described by either the advection by the mean flow or the flux-divergence separately, because the latter two have a high correlation with each other. For kilometer scale heterogeneity, we notice a clear dependence of the updrafts and downdrafts on the surface heterogeneity and likewise we also see a dependence of the energy

Imaging near-surface heterogeneities by natural migration of backscattered surface waves

KAUST Repository

AlTheyab, Abdullah

2016-02-01

We present a migration method that does not require a velocity model to migrate backscattered surface waves to their projected locations on the surface. This migration method, denoted as natural migration, uses recorded Green\\'s functions along the surface instead of simulated Green\\'s functions. The key assumptions are that the scattering bodies are within the depth interrogated by the surface waves, and the Green\\'s functions are recorded with dense receiver sampling along the free surface. This natural migration takes into account all orders of multiples, mode conversions and non-linear effects of surface waves in the data. The natural imaging formulae are derived for both active source and ambient-noise data, and computer simulations show that natural migration can effectively image near-surface heterogeneities with typical ambient-noise sources and geophone distributions.

Attainment of chemical equilibrium in effusive beam sources of the heterogeneous reaction type

International Nuclear Information System (INIS)

Hildenbrand, D.L.

1979-01-01

Effusive beam sources derived from gas-solid reactions provide a very important pathway for widening the scope of high temperature thermodynamic studies, but the attainment of chemical equilibrium within these sources is problematical. Some of the underlying kinetic factors associated with the use of these sources are discussed. As one might expect, it is important to maximize the ratio of reactive surface area to exit orifice area. Equilibrium seems to be achieved more readily among the products of gas-solid reactions than among reactant and products, as suggested by the quasi-equilibrium model. Some experiences with the use of heterogeneous reaction sources are described, and two definitive tests for the establishment of equilibrium are outlined

MONTE CARLO SIMULATIONS OF THE ADSORPTION OF DIMERS ON STRUCTURED HETEROGENEOUS SURFACES

Directory of Open Access Journals (Sweden)

Abreu C.R.A.

2001-01-01

Full Text Available The effect of surface topography upon the adsorption of dimer molecules is analyzed by means of grand canonical ensemble Monte Carlo simulations. Heterogeneous surfaces were assumed to consist of a square lattice containing active sites with two different energies. These were distributed in three different configurations: a random distribution of isolated sites; a random distribution of grains with four high-energy sites; and a random distribution of grains with nine high-energy sites. For the random distribution of isolated sites, the results are in good agreement with the molecular simulations performed by Nitta et al. (1997. In general, the comparison with theoretical models shows that the Nitta et al. (1984 isotherm presents good predictions of dimer adsorption both on homogeneous and heterogeneous surfaces with sites having small differences in characteristic energies. The molecular simulation results also show that the energy topology of the solid surfaces plays an important role in the adsorption of dimers on solids with large differences in site energies. For these cases, the Nitta et al. model does not describe well the data on dimer adsorption on random heterogeneous surfaces (grains with one acid site, but does describe reasonably well the adsorption of dimers on more patchwise heterogeneous surfaces (grains with nine acid sites.

Chemical Evidence for Vertical Transport from Magma Chambers to the Surface During Mid-Ocean Ridge Volcanic Eruptions

Science.gov (United States)

Sinton, J. M.; Rubin, K. H.

2009-12-01

Many mid-ocean ridge eruptions show significant internal chemical heterogeneity; in general, the amount of chemical heterogeneity within eruptions scales with erupted volume. These variations reflect magmatic processes occurring in magma reservoirs prior to or possibly during eruption. For example, systematic variations in Mg# with along-axis distance in the early 90’s Aldo-Kihi (S. EPR near 17.5°S), 1996 N. Gorda, 1993 Co-Axial (Juan de Fuca Ridge), and 1991-2 and 2005-6 9°50’N EPR eruptions is unlikely to be related to fractionation during emplacement, and rather reflects variations in sub-axial magma reservoirs prior to eruption. Such variations are inconsistent with well-mixed sub-axial reservoirs and, in some cases, require relatively long-lived, systematic variations in reservoir temperatures along axis. Chemical heterogeneity within the Aldo-Kihi eruption preserves spatial variations in mantle-derived isotopic and trace element ratios with implications for the temporal and spatial scales of magma injections to the crust and along-axis mixing within shallow reservoirs. These spatial variations are difficult to reconcile with significant (> ~1 km) along-axis magma transport, as are striking correlations of chemical compositions with surface geological discontinuities or seismically imaged sub-axial magma chamber reflectors in the S. Hump (S. EPR), 9°50’N EPR, N. Gorda and 1975-1984 Krafla (N. Iceland) eruptive units. Rather, spatial correlations between surface lava compositions and sub-axial magma chamber properties or long-lived axial morphology suggest that most of the erupted magma was transported nearly vertically from the underlying reservoirs to the surface during these eruptions. In the case of the Krafla eruption, coincident deformation suggests a component of lateral melt migration at depth, despite chemical evidence for vertical transport of erupted lava from more than one chemical reservoir. In addition, along-ridge movement of earthquake

Surface heterogeneity impacts on boundary layer dynamics via energy balance partitioning

Science.gov (United States)

The role of land-atmosphere interactions under heterogeneous surface conditions is investigated in order to identify mechanisms responsible for altering surface heat and moisture fluxes. Twelve coupled land surface – large eddy simulation scenarios with four different length scales of surface variab...

Impact of supersonic and subsonic aircraft on ozone: Including heterogeneous chemical reaction mechanisms

International Nuclear Information System (INIS)

Kinnison, D.E.; Wuebbles, D.J.

1992-01-01

Preliminary calculations suggest that heterogeneous reactions are important in calculating the impact on ozone from emissions of trace gases from aircraft fleets. In this study, three heterogeneous chemical processes that occur on background sulfuric acid aerosols are included and their effects on O 3 , NO x , Cl x , HCl, N 2 O 5 , ClONO 2 are calculated

Imaging near-surface heterogeneities by natural migration of backscattered surface waves: Field data test

KAUST Repository

Liu, Zhaolun; AlTheyab, Abdullah; Hanafy, Sherif M.; Schuster, Gerard T.

2017-01-01

We have developed a methodology for detecting the presence of near-surface heterogeneities by naturally migrating backscattered surface waves in controlled-source data. The near-surface heterogeneities must be located within a depth of approximately one-third the dominant wavelength λ of the strong surface-wave arrivals. This natural migration method does not require knowledge of the near-surface phase-velocity distribution because it uses the recorded data to approximate the Green’s functions for migration. Prior to migration, the backscattered data are separated from the original records, and the band-passed filtered data are migrated to give an estimate of the migration image at a depth of approximately one-third λ. Each band-passed data set gives a migration image at a different depth. Results with synthetic data and field data recorded over known faults validate the effectiveness of this method. Migrating the surface waves in recorded 2D and 3D data sets accurately reveals the locations of known faults. The limitation of this method is that it requires a dense array of receivers with a geophone interval less than approximately one-half λ.

Imaging near-surface heterogeneities by natural migration of backscattered surface waves: Field data test

KAUST Repository

Liu, Zhaolun

2017-03-06

We have developed a methodology for detecting the presence of near-surface heterogeneities by naturally migrating backscattered surface waves in controlled-source data. The near-surface heterogeneities must be located within a depth of approximately one-third the dominant wavelength λ of the strong surface-wave arrivals. This natural migration method does not require knowledge of the near-surface phase-velocity distribution because it uses the recorded data to approximate the Green’s functions for migration. Prior to migration, the backscattered data are separated from the original records, and the band-passed filtered data are migrated to give an estimate of the migration image at a depth of approximately one-third λ. Each band-passed data set gives a migration image at a different depth. Results with synthetic data and field data recorded over known faults validate the effectiveness of this method. Migrating the surface waves in recorded 2D and 3D data sets accurately reveals the locations of known faults. The limitation of this method is that it requires a dense array of receivers with a geophone interval less than approximately one-half λ.

Particle-based modeling of heterogeneous chemical kinetics including mass transfer.

Science.gov (United States)

Sengar, A; Kuipers, J A M; van Santen, Rutger A; Padding, J T

2017-08-01

Connecting the macroscopic world of continuous fields to the microscopic world of discrete molecular events is important for understanding several phenomena occurring at physical boundaries of systems. An important example is heterogeneous catalysis, where reactions take place at active surfaces, but the effective reaction rates are determined by transport limitations in the bulk fluid and reaction limitations on the catalyst surface. In this work we study the macro-micro connection in a model heterogeneous catalytic reactor by means of stochastic rotation dynamics. The model is able to resolve the convective and diffusive interplay between participating species, while including adsorption, desorption, and reaction processes on the catalytic surface. Here we apply the simulation methodology to a simple straight microchannel with a catalytic strip. Dimensionless Damkohler numbers are used to comment on the spatial concentration profiles of reactants and products near the catalyst strip and in the bulk. We end the discussion with an outlook on more complicated geometries and increasingly complex reactions.

Particle-based modeling of heterogeneous chemical kinetics including mass transfer

Science.gov (United States)

Sengar, A.; Kuipers, J. A. M.; van Santen, Rutger A.; Padding, J. T.

2017-08-01

Connecting the macroscopic world of continuous fields to the microscopic world of discrete molecular events is important for understanding several phenomena occurring at physical boundaries of systems. An important example is heterogeneous catalysis, where reactions take place at active surfaces, but the effective reaction rates are determined by transport limitations in the bulk fluid and reaction limitations on the catalyst surface. In this work we study the macro-micro connection in a model heterogeneous catalytic reactor by means of stochastic rotation dynamics. The model is able to resolve the convective and diffusive interplay between participating species, while including adsorption, desorption, and reaction processes on the catalytic surface. Here we apply the simulation methodology to a simple straight microchannel with a catalytic strip. Dimensionless Damkohler numbers are used to comment on the spatial concentration profiles of reactants and products near the catalyst strip and in the bulk. We end the discussion with an outlook on more complicated geometries and increasingly complex reactions.

A Simple Approach for Local Contact Angle Determination on a Heterogeneous Surface

KAUST Repository

Wu, Jinbo

2011-05-17

We report a simple approach for measuring the local contact angle of liquids on a heterogeneous surface consisting of intersected hydrophobic and hydrophilic patch arrays, specifically by employing confocal microscopy and the addition of a very low concentration of Rhodamine-B (RB) (2 × 10 -7 mol/L). Interestingly, RB at that concentration was found to be aggregated at the air-liquid and solid (hydrophobic patch only)-liquid interfaces, which helps us to distinguish the liquid and solid interfaces as well as hydrophobic and hydrophilic patches by their corresponding fluorescent intensities. From the measured local contact angles, the line tension can be easily derived and the value is found to be (-2.06-1.53) × 10-6 J/m. © 2011 American Chemical Society.

A new design of the LAPS land surface scheme for use over and through heterogeneous and non-heterogeneous surfaces: Numerical simulations and tests

Science.gov (United States)

Mihailovic, Dragutin T.; Lazic, Jelena; Leśny, Jacek; Olejnik, Janusz; Lalic, Branislava; Kapor, Darko; Cirisan, Ana

2010-05-01

Numerical simulations and tests with the recently redesigned land-air parameterization scheme (LAPS) are presented. In all experiments, supported either by one-point micrometeorological, 1D or 3D simulations, the attention has been directed to: (1) comparison of simulation outputs, expressing the energy transfer over and through heterogeneous and non-heterogeneous surfaces, versus observations and (2) analysis of uncertainties occurring in the solution of the energy balance equation at the land-air interface. To check the proposed method for aggregation of albedo, "propagating hole" sensitivity tests with LAPS over a sandstone rock grid cell have been performed with the forcing meteorological data for July 17, 1999 in Baxter site, Philadelphia (USA). Micrometeorological and biophysical measurements from the surface experiments conducted over crops and apple orchard in Serbia, Poland, Austria and France were used to test the operation of LAPS in calculating surface fluxes and canopy environment temperatures within and above plant covers of different densities. In addition, sensitivity tests with single canopy covers over the Central Europe region and comparison against the observations taken from SYNOP data using 3D simulations were made. Validation of LAPS performances over a solid surface has been done by comparison of 2 m air temperature observations against 5-day simulations over the Sahara Desert rocky ground using 3D model. To examine how realistically the LAPS simulates surface processes over a heterogeneous surface, we compared the air temperature measured at 2 m and that predicted by the 1D model with the LAPS as the surface scheme. Finally, the scheme behaviour over urban surface was tested by runs over different parts of a hypothetical urban area. The corresponding 1D simulations were carried out with an imposed meteorological dataset collected during HAPEX-MOBILHY experiment at Caumont (France). The quantities predicted by the LAPS compare well with the

The Role of Electronic Excitations on Chemical Reaction Dynamics at Metal, Semiconductor and Nanoparticle Surfaces

Energy Technology Data Exchange (ETDEWEB)

Tully, John C. [Yale Univ., New Haven, CT (United States)

2017-06-10

Chemical reactions are often facilitated and steered when carried out on solid surfaces, essential for applications such as heterogeneous catalysis, solar energy conversion, corrosion, materials processing, and many others. A critical factor that can determine the rates and pathways of chemical reactions at surfaces is the efficiency and specificity of energy transfer; how fast does energy move around and where does it go? For reactions on insulator surfaces energy transfer generally moves in and out of vibrations of the adsorbed molecule and the underlying substrate. By contrast, on metal surfaces, metallic nanoparticles and semiconductors, another pathway for energy flow opens up, excitation and de-excitation of electrons. This so-called “nonadiabatic” mechanism often dominates the transfer of energy and can directly impact the course of a chemical reaction. Conventional computational methods such as molecular dynamics simulation do not account for this nonadiabatic behavior. The current DOE-BES funded project has focused on developing the underlying theoretical foundation and the computational methodology for the prediction of nonadiabatic chemical reaction dynamics at surfaces. The research has successfully opened up new methodology and new applications for molecular simulation. In particular, over the last three years, the “Electronic Friction” theory, pioneered by the PI, has now been developed into a stable and accurate computational method that is sufficiently practical to allow first principles “on-the-fly” simulation of chemical reaction dynamics at metal surfaces.

Heterogeneous Ice Nucleation: Interplay of Surface Properties and Their Impact on Water Orientations.

Science.gov (United States)

Glatz, Brittany; Sarupria, Sapna

2018-01-23

Ice is ubiquitous in nature, and heterogeneous ice nucleation is the most common pathway of ice formation. How surface properties affect the propensity to observe ice nucleation on that surface remains an open question. We present results of molecular dynamics studies of heterogeneous ice nucleation on model surfaces. The models surfaces considered emulate the chemistry of kaolinite, an abundant component of mineral dust. We investigate the interplay of surface lattice and hydrogen bonding properties in affecting ice nucleation. We find that lattice matching and hydrogen bonding are necessary but not sufficient conditions for observing ice nucleation at these surfaces. We correlate this behavior to the orientations sampled by the metastable supercooled water in contact with the surfaces. We find that ice is observed in cases where water molecules not only sample orientations favorable for bilayer formation but also do not sample unfavorable orientations. This distribution depends on both surface-water and water-water interactions and can change with subtle modifications to the surface properties. Our results provide insights into the diverse behavior of ice nucleation observed at different surfaces and highlight the complexity in elucidating heterogeneous ice nucleation.

Self-consistent nonlocal feedback theory for electrocatalytic swimmers with heterogeneous surface chemical kinetics

Science.gov (United States)

Nourhani, Amir; Crespi, Vincent H.; Lammert, Paul E.

2015-06-01

We present a self-consistent nonlocal feedback theory for the phoretic propulsion mechanisms of electrocatalytic micromotors or nanomotors. These swimmers, such as bimetallic platinum and gold rods catalyzing decomposition of hydrogen peroxide in aqueous solution, have received considerable theoretical attention. In contrast, the heterogeneous electrochemical processes with nonlocal feedback that are the actual "engines" of such motors are relatively neglected. We present a flexible approach to these processes using bias potential as a control parameter field and a locally-open-circuit reference state, carried through in detail for a spherical motor. While the phenomenological flavor makes meaningful contact with experiment easier, required inputs can also conceivably come from, e.g., Frumkin-Butler-Volmer kinetics. Previously obtained results are recovered in the weak-heterogeneity limit and improved small-basis approximations tailored to structural heterogeneity are presented. Under the assumption of weak inhomogeneity, a scaling form is deduced for motor speed as a function of fuel concentration and swimmer size. We argue that this form should be robust and demonstrate a good fit to experimental data.

Untangling the Chemical Evolution of Titan's Atmosphere and Surface -- From Homogeneous to Heterogeneous Chemistry

Energy Technology Data Exchange (ETDEWEB)

Kaiser, Ralf I.; Maksyutenko, Pavlo; Ennis, Courtney; Zhang, Fangtong; Gu, Xibin; Krishtal, Sergey P.; Mebel, Alexander M.; Kostko, Oleg; Ahmed, Musahid

2010-03-16

The arrival of the Cassini-Huygens probe at Saturn's moon Titan - the only Solar System body besides Earth and Venus with a solid surface and a thick atmosphere with a pressure of 1.4 atm at surface level - in 2004 opened up a new chapter in the history of Solar System exploration. The mission revealed Titan as a world with striking Earth-like landscapes involving hydrocarbon lakes and seas as well as sand dunes and lava-like features interspersed with craters and icy mountains of hitherto unknown chemical composition. The discovery of a dynamic atmosphere and active weather system illustrates further the similarities between Titan and Earth. The aerosol-based haze layers, which give Titan its orange-brownish color, are not only Titan's most prominent optically visible features, but also play a crucial role in determining Titan's thermal structure and chemistry. These smog-like haze layers are thought to be very similar to those that were present in Earth's atmosphere before life developed more than 3.8 billion years ago, absorbing the destructive ultraviolet radiation from the Sun, thus acting as 'prebiotic ozone' to preserve astrobiologically important molecules on Titan. Compared to Earth, Titan's low surface temperature of 94 K and the absence of liquid water preclude the evolution of biological chemistry as we know it. Exactly because of these low temperatures, Titan provides us with a unique prebiotic 'atmospheric laboratory' yielding vital clues - at the frozen stage - on the likely chemical composition of the atmosphere of the primitive Earth. However, the underlying chemical processes, which initiate the haze formation from simple molecules, have been not understood well to date.

Impact of mixing chemically heterogeneous groundwaters on the sustainability of an open-loop groundwater heat pump

Science.gov (United States)

Burté, L.; Farasin, J.; Cravotta, C., III; Gerard, M. F.; Cotiche Baranger, C.; Aquilina, L.; Le Borgne, T.

2017-12-01

Geothermal systems using shallow aquifers are commonly used for heating and cooling. The sustainability of these systems can be severely impacted by the occurrence of clogging process. The geothermal loop operation (including pumping of groundwater, filtering and heat extraction through exchangers and cooled water injection) can lead to an unexpected biogeochemical reactivity and scaling formation that can ultimately lead to the shutdown of the geothermal doublet. Here, we report the results of investigations carried out on a shallow geothermal doublet (dynamic). Hydrochemical data collected at the pumping well showed that groundwater was chemically heterogeneous long the 11 meters well screen. While the aquifer was dominantly oxic, a localized inflow of anoxic water was detected and evaluated to produce about 40% of the total flow . The mixture of chemically heterogeneous water induced by pumping lead to the oxidation of reductive species and thus to the formation of biogenic precipitates responsible for clogging. The impact of pumping waters of different redox potential and chemical characteristics was quantified by numerical modeling using PHREEQC. These results shows that natural chemical heterogeneity can occur at a small scale in heterogeneous aquifers and highlight the importance of their characterization during the production well testing and the geothermal loop operation in order to take preventive measures to avoid clogging.

Light-induced heterogeneous reactions of NO2 on indoor surfaces: How they affect the balance of nitrous acid

Science.gov (United States)

Gomez Alvarez, E.; Soergel, M.; Bassil, S.; Zetzsch, C.; Gligorovski, S.; Wortham, H.

2011-12-01

Nitrous acid (HONO) is an important indoor pollutant. The adverse health effects due to the formation of nitrosamines are well known. HONO acts as a nitrosating agent after wall reactions of HONO with nicotine [Sleiman et al., 2010]. Indoor air can be surprisingly rich in HONO (homes with fireplaces, stoves, gas heating and cooking) and also surfaces are abundant. High HONO concentrations have been measured in indoor environments, from the direct emissions and heterogeneous reactions of NO2 in darkness. However, the measured HONO concentrations do not correspond to the HONO levels determined by the models [Carslaw, 2007]. We have tested in a flow tube reactor on-line coupled to a NOx analyzer and a sensitive Long Path Absorption Photometry instrument, the behaviour of various indoor surfaces towards NO2 under simulated solar light irradiation (λ= 300-700 nm). Our study has allowed us to obtain a deeper knowledge on the mechanisms of heterogeneous formation of HONO, quantifying the dependence of HONO formation on behalf of NO2 concentration and relative humidity and the enhancement of HONO formation in the presence of light. Pyrex, acidic detergent, alkaline detergent, paint and lacquer were tested on behalf of their heterogeneous reactivity towards NO2 in the absence and in presence of light. The results obtained demonstrated that indoor surfaces are photo-chemically active under atmospherically relevant conditions. The strongly alkaline surfaces (such as certain types of detergent) show a strong long-term uptake capacity. However, other surfaces such as detergents with a more acidic character released HONO. In some cases such as paint and varnish, a strong HONO release with light was detected, which was significantly higher than that obtained over clean glass surfaces. Certain organics present on their composition could exert a photo-sensitizing effect that may explain their increased reactivity. Unfortunately, the final balance points towards an important net

Kinetics and mechanism of heterogeneous oxidation of sulfur dioxide by ozone on surface of calcium carbonate

Directory of Open Access Journals (Sweden)

L. Li

2006-01-01

Full Text Available Sulfate particles play a key role in the air quality and the global climate, but the heterogeneous formation mechanism of sulfates on surfaces of atmospheric particles is not well established. Carbonates, which act as a reactive component in mineral dust due to their special chemical properties, may contribute significantly to the sulfate formation by heterogeneous processes. This paper presents a study on the oxidation of SO2 by O3 on CaCO3 particles. Using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS, the formation of sulfite and sulfate on the surface was identified, and the roles of O3 and water in oxidation processes were determined. The results showed that in the presence of O3, SO2can be oxidized to sulfate on the surface of CaCO3 particles. The reaction is first order in SO2 and zero order in O3. The reactive uptake coefficient for SO2 [(0.6–9.8×1014 molecule cm-3] oxidation by O3 [(1.2–12×1014 molecule cm-3] was determined to be (1.4±0.3×10-7 using the BET area as the reactive area and (7.7±1.6×10-4 using the geometric area. A two-stage mechanism that involves adsorption of SO2 followed by O3 oxidation is proposed and the adsorption of SO2 on the CaCO3 surface is the rate-determining step. The proposed mechanism can well explain the experiment results. The atmospheric implications were explored based on a box model calculation. It was found that the heterogeneous reaction might be an important pathway for sulfate formation in the atmosphere.

Effective Wettability of Heterogenous Fracture Surfaces Using the Lattice-Boltzmann Method

Science.gov (United States)

E Santos, J.; Prodanovic, M.; Landry, C. J.

2017-12-01

Fracture walls in the subsurface are often structured by minerals of different composition (potentially further altered in contact with fluids during hydrocarbon extraction or CO2 sequestration), this yields in a heterogeneous wettability of the surface in contact with the fluids. The focus of our work is to study how surfaces presenting different mineralogy and roughness affect multiphase flow in fractures. Using the Shan-Chen model of the lattice-Boltzmann method (LBM) we define fluid interaction and surface attraction parameters to simulate a system of a wetting and a non-wetting fluid. In this work, we use synthetically created fractures presenting different arrangements of wetting and non-wetting patches, and with or without roughness; representative of different mineralogy, similar workflow can be applied to fractures extracted from X-ray microtomography images of fractures porous media. The results from the LBM simulations provide an insight on how the distribution of mineralogy and surface roughness are related with the observed macroscopic contact angle. We present a comparison between the published analytical models, and our results based on surface areas, spatial distribution and local fracture aperture. The understanding of the variables that affect the contact angle is useful for the comprehension of multiphase processes in naturally fractured reservoirs like primary oil production, enhanced oil recovery and CO2 sequestration. The macroscopic contact angle analytical equations for heterogeneous surfaces with variable roughness are no longer valid in highly heterogeneous systems; we quantify the difference thus offering an alternative to analytical models.

Pinning of the Contact Line during Evaporation on Heterogeneous Surfaces: Slowdown or Temporary Immobilization? Insights from a Nanoscale Study.

Science.gov (United States)

Zhang, Jianguo; Müller-Plathe, Florian; Leroy, Frédéric

2015-07-14

The question of the effect of surface heterogeneities on the evaporation of liquid droplets from solid surfaces is addressed through nonequilibrium molecular dynamics simulations. The mechanism behind contact line pinning which is still unclear is discussed in detail on the nanoscale. Model systems with the Lennard-Jones interaction potential were employed to study the evaporation of nanometer-sized cylindrical droplets from a flat surface. The heterogeneity of the surface was modeled through alternating stripes of equal width but two chemical types. The first type leads to a contact angle of 67°, and the other leads to a contact angle of 115°. The stripe width was varied between 2 and 20 liquid-particle diameters. On the surface with the narrowest stripes, evaporation occurred at constant contact angle as if the surface was homogeneous, with a value of the contact angle as predicted by the regular Cassie-Baxter equation. When the width was increased, the contact angle oscillated during evaporation between two boundaries whose values depend on the stripe width. The evaporation behavior was thus found to be a direct signature of the typical size of the surface heterogeneity domains. The contact angle both at equilibrium and during evaporation could be predicted from a local Cassie-Baxter equation in which the surface composition within a distance of seven fluid-particle diameters around the contact line was considered, confirming the local nature of the interactions that drive the wetting behavior of droplets. More importantly, we propose a nanoscale explanation of pinning during evaporation. Pinning should be interpreted as a drastic slowdown of the contact line dynamics rather than a complete immobilization of it during a transition between two contact angle boundaries.

Surface decontamination by heterogeneous foams and suspensions

International Nuclear Information System (INIS)

Polyakov, A.; Poluektov, P.; Emets, E.; Kuchumov, V.; Rybakov, K.; Teterin, E.

2000-01-01

A variety of methods was used to investigate the surface of stainless steel as delivered or treated (electrochemically polished, machine ground). Micro X-ray spectral analysis evidenced a uniform distribution of alloying elements. Auger spectroscopy revealed the layer-by-layer composition by elements and the thickness of the superficial oxide film. The distribution of heterogeneous uranium dioxide powders on the stainless steel surface was examined by microprobe analysis (using Comebax). In the order of increasing contamination by uranium dioxide, the surfaces can be arranged as: untreated - polished - ground. The behaviour of hydrogen peroxide in alkaline solutions was studied by spectrophotometry and laser analysis. Decontamination of stainless steel surfaces from UO 2 by microgaseous emulsions in alkaline media with surfactants present was tested. The decontamination factor was determined as a function of the size and volume of gas bubbles. It was shown to rise with increasing gas content. (author)

Molecular surface science of heterogeneous catalysis. History and perspective

International Nuclear Information System (INIS)

Somorjai, G.A.

1983-08-01

A personal account is given of how the author became involved with modern surface science and how it was employed for studies of the chemistry of surfaces and heterogeneous catalysis. New techniques were developed for studying the properties of the surface monolayers: Auger electron spectroscopy, LEED, XPS, molecular beam surface scattering, etc. An apparatus was developed and used to study hydrocarbon conversion reactions on Pt, CO hydrogenation on Rh and Fe, and NH 3 synthesis on Fe. A model has been developed for the working Pt reforming catalyst. The three molecular ingredients that control catalytic properties are atomic surface structure, an active carbonaceous deposit, and the proper oxidation state of surface atoms. 40 references, 21 figures

Molecular surface science of heterogeneous catalysis. History and perspective

Energy Technology Data Exchange (ETDEWEB)

Somorjai, G.A.

1983-08-01

A personal account is given of how the author became involved with modern surface science and how it was employed for studies of the chemistry of surfaces and heterogeneous catalysis. New techniques were developed for studying the properties of the surface monolayers: Auger electron spectroscopy, LEED, XPS, molecular beam surface scattering, etc. An apparatus was developed and used to study hydrocarbon conversion reactions on Pt, CO hydrogenation on Rh and Fe, and NH/sub 3/ synthesis on Fe. A model has been developed for the working Pt reforming catalyst. The three molecular ingredients that control catalytic properties are atomic surface structure, an active carbonaceous deposit, and the proper oxidation state of surface atoms. 40 references, 21 figures. (DLC)

Distinction of heterogeneity on Au nanostructured surface based on phase contrast imaging of atomic force microscopy

International Nuclear Information System (INIS)

Jung, Mi; Choi, Jeong-Woo

2010-01-01

The discrimination of the heterogeneity of different materials on nanostructured surfaces has attracted a great deal of interest in biotechnology as well as nanotechnology. Phase imaging through tapping mode of atomic force microscopy (TMAFM) can be used to distinguish the heterogeneity on a nanostructured surface. Nanostructures were fabricated using anodic aluminum oxide (AAO). An 11-mercaptoundecanoic acid (11-MUA) layer adsorbed onto the Au nanodots through self-assembly to improve the bio-compatibility. The Au nanostructures that were modified with 11-MUA and the concave surfaces were investigated using the TMAFM phase images to compare the heterogeneous and homogeneous nanostructured surfaces. Although the topography and phase images were taken simultaneously, the images were different. Therefore, the contrast in the TMAFM phase images revealed the different compositional materials on the heterogeneous nanostructure surface.

Prediction of Nanoparticle and Colloid Attachment on Unfavorable Mineral Surfaces Using Representative Discrete Heterogeneity.

Science.gov (United States)

Trauscht, Jacob; Pazmino, Eddy; Johnson, William P

2015-09-01

Despite several decades of research there currently exists no mechanistic theory to predict colloid attachment in porous media under environmental conditions where colloid-collector repulsion exists (unfavorable conditions for attachment). It has long been inferred that nano- to microscale surface heterogeneity (herein called discrete heterogeneity) drives colloid attachment under unfavorable conditions. Incorporating discrete heterogeneity into colloid-collector interaction calculations in particle trajectory simulations predicts colloid attachment under unfavorable conditions. As yet, discrete heterogeneity cannot be independently measured by spectroscopic or other approaches in ways directly relevant to colloid-surface interaction. This, combined with the fact that a given discrete heterogeneity representation will interact differently with differently sized colloids as well as different ionic strengths for a given sized colloid, suggests a strategy to back out representative discrete heterogeneity by a comparison of simulations to experiments performed across a range of colloid size, solution IS, and fluid velocity. This has recently been performed for interaction of carboxylate-modified polystyrene latex (CML) microsphere attachment to soda lime glass at pH 6.7 with NaCl electrolyte. However, extension to other surfaces, pH values, and electrolytes is needed. For this reason, the attachment of CML (0.25, 1.1, and 2.0 μm diameters) from aqueous suspension onto a variety of unfavorable mineral surfaces (soda lime glass, muscovite, and albite) was examined for pH values of 6.7 and 8.0), fluid velocities (1.71 × 10(-3) and 5.94 × 10(-3) m s(-1)), IS (6.0 and 20 mM), and electrolytes (NaCl, CaSO4, and multivalent mixtures). The resulting representative heterogeneities (heterodomain size and surface coverage, where heterodomain refers to nano- to microscale attractive domains) yielded colloid attachment predictions that were compared to predictions from existing

Investigation of heterogeneous reactions of NO2 on aqueous surfaces

International Nuclear Information System (INIS)

Mertes, S.

1992-01-01

A microjet apparatus was developed for the purpose of measuring the loss in the gaseous phase and the uptake in the liquid phase of nitrogen on the basis of heterogeneous processes on a liquid surface. The measurements were to provide information on the mass accomodation coefficient α and on assumed surface reactions of NO 2 . (orig./BBR) [de

Heterogeneous reaction of SO2 with soot: The roles of relative humidity and surface composition of soot in surface sulfate formation

Science.gov (United States)

Zhao, Yan; Liu, Yongchun; Ma, Jinzhu; Ma, Qingxin; He, Hong

2017-03-01

The conversion of SO2 to sulfates on the surface of soot is still poorly understood. Soot samples with different fractions of unsaturated hydrocarbons and oxygen-containing groups were prepared by combusting n-hexane under well-controlled conditions. The heterogeneous reaction of SO2 with soot was investigated using in situ attenuated total internal reflection infrared (ATR-IR) spectroscopy, ion chromatography (IC) and a flow tube reactor at the ambient pressure and relative humidity (RH). Water promoted SO2 adsorption and sulfate formation at the RH range from 6% to 70%, while exceeded water condensed on soot was unfavorable for sulfate formation due to inhibition of SO2 adsorption when RH was higher than 80%. The surface composition of soot, which was governed by combustion conditions, also played an important role in the heterogeneous reaction of SO2 with soot. This effect was found to greatly depend on RH. At low RH of 6%, soot with the highest fuel/oxygen ratio of 0.162 exhibited a maximum uptake capacity for SO2 because it contained a large amount of aromatic Csbnd H groups, which acted as active sites for SO2 adsorption. At RH of 54%, soot produced with a fuel/oxygen ratio of 0.134 showed the highest reactivity toward SO2 because it contained appropriate amounts of aromatic Csbnd H groups and oxygen-containing groups, subsequently leading to the optimal surface concentrations of both SO2 and water. These results suggest that variation in the surface composition of soot from different sources and/or resulting from chemical aging in the atmosphere likely affects the conversion of SO2 to sulfates.

Surface chemical reactions probed with scanning force microscopy

NARCIS (Netherlands)

Werts, M.P L; van der Vegte, E.W.; Hadziioannou, G

1997-01-01

In this letter we report the study of surface chemical reactions with scanning force microscopy (SFM) with chemical specificity. Using chemically modified SFM probes, we can determine the local surface reaction conversion during a chemical surface modification. The adhesion forces between a

Low-temperature wafer direct bonding of silicon and quartz glass by a two-step wet chemical surface cleaning

Science.gov (United States)

Wang, Chenxi; Xu, Jikai; Zeng, Xiaorun; Tian, Yanhong; Wang, Chunqing; Suga, Tadatomo

2018-02-01

We demonstrate a facile bonding process for combining silicon and quartz glass wafers by a two-step wet chemical surface cleaning. After a post-annealing at 200 °C, strong bonding interfaces with no defects or microcracks were obtained. On the basis of the detailed surface and bonding interface characterizations, the bonding mechanism was explored and discussed. The amino groups terminated on the cleaned surfaces might contribute to the bonding strength enhancement during the annealing. This cost-effective bonding process has great potentials for silicon- and glass-based heterogeneous integrations without requiring a vacuum system.

Response of Moist Convection to Multi-scale Surface Flux Heterogeneity

Science.gov (United States)

Kang, S. L.; Ryu, J. H.

2015-12-01

We investigate response of moist convection to multi-scale feature of the spatial variation of surface sensible heat fluxes (SHF) in the afternoon evolution of the convective boundary layer (CBL), utilizing a mesoscale-domain large eddy simulation (LES) model. The multi-scale surface heterogeneity feature is analytically created as a function of the spectral slope in the wavelength range from a few tens of km to a few hundreds of m in the spectrum of surface SHF on a log-log scale. The response of moist convection to the κ-3 - slope (where κ is wavenumber) surface SHF field is compared with that to the κ-2 - slope surface, which has a relatively weak mesoscale feature, and the homogeneous κ0 - slope surface. Given the surface energy balance with a spatially uniform available energy, the prescribed SHF has a 180° phase lag with the latent heat flux (LHF) in a horizontal domain of (several tens of km)2. Thus, warmer (cooler) surface is relatively dry (moist). For all the cases, the same observation-based sounding is prescribed for the initial condition. For all the κ-3 - slope surface heterogeneity cases, early non-precipitating shallow clouds further develop into precipitating deep thunderstorms. But for all the κ-2 - slope cases, only shallow clouds develop. We compare the vertical profiles of domain-averaged fluxes and variances, and the contribution of the mesoscale and turbulence contributions to the fluxes and variances, between the κ-3 versus κ-2 slope cases. Also the cross-scale processes are investigated.

Apparent thermal inertia and the surface heterogeneity of Mars

Science.gov (United States)

Putzig, Nathaniel E.; Mellon, Michael T.

2007-11-01

Thermal inertia derivation techniques generally assume that surface properties are uniform at horizontal scales below the footprint of the observing instrument and to depths of several decimeters. Consequently, surfaces with horizontal or vertical heterogeneity may yield apparent thermal inertia which varies with time of day and season. To investigate these temporal variations, we processed three Mars years of Mars Global Surveyor Thermal Emission Spectrometer observations and produced global nightside and dayside seasonal maps of apparent thermal inertia. These maps show broad regions with diurnal and seasonal differences up to 200 J m -2 K -1s -1/2 at mid-latitudes (60° S to 60° N) and 600 J m -2 K -1s -1/2 or greater in the polar regions. We compared the seasonal mapping results with modeled apparent thermal inertia and created new maps of surface heterogeneity at 5° resolution, delineating regions that have thermal characteristics consistent with horizontal mixtures or layers of two materials. The thermal behavior of most regions on Mars appears to be dominated by layering, with upper layers of higher thermal inertia (e.g., duricrusts or desert pavements over fines) prevailing in mid-latitudes and upper layers of lower thermal inertia (e.g., dust-covered rock, soils with an ice table at shallow depths) prevailing in polar regions. Less common are regions dominated by horizontal mixtures, such as those containing differing proportions of rocks, sand, dust, and duricrust or surfaces with divergent local slopes. Other regions show thermal behavior that is more complex and not well-represented by two-component surface models. These results have important implications for Mars surface geology, climate modeling, landing-site selection, and other endeavors that employ thermal inertia as a tool for characterizing surface properties.

Surface Modification of α-Fe Metal Particles by Chemical Surface Coating

Institute of Scientific and Technical Information of China (English)

无

2003-01-01

The structure of α-Fe metal magnetic recording particles coated with silane coupling agents have been studied by TEM, FT-IR, EXAFS, Mossbauer. The results show that a close, uniform, firm and ultra thin layer, which is beneficial to the magnetic and chemical stability, has been formed by the cross-linked chemical bond Si-O-Si. And the organic molecule has chemically bonded to the particle surface, which has greatly affected the surface Fe atom electronic structure. Furthermore, the covalent bond between metal particle surface and organic molecule has obvious effect on the near edge structure of the surface Fe atoms.

Analysis of Surface Heterogeneity Effects with Mesoscale Terrestrial Modeling Platforms

Science.gov (United States)

Simmer, C.

2015-12-01

An improved understanding of the full variability in the weather and climate system is crucial for reducing the uncertainty in weather forecasting and climate prediction, and to aid policy makers to develop adaptation and mitigation strategies. A yet unknown part of uncertainty in the predictions from the numerical models is caused by the negligence of non-resolved land surface heterogeneity and the sub-surface dynamics and their potential impact on the state of the atmosphere. At the same time, mesoscale numerical models using finer horizontal grid resolution [O(1)km] can suffer from inconsistencies and neglected scale-dependencies in ABL parameterizations and non-resolved effects of integrated surface-subsurface lateral flow at this scale. Our present knowledge suggests large-eddy-simulation (LES) as an eventual solution to overcome the inadequacy of the physical parameterizations in the atmosphere in this transition scale, yet we are constrained by the computational resources, memory management, big-data, when using LES for regional domains. For the present, there is a need for scale-aware parameterizations not only in the atmosphere but also in the land surface and subsurface model components. In this study, we use the recently developed Terrestrial Systems Modeling Platform (TerrSysMP) as a numerical tool to analyze the uncertainty in the simulation of surface exchange fluxes and boundary layer circulations at grid resolutions of the order of 1km, and explore the sensitivity of the atmospheric boundary layer evolution and convective rainfall processes on land surface heterogeneity.

Modelling the collective response of heterogeneous cell populations to stationary gradients and chemical signal relay

Science.gov (United States)

Pineda, M.; Eftimie, R.

2017-12-01

The directed motion of cell aggregates toward a chemical source occurs in many relevant biological processes. Understanding the mechanisms that control this complex behavior is of great relevance for our understanding of developmental biological processes and many diseases. In this paper, we consider a self-propelled particle model for the movement of heterogeneous subpopulations of chemically interacting cells towards an imposed stable chemical gradient. Our simulations show explicitly how self-organisation of cell populations (which could lead to engulfment or complete cell segregation) can arise from the heterogeneity of chemotactic responses alone. This new result complements current theoretical and experimental studies that emphasise the role of differential cell-cell adhesion on self-organisation and spatial structure of cellular aggregates. We also investigate how the speed of individual cell aggregations increases with the chemotactic sensitivity of the cells, and decreases with the number of cells inside the aggregates

High-resolution observations of combustion in heterogeneous surface fuels

Science.gov (United States)

E. Louise Loudermilk; Gary L. Achtemeier; Joseph J. O' Brien; J. Kevin Hiers; Benjamin S. Hornsby

2014-01-01

In ecosystems with frequent surface fires, fire and fuel heterogeneity at relevant scales have been largely ignored. This could be because complete burns give an impression of homogeneity, or due to the difficulty in capturing fine-scale variation in fuel characteristics and fire behaviour. Fire movement between patches of fuel can have implications for modelling fire...

Effect of droplet size on the droplet behavior on the heterogeneous surface

Energy Technology Data Exchange (ETDEWEB)

Choi, Ho Yeon; Son, Sung Wan; Ha, ManYeong [Pusan National University, Busan (Korea, Republic of); Park, Yong Gap [Pusan National University, Busan (Korea, Republic of)

2017-06-15

The characteristics of a three-dimensional hemispherical droplet on a heterogeneous surface were studied using the Lattice Boltzmann method (LBM). The hydrophilic surface has a hydrophobic part at the center. The hemispherical droplets are located at the center of the heterogeneous surface. According to the contact angles of hydrophilic and hydrophobic bottom surfaces, the droplet either separates or reaches a new equilibrium state. The separation time varies according to the change in droplet size, and it affects the status of droplet separation. The droplet separation behavior was investigated by analyzing the velocity vector around the phase boundary line. The shape and separation time of a droplet are determined by the contact angle of each surface. The speed of droplet separation increases as the difference in contact angle increases between the hydrophobic surface and hydrophilic surface. The separation status and the separation time of a droplet are also determined by the change of the droplet size. As the size of the droplet decreases, the effect of surface tension decreases, and the separation time of the droplet also decreases. On the other hand, as the droplet becomes larger, the effect of surface tension increases and the time required for the droplet to separate also increases.

Modeling heat dissipation at the nanoscale: an embedding approach for chemical reaction dynamics on metal surfaces.

Science.gov (United States)

Meyer, Jörg; Reuter, Karsten

2014-04-25

We present an embedding technique for metallic systems that makes it possible to model energy dissipation into substrate phonons during surface chemical reactions from first principles. The separation of chemical and elastic contributions to the interaction potential provides a quantitative description of both electronic and phononic band structure. Application to the dissociation of O2 at Pd(100) predicts translationally "hot" oxygen adsorbates as a consequence of the released adsorption energy (ca. 2.6 eV). This finding questions the instant thermalization of reaction enthalpies generally assumed in models of heterogeneous catalysis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Heterogeneous Amyloid β-Sheet Polymorphs Identified on Hydrogen Bond Promoting Surfaces Using 2D SFG Spectroscopy.

Science.gov (United States)

Ho, Jia-Jung; Ghosh, Ayanjeet; Zhang, Tianqi O; Zanni, Martin T

2018-02-08

Two-dimensional sum-frequency generation spectroscopy (2D SFG) is used to study the structures of the pentapeptide FGAIL on hydrogen bond promoting surfaces. FGAIL is the most amyloidogenic portion of the human islet amyloid polypeptide (hIAPP or amylin). In the presence of a pure gold surface, FGAIL does not form ordered structures. When the gold is coated with a self-assembled monolayer of mercaptobenzoic acid (MBA), 2D SFG spectra reveal features associated with β-sheets. Also observed are cross peaks between the FGAIL peptides and the carboxylic acid groups of the MBA monolayer, indicating that the peptides are in close contact with the surface headgroups. In the second set of samples, FGAIL peptides chemically ligated to the MBA monolayer also exhibited β-sheet features but with a much simpler spectrum. From simulations of the experiments, we conclude that the hydrogen bond promoting surface catalyzes the formation of both parallel and antiparallel β-sheet structures with several different orientations. When ligated, parallel sheets with only a single orientation are the primary structure. Thus, this hydrogen bond promoting surface creates a heterogeneous distribution of polymorph structures, consistent with a concentration effect that allows nucleation of many different amyloid seeding structures. A single well-defined seed favors one polymorph over the others, showing that the concentrating influence of a membrane can be counterbalanced by factors that favor directed fiber growth. These experiments lay the foundation for the measurement and interpretation of β-sheet structures with heterodyne-detected 2D SFG spectroscopy. The results of this model system suggest that a heterogeneous distribution of polymorphs found in nature are an indication of nonselective amyloid aggregation whereas a narrow distribution of polymorph structures is consistent with a specific protein or lipid interaction that directs fiber growth.

Fractal characteristics of an asphaltene deposited heterogeneous surface

International Nuclear Information System (INIS)

Amin, J. Sayyad; Ayatollahi, Sh.; Alamdari, A.

2009-01-01

Several methods have been employed in recent years to investigate homogeneous surface topography based on image analysis, such as AFM (atomic force microscopy) and SEM (scanning electron microscopy). Fractal analysis of the images provides fractal dimension of the surface which is used as one of the most common surface indices. Surface topography has generally been considered to be mono-fractal. On the other hand, precipitation of organic materials on a rough surface and its irregular growth result in morphology alteration and converts a homogeneous surface to a heterogeneous one. In this case a mono-fractal description of the surface does not completely describe the nature of the altered surface. This work aims to investigate the topography alteration of a glass surface as a result of asphaltene precipitation and its growth at various pressures using a bi-fractal approach. The experimental results of the deposited surfaces were clearly indicating two regions of micro- and macro-asperities namely, surface types I and II, respectively. The fractal plots were indicative of bi-fractal behavior and for each surface type one fractal dimension was calculated. The topography information of the surfaces was obtained by two image analyses, AFM and SEM imaging techniques. Results of the bi-fractal analysis demonstrated that topography alteration in surface type II (macro-asperities) is more evident than that in surface type I (micro-asperities). Compared to surface type II, a better correlation was observed between the fractal dimensions inferred from the AFM images (D A ) and those of the SEM images (D S ) in surface type I.

Effects of surface roughness and electrokinetic heterogeneity on electroosmotic flow in microchannel

Energy Technology Data Exchange (ETDEWEB)

Masilamani, Kannan; Ganguly, Suvankar; Feichtinger, Christian; Bartuschat, Dominik; Rüde, Ulrich, E-mail: suva_112@yahoo.co.in [Department of Computer Science 10 University of Erlangen-Nuremberg, Cauerstr.11 91058 Erlangen (Germany)

2015-06-15

In this paper, a hybrid lattice-Boltzmann and finite-difference (LB-FD) model is applied to simulate the effects of three-dimensional surface roughness and electrokinetic heterogeneity on electroosmotic flow (EOF) in a microchannel. The lattice-Boltzmann (LB) method has been employed to obtain the flow field and a finite-difference (FD) method is used to solve the Poisson-Boltzmann (PB) equation for the electrostatic potential distribution. Numerical simulation of flow through a square cross-section microchannel with designed roughness is conducted and the results are critically analysed. The effects of surface heterogeneity on the electroosmotic transport are investigated for different roughness height, width, roughness interval spacing, and roughness surface potential. Numerical simulations reveal that the presence of surface roughness changes the nature of electroosmotic transport through the microchannel. It is found that the electroosmotic velocity decreases with the increase in roughness height and the velocity profile becomes asymmetric. For the same height of the roughness elements, the EOF velocity rises with the increase in roughness width. For the heterogeneously charged rough channel, the velocity profile shows a distinct deviation from the conventional plug-like flow pattern. The simulation results also indicate locally induced flow vortices which can be utilized to enhance the flow and mixing within the microchannel. The present study has important implications towards electrokinetic flow control in the microchannel, and can provide an efficient way to design a microfluidic system of practical interest. (paper)

Random Process Theory Approach to Geometric Heterogeneous Surfaces: Effective Fluid-Solid Interaction

Science.gov (United States)

Khlyupin, Aleksey; Aslyamov, Timur

2017-06-01

Realistic fluid-solid interaction potentials are essential in description of confined fluids especially in the case of geometric heterogeneous surfaces. Correlated random field is considered as a model of random surface with high geometric roughness. We provide the general theory of effective coarse-grained fluid-solid potential by proper averaging of the free energy of fluid molecules which interact with the solid media. This procedure is largely based on the theory of random processes. We apply first passage time probability problem and assume the local Markov properties of random surfaces. General expression of effective fluid-solid potential is obtained. In the case of small surface irregularities analytical approximation for effective potential is proposed. Both amorphous materials with large surface roughness and crystalline solids with several types of fcc lattices are considered. It is shown that the wider the lattice spacing in terms of molecular diameter of the fluid, the more obtained potentials differ from classical ones. A comparison with published Monte-Carlo simulations was discussed. The work provides a promising approach to explore how the random geometric heterogeneity affects on thermodynamic properties of the fluids.

Chemical surface tuning electrocatalysis of redox-active nanoparticles

DEFF Research Database (Denmark)

Zhu, Nan; Ulstrup, Jens; Chi, Qijin

This work focuses on electron transfer (ET) and electrocatalysis of inorganic hybrid Prussian blue nanoparticles (PBNPs, 6 nm) immobilized on different chemical surfaces. Through surface self-assembly chemistry, we have enabled to tune chemical properties of the electrode surface. Stable immobili...

Coalescence-induced jumping of micro-droplets on heterogeneous superhydrophobic surfaces

Science.gov (United States)

Attarzadeh, Reza; Dolatabadi, Ali

2017-01-01

The phenomenon of droplets coalescence-induced self-propelled jumping on homogeneous and heterogeneous superhydrophobic surfaces was numerically modeled using the volume of fluid method coupled with a dynamic contact angle model. The heterogeneity of the surface was directly modeled as a series of micro-patterned pillars. To resolve the influence of air around a droplet and between the pillars, extensive simulations were performed for different droplet sizes on a textured surface. Parallel computations with the OpenMP algorithm were used to accelerate computation speed to meet the convergence criteria. The composition of the air-solid surface underneath the droplet facilitated capturing the transition from a no-slip/no-penetration to a partial-slip with penetration as the contact line at triple point started moving to the air pockets. The wettability effect from the nanoscopic roughness and the coating was included in the model by using the intrinsic contact angle obtained from a previously published study. As the coalescence started, the radial velocity of the coalescing liquid bridge was partially reverted to the upward direction due to the counter-action of the surface. However, we found that the velocity varied with the size of the droplets. A part of the droplet kinetic energy was dissipated as the merged droplet started penetrating into the cavities. This was due to a different area in contact between the liquid and solid and, consequently, a higher viscous dissipation rate in the system. We showed that the effect of surface roughness is strongly significant when the size of the micro-droplet is comparable with the size of the roughness features. In addition, the relevance of droplet size to surface roughness (critical relative roughness) was numerically quantified. We also found that regardless of the viscous cutoff radius, as the relative roughness approached the value of 44, the direct inclusion of surface topography was crucial in the modeling of the

Mechanical and chemical decontamination of surfaces

International Nuclear Information System (INIS)

Kienhoefer, M.

1982-01-01

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

The surface chemical reactivity of particles and its impact on human health

Science.gov (United States)

Setyan, A.; Sauvain, J. J.; Riediker, M.; Guillemin, M.; Rossi, M. J.

2017-12-01

The chemical composition of the particle-air interface is the gateway to chemical reactions of gases with condensed phase particles. It is of prime importance to understand the reactivity of particles and their interaction with surrounding gases, biological membranes, and solid supports. We used a Knudsen flow reactor to quantify functional groups on the surface of a few selected particle types. This technique is based on a heterogeneous titration reaction between a probe gas and a specific functional group on the particle surface. Six probe gases have been selected for the identification and quantification of important functional groups: N(CH3)3 for the titration of acidic sites, NH2OH for the detection of carbonyl functions (aldehydes and ketones) and/or oxidized sites owing to its strong reducing properties, CF3COOH and HCl for basic sites of different strength, O3 and NO2 for oxidizable groups. We also studied the kinetics of the reactions between particles and probe gases (uptake coefficient γ0). We tested the surface chemical composition and oxidation states of laboratory-generated aerosols (3 amorphous carbons, 2 flame soots, 2 Diesel particles, 2 secondary organic aerosols [SOA], 4 multiwall carbon nanotubes [MWCNT], 3 TiO2, and 2 metal salts) and of aerosols sampled in several bus depots. The sampling of particles in the bus depots was accompanied by the collection of urine samples of mechanics working full-time in these bus depots, and the quantification of 8-hydroxy-2'-deoxyguanosine, a biomarker of oxidative stress. The increase in oxidative stress biomarker levels over a working day was correlated (pcellular antioxidants.

Final Technical Report: Metal—Organic Surface Catalyst for Low-temperature Methane Oxidation: Bi-functional Union of Metal—Organic Complex and Chemically Complementary Surface

Energy Technology Data Exchange (ETDEWEB)

Tait, Steven L. [Indiana Univ., Bloomington, IN (United States)

2016-10-01

Stabilization and chemical control of transition metal centers is a critical problem in the advancement of heterogeneous catalysts to next-generation catalysts that exhibit high levels of selectivity, while maintaining strong activity and facile catalyst recycling. Supported metal nanoparticle catalysts typically suffer from having a wide range of metal sites with different coordination numbers and varying chemistry. This project is exploring new possibilities in catalysis by combining features of homogeneous catalysts with those of heterogeneous catalysts to develop new, bi-functional systems. The systems are more complex than traditional heterogeneous catalysts in that they utilize sequential active sites to accomplish the desired overall reaction. The interaction of metal—organic catalysts with surface supports and their interactions with reactants to enable the catalysis of critical reactions at lower temperatures are at the focus of this study. Our work targets key fundamental chemistry problems. How do the metal—organic complexes interact with the surface? Can those metal center sites be tuned for selectivity and activity as they are in the homogeneous system by ligand design? What steps are necessary to enable a cooperative chemistry to occur and open opportunities for bi-functional catalyst systems? Study of these systems will develop the concept of bringing together the advantages of heterogeneous catalysis with those of homogeneous catalysis, and take this a step further by pursuing the objective of a bi-functional system. The use of metal-organic complexes in surface catalysts is therefore of interest to create well-defined and highly regular single-site centers. While these are not likely to be stable in the high temperature environments (> 300 °C) typical of industrial heterogeneous catalysts, they could be applied in moderate temperature reactions (100-300 °C), made feasible by lowering reaction temperatures by better catalyst control. They also

Titanium Dioxide as a Catalyst Support in Heterogeneous Catalysis

Science.gov (United States)

Bagheri, Samira; Muhd Julkapli, Nurhidayatullaili; Bee Abd Hamid, Sharifah

2014-01-01

The lack of stability is a challenge for most heterogeneous catalysts. During operations, the agglomeration of particles may block the active sites of the catalyst, which is believed to contribute to its instability. Recently, titanium oxide (TiO2) was introduced as an alternative support material for heterogeneous catalyst due to the effect of its high surface area stabilizing the catalysts in its mesoporous structure. TiO2 supported metal catalysts have attracted interest due to TiO2 nanoparticles high activity for various reduction and oxidation reactions at low pressures and temperatures. Furthermore, TiO2 was found to be a good metal oxide catalyst support due to the strong metal support interaction, chemical stability, and acid-base property. The aforementioned properties make heterogeneous TiO2 supported catalysts show a high potential in photocatalyst-related applications, electrodes for wet solar cells, synthesis of fine chemicals, and others. This review focuses on TiO2 as a support material for heterogeneous catalysts and its potential applications. PMID:25383380

Supersonic molecular beam experiments on surface chemical reactions.

Science.gov (United States)

Okada, Michio

2014-10-01

The interaction of a molecule and a surface is important in various fields, and in particular in complex systems like biomaterials and their related chemistry. However, the detailed understanding of the elementary steps in the surface chemistry, for example, stereodynamics, is still insufficient even for simple model systems. In this Personal Account, I review our recent studies of chemical reactions on single-crystalline Cu and Si surfaces induced by hyperthermal oxygen molecular beams and by oriented molecular beams, respectively. Studies of oxide formation on Cu induced by hyperthermal molecular beams demonstrate a significant role of the translational energy of the incident molecules. The use of hyperthermal molecular beams enables us to open up new chemical reaction paths specific for the hyperthermal energy region, and to develop new methods for the fabrication of thin films. On the other hand, oriented molecular beams also demonstrate the possibility of understanding surface chemical reactions in detail by varying the orientation of the incident molecules. The steric effects found on Si surfaces hint at new ways of material fabrication on Si surfaces. Controlling the initial conditions of incoming molecules is a powerful tool for finely monitoring the elementary step of the surface chemical reactions and creating new materials on surfaces. Copyright © 2014 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface morphology study of some Cu–Ni reference alloys using laser induced breakdown spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Sheta, S.A. [National Institute of Laser Enhanced Science (NILES), Cairo University, 12613, Giza (Egypt); Di Carlo, G.; Ingo, G.M. [Istituto per lo Studio dei Materiali Nanostrutturati (ISMN-CNR), Area della Ricerca Roma 1 Montelibretti, 00016, Monterotondo Scalo, Rome (Italy); Harith, M.A., E-mail: mharithm@niles.edu.eg [National Institute of Laser Enhanced Science (NILES), Cairo University, 12613, Giza (Egypt)

2016-04-15

In the present work a detailed study of the surface morphology of purposely-prepared Cu–Ni reference alloys has been performed. These alloys have been prepared via tailored casting methods in order to have samples with same chemical composition and different local chemical enrichments of both metals. A micro-LIBS system for surface spatial scanning was set up based on a second harmonic Nd:YAG laser at 532 nm and using a focusing lens of focal length 7 cm to disclose the local chemical composition variation. Surface morphological scanning was performed for some of the binary Cu–Ni reference alloys to differentiate between chemically homogeneous and heterogeneous alloys. LIBS results were compared with the information of the Scanning Electron Microscope coupled with Energy Dispersive X-ray (SEMEDS) investigation carried out to provide surface local large-area chemical analysis via EDS technique. It has been proved that LIBS is a simple, sensitive and direct technique in the determination of homogeneity or heterogeneity of the sample's surface. The LIBS results have been shown to be more sensitive and accurate in the heterogeneity determination than other used conventional analytical techniques. - Highlights: • Surface LIBS scanning was performed for Cu–Ni reference alloy samples. • LIBS system was based on a 2nd harmonic Nd:YAG laser and a focusing lens (f = 7 cm). • LIBS results were compared with SEM imaging and EDS chemical analysis. • Surface homogeneity and heterogeneity have been differentiated successfully. • LIBS is a sensitive analytical tool in surface metallurgical study.

Antibiotic Algae by Chemical Surface Engineering.

Science.gov (United States)

Kerschgens, Isabel P; Gademann, Karl

2018-03-02

Chemical cell-surface engineering is a tool for modifying and altering cellular functions. Herein, we report the introduction of an antibiotic phenotype to the green alga Chlamydomonas reinhardtii by chemically modifying its cell surface. Flow cytometry and confocal microscopy studies demonstrated that a hybrid of the antibiotic vancomycin and a 4-hydroxyproline oligomer binds reversibly to the cell wall without affecting the viability or motility of the cells. The modified cells were used to inhibit bacterial growth of Gram-positive Bacillus subtilis cultures. Delivery of the antibiotic from the microalgae to the bacterial cells was verified by microscopy. Our studies provide compelling evidence that 1) chemical surface engineering constitutes a useful tool for the introduction of new, previously unknown functionality, and 2) living microalgae can serve as new platforms for drug delivery. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface chemical problems in coal flotation

Science.gov (United States)

Taylor, S. R.; Miller, K. J.; Deurbrouck, A. W.

1981-02-01

As the use of coal increases and more fine material is produced by mining and processing, the need for improved methods of coal beneficiation increases. While flotation techniques can help meet these needs, the technique is beset with many problems. These problems involve surface chemical and interfacial properties of the coal-mineral-water slurry systems used in coal flotation. The problems associated with coal flotation include non-selectivity, inefficient reagent utilization, and excessive variablity of results. These problems can be broadely classified as a lack of predictability. The present knowledge of coal flotation is not sufficient, in terms of surface chemical parameters, to allow prediction of the flotation response of a given coal. In this paper, some of the surface chemical properties of coal and coal minerals that need to be defined will be discussed in terms of the problems noted above and their impact on coal cleaning.

Cell behaviour on chemically microstructured surfaces

International Nuclear Information System (INIS)

Magnani, Agnese; Priamo, Alfredo; Pasqui, Daniela; Barbucci, Rolando

2003-01-01

Micropatterned surfaces with different chemical topographies were synthesised in order to investigate the influence of surface chemistry and topography on cell behaviour. The microstructured materials were synthesised by photoimmobilising natural Hyaluronan (Hyal) and its sulphated derivative (HyalS), both adequately functionalised with a photorective moiety, on glass substrates. Four different grating patterns (10, 25, 50 and 100 μm) were used to pattern the hyaluronan. The micropatterned samples were analysed by Secondary Ions Mass Spectrometry, Scanning Electron Microscopy (SEM) and Atomic Force Microscopy to investigate the chemistry and the topography of the surfaces. The spectroscopic and microscopic analysis of the microstructured surfaces revealed that the photoimmobilisation process was successful, demonstrating that the photomask patterns were well reproduced on the sample surface. The influence of chemical topographies on the cell behaviour was then analysed. Human and 3T3 fibroblasts, bovine aortic and human (HGTFN line) endothelial cells were used and their behaviour on the micropatterned surfaces was analysed in terms of adhesion, proliferation, locomotion and orientation. Both chemical and topographical controls were found to be important for cell guidance. By decreasing the stripe dimensions, a more fusiform shape of cell was observed. At the same time, the cell locomotion and orientation parallel to the structure increased. However, differences in cell behaviour were detected according to both cell type and micropattern dimensions

A Simple Approach for Local Contact Angle Determination on a Heterogeneous Surface

KAUST Repository

Wu, Jinbo; Zhang, Mengying; Wang, Xiang; Li, Shunbo; Wen, Weijia

2011-01-01

We report a simple approach for measuring the local contact angle of liquids on a heterogeneous surface consisting of intersected hydrophobic and hydrophilic patch arrays, specifically by employing confocal microscopy and the addition of a very low

Molecular dynamics simulation of nanoscale surface diffusion of heterogeneous adatoms clusters

International Nuclear Information System (INIS)

Imran, Muhammad; Hussain, Fayyaz; Ullah, Hafeez; Ahmad, Ejaz; Rashid, Muhammad; Ismail, Muhammad; Cai, Yongqing; Javid, M Arshad; Ahmad, S A

2016-01-01

Molecular dynamics simulation employing the embedded atom method potential is utilized to investigate nanoscale surface diffusion mechanisms of binary heterogeneous adatoms clusters at 300 K, 500 K, and 700 K. Surface diffusion of heterogeneous adatoms clusters can be vital for the binary island growth on the surface and can be useful for the formation of alloy-based thin film surface through atomic exchange process. The results of the diffusion process show that at 300 K, the diffusion of small adatoms clusters shows hopping, sliding, and shear motion; whereas for large adatoms clusters (hexamer and above), the diffusion is negligible. At 500 K, small adatoms clusters, i.e., dimer, show almost all possible diffusion mechanisms including the atomic exchange process; however no such exchange is observed for adatoms clusters greater than dimer. At 700 K, the exchange mechanism dominates for all types of clusters, where Zr adatoms show maximum tendency and Ag adatoms show minimum or no tendency toward the exchange process. Separation and recombination of one or more adatoms are also observed at 500 K and 700 K. The Ag adatoms also occupy pop-up positions over the adatoms clusters for short intervals. At 700 K, the vacancies are also generated in the vicinity of the adatoms cluster, vacancy formation, filling, and shifting can be observed from the results. (paper)

A statistical model for the wettability of surfaces with heterogeneous pore geometries

Science.gov (United States)

Brockway, Lance; Taylor, Hayden

2016-10-01

We describe a new approach to modeling the wetting behavior of micro- and nano-textured surfaces with varying degrees of geometrical heterogeneity. Surfaces are modeled as pore arrays with a Gaussian distribution of sidewall reentrant angles and a characteristic wall roughness. Unlike conventional wettability models, our model considers the fraction of a surface’s pores that are filled at any time, allowing us to capture more subtle dependences of a liquid’s apparent contact angle on its surface tension. The model has four fitting parameters and is calibrated for a particular surface by measuring the apparent contact angles between the surface and at least four probe liquids. We have calibrated the model for three heterogeneous nanoporous surfaces that we have fabricated: a hydrothermally grown zinc oxide, a film of polyvinylidene fluoride (PVDF) microspheres formed by spinodal decomposition, and a polytetrafluoroethylene (PTFE) film with pores defined by sacrificial polystyrene microspheres. These three surfaces show markedly different dependences of a liquid’s apparent contact angle on the liquid’s surface tension, and the results can be explained by considering geometric variability. The highly variable PTFE pores yield the most gradual variation of apparent contact angle with probe liquid surface tension. The PVDF microspheres are more regular in diameter and, although connected in an irregular manner, result in a much sharper transition from non-wetting to wetting behavior as surface tension reduces. We also demonstrate, by terminating porous zinc oxide with three alternative hydrophobic molecules, that a single geometrical model can capture a structure’s wetting behavior for multiple surface chemistries and liquids. Finally, we contrast our results with those from a highly regular, lithographically-produced structure which shows an extremely sharp dependence of wettability on surface tension. This new model could be valuable in designing and

Beyond Cassie equation: Local structure of heterogeneous surfaces determines the contact angles of microdroplets

Science.gov (United States)

Zhang, Bo; Wang, Jianjun; Liu, Zhiping; Zhang, Xianren

2014-01-01

The application of Cassie equation to microscopic droplets is recently under intense debate because the microdroplet dimension is often of the same order of magnitude as the characteristic size of substrate heterogeneities, and the mechanism to describe the contact angle of microdroplets is not clear. By representing real surfaces statistically as an ensemble of patterned surfaces with randomly or regularly distributed heterogeneities (patches), lattice Boltzmann simulations here show that the contact angle of microdroplets has a wide distribution, either continuous or discrete, depending on the patch size. The origin of multiple contact angles observed is ascribed to the contact line pinning effect induced by substrate heterogeneities. We demonstrate that the local feature of substrate structure near the contact line determines the range of contact angles that can be stabilized, while the certain contact angle observed is closely related to the contact line width. PMID:25059292

A Universal Isotherm Model to Capture Adsorption Uptake and Energy Distribution of Porous Heterogeneous Surface

KAUST Repository

Ng, Kim Choon; Burhan, Muhammad; Shahzad, Muhammad Wakil; Ismail, Azahar Bin

2017-01-01

The adsorbate-adsorbent thermodynamics are complex as it is influenced by the pore size distributions, surface heterogeneity and site energy distribution, as well as the adsorbate properties. Together, these parameters defined the adsorbate uptake forming the state diagrams, known as the adsorption isotherms, when the sorption site energy on the pore surfaces are favorable. The available adsorption models for describing the vapor uptake or isotherms, hitherto, are individually defined to correlate to a certain type of isotherm patterns. There is yet a universal approach in developing these isotherm models. In this paper, we demonstrate that the characteristics of all sorption isotherm types can be succinctly unified by a revised Langmuir model when merged with the concepts of Homotattic Patch Approximation (HPA) and the availability of multiple sets of site energy accompanied by their respective fractional probability factors. The total uptake (q/q*) at assorted pressure ratios (P/P s ) are inextricably traced to the manner the site energies are spread, either naturally or engineered by scientists, over and across the heterogeneous surfaces. An insight to the porous heterogeneous surface characteristics, in terms of adsorption site availability has been presented, describing the unique behavior of each isotherm type.

A Universal Isotherm Model to Capture Adsorption Uptake and Energy Distribution of Porous Heterogeneous Surface

KAUST Repository

Ng, Kim Choon

2017-08-31

The adsorbate-adsorbent thermodynamics are complex as it is influenced by the pore size distributions, surface heterogeneity and site energy distribution, as well as the adsorbate properties. Together, these parameters defined the adsorbate uptake forming the state diagrams, known as the adsorption isotherms, when the sorption site energy on the pore surfaces are favorable. The available adsorption models for describing the vapor uptake or isotherms, hitherto, are individually defined to correlate to a certain type of isotherm patterns. There is yet a universal approach in developing these isotherm models. In this paper, we demonstrate that the characteristics of all sorption isotherm types can be succinctly unified by a revised Langmuir model when merged with the concepts of Homotattic Patch Approximation (HPA) and the availability of multiple sets of site energy accompanied by their respective fractional probability factors. The total uptake (q/q*) at assorted pressure ratios (P/P s ) are inextricably traced to the manner the site energies are spread, either naturally or engineered by scientists, over and across the heterogeneous surfaces. An insight to the porous heterogeneous surface characteristics, in terms of adsorption site availability has been presented, describing the unique behavior of each isotherm type.

Heterogeneous nucleation from a supercooled ionic liquid on a carbon surface.

Science.gov (United States)

He, Xiaoxia; Shen, Yan; Hung, Francisco R; Santiso, Erik E

2016-12-07

Classical molecular dynamics simulations were used to study the nucleation of the crystal phase of the ionic liquid [dmim + ][Cl - ] from its supercooled liquid phase, both in the bulk and in contact with a graphitic surface of D = 3 nm. By combining the string method in collective variables [Maragliano et al., J. Chem. Phys. 125, 024106 (2006)], with Markovian milestoning with Voronoi tessellations [Maragliano et al., J. Chem. Theory Comput. 5, 2589-2594 (2009)] and order parameters for molecular crystals [Santiso and Trout, J. Chem. Phys. 134, 064109 (2011)], we computed minimum free energy paths, the approximate size of the critical nucleus, the free energy barrier, and the rates involved in these nucleation processes. For homogeneous nucleation, the subcooled liquid phase has to overcome a free energy barrier of ∼85 kcal/mol to form a critical nucleus of size ∼3.6 nm, which then grows into the monoclinic crystal phase. This free energy barrier becomes about 42% smaller (∼49 kcal/mol) when the subcooled liquid phase is in contact with a graphitic disk, and the critical nucleus formed is about 17% smaller (∼3.0 nm) than the one observed for homogeneous nucleation. The crystal formed in the heterogeneous nucleation scenario has a structure that is similar to that of the bulk crystal, with the exception of the layers of ions next to the graphene surface, which have larger local density and the cations lie with their imidazolium rings parallel to the graphitic surface. The critical nucleus forms near the graphene surface separated only by these layers of ions. The heterogeneous nucleation rate (∼4.8 × 10 11 cm -3 s -1 ) is about one order of magnitude faster than the homogeneous rate (∼6.6 × 10 10 cm -3 s -1 ). The computed free energy barriers and nucleation rates are in reasonable agreement with experimental and simulation values obtained for the homogeneous and heterogeneous nucleation of other systems (ice, urea, Lennard-Jones spheres, and oxide

Effects of physical and chemical heterogeneity on water-quality samples obtained from wells

Science.gov (United States)

Reilly, Thomas E.; Gibs, Jacob

1993-01-01

Factors that affect the mass of chemical constituents entering a well include the distributions of flow rate and chemical concentrations along and near the screened or open section of the well. Assuming a layered porous medium (with each layer being characterized by a uniform hydraulic conductivity and chemical concentration), a knowledge of the flow from each layer along the screened zone and of the chemical concentrations in each layer enables the total mass entering the well to be determined. Analyses of hypothetical systems and a site at Galloway, NJ, provide insight into the temporal variation of water-quality data observed when withdrawing water from screened wells in heterogeneous ground-water systems.The analyses of hypothetical systems quantitatively indicate the cause-and-effect relations that cause temporal variability in water samples obtained from wells. Chemical constituents that have relatively uniform concentrations with depth may not show variations in concentrations in the water discharged from a well after the well is purged (evacuation of standing water in the well casing). However, chemical constituents that do not have uniform concentrations near the screened interval of the well may show variations in concentrations in the well discharge water after purging because of the physics of ground-water flow in the vicinity of the screen.Water-quality samples were obtained through time over a 30 minute period from a site at Galloway, NJ. The water samples were analyzed for aromatic hydrocarbons, and the data for benzene, toluene, and meta+para xylene were evaluated for temporal variations. Samples were taken from seven discrete zones, and the flow-weighted concentrations of benzene, toluene, and meta+para xylene all indicate an increase in concentration over time during pumping. These observed trends in time were reproduced numerically based on the estimated concentration distribution in the aquifer and the flow rates from each zone.The results of

Surface qualities after chemical-mechanical polishing on thin films

International Nuclear Information System (INIS)

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

2009-01-01

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

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

Science.gov (United States)

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.

Chemical and electrical passivation of Si(1 1 1) surfaces

International Nuclear Information System (INIS)

Tian Fangyuan; Yang Dan; Opila, Robert L.; Teplyakov, Andrew V.

2012-01-01

This paper compares the physical and chemical properties of hydrogen-passivated Si(1 1 1) single crystalline surfaces prepared by two main chemical preparation procedures. The modified RCA cleaning is commonly used to prepare atomically flat stable surfaces that are easily identifiable spectroscopically and are the standard for chemical functionalization of silicon. On the other hand electronic properties of these surfaces are sometimes difficult to control. A much simpler silicon surface preparation procedure includes HF dipping for a short period of time. This procedure yields an atomically rough surface, whose chemical identity is not well-defined. However, the surfaces prepared by this approach often exhibit exceptionally attractive electronic properties as determined by long charge carrier lifetimes. This work utilizes infrared spectroscopy and X-ray photoelectron spectroscopy to investigate chemical modification of the surfaces prepared by these two different procedures with PCl 5 (leading to surface chlorination) and with short- and long-alkyl-chain alkenes (1-decene and 1-octodecene, respectively) and follows the electronic properties of the starting surfaces produced by measuring charge-carrier lifetimes.

Chemical and electrical passivation of Si(1 1 1) surfaces

Science.gov (United States)

Tian, Fangyuan; Yang, Dan; Opila, Robert L.; Teplyakov, Andrew V.

2012-01-01

This paper compares the physical and chemical properties of hydrogen-passivated Si(1 1 1) single crystalline surfaces prepared by two main chemical preparation procedures. The modified RCA cleaning is commonly used to prepare atomically flat stable surfaces that are easily identifiable spectroscopically and are the standard for chemical functionalization of silicon. On the other hand electronic properties of these surfaces are sometimes difficult to control. A much simpler silicon surface preparation procedure includes HF dipping for a short period of time. This procedure yields an atomically rough surface, whose chemical identity is not well-defined. However, the surfaces prepared by this approach often exhibit exceptionally attractive electronic properties as determined by long charge carrier lifetimes. This work utilizes infrared spectroscopy and X-ray photoelectron spectroscopy to investigate chemical modification of the surfaces prepared by these two different procedures with PCl5 (leading to surface chlorination) and with short- and long-alkyl-chain alkenes (1-decene and 1-octodecene, respectively) and follows the electronic properties of the starting surfaces produced by measuring charge-carrier lifetimes.

Multi-sensor remote sensing parameterization of heat fluxes over heterogeneous land surfaces

NARCIS (Netherlands)

Faivre, R.D.

2014-01-01

The parameterization of heat transfer by remote sensing, and based on SEBS scheme for turbulent heat fluxes retrieval, already proved to be very convenient for estimating evapotranspiration (ET) over homogeneous land surfaces. However, the use of such a method over heterogeneous landscapes (e.g.

Building surface decontamination for chemical counter-terrorism

Energy Technology Data Exchange (ETDEWEB)

Harrison, S.; Thouin, G.; Kuang, W. [SAIC Canada, Ottawa, ON (Canada); Volchek, K.; Fingas, M.; Li, K. [Environment Canada, Ottawa, ON (Canada). Emergencies Science and Technology Division, Environmental Technology Centre, Science and Technology Branch

2006-07-01

A test method to compare and evaluate surface decontamination methods for buildings affected by chemical attacks was developed. Decontamination techniques generally depend on the nature and quantity of the weapon agent, the type of construction material and the location. Cleanup methods can be either physical, chemical or biological. This paper addressed chemical decontamination methods which use reactants to change the molecular structure of the contaminant. Peroxycarboxylic and peroxyacetic acids (PAA) are being used increasingly for both disinfection and environmental protection. In this study, 4 materials were chosen to represent common building materials. Samples were spiked with 10 mg of pesticides such as malathion and diazinon. Decontamination agents included the commercial decontamination agent CASCAD prepared in liquid form, a chemical preparation of PAA, and reagent grade peroxypropionic acid (PPA). The newly developed surface decontamination procedure can evaluate and compare the effectiveness of different chemical decontamination agents. The procedures were used on porous ceiling tile and carpet as well as on non-porous floor tile and painted steel surfaces. Rinse water was collected and analyzed in order to determine if decontamination was a result of chemical destruction or mechanical removal. The extraction efficiencies were found to be acceptable for all materials, with the exception of the highly porous ceiling tile. The extraction of diazinon from all surfaces was less efficient than the extraction of malathion. Results suggest that the performance of decontamination agents can be improved by repeated application of the decontamination agent, along with greater volumes and a combination of chemical and mechanical actions. It was also suggested that breakdown methods and wastewater treatment procedures should be developed because hazardous byproducts were detected in many samples. 18 refs., 1 tab., 17 figs.

Gas-surface interactions and heterogeneous chemistry on interstellar grains analogues

Directory of Open Access Journals (Sweden)

Cazaux S.

2012-01-01

Full Text Available Detailed laboratory studies and progress in surface science technique, have allowed in recent years the first experimental confirmation of surface reaction schemes, as introduced by Tielens, Hagen and Charnley [1,2]. In this paper, we review few heterogeneous processes which give routes to form elementary molecules considered as precursors for explaining the variety and richness of molecular species in the interstellar medium. Adsorption, diffusion and reaction processes are discussed. With emphasis on the experimental approaches, but also supported by theoretical developments, progresses in the understanding of the “catalytic role” of a dust grain surface in various physical conditions are described. Recent advances made on few important species (H2, H2O, CH3OH are used to illustrate basic properties and raise open questions.

Effect of surface free energies on the heterogeneous nucleation of water droplet: A molecular dynamics simulation approach

Energy Technology Data Exchange (ETDEWEB)

Xu, W.; Lan, Z.; Peng, B. L.; Wen, R. F.; Ma, X. H., E-mail: xuehuma@dlut.edu.cn [Liaoning Provincial Key Laboratory of Clean Utilization of Chemical Resources, Institute of Chemical Engineering, Dalian University of Technology, Dalian 116024 (China)

2015-02-07

Heterogeneous nucleation of water droplet on surfaces with different solid-liquid interaction intensities is investigated by molecular dynamics simulation. The interaction potentials between surface atoms and vapor molecules are adjusted to obtain various surface free energies, and the nucleation process and wetting state of nuclei on surfaces are investigated. The results indicate that near-constant contact angles are already established for nano-scale nuclei on various surfaces, with the contact angle decreasing with solid-liquid interaction intensities linearly. Meanwhile, noticeable fluctuation of vapor-liquid interfaces can be observed for the nuclei that deposited on surfaces, which is caused by the asymmetric forces from vapor molecules. The formation and growth rate of nuclei are increasing with the solid-liquid interaction intensities. For low energy surface, the attraction of surface atoms to water molecules is comparably weak, and the pre-existing clusters can depart from the surface and enter into the bulk vapor phase. The distribution of clusters within the bulk vapor phase becomes competitive as compared with that absorbed on surface. For moderate energy surfaces, heterogeneous nucleation predominates and the formation of clusters within bulk vapor phase is suppressed. The effect of high energy particles that embedded in low energy surface is also discussed under the same simulation system. The nucleation preferably initiates on the high energy particles, and the clusters that formed on the heterogeneous particles are trapped around their original positions instead of migrating around as that observed on smooth surfaces. This feature makes it possible for the heterogeneous particles to act as fixed nucleation sites, and simulation results also suggest that the number of nuclei increases monotonously with the number of high energy particles. The growth of nuclei on high energy particles can be divided into three sub-stages, beginning with the formation

Some approaches to the quantum-chemical theory of heterogeneous catalysis

Energy Technology Data Exchange (ETDEWEB)

Zhidomirov, G M

1977-09-01

A discussion of mathematical methods, models, and parameters used in various quantum-chemical descriptions of chemisorption and reaction at silica and aluminosilicate surfaces covers the continuous-surface model, the cluster model of the surface, the variation of pseudo-atom parameters to reduce the magnitude of boundary effects in the cluster model, the calculation of individual bond strengths in chemisorbed molecules, dissociative adsorption, applications to adsorption on silica and aluminosilicates, the mechanisms of hydrogen-deuterium exchange, etc. Diagrams, graphs, and 42 references.

The effect of hot electrons and surface plasmons on heterogeneous catalysis

International Nuclear Information System (INIS)

Kim, Sun Mi; Lee, Si Woo; Moon, Song Yi; Park, Jeong Young

2016-01-01

Hot electrons and surface-plasmon-driven chemistry are amongst the most actively studied research subjects because they are deeply associated with energy dissipation and the conversion processes at the surface and interfaces, which are still open questions and key issues in the surface science community. In this topical review, we give an overview of the concept of hot electrons or surface-plasmon-mediated hot electrons generated under various structural schemes (i.e. metals, metal–semiconductor, and metal–insulator–metal) and their role affecting catalytic activity in chemical reactions. We highlight recent studies on the relation between hot electrons and catalytic activity on metallic surfaces. We discuss possible mechanisms for how hot electrons participate in chemical reactions. We also introduce controlled chemistry to describe specific pathways for selectivity control in catalysis on metal nanoparticles. (topical review)

Chemical and Physical Interactions of Martian Surface Material

Science.gov (United States)

Bishop, J. L.

1999-09-01

A model of alteration and maturation of the Martian surface material is described involving both chemical and physical interactions. Physical processes involve distribution and mixing of the fine-grained soil particles across the surface and into the atmosphere. Chemical processes include reaction of sulfate, salt and oxidizing components of the soil particles; these agents in the soils deposited on rocks will chew through the rock minerals forming coatings and will bind surface soils together to form duricrust deposits. Formation of crystalline iron oxide/oxyhydroxide minerals through hydrothermal processes and of poorly crystalline and amorphous phases through palagonitic processes both contribute to formation of the soil particles. Chemical and physical alteration of these soil minerals and phases contribute to producing the chemical, magnetic and spectroscopic character of the Martian soil as observed by Mars Pathfinder and Mars Global Surveyor. Minerals such as maghemite/magnetite and jarosite/alunite have been observed in terrestrial volcanic soils near steam vents and may be important components of the Martian surface material. The spectroscopic properties of several terrestrial volcanic soils containing these minerals have been analyzed and evaluated in terms of the spectroscopic character of the surface material on Mars.

Reduced chemical warfare agent sorption in polyurethane-painted surfaces via plasma-enhanced chemical vapor deposition of perfluoroalkanes.

Science.gov (United States)

Gordon, Wesley O; Peterson, Gregory W; Durke, Erin M

2015-04-01

Perfluoralkalation via plasma chemical vapor deposition has been used to improve hydrophobicity of surfaces. We have investigated this technique to improve the resistance of commercial polyurethane coatings to chemicals, such as chemical warfare agents. The reported results indicate the surface treatment minimizes the spread of agent droplets and the sorption of agent into the coating. The improvement in resistance is likely due to reduction of the coating's surface free energy via fluorine incorporation, but may also have contributing effects from surface morphology changes. The data indicates that plasma-based surface modifications may have utility in improving chemical resistance of commercial coatings.

Shallow to Deep Convection Transition over a Heterogeneous Land Surface Using the Land Model Coupled Large-Eddy Simulation

Science.gov (United States)

Lee, J.; Zhang, Y.; Klein, S. A.

2017-12-01

The triggering of the land breeze, and hence the development of deep convection over heterogeneous land should be understood as a consequence of the complex processes involving various factors from land surface and atmosphere simultaneously. That is a sub-grid scale process that many large-scale models have difficulty incorporating it into the parameterization scheme partly due to lack of our understanding. Thus, it is imperative that we approach the problem using a high-resolution modeling framework. In this study, we use SAM-SLM (Lee and Khairoutdinov, 2015), a large-eddy simulation model coupled to a land model, to explore the cloud effect such as cold pool, the cloud shading and the soil moisture memory on the land breeze structure and the further development of cloud and precipitation over a heterogeneous land surface. The atmospheric large scale forcing and the initial sounding are taken from the new composite case study of the fair-weather, non-precipitating shallow cumuli at ARM SGP (Zhang et al., 2017). We model the land surface as a chess board pattern with alternating leaf area index (LAI). The patch contrast of the LAI is adjusted to encompass the weak to strong heterogeneity amplitude. The surface sensible- and latent heat fluxes are computed according to the given LAI representing the differential surface heating over a heterogeneous land surface. Separate from the surface forcing imposed from the originally modeled surface, the cases that transition into the moist convection can induce another layer of the surface heterogeneity from the 1) radiation shading by clouds, 2) adjusted soil moisture pattern by the rain, 3) spreading cold pool. First, we assess and quantifies the individual cloud effect on the land breeze and the moist convection under the weak wind to simplify the feedback processes. And then, the same set of experiments is repeated under sheared background wind with low level jet, a typical summer time wind pattern at ARM SGP site, to

Effects of geometric modulation and surface potential heterogeneity on electrokinetic flow and solute transport in a microchannel

Science.gov (United States)

Bera, Subrata; Bhattacharyya, S.

2018-04-01

A numerical investigation is performed on the electroosmotic flow (EOF) in a surface-modulated microchannel to induce enhanced solute mixing. The channel wall is modulated by placing surface-mounted obstacles of trigonometric shape along which the surface potential is considered to be different from the surface potential of the homogeneous part of the wall. The characteristics of the electrokinetic flow are governed by the Laplace equation for the distribution of external electric potential; the Poisson equation for the distribution of induced electric potential; the Nernst-Planck equations for the distribution of ions; and the Navier-Stokes equations for fluid flow simultaneously. These nonlinear coupled set of governing equations are solved numerically by a control volume method over the staggered system. The influence of the geometric modulation of the surface, surface potential heterogeneity and the bulk ionic concentration on the EOF is analyzed. Vortical flow develops near a surface modulation, and it becomes stronger when the surface potential of the modulated region is in opposite sign to the surface potential of the homogeneous part of the channel walls. Vortical flow also depends on the Debye length when the Debye length is in the order of the channel height. Pressure drop along the channel length is higher for a ribbed wall channel compared to the grooved wall case. The pressure drop decreases with the increase in the amplitude for a grooved channel, but increases for a ribbed channel. The mixing index is quantified through the standard deviation of the solute distribution. Our results show that mixing index is higher for the ribbed channel compared to the grooved channel with heterogeneous surface potential. The increase in potential heterogeneity in the modulated region also increases the mixing index in both grooved and ribbed channels. However, the mixing performance, which is the ratio of the mixing index to pressure drop, reduces with the rise in

Spectral force analysis using atomic force microscopy reveals the importance of surface heterogeneity in bacterial and colloid adhesion to engineered surfaces.

Science.gov (United States)

Ma, Huilian; Winslow, Charles J; Logan, Bruce E

2008-04-01

Coatings developed to reduce biofouling of engineered surfaces do not always perform as expected based on their native properties. One reason is that a relatively small number of highly adhesive sites, or the heterogeneity of the coated surface, may control the overall response of the system to initial bacterial deposition. It is shown here using an approach we call spectral force analysis (SFA), based on force volume imaging of the surface with atomic force microscopy, that the behavior of surfaces and coatings can be better understood relative to bacterial adhesion. The application of vapor deposited TiO(2) metal oxide increased bacterial and colloid adhesion, but coating the surface with silica oxide reduced adhesion in a manner consistent with SFA based on analysis of the "stickiest" sites. Application of a TiO(2)-based paint to a surface produced a relatively non-fouling surface. Addition of a hydrophilic layer coating to this surface should have decreased fouling. However, it was observed that this coating actually increased fouling. Using SFA it was shown that the reason for the increased adhesion of bacteria and particles to the hydrophilic layer was that the surface produced by this coating was highly heterogeneous, resulting in a small number of sites that created a stickier surface. These results show that while it is important to manufacture surfaces with coatings that are relatively non-adhesive to bacteria, it is also essential that these coatings have a highly uniform surface chemistry.

Precise Chemical Analyses of Planetary Surfaces

Science.gov (United States)

Kring, David; Schweitzer, Jeffrey; Meyer, Charles; Trombka, Jacob; Freund, Friedemann; Economou, Thanasis; Yen, Albert; Kim, Soon Sam; Treiman, Allan H.; Blake, David;

Wetting at the nanometer scale: effects of long-range forces and substrate heterogeneities

International Nuclear Information System (INIS)

Checco, Antonio

2003-01-01

Wetting phenomena on the nano-scale remain poorly understood in spite of their growing theoretical and practical interest. In this context, the present work aimed at studying partial wetting of nanometer-sized alkane droplets on 'model' surfaces build by self-assembly of organic monolayers. For this purpose a novel technique, based on 'noncontact' Atomic Force Microscopy (AFM), has been developed to image, with minimal artefacts, drops of adjustable size directly condensed on so- lid surfaces. We have thus shown that contact angle of alkanes, wetting a weakly heterogeneous, silanized substrate, noticeably decreases from its macroscopic value for droplets sizes in the submicron range. The line tension, arising in this case from purely dispersive long-range interactions between the liquid and the substrate, is theoretically too weak to be responsible for the observed effect. Therefore we have supposed that contact angle is affected by mesoscopic chemical heterogeneities of the substrate whenever the droplets size becomes sufficiently small. This scenario has been supported by numerical simulations based on a simplified model of the spatial distribution of surface defects. Similar experiments, performed on different substrates (monolayers made of alkane-thiols self-assembled on gold and of alkyl chains covalently bound onto a silicon surface), have also shown that wetting on small scales is strongly affected by minimal physical and chemical surface heterogeneities. Finally, to provide further examples of the potential of the above mentioned AFM technique, we have studied the wettability of nano-structured surfaces and the local wetting properties of hair. (author) [fr

Nitric oxide reduction in coal combustion: role of char surface complexes in heterogeneous reactions

Energy Technology Data Exchange (ETDEWEB)

Arenillas, A.; Rubiera, F.; Pis, J.J. [Instituto Nacional del Carbon, CSIC, Oviedo (Spain)

2002-12-15

Nitrogen oxides are one of the major environmental problems arising from fossil fuel combustion. Coal char is relatively rich in nitrogen, and so this is an important source of nitrogen oxides during coal combustion. However, due to its carbonaceous nature, char can also reduce NO through heterogeneous reduction. The objectives of this work were on one hand to compare NO emissions from coal combustion in two different types of equipment and on the other hand to study the influence of char surface chemistry on NO reduction. A series of combustion tests were carried out in two different scale devices: a thermogravimetric analyzer coupled to a mass spectrometer and an FTIR (TG-MS-FTIR) and a fluidized bed reactor with on-line battery of analyzers. According to the results obtained, it can be said that the TG-MS-FTIR system provides valuable information about NO heterogeneous reduction and it can give good trends of the behaviour in other combustion equipments, i.e. fluidized bed combustors. It has been also pointed out that NO-char interaction depends to a large extent on temperature. In the low-temperature range NO heterogeneous reduction seems to be controlled by the evolution of surface complexes. In the high-temperature range a different mechanism is involved in NO heterogeneous reduction, the nature of the carbon matrix being a key factor. 27 refs., 6 figs., 1 tab.

The Migration and Entrapment of DNAPLs in Physically and Chemically Heterogeneous Porous Media - Final Report - 09/15/1996 - 09/15/2000; FINAL

International Nuclear Information System (INIS)

Abriola, L. M.; Demond, A. H.

2000-01-01

Hazardous dense nonaqueous phase liquids (DNAPLs), such as chlorinated solvents, are slightly water soluble and pose a serious threat to soil and groundwater supplies in many portions of the United States. The migration and entrapment of DNAPLs in the subsurface environment is typically believed to be controlled by physical heterogeneities; i.e, layers and lenses of contrasting soil texture. The rationale for this assumption is that capillarity, as determined by the soil texture, is the dominant transport mechanism. Capillarity also depends on interfacial tension and medium wettability. Interfacial tension and medium wettability may be spatially and temporally dependent due to variations in aqueous phase chemistry, contaminant aging, and/or variations in mineralogy and organic matter distributions. Such chemical heterogeneities have largely been ignored to date, even though they are known to have dramatic effects on the hydraulic property relations. Numerical multiphase flow and transport models typically assume that solids are water-wet and that interfacial tension is constant. The primary objective of this research is to investigate the influence of coupled physical and chemical heterogeneities on the migration and entrapment of DNAPLs. This objective will be accomplished through a combination of laboratory and numerical experiments. Laboratory experiments will be conducted to examine: (i) aqueous phase chemistry effects on medium wettability and interfacial tension; and (ii) relative permeability-saturation-capillary pressure relations for chemically heterogeneous systems. An important objective of this research is to modify a two-dimensional multiphase flow and transport model to account for chemically and physically heterogeneous systems. This numerical simulator will be used in conjunction with independently measured parameters to simulate two-dimensional DNAPL infiltration experiments. Comparisons of simulated and laboratory data will provide a means to

The Modelling Analysis of the Response of Convective Transport of Energy and Water to Multiscale Surface Heterogeneity over Tibetan Plateau

Science.gov (United States)

SUN, G.; Hu, Z.; Ma, Y.; Ma, W.

2017-12-01

The land-atmospheric interactions over a heterogeneous surface is a tricky issue for accurately understanding the energy-water exchanges between land surface and atmosphere. We investigate the vertical transport of energy and water over a heterogeneous land surface in Tibetan Plateau during the evolution of the convective boundary layer using large eddy simulation (WRF_LES). The surface heterogeneity is created according to remote sensing images from high spatial resolution LandSat ETM+ images. The PBL characteristics over a heterogeneous surface are analyzed in terms of secondary circulations under different background wind conditions based on the horizontal and vertical distribution and evolution of wind. The characteristics of vertical transport of energy and heat over a heterogeneous surface are analyzed in terms of the horizontal distribution as well as temporal evolution of sensible and latent heat fluxes at different heights under different wind conditions on basis of the simulated results from WRF_LES. The characteristics of the heat and water transported into the free atmosphere from surface are also analyzed and quantified according to the simulated results from WRF_LES. The convective transport of energy and water are analyzed according to horizontal and vertical distributions of potential temperature and vapor under different background wind conditions. With the analysis based on the WRF_LES simulation, the performance of PBL schemes of mesoscale simulation (WRF_meso) is evaluated. The comparison between horizontal distribution of vertical fluxes and domain-averaged vertical fluxes of the energy and water in the free atmosphere is used to evaluate the performance of PBL schemes of WRF_meso in the simulation of vertical exchange of energy and water. This is an important variable because only the energy and water transported into free atmosphere is able to influence the regional and even global climate. This work would will be of great significance not

Mars Surface Heterogeneity From Variations in Apparent Thermal Inertia

Science.gov (United States)

Putzig, N. E.; Mellon, M. T.

2005-12-01

Current techniques used in the calculation of thermal inertia from observed brightness temperatures typically assume that planetary surface properties are uniform on the scale of the instrument's observational footprint. Mixed or layered surfaces may yield different apparent thermal inertia values at different seasons or times of day due to the nonlinear relationship between temperature and thermal inertia. To obtain sufficient data coverage for investigating temporal changes, we processed three Mars years of observations from the Mars Global Surveyor Thermal Emission Spectrometer and produced seasonal nightside and dayside maps of apparent thermal inertia. These maps show broad regions with seasonal and diurnal differences as large as 200 J m-2 K-1 s-½ at mid-latitudes (60°S to 60°N) and ranging up to 600 J m-2 K-1 s-½ or greater in the polar regions. Comparison of the maps with preliminary results from forward-modeling of heterogeneous surfaces indicates that much of the martian surface may be dominated by (1) horizontally mixed surfaces, such as those containing differing proportions of rocks, sand, dust, duricrust, and localized frosts; (2) higher thermal inertia layers over lower thermal inertia substrates, such as duricrust or desert pavements; and (3) lower thermal inertia layers over higher thermal inertia substrates, such as dust over sand or rocks and soils with an ice table at depth.

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

International Nuclear Information System (INIS)

1990-03-01

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

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

Energy Technology Data Exchange (ETDEWEB)

1990-03-01

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

Nitric oxide reduction in coal combustion: role of char surface complexes in heterogeneous reactions.

Science.gov (United States)

Arenillas, Ana; Rubiera, Fernando; Pis, José J

2002-12-15

Nitrogen oxides are one of the major environmental problems arising from fossil fuel combustion. Coal char is relatively rich in nitrogen, and so this is an important source of nitrogen oxides during coal combustion. However, due to its carbonaceous nature, char can also reduce NO through heterogeneous reduction. The objectives of this work were on one hand to compare NO emissions from coal combustion in two different types of equipment and on the other hand to study the influence of char surface chemistry on NO reduction. A series of combustion tests were carried out in two different scale devices: a thermogravimetric analyzer coupled to a mass spectrometer and an FTIR (TG-MS-FTIR) and a fluidized bed reactor with an on line battery of analyzers. The TG-MS-FTIR system was also used to perform a specific study on NO heterogeneous reduction reactions using chars with different surface chemistry. According to the results obtained, it can be said that the TG-MS-FTIR system provides valuable information about NO heterogeneous reduction and it can give good trends of the behavior in other combustion equipments (i.e., fluidized bed combustors). It has been also pointed out that NO-char interaction depends to a large extent on temperature. In the low-temperature range (800 degrees C), a different mechanism is involved in NO heterogeneous reduction, the nature of the carbon matrix being a key factor.

XXI symposium Modern chemical physics. Tuapse 2009. Summaries of reports

International Nuclear Information System (INIS)

2009-01-01

The materials of the XXI symposium Modern chemical physics, Tuapse 2009 (25 September - 6 October, 2009) are presented. Scientific program includes lectures, presentations and poster sessions on photochemistry and radiation chemistry, elementary processes, homogeneous and heterogeneous catalysis. The problems of chemical reaction kinetics, quantum chemistry, chemical spectroscopy, macromolecular chemistry are discussed. Topics of chemical physics of surface, nanochemistry, nanophysics and nanotechnology are treated [ru

Liquid-solid interface project in nuclear engineering. Systematization of sorption theory in heterogeneous surface and it's application to radioactive waste disposal. JAERI's nuclear research promotion program, H10-032. Contract research

International Nuclear Information System (INIS)

Tanaka, Satoru

2002-03-01

Combining of the In-Situ and Ex-situ experiments with quantum chemical calculation, we can draw the following conclusions on the sorption at heterogeneous interfaces, based on the structure of solid surfaces and the profile of charge/electron at surface: (1) Redox sensitive species Np(V) is reduced to Np(IV) by Fe(II) contained in iron oxides. (2) Interactions of ions with C-S-H gels, which is a main component of cementitious materials, consist of replacement of Ca, association with Si and ion exchange. (3) Iodate ions adsorb on the two kinds of sorption sites located on the outer surface of hydrotalcite. (4) Interaction potential between particles and solid surfaces decrease due to the microscopic roughness of solid surface and localized distribution of charge on the surface, leading to the increase in the deposition of particles. (5) Some information on the association situation of water molecules on the metal oxides are obtained. These results suggests that the microscopic heterogeneity of solid surfaces facilities the interaction of ions and particles with solid surfaces. These phenomena can not be explained by the conventional sorption theory. We have to develop the sorption theory by considering the interactions from the microscopic point of view. (author)

Heterogeneous Metal Catalysts for Oxidation Reactions

Directory of Open Access Journals (Sweden)

Md. Eaqub Ali

2014-01-01

Full Text Available Oxidation reactions may be considered as the heart of chemical synthesis. However, the indiscriminate uses of harsh and corrosive chemicals in this endeavor are threating to the ecosystems, public health, and terrestrial, aquatic, and aerial flora and fauna. Heterogeneous catalysts with various supports are brought to the spotlight because of their excellent capabilities to accelerate the rate of chemical reactions with low cost. They also minimize the use of chemicals in industries and thus are friendly and green to the environment. However, heterogeneous oxidation catalysis are not comprehensively presented in literature. In this short review, we clearly depicted the current state of catalytic oxidation reactions in chemical industries with specific emphasis on heterogeneous catalysts. We outlined here both the synthesis and applications of important oxidation catalysts. We believe it would serve as a reference guide for the selection of oxidation catalysts for both industries and academics.

Strain and Structure Heterogeneity in MoS2 Atomic Layers Grown by Chemical Vapour Deposition

Science.gov (United States)

2014-11-18

cture heterogeneity in MoS2 atomiclayers grown by chemical vapour deposition 6. AUTHORS Zheng Liu, Matin Amani, Sina Najmaei, Quan Xu, Xiaolong Zou...deposition Zheng Liu1•2•3·*, Matin Amani4·*, Sina Najmaei5·*, Quan Xu6•7, Xiaolong Zou5, Wu Zhou8, Ting Yu9, Caiyu Qiu9, A Glen Birdwell4, Frank J. Crowne4

Chemical placement in heterogeneous and long reach horizontal wells

Energy Technology Data Exchange (ETDEWEB)

Stalker, Robert; Wahid, Fazrie; Graham, Gordon M.

2006-03-15

The effective placement of chemical squeeze treatments in heterogeneous wells and long reach horizontal wells has proved a significant challenge, with various factors including heterogeneity, crossflow and pressure gradients between otherwise non-communicating zones within the well, all contributing to an uneven placement of the scale squeeze treatment into the reservoir. Current methods to circumvent these problems often rely on extremely expensive coiled tubing operations, staged diversion (temporary shut off) treatments or by designing treatments to deliberately overdose some zones in order to gain placement in other (e.g. low permeability) zones. Moreover for deepwater sub sea horizontal wells the costs associated with ''spot'' treating along the length of horizontal wells by coil tubing tractor operations can often be prohibitively expensive. For other very near well bore treatments such as acid stimulation a number of self diverting strategies including gelled acid treatments, staged viscoelastic surfactant treatments and foams have been applied in field treatments with some success. However the properties which make such treatments applicable for acid stimulation may also make them inappropriate for bullhead scale squeeze treatments. Recent work by the current authors has however indicated the possible benefits of using modified injection fluids to aid uniform scale inhibitor placement in such wells in order to effect more even placement. In summary this paper will describe the various options available for achieving self diversion and describes the potential drawbacks associated with the viscous placement fluids commonly used for acid simulation techniques. In addition, various simulation packages commonly used for scale related calculations are reviewed and their limitations, primarily due to the inherent assumptions made and input parameters used, for modelling squeeze treatments using such modified fluids are described. The paper

The chemical physics of surfaces

CERN Document Server

Morrison, Stanley Roy

1990-01-01

Even more importantly, some authors who have contributed substantially to an area may have been overlooked. For this I apologize. I have, however, not attempted to trace techniques or observa­ tions historically, so there is no implication (unless specified) that the authors referred to were or were not the originators of a given method or observation. I would like to acknowledge discussions with co-workers at SFU for input relative to their specialties, to acknowledge the help of students who have pointed out errors and difficulties in the earlier presentation, and to acknowledge the infinite patience of my wife Phyllis while I spent my sabbatical and more in libraries and punching computers. S. Roy Morrison 0 1 Contents Notation XV 1. Introduction 1 1. 1. Surface States and Surface Sites . 1 1. 1. 1. The Chemical versus Electronic Representation of the Surface. 1 1. 1. 2. The Surface State on the Band Diagram 4 1. 1. 3. The Fermi Energy in the Surface State Model. 6 1. 1. 4. Need for Both Surface...

Heterogeneous propellant internal ballistics: criticism and regeneration

Science.gov (United States)

Glick, R. L.

2011-10-01

Although heterogeneous propellant and its innately nondeterministic, chemically discrete morphology dominates applications, ballisticcharacterization deterministic time-mean burning rate and acoustic admittance measures' absence of explicit, nondeterministic information requires homogeneous propellant with a smooth, uniformly regressing burning surface: inadequate boundary conditions for heterogeneous propellant grained applications. The past age overcame this dichotomy with one-dimensional (1D) models and empirical knowledge from numerous, adequately supported motor developments and supplementary experiments. However, current cost and risk constraints inhibit this approach. Moreover, its fundamental science approach is more sensitive to incomplete boundary condition information (garbage-in still equals garbage-out) and more is expected. This work critiques this situation and sketches a path forward based on enhanced ballistic and motor characterizations in the workplace and approximate model and apparatus developments mentored by CSAR DNS capabilities (or equivalent).

Modeling the large-scale effects of surface moisture heterogeneity on wetland carbon fluxes in the West Siberian Lowland

Directory of Open Access Journals (Sweden)

T. J. Bohn

2013-10-01

Full Text Available We used a process-based model to examine the role of spatial heterogeneity of surface and sub-surface water on the carbon budget of the wetlands of the West Siberian Lowland over the period 1948–2010. We found that, while surface heterogeneity (fractional saturated area had little overall effect on estimates of the region's carbon fluxes, sub-surface heterogeneity (spatial variations in water table depth played an important role in both the overall magnitude and spatial distribution of estimates of the region's carbon fluxes. In particular, to reproduce the spatial pattern of CH4 emissions recorded by intensive in situ observations across the domain, in which very little CH4 is emitted north of 60° N, it was necessary to (a account for CH4 emissions from unsaturated wetlands and (b use spatially varying methane model parameters that reduced estimated CH4 emissions in the northern (permafrost half of the domain (and/or account for lower CH4 emissions under inundated conditions. Our results suggest that previous estimates of the response of these wetlands to thawing permafrost may have overestimated future increases in methane emissions in the permafrost zone.

Effect of chemical heterogeneity on photoluminescence of graphite oxide treated with S-/N-containing modifiers

Science.gov (United States)

Ebrahim, Amani M.; Rodríguez-Castellón, Enrique; Montenegro, José María; Bandosz, Teresa J.

2015-03-01

Graphite oxide (GO) obtained using Hummers method was modified by hydrothermal treatment either with sulfanilic acid or polystyrene (3-ammonium) sulfonate at 100 °C or 85 °C, respectively. Both modifiers contain sulfur in the oxidized forms and nitrogen in the reduced forms. The materials were characterized using FTIR, XPS, thermal analysis, potentiometric titration and SEM. Their photoluminescent properties and their alteration with an addition of Ag+ were also measured. As a result of these modifications nitrogen was introduced to the graphene layers as amines, imides, amides, and sulfur as sulfones and sulfonic acids. Moreover, the presence of polyaniline was detected. This significantly affected the polarity, acid-base character, and conductivity of the materials. Apparently carboxylic groups of GO were involved in the surface reactions. The modified GOs lost their layered structure and the modifications resulted in the high degree of structural and chemical heterogeneity. Photoluminescence in visible light was recorded and linked to the presence of heteroatoms. For the polystyrene (3-ammonium) sulfonate modified sample addition of Ag+ quenched the photoluminescence at low wavelength showing sensitivity as a possible optical detector. No apparent effect was found for the sulfanilic acid modified sample.

Modeling and simulation of diffusion-convection-reaction in heterogeneous nanochannels using OpenFOAM

NARCIS (Netherlands)

Pimpalgaonkar, H.G.; van Steijn, V.; Kreutzer, M.T.; Kleijn, C.R.; Simos, Theodore; Tsitouras, Charalambos

2016-01-01

We present a finite volume implementation of a phase field method in OpenFOAM as a tool to simulate reactive multiphase flows on heterogeneous surfaces. Using this tool, we simulate the formation and growth of a droplet due to a chemical reaction on a hydrophilic catalytic patch surrounded by a

Atomic Resolution Imaging and Quantification of Chemical Functionality of Surfaces

Energy Technology Data Exchange (ETDEWEB)

Schwarz, Udo D. [Yale Univ., New Haven, CT (United States). Dept. of Mechanical Engineering and Materials Science; Altman, Eric I. [Yale Univ., New Haven, CT (United States). Dept. of Chemical and Environmental Engineering

2014-12-10

The work carried out from 2006-2014 under DoE support was targeted at developing new approaches to the atomic-scale characterization of surfaces that include species-selective imaging and an ability to quantify chemical surface interactions with site-specific accuracy. The newly established methods were subsequently applied to gain insight into the local chemical interactions that govern the catalytic properties of model catalysts of interest to DoE. The foundation of our work was the development of three-dimensional atomic force microscopy (3DAFM), a new measurement mode that allows the mapping of the complete surface force and energy fields with picometer resolution in space (x, y, and z) and piconewton/millielectron volts in force/energy. From this experimental platform, we further expanded by adding the simultaneous recording of tunneling current (3D-AFM/STM) using chemically well-defined tips. Through comparison with simulations, we were able to achieve precise quantification and assignment of local chemical interactions to exact positions within the lattice. During the course of the project, the novel techniques were applied to surface-oxidized copper, titanium dioxide, and silicon oxide. On these materials, defect-induced changes to the chemical surface reactivity and electronic charge density were characterized with site-specific accuracy.

Chemical diffusion on solid surfaces. Final report

International Nuclear Information System (INIS)

Hudson, J.B.

1980-12-01

The techniques of surface science have been applied to the problem of the measurement of the surface diffusion rate of an adsorbed species over the surface of a chemically dissimilar material. Studies were carried out for hydrogen and nitrogen adatoms on a Ni(100) surface and for silver adatoms on a sapphire surface. Positive results were obtained only for the case of nitrogen on Ni(100). In this system the diffusivity is characterized by the expression D = D 0 exp (/sup -ΔH//RT), with D 0 = 0.25 cm 2 /sec and ΔH = 28kcal/mol

Atrazine degradation using chemical-free process of USUV: Analysis of the micro-heterogeneous environments and the degradation mechanisms

International Nuclear Information System (INIS)

Xu, L.J.; Chu, W.; Graham, Nigel

2014-01-01

Graphical abstract: - Highlights: • Two chemical-free AOP processes are combined to enhance atrazine degradation. • ATZ degradation in sonophotolytic process was analyzed using a previous proposed model. • The micro-bubble/liquid heterogeneous environments in sonolytic processes were investigated. • The salt effects on different sonolytic processes were examined. • ATZ degradation mechanisms were investigated and pathways were proposed. - Abstract: The effectiveness of sonolysis (US), photolysis (UV), and sonophotolysis (USUV) for the degradation of atrazine (ATZ) was investigated. An untypical kinetics analysis was found useful to describe the combined process, which is compatible to pseudo first-order kinetics. The heterogeneous environments of two different ultrasounds (20 and 400 kHz) were evaluated. The heterogeneous distribution of ATZ in the ultrasonic solution was found critical in determining the reaction rates at different frequencies. The presence of NaCl would promote/inhibit the rates by the growth and decline of “salting out” effect and surface tension. The benefits of combining these two processes were for the first time investigated from the aspect of promoting the intermediates degradation which were resistant in individual processes. UV caused a rapid transformation of ATZ to 2-hydroxyatrazine (OIET), which was insensitive to UV irradiation; however, US and USUV were able to degrade OIET and other intermediates through • OH attack. On the other hand, UV irradiation also could promote radical generation via H 2 O 2 decomposition, thereby resulting in less accumulation of more hydrophilic intermediates, which are difficult to degradation in the US process. Reaction pathways for ATZ degradation by all three processes are proposed. USUV achieved the greatest degree of ATZ mineralization with more than 60% TOC removed, contributed solely by the oxidation of side chains. Ammeline was found to be the only end-product in both US and USUV

Atrazine degradation using chemical-free process of USUV: Analysis of the micro-heterogeneous environments and the degradation mechanisms

Energy Technology Data Exchange (ETDEWEB)

Xu, L.J., E-mail: xulijie827@gmail.com [Department of Civil and Environmental Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon (Hong Kong); Chu, W., E-mail: cewchu@polyu.edu.hk [Department of Civil and Environmental Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon (Hong Kong); Graham, Nigel, E-mail: n.graham@imperial.ac.uk [Department of Civil and Environmental Engineering, Imperial College London, South Kensington Campus, London SW7 2AZ (United Kingdom)

2014-06-30

Graphical abstract: - Highlights: • Two chemical-free AOP processes are combined to enhance atrazine degradation. • ATZ degradation in sonophotolytic process was analyzed using a previous proposed model. • The micro-bubble/liquid heterogeneous environments in sonolytic processes were investigated. • The salt effects on different sonolytic processes were examined. • ATZ degradation mechanisms were investigated and pathways were proposed. - Abstract: The effectiveness of sonolysis (US), photolysis (UV), and sonophotolysis (USUV) for the degradation of atrazine (ATZ) was investigated. An untypical kinetics analysis was found useful to describe the combined process, which is compatible to pseudo first-order kinetics. The heterogeneous environments of two different ultrasounds (20 and 400 kHz) were evaluated. The heterogeneous distribution of ATZ in the ultrasonic solution was found critical in determining the reaction rates at different frequencies. The presence of NaCl would promote/inhibit the rates by the growth and decline of “salting out” effect and surface tension. The benefits of combining these two processes were for the first time investigated from the aspect of promoting the intermediates degradation which were resistant in individual processes. UV caused a rapid transformation of ATZ to 2-hydroxyatrazine (OIET), which was insensitive to UV irradiation; however, US and USUV were able to degrade OIET and other intermediates through • OH attack. On the other hand, UV irradiation also could promote radical generation via H{sub 2}O{sub 2} decomposition, thereby resulting in less accumulation of more hydrophilic intermediates, which are difficult to degradation in the US process. Reaction pathways for ATZ degradation by all three processes are proposed. USUV achieved the greatest degree of ATZ mineralization with more than 60% TOC removed, contributed solely by the oxidation of side chains. Ammeline was found to be the only end-product in both US

Advances in Surface Plasmon Resonance Imaging enable quantitative measurement of laterally heterogeneous coatings of nanoscale thickness

Science.gov (United States)

Raegen, Adam; Reiter, Kyle; Clarke, Anthony; Lipkowski, Jacek; Dutcher, John

2013-03-01

The Surface Plasmon Resonance (SPR) phenomenon is routinely exploited to qualitatively probe changes to the optical properties of nanoscale coatings on thin metallic surfaces, for use in probes and sensors. Unfortunately, extracting truly quantitative information is usually limited to a select few cases - uniform absorption/desorption of small biomolecules and films, in which a continuous ``slab'' model is a good approximation. We present advancements in the SPR technique that expand the number of cases for which the technique can provide meaningful results. Use of a custom, angle-scanning SPR imaging system, together with a refined data analysis method, allow for quantitative kinetic measurements of laterally heterogeneous systems. We first demonstrate the directionally heterogeneous nature of the SPR phenomenon using a directionally ordered sample, then show how this allows for the calculation of the average coverage of a heterogeneous sample. Finally, the degradation of cellulose microfibrils and bundles of microfibrils due to the action of cellulolytic enzymes will be presented as an excellent example of the capabilities of the SPR imaging system.

Two Iron Complexes as Homogeneous and Heterogeneous Catalysts for the Chemical Fixation of Carbon Dioxide.

Science.gov (United States)

Karan, Chandan Kumar; Bhattacharjee, Manish

2018-04-16

Two new bimetallic iron-alkali metal complexes of amino acid (serine)-based reduced Schiff base ligand were synthesized and structurally characterized. Their efficacy as catalysts for the chemical fixation of carbon dioxide was explored. The heterogeneous version of the catalytic reaction was developed by the immobilization of these homogeneous bimetallic iron-alkali metal complexes in an anion-exchange resin. The resin-bound complexes can be used as recyclable catalysts up to six cycles.

Heterogeneous nucleation of protein crystals on fluorinated layered silicate.

Directory of Open Access Journals (Sweden)

Keita Ino

Full Text Available Here, we describe an improved system for protein crystallization based on heterogeneous nucleation using fluorinated layered silicate. In addition, we also investigated the mechanism of nucleation on the silicate surface. Crystallization of lysozyme using silicates with different chemical compositions indicated that fluorosilicates promoted nucleation whereas the silicates without fluorine did not. The use of synthesized saponites for lysozyme crystallization confirmed that the substitution of hydroxyl groups contained in the lamellae structure for fluorine atoms is responsible for the nucleation-inducing property of the nucleant. Crystallization of twelve proteins with a wide range of pI values revealed that the nucleation promoting effect of the saponites tended to increase with increased substitution rate. Furthermore, the saponite with the highest fluorine content promoted nucleation in all the test proteins regardless of their overall net charge. Adsorption experiments of proteins on the saponites confirmed that the density of adsorbed molecules increased according to the substitution rate, thereby explaining the heterogeneous nucleation on the silicate surface.

Analyzing relationships between surface perturbations and local chemical reactivity of metal sites: Alkali promotion of O2 dissociation on Ag(111)

Science.gov (United States)

Xin, Hongliang; Linic, Suljo

2016-06-01

Many commercial heterogeneous catalysts are complex structures that contain metal active sites promoted by multiple additives. Developing fundamental understanding about the impact of these perturbations on the local surface reactivity is crucial for catalyst development and optimization. In this contribution, we develop a general framework for identifying underlying mechanisms that control the changes in the surface reactivity of a metal site (more specifically the adsorbate-surface interactions) upon a perturbation in the local environment. This framework allows us to interpret fairly complex interactions on metal surfaces in terms of specific, physically transparent contributions that can be evaluated independently of each other. We use Cs-promoted dissociation of O2 as an example to illustrate our approach. We concluded that the Cs adsorbate affects the outcome of the chemical reaction through a strong alkali-induced electric field interacting with the static dipole moment of the O2/Ag(111) system.

Radiation-heterogeneous processes on the surface of stainless steel in contact with water

International Nuclear Information System (INIS)

Garibov, A.; Agayev, T.N.; Velibekova, G.Z.; Ismayilov, Sh.S.; Aliyev, A.G.

2003-01-01

Full text: Stainless steels are one of prevailing materials of nuclear power engineering. Under operating conditions in real systems they are exposed to influence of ionizing radiation in contact with various environments. Therefore in the processes of corrosion and destruction of stainless steels special significance takes on surface processes and subsequent heterogeneous processes with their participation. In this report the results of research of nuclear-heterogeneous processes regularities in contact with stainless steel of nuclear reactors with water under influence of γ-quanta in the temperature range 300-573 K are given. Radiolytic processes in water are investigated comprehensively and therefore it was taken as modelling system for titration of surface defects and secondary electrons, emitted from metal. It was determined, that radiation processes in stainless steel give rise to the increasing of energy output of molecular hydrogen at water radiolysis from 0.45 molecule/100 eV at pure water radiolysis at 296 K up to 3.4 molecule/100 eV at the presence of stainless steel at 300 K. With increase of temperature the output of molecular hydrogen increases up to 8.2 molecule/100 eV at 573 K. Processes of lattice damage in samples of stainless steel under influence of γ-rays were investigated by electrophysical method. Influence of γ-radiation on stainless steel in contact with water at temperatures T ≤ 423 K and initial values of radiation dose D ≤ 200 kGy given rise to the reduction of electrical resistivity of samples. At doses D≥200 kGy electrical resistivity is increased. Increase of temperature from 333 K up to 423 K lead to the reduction of dose value, at which the transition to resistance increase, from 200 kGy up to 100 kGy occurs. At T≥523 K insoluble oxide phase is formed on a surface of metal which give rise to the increase of electrical resistivity of stainless steel samples. Surface oxide film formed in contact of stainless steel + H 2 O

Investigation of interaction between the Pt(II) ions and aminosilane-modified silica surface in heterogeneous system

Science.gov (United States)

Nowicki, Waldemar; Gąsowska, Anna; Kirszensztejn, Piotr

2016-05-01

UV-vis spectroscopy measurements confirmed the reaction in heterogeneous system between Pt(II) ions and ethylenediamine type ligand, n-(2-aminoethyl)-3-aminopropyl-trimethoxysilane, immobilized at the silica surface. The formation of complexes is a consequence of interaction between the amine groups from the ligand grafted onto SiO2 and ions of platinum. A potentiometric titration technique was to determine the stability constants of complexes of Pt(II) with immobilized insoluble ligand (SG-L), on the silica gel. The results show the formation of three surface complexes of the same type (PtHSG-L, Pt(HSG-L)2, PtSG-L) with SG-L ligand, in a wide range of pH for different Debye length. The concentration distribution of the complexes in a heterogeneous system is evaluated.

Cirrus cloud mimic surfaces in the laboratory: organic acids, bases and NOx heterogeneous reactions

Science.gov (United States)

Sodeau, J.; Oriordan, B.

2003-04-01

CIRRUS CLOUD MIMIC SURFACES IN THE LABORATORY:ORGANIC ACIDS, BASES AND NOX HETEROGENEOUS REACTIONS. B. ORiordan, J. Sodeau Department of Chemistry and Environment Research Institute, University College Cork, Ireland j.sodeau@ucc.ie /Fax: +353-21-4902680 There are a variety of biogenic and anthropogenic sources for the simple carboxylic acids to be found in the troposphere giving rise to levels as high as 45 ppb in certain urban areas. In this regard it is of note that ants of genus Formica produce some 10Tg of formic acid each year; some ten times that produced by industry. The expected sinks are those generally associated with tropospheric chemistry: the major routes studied, to date, being wet and dry deposition. No studies have been carried out hitherto on the role of water-ice surfaces in the atmospheric chemistry of carboxylic acids and the purpose of this paper is to indicate their potential function in the heterogeneous release of atmospheric species such as HONO. The deposition of formic acid on a water-ice surface was studied using FT-RAIR spectroscopy over a range of temperatures between 100 and 165K. In all cases ionization to the formate (and oxonium) ions was observed. The results were confirmed by TPD (Temperature Programmed Desorption) measurements, which indicated that two distinct surface species adsorb to the ice. Potential reactions between the formic acid/formate ion surface and nitrogen dioxide were subsequently investigated by FT-RAIRS. Co-deposition experiments showed that N2O3 and the NO+ ion (associated with water) were formed as products. A mechanism is proposed to explain these results, which involves direct reaction between the organic acid and nitrogen dioxide. Similar experiments involving acetic acid also indicate ionization on a water-ice surface. The results are put into the context of atmospheric chemistry potentially occuring on cirrus cloud surfaces.

Heterogeneous chromatin target model

International Nuclear Information System (INIS)

Watanabe, Makoto

1996-01-01

The higher order structure of the entangled chromatin fibers in a chromosome plays a key role in molecular control mechanism involved in chromosome mutation due to ionizing radiations or chemical mutagens. The condensed superstructure of chromatin is not so rigid and regular as has been postulated in general. We have proposed a rheological explanation for the flexible network system ('chromatin network') that consists of the fluctuating assembly of nucleosome clusters linked with supertwisting DNA in a chromatin fiber ('Supertwisting Particulate Model'). We have proposed a 'Heterosensitive Target Model' for cellular radiosensitivity that is a modification of 'Heterogeneous Target Model'. The heterogeneity of chromatin target is derived from the highly condensed organization of chromatin segments consist of unstable and fragile sites in the fluctuating assembly of nucleosome clusters, namely 'supranucleosomal particles' or 'superbeads'. The models have been principally supported by our electron microscopic experiments employing 'surface - spreading whole - mount technique' since 1967. However, some deformation and artifacts in the chromatin structure are inevitable with these electron microscopic procedures. On the contrary, the 'atomic force microscope (AFM)' can be operated in liquid as well as in the air. A living specimen can be examined without any preparative procedures. Micromanipulation of the isolated chromosome is also possible by the precise positional control of a cantilever on the nanometer scale. The living human chromosomes were submerged in a solution of culture medium and observed by AFM using a liquid immersion cell. The surface - spreading whole - mount technique was applicable for this observation. The particulate chromatin segments of nucleosome clusters were clearly observed within mitotic human chromosomes in a living hydrated condition. These findings support the heterogeneity of chromatin target in a living cell. (J.P.N.)

Semiconductor Sensors Application for Definition of Factor of Ozone Heterogeneous Destruction on Teflon Surface

Directory of Open Access Journals (Sweden)

Nataliya V. Finogenova

2003-12-01

Full Text Available In our paper we present the results of our research, which was carried out by means of semiconductor sensor techniques (SCS, which allowed evaluating heterogeneous death-rate of ozone (γ Teflon surface. When ozone concentration is near to Ambient Air Standard value, γ is assessed to be equal to 6,57*10-7. High technique response provide possibility to determine ozone contents in the air media and the percentage of ozone, decomposed on the communication surfaces and on the surfaces of installation in the low concentration range (1–100 ppb.

Significant impacts of heterogeneous reactions on the chemical composition and mixing state of dust particles: A case study during dust events over northern China

Science.gov (United States)

Wang, Zhe; Pan, Xiaole; Uno, Itsushi; Li, Jie; Wang, Zifa; Chen, Xueshun; Fu, Pingqing; Yang, Ting; Kobayashi, Hiroshi; Shimizu, Atsushi; Sugimoto, Nobuo; Yamamoto, Shigekazu

2017-06-01

The impact of heterogeneous reactions on the chemical components and mixing state of dust particles are investigated by observations and an air quality model over northern China between March 27, 2015 and April 2, 2015. Synergetic observations were conducted using a polarization optical particle counter (POPC), a depolarized two-wavelength Lidar and filter samples in Beijing. During this period, dust plume passed through Beijing on March 28, and flew back on March 29 because of synoptic weather changes. Mineral dust mixed with anthropogenic pollutants was simulated using the Nested Air Quality Prediction Modeling System (NAQPMS) to examine the role of heterogeneous processes on the dust. A comparison of observations shows that the NAQPMS successfully reproduces the time series of the vertical profile, particulate matter concentration, and chemical components of fine mode (diameter ≤ 2.5 μm) and coarse mode (2.5 μm mixed with dust particles. The significant alterations of the chemical composition and mixing state of particles due to heterogeneous reactions are important for the direct and indirect climate effects of dust and anthropogenic aerosols.

Capturing Structural Heterogeneity in Chromatin Fibers.

Science.gov (United States)

Ekundayo, Babatunde; Richmond, Timothy J; Schalch, Thomas

2017-10-13

Chromatin fiber organization is implicated in processes such as transcription, DNA repair and chromosome segregation, but how nucleosomes interact to form higher-order structure remains poorly understood. We solved two crystal structures of tetranucleosomes with approximately 11-bp DNA linker length at 5.8 and 6.7 Å resolution. Minimal intramolecular nucleosome-nucleosome interactions result in a fiber model resembling a flat ribbon that is compatible with a two-start helical architecture, and that exposes histone and DNA surfaces to the environment. The differences in the two structures combined with electron microscopy reveal heterogeneous structural states, and we used site-specific chemical crosslinking to assess the diversity of nucleosome-nucleosome interactions through identification of structure-sensitive crosslink sites that provide a means to characterize fibers in solution. The chromatin fiber architectures observed here provide a basis for understanding heterogeneous chromatin higher-order structures as they occur in a genomic context. Copyright © 2017 Elsevier Ltd. All rights reserved.

Heterogeneous Photochemistry of Agrochemicals at the Leaf Surface: A Case Study of Plant Activator Acibenzolar-S-methyl.

Science.gov (United States)

Sleiman, M; de Sainte Claire, P; Richard, C

2017-09-06

The photoreactivity of plant activator benzo(1,2,3)thiadiazole-7-carbothioic acid S-methyl ester (BTH), commonly named acibenzolar-S-methyl, was studied on the surfaces of glass, paraffinic wax films, and apple leaves. Experiments were carried out in a solar simulator using pure and formulated BTH (BION). Surface photoproducts were identified using liquid chromatography coupled with electrospray ionization and high-resolution Orbitrap mass spectrometry, while volatile photoproducts were characterized using an online thermal desorption system coupled to a gas chromatography-mass spectrometry (GC-MS) system. Pure BTH degraded quickly on wax surfaces with a half-life of 5.0 ± 0.5 h, whereas photolysis of formulated BTH was 7 times slower (t 1/2 = 36 ± 14 h). On the other hand, formulated BTH was found to photolyze quickly on detached apple leaves with a half-life of 2.8 h ± 0.4 h. This drastic difference in photoreactivity was attributed to the nature and spreading of the BTH deposit, as influenced by the surfactant and surface characteristics. Abiotic stress of irradiated apple leaf was also shown to produce OH radicals which might contribute to the enhanced photodegradability. Eight surface photoproducts were identified, whereas GC-MS analyses revealed the formation of gaseous dimethyl disulfide and methanethiol. The yield of dimethyl disulfide ranged between 1.5% and 12%, and a significant fraction of dimethyl disulfide produced was found to be absorbed by the leaf. This is the first study to report on the formation of volatile chemicals and OH radicals during agrochemical photolysis on plant surfaces. The developed experimental approach can provide valuable insights into the heterogeneous photoreactivity of sprayed agrochemicals and could help improve dissipation models.

Forensic collection of trace chemicals from diverse surfaces with strippable coatings.

Science.gov (United States)

Jakubowski, Michael J; Beltis, Kevin J; Drennan, Paul M; Pindzola, Bradford A

2013-11-07

Surface sampling for chemical analysis plays a vital role in environmental monitoring, industrial hygiene, homeland security and forensics. The standard surface sampling tool, a simple cotton gauze pad, is failing to meet the needs of the community as analytical techniques become more sensitive and the variety of analytes increases. In previous work, we demonstrated the efficacy of non-destructive, conformal, spray-on strippable coatings for chemical collection from simple glass surfaces. Here we expand that work by presenting chemical collection at a low spiking level (0.1 g m(-2)) from a diverse array of common surfaces - painted metal, engineering plastics, painted wallboard and concrete - using strippable coatings. The collection efficiency of the strippable coatings is compared to and far exceeds gauze pads. Collection from concrete, a particular challenge for wipes like gauze, averaged 73% over eight chemically diverse compounds for the strippable coatings whereas gauze averaged 10%.

Simple heterogeneity parametrization for sea surface temperature and chlorophyll

Science.gov (United States)

Skákala, Jozef; Smyth, Timothy J.

2016-06-01

Using satellite maps this paper offers a complex analysis of chlorophyll & SST heterogeneity in the shelf seas around the southwest of the UK. The heterogeneity scaling follows a simple power law and is consequently parametrized by two parameters. It is shown that in most cases these two parameters vary only relatively little with time. The paper offers a detailed comparison of field heterogeneity between different regions. How much heterogeneity is in each region preserved in the annual median data is also determined. The paper explicitly demonstrates how one can use these results to calculate representative measurement area for in situ networks.

Liquid-solid interface project in nuclear engineering. Systematization of sorption theory in heterogeneous surface and it's application to radioactive waste disposal. JAERI's nuclear research promotion program, H10-032. Contract research

Energy Technology Data Exchange (ETDEWEB)

Tanaka, Satoru [Tokyo Univ., Graduate School of Engineering, Tokyo (Japan)

2002-03-01

Combining of the In-Situ and Ex-situ experiments with quantum chemical calculation, we can draw the following conclusions on the sorption at heterogeneous interfaces, based on the structure of solid surfaces and the profile of charge/electron at surface: (1) Redox sensitive species Np(V) is reduced to Np(IV) by Fe(II) contained in iron oxides. (2) Interactions of ions with C-S-H gels, which is a main component of cementitious materials, consist of replacement of Ca, association with Si and ion exchange. (3) Iodate ions adsorb on the two kinds of sorption sites located on the outer surface of hydrotalcite. (4) Interaction potential between particles and solid surfaces decrease due to the microscopic roughness of solid surface and localized distribution of charge on the surface, leading to the increase in the deposition of particles. (5) Some information on the association situation of water molecules on the metal oxides are obtained. These results suggests that the microscopic heterogeneity of solid surfaces facilities the interaction of ions and particles with solid surfaces. These phenomena can not be explained by the conventional sorption theory. We have to develop the sorption theory by considering the interactions from the microscopic point of view. (author)

The Effects of Realistic Geological Heterogeneity on Seismic Modeling: Applications in Shear Wave Generation and Near-Surface Tunnel Detection

Science.gov (United States)

Sherman, Christopher Scott

Naturally occurring geologic heterogeneity is an important, but often overlooked, aspect of seismic wave propagation. This dissertation presents a strategy for modeling the effects of heterogeneity using a combination of geostatistics and Finite Difference simulation. In the first chapter, I discuss my motivations for studying geologic heterogeneity and seis- mic wave propagation. Models based upon fractal statistics are powerful tools in geophysics for modeling heterogeneity. The important features of these fractal models are illustrated using borehole log data from an oil well and geomorphological observations from a site in Death Valley, California. A large part of the computational work presented in this disserta- tion was completed using the Finite Difference Code E3D. I discuss the Python-based user interface for E3D and the computational strategies for working with heterogeneous models developed over the course of this research. The second chapter explores a phenomenon observed for wave propagation in heteroge- neous media - the generation of unexpected shear wave phases in the near-source region. In spite of their popularity amongst seismic researchers, approximate methods for modeling wave propagation in these media, such as the Born and Rytov methods or Radiative Trans- fer Theory, are incapable of explaining these shear waves. This is primarily due to these method's assumptions regarding the coupling of near-source terms with the heterogeneities and mode conversion. To determine the source of these shear waves, I generate a suite of 3D synthetic heterogeneous fractal geologic models and use E3D to simulate the wave propaga- tion for a vertical point force on the surface of the models. I also present a methodology for calculating the effective source radiation patterns from the models. The numerical results show that, due to a combination of mode conversion and coupling with near-source hetero- geneity, shear wave energy on the order of 10% of the

Theoretical Studies in Heterogenous Catalysis: Towards a Rational Design of Novel Catalysts for Hydrodesulfurization and Hydrogen Production

Energy Technology Data Exchange (ETDEWEB)

Rodriguez,J.A.; Liu, P.

2008-10-01

Traditionally, knowledge in heterogeneous catalysis has come through empirical research. Nowadays, there is a clear interest to change this since millions of dollars in products are generated every year in the chemical and petrochemical industries through catalytic processes. To obtain a fundamental knowledge of the factors that determine the activity of heterogeneous catalysts is a challenge for modern science since many of these systems are very complex in nature. In principle, when a molecule adsorbs on the surface of a heterogeneous catalyst, it can interact with a large number of bonding sites. It is known that the chemical properties of these bonding sites depend strongly on the chemical environment around them. Thus, there can be big variations in chemical reactivity when going from one region to another in the surface of a heterogeneous catalyst. A main objective is to understand how the structural and electronic properties of a surface affect the energetics for adsorption processes and the paths for dissociation and chemical reactions. In recent years, advances in instrumentation and experimental procedures have allowed a large series of detailed works on the surface chemistry of heterogeneous catalysts. In many cases, these experimental studies have shown interesting and unique phenomena. Theory is needed to unravel the basic interactions behind these phenomena and to provide a general framework for the interpretation of experimental results. Ideally, theoretical calculations based on density-functional theory have evolved to the point that one should be able to predict patterns in the activity of catalytic surfaces. As in the case of experimental techniques, no single theoretical approach is able to address the large diversity of phenomena occurring on a catalyst. Catalytic surfaces are usually modeled using either a finite cluster or a two-dimensionally periodic slab. Many articles have been published comparing the results of these two approaches. An

Influence of surface coverage on the chemical desorption process

Energy Technology Data Exchange (ETDEWEB)

Minissale, M.; Dulieu, F., E-mail: francois.dulieu@obspm.fr [LERMA, Université de Cergy Pontoise et Observatoire de Paris, UMR 8112 du CNRS. 5, mail Gay Lussac, 95031 Cergy Pontoise (France)

2014-07-07

In cold astrophysical environments, some molecules are observed in the gas phase whereas they should have been depleted, frozen on dust grains. In order to solve this problem, astrochemists have proposed that a fraction of molecules synthesized on the surface of dust grains could desorb just after their formation. Recently the chemical desorption process has been demonstrated experimentally, but the key parameters at play have not yet been fully understood. In this article, we propose a new procedure to analyze the ratio of di-oxygen and ozone synthesized after O atoms adsorption on oxidized graphite. We demonstrate that the chemical desorption efficiency of the two reaction paths (O+O and O+O{sub 2}) is different by one order of magnitude. We show the importance of the surface coverage: for the O+O reaction, the chemical desorption efficiency is close to 80% at zero coverage and tends to zero at one monolayer coverage. The coverage dependence of O+O chemical desorption is proved by varying the amount of pre-adsorbed N{sub 2} on the substrate from 0 to 1.5 ML. Finally, we discuss the relevance of the different physical parameters that could play a role in the chemical desorption process: binding energy, enthalpy of formation, and energy transfer from the new molecule to the surface or to other adsorbates.

Chemical Reactions at Surfaces. Final Progress Report

Energy Technology Data Exchange (ETDEWEB)

Freud, Hans-Joachim [Max-Planck-Gesellschaft, Berlin (Germany). Fritz-Haber-Inst.

2003-02-21

The Gordon Research Conference (GRC) on Chemical Reactions at Surfaces was held at Holiday Inn, Ventura, California, 2/16-21/03. Emphasis was placed on current unpublished research and discussion of the future target areas in this field.

Next-Generation Catalysis for Renewables: Combining Enzymatic with Inorganic Heterogeneous Catalysis for Bulk Chemical Production

DEFF Research Database (Denmark)

Vennestrøm, Peter Nicolai Ravnborg; Christensen, C.H.; Pedersen, S.

2010-01-01

chemical platform under different conditions than those conventionally employed. Indeed, new process and catalyst concepts need to be established. Both enzymatic catalysis (biocatalysis) and heterogeneous inorganic catalysis are likely to play a major role and, potentially, be combined. One type...... of combination involves one-pot cascade catalysis with active sites from bio- and inorganic catalysts. In this article the emphasis is placed specifically on oxidase systems involving the coproduction of hydrogen peroxide, which can be used to create new in situ collaborative oxidation reactions for bulk...

Reactive solute transport in physically and chemically heterogeneous porous media with multimodal reactive mineral facies: the Lagrangian approach.

Science.gov (United States)

Soltanian, Mohamad Reza; Ritzi, Robert W; Dai, Zhenxue; Huang, Chao Cheng

2015-03-01

Physical and chemical heterogeneities have a large impact on reactive transport in porous media. Examples of heterogeneous attributes affecting reactive mass transport are the hydraulic conductivity (K), and the equilibrium sorption distribution coefficient (Kd). This paper uses the Deng et al. (2013) conceptual model for multimodal reactive mineral facies and a Lagrangian-based stochastic theory in order to analyze the reactive solute dispersion in three-dimensional anisotropic heterogeneous porous media with hierarchical organization of reactive minerals. An example based on real field data is used to illustrate the time evolution trends of reactive solute dispersion. The results show that the correlation between the hydraulic conductivity and the equilibrium sorption distribution coefficient does have a significant effect on reactive solute dispersion. The anisotropy ratio does not have a significant effect on reactive solute dispersion. Furthermore, through a sensitivity analysis we investigate the impact of changing the mean, variance, and integral scale of K and Kd on reactive solute dispersion. Copyright © 2014 Elsevier Ltd. All rights reserved.

Engineering Microbial Metabolite Dynamics and Heterogeneity.

Science.gov (United States)

Schmitz, Alexander C; Hartline, Christopher J; Zhang, Fuzhong

2017-10-01

As yields for biological chemical production in microorganisms approach their theoretical maximum, metabolic engineering requires new tools, and approaches for improvements beyond what traditional strategies can achieve. Engineering metabolite dynamics and metabolite heterogeneity is necessary to achieve further improvements in product titers, productivities, and yields. Metabolite dynamics, the ensemble change in metabolite concentration over time, arise from the need for microbes to adapt their metabolism in response to the extracellular environment and are important for controlling growth and productivity in industrial fermentations. Metabolite heterogeneity, the cell-to-cell variation in a metabolite concentration in an isoclonal population, has a significant impact on ensemble productivity. Recent advances in single cell analysis enable a more complete understanding of the processes driving metabolite heterogeneity and reveal metabolic engineering targets. The authors present an overview of the mechanistic origins of metabolite dynamics and heterogeneity, why they are important, their potential effects in chemical production processes, and tools and strategies for engineering metabolite dynamics and heterogeneity. The authors emphasize that the ability to control metabolite dynamics and heterogeneity will bring new avenues of engineering to increase productivity of microbial strains. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaporation of liquids on chemically patterned surfaces

NARCIS (Netherlands)

Vieyra Salas, J.A.; Darhuber, A.A.

2011-01-01

We studied evaporation rates of volatile liquids deposited onto chemically patterned surfaces by means of experiments and numerical simulations. We quantified the influence of the droplet geometry, in particular circular, triangular, rectangular and square shapes, as well as the influence of contact

Application of surface plasmons to biological and chemical sensors

International Nuclear Information System (INIS)

Kajikawa, Kotaro

2015-01-01

Surface plasmons (SPs) are a collective normal mode of electrons localized at a metallic surface. It has been used for biological sensors since 1990s. This is because it has the following specific characters: (a) The resonance condition is sensitive to the surrounding dielectric constants (refractive indexes) and (b) Highly enhanced optical-electric-fields are produced adjacent to SPs. A brief introduction is given on the principle of the biological and chemical sensors based on SPs for the readers working in the fields other than SPs, followed by a review on the recent developments of the biological and chemical sensors. (author)

Probabilistic human health risk assessment of degradation-related chemical mixtures in heterogeneous aquifers: Risk statistics, hot spots, and preferential channels

Science.gov (United States)

Henri, Christopher V.; Fernàndez-Garcia, Daniel; de Barros, Felipe P. J.

2015-06-01

The increasing presence of toxic chemicals released in the subsurface has led to a rapid growth of social concerns and the need to develop and employ models that can predict the impact of groundwater contamination on human health risk under uncertainty. Monitored natural attenuation is a common remediation action in many contamination cases. However, natural attenuation can lead to the production of daughter species of distinct toxicity that may pose challenges in pollution management strategies. The actual threat that these contaminants pose to human health depends on the interplay between the complex structure of the geological media and the toxicity of each pollutant byproduct. This work addresses human health risk for chemical mixtures resulting from the sequential degradation of a contaminant (such as a chlorinated solvent) under uncertainty through high-resolution three-dimensional numerical simulations. We systematically investigate the interaction between aquifer heterogeneity, flow connectivity, contaminant injection model, and chemical toxicity in the probabilistic characterization of health risk. We illustrate how chemical-specific travel times control the regime of the expected risk and its corresponding uncertainties. Results indicate conditions where preferential flow paths can favor the reduction of the overall risk of the chemical mixture. The overall human risk response to aquifer connectivity is shown to be nontrivial for multispecies transport. This nontriviality is a result of the interaction between aquifer heterogeneity and chemical toxicity. To quantify the joint effect of connectivity and toxicity in health risk, we propose a toxicity-based Damköhler number. Furthermore, we provide a statistical characterization in terms of low-order moments and the probability density function of the individual and total risks.

Enhancement of Bacterial Transport in Aerobic and Anaerobic Environments: Assessing the Effect of Metal Oxide Chemical Heterogeneities

International Nuclear Information System (INIS)

T.C. Onstott

2005-01-01

The goal of our research was to understand the fundamental processes that control microbial transport in physically and chemically heterogeneous aquifers and from this enhanced understanding determine the requirements for successful, field-scale delivery of microorganisms to metal contaminated subsurface sites. Our specific research goals were to determine; (1) the circumstances under which the preferential adsorption of bacteria to Fe, Mn, and Al oxyhydroxides influences field-scale bacterial transport, (2) the extent to which the adhesion properties of bacterial cells affect field-scale bacterial transport, (3) whether microbial Fe(III) reduction can enhance field-scale transport of Fe reducing bacteria (IRB) and other microorganisms and (4) the effect of field-scale physical and chemical heterogeneity on all three processes. Some of the spin-offs from this basic research that can improve biostimulation and bioaugmentation remediation efforts at contaminated DOE sites have included; (1) new bacterial tracking tools for viable bacteria; (2) an integrated protocol which combines subsurface characterization, laboratory-scale experimentation, and scale-up techniques to accurately predict field-scale bacterial transport; and (3) innovative and inexpensive field equipment and methods that can be employed to enhance Fe(III) reduction and microbial transport and to target microbial deposition under both aerobic and anaerobic conditions

Chemical bonding of water to metal surfaces studied with core-level spectroscopies

DEFF Research Database (Denmark)

Schiros, T.; Andersson, Klas Jerker; Pettersson, L.G.M.

2010-01-01

The nature of the contact layer of water on surfaces is of relevance for many practical fields, including corrosion, electrochemistry, environmental science and heterogeneous catalysis. Here we focus on the geometric and electronic structure of the water contact layer on transition metal surfaces......-specific information on the partial local density of states, local atomic structure, geometrical parameters and molecular orientation, allowing general principles for water-metal interaction to be derived....

Features of the kinetics of heterogeneous reactions with phase transformations on catalyst surfaces

Energy Technology Data Exchange (ETDEWEB)

Berman, A D; Krylov, O V

1978-01-01

This paper presents a review of 41 bibliographic references to experiments on the adsorption of various gases (e.g., carbon monoxide, formic acid, ammonia, and oxygen) on metals (e.g., nickel, molybdenum, and platinum) and oxides covers observations of two-dimensional phases during adsorption; the kinetics of adsorption and catalysis associated with two-dimensional phase transitions; and several approximate models for describing the kinetics of heterogeneous catalysis which account for two-dimensional phase transformations on catalyst surfaces.

The heterogeneity and spatial patterning of structure and physiology across the leaf surface in giant leaves of Alocasia macrorrhiza.

Directory of Open Access Journals (Sweden)

Shuai Li

Full Text Available Leaf physiology determines the carbon acquisition of the whole plant, but there can be considerable variation in physiology and carbon acquisition within individual leaves. Alocasia macrorrhiza (L. Schott is an herbaceous species that can develop very large leaves of up to 1 m in length. However, little is known about the hydraulic and photosynthetic design of such giant leaves. Based on previous studies of smaller leaves, and on the greater surface area for trait variation in large leaves, we hypothesized that A. macrorrhiza leaves would exhibit significant heterogeneity in structure and function. We found evidence of reduced hydraulic supply and demand in the outer leaf regions; leaf mass per area, chlorophyll concentration, and guard cell length decreased, as did stomatal conductance, net photosynthetic rate and quantum efficiency of photosystem II. This heterogeneity in physiology was opposite to that expected from a thinner boundary layer at the leaf edge, which would have led to greater rates of gas exchange. Leaf temperature was 8.8°C higher in the outer than in the central region in the afternoon, consistent with reduced stomatal conductance and transpiration caused by a hydraulic limitation to the outer lamina. The reduced stomatal conductance in the outer regions would explain the observed homogeneous distribution of leaf water potential across the leaf surface. These findings indicate substantial heterogeneity in gas exchange across the leaf surface in large leaves, greater than that reported for smaller-leafed species, though the observed structural differences across the lamina were within the range reported for smaller-leafed species. Future work will determine whether the challenge of transporting water to the outer regions can limit leaf size for plants experiencing drought, and whether the heterogeneity of function across the leaf surface represents a particular disadvantage for large simple leaves that might explain their

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

International Nuclear Information System (INIS)

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

2005-01-01

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

Stability and dynamics of reactors with heterogeneously catalyzed reactions

Energy Technology Data Exchange (ETDEWEB)

Eigenberger, G [BASF A.G., Ludwigshafen am Rhein (Germany, F.R.)

1978-12-01

Our knowledge of causes and consequences of problems arising from instability and dynamic effects in reactors with heterogeneously catalyzed reactions has increased remarkably in recent years. Especially thermal effects, caused by the self-acceleration of an exothermic reaction in combination with heat and mass transport, are now well understood. In addition, kinetic effects, i.e. phenomena which have to be explained by the kinetic peculiarities of surface reactions, have attracted increasing interest. For both cases the state of the art will be reviewed, highlighting the physical and chemical causes of the observed phenomena.

Heterogeneous free-surface profile of B4C polycrystal under shock compression

International Nuclear Information System (INIS)

Mashimo, T.; Uchino, M.

1997-01-01

Observations of the free-surface behavior under shock compression by the gapped-flat mirror method were performed on B 4 C and Si 3 N 4 ceramics to study their shock-yielding properties. Jagged profiles of the moving free-surface in the plastic region, with a special scale of about one mm and a maximum local displacement of a few 10s of μm, were observed for B 4 C polycrystals. Similar profiles for Si 3 N 4 polycrystals were smooth. Such profiles for B 4 C polycrystals were also observed in the elastic region. It is suggested that these observations reflect the heterogeneous nature of shock compression in solids, and further indicate that a macroscopic slip system plays an important role in the elastoplastic transition of B 4 C material under shock compression and decompression. copyright 1997 American Institute of Physics

Molecular-Level Design of Heterogeneous Chiral Catalysis

International Nuclear Information System (INIS)

Zaera, Francisco

2012-01-01

, and the development of ways to imprint chiral centers on achiral solid surfaces. Chiral catalysis is not only a problem of great importance in its own right, but also the ultimate test of how to control selectivity in catalysis. The time is ripe for fundamental work in heterogeneous chiral catalysis to provide the U.S. with a leadership role in developing the next generation of catalytic processes for medicinal and agrochemical manufacturing. Our team provides the required expertise for a synergistic and comprehensive integration of physical and chemical experimentation with solid state and molecular reactivity theories to solve this problem.

Topological surface states of Bi{sub 2}Te{sub 2}Se are robust against surface chemical modification

Energy Technology Data Exchange (ETDEWEB)

Thomas, Conor R.; Sahasrabudhe, Girija; Kushwaha, Satya Kumar; Cava, Robert J.; Schwartz, Jeffrey [Department of Chemistry, Princeton University, Princeton, NJ (United States); Xiong, Jun [Department of Physics, Princeton University, Princeton, NJ (United States)

2014-12-01

The robustness of the Dirac-like electronic states on the surfaces of topological insulators (TIs) during materials process-ing is a prerequisite for their eventual device application. Here, the (001) cleavage surfaces of crystals of the topological insulator Bi{sub 2}Te{sub 2}Se (BTS) were subjected to several surface chemical modification procedures that are common for electronic materials. Through measurement of Shubnikov-de Hass (SdH) oscillations, which are the most sensitive measure of their quality, the surface states of the treated surfaces were compared to those of pristine BTS that had been exposed to ambient conditions. In each case - surface oxidation, deposition of thin layers of Ti or Zr oxides, or chemical modification of the surface oxides - the robustness of the topological surface electronic states was demonstrated by noting only very small changes in the frequency and amplitude of the SdH oscillations. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Design of a surface alloy catalyst for steam reforming

DEFF Research Database (Denmark)

Besenbacher, F.; Chorkendorff, Ib; Clausen, B.S.

1998-01-01

Detailed studies of elementary chemical processes on well-characterized single crystal surfaces have contributed substantially to the understanding of heterogeneous catalysis. insight into the structure of surface alloys combined with an understanding of the relation between the surface compositi...... and reactivity is shown to lead directly to new ideas for catalyst design, The feasibility of such an approach is illustrated by the synthesis, characterization, and tests of a high-surface area gold-nickel catalyst for steam reforming....

Plasma-assisted heterogeneous catalysis for NOx reduction in lean-burn engine exhaust

Energy Technology Data Exchange (ETDEWEB)

Penetrante, B.M.; Hsaio, M.C.; Merritt, B.T.; Vogtlin, G.E. [Lawrence Livermore National Lab., CA (United States); Wan, C.Z.; Rice, G.W.; Voss, K.E. [Engelhard Corp., Iselin, NJ (United States)

1997-12-31

This paper discusses the combination of a plasma with a catalyst to improve the reduction of NO{sub x} under lean-burn conditions. The authors have been investigating the effects of a plasma on the NO{sub x} reduction activity and temperature operating window of various catalytic materials. One of the goals is to develop a fundamental understanding of the interaction between the gas-phase plasma chemistry and the heterogeneous chemistry on the catalyst surface. The authors have observed that plasma assisted heterogeneous catalysis can facilitate NO{sub x} reduction under conditions that normally make it difficult for either the plasma or the catalyst to function by itself. By systematically varying the plasma electrode and catalyst configuration, they have been able to elucidate the process by which the plasma chemistry affects the chemical reduction of NO{sub x} on the catalyst surface. They have discovered that the main effect of the plasma is to induce the gas-phase oxidation of NO to NO{sub 21}. The reduction of NO{sub x} to N{sub 2} is then accomplished by heterogeneous reaction of O with activated hydrocarbons on the catalyst surface. The use of a plasma opens the opportunity for a new class of catalysts that are potentially more durable, more active, more selective and more sulfur-tolerant compared to conventional lean-NO{sub x} catalysts.

Airborne-Measured Spatially-Averaged Temperature and Moisture Turbulent Structure Parameters Over a Heterogeneous Surface

Science.gov (United States)

Platis, Andreas; Martinez, Daniel; Bange, Jens

2014-05-01

Turbulent structure parameters of temperature and humidity can be derived from scintillometer measurements along horizontal paths of several 100 m to several 10 km. These parameters can be very useful to estimate the vertical turbulent heat fluxes at the surface (applying MOST). However, there are many assumptions required by this method which can be checked using in situ data, e.g. 1) Were CT2 and CQ2 correctly derived from the initial CN2 scintillometer data (structure parameter of density fluctuations or refraction index, respectively)? 2) What is the influence of the surround hetereogeneous surface regarding its footprint and the weighted averaging effect of the scintillometer method 3) Does MOST provide the correct turbulent fluxes from scintillometer data. To check these issues, in situ data from low-level flight measurements are well suited, since research aircraft cover horizontal distances in very short time (Taylor's hypothesis of a frozen turbulence structure can be applyed very likely). From airborne-measured time series the spatial series are calculated and then their structure functions that finally provide the structure parameters. The influence of the heterogeneous surface can be controlled by the definition of certain moving-average window sizes. A very useful instrument for this task are UAVs since they can fly very low and maintain altitude very precisely. However, the data base of such unmanned operations is still quite thin. So in this contribution we want to present turbulence data obtained with the Helipod, a turbulence probe hanging below a manned helicopter. The structure parameters of temperature and moisture, CT2 and CQ2, in the lower convective boundary layer were derived from data measured using the Helipod in 2003. The measurements were carried out during the LITFASS03 campaign over a heterogeneous land surface around the boundary-layer field site of the Lindenberg Meteorological Observatory-Richard-Aßmann-Observatory (MOL) of the

Sequence heterogeneity accelerates protein search for targets on DNA

International Nuclear Information System (INIS)

Shvets, Alexey A.; Kolomeisky, Anatoly B.

2015-01-01

The process of protein search for specific binding sites on DNA is fundamentally important since it marks the beginning of all major biological processes. We present a theoretical investigation that probes the role of DNA sequence symmetry, heterogeneity, and chemical composition in the protein search dynamics. Using a discrete-state stochastic approach with a first-passage events analysis, which takes into account the most relevant physical-chemical processes, a full analytical description of the search dynamics is obtained. It is found that, contrary to existing views, the protein search is generally faster on DNA with more heterogeneous sequences. In addition, the search dynamics might be affected by the chemical composition near the target site. The physical origins of these phenomena are discussed. Our results suggest that biological processes might be effectively regulated by modifying chemical composition, symmetry, and heterogeneity of a genome

Sequence heterogeneity accelerates protein search for targets on DNA

Energy Technology Data Exchange (ETDEWEB)

Shvets, Alexey A.; Kolomeisky, Anatoly B., E-mail: tolya@rice.edu [Department of Chemistry and Center for Theoretical Biological Physics, Rice University, Houston, Texas 77005 (United States)

2015-12-28

The process of protein search for specific binding sites on DNA is fundamentally important since it marks the beginning of all major biological processes. We present a theoretical investigation that probes the role of DNA sequence symmetry, heterogeneity, and chemical composition in the protein search dynamics. Using a discrete-state stochastic approach with a first-passage events analysis, which takes into account the most relevant physical-chemical processes, a full analytical description of the search dynamics is obtained. It is found that, contrary to existing views, the protein search is generally faster on DNA with more heterogeneous sequences. In addition, the search dynamics might be affected by the chemical composition near the target site. The physical origins of these phenomena are discussed. Our results suggest that biological processes might be effectively regulated by modifying chemical composition, symmetry, and heterogeneity of a genome.

Surface characteristics of bioactive Ti fabricated by chemical treatment for cartilaginous-integration.

Science.gov (United States)

Miyajima, Hiroyuki; Ozer, Fusun; Imazato, Satoshi; Mante, Francis K

2017-09-01

Artificial hip joints are generally expected to fail due to wear after approximately 15years and then have to be replaced by revision surgery. If articular cartilage can be integrated onto the articular surfaces of artificial joints in the same way as osseo-integration of titanium dental implants, the wear of joint implants may be reduced or prevented. However, very few studies have focused on the relationship between Ti surface and cartilage. To explore the possibility of cartilaginous-integration, we fabricated chemically treated Ti surfaces with H 2 O 2 /HCl, collagen type II and SBF, respectively. Then, we evaluated surface characteristics of the prepared Ti samples and assessed the cartilage formation by culturing chondrocytes on the Ti samples. When oxidized Ti was immersed in SBF for 7days, apatite was formed on the Ti surface. The surface characteristics of Ti indicated that the wettability was increased by all chemical treatments compared to untreated Ti, and that H 2 O 2 /HCl treated surface had significantly higher roughness compared to the other three groups. Chondrocytes produced significantly more cartilage matrix on all chemically treated Ti surfaces compared to untreated Ti. Thus, to realize cartilaginous-integration and to prevent wear of the implants in joints, application of bioactive Ti formed by chemical treatment would be a promising and effective strategy to improve durability of joint replacement. Copyright © 2017 Elsevier B.V. All rights reserved.

Surface chemical and photocatalytic consequences of Ca-doping of BiFeO{sub 3} as probed by XPS and H{sub 2}O{sub 2} decomposition studies

Energy Technology Data Exchange (ETDEWEB)

Zaki, Mohamed I., E-mail: mizaki@link.net [Chemistry Department, Faculty of Science, Minia University, El-Minia 61519 (Egypt); Ramadan, Wegdan [Physics Department, Faculty of Science, Alexandria University, Alexandria 21511 (Egypt); Katrib, Ali [Chemistry Department, Faculty of Science, Kuwait University, P.O. Box 5969, Safat 13060 (Kuwait); Rabee, Abdallah I.M. [Chemistry Department, Faculty of Science, Minia University, El-Minia 61519 (Egypt)

2014-10-30

Graphical abstract: - Highlights: • BiFeO{sub 3} is a modest visible-light heterogeneous photocatalyst for H{sub 2}O{sub 2} decomposition. • The ferrite activity is promoted with Ca-doping up to 10 wt%-Ca. • Favourable consequences are enhanced surface metal redoxability and oxide basicity. • Furthering doping to >10 wt%-Ca retrogresses the ferrite photocatalytic activity. • A retrogressive doping consequence is bulk phase separation of α(γ)-Fe{sub 2}O{sub 3}. - Abstract: Pure and Ca-doped Bi{sub 1−x}Ca{sub x}FeO{sub 3} samples were prepared with x = 0.0–0.2, adopting a sol–gel method. Previously reported studies performed on similarly composed and prepared samples revealed that Ca-doping, above solubility limit (namely at ≥10%-Ca), results in phase separation and formation of BiFeO{sub 3}/α(γ)-Fe{sub 2}O{sub 3} nanocomposite particles. Hetero p/n nanojunctions thus established were considered to help separating photo-generated electron–hole pairs and, therefore, explain consequent promotion of photo-Fenton catalytic activity of BiFeO{sub 3} towards methylene blue degradation in presence of H{sub 2}O{sub 2} additive. However, the encompassed decomposition of H{sub 2}O{sub 2} was not addressed. To bridge this gap of knowledge, the present investigation was designed to assess Ca-doping-effected surface chemical modifications and gauge its impact on the heterogeneous photo-/thermo-catalytic activity of BiFeO{sub 3} towards H{sub 2}O{sub 2} decomposition, by means of X-ray photoelectron spectroscopy (XPS) and H{sub 2}O{sub 2} decomposition gravimetry. XPS results revealed generation of high binding energy Bi 4f and Fe 2p states, as well as enhancement of the surface basicity, upon doping to 10%-Ca. These surface chemical consequences are rendered hardly detectable upon further increase of the dopant magnitude to 20%-Ca. In parallel, the H{sub 2}O{sub 2} decomposition activity of the ferrite, under natural visible light, is enhanced to optimize

Surface Acoustic Wave (SAW-Enhanced Chemical Functionalization of Gold Films

Directory of Open Access Journals (Sweden)

Gina Greco

2017-10-01

Full Text Available Surface chemical and biochemical functionalization is a fundamental process that is widely applied in many fields to add new functions, features, or capabilities to a material’s surface. Here, we demonstrate that surface acoustic waves (SAWs can enhance the chemical functionalization of gold films. This is shown by using an integrated biochip composed by a microfluidic channel coupled to a surface plasmon resonance (SPR readout system and by monitoring the adhesion of biotin-thiol on the gold SPR areas in different conditions. In the case of SAW-induced streaming, the functionalization efficiency is improved ≈ 5 times with respect to the case without SAWs. The technology here proposed can be easily applied to a wide variety of biological systems (e.g., proteins, nucleic acids and devices (e.g., sensors, devices for cell cultures.

Spatially Resolved Quantification of the Surface Reactivity of Solid Catalysts.

Science.gov (United States)

Huang, Bing; Xiao, Li; Lu, Juntao; Zhuang, Lin

2016-05-17

A new property is reported that accurately quantifies and spatially describes the chemical reactivity of solid surfaces. The core idea is to create a reactivity weight function peaking at the Fermi level, thereby determining a weighted summation of the density of states of a solid surface. When such a weight function is defined as the derivative of the Fermi-Dirac distribution function at a certain non-zero temperature, the resulting property is the finite-temperature chemical softness, termed Fermi softness (SF ), which turns out to be an accurate descriptor of the surface reactivity. The spatial image of SF maps the reactive domain of a heterogeneous surface and even portrays morphological details of the reactive sites. SF analyses reveal that the reactive zones on a Pt3 Y(111) surface are the platinum sites rather than the seemingly active yttrium sites, and the reactivity of the S-dimer edge of MoS2 is spatially anisotropic. Our finding is of fundamental and technological significance to heterogeneous catalysis and industrial processes demanding rational design of solid catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A coupling alternative to reactive transport simulations for long-term prediction of chemical reactions in heterogeneous CO2 storage systems

Directory of Open Access Journals (Sweden)

M. De Lucia

2015-02-01

Full Text Available Fully coupled, multi-phase reactive transport simulations of CO2 storage systems can be approximated by a simplified one-way coupling of hydrodynamics and reactive chemistry. The main characteristics of such systems, and hypotheses underlying the proposed alternative coupling, are (i that the presence of CO2 is the only driving force for chemical reactions and (ii that its migration in the reservoir is only marginally affected by immobilisation due to chemical reactions. In the simplified coupling, the exposure time to CO2 of each element of the hydrodynamic grid is estimated by non-reactive simulations and the reaction path of one single batch geochemical model is applied to each grid element during its exposure time. In heterogeneous settings, analytical scaling relationships provide the dependency of velocity and amount of reactions to porosity and gas saturation. The analysis of TOUGHREACT fully coupled reactive transport simulations of CO2 injection in saline aquifer, inspired to the Ketzin pilot site (Germany, both in homogeneous and heterogeneous settings, confirms that the reaction paths predicted by fully coupled simulations in every element of the grid show a high degree of self-similarity. A threshold value for the minimum concentration of dissolved CO2 considered chemically active is shown to mitigate the effects of the discrepancy between dissolved CO2 migration in non-reactive and fully coupled simulations. In real life, the optimal threshold value is unknown and has to be estimated, e.g. by means of 1-D or 2-D simulations, resulting in an uncertainty ultimately due to the process de-coupling. However, such uncertainty is more than acceptable given that the alternative coupling enables using grids of the order of millions of elements, profiting from much better description of heterogeneous reservoirs at a fraction of the calculation time of fully coupled models.

Experimental study on soluble chemical transfer to surface runoff from soil.

Science.gov (United States)

Tong, Juxiu; Yang, Jinzhong; Hu, Bill X; Sun, Huaiwei

2016-10-01

Prevention of chemical transfer from soil to surface runoff, under condition of irrigation and subsurface drainage, would improve surface water quality. In this paper, a series of laboratory experiments were conducted to assess the effects of various soil and hydraulic factors on chemical transfer from soil to surface runoff. The factors include maximum depth of ponding water on soil surface, initial volumetric water content of soil, depth of soil with low porosity, type or texture of soil and condition of drainage. In the experiments, two soils, sand and loam, mixed with different quantities of soluble KCl were filled in the sandboxes and prepared under different initial saturated conditions. Simulated rainfall induced surface runoff are operated in the soils, and various ponding water depths on soil surface are simulated. Flow rates and KCl concentration of surface runoff are measured during the experiments. The following conclusions are made from the study results: (1) KCl concentration in surface runoff water would decrease with the increase of the maximum depth of ponding water on soil surface; (2) KCl concentration in surface runoff water would increase with the increase of initial volumetric water content in the soil; (3) smaller depth of soil with less porosity or deeper depth of soil with larger porosity leads to less KCl transfer to surface runoff; (4) the soil with finer texture, such as loam, could keep more fertilizer in soil, which will result in more KCl concentration in surface runoff; and (5) good subsurface drainage condition will increase the infiltration and drainage rates during rainfall event and will decrease KCl concentration in surface runoff. Therefore, it is necessary to reuse drained fertile water effectively during rainfall, without polluting groundwater. These study results should be considered in agriculture management to reduce soluble chemical transfer from soil to surface runoff for reducing non-point sources pollution.

Laser and chemical surface modifications of titanium grade 2 for medical application

Energy Technology Data Exchange (ETDEWEB)

Kwaśniak, P. [Faculty of Materials Science and Engineering, Warsaw University of Technology, Warsaw (Poland); Pura, J., E-mail: jaroslawpura@gmail.com [Faculty of Materials Science and Engineering, Warsaw University of Technology, Warsaw (Poland); Zwolińska, M.; Wieciński, P. [Faculty of Materials Science and Engineering, Warsaw University of Technology, Warsaw (Poland); Skarżyński, H.; Olszewski, L. [Institute of Physiology and Pathology of Hearing, Warsaw (Poland); World Hearing Center, Kajetany (Poland); Marczak, J. [Military University of Technology, Institute of Optoelectronics, Warsaw (Poland); Garbacz, H.; Kurzydłowski, K.J. [Faculty of Materials Science and Engineering, Warsaw University of Technology, Warsaw (Poland)

2015-05-01

Highlights: • DLIL technique and etching were used for functionalization of Ti grade 2 surface. • Modification was performed on semi-finished flat and curved Ti surfaces. • Modification results in periodic multimodal (micro and nano-size) Ti topography. - Abstract: The article presents combined, chemical and physical approach to titanium surface functionalization designed for biomedical applications. The topography modification has been obtained by employing the double laser beam interference technique and chemical etching. In the outcome, clean and smooth Ti surface as well as periodic striated topography with the roughness range from nano- to micrometers were created. The obtained structures were characterized in terms of shape, roughness, chemical composition, mechanical properties and microstructures. In order to achieve all information, numerous of research methods have been used: scanning electron microscopy, atomic force microscopy, optical profilometry and microhardness measurements. Demonstrated methodology can be used as an effective tool for manufacturing controlled surface structures improving the bone–implants interactions.

Mechanistic insights into heterogeneous methane activation

International Nuclear Information System (INIS)

Latimer, Allegra A.; Aljama, Hassan; Kakekhani, Arvin; Yoo, Jong Suk; Kulkarni, Ambarish

2017-01-01

While natural gas is an abundant chemical fuel, its low volumetric energy density has prompted a search for catalysts able to transform methane into more useful chemicals. This search has often been aided through the use of transition state (TS) scaling relationships, which estimate methane activation TS energies as a linear function of a more easily calculated descriptor, such as final state energy, thus avoiding tedious TS energy calculations. It has been shown that methane can be activated via a radical or surface-stabilized pathway, both of which possess a unique TS scaling relationship. Herein, we present a simple model to aid in the prediction of methane activation barriers on heterogeneous catalysts. Analogous to the universal radical TS scaling relationship introduced in a previous publication, we show that a universal TS scaling relationship that transcends catalysts classes also seems to exist for surface-stabilized methane activation if the relevant final state energy is used. We demonstrate that this scaling relationship holds for several reducible and irreducible oxides, promoted metals, and sulfides. By combining the universal scaling relationships for both radical and surface-stabilized methane activation pathways, we show that catalyst reactivity must be considered in addition to catalyst geometry to obtain an accurate estimation for the TS energy. Here, this model can yield fast and accurate predictions of methane activation barriers on a wide range of catalysts, thus accelerating the discovery of more active catalysts for methane conversion.

Atomic force microscopy characterization of the surface wettability of natural fibres

International Nuclear Information System (INIS)

Pietak, Alexis; Korte, Sandra; Tan, Emelyn; Downard, Alison; Staiger, Mark P.

2007-01-01

Natural fibres represent a readily available source of ecologically friendly and inexpensive reinforcement in composites with degradable thermoplastics, however chemical treatments of fibres are required to prepare feasible composites. It is desirable to characterize the surface wettability of fibres after chemical treatment as the polarity of cellulose-based fibres influences compatibility with a polymer matrix. Assessment of the surface wettability of natural fibres using conventional methods presents a challenge as the surfaces are morphologically and chemically heterogeneous, rough, and can be strongly wicking. In this work it is shown that under atmospheric conditions the adhesion force between an atomic force microscopy (AFM) tip and the fibre surface can estimate the water contact angle and surface wettability of the fibre. AFM adhesion force measurements are suitable for the more difficult surfaces of natural fibres and in addition allow for correlations between microstructural features and surface wettability characteristics

High-throughput heterogeneous catalyst research

Science.gov (United States)

Turner, Howard W.; Volpe, Anthony F., Jr.; Weinberg, W. H.

2009-06-01

With the discovery of abundant and low cost crude oil in the early 1900's came the need to create efficient conversion processes to produce low cost fuels and basic chemicals. Enormous investment over the last century has led to the development of a set of highly efficient catalytic processes which define the modern oil refinery and which produce most of the raw materials and fuels used in modern society. Process evolution and development has led to a refining infrastructure that is both dominated and enabled by modern heterogeneous catalyst technologies. Refineries and chemical manufacturers are currently under intense pressure to improve efficiency, adapt to increasingly disadvantaged feedstocks including biomass, lower their environmental footprint, and continue to deliver their products at low cost. This pressure creates a demand for new and more robust catalyst systems and processes that can accommodate them. Traditional methods of catalyst synthesis and testing are slow and inefficient, particularly in heterogeneous systems where the structure of the active sites is typically complex and the reaction mechanism is at best ill-defined. While theoretical modeling and a growing understanding of fundamental surface science help guide the chemist in designing and synthesizing targets, even in the most well understood areas of catalysis, the parameter space that one needs to explore experimentally is vast. The result is that the chemist using traditional methods must navigate a complex and unpredictable diversity space with a limited data set to make discoveries or to optimize known systems. We describe here a mature set of synthesis and screening technologies that together form a workflow that breaks this traditional paradigm and allows for rapid and efficient heterogeneous catalyst discovery and optimization. We exemplify the power of these new technologies by describing their use in the development and commercialization of a novel catalyst for the

Microbes and associated soluble and volatile chemicals on periodically wet household surfaces.

Science.gov (United States)

Adams, Rachel I; Lymperopoulou, Despoina S; Misztal, Pawel K; De Cassia Pessotti, Rita; Behie, Scott W; Tian, Yilin; Goldstein, Allen H; Lindow, Steven E; Nazaroff, William W; Taylor, John W; Traxler, Matt F; Bruns, Thomas D

2017-09-26

Microorganisms influence the chemical milieu of their environment, and chemical metabolites can affect ecological processes. In built environments, where people spend the majority of their time, very little is known about how surface-borne microorganisms influence the chemistry of the indoor spaces. Here, we applied multidisciplinary approaches to investigate aspects of chemical microbiology in a house. We characterized the microbial and chemical composition of two common and frequently wet surfaces in a residential setting: kitchen sink and bathroom shower. Microbial communities were studied using culture-dependent and independent techniques, including targeting RNA for amplicon sequencing. Volatile and soluble chemicals from paired samples were analyzed using state-of-the-art techniques to explore the links between the observed microbiota and chemical exudates. Microbial analysis revealed a rich biological presence on the surfaces exposed in kitchen sinks and bathroom shower stalls. Microbial composition, matched for DNA and RNA targets, varied by surface type and sampling period. Bacteria were found to have an average of 25× more gene copies than fungi. Biomass estimates based on qPCR were well correlated with measured total volatile organic compound (VOC) emissions. Abundant VOCs included products associated with fatty acid production. Molecular networking revealed a diversity of surface-borne compounds that likely originate from microbes and from household products. Microbes played a role in structuring the chemical profiles on and emitted from kitchen sinks and shower stalls. Microbial VOCs (mVOCs) were predominately associated with the processing of fatty acids. The mVOC composition may be more stable than that of microbial communities, which can show temporal and spatial variation in their responses to changing environmental conditions. The mVOC output from microbial metabolism on kitchen sinks and bathroom showers should be apparent through careful

In-situ characterization of heterogeneous catalysts

CERN Document Server

Rodriguez, Jose A; Chupas, Peter J

2013-01-01

Helps researchers develop new catalysts for sustainable fuel and chemical production Reviewing the latest developments in the field, this book explores the in-situ characterization of heterogeneous catalysts, enabling readers to take full advantage of the sophisticated techniques used to study heterogeneous catalysts and reaction mechanisms. In using these techniques, readers can learn to improve the selectivity and the performance of catalysts and how to prepare catalysts as efficiently as possible, with minimum waste. In-situ Characterization of Heterogeneous Catalysts feat

Morpho-chemical characterization and surface properties of carcinogenic zeolite fibers

International Nuclear Information System (INIS)

Mattioli, Michele; Giordani, Matteo; Dogan, Meral; Cangiotti, Michela; Avella, Giuseppe; Giorgi, Rodorico; Dogan, A. Umran; Ottaviani, Maria Francesca

2016-01-01

Highlights: • Differently carcinogenic zeolite fibers were investigated combining physico-chemical methods. • For the first time, zeolite fibers were studied by means of the EPR technique using different spin probes. • The structural properties and the adsorption capability are function of different types and distributions of adsorption sites. • The interacting ability of erionite is higher than that of other fibrous zeolites. • The surface interacting properties may be related with the carcinogenicity of the zeolite fibers. - Abstract: Erionite belonging to the zeolite family is a human health-hazard, since it was demonstrated to be carcinogenic. Conversely, offretite family zeolites were suspected carcinogenic. Mineralogical, morphological, chemical, and surface characterizations were performed on two erionites (GF1, MD8) and one offretite (BV12) fibrous samples and, for comparison, one scolecite (SC1) sample. The specific surface area analysis indicated a larger availability of surface sites for the adsorption onto GF1, while SC1 shows the lowest one and the presence of large pores in the poorly fibrous zeolite aggregates. Selected spin probes revealed a high adsorption capacity of GF1 compared to the other zeolites, but the polar/charged interacting sites were well distributed, intercalated by less polar sites (Si–O–Si). MD8 surface is less homogeneous and the polar/charged sites are more interacting and closer to each other compared to GF1. The interacting ability of BV12 surface is much lower than that found for GF1 and MD8 and the probes are trapped in small pores into the fibrous aggregates. In comparison with the other zeolites, the non-carcinogenic SC1 shows a poor interacting ability and a lower surface polarity. These results helped to clarify the chemical properties and the surface interacting ability of these zeolite fibers which may be related to their carcinogenicity.

Quantification of chemical transport processes from the soil to surface runoff.

Science.gov (United States)

Tian, Kun; Huang, Chi-Hua; Wang, Guang-Qian; Fu, Xu-Dong; Parker, Gary

2013-01-01

There is a good conceptual understanding of the processes that govern chemical transport from the soil to surface runoff, but few studies have actually quantified these processes separately. Thus, we designed a laboratory flow cell and experimental procedures to quantify the chemical transport from soil to runoff water in the following individual processes: (i) convection with a vertical hydraulic gradient, (ii) convection via surface flow or the Bernoulli effect, (iii) diffusion, and (iv) soil loss. We applied different vertical hydraulic gradients by setting the flow cell to generate different seepage or drainage conditions. Our data confirmed the general form of the convection-diffusion equation. However, we now have additional quantitative data that describe the contribution of each individual chemical loading process in different surface runoff and soil hydrological conditions. The results of this study will be useful for enhancing our understanding of different geochemical processes in the surface soil mixing zone. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Superhydrophobic coatings for aluminium surfaces synthesized by chemical etching process

Directory of Open Access Journals (Sweden)

Priya Varshney

2016-10-01

Full Text Available In this paper, the superhydrophobic coatings on aluminium surfaces were prepared by two-step (chemical etching followed by coating and one-step (chemical etching and coating in a single step processes using potassium hydroxide and lauric acid. Besides, surface immersion time in solutions was varied in both processes. Wettability and surface morphologies of treated aluminium surfaces were characterized using contact angle measurement technique and scanning electron microscopy, respectively. Microstructures are formed on the treated aluminium surfaces which lead to increase in contact angle of the surface (>150°. Also on increasing immersion time, contact angle further increases due to increase in size and depth of microstructures. Additionally, these superhydrophobic coatings show excellent self-cleaning and corrosion-resistant behavior. Water jet impact, floatation on water surface, and low temperature condensation tests assert the excellent water-repellent nature of coatings. Further, coatings are to be found mechanically, thermally, and ultraviolet stable. Along with, these coatings are found to be excellent regeneration ability as verified experimentally. Although aforesaid both processes generate durable and regenerable superhydrophobic aluminium surfaces with excellent self-cleaning, corrosion-resistant, and water-repellent characteristics, but one-step process is proved more efficient and less time consuming than two-step process and promises to produce superhydrophobic coatings for industrial applications.

A comparison of chemical compositions of reported altered oceanic crusts and global MORB data set: implication for isotopic heterogeneity of recycled materials

Science.gov (United States)

Shimoda, G.; Kogiso, T.

2017-12-01

Chemical composition of altered oceanic crust is one of important constraints to delineate chemical heterogeneity of the mantle. Accordingly, many researchers have been studied to determine bulk chemical composition of altered oceanic crust mainly based on chemical compositions of old oceanic crusts at Site 801 and Site 417/418, and young crust at Site 504 (e.g., Staudigel et al., 1996; Bach et al. 2003; Kuo et al., 2016). Their careful estimation provided reliable bulk chemical compositions of these Sites and revealed common geochemical feature of alteration. To assess effect of recycling of altered oceanic crust on chemical evolution of the mantle, it might be meaningful to discuss whether the reported chemical compositions of altered oceanic crusts can represent chemical composition of globally subducted oceanic crusts. Reported chemical compositions of fresh glass or less altered samples from Site 801, 417/418 and 504 were highly depleted compared to that of global MORB reported by Gale et al. (2013), suggesting that there might be sampling bias. Hence, it could be important to consider chemical difference between oceanic crusts of these three Sites and global MORB to discuss effect of recycling of oceanic crust on isotopic heterogeneity of the mantle. It has been suggested that one of controlling factors of chemical variation of oceanic crust is crustal spreading rate because different degree of partial melting affects chemical composition of magmas produced at a mid-ocean ridge. Crustal spreading rate could also affect intensity of alteration. Namely, oceanic crusts produced at slow-spreading ridges may prone to be altered due to existence of larger displacement faults compared to fast spreading ridges which have relatively smooth topography. Thus, it might be significant to evaluate isotopic evolution of oceanic crusts those were produced at different spreading rates. In this presentation, we will provide a possible chemical variation of altered oceanic

Estimation of the advection effects induced by surface heterogeneities in the surface energy budget

NARCIS (Netherlands)

Cuxart, J.; Wrenger, B.; Martinez-Villagrasa, D.; Reuder, J.; Jonassen, M.O.; Jimenez, M.A.; Lothon, M.; Hartogensis, O.K.; Dunnermann, J.; Conangla, L.; Garai, A.

2016-01-01

The effect of terrain heterogeneities in one-point
measurements is a continuous subject of discussion. Here
we focus on the order of magnitude of the advection term
in the equation of the evolution of temperature as generated
by documented terrain heterogeneities and we estimate

A Monte Carlo simulation of the exchange reaction between gaseous molecules and the atoms on a heterogeneous solid surface

International Nuclear Information System (INIS)

Imai, Hisao

1980-01-01

A method of the Monte Carlo simulation of the isotopic exchange reaction between gaseous molecules and the atoms on an arbitrarily heterogeneous solid surface is described by employing hydrogen as an example. (author)

Single-molecule resolution of protein dynamics on polymeric membrane surfaces: the roles of spatial and population heterogeneity.

Science.gov (United States)

Langdon, Blake B; Mirhossaini, Roya B; Mabry, Joshua N; Sriram, Indira; Lajmi, Ajay; Zhang, Yanxia; Rojas, Orlando J; Schwartz, Daniel K

2015-02-18

Although polymeric membranes are widely used in the purification of protein pharmaceuticals, interactions between biomolecules and membrane surfaces can lead to reduced membrane performance and damage to the product. In this study, single-molecule fluorescence microscopy provided direct observation of bovine serum albumin (BSA) and human monoclonal antibody (IgG) dynamics at the interface between aqueous buffer and polymeric membrane materials including regenerated cellulose and unmodified poly(ether sulfone) (PES) blended with either polyvinylpyrrolidone (PVP), polyvinyl acetate-co-polyvinylpyrrolidone (PVAc-PVP), or polyethylene glycol methacrylate (PEGM) before casting. These polymer surfaces were compared with model surfaces composed of hydrophilic bare fused silica and hydrophobic trimethylsilane-coated fused silica. At extremely dilute protein concentrations (10(-3)-10(-7) mg/mL), protein surface exchange was highly dynamic with protein monomers desorbing from the surface within ∼1 s after adsorption. Protein oligomers (e.g., nonspecific dimers, trimers, or larger aggregates), although less common, remained on the surface for 5 times longer than monomers. Using newly developed super-resolution methods, we could localize adsorption sites with ∼50 nm resolution and quantify the spatial heterogeneity of the various surfaces. On a small anomalous subset of the adsorption sites, proteins adsorbed preferentially and tended to reside for significantly longer times (i.e., on "strong" sites). Proteins resided for shorter times overall on surfaces that were more homogeneous and exhibited fewer strong sites (e.g., PVAc-PVP/PES). We propose that strong surface sites may nucleate protein aggregation, initiated preferentially by protein oligomers, and accelerate ultrafiltration membrane fouling. At high protein concentrations (0.3-1.0 mg/mL), fewer strong adsorption sites were observed, and surface residence times were reduced. This suggests that at high concentrations

Surface properties of hydrogenated nanodiamonds: a chemical investigation.

Science.gov (United States)

Girard, H A; Petit, T; Perruchas, S; Gacoin, T; Gesset, C; Arnault, J C; Bergonzo, P

2011-06-28

Hydrogen terminations (C-H) confer to diamond layers specific surface properties such as a negative electron affinity and a superficial conductive layer, opening the way to specific functionalization routes. For example, efficient covalent bonding of diazonium salts or of alkene moieties can be performed on hydrogenated diamond thin films, owing to electronic exchanges at the interface. Here, we report on the chemical reactivity of fully hydrogenated High Pressure High Temperature (HPHT) nanodiamonds (H-NDs) towards such grafting, with respect to the reactivity of as-received NDs. Chemical characterizations such as FTIR, XPS analysis and Zeta potential measurements reveal a clear selectivity of such couplings on H-NDs, suggesting that C-H related surface properties remain dominant even on particles at the nanoscale. These results on hydrogenated NDs open up the route to a broad range of new functionalizations for innovative NDs applications development. This journal is © the Owner Societies 2011

Collisions of polyatomic ions with surfaces: incident energy partitioning and chemical reactions

International Nuclear Information System (INIS)

Zabka, J.; Roithova, J.; Dolejsek, Z.; Herman, Z.

2002-01-01

Collision of polyatomic ions with surfaces were investigated in ion-surface scattering experiments to obtain more information on energy partitioning in ion-surface collision and on chemical reactions at surfaces. Mass spectra, translation energy and angular distributions of product ions were measured in dependence on the incident energy and the incident angle of polyatomic projectiles. From these data distributions of energy fractions resulting in internal excitation of the projectile, translation energy of the product ions, and energy absorbed by the surface were determined. The surface investigated were a standard stainless steel surface, covered by hydrocarbons, carbon surfaces at room and elevated temperatures, and several surfaces covered by a self-assembled monolayers (C 12 -hydrocarbon SAM, C 11 -perfluorohydrocarbon SAM, and C 11 hydrocarbon with terminal -COOH group SAM). The main processes observed at collision energies of 10 - 50 eV were: neutralization of the ions at surfaces, inelastic scattering and dissociations of the projectile ions, quasi elastic scattering of the projectile ions, and chemical reactions with the surface material (usually hydrogen-atom transfer reactions). The ion survival factor was estimated to be a few percent for even-electron ions (like protonated ethanol ion, C 2 H 5 O + , CD 5 + ) and about 10 - 10 2 times lower for radical ions (like ethanol and benzene molecular ions, CD 4 + ). In the polyatomic ion -surface energy transfer experiments, the ethanol molecular ion was used as a well-characterized projectile ion. The results with most of the surfaces studied showed in the collision energy range of 13 - 32 eV that most collisions were strongly inelastic with about 6 - 8 % of the incident projectile energy transformed into internal excitation of the projectile (independent of the incident angle) and led partially to its further dissociation in a unimolecular way after the interaction with the surface. The incident energy

CHEMICAL REACTIONS ON ADSORBING SURFACE: KINETIC LEVEL OF DESCRIPTION

Directory of Open Access Journals (Sweden)

P.P.Kostrobii

2003-01-01

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

Large-eddy simulations of surface-induced turbulence and its implications to the interpretation of eddy-covariance measurements in heterogeneous landscapes

Science.gov (United States)

Bohrer, G.; Kenny, W.; Morin, T. H.

2015-12-01

We used the RAMS-based Forest Large Eddy Simulations (RAFLES) to evaluate the sensitivity of eddy covariance measurements to land-surface discontinuity. While the sensitivity of eddy covariance measurements to surface heterogeneity is well known, it is, in most cases, no feasible to restrict measurements only to sites where the surface include undisturbed and homogeneous land cover over vast distances around the observation tower. The common approach to handle surface heterogeneity is to use a footprint model and reject observations obtained while the source of observed signal is from a mixture of land-use types, and maintain only measurements where the signal originates mostly from the land-use type of interest. We simulated two scenarios - measurements of fluxes from a small forest-surrounded lake, and measurements near a forest edge. These are two very common scenarios where measurements are bound to be affected by heterogeneity - measurements in small lakes, will, by definition, be in some non-negligible proximity or the lake edge; forest edges are common in any forest, near the forest patch edge but also around disturbed patches and forest gaps. We identify regions where the surface heterogeneity is creating persistent updraft or downdraft. A non-zero mean vertical wind is typically neglected in eddy-covariance measurements. We find that these circulations lead to both vertical and horizontal advection that cannot be easily measured by a single eddy-covariance tower. We identify downwind effects, which are well known, but also quantify the upwind effects. We find that surface-induced circulations may affect the flux measured from a tower up to several canopy heights ahead of the discontinuity. We used the High-resolution Volatile Organic Compound Atmospheric Chemistry in Canopies (Hi-VACC) model to determine the actual measurement footprints throughout the RAFLES domain. We estimated the land-cover type distribution of the source signal at different virtual

Empirical isotropic chemical shift surfaces

International Nuclear Information System (INIS)

Czinki, Eszter; Csaszar, Attila G.

2007-01-01

A list of proteins is given for which spatial structures, with a resolution better than 2.5 A, are known from entries in the Protein Data Bank (PDB) and isotropic chemical shift (ICS) values are known from the RefDB database related to the Biological Magnetic Resonance Bank (BMRB) database. The structures chosen provide, with unknown uncertainties, dihedral angles φ and ψ characterizing the backbone structure of the residues. The joint use of experimental ICSs of the same residues within the proteins, again with mostly unknown uncertainties, and ab initio ICS(φ,ψ) surfaces obtained for the model peptides For-(l-Ala) n -NH 2 , with n = 1, 3, and 5, resulted in so-called empirical ICS(φ,ψ) surfaces for all major nuclei of the 20 naturally occurring α-amino acids. Out of the many empirical surfaces determined, it is the 13C α ICS(φ,ψ) surface which seems to be most promising for identifying major secondary structure types, α-helix, β-strand, left-handed helix (α D ), and polyproline-II. Detailed tests suggest that Ala is a good model for many naturally occurring α-amino acids. Two-dimensional empirical 13C α - 1 H α ICS(φ,ψ) correlation plots, obtained so far only from computations on small peptide models, suggest the utility of the experimental information contained therein and thus they should provide useful constraints for structure determinations of proteins

Landsat and Local Land Surface Temperatures in a Heterogeneous Terrain Compared to MODIS Values

Directory of Open Access Journals (Sweden)

Gemma Simó

2016-10-01

Full Text Available Land Surface Temperature (LST as provided by remote sensing onboard satellites is a key parameter for a number of applications in Earth System studies, such as numerical modelling or regional estimation of surface energy and water fluxes. In the case of Moderate Resolution Imaging Spectroradiometer (MODIS onboard Terra or Aqua, pixels have resolutions near 1 km 2 , LST values being an average of the real subpixel variability of LST, which can be significant for heterogeneous terrain. Here, we use Landsat 7 LST decametre-scale fields to evaluate the temporal and spatial variability at the kilometre scale and compare the resulting average values to those provided by MODIS for the same observation time, for the very heterogeneous Campus of the University of the Balearic Islands (Mallorca, Western Mediterranean, with an area of about 1 km 2 , for a period between 2014 and 2016. Variations of LST between 10 and 20 K are often found at the sub-kilometre scale. In addition, MODIS values are compared to the ground truth for one point in the Campus, as obtained from a four-component net radiometer, and a bias of 3.2 K was found in addition to a Root Mean Square Error (RMSE of 4.2 K. An indication of a more elaborated local measurement strategy in the Campus is given, using an array of radiometers distributed in the area.

Magnetism in heterogeneous thin film systems: Resonant X-ray scattering studies

International Nuclear Information System (INIS)

Kortright, J.B.; Jiang, J.S.; Bader, S.D.; Hellwig, O.; Marguiles, D.T.; Fullerton, E.E.

2002-01-01

Magnetic and chemical heterogeneity are common in a broad range of magnetic thin film systems. Emerging resonant soft x-ray scattering techniques are well suited to resolve such heterogeneity at relevant length scales. Resonant x-ray magneto-optical Kerr effect measurements laterally average over heterogeneity but can provide depth resolution in different ways, as illustrated in measurements resolving reversible and irreversible changes in different layers of exchange-spring heterostructures. Resonant small-angle scattering measures in-plane heterogeneity and can resolve magnetic and chemical scattering sources in different ways, as illustrated in measurements of granular alloy recording media

Impacts of physical and chemical aquifer heterogeneity on basin-scale solute transport: Vulnerability of deep groundwater to arsenic contamination in Bangladesh

Science.gov (United States)

Michael, Holly A.; Khan, Mahfuzur R.

2016-12-01

Aquifer heterogeneity presents a primary challenge in predicting the movement of solutes in groundwater systems. The problem is particularly difficult on very large scales, across which permeability, chemical properties, and pumping rates may vary by many orders of magnitude and data are often sparse. An example is the fluvio-deltaic aquifer system of Bangladesh, where naturally-occurring arsenic (As) exists over tens of thousands of square kilometers in shallow groundwater. Millions of people in As-affected regions rely on deep (≥150 m) groundwater as a safe source of drinking water. The sustainability of this resource has been evaluated with models using effective properties appropriate for a basin-scale contamination problem, but the extent to which preferential flow affects the timescale of downward migration of As-contaminated shallow groundwater is unknown. Here we embed detailed, heterogeneous representations of hydraulic conductivity (K), pumping rates, and sorptive properties (Kd) within a basin-scale numerical groundwater flow and solute transport model to evaluate their effects on vulnerability and deviations from simulations with homogeneous representations in two areas with different flow systems. Advective particle tracking shows that heterogeneity in K does not affect average travel times from shallow zones to 150 m depth, but the travel times of the fastest 10% of particles decreases by a factor of ∼2. Pumping distributions do not strongly affect travel times if irrigation remains shallow, but increases in the deep pumping rate substantially reduce travel times. Simulation of advective-dispersive transport with sorption shows that deep groundwater is protected from contamination over a sustainable timeframe (>1000 y) if the spatial distribution of Kd is uniform. However, if only low-K sediments sorb As, 30% of the aquifer is not protected. Results indicate that sustainable management strategies in the Bengal Basin should consider impacts of both

Surface chemical modification for exceptional wear life of MEMS materials

Directory of Open Access Journals (Sweden)

R. Arvind Singh

2011-12-01

Full Text Available Micro-Electro-Mechanical-Systems (MEMS are built at micro/nano-scales. At these scales, the interfacial forces are extremely strong. These forces adversely affect the smooth operation and cause wear resulting in the drastic reduction in wear life (useful operating lifetime of actuator-based devices. In this paper, we present a surface chemical modification method that reduces friction and significantly extends the wear life of the two most popular MEMS structural materials namely, silicon and SU-8 polymer. The method includes surface chemical treatment using ethanolamine-sodium phosphate buffer, followed by coating of perfluoropolyether (PFPE nanolubricant on (i silicon coated with SU-8 thin films (500 nm and (ii MEMS process treated SU-8 thick films (50 μm. After the surface chemical modification, it was observed that the steady-state coefficient of friction of the materials reduced by 4 to 5 times and simultaneously their wear durability increased by more than three orders of magnitude (> 1000 times. The significant reduction in the friction coefficients is due to the lubrication effect of PFPE nanolubricant, while the exceptional increase in their wear life is attributed to the bonding between the -OH functional group of ethanolamine treated SU-8 thin/thick films and the -OH functional group of PFPE. The surface chemical modification method acts as a common route to enhance the performance of both silicon and SU-8 polymer. It is time-effective (process time ≤ 11 min, cost-effective and can be readily integrated into MEMS fabrication/assembly processes. It can also work for any kind of structural material from which the miniaturized devices are/can be made.

Increased Surface Roughness in Polydimethylsiloxane Films by Physical and Chemical Methods

Directory of Open Access Journals (Sweden)

Jorge Nicolás Cabrera

2017-08-01

Full Text Available Two methods, the first physical and the other chemical, were investigated to modify the surface roughness of polydimethylsiloxane (PDMS films. The physical method consisted of dispersing multi-walled carbon nanotubes (MWCNTs and magnetic cobalt ferrites (CoFe2O4 prior to thermal cross-linking, and curing the composite system in the presence of a uniform magnetic field H. The chemical method was based on exposing the films to bromine vapours and then UV-irradiating. The characterizing techniques included scanning electron microscopy (SEM, energy-dispersive spectroscopy (EDS, Fourier transform infrared (FTIR spectroscopy, optical microscopy, atomic force microscopy (AFM and magnetic force microscopy (MFM. The surface roughness was quantitatively analyzed by AFM. In the physical method, the random dispersion of MWCNTs (1% w/w and magnetic nanoparticles (2% w/w generated a roughness increase of about 200% (with respect to PDMS films without any treatment, but that change was 400% for films cured in the presence of H perpendicular to the surface. SEM, AFM and MFM showed that the magnetic particles always remained attached to the carbon nanotubes, and the effect on the roughness was interpreted as being due to a rupture of dispersion randomness and a possible induction of structuring in the direction of H. In the chemical method, the increase in roughness was even greater (1000%. Wells were generated with surface areas that were close to 100 μm2 and depths of up to 500 nm. The observations of AFM images and FTIR spectra were in agreement with the hypothesis of etching by Br radicals generated by UV on the polymer chains. Both methods induced important changes in the surface roughness (the chemical method generated the greatest changes due to the formation of surface wells, which are of great importance in superficial technological processes.

Basin-scale heterogeneity in Antarctic precipitation and its impact on surface mass variability

Directory of Open Access Journals (Sweden)

J. Fyke

2017-11-01

Full Text Available Annually averaged precipitation in the form of snow, the dominant term of the Antarctic Ice Sheet surface mass balance, displays large spatial and temporal variability. Here we present an analysis of spatial patterns of regional Antarctic precipitation variability and their impact on integrated Antarctic surface mass balance variability simulated as part of a preindustrial 1800-year global, fully coupled Community Earth System Model simulation. Correlation and composite analyses based on this output allow for a robust exploration of Antarctic precipitation variability. We identify statistically significant relationships between precipitation patterns across Antarctica that are corroborated by climate reanalyses, regional modeling and ice core records. These patterns are driven by variability in large-scale atmospheric moisture transport, which itself is characterized by decadal- to centennial-scale oscillations around the long-term mean. We suggest that this heterogeneity in Antarctic precipitation variability has a dampening effect on overall Antarctic surface mass balance variability, with implications for regulation of Antarctic-sourced sea level variability, detection of an emergent anthropogenic signal in Antarctic mass trends and identification of Antarctic mass loss accelerations.

Nanoscale-Agglomerate-Mediated Heterogeneous Nucleation.

Science.gov (United States)

Cha, Hyeongyun; Wu, Alex; Kim, Moon-Kyung; Saigusa, Kosuke; Liu, Aihua; Miljkovic, Nenad

2017-12-13

Water vapor condensation on hydrophobic surfaces has received much attention due to its ability to rapidly shed water droplets and enhance heat transfer, anti-icing, water harvesting, energy harvesting, and self-cleaning performance. However, the mechanism of heterogeneous nucleation on hydrophobic surfaces remains poorly understood and is attributed to defects in the hydrophobic coating exposing the high surface energy substrate. Here, we observe the formation of high surface energy nanoscale agglomerates on hydrophobic coatings after condensation/evaporation cycles in ambient conditions. To investigate the deposition dynamics, we studied the nanoscale agglomerates as a function of condensation/evaporation cycles via optical and field emission scanning electron microscopy (FESEM), microgoniometric contact angle measurements, nucleation statistics, and energy dispersive X-ray spectroscopy (EDS). The FESEM and EDS results indicated that the nanoscale agglomerates stem from absorption of sulfuric acid based aerosol particles inside the droplet and adsorption of volatile organic compounds such as methanethiol (CH 3 SH), dimethyl disulfide (CH 3 SSCH), and dimethyl trisulfide (CH 3 SSSCH 3 ) on the liquid-vapor interface during water vapor condensation, which act as preferential sites for heterogeneous nucleation after evaporation. The insights gained from this study elucidate fundamental aspects governing the behavior of both short- and long-term heterogeneous nucleation on hydrophobic surfaces, suggest previously unexplored microfabrication and air purification techniques, and present insights into the challenges facing the development of durable dropwise condensing surfaces.

Breast Cancer Redox Heterogeneity Detectable with Chemical Exchange Satruation Transfer (CEST) MRI

Science.gov (United States)

Cai, Kejia; Xu, He N.; Singh, Anup; Moon, Lily; Haris, Mohammad; Reddy, Ravinder; Li, Lin

2014-01-01

Purpose Tissue redox state is an important mediator of various biological processes in health and diseases such as cancer. Previously, we discovered that the mitochondrial redox state of ex vivo tissues detected by redox scanning (an optical imaging method) revealed interesting tumor redox state heterogeneity that could differentiate tumor aggressiveness. Because the noninvasive chemical exchange saturation transfer (CEST) MRI can probe the proton transfer and generate contrasts from endogenous metabolites, we aim to investigate if the in vivo CEST contrast is sensitive to proton transfer of the redox reactions so as to reveal the tissue redox states in breast cancer animal models. Procedures CEST MRI has been employed to characterize tumor metabolic heterogeneity and correlated with the redox states measured by the redox scanning in two human breast cancer mouse xenograft models, MDA-MB-231 and MCF-7. The possible biological mechanism on the correlation between the two imaging modalities was further investigated by phantom studies where the reductants and the oxidants of the representative redox reactions were measured. Results The CEST contrast is found linearly correlated with NADH concentration and the NADH redox ratio with high statistical significance, where NADH is the reduced form of nicotinamide adenine dinucleotide. The phantom studies showed that the reductants of the redox reactions have more CEST contrast than the corresponding oxidants, indicating that higher CEST effect corresponds to the more reduced redox state. Conclusions This preliminary study suggests that CEST MRI, once calibrated, might provide a novel noninvasive imaging surrogate for the tissue redox state and a possible diagnostic biomarker for breast cancer in the clinic. PMID:24811957

Molecular ingredients of heterogeneous catalysis

International Nuclear Information System (INIS)

Somorjai, G.A.

1982-06-01

The purpose of this paper is to present a review and status report to those in theoretical chemistry of the rapidly developing surface science of heterogeneous catalysis. The art of catalysis is developing into science. This profound change provides one with opportunities not only to understand the molecular ingredients of important catalytic systems but also to develop new and improved catalyst. The participation of theorists to find answers to important questions is sorely needed for the sound development of the field. It is the authors hope that some of the outstanding problems of heterogeneous catalysis that are identified in this paper will be investigated. For this purpose the paper is divided into several sections. The brief Introduction to the methodology and recent results of the surface science of heterogeneous catalysis is followed by a review of the concepts of heterogeneous catalysis. Then, the experimental results that identified the three molecular ingredients of catalysis, structure, carbonaceous deposit and the oxidation state of surface atoms are described. Each section is closed with a summary and a list of problems that require theoretical and experimental scrutiny. Finally attempts to build new catalyst systems and the theoretical and experimental problems that appeared in the course of this research are described

Molecular ingredients of heterogeneous catalysis

Energy Technology Data Exchange (ETDEWEB)

Somorjai, G.A.

1982-06-01

The purpose of this paper is to present a review and status report to those in theoretical chemistry of the rapidly developing surface science of heterogeneous catalysis. The art of catalysis is developing into science. This profound change provides one with opportunities not only to understand the molecular ingredients of important catalytic systems but also to develop new and improved catalyst. The participation of theorists to find answers to important questions is sorely needed for the sound development of the field. It is the authors hope that some of the outstanding problems of heterogeneous catalysis that are identified in this paper will be investigated. For this purpose the paper is divided into several sections. The brief Introduction to the methodology and recent results of the surface science of heterogeneous catalysis is followed by a review of the concepts of heterogeneous catalysis. Then, the experimental results that identified the three molecular ingredients of catalysis, structure, carbonaceous deposit and the oxidation state of surface atoms are described. Each section is closed with a summary and a list of problems that require theoretical and experimental scrutiny. Finally attempts to build new catalyst systems and the theoretical and experimental problems that appeared in the course of this research are described.

Resonant surface acoustic wave chemical detector

Science.gov (United States)

Brocato, Robert W.; Brocato, Terisse; Stotts, Larry G.

2017-08-08

Apparatus for chemical detection includes a pair of interdigitated transducers (IDTs) formed on a piezoelectric substrate. The apparatus includes a layer of adsorptive material deposited on a surface of the piezoelectric substrate between the IDTs, where each IDT is conformed, and is dimensioned in relation to an operating frequency and an acoustic velocity of the piezoelectric substrate, so as to function as a single-phase uni-directional transducer (SPUDT) at the operating frequency. Additionally, the apparatus includes the pair of IDTs is spaced apart along a propagation axis and mutually aligned relative to said propagation axis so as to define an acoustic cavity that is resonant to surface acoustic waves (SAWs) at the operating frequency, where a distance between each IDT of the pair of IDTs ranges from 100 wavelength of the operating frequency to 400 wavelength of the operating frequency.

Surface characterization and chemical analysis of bamboo substrates pretreated by alkali hydrogen peroxide.

Science.gov (United States)

Song, Xueping; Jiang, Yan; Rong, Xianjian; Wei, Wei; Wang, Shuangfei; Nie, Shuangxi

2016-09-01

The surface characterization and chemical analysis of bamboo substrates by alkali hydrogen peroxide pretreatment (AHPP) were investigated in this study. The results tended to manifest that AHPP prior to enzymatic and chemical treatment was potential for improving accessibility and reactivity of bamboo substrates. The inorganic components, organic solvent extractives and acid-soluble lignin were effectively removed by AHPP. X-ray photoelectron spectroscopy (XPS) analysis indicated that the surface of bamboo chips had less lignin but more carbohydrate after pre-treatment. Fiber surfaces became etched and collapsed, and more pores and debris on the substrate surface were observed with Scanning Electron Microscopy (SEM). Brenauer-Emmett-Teller (BET) results showed that both of pore volume and surface area were increased after AHPP. Although XRD analysis showed that AHPP led to relatively higher crystallinity, pre-extraction could overall enhance the accessibility of enzymes and chemicals into the bamboo structure. Copyright © 2016. Published by Elsevier Ltd.

Chemical milling solution produces smooth surface finish on aluminum

Science.gov (United States)

Lorenzen, H. C.

1966-01-01

Elementary sulfur mixed into a solution of caustic soda and salts produces an etchant which will chemically mill end-grain surfaces on aluminum plate. This composition results in the least amount of thickness variation and pitting.

Electronic dissipation processes during chemical reactions on surfaces

CERN Document Server

Stella, Kevin

2012-01-01

Hauptbeschreibung Every day in our life is larded with a huge number of chemical reactions on surfaces. Some reactions occur immediately, for others an activation energy has to be supplied. Thus it happens that though a reaction should thermodynamically run off, it is kinetically hindered. Meaning the partners react only to the thermodynamically more stable product state within a mentionable time if the activation energy of the reaction is supplied. With the help of catalysts the activation energy of a reaction can be lowered. Such catalytic processes on surfaces are widely used in industry. A

Local Chemical Reactivity of a Metal Alloy Surface

DEFF Research Database (Denmark)

Hammer, Bjørk; Scheffler, Matthias

1995-01-01

The chemical reactivity of a metal alloy surface is studied by density functional theory investigating the interaction of H2 with NiAl(110). The energy barrier for H2 dissociation is largely different over the Al and Ni sites without, however, reflecting the barriers over the single component metal...

The localization of focal heart activity via body surface potential measurements: tests in a heterogeneous torso phantom

International Nuclear Information System (INIS)

Wetterling, F; Liehr, M; Haueisen, J; Schimpf, P; Liu, H

2009-01-01

The non-invasive localization of focal heart activity via body surface potential measurements (BSPM) could greatly benefit the understanding and treatment of arrhythmic heart diseases. However, the in vivo validation of source localization algorithms is rather difficult with currently available measurement techniques. In this study, we used a physical torso phantom composed of different conductive compartments and seven dipoles, which were placed in the anatomical position of the human heart in order to assess the performance of the Recursively Applied and Projected Multiple Signal Classification (RAP-MUSIC) algorithm. Electric potentials were measured on the torso surface for single dipoles with and without further uncorrelated or correlated dipole activity. The localization error averaged 11 ± 5 mm over 22 dipoles, which shows the ability of RAP-MUSIC to distinguish an uncorrelated dipole from surrounding sources activity. For the first time, real computational modelling errors could be included within the validation procedure due to the physically modelled heterogeneities. In conclusion, the introduced heterogeneous torso phantom can be used to validate state-of-the-art algorithms under nearly realistic measurement conditions.

The localization of focal heart activity via body surface potential measurements: tests in a heterogeneous torso phantom

Science.gov (United States)

Wetterling, F.; Liehr, M.; Schimpf, P.; Liu, H.; Haueisen, J.

2009-09-01

The non-invasive localization of focal heart activity via body surface potential measurements (BSPM) could greatly benefit the understanding and treatment of arrhythmic heart diseases. However, the in vivo validation of source localization algorithms is rather difficult with currently available measurement techniques. In this study, we used a physical torso phantom composed of different conductive compartments and seven dipoles, which were placed in the anatomical position of the human heart in order to assess the performance of the Recursively Applied and Projected Multiple Signal Classification (RAP-MUSIC) algorithm. Electric potentials were measured on the torso surface for single dipoles with and without further uncorrelated or correlated dipole activity. The localization error averaged 11 ± 5 mm over 22 dipoles, which shows the ability of RAP-MUSIC to distinguish an uncorrelated dipole from surrounding sources activity. For the first time, real computational modelling errors could be included within the validation procedure due to the physically modelled heterogeneities. In conclusion, the introduced heterogeneous torso phantom can be used to validate state-of-the-art algorithms under nearly realistic measurement conditions.

Catalysis by Design: Well-Defined Single-Site Heterogeneous Catalysts

KAUST Repository

Pelletier, Jeremie

2016-03-09

ConspectusHeterogeneous catalysis, a field important industrially and scientifically, is increasingly seeking and refining strategies to render itself more predictable. The main issue is due to the nature and the population of catalytically active sites. Their number is generally low to very low, their "acid strengths" or " redox properties" are not homogeneous, and the material may display related yet inactive sites on the same material. In many heterogeneous catalysts, the discovery of a structure-activity reationship is at best challenging. One possible solution is to generate single-site catalysts in which most, if not all, of the sites are structurally identical. Within this context and using the right tools, the catalyst structure can be designed and well-defined, to reach a molecular understanding. It is then feasible to understand the structure-activity relationship and to develop predictable heterogeneous catalysis. Single-site well-defined heterogeneous catalysts can be prepared using concepts and tools of surface organometallic chemistry (SOMC). This approach operates by reacting organometallic compounds with surfaces of highly divided oxides (or of metal nanoparticles). This strategy has a solid track record to reveal structure-activity relationship to the extent that it is becoming now quite predictable. Almost all elements of the periodical table have been grafted on surfaces of oxides (from simple oxides such as silica or alumina to more sophisticated materials regarding composition or porosity).Considering catalytic hydrocarbon transformations, heterogeneous catalysis outcome may now be predicted based on existing mechanistic proposals and the rules of molecular chemistry (organometallic, organic) associated with some concepts of surface sciences. A thorough characterization of the grafted metal centers must be carried out using tools spanning from molecular organometallic or surface chemistry. By selection of the metal, its ligand set, and the

Long-range interaction between heterogeneously charged membranes.

Science.gov (United States)

Jho, Y S; Brewster, R; Safran, S A; Pincus, P A

2011-04-19

Despite their neutrality, surfaces or membranes with equal amounts of positive and negative charge can exhibit long-range electrostatic interactions if the surface charge is heterogeneous; this can happen when the surface charges form finite-size domain structures. These domains can be formed in lipid membranes where the balance of the different ranges of strong but short-ranged hydrophobic interactions and longer-ranged electrostatic repulsion result in a finite, stable domain size. If the domain size is large enough, oppositely charged domains in two opposing surfaces or membranes can be strongly correlated by the electrostatic interactions; these correlations give rise to an attractive interaction of the two membranes or surfaces over separations on the order of the domain size. We use numerical simulations to demonstrate the existence of strong attractions at separations of tens of nanometers. Large line tensions result in larger domains but also increase the charge density within the domain. This promotes correlations and, as a result, increases the intermembrane attraction. On the other hand, increasing the salt concentration increases both the domain size and degree of domain anticorrelation, but the interactions are ultimately reduced due to increased screening. The result is a decrease in the net attraction as salt concentration is increased. © 2011 American Chemical Society

Unequal diffusivities case of homogeneous–heterogeneous reactions within viscoelastic fluid flow in the presence of induced magnetic-field and nonlinear thermal radiation

Directory of Open Access Journals (Sweden)

I.L. Animasaun

2016-06-01

Full Text Available This article presents the effects of nonlinear thermal radiation and induced magnetic field on viscoelastic fluid flow toward a stagnation point. It is assumed that there exists a kind of chemical reaction between chemical species A and B. The diffusion coefficients of the two chemical species in the viscoelastic fluid flow are unequal. Since chemical species B is a catalyst at the horizontal surface, hence homogeneous and heterogeneous schemes are of the isothermal cubic autocatalytic reaction and first order reaction respectively. The transformed governing equations are solved numerically using Runge–Kutta integration scheme along with Newton’s method. Good agreement is obtained between present and published numerical results for a limiting case. The influence of some pertinent parameters on skin friction coefficient, local heat transfer rate, together with velocity, induced magnetic field, temperature, and concentration profiles is illustrated graphically and discussed. Based on all of these assumptions, results indicate that the effects of induced magnetic and viscoelastic parameters on velocity, transverse velocity and velocity of induced magnetic field are almost the same but opposite in nature. The strength of heterogeneous reaction parameter is very helpful to reduce the concentration of bulk fluid and increase the concentration of catalyst at the surface.

Nano-sized metabolic precursors for heterogeneous tumor-targeting strategy using bioorthogonal click chemistry in vivo.

Science.gov (United States)

Lee, Sangmin; Jung, Seulhee; Koo, Heebeom; Na, Jin Hee; Yoon, Hong Yeol; Shim, Man Kyu; Park, Jooho; Kim, Jong-Ho; Lee, Seulki; Pomper, Martin G; Kwon, Ick Chan; Ahn, Cheol-Hee; Kim, Kwangmeyung

2017-12-01

Herein, we developed nano-sized metabolic precursors (Nano-MPs) for new tumor-targeting strategy to overcome the intrinsic limitations of biological ligands such as the limited number of biological receptors and the heterogeneity in tumor tissues. We conjugated the azide group-containing metabolic precursors, triacetylated N-azidoacetyl-d-mannosamine to generation 4 poly(amidoamine) dendrimer backbone. The nano-sized dendrimer of Nano-MPs could generate azide groups on the surface of tumor cells homogeneously regardless of cell types via metabolic glycoengineering. Importantly, these exogenously generated 'artificial chemical receptors' containing azide groups could be used for bioorthogonal click chemistry, regardless of phenotypes of different tumor cells. Furthermore, in tumor-bearing mice models, Nano-MPs could be mainly localized at the target tumor tissues by the enhanced permeation and retention (EPR) effect, and they successfully generated azide groups on tumor cells in vivo after an intravenous injection. Finally, we showed that these azide groups on tumor tissues could be used as 'artificial chemical receptors' that were conjugated to bioorthogonal chemical group-containing liposomes via in vivo click chemistry in heterogeneous tumor-bearing mice. Therefore, overall results demonstrated that our nano-sized metabolic precursors could be extensively applied to new alternative tumor-targeting technique for molecular imaging and drug delivery system, regardless of the phenotype of heterogeneous tumor cells. Copyright © 2017 Elsevier Ltd. All rights reserved.

Chemically resistant, biocompatible and microstructured surface protection

International Nuclear Information System (INIS)

Hoffmann, W.; Pham, M.T.; Hueller, J.

1984-01-01

Subject of the invention are chemicallly resistant, biocompatible, and microstructured surface protective coatings of electronic elements and sensors including chemical sensors. Such coatings consist of a radiation-modified organic substance made of a microlithographic material. Modification can be achieved by irradiation with ions, atoms or molecules having an energy between 1 KeV and 1 MeV and a flux between 10 13 and 10 18 particles per cm 2

Analysis of the influence of chemical treatment to the strength and surface roughness of FDM

Science.gov (United States)

Hambali, R. H.; Cheong, K. M.; Azizan, N.

2017-06-01

The applications of Additive Manufacturing (AM) technology have a greater functionality and wider range of application beyond an intention of prototyping. AM is the process of joining materials to form objects from Computer-Aided Design (CAD) models via layer upon layer process. One of AM technologies is the Fused Deposition Modelling (FDM), which use an extrusion method to create a part. FDM has been applied in many manufacturing applications includes an end-used parts. However, FDM tends to have bad surface quality due to staircase effect and post treatment is required. This chemical treatment is one of a way to improve the surface roughness of FDM fabricated parts. This method is one of economical and faster method. In order to enhance the surface finish of Acrylonitrile-Butadiene-Styrene (ABS) FDM parts by performing chemical treatment in an acetone solution as acetone has very low toxicity, high diffusion and low cost chemical solution. Therefore, the aim of this research is to investigate the influence of chemical treatment to the FDM used part in terms of surface roughness as well as the strength. In this project, ten specimens of standard ASTM D638 dogbone specimens have been fabricated using MOJO 3D printer. Five specimens from the dogbone were tested for surface roughness and tensile testing while another five were immersed in the chemical solution before the same testing. Based on results, the surface roughness of chemically treated dogbone has dramatically improved, compared to untreated dogbone with 97.2% of improvement. However, in term of strength, the tensile strength of dogbone is reduced 42.58% due to the rearrange of material properties and chemical effects to the joining of the filaments. In conclusion, chemical treatment is an economical and sustainable approach to enhance the surface quality of AM parts.

SEM, Scanning Auger and XPS characterization of chemically pretreated Ti surfaces intended for biomedical applications

Energy Technology Data Exchange (ETDEWEB)

Pisarek, M. [Faculty of Materials Science and Engineering, Warsaw University of Technology, Woloska 141, 02-507 Warsaw (Poland); Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland)], E-mail: marcinp@ichf.edu.pl; Lewandowska, M. [Faculty of Materials Science and Engineering, Warsaw University of Technology, Woloska 141, 02-507 Warsaw (Poland); Roguska, A. [Faculty of Materials Science and Engineering, Warsaw University of Technology, Woloska 141, 02-507 Warsaw (Poland); Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland); Kurzydlowski, K.J. [Faculty of Materials Science and Engineering, Warsaw University of Technology, Woloska 141, 02-507 Warsaw (Poland); Janik-Czachor, M. [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland)

2007-07-15

Titanium is known as a biocompatible metal characterized by biological and corrosion immunity and good mechanical properties, including a high fracture toughness. In a variety of environments, this metal undergoes 'natural' oxidation which determine its resistance to corrosion. It can also be exposed to chemical treatments in acidic or alkaline solutions which 'enforces' chemical and morphological changes of Ti surface. Those methods, if well controlled, may increase the effective Ti surface area, making it more biocompatible. However, the morphological and chemical factors responsible for their interactions with biological cells are still not well known. The aim of this work was to compare surface chemical and morphological changes introduced by commonly used aqueous NaOH pretreatment with those occurring in a new 'piranha' acidic solution. Particular attention was paid to possible changes which may be decisive for the biocompatibility of the Ti-elements subjected to these surface modifications. Surface analytical techniques such as Auger electron spectroscopy (AES) or X-ray photoelectron spectroscopy (XPS) combined with Ar{sup +} ion sputtering allowed us to investigate in detail the chemical composition of Ti oxide layers. SEM examinations provided morphological characterization of the surface of Ti samples. The results revealed large difference in morphology of Ti surfaces pretreated with different procedures whereas only minor difference in the chemistry of the surfaces were detected.

Molecular-level Design of Heterogeneous Chiral Catalysts

Energy Technology Data Exchange (ETDEWEB)

Gellman, Andrew John [Carnegie Mellon University; Sholl, David S. [Georgia Institute of Technology; Tysoe, Wilfred T. [University of Wisconsin - Milwaukee; Zaera, Francisco [University of California at Riverside

2013-04-28

Understanding and controlling selectivity is one of the key challenges in heterogeneous catalysis. Among problems in catalytic selectivity enantioselectivity is perhaps the most the most challenging. The primary goal of the project on “Molecular-level Design of Heterogeneous Chiral Catalysts” is to understand the origins of enantioselectivity on chiral heterogeneous surfaces and catalysts. The efforts of the project team include preparation of chiral surfaces, characterization of chiral surfaces, experimental detection of enantioselectivity on such surfaces and computational modeling of the interactions of chiral probe molecules with chiral surfaces. Over the course of the project period the team of PI’s has made some of the most detailed and insightful studies of enantioselective chemistry on chiral surfaces. This includes the measurement of fundamental interactions and reaction mechanisms of chiral molecules on chiral surfaces and leads all the way to rationale design and synthesis of chiral surfaces and materials for enantioselective surface chemistry. The PI’s have designed and prepared new materials for enantioselective adsorption and catalysis. Naturally Chiral Surfaces • Completion of a systematic study of the enantiospecific desorption kinetics of R-3-methylcyclohexanone (R-3-MCHO) on 9 achiral and 7 enantiomeric pairs of chiral Cu surfaces with orientations that span the stereographic triangle. • Discovery of super-enantioselective tartaric acid (TA) and aspartic acid (Asp) decomposition as a result of a surface explosion mechanism on Cu(643)R&S. Systematic study of super-enantiospecific TA and Asp decomposition on five enantiomeric pairs of chiral Cu surfaces. • Initial observation of the enantiospecific desorption of R- and S-propylene oxide (PO) from Cu(100) imprinted with {3,1,17} facets by L-lysine adsorption. Templated Chiral Surfaces • Initial observation of the enantiospecific desorption of R- and S-PO from Pt(111) and Pd(111

Optimizing surface acoustic wave sensors for trace chemical detection

Energy Technology Data Exchange (ETDEWEB)

Frye, G.C.; Kottenstette, R.J.; Heller, E.J. [and others

1997-06-01

This paper describes several recent advances for fabricating coated surface acoustic wave (SAW) sensors for applications requiring trace chemical detection. Specifically, we have demonstrated that high surface area microporous oxides can provide 100-fold improvements in SAW sensor responses compared with more typical polymeric coatings. In addition, we fabricated GaAs SAW devices with frequencies up to 500 MHz to provide greater sensitivity and an ideal substrate for integration with high-frequency electronics.

Topographical Anisotropy and Wetting of Ground Stainless Steel Surfaces

Directory of Open Access Journals (Sweden)

Cornelia Bellmann

2012-12-01

Full Text Available Microscopic and physico-chemical methods were used for a comprehensive surface characterization of different mechanically modified stainless steel surfaces. The surfaces were analyzed using high-resolution confocal microscopy, resulting in detailed information about the topographic properties. In addition, static water contact angle measurements were carried out to characterize the surface heterogeneity of the samples. The effect of morphological anisotropy on water contact angle anisotropy was investigated. The correlation between topography and wetting was studied by means of a model of wetting proposed in the present work, that allows quantifying the air volume of the interface water drop-stainless steel surface.

Physically and chemically stable ionic liquid-infused textured surfaces showing excellent dynamic omniphobicity

Energy Technology Data Exchange (ETDEWEB)

Miranda, Daniel F.; Urata, Chihiro; Masheder, Benjamin; Dunderdale, Gary J.; Hozumi, Atsushi, E-mail: a.hozumi@aist.go.jp [National Institute of Advanced Industrial Science and Technology (AIST), 2266-98, Anagahora, Shimo-Shidami, Moriyama-ku, Nagoya, Aichi 463-8560 (Japan); Yagihashi, Makoto [Nagoya Municipal Industrial Research Institute, Rokuban, Atsuta-ku, Nagoya 456-0058 (Japan)

2014-05-01

A fluorinated and hydrophobic ionic liquid (IL), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide, effectively served as an advantageous lubricating liquid for the preparation of physically and chemically stable omniphobic surfaces based on slippery liquid-infused porous surfaces. Here, we used particulate microstructures as supports, prepared by the chemical vapor deposition of 1,3,5,7-tetramethylcyclotetrasiloxane and subsequent surface modification with (3-aminopropyl)triethoxysilane. Confirmed by SEM and contact angle measurements, the resulting IL-infused microtextured surfaces are smooth and not only water but also various low surface tension liquids can easily slide off at low substrate tilt angles of <5°, even after exposure to high temperature, vacuum, and UV irradiation.

Physically and chemically stable ionic liquid-infused textured surfaces showing excellent dynamic omniphobicity

Directory of Open Access Journals (Sweden)

Daniel F. Miranda

2014-05-01

Full Text Available A fluorinated and hydrophobic ionic liquid (IL, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl imide, effectively served as an advantageous lubricating liquid for the preparation of physically and chemically stable omniphobic surfaces based on slippery liquid-infused porous surfaces. Here, we used particulate microstructures as supports, prepared by the chemical vapor deposition of 1,3,5,7-tetramethylcyclotetrasiloxane and subsequent surface modification with (3-aminopropyltriethoxysilane. Confirmed by SEM and contact angle measurements, the resulting IL-infused microtextured surfaces are smooth and not only water but also various low surface tension liquids can easily slide off at low substrate tilt angles of <5°, even after exposure to high temperature, vacuum, and UV irradiation.

Converting chemical energy into electricity through a functionally cooperating device with diving-surfacing cycles.

Science.gov (United States)

Song, Mengmeng; Cheng, Mengjiao; Ju, Guannan; Zhang, Yajun; Shi, Feng

2014-11-05

A smart device that can dive or surface in aqueous medium has been developed by combining a pH-responsive surface with acid-responsive magnesium. The diving-surfacing cycles can be used to convert chemical energy into electricity. During the diving-surfacing motion, the smart device cuts magnetic flux lines and produces a current, demonstrating that motional energy can be realized by consuming chemical energy of magnesium, thus producing electricity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Exploring the chemical enhancement for surface-enhanced Raman scattering with Au bowtie nanoantennas

International Nuclear Information System (INIS)

Fromm, David P.; Sundaramurthy, Arvind; Kinkhabwala, Anika; Schuck, P. James; Kino, Gordon S.; Moerner, W.E.

2006-01-01

Single metallic bowtie nanoantennas provide a controllable environment for surface-enhanced Raman scattering (SERS) of adsorbed molecules. Bowties have experimentally measured electromagnetic enhancements, enabling estimation of chemical enhancement for both the bulk and the few-molecule regime. Strong fluctuations of selected Raman lines imply that a small number of p-mercaptoaniline molecules on a single bowtie show chemical enhancement >10 7 , much larger than previously believed, likely due to charge transfer between the Au surface and the molecule. This chemical sensitivity of SERS has significant implications for ultra-sensitive detection of single molecules

Land surface temperature representativeness in a heterogeneous area through a distributed energy-water balance model and remote sensing data

Directory of Open Access Journals (Sweden)

C. Corbari

2010-10-01

Full Text Available Land surface temperature is the link between soil-vegetation-atmosphere fluxes and soil water content through the energy water balance. This paper analyses the representativeness of land surface temperature (LST for a distributed hydrological water balance model (FEST-EWB using LST from AHS (airborne hyperspectral scanner, with a spatial resolution between 2–4 m, LST from MODIS, with a spatial resolution of 1000 m, and thermal infrared radiometric ground measurements that are compared with the representative equilibrium temperature that closes the energy balance equation in the distributed hydrological model.

Diurnal and nocturnal images are analyzed due to the non stable behaviour of the thermodynamic temperature and to the non linear effects induced by spatial heterogeneity.

Spatial autocorrelation and scale of fluctuation of land surface temperature from FEST-EWB and AHS are analysed at different aggregation areas to better understand the scale of representativeness of land surface temperature in a hydrological process.

The study site is the agricultural area of Barrax (Spain that is a heterogeneous area with a patchwork of irrigated and non irrigated vegetated fields and bare soil. The used data set was collected during a field campaign from 10 to 15 July 2005 in the framework of the SEN2FLEX project.

Surface roughness of polyvinyl siloxane impression materials following chemical disinfection, autoclave and microwave sterilization.

Science.gov (United States)

Al Kheraif, Abdulaziz Abdullah

2013-05-01

Autoclave sterilization and microwave sterilization has been suggested as the effective methods for the disinfection of elastomeric impressions, but subjecting elastomeric impressions to extreme temperature may have adverse effects on critical properties of the elastomers. To evaluate the effect of chemical disinfection as well as autoclave and microwave sterilization on the surface roughness of elastomeric impression materials. The surface roughness of five commercially available polyvinyl siloxane impression materials (Coltene President, Affinis Perfect impression, Aquasil, 3M ESPE Express and GC Exafast) were evaluated after subjecting them to chemical disinfection, autoclaving and microwave sterilization using a Talysurf Intra 50 instrument. Twenty specimens from each material were fabricated and divided into four equal groups, three experimental and one control (n=25). The differences in the mean surface roughness between the treatment groups were recorded and statistically analyzed. No statistically significant increase in the surface roughness was observed when the specimens were subjected to chemical disinfection and autoclave sterilization, increase in roughness and discoloration was observed in all the materials when specimens were subjected to microwave sterilization. Chemical disinfection did not have a significant effect but, since it is less effective, autoclave sterilization can be considered effective and autoclaving did not show any specimen discoloration as in microwave sterilization. Microwave sterilization may be considered when impressions are used to make diagnostic casts. A significant increase in surface roughness may produce rougher casts, resulting in rougher tissue surfaces for denture and cast restorations. Autoclave sterilization of vinyl polysiloxane elastomeric impressions for 5 minutes at 134°C at 20 psi may be considered an effective method over chemical disinfection and microwave sterilization, because chemical disinfection does

Surface treatments for biological, chemical and physical applications

CERN Document Server

Karaman, Mustafa

2017-01-01

A step-by-step guide to the topic with a mix of theory and practice in the fields of biology, chemistry and physics. Straightforward and well-structured, the first chapter introduces fundamental aspects of surface treatments, after which examples from nature are given. Subsequent chapters discuss various methods to surface modification, including chemical and physical approaches, followed by the characterization of the functionalized surfaces. Applications discussed include the lotus effect, diffusion barriers, enzyme immobilization and catalysis. Finally, the book concludes with a look at future technology advances. Throughout the text, tutorials and case studies are used for training purposes to grant a deeper understanding of the topic, resulting in an essential reference for students as well as for experienced engineers in R&D.

Bacterial transport in heterogeneous porous media: Observations from laboratory experiments

Science.gov (United States)

Silliman, S. E.; Dunlap, R.; Fletcher, M.; Schneegurt, M. A.

2001-11-01

Transport of bacteria through heterogeneous porous media was investigated in small-scale columns packed with sand and in a tank designed to allow the hydraulic conductivity to vary as a two-dimensional, lognormally distributed, second-order stationary, exponentially correlated random field. The bacteria were Pseudomonas ftuorescens R8, a strain demonstrating appreciable attachment to surfaces, and strain Ml, a transposon mutant of strain R8 with reduced attachment ability. In bench top, sand-filled columns, transport was determined by measuring intensity of fluorescence of stained cells in the effluent or by measuring radiolabeled cells that were retained in the sand columns. Results demonstrated that strain Ml was transported more efficiently than strain R8 through columns packed with either a homogeneous silica sand or a more heterogeneous sand with iron oxide coatings. Two experiments conducted in the tank involved monitoring transport of bacteria to wells via sampling from wells and sample ports in the tank. Bacterial numbers were determined by direct plate count. At the end of the first experiment, the distribution of the bacteria in the sediment was determined by destructive sampling and plating. The two experiments produced bacterial breakthrough curves that were quite similar even though the similarity between the two porous media was limited to first- and second-order statistical moments. This result appears consistent with the concept of large-scale, average behavior such as has been observed for the transport of conservative chemical tracers. The transported bacteria arrived simultaneously with a conservative chemical tracer (although at significantly lower normalized concentration than the tracer). However, the bacterial breakthrough curves showed significant late time tailing. The concentrations of bacteria attached to the sediment surfaces showed considerably more spatial variation than did the concentrations of bacteria in the fluid phase. This

Wet-chemical passivation of InAs: toward surfaces with high stability and low toxicity.

Science.gov (United States)

Jewett, Scott A; Ivanisevic, Albena

2012-09-18

In a variety of applications where the electronic and optical characteristics of traditional, siliconbased materials are inadequate, recently researchers have employed semiconductors made from combinations of group III and V elements such as InAs. InAs has a narrow band gap and very high electron mobility in the near-surface region, which makes it an attractive material for high performance transistors, optical applications, and chemical sensing. However, silicon-based materials remain the top semiconductors of choice for biological applications, in part because of their relatively low toxicity. In contrast to silicon, InAs forms an unstable oxide layer under ambient conditions, which can corrode over time and leach toxic indium and arsenic components. To make InAs more attractive for biological applications, researchers have investigated passivation, chemical and electronic stabilization, of the surface by adlayer adsorption. Because of the simplicity, low cost, and flexibility in the type of passivating molecule used, many researchers are currently exploring wet-chemical methods of passivation. This Account summarizes much of the recent work on the chemical passivation of InAs with a particular focus on the chemical stability of the surface and prevention of oxide regrowth. We review the various methods of surface preparation and discuss how crystal orientation affects the chemical properties of the surface. The correct etching of InAs is critical as researchers prepare the surface for subsequent adlayer adsorption. HCl etchants combined with a postetch annealing step allow the tuning of the chemical properties in the near-surface region to either arsenic- or indium-rich environments. Bromine etchants create indium-rich surfaces and do not require annealing after etching; however, bromine etchants are harsh and potentially destructive to the surface. The simultaneous use of NH(4)OH etchants with passivating molecules prevents contact with ambient air that can

Nano-catalysts: Bridging the gap between homogeneous and heterogeneous catalysis

Science.gov (United States)

Functionalized nanoparticles have emerged as sustainable alternatives to conventional materials, as robust, high-surface-area heterogeneous catalyst supports. We envisioned a catalyst system, which can bridge the homogenous and heterogeneous system. Postsynthetic surface modifica...

Morpho-chemical characterization and surface properties of carcinogenic zeolite fibers.

Science.gov (United States)

Mattioli, Michele; Giordani, Matteo; Dogan, Meral; Cangiotti, Michela; Avella, Giuseppe; Giorgi, Rodorico; Dogan, A Umran; Ottaviani, Maria Francesca

2016-04-05

Erionite belonging to the zeolite family is a human health-hazard, since it was demonstrated to be carcinogenic. Conversely, offretite family zeolites were suspected carcinogenic. Mineralogical, morphological, chemical, and surface characterizations were performed on two erionites (GF1, MD8) and one offretite (BV12) fibrous samples and, for comparison, one scolecite (SC1) sample. The specific surface area analysis indicated a larger availability of surface sites for the adsorption onto GF1, while SC1 shows the lowest one and the presence of large pores in the poorly fibrous zeolite aggregates. Selected spin probes revealed a high adsorption capacity of GF1 compared to the other zeolites, but the polar/charged interacting sites were well distributed, intercalated by less polar sites (Si-O-Si). MD8 surface is less homogeneous and the polar/charged sites are more interacting and closer to each other compared to GF1. The interacting ability of BV12 surface is much lower than that found for GF1 and MD8 and the probes are trapped in small pores into the fibrous aggregates. In comparison with the other zeolites, the non-carcinogenic SC1 shows a poor interacting ability and a lower surface polarity. These results helped to clarify the chemical properties and the surface interacting ability of these zeolite fibers which may be related to their carcinogenicity. Copyright © 2015 Elsevier B.V. All rights reserved.

Chemical Separation on Silver Nanorods Surface Monitored by TOF-SIMS

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Ondrej Petruš

2017-01-01

Full Text Available The article introduces a possible chemical separation of a mixture of two compounds on the metal nanorods surface. A silver nanorods surface has been prepared by controlled electrochemical deposition in anodic alumina oxide (AAO template. Rhodamine 6G and 4-aminothiophenol have been directly applied to the sampling point on a silver nanorods surface in an aliquot mixture. The position of the resolved compounds was analysed by time-of-flight secondary ion mass spectrometry (TOF-SIMS which measured the fragments and the molecular ions of the two compounds separated on the silver nanorods surface. Rhodamine 6G has been preconcentrated as 1.5 mm radial from the sampling point while 4-aminothiophenol formed a continuous self-assembled monolayer on the silver nanorods surface with a maximum molecular ion intensity at a distance of 0.5 mm from the sampling point. The separation of the single chemical components from the two-component mixture over the examined silver nanostructured films could clearly be shown. A fast separation on the mentioned nanotextured films was observed (within 50 s. This procedure can be easily integrated into the micro/nanofluidic systems or chips and different detection systems can be applied.

Chemical profiles of body surfaces and nests from six Bornean stingless bee species.

Science.gov (United States)

Leonhardt, Sara Diana; Blüthgen, Nico; Schmitt, Thomas

2011-01-01

Stingless bees (Apidae: Meliponini) are the most diverse group of Apid bees and represent common pollinators in tropical ecosystems. Like honeybees they live in large eusocial colonies and rely on complex chemical recognition and communication systems. In contrast to honeybees, their ecology and especially their chemical ecology have received only little attention, particularly in the Old World. We previously have analyzed the chemical profiles of six paleotropical stingless bee species from Borneo and revealed the presence of species-specific cuticular terpenes- an environmentally derived compound class so far unique among social insects. Here, we compared the bees' surface profiles to the chemistry of their nest material. Terpenes, alkanes, and alkenes were the dominant compound groups on both body surfaces and nest material. However, bee profiles and nests strongly differed in their chemical composition. Body surfaces thus did not merely mirror nests, rendering a passive compound transfer from nests to bees unlikely. The difference between nests and bees was particularly pronounced when all resin-derived compounds (terpenes) were excluded and only genetically determined compounds were considered. When terpenes were included, bee profiles and nest material still differed, because whole groups of terpenes (e.g., sesquiterpenes) were found in nest material of some species, but missing in their chemical profile, indicating that bees are able to influence the terpene composition both in their nests and on their surfaces.

Chemical grafting of the superhydrophobic surface on copper with hierarchical microstructure and its formation mechanism

Science.gov (United States)

Cai, Junyan; Wang, Shuhui; Zhang, Junhong; Liu, Yang; Hang, Tao; Ling, Huiqin; Li, Ming

2018-04-01

In this paper, a superhydrophobic surface with hierarchical structure was fabricated by chemical deposition of Cu micro-cones array, followed by chemical grafting of poly(methyl methacrylate) (PMMA). Water contact measurements give contact angle of 131.0° on these surfaces after PMMA grafting of 2 min and 165.2° after 6 min. The superhydrophobicity results from two factors: (1) the hierarchical structure due to Cu micro-cones array and the second level structure caused by intergranular corrosion during grafting of PMMA (confirmed by the scanning electron microscopy) and (2) the chemical modification of a low surface energy PMMA layer (confirmed by Fourier transform infrared spectrometer and X-ray photoelectron spectroscopy). In the chemical grafting process, the spontaneous reduction of nitrobenzene diazonium (NBD) tetrafluoroborate not only causes the corrosion of the Cu surface that leads to a hierarchical structure, but also initiates the polymerization of methyl methacrylate (MMA) monomers and thus the low free energy surface. Such a robust approach to fabricate the hierarchical structured surface with superhydrophobicity is expected to have practical application in anti-corrosion industry.

A procedure to create isoconcentration surfaces in low-chemical-partitioning, high-solute alloys

International Nuclear Information System (INIS)

Hornbuckle, B.C.; Kapoor, M.; Thompson, G.B.

2015-01-01

A proximity histogram or proxigram is the prevailing technique of calculating 3D composition profiles of a second phase in atom probe tomography. The second phase in the reconstruction is delineated by creating an isoconcentration surface, i.e. the precipitate–matrix interface. The 3D composition profile is then calculated with respect to this user-defined isoconcentration surface. Hence, the selection of the correct isoconcentration surface is critical. In general, the preliminary selection of an isoconcentration value is guided by the visual observation of a chemically partitioned second phase. However, in low-chemical -partitioning systems, such a visual guide is absent. The lack of a priori composition information of the precipitate phase may further confound the issue. This paper presents a methodology of selecting an appropriate elemental species and subsequently obtaining an isoconcentration value to create an accurate isoconcentration surface that will act as the precipitate–matrix interface. We use the H-phase precipitate in the Ni–Ti–Hf shape memory alloy as our case study to illustrate the procedure. - Highlights: • A procedure for creating accurate isoconcentration surface for low-chemical-partitioning, high-solute alloys. • Determine the appropriate element to create the isosconcentration surface. • Subsequently identify the accurate isoconcentration value to create an isoconcentration surface.

Comprehensive investigation of the corrosion and surface chemical effects of the decontamination technologies

International Nuclear Information System (INIS)

Szabo-Nagy, Andrea; Varga, Kalman; Deak-Horvath, Emese; Nemeth, Zoltan; Horvath, David; Schunk, Janos; Patek, Gabor

2012-09-01

Decontamination technologies are mainly developed to reduce the collective dose of the maintenance personnel at NPPs. The highest efficiency (i.e., the highest DF values) available without detrimental modification of the treated surface of structural material is the most important goal in the course of the application of a decontamination technology. A so-called 'soft' chemical decontamination technology has been developed - supported by the Paks Nuclear Power Plant - at the Institute of Radiochemistry and Radioecology of the University of Pannonia. The novel base technology can be effectively applied for the decontamination of the heat exchanger tubes of steam generators. In addition, by optimizing the main technological parameters (temperature, concentration of the liquid chemicals, flow rates, contact time, etc.) it can be utilized for specific applications such as decontamination of some dismountable devices and separable equipment or the total decontamination prior to plant dismantling (decommissioning) in the future. The aim of this work is to compare the efficiency, corrosion and surface chemical effects of some improved versions of the novel base-technology elaborated for decontamination of austenitic stainless steel surfaces. The experiments have been performed at laboratory conditions in decontamination model systems. The applied methods: γ-spectrometry, ICP-OES, voltammetry and SEM-EDX. The experimental results revealed that the efficiency of the base-technology mainly depends on the surface features of the stainless steel samples such as the chemical composition and thickness of the oxide layer, the nature (quantity, morphology and chemical composition) of the crystalline deposits. It has been documented that the improved version of the base-technology are suitable for the decontamination of both steel surfaces covered by chemically resistant large Cr-content crystals and that having compact oxide-layers (up to a thickness of 10 �

Cell surface profiling using high-throughput flow cytometry: a platform for biomarker discovery and analysis of cellular heterogeneity.

Directory of Open Access Journals (Sweden)

Craig A Gedye

Full Text Available Cell surface proteins have a wide range of biological functions, and are often used as lineage-specific markers. Antibodies that recognize cell surface antigens are widely used as research tools, diagnostic markers, and even therapeutic agents. The ability to obtain broad cell surface protein profiles would thus be of great value in a wide range of fields. There are however currently few available methods for high-throughput analysis of large numbers of cell surface proteins. We describe here a high-throughput flow cytometry (HT-FC platform for rapid analysis of 363 cell surface antigens. Here we demonstrate that HT-FC provides reproducible results, and use the platform to identify cell surface antigens that are influenced by common cell preparation methods. We show that multiple populations within complex samples such as primary tumors can be simultaneously analyzed by co-staining of cells with lineage-specific antibodies, allowing unprecedented depth of analysis of heterogeneous cell populations. Furthermore, standard informatics methods can be used to visualize, cluster and downsample HT-FC data to reveal novel signatures and biomarkers. We show that the cell surface profile provides sufficient molecular information to classify samples from different cancers and tissue types into biologically relevant clusters using unsupervised hierarchical clustering. Finally, we describe the identification of a candidate lineage marker and its subsequent validation. In summary, HT-FC combines the advantages of a high-throughput screen with a detection method that is sensitive, quantitative, highly reproducible, and allows in-depth analysis of heterogeneous samples. The use of commercially available antibodies means that high quality reagents are immediately available for follow-up studies. HT-FC has a wide range of applications, including biomarker discovery, molecular classification of cancers, or identification of novel lineage specific or stem cell

Cell surface profiling using high-throughput flow cytometry: a platform for biomarker discovery and analysis of cellular heterogeneity.

Science.gov (United States)

Gedye, Craig A; Hussain, Ali; Paterson, Joshua; Smrke, Alannah; Saini, Harleen; Sirskyj, Danylo; Pereira, Keira; Lobo, Nazleen; Stewart, Jocelyn; Go, Christopher; Ho, Jenny; Medrano, Mauricio; Hyatt, Elzbieta; Yuan, Julie; Lauriault, Stevan; Meyer, Mona; Kondratyev, Maria; van den Beucken, Twan; Jewett, Michael; Dirks, Peter; Guidos, Cynthia J; Danska, Jayne; Wang, Jean; Wouters, Bradly; Neel, Benjamin; Rottapel, Robert; Ailles, Laurie E

2014-01-01

Cell surface proteins have a wide range of biological functions, and are often used as lineage-specific markers. Antibodies that recognize cell surface antigens are widely used as research tools, diagnostic markers, and even therapeutic agents. The ability to obtain broad cell surface protein profiles would thus be of great value in a wide range of fields. There are however currently few available methods for high-throughput analysis of large numbers of cell surface proteins. We describe here a high-throughput flow cytometry (HT-FC) platform for rapid analysis of 363 cell surface antigens. Here we demonstrate that HT-FC provides reproducible results, and use the platform to identify cell surface antigens that are influenced by common cell preparation methods. We show that multiple populations within complex samples such as primary tumors can be simultaneously analyzed by co-staining of cells with lineage-specific antibodies, allowing unprecedented depth of analysis of heterogeneous cell populations. Furthermore, standard informatics methods can be used to visualize, cluster and downsample HT-FC data to reveal novel signatures and biomarkers. We show that the cell surface profile provides sufficient molecular information to classify samples from different cancers and tissue types into biologically relevant clusters using unsupervised hierarchical clustering. Finally, we describe the identification of a candidate lineage marker and its subsequent validation. In summary, HT-FC combines the advantages of a high-throughput screen with a detection method that is sensitive, quantitative, highly reproducible, and allows in-depth analysis of heterogeneous samples. The use of commercially available antibodies means that high quality reagents are immediately available for follow-up studies. HT-FC has a wide range of applications, including biomarker discovery, molecular classification of cancers, or identification of novel lineage specific or stem cell markers.

Heterogeneous Photocatalysis: Fundamentals and Application for Treatment of Polluted Air

Directory of Open Access Journals (Sweden)

Tomašić, V.

2011-07-01

Full Text Available The use of heterogeneous photocatalysts for the abatement of environmental problems has received increased attention during the last three decades. The photocatalyst used in most of these studies was titanium dioxide. This fact relates to the unique physical and chemical properties of titanium dioxide and similar semiconductor materials, such as ZnO, MgO,WO3, Fe2Oa, CdS, etc. that may be utilized for a wide range of potential applications. Specifically, upon ultraviolet irradiation these materials exhibit photocatalytic activity that enables the oxidative destruction of a wide range of organic compounds and biological species on their surface. In addition, these materials may also exhibit photocatalytically induced superhydrophilicity that converts the hydrophobic character of the surface to hydrophilic when exposed to UV light. This causes the formation of uniform water films on the surface of these materials, which prevents the adhesion of inorganic or organic components and thus retains a clean surface on the photocatalyst. Photocatalytic materials may be deployed on surfaces of various substrates, such as glass, ceramics or metals to provide layers that exhibit photocatalytic activity when they are exposed to light. Excitation of a photocatalyst leads to the creation of electrons and holes in the semiconductor material. Furthermore, these electrons and holes interact with molecules adsorbed on the semiconductor and can induce charge transfer process that results in the degradation of the adsorbate. The commercial potentials of heterogeneous photocatalysis are huge, including medical applications, application in the field of architecture (particularly for the cultural heritage purposes, facade paints, etc., automotive and food industries (cleaner technologies, non-fogging glass and mirrors, product safety, textile and glass industry, as well as in environmental protection (water and air purification and disinfection. After the discovery that

Chemical Reactive Anchoring Lipids with Different Performance for Cell Surface Re-engineering Application.

Science.gov (United States)

Vabbilisetty, Pratima; Boron, Mallorie; Nie, Huan; Ozhegov, Evgeny; Sun, Xue-Long

2018-02-28

Introduction of selectively chemical reactive groups at the cell surface enables site-specific cell surface labeling and modification opportunity, thus facilitating the capability to study the cell surface molecular structure and function and the molecular mechanism it underlies. Further, it offers the opportunity to change or improve a cell's functionality for interest of choice. In this study, two chemical reactive anchor lipids, phosphatidylethanolamine-poly(ethylene glycol)-dibenzocyclooctyne (DSPE-PEG 2000 -DBCO) and cholesterol-PEG-dibenzocyclooctyne (CHOL-PEG 2000 -DBCO) were synthesized and their potential application for cell surface re-engineering via lipid fusion were assessed with RAW 264.7 cells as a model cell. Briefly, RAW 264.7 cells were incubated with anchor lipids under various concentrations and at different incubation times. The successful incorporation of the chemical reactive anchor lipids was confirmed by biotinylation via copper-free click chemistry, followed by streptavidin-fluorescein isothiocyanate binding. In comparison, the cholesterol-based anchor lipid afforded a higher cell membrane incorporation efficiency with less internalization than the phospholipid-based anchor lipid. Low cytotoxicity of both anchor lipids upon incorporation into the RAW 264.7 cells was observed. Further, the cell membrane residence time of the cholesterol-based anchor lipid was evaluated with confocal microscopy. This study suggests the potential cell surface re-engineering applications of the chemical reactive anchor lipids.

Chemical Reactive Anchoring Lipids with Different Performance for Cell Surface Re-engineering Application

Science.gov (United States)

2018-01-01

Introduction of selectively chemical reactive groups at the cell surface enables site-specific cell surface labeling and modification opportunity, thus facilitating the capability to study the cell surface molecular structure and function and the molecular mechanism it underlies. Further, it offers the opportunity to change or improve a cell’s functionality for interest of choice. In this study, two chemical reactive anchor lipids, phosphatidylethanolamine–poly(ethylene glycol)–dibenzocyclooctyne (DSPE–PEG2000–DBCO) and cholesterol–PEG–dibenzocyclooctyne (CHOL–PEG2000–DBCO) were synthesized and their potential application for cell surface re-engineering via lipid fusion were assessed with RAW 264.7 cells as a model cell. Briefly, RAW 264.7 cells were incubated with anchor lipids under various concentrations and at different incubation times. The successful incorporation of the chemical reactive anchor lipids was confirmed by biotinylation via copper-free click chemistry, followed by streptavidin-fluorescein isothiocyanate binding. In comparison, the cholesterol-based anchor lipid afforded a higher cell membrane incorporation efficiency with less internalization than the phospholipid-based anchor lipid. Low cytotoxicity of both anchor lipids upon incorporation into the RAW 264.7 cells was observed. Further, the cell membrane residence time of the cholesterol-based anchor lipid was evaluated with confocal microscopy. This study suggests the potential cell surface re-engineering applications of the chemical reactive anchor lipids. PMID:29503972

Atomic-level spatial distributions of dopants on silicon surfaces: toward a microscopic understanding of surface chemical reactivity

Science.gov (United States)

Hamers, Robert J.; Wang, Yajun; Shan, Jun

1996-11-01

We have investigated the interaction of phosphine (PH 3) and diborane (B 2H 6) with the Si(001) surface using scanning tunneling microscopy, infrared spectroscopy, and ab initio molecular orbital calculations. Experiment and theory show that the formation of PSi heterodimers is energetically favorable compared with formation of PP dimers. The stability of the heterodimers arises from a large strain energy associated with formation of PP dimers. At moderate P coverages, the formation of PSi heterodimers leaves the surface with few locations where there are two adjacent reactive sites. This in turn modifies the chemical reactivity toward species such as PH 3, which require only one site to adsorb but require two adjacent sites to dissociate. Boron on Si(001) strongly segregates into localized regions of high boron concentration, separated by large regions of clean Si. This leads to a spatially-modulated chemical reactivity which during subsequent growth by chemical vapor deposition (CVD) leads to formation of a rough surface. The implications of the atomic-level spatial distribution of dopants on the rates and mechanisms of CVD growth processes are discussed.

The Ocular Surface Chemical Burns

Directory of Open Access Journals (Sweden)

Medi Eslani

2014-01-01

Full Text Available Ocular chemical burns are common and serious ocular emergencies that require immediate and intensive evaluation and care. The victims of such incidents are usually young, and therefore loss of vision and disfigurement could dramatically affect their lives. The clinical course can be divided into immediate, acute, early, and late reparative phases. The degree of limbal, corneal, and conjunctival involvement at the time of injury is critically associated with prognosis. The treatment starts with simple but vision saving steps and is continued with complicated surgical procedures later in the course of the disease. The goal of treatment is to restore the normal ocular surface anatomy and function. Limbal stem cell transplantation, amniotic membrane transplantation, and ultimately keratoprosthesis may be indicated depending on the patients’ needs.

Transport-induced shifts in condensate dew-point and composition in multicomponent systems with chemical reaction

Science.gov (United States)

Rosner, D. E.; Nagarajan, R.

1985-01-01

Partial heterogeneous condensation phenomena in multicomponent reacting systems are analyzed taking into consideration the chemical element transport phenomena. It is demonstrated that the dew-point surface temperature in chemically reactive systems is not a purely thermodynamic quantity, but is influenced by the multicomponent diffusion and Soret-mass diffusion phenomena. Several distinct dew-points are shown to exist in such systems and, as a result of transport constraints, the 'sharp' locus between two chemically distinct condensates is systematically moved to a difference mainstream composition.

Surface chemical reactions induced by molecules electronically-excited in the gas

DEFF Research Database (Denmark)

Petrunin, Victor V.

2011-01-01

and alignment are taking place, guiding all the molecules towards the intersections with the ground state PES, where transitions to the ground state PES will occur with minimum energy dissipation. The accumulated kinetic energy may be used to overcome the chemical reaction barrier. While recombination chemical...... be readily produced. Products of chemical adsorption and/or chemical reactions induced within adsorbates are aggregated on the surface and observed by light scattering. We will demonstrate how pressure and spectral dependencies of the chemical outcomes, polarization of the light and interference of two laser...... beams inducing the reaction can be used to distinguish the new process we try to investigate from chemical reactions induced by photoexcitation within adsorbed molecules and/or gas phase photolysis....

Surface with two paint strips for detection and warning of chemical warfare and radiological agents

Science.gov (United States)

Farmer, Joseph C.

2013-04-02

A system for warning of corrosion, chemical, or radiological substances. The system comprises painting a surface with a paint or coating that includes an indicator material and monitoring the surface for indications of the corrosion, chemical, or radiological substances.

Antioxidant Deactivation on Graphenic Nanocarbon Surfaces

Energy Technology Data Exchange (ETDEWEB)

Liu, Xinyuan [ORNL; Sen, Sujat [Brown University; Liu, Jingyu [Brown University; Kulaots, Indrek [Brown University; Geohegan, David B [ORNL; Kane, Agnes [Brown University; Puretzky, Alexander A [ORNL; Rouleau, Christopher M [ORNL; More, Karren Leslie [ORNL; Palmore, G. Tayhas R. [Brown University; Hurt, Robert H. [Brown University

2011-01-01

This article reports a direct chemical pathway for antioxidant deactivation on the surfaces of carbon nanomaterials. In the absence of cells, carbon nanotubes are shown to deplete the key physiological antioxidant glutathione (GSH) in a reaction involving dissolved dioxygen that yields the oxidized dimer, GSSG, as the primary product. In both chemical and electrochemical experiments, oxygen is only consumed at a significant steady-state rate in the presence of both nanotubes and GSH. GSH deactivation occurs for single- and multi-walled nanotubes, graphene oxide, nanohorns, and carbon black at varying rates that are characteristic of the material. The GSH depletion rates can be partially unified by surface area normalization, are accelerated by nitrogen doping, and suppressed by defect annealing or addition of proteins or surfactants. It is proposed that dioxygen reacts with active sites on graphenic carbon surfaces to produce surface-bound oxygen intermediates that react heterogeneously with glutathione to restore the carbon surface and complete a catalytic cycle. The direct catalytic reaction between nanomaterial surfaces and antioxidants may contribute to oxidative stress pathways in nanotoxicity, and the dependence on surface area and structural defects suggest strategies for safe material design.

Modelling and investigation of partial wetting surfaces for drop dynamics using lattice Boltzmann method

Energy Technology Data Exchange (ETDEWEB)

Pravinraj, T., E-mail: pravinraj1711@gmail.com; Patrikar, Rajendra

2017-07-01

Highlights: • A LBM model on partial wetting surface for droplet dynamics is presented by introducing a simple initial partial wetting boundary condition in SC model. • With our approach one can tune the splitting volume and time by carefully choosing strip width and position. • It is shown that the droplet spreading on chemically heterogeneous surfaces can be controlled not only by Weber number but also by tuning strip width ratio. • The directional transportation of a droplet due to chemical wetting gradient is simulated and analyzed using hybrid thermodynamic-image processing technique. • Microstructure surface and its influence on the directional wetting based transportation of droplet are demonstrated. - Abstract: Partial wetting surfaces and its influence on the droplet movement of micro and nano scale being contemplated for many useful applications. The dynamics of the droplet usually analyzed with a multiphase lattice Boltzmann method (LBM). In this paper, the influence of partial wetting surface on the dynamics of droplet is systematically analyzed for various cases. Splitting of droplets due to chemical gradient of the surface is studied and analyses of splitting time for various widths of the strips for different Weber numbers are computed. With the proposed model one can tune the splitting volume and time by carefully choosing a strip width and droplet position. The droplet spreading on chemically heterogeneous surfaces shows that the spreading can be controlled not only by parameters of Weber number but also by tuning strip width ratio. The transportation of the droplet from hydrophobic surface to hydrophilic surface due to chemical gradient is simulated and analyzed using our hybrid thermodynamic-image processing technique. The results prove that with the progress of time the surface free energy decreases with increase in spreading area. Finally, the transportation of a droplet on microstructure gradient is demonstrated. The model explains

Heterogeneous reaction mechanisms and kinetics relevant to the CVD of semiconductor materials

Energy Technology Data Exchange (ETDEWEB)

Creighton, J.R.; Coltrin, M.E.

1994-03-01

This report documents the state of the art in experimental and theoretical techniques for determining reaction mechanisms and chemical kinetics of heterogeneous reactions relevant to the chemical vapor deposition of semiconductor materials. It summarizes the most common ultra-high vacuum experimental techniques that are used and the types of rate information available from each. Several case studies of specific chemical systems relevant to the microelectronics industry are described. Theoretical methods for calculating heterogeneous reaction rate constants are also summarized.

Effect of Coatings on the Uptake Rate and HONO Yield in Heterogeneous Reaction of Soot with NO2

Science.gov (United States)

Cruz-Quiñones, M.; Khalizov, A. F.; Zhang, R.

2009-12-01

Heterogeneous reaction of nitrogen dioxide on carbon soot aerosols has been suggested as a possible source of nighttime nitrous acid (HONO) in atmosphere boundary layer. Available laboratory data show significant variability in the measured reaction probabilities and HONO yields, making it difficult to asses the atmospheric significance of this process. Moreover, little is known of how aging of soot aerosol through internal mixing with other atmospheric trace constituents will affect the heterogeneous reactivity and HONO production. In this work, the heterogeneous reaction of NO2 on fresh and aged soot films leading to HONO formation was studied through a series of kinetic uptake experiments and HONO yield measurements. Soot samples were prepared by incomplete combustion of propane and kerosene fuels under lean and rich flame conditions. Experiments were performed in a low-pressure, fast-flow reactor coupled to a chemical ionization mass spectrometer (CIMS), using atmospheric-level NO2 concentrations. Heterogeneous uptake coefficients, γ(geom) and γ(BET), were calculated using geometric and internal BET soot surface areas, respectively. The uptake coefficient and the HONO yield depend on the type of fuel and combustion regime and are the highest for soot samples prepared using rich kerosene flame. Although, the internal surface area of soot measured by BET method is a factor of 50 to 500 larger than the geometric surface area, only the top soot layers are involved in heterogeneous reaction with NO2 as follows from the observed weak dependence of γ(geom) and decrease in γ(BET) with increasing sample mass. Heating the soot samples before exposure to NO2 increases the BET surface area, the HONO yield, and the NO2 uptake coefficient due to the removal of the organic fraction from the soot backbone that unblocks active sites and makes them accessible for physical adsorption and chemical reactions. Our results support the oxidation-reduction mechanism involving

Accessible surface area from NMR chemical shifts

Energy Technology Data Exchange (ETDEWEB)

Hafsa, Noor E.; Arndt, David; Wishart, David S., E-mail: david.wishart@ualberta.ca [University of Alberta, Department of Computing Science (Canada)

2015-07-15

Accessible surface area (ASA) is the surface area of an atom, amino acid or biomolecule that is exposed to solvent. The calculation of a molecule’s ASA requires three-dimensional coordinate data and the use of a “rolling ball” algorithm to both define and calculate the ASA. For polymers such as proteins, the ASA for individual amino acids is closely related to the hydrophobicity of the amino acid as well as its local secondary and tertiary structure. For proteins, ASA is a structural descriptor that can often be as informative as secondary structure. Consequently there has been considerable effort over the past two decades to try to predict ASA from protein sequence data and to use ASA information (derived from chemical modification studies) as a structure constraint. Recently it has become evident that protein chemical shifts are also sensitive to ASA. Given the potential utility of ASA estimates as structural constraints for NMR we decided to explore this relationship further. Using machine learning techniques (specifically a boosted tree regression model) we developed an algorithm called “ShiftASA” that combines chemical-shift and sequence derived features to accurately estimate per-residue fractional ASA values of water-soluble proteins. This method showed a correlation coefficient between predicted and experimental values of 0.79 when evaluated on a set of 65 independent test proteins, which was an 8.2 % improvement over the next best performing (sequence-only) method. On a separate test set of 92 proteins, ShiftASA reported a mean correlation coefficient of 0.82, which was 12.3 % better than the next best performing method. ShiftASA is available as a web server ( http://shiftasa.wishartlab.com http://shiftasa.wishartlab.com ) for submitting input queries for fractional ASA calculation.

Aerosol simulation including chemical and nuclear reactions

International Nuclear Information System (INIS)

Marwil, E.S.; Lemmon, E.C.

1985-01-01

The numerical simulation of aerosol transport, including the effects of chemical and nuclear reactions presents a challenging dynamic accounting problem. Particles of different sizes agglomerate and settle out due to various mechanisms, such as diffusion, diffusiophoresis, thermophoresis, gravitational settling, turbulent acceleration, and centrifugal acceleration. Particles also change size, due to the condensation and evaporation of materials on the particle. Heterogeneous chemical reactions occur at the interface between a particle and the suspending medium, or a surface and the gas in the aerosol. Homogeneous chemical reactions occur within the aersol suspending medium, within a particle, and on a surface. These reactions may include a phase change. Nuclear reactions occur in all locations. These spontaneous transmutations from one element form to another occur at greatly varying rates and may result in phase or chemical changes which complicate the accounting process. This paper presents an approach for inclusion of these effects on the transport of aerosols. The accounting system is very complex and results in a large set of stiff ordinary differential equations (ODEs). The techniques for numerical solution of these ODEs require special attention to achieve their solution in an efficient and affordable manner. 4 refs

Mass transfer in porous media with heterogeneous chemical reaction

Directory of Open Access Journals (Sweden)

Souza S.M.A.G.Ulson de

2003-01-01

Full Text Available In this paper, the modeling of the mass transfer process in packed-bed reactors is presented and takes into account dispersion in the main fluid phase, internal diffusion of the reactant in the pores of the catalyst, and surface reaction inside the catalyst. The method of volume averaging is applied to obtain the governing equation for use on a small scale. The local mass equilibrium is assumed for obtaining the one-equation model for use on a large scale. The closure problems are developed subject to the length-scale constraints and the model of a spatially periodic porous medium. The expressions for effective diffusivity, hydrodynamic dispersion, total dispersion and the Darcy's law permeability tensors are presented. Solution of the set of final equations permits the variations of velocity and concentration of the chemical species along the packed-bed reactors to be obtained.

Analysis of Wetting and Contact Angle Hysteresis on Chemically Patterned Surfaces

KAUST Repository

Xu, Xianmin; Wang, Xiaoping

2011-01-01

Wetting and contact angle hysteresis on chemically patterned surfaces in two dimensionsare analyzed from a stationary phase-field model for immiscible two phase fluids. We first study the sharp-interface limit of the model by the method of matched asymptotic expansions. We then justify the results rigorously by the γ-convergence theory for the related variational problem and study the properties of the limiting minimizers. The results also provide a clear geometric picture of the equilibrium configuration of the interface. This enables us to explicitly calculate the total surface energy for the two phase systems on chemically patterned surfaces with simple geometries, namely the two phase flow in a channel and the drop spreading. By considering the quasi-staticmotion of the interface described by the change of volume (or volume fraction), we can follow the change-of-energy landscape which also reveals the mechanism for the stick-slip motion of the interface and contact angle hysteresis on the chemically patterned surfaces. As the interface passes throughpatterned surfaces, we observe not only stick-slip of the interface and switching of the contact angles but also the hysteresis of contact point and contact angle. Furthermore, as the size of the patternde creases to zero, the stick-slip becomes weaker but the hysteresis becomes stronger in the sense that one observes either the advancing contact angle or the receding contact angle (when the interface ismoving in the opposite direction) without the switching in between. © 2011 Society for Industrial and Applied Mathematics.

Heterogeneous chemical reaction of chlorine nitrate and water on sulfuric-acid surfaces at room temperature

Science.gov (United States)

Rossi, Michel J.; Malhotra, Ripudaman; Golden, David M.

1987-01-01

The use of H2SO4 as a catalyst for aerosol production of chlorine compounds in the chemistry of the antarctic stratosphere was investigated in laboratory trials. The experiments involved the gas surface collision rate of a molecule on a given surface during its residence time in a Knudsen cell in molecular flow conditions. Chlorine nitrate gas was made to flow through a chamber exposed to a container holding a 95.6 pct H2SO4 solution. Gas leaving the cell was scanned with a mass spectrometer. A sticking coefficient of 0.00032 was found for the chlorine nitrate, a value five times that previously reported.

Analysis of the Si(111) surface prepared in chemical vapor ambient for subsequent III-V heteroepitaxy

International Nuclear Information System (INIS)

Zhao, W.; Steidl, M.; Paszuk, A.; Brückner, S.; Dobrich, A.; Supplie, O.; Kleinschmidt, P.; Hannappel, T.

2017-01-01

Highlights: • We investigate the Si(111) surface prepared in CVD ambient at 1000 °C in 950 mbar H_2. • UHV-based XPS, LEED, STM and FTIR as well as ambient AFM are applied. • After processing the Si(111) surface is free of contamination and atomically flat. • The surface exhibits a (1 × 1) reconstruction and monohydride termination. • Wet-chemical pretreatment and homoepitaxy are required for a regular step structure. - Abstract: For well-defined heteroepitaxial growth of III-V epilayers on Si(111) substrates the atomic structure of the silicon surface is an essential element. Here, we study the preparation of the Si(111) surface in H_2-based chemical vapor ambient as well as its atomic structure after contamination-free transfer to ultrahigh vacuum (UHV). Applying complementary UHV-based techniques, we derive a complete picture of the atomic surface structure and its chemical composition. X-ray photoelectron spectroscopy measurements after high-temperature annealing confirm a Si surface free of any traces of oxygen or other impurities. The annealing in H_2 ambient leads to a monohydride surface termination, as verified by Fourier-transform infrared spectroscopy. Scanning tunneling microscopy confirms a well ordered, atomically smooth surface, which is (1 × 1) reconstructed, in agreement with low energy electron diffraction patterns. Atomic force microscopy reveals a significant influence of homoepitaxy and wet-chemical pretreatment on the surface morphology. Our findings show that wet-chemical pretreatment followed by high-temperature annealing leads to contamination-free, atomically flat Si(111) surfaces, which are ideally suited for subsequent III-V heteroepitaxy.

Two-wavelength Method Estimates Heat fluxes over Heterogeneous Surface in North-China

Science.gov (United States)

Zhang, G.; Zheng, N.; Zhang, J.

2017-12-01

Heat fluxes is a key process of hydrological and heat transfer of soil-plant-atmosphere continuum (SPAC), and now it is becoming an important topic in meteorology, hydrology, ecology and other related research areas. Because the temporal and spatial variation of fluxes at regional scale is very complicated, it is still difficult to measure fluxes at the kilometer scale over a heterogeneous surface. A technique called "two-wavelength method" which combines optical scintillometer with microwave scintillometer is able to measure both sensible and latent heat fluxes over large spatial scales at the same time. The main purpose of this study is to investigate the fluxes over non-uniform terrain in North-China. Estimation of heat fluxes was carried out with the optical-microwave scintillometer and an eddy covariance (EC) system over heterogeneous surface in Tai Hang Mountains, China. EC method was set as a benchmark in the study. Structure parameters obtained from scintillometer showed that the typical measurement values of Cn2 are around 10-13 m-2/3 for microwave scintillometer, and values of Cn2 were around 10-15 m-2/3 for optical scintillometer. The correlation of heat fluxes (H) derived from scintillometer and EC system showed as a ratio of 1.05,and with R2=0.75, while the correlation of latent heat fluxes (LE) showed as 1.29 with R2=0.67. It was also found that heat fluxes derived from the two system showed good agreement (R2=0.9 for LE, R2=0.97 for H) when the Bowen ratio (β) was 1.03, while discrepancies showed significantly when β=0.75, and RMSD in H was 139.22 W/m2, 230.85 W/m2 in LE respectively.Experiment results in our research shows that, the two-wavelength method gives a larger heat fluxes over the study area, and a deeper study should be conduct. We expect that our investigate and analysis can be promoted the application of scintillometry method in regional evapotranspiration measurements and relevant disciplines.

Theoretical study of adsorption of organic phosphines on transition metal surfaces

Science.gov (United States)

Lou, Shujie; Jiang, Hong

2018-04-01

The adsorption properties of organic phosphines on transition metal (TM) surfaces (Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) have been studied to explore the possibility of building novel heterogeneous chiral catalytic systems based on organic phosphines. Preferred adsorption sites, adsorption energies and surface electronic structures of a selected set of typical organic phosphines adsorbed on TM surfaces are calculated with density-functional theory to obtain a systematic understanding on the nature of adsorption interactions. All organic phosphines considered are found to chemically adsorb on these TM surfaces with the atop site as the most preferred one, and the TM-P bond is formed via the lone-pair electrons of the P atom and the directly contacted TM atom. These findings imply that it is indeed possible to build heterogeneous chiral catalytic systems based on organic phosphines adsorbed on TM surfaces, which, however, requires a careful design of molecular structure of organic phosphines.

Nanosecond laser textured superhydrophobic metallic surfaces and their chemical sensing applications

Science.gov (United States)

Ta, Duong V.; Dunn, Andrew; Wasley, Thomas J.; Kay, Robert W.; Stringer, Jonathan; Smith, Patrick J.; Connaughton, Colm; Shephard, Jonathan D.

2015-12-01

This work demonstrates superhydrophobic behavior on nanosecond laser patterned copper and brass surfaces. Compared with ultrafast laser systems previously used for such texturing, infrared nanosecond fiber lasers offer a lower cost and more robust system combined with potentially much higher processing rates. The wettability of the textured surfaces develops from hydrophilicity to superhydrophobicity over time when exposed to ambient conditions. The change in the wetting property is attributed to the partial deoxidation of oxides on the surface induced during laser texturing. Textures exhibiting steady state contact angles of up to ∼152° with contact angle hysteresis of around 3-4° have been achieved. Interestingly, the superhydrobobic surfaces have the self-cleaning ability and have potential for chemical sensing applications. The principle of these novel chemical sensors is based on the change in contact angle with the concentration of methanol in a solution. To demonstrate the principle of operation of such a sensor, it is found that the contact angle of methanol solution on the superhydrophobic surfaces exponentially decays with increasing concentration. A significant reduction, of 128°, in contact angle on superhydrophobic brass is observed, which is one order of magnitude greater than that for the untreated surface (12°), when percent composition of methanol reaches to 28%.

Simultaneous tuning of chemical composition and topography of copolymer surfaces: micelles as building blocks.

Science.gov (United States)

Zhao, Ning; Zhang, Xiaoyan; Zhang, Xiaoli; Xu, Jian

2007-05-14

A simple method is described for controlling the surface chemical composition and topography of the diblock copolymer poly(styrene)-b-poly(dimethylsiloxane)(PS-b-PDMS) by casting the copolymer solutions from solvents with different selectivities. The surface morphology and chemical composition were characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), respectively, and the wetting behavior was studied by water contact angle (CA) and sliding angle (SA) and by CA hysteresis. Chemical composition and morphology of the surface depend on solvent properties, humidity of the air, solution concentration, and block lengths. If the copolymer is cast from a common solvent, the resultant surface is hydrophobic, with a flat morphology, and dominated by PDMS on the air side. From a PDMS-selective solvent, the surface topography depends on the morphology of the micelles. Starlike micelles give rise to a featureless surface nearly completely covered by PDMS, while crew-cut-like micelles lead to a rough surface with a hierarchical structure that consists partly of PDMS. From a PS-selective solvent, however, surface segregation of PDMS was restricted, and the surface morphology can be controlled by vapor-induced phase separation. On the basis of the tunable surface roughness and PDMS concentration on the air side, water repellency of the copolymer surface could be tailored from hydrophobic to superhydrophobic. In addition, reversible switching behavior between hydrophobic and superhydrophobic can be achieved by exposing the surface to solvents with different selectivities.

Coupling chemical and biological catalysis: a flexible paradigm for producing biobased chemicals.

Science.gov (United States)

Schwartz, Thomas J; Shanks, Brent H; Dumesic, James A

2016-04-01

Advances in metabolic engineering have allowed for the development of new biological catalysts capable of selectively de-functionalizing biomass to yield platform molecules that can be upgraded to biobased chemicals using high efficiency continuous processing allowed by heterogeneous chemical catalysis. Coupling these disciplines overcomes the difficulties of selectively activating COH bonds by heterogeneous chemical catalysis and producing petroleum analogues by biological catalysis. We show that carboxylic acids, pyrones, and alcohols are highly flexible platforms that can be used to produce biobased chemicals by this approach. More generally, we suggest that molecules with three distinct functionalities may represent a practical upper limit on the extent of functionality present in the platform molecules that serve as the bridge between biological and chemical catalysis. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effects of vegetation heterogeneity and surface topography on spatial scaling of net primary productivity

Science.gov (United States)

Chen, J. M.; Chen, X.; Ju, W.

2013-07-01

Due to the heterogeneous nature of the land surface, spatial scaling is an inevitable issue in the development of land models coupled with low-resolution Earth system models (ESMs) for predicting land-atmosphere interactions and carbon-climate feedbacks. In this study, a simple spatial scaling algorithm is developed to correct errors in net primary productivity (NPP) estimates made at a coarse spatial resolution based on sub-pixel information of vegetation heterogeneity and surface topography. An eco-hydrological model BEPS-TerrainLab, which considers both vegetation and topographical effects on the vertical and lateral water flows and the carbon cycle, is used to simulate NPP at 30 m and 1 km resolutions for a 5700 km2 watershed with an elevation range from 518 m to 3767 m in the Qinling Mountain, Shanxi Province, China. Assuming that the NPP simulated at 30 m resolution represents the reality and that at 1 km resolution is subject to errors due to sub-pixel heterogeneity, a spatial scaling index (SSI) is developed to correct the coarse resolution NPP values pixel by pixel. The agreement between the NPP values at these two resolutions is improved considerably from R2 = 0.782 to R2 = 0.884 after the correction. The mean bias error (MBE) in NPP modelled at the 1 km resolution is reduced from 14.8 g C m-2 yr-1 to 4.8 g C m-2 yr-1 in comparison with NPP modelled at 30 m resolution, where the mean NPP is 668 g C m-2 yr-1. The range of spatial variations of NPP at 30 m resolution is larger than that at 1 km resolution. Land cover fraction is the most important vegetation factor to be considered in NPP spatial scaling, and slope is the most important topographical factor for NPP spatial scaling especially in mountainous areas, because of its influence on the lateral water redistribution, affecting water table, soil moisture and plant growth. Other factors including leaf area index (LAI) and elevation have small and additive effects on improving the spatial scaling

Effects of vegetation heterogeneity and surface topography on spatial scaling of net primary productivity

Directory of Open Access Journals (Sweden)

J. M. Chen

2013-07-01

Full Text Available Due to the heterogeneous nature of the land surface, spatial scaling is an inevitable issue in the development of land models coupled with low-resolution Earth system models (ESMs for predicting land-atmosphere interactions and carbon-climate feedbacks. In this study, a simple spatial scaling algorithm is developed to correct errors in net primary productivity (NPP estimates made at a coarse spatial resolution based on sub-pixel information of vegetation heterogeneity and surface topography. An eco-hydrological model BEPS-TerrainLab, which considers both vegetation and topographical effects on the vertical and lateral water flows and the carbon cycle, is used to simulate NPP at 30 m and 1 km resolutions for a 5700 km2 watershed with an elevation range from 518 m to 3767 m in the Qinling Mountain, Shanxi Province, China. Assuming that the NPP simulated at 30 m resolution represents the reality and that at 1 km resolution is subject to errors due to sub-pixel heterogeneity, a spatial scaling index (SSI is developed to correct the coarse resolution NPP values pixel by pixel. The agreement between the NPP values at these two resolutions is improved considerably from R2 = 0.782 to R2 = 0.884 after the correction. The mean bias error (MBE in NPP modelled at the 1 km resolution is reduced from 14.8 g C m−2 yr−1 to 4.8 g C m−2 yr−1 in comparison with NPP modelled at 30 m resolution, where the mean NPP is 668 g C m−2 yr−1. The range of spatial variations of NPP at 30 m resolution is larger than that at 1 km resolution. Land cover fraction is the most important vegetation factor to be considered in NPP spatial scaling, and slope is the most important topographical factor for NPP spatial scaling especially in mountainous areas, because of its influence on the lateral water redistribution, affecting water table, soil moisture and plant growth. Other factors including leaf area index (LAI and elevation have small and additive effects on improving

Sub-Tg enthalpy relaxation in an unstable oxide glass former: insights into the structural heterogeneity

DEFF Research Database (Denmark)

Yue, Yuanzheng; Zhang, Yanfei

Structural heterogeneity plays a crucial role in determining functionality of glasses. In this work we have found that the sub-Tg enthalpy relaxation pattern in a hyperquenched glass is highly sensitive to structural heterogeneity. As a consequence, the former can be used as an effective approach...... to detect and quantify the structural heterogeneity in glass-forming liquids. However, the chemical nature of structural heterogeneity should be revealed by other means such as high resolution microscopic and spectroscopic methods. To study the impact of the structural heterogeneity on the sub-Tg relaxation...... chemical features and degrees of structural heterogeneity in glass-forming liquids. This finding contributes to the microscopic origin of both the primary and secondary relaxation in terms of structural heterogeneity. Finally the results provide insights into the relation between structural heterogeneity...

Analysis of the land surface heterogeneity and its impact on atmospheric variables and the aerodynamic and thermodynamic roughness lengths

NARCIS (Netherlands)

Ma, Y.M.; Menenti, M.; Feddes, R.A.; Wang, J.M.

2008-01-01

The land surface heterogeneity has a very significant impact on atmospheric variables (air temperature T-a, wind speed u, and humidity q), the aerodynamic roughness length z(0m), thermodynamic roughness length z(0h), and the excess resistance to heat transfer kB(-1). First, in this study the land

Conditioning of Si-interfaces by wet-chemical oxidation: Electronic interface properties study by surface photovoltage measurements

Energy Technology Data Exchange (ETDEWEB)

Angermann, Heike, E-mail: angermann@helmholtz-berlin.de

2014-09-01

Highlights: • Determination of electronic interface properties by contact-less surface photovoltage (SPV) technique. • Systematic correlations of substrate morphology and surface electronic properties. • Optimization of surface pre-treatment for flat, saw damage etched, and textured Si solar cell substrates. • Ultra-thin passivating Si oxide layers with low densities of rechargeable states by wet-chemical oxidation and subsequent annealing. • Environmentally acceptable processes, utilizing hot water, diluted HCl, or ozone low cost alternative to current approaches with concentrated chemicals. • The effect of optimized wet-chemical pre-treatments can be preserved during subsequent layer deposition. - Abstract: The field-modulated surface photovoltage (SPV) method, a very surface sensitive technique, was utilized to determine electronic interface properties on wet-chemically oxidized and etched silicon (Si) interfaces. The influence of preparation-induced surface micro-roughness and un-stoichiometric oxides on the resulting the surface charge, energetic distribution D{sub it}(E), and density D{sub it,min} of rechargeable states was studied by simultaneous, spectroscopic ellipsometry (SE) measurements on polished Si(111) and Si(100) substrates. Based on previous findings and new research, a study of conventional and newly developed wet-chemical oxidation methods was established, correlating the interactions between involved oxidizing and etching solutions and the initial substrate morphology to the final surface conditioning. It is shown, which sequences of wet-chemical oxidation and oxide removal, have to be combined in order to achieve atomically smooth, hydrogen terminated surfaces, as well as ultra-thin oxide layers with low densities of rechargeable states on flat, saw damage etched, and textured Si substrates, as commonly applied in silicon device and solar cell manufacturing. These conventional strategies for wet-chemical pre-treatment are mainly

Conditioning of Si-interfaces by wet-chemical oxidation: Electronic interface properties study by surface photovoltage measurements

International Nuclear Information System (INIS)

Angermann, Heike

2014-01-01

Highlights: • Determination of electronic interface properties by contact-less surface photovoltage (SPV) technique. • Systematic correlations of substrate morphology and surface electronic properties. • Optimization of surface pre-treatment for flat, saw damage etched, and textured Si solar cell substrates. • Ultra-thin passivating Si oxide layers with low densities of rechargeable states by wet-chemical oxidation and subsequent annealing. • Environmentally acceptable processes, utilizing hot water, diluted HCl, or ozone low cost alternative to current approaches with concentrated chemicals. • The effect of optimized wet-chemical pre-treatments can be preserved during subsequent layer deposition. - Abstract: The field-modulated surface photovoltage (SPV) method, a very surface sensitive technique, was utilized to determine electronic interface properties on wet-chemically oxidized and etched silicon (Si) interfaces. The influence of preparation-induced surface micro-roughness and un-stoichiometric oxides on the resulting the surface charge, energetic distribution D it (E), and density D it,min of rechargeable states was studied by simultaneous, spectroscopic ellipsometry (SE) measurements on polished Si(111) and Si(100) substrates. Based on previous findings and new research, a study of conventional and newly developed wet-chemical oxidation methods was established, correlating the interactions between involved oxidizing and etching solutions and the initial substrate morphology to the final surface conditioning. It is shown, which sequences of wet-chemical oxidation and oxide removal, have to be combined in order to achieve atomically smooth, hydrogen terminated surfaces, as well as ultra-thin oxide layers with low densities of rechargeable states on flat, saw damage etched, and textured Si substrates, as commonly applied in silicon device and solar cell manufacturing. These conventional strategies for wet-chemical pre-treatment are mainly based on

Surface Nano Structures Manufacture Using Batch Chemical Processing Methods for Tooling Applications

DEFF Research Database (Denmark)

Tosello, Guido; Calaon, Matteo; Gavillet, J.

2011-01-01

The patterning of large surface areas with nano structures by using chemical batch processes to avoid using highenergy intensive nano machining processes was investigated. The capability of different surface treatment methods of creating micro and nano structured adaptable mould inserts for subse...

Analysis of the Si(111) surface prepared in chemical vapor ambient for subsequent III-V heteroepitaxy

Energy Technology Data Exchange (ETDEWEB)

Zhao, W.; Steidl, M.; Paszuk, A. [Technische Universität Ilmenau, Institut für Physik, 98693 Ilmenau (Germany); Brückner, S. [Technische Universität Ilmenau, Institut für Physik, 98693 Ilmenau (Germany); Helmholtz-Zentrum Berlin, Institut für Solare Brennstoffe, 14109 Berlin (Germany); Dobrich, A. [Technische Universität Ilmenau, Institut für Physik, 98693 Ilmenau (Germany); Supplie, O. [Technische Universität Ilmenau, Institut für Physik, 98693 Ilmenau (Germany); Helmholtz-Zentrum Berlin, Institut für Solare Brennstoffe, 14109 Berlin (Germany); Kleinschmidt, P. [Technische Universität Ilmenau, Institut für Physik, 98693 Ilmenau (Germany); Hannappel, T., E-mail: thomas.hannappel@tu-ilmenau.de [Technische Universität Ilmenau, Institut für Physik, 98693 Ilmenau (Germany); Helmholtz-Zentrum Berlin, Institut für Solare Brennstoffe, 14109 Berlin (Germany)

2017-01-15

Highlights: • We investigate the Si(111) surface prepared in CVD ambient at 1000 °C in 950 mbar H{sub 2}. • UHV-based XPS, LEED, STM and FTIR as well as ambient AFM are applied. • After processing the Si(111) surface is free of contamination and atomically flat. • The surface exhibits a (1 × 1) reconstruction and monohydride termination. • Wet-chemical pretreatment and homoepitaxy are required for a regular step structure. - Abstract: For well-defined heteroepitaxial growth of III-V epilayers on Si(111) substrates the atomic structure of the silicon surface is an essential element. Here, we study the preparation of the Si(111) surface in H{sub 2}-based chemical vapor ambient as well as its atomic structure after contamination-free transfer to ultrahigh vacuum (UHV). Applying complementary UHV-based techniques, we derive a complete picture of the atomic surface structure and its chemical composition. X-ray photoelectron spectroscopy measurements after high-temperature annealing confirm a Si surface free of any traces of oxygen or other impurities. The annealing in H{sub 2} ambient leads to a monohydride surface termination, as verified by Fourier-transform infrared spectroscopy. Scanning tunneling microscopy confirms a well ordered, atomically smooth surface, which is (1 × 1) reconstructed, in agreement with low energy electron diffraction patterns. Atomic force microscopy reveals a significant influence of homoepitaxy and wet-chemical pretreatment on the surface morphology. Our findings show that wet-chemical pretreatment followed by high-temperature annealing leads to contamination-free, atomically flat Si(111) surfaces, which are ideally suited for subsequent III-V heteroepitaxy.

The role of high temperature heterogeneous reaction kinetics in the rate of radionuclide vaporisation during core-concrete interactions

International Nuclear Information System (INIS)

Raymond, D.P.; Clough, P.N.

1989-09-01

Heterogeneous reactions may cause enhanced release of radionuclides during the core-concrete interaction (CCl) stage of a PWR severe accident. The VANESA computer code models these CCI releases using chemical equilibrium assumptions; however, the possibility that chemical kinetics could prevent equilibrium from being achieved is considered in this report. Direct experimental evidence is lacking on these reactions. Therefore, some analogues studies are reviewed, including examples of Eyring's surface reaction rate theory; sequential vaporisation-oxidation processes; iron and steelmaking chemistry; radionuclide evaporation from solid UO 2 . This circumstantial evidence appeared to agree with the current assumptions, in VANESA and some UK modelling studies, that mass transfer, rather than chemical kinetics will limit the rate at which equilibrium is attained. (author)

Direct instrumental identification of catalytically active surface sites

Science.gov (United States)

Pfisterer, Jonas H. K.; Liang, Yunchang; Schneider, Oliver; Bandarenka, Aliaksandr S.

2017-09-01

The activity of heterogeneous catalysts—which are involved in some 80 per cent of processes in the chemical and energy industries—is determined by the electronic structure of specific surface sites that offer optimal binding of reaction intermediates. Directly identifying and monitoring these sites during a reaction should therefore provide insight that might aid the targeted development of heterogeneous catalysts and electrocatalysts (those that participate in electrochemical reactions) for practical applications. The invention of the scanning tunnelling microscope (STM) and the electrochemical STM promised to deliver such imaging capabilities, and both have indeed contributed greatly to our atomistic understanding of heterogeneous catalysis. But although the STM has been used to probe and initiate surface reactions, and has even enabled local measurements of reactivity in some systems, it is not generally thought to be suited to the direct identification of catalytically active surface sites under reaction conditions. Here we demonstrate, however, that common STMs can readily map the catalytic activity of surfaces with high spatial resolution: we show that by monitoring relative changes in the tunnelling current noise, active sites can be distinguished in an almost quantitative fashion according to their ability to catalyse the hydrogen-evolution reaction or the oxygen-reduction reaction. These data allow us to evaluate directly the importance and relative contribution to overall catalyst activity of different defects and sites at the boundaries between two materials. With its ability to deliver such information and its ready applicability to different systems, we anticipate that our method will aid the rational design of heterogeneous catalysts.

Heterogeneous silicon mesostructures for lipid-supported bioelectric interfaces

Energy Technology Data Exchange (ETDEWEB)

Jiang, Yuanwen; Carvalho-de-Souza, João L.; Wong, Raymond C. S.; Luo, Zhiqiang; Isheim, Dieter; Zuo, Xiaobing; Nicholls, Alan W.; Jung, Il Woong; Yue, Jiping; Liu, Di-Jia; Wang, Yucai; De Andrade, Vincent; Xiao, Xianghui; Navrazhnykh, Luizetta; Weiss, Dara E.; Wu, Xiaoyang; Seidman, David N.; Bezanilla, Francisco; Tian, Bozhi

2016-06-27

Silicon-based materials have widespread application as biophysical tools and biomedical devices. Here we introduce a biocompatible and degradable mesostructured form of silicon with multi-scale structural and chemical heterogeneities. The material was synthesized using mesoporous silica as a template through a chemical vapour deposition process. It has an amorphous atomic structure, an ordered nanowire-based framework and random submicrometre voids, and shows an average Young’s modulus that is 2–3 orders of magnitude smaller than that of single-crystalline silicon. In addition, we used the heterogeneous silicon mesostructures to design a lipid-bilayer-supported bioelectric interface that is remotely controlled and temporally transient, and that permits non-genetic and subcellular optical modulation of the electrophysiology dynamics in single dorsal root ganglia neurons. Our findings suggest that the biomimetic expansion of silicon into heterogeneous and deformable forms can open up opportunities in extracellular biomaterial or bioelectric systems.

An infrared measurement of chemical desorption from interstellar ice analogues

Science.gov (United States)

Oba, Y.; Tomaru, T.; Lamberts, T.; Kouchi, A.; Watanabe, N.

2018-03-01

In molecular clouds at temperatures as low as 10 K, all species except hydrogen and helium should be locked in the heterogeneous ice on dust grain surfaces. Nevertheless, astronomical observations have detected over 150 different species in the gas phase in these clouds. The mechanism by which molecules are released from the dust surface below thermal desorption temperatures to be detectable in the gas phase is crucial for understanding the chemical evolution in such cold clouds. Chemical desorption, caused by the excess energy of an exothermic reaction, was first proposed as a key molecular release mechanism almost 50 years ago1. Chemical desorption can, in principle, take place at any temperature, even below the thermal desorption temperature. Therefore, astrochemical network models commonly include this process2,3. Although there have been a few previous experimental efforts4-6, no infrared measurement of the surface (which has a strong advantage to quantify chemical desorption) has been performed. Here, we report the first infrared in situ measurement of chemical desorption during the reactions H + H2S → HS + H2 (reaction 1) and HS + H → H2S (reaction 2), which are key to interstellar sulphur chemistry2,3. The present study clearly demonstrates that chemical desorption is a more efficient process for releasing H2S into the gas phase than was previously believed. The obtained effective cross-section for chemical desorption indicates that the chemical desorption rate exceeds the photodesorption rate in typical interstellar environments.

Polyfluorinated chemicals in European surface waters, ground- and drinking waters

NARCIS (Netherlands)

Eschauzier, C.; de Voogt, P.; Brauch, H.-J.; Lange, F.T.; Knepper, T.P.; Lange, F.T.

2012-01-01

Polyfluorinated chemicals (PFCs), especially short chain fluorinated alkyl sulfonates and carboxylates, are ubiquitously found in the environment. This chapter aims at giving an overview of PFC concentrations found in European surface, ground- and drinking waters and their behavior during

Surface chemical composition of human maxillary first premolar as assessed by X-ray photoelectron spectroscopy (XPS)

Science.gov (United States)

Lou, Leo; Nelson, Alan E.; Heo, Giseon; Major, Paul W.

2008-08-01

The surface chemical composition of dental enamel has been postulated as a contributing factor in the variation of bond strength of brackets bonded to teeth, and hence, the probability of bracket failure during orthodontic treatment. This study systematically investigated the chemical composition of 98 bonding surfaces of human maxillary premolars using X-ray photoelectron spectroscopy (XPS) to ascertain compositional differences between right and left first premolars. The major elements detected in all samples were calcium, phosphorus, oxygen, nitrogen and carbon. Surface compositions were highly variable between samples and several elements were found to be highly correlated. No statistical significant difference in the chemical composition of the maxillary right and left first premolars was found ( p > 0.05). Knowledge of the chemical composition of enamel surfaces will facilitate future studies that relate this information to the variations in dental enamel bond strength.

Surface chemical composition of human maxillary first premolar as assessed by X-ray photoelectron spectroscopy (XPS)

Energy Technology Data Exchange (ETDEWEB)

Lou, Leo [Orthodontic Graduate Program, Faculty of Medicine and Dentistry, University of Alberta (Canada); Nelson, Alan E. [Department of Chemical and Materials Engineering, University of Alberta (Canada)], E-mail: aenelson@dow.com; Heo, Giseon [Department of Statistics, Department of Dentistry, University of Alberta (Canada); Major, Paul W. [Orthodontic Graduate Program, Faculty of Medicine and Dentistry, University of Alberta (Canada)

2008-08-30

The surface chemical composition of dental enamel has been postulated as a contributing factor in the variation of bond strength of brackets bonded to teeth, and hence, the probability of bracket failure during orthodontic treatment. This study systematically investigated the chemical composition of 98 bonding surfaces of human maxillary premolars using X-ray photoelectron spectroscopy (XPS) to ascertain compositional differences between right and left first premolars. The major elements detected in all samples were calcium, phosphorus, oxygen, nitrogen and carbon. Surface compositions were highly variable between samples and several elements were found to be highly correlated. No statistical significant difference in the chemical composition of the maxillary right and left first premolars was found (p > 0.05). Knowledge of the chemical composition of enamel surfaces will facilitate future studies that relate this information to the variations in dental enamel bond strength.

Surface chemical composition of human maxillary first premolar as assessed by X-ray photoelectron spectroscopy (XPS)

International Nuclear Information System (INIS)

Lou, Leo; Nelson, Alan E.; Heo, Giseon; Major, Paul W.

2008-01-01

The surface chemical composition of dental enamel has been postulated as a contributing factor in the variation of bond strength of brackets bonded to teeth, and hence, the probability of bracket failure during orthodontic treatment. This study systematically investigated the chemical composition of 98 bonding surfaces of human maxillary premolars using X-ray photoelectron spectroscopy (XPS) to ascertain compositional differences between right and left first premolars. The major elements detected in all samples were calcium, phosphorus, oxygen, nitrogen and carbon. Surface compositions were highly variable between samples and several elements were found to be highly correlated. No statistical significant difference in the chemical composition of the maxillary right and left first premolars was found (p > 0.05). Knowledge of the chemical composition of enamel surfaces will facilitate future studies that relate this information to the variations in dental enamel bond strength

Studies of Heterogenous Palladium and Related Catalysts for Aerobic Oxidation of Primary Alcohols

Science.gov (United States)

Ahmed, Maaz S.

Development of aerobic oxidation methods is of critical importance for the advancement of green chemistry, where the only byproduct produced is water. Recent work by our lab has produced an efficient Pd based heterogenous catalyst capable of preforming the aerobic oxidation of a wide spectrum of alcohols to either carboxylic acid or methyl ester. The well-defined catalyst PdBi 0.35Te0.23/C (PBT/C) catalyst has been shown to can perform the aerobic oxidation of alcohols to carboxylic acids in basic conditions. Additionally, we explored this catalyst for a wide range of alcohols and probed the nature of the selectivity of PBT/C for methyl esterification over other side products. Finally, means by which the catalyst operates with respect to oxidation states of the three components, Pd, Bi, and Te, was probed. Carboxylic acids are an important functional group due to their prevalence in various pharmaceutically active agents, agrochemicals, and commodity scale chemicals. The well-defined catalyst PBT/C catalyst was discovered to be effective for the oxidation of a wide spectrum of alcohols to carboxylic acid. The demonstrated substrate scope and functional group tolerance are the widest reported for an aerobic heterogeneous catalyst. Additionally, the catalyst has been implemented in a packed bed reactor with quantitative yield of benzoic acid maintained throughout a two-day run. Biomass derived 5-(hydroxymethyl)furfural (HMF) is also oxidized to 2,5-furandicarboxylic acid (FDCA) in high yield. Exploration of PBT/C for the oxidative methyl esterification was found to exhibit exquisite selectivity for the initial oxidation of primary alcohol instead of methanol, which is the bulk solvent. We explored this selectivity and conclude that it results from various substrate-surface interactions, which are not attainable by methanol. The primary alcohol can outcompete the methanol for binding on the catalyst surface through various interactions between the side chain of the

How Important Is Connectivity for Surface Water Fluxes? A Generalized Expression for Flow Through Heterogeneous Landscapes

Science.gov (United States)

Larsen, Laurel G.; Ma, Jie; Kaplan, David

2017-10-01

How important is hydrologic connectivity for surface water fluxes through heterogeneous floodplains, deltas, and wetlands? While significant for management, this question remains poorly addressed. Here we adopt spatial resistance averaging, based on channel and patch configuration metrics quantifiable from aerial imagery, to produce an upscaled rate law for discharge. Our model suggests that patch coverage largely controls discharge sensitivity, with smaller effects from channel connectivity and vegetation patch fractal dimension. However, connectivity and patch configuration become increasingly important near the percolation threshold and at low water levels. These effects can establish positive feedbacks responsible for substantial flow change in evolving landscapes (14-36%, in our Everglades case study). Connectivity also interacts with other drivers; flow through poorly connected hydroscapes is less resilient to perturbations in other drivers. Finally, we found that flow through heterogeneous patches is alone sufficient to produce non-Manning flow-depth relationships commonly observed in wetlands but previously attributed to depth-varying roughness.

The Chemical Origin of SEY at Technical Surfaces

CERN Document Server

Larciprete, R.; Commisso, M.; Flammini, R.; Cimino, R.

2013-04-22

The secondary emission yield (SEY) properties of colaminated Cu samples for LHC beam screens are correlated to the surface chemical composition determined by X-ray photoelectron spectroscopy. The surface of the "as received" samples is characterized by the presence of significant quantities of contaminating adsorbates and by the maximum of the SEY curve (dmax) being as high as 2.2. After extended electron scrubbing at kinetic energy of 10 and 500 eV, the dmax value drops to the ultimate values of 1.35 and 1.1, respectively. In both cases the surface oxidized phases are significantly reduced, whereas only in the sample scrubbed at 500 eV the formation of a graphitic-like C layer is observed. We find that the electron scrubbing of technical Cu surfaces can be described as occurring in two steps, where the first step consists in the electron induced desorption of weakly bound contaminants that occurs indifferently at 10 and at 500 eV and corresponds to a partial decrease of dmax, and the second step, activated b...

Specifics of adsorption and chemical processes on the surface of gamma-irradiated vanadium dioxide

International Nuclear Information System (INIS)

Kaurkovskaya, V.N.; Dzyubenko, L.S.; Doroshenko, V.N.; Chujko, A.A.; Shakhov, A.P.

2006-01-01

Effect of γ-irradiation on electrophysical properties and processes of thermal desorption of water from the surface of vanadium oxides V 2 O 3 -VO 2-δ -VO 2+δ -V 2 O 5 was investigated by derivatography and electric conductivity. Content of adsorbed water at the surface and phase composition of the surface was demonstrated to change under the action of low radiation doses. Surface electric conductivity of the irradiated samples VO 2-δ in the process of chemical reactions of adsorbed following irradiation benzoic acid and ethanol was established to be much above than in irradiated-free ones. It is presumed that metal-semiconductor phase transition at the surface of VO 2-δ during chemical reaction is intensified by irradiation [ru

Characterization of surface topography and chemical composition of mini-implants

OpenAIRE

Knop, Luegya Amorim Henriques; Soares, Ana Prates; Shintcovsk, Ricardo Lima; Martins, Lidia Parsekian; Gandini Jr., Luiz Gonzaga

2015-01-01

Abstract Aim : To assess the surface topography and chemical composition of three brands of as-received mini-implants (SIN(r), Morelli(r), and Conexao(r)). Methods: Twelve mini-implants of each brand were analyzed by scanning electron microscopy and energy dispersive X-ray (EDX). Results: There was no significant differences among SIN(r), Morelli(r), and Conexao(r) mini-implants comparing their surface topography by visualization of SEM micrographs and analysis of scores. The EDX analysis ...

Impacts of thermal and chemical discharges to surface water

International Nuclear Information System (INIS)

Stober, Q.J.

1974-01-01

Various aspects of thermal and chemical discharges to surface water are outlined. The major impacts of nuclear power plants on aquatic resources are disruption during construction, intake of cooling water, discharge problems, and interactions with other water users. The following topics are included under the heading, assessment of aquatic ecology: identification of flora and fauna; abundance of aquatic organisms; species-environment relationships; and identification of pre-existing environmental stress. The following topics are included under the heading, environmental effects of plant operation: entrapment of fish by cooling water; passage of plankton through cooling system; discharge area and thermal plume; chemical effluents; and plant construction. (U.S.)

Computational Study on Atomic Structures, Electronic Properties, and Chemical Reactions at Surfaces and Interfaces and in Biomaterials

Science.gov (United States)

Takano, Yu; Kobayashi, Nobuhiko; Morikawa, Yoshitada

2018-06-01

Through computer simulations using atomistic models, it is becoming possible to calculate the atomic structures of localized defects or dopants in semiconductors, chemically active sites in heterogeneous catalysts, nanoscale structures, and active sites in biological systems precisely. Furthermore, it is also possible to clarify physical and chemical properties possessed by these nanoscale structures such as electronic states, electronic and atomic transport properties, optical properties, and chemical reactivity. It is sometimes quite difficult to clarify these nanoscale structure-function relations experimentally and, therefore, accurate computational studies are indispensable in materials science. In this paper, we review recent studies on the relation between local structures and functions for inorganic, organic, and biological systems by using atomistic computer simulations.

Surface emitting ring quantum cascade lasers for chemical sensing

Science.gov (United States)

Szedlak, Rolf; Hayden, Jakob; Martín-Mateos, Pedro; Holzbauer, Martin; Harrer, Andreas; Schwarz, Benedikt; Hinkov, Borislav; MacFarland, Donald; Zederbauer, Tobias; Detz, Hermann; Andrews, Aaron Maxwell; Schrenk, Werner; Acedo, Pablo; Lendl, Bernhard; Strasser, Gottfried

2018-01-01

We review recent advances in chemical sensing applications based on surface emitting ring quantum cascade lasers (QCLs). Such lasers can be implemented in monolithically integrated on-chip laser/detector devices forming compact gas sensors, which are based on direct absorption spectroscopy according to the Beer-Lambert law. Furthermore, we present experimental results on radio frequency modulation up to 150 MHz of surface emitting ring QCLs. This technique provides detailed insight into the modulation characteristics of such lasers. The gained knowledge facilitates the utilization of ring QCLs in combination with spectroscopic techniques, such as heterodyne phase-sensitive dispersion spectroscopy for gas detection and analysis.

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

Energy Technology Data Exchange (ETDEWEB)

Somorjai, Gabor A.; Li, Yimin

2009-11-21

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

Concatenation of electrochemical grafting with chemical or electrochemical modification for preparing electrodes with specific surface functionality

International Nuclear Information System (INIS)

Verma, Pallavi; Maire, Pascal; Novak, Petr

2011-01-01

Surface modified electrodes are used in electro-analysis, electro-catalysis, sensors, biomedical applications, etc. and could also be used in batteries. The properties of modified electrodes are determined by the surface functionality. Therefore, the steps involved in the surface modification of the electrodes to obtain specific functionality are of prime importance. We illustrate here bridging of two routes of surface modifications namely electrochemical grafting, and chemical or electrochemical reduction. First, by electrochemical grafting an organic moiety is covalently immobilized on the surface. Then, either by chemical or by electrochemical route the terminal functional group of the grafted moiety is transformed. Using the former route we prepared lithium alkyl carbonate (-O(CH 2 ) 3 OCO 2 Li) modified carbon with potential applications in batteries, and employing the latter we prepared phenyl hydroxyl amine (-C 6 H 4 NHOH) modified carbon which may find application in biosensors. Benzyl alcohol (-C 6 H 4 CH 2 OH) modified carbon was prepared by both chemical as well as electrochemical route. We report combinations of conjugating the two steps of surface modifications and show how the optimal route of terminal functional group modification depends on the chemical nature of the moiety attached to the surface in the electrochemical grafting step.

Concatenation of electrochemical grafting with chemical or electrochemical modification for preparing electrodes with specific surface functionality

Energy Technology Data Exchange (ETDEWEB)

Verma, Pallavi; Maire, Pascal [Paul Scherrer Institut, Electrochemistry Laboratory, Section Electrochemical Energy Storage, CH-5232 Villigen PSI (Switzerland); Novak, Petr, E-mail: petr.novak@psi.c [Paul Scherrer Institut, Electrochemistry Laboratory, Section Electrochemical Energy Storage, CH-5232 Villigen PSI (Switzerland)

2011-04-01

Surface modified electrodes are used in electro-analysis, electro-catalysis, sensors, biomedical applications, etc. and could also be used in batteries. The properties of modified electrodes are determined by the surface functionality. Therefore, the steps involved in the surface modification of the electrodes to obtain specific functionality are of prime importance. We illustrate here bridging of two routes of surface modifications namely electrochemical grafting, and chemical or electrochemical reduction. First, by electrochemical grafting an organic moiety is covalently immobilized on the surface. Then, either by chemical or by electrochemical route the terminal functional group of the grafted moiety is transformed. Using the former route we prepared lithium alkyl carbonate (-O(CH{sub 2}){sub 3}OCO{sub 2}Li) modified carbon with potential applications in batteries, and employing the latter we prepared phenyl hydroxyl amine (-C{sub 6}H{sub 4}NHOH) modified carbon which may find application in biosensors. Benzyl alcohol (-C{sub 6}H{sub 4}CH{sub 2}OH) modified carbon was prepared by both chemical as well as electrochemical route. We report combinations of conjugating the two steps of surface modifications and show how the optimal route of terminal functional group modification depends on the chemical nature of the moiety attached to the surface in the electrochemical grafting step.

Isotopes in heterogeneous catalysis

CERN Document Server

Hargreaves, Justin SJ

2006-01-01

The purpose of this book is to review the current, state-of-the-art application of isotopic methods to the field of heterogeneous catalysis. Isotopic studies are arguably the ultimate technique in in situ methods for heterogeneous catalysis. In this review volume, chapters have been contributed by experts in the field and the coverage includes both the application of specific isotopes - Deuterium, Tritium, Carbon-14, Sulfur-35 and Oxygen-18 - as well as isotopic techniques - determination of surface mobility, steady state transient isotope kinetic analysis, and positron emission profiling.

Surface chemical functionalities affect the behavior of human adipose-derived stem cells in vitro

International Nuclear Information System (INIS)

Liu, Xujie; Feng, Qingling; Bachhuka, Akash; Vasilev, Krasimir

2013-01-01

This study examines the effect of surface chemical functionalities on the behavior of human adipose-derived stem cells (hASCs) in vitro. Plasma polymerized films rich in amine (-NH 2 ), carboxyl (-COOH) and methyl (-CH 3 ), were generated on hydroxyapatite (HAp) substrates. The surface chemical functionalities were characterized by X-ray photoelectron spectroscopy (XPS). The ability of different substrates to absorb proteins was evaluated. The results showed that substrates modified with hydrophilic functional group (-COOH and -NH 2 ) can absorb more proteins than these modified with more hydrophobic functional group (-CH 3 ). The behavior of human adipose-derived stem cells (hASCs) cultured on different substrates was investigated in vitro: cell counting kit-8 (CCK-8) analysis was used to characterize cell proliferation, scanning electronic microscopy (SEM) analysis was used to characterize cell morphology and alkaline phosphatase (ALP) activity analysis was used to account for differentiation. The results of this study demonstrated that the -NH 2 modified surfaces encourage osteogenic differentiation; the -COOH modified surfaces promote cell adhesion and spreading and the -CH 3 modified surfaces have the lowest ability to induce osteogenic differentiation. These findings confirmed that the surface chemical states of biomaterials can affect the behavior of hASCs in vitro.

Surface chemical functionalities affect the behavior of human adipose-derived stem cells in vitro

Energy Technology Data Exchange (ETDEWEB)

Liu, Xujie [State key laboratory of new ceramics and fine processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084 (China); Feng, Qingling, E-mail: biomater@mail.tsinghua.edu.cn [State key laboratory of new ceramics and fine processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084 (China); Bachhuka, Akash [Mawson Institute, University of South Australia, Mawson Lakes 5095 (Australia); Vasilev, Krasimir [Mawson Institute, University of South Australia, Mawson Lakes 5095 (Australia); School of Advanced Manufacturing, University of South Australia, Mawson Lakes 5095 (Australia)

2013-04-01

This study examines the effect of surface chemical functionalities on the behavior of human adipose-derived stem cells (hASCs) in vitro. Plasma polymerized films rich in amine (-NH{sub 2}), carboxyl (-COOH) and methyl (-CH{sub 3}), were generated on hydroxyapatite (HAp) substrates. The surface chemical functionalities were characterized by X-ray photoelectron spectroscopy (XPS). The ability of different substrates to absorb proteins was evaluated. The results showed that substrates modified with hydrophilic functional group (-COOH and -NH{sub 2}) can absorb more proteins than these modified with more hydrophobic functional group (-CH{sub 3}). The behavior of human adipose-derived stem cells (hASCs) cultured on different substrates was investigated in vitro: cell counting kit-8 (CCK-8) analysis was used to characterize cell proliferation, scanning electronic microscopy (SEM) analysis was used to characterize cell morphology and alkaline phosphatase (ALP) activity analysis was used to account for differentiation. The results of this study demonstrated that the -NH{sub 2} modified surfaces encourage osteogenic differentiation; the -COOH modified surfaces promote cell adhesion and spreading and the -CH{sub 3} modified surfaces have the lowest ability to induce osteogenic differentiation. These findings confirmed that the surface chemical states of biomaterials can affect the behavior of hASCs in vitro.

47nm alumina–water nanofluid flow within boundary layer formed on upper horizontal surface of paraboloid of revolution in the presence of quartic autocatalysis chemical reaction

Directory of Open Access Journals (Sweden)

Isaac Lare Animasaun

2016-09-01

Full Text Available In this article, a modified version of buoyancy-induced model is considered to investigate the flow of 47nm alumina–water nanofluid along an upper surface of horizontal paraboloid of revolution in the presence of nonlinear thermal radiation, Lorentz force and quartic autocatalysis kind of homogeneous heterogeneous chemical reaction. The case of unequal diffusion coefficients of reactant A (bulk fluid and B (high concentration of catalyst at the surface in the presence of bioconvection is considered. Governing equation suitable to unravel the thermophoresis which takes place within the boundary layer is presented. Since chemical reactant B is of higher concentration at the surface more than the concept described as cubic autocatalytic, the suitable schemes are herein described as isothermal quartic autocatalytic reaction and first order reaction. The viscosity and thermal conductivity are assumed to vary with volume fraction (ϕ and suitable models for the case 0%⩽ϕ⩽0.8% are adopted. The transformed governing equations are solved numerically using Runge–Kutta fourth order along with shooting technique (RK4SM. Good agreement is obtained between the solutions of RK4SM and MATLAB bvp5c for a limiting case. The influence of some pertinent parameters on velocity, temperature, diffusion of motile microorganism, concentration of bulk fluid and catalyst is illustrated graphically and discussed.

Depressurization accident analysis of MPBR by PBRSIM with chemical reaction model

International Nuclear Information System (INIS)

No, Hee Cheon; Kadak, A. C.

2002-01-01

The simple model for natural circulation is implemented into PBR S IM to provide air inlet velocity from the containment air space. For the friction and form loss only the pebble region is considered conservatively modeling laminar flow through a packed bed. For the chemical reaction model of PBR S IM the oxidation rate is determined as the minimum value of three mechanisms estimated at each time step: oxygen mass flow rate entering the bottom of the reflector, oxidation rate by kinetics, and oxygen mass flow rate arriving at the graphite surface by diffusion. Oxygen mass flux arriving at the graphite surface by diffusion is estimated based on energy-mass analogy. Two types of exothermic chemical reaction are considered: (C + zO 2 → xCO + yCO 2 ) and (2CO + O 2 2CO 2 ). The heterogeneous and homogeneous chemical reaction rates by kinetics are determined by INEEL and Bruno correlations, respectively. The instantaneous depressurization accident of MPBR is simulated using PBR S IM with chemical model. The air inlet velocity is initially rapidly dropped within 10 hr and reaches a saturation value of about 1.5cm/s. The oxidation rate by the diffusion process becomes lower than that by the chemical kinetics above 600K. The maximum pebble bed temperatures without and with chemical reaction reach the peak values of 1560 and 1617 .deg. C at 80 hr and 92 hr, respectively. As the averaged temperatures in the bottom reflector and the pebble bed regions increase with time, (C+1/2O2 ->CO) reaction becomes dominant over (C+O 2 →CO 2 ) reaction. Also, the CO generated by (C+1/2O 2 →CO) reaction will be consumed by (2CO+O 2 →2CO 2 ) reaction and the energy homogeneously generated by this CO depletion reaction becomes dominant over the heterogeneous reaction

Chemical kinetics: on the heterogeneous catalysis processes leading to an exchange between two phases. Example: isotopic exchange reactions; Cinetique chimique: sur les processus de catalyse 'heterogene' conduisant a un echange entre deux phases. Exemple: reactions d'echange isotopique

Energy Technology Data Exchange (ETDEWEB)

Dirian, G; Grandcollot, P [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1961-07-01

For an exchange reaction between a gaseous and a liquid phase proceeding by 'heterogeneous' catalysis in the liquid phase, diffusion in the liquid and the chemical reaction are two simultaneous and indivisible processes. We have nevertheless been able to establish criteria making it possible to distinguish between a really homogeneous kinetic process and a pseudo-homogeneous one. (author) [French] Pour une reaction d'echange entre une phase gazeuse et une phase liquide procedant par catalyse 'heterogene' en phase liquide, la diffusion dans le liquide et la reaction chimique sont deux etapes simultanees et indissociables. Nous avons pu neanmoins etablir des criteres permettant de distinguer entre une cinetique homogene vraie et une cinetique pseudo-homogene. (auteur)

Modification of Textile Materials' Surface Properties Using Chemical Softener

Directory of Open Access Journals (Sweden)

Jurgita KOŽENIAUSKIENĖ

2011-03-01

Full Text Available In the present study the effect of technological treatment involving the processes of washing or washing and softening with chemical cationic softener "Surcase" produced in Great Britain on the surface properties of cellulosic textile materials manufactured from cotton, bamboo and viscose spun yarns was investigated. The changes in textile materials surface properties were evaluated using KTU-Griff-Tester device and FEI Quanta 200 FEG scanning electron microscope (SEM. It was observed that the worst hand properties and the higher surface roughness are observed of cotton materials if compared with those of bamboo and viscose materials. Also, it was shown that depending on the material structure the handle parameters of knitted materials are the better than the ones of woven fabrics.http://dx.doi.org/10.5755/j01.ms.17.1.249

Internal and Surface Phenomena in Heterogenous Metal Combustion

Science.gov (United States)

Dreizin, Edward L.

1997-01-01

The phenomenon of gas dissolution in burning metals was observed in recent metal combustion studies, but it could not be adequately explained by the traditional metal combustion models. The research reported here addresses heterogeneous metal combustion with emphasis on the processes of oxygen penetration inside burning metal and its influence on the metal combustion rate, temperature history, and disruptive burning. The unique feature of this work is the combination of the microgravity environment with a novel micro-arc generator of monodispersed metal droplets, ensuring repeatable formation and ignition of uniform metal droplets with a controllable initial temperature and velocity. Burning droplet temperature is measured in real time with a three wavelength pyrometer. In addition, particles are rapidly quenched at different combustion times, cross-sectioned, and examined using SEM-based techniques to retrieve the internal composition history of burning metal particles. When the initial velocity of a spherical particle is nearly zero, the microgravity environment makes it possible to study the flame structure, the development of flame nonsymmetry, and correlation of the flame shape with the heterogeneous combustion processes.

Re-discovering surface mass spectrometry: chemical mapping from micro to macro

Energy Technology Data Exchange (ETDEWEB)

Lloyd, K.G.; O' Keefe, D.P

2004-06-15

New developments in electronics, devices, micro-encapsulation, and other areas demand the ability to acquire molecularly-specific information from smaller and smaller features. ToF-SIMS provides molecularly-specific mass spectral data, but sufficient high-mass signal has historically been difficult to obtain from organic/polymeric surfaces in the point-mapping mode of operation. Use of chemometric data reduction methods and the development of heavier primary ion sources enhance and extend the chemical information in the mapping data. Large-area chemical mapping via sample stage rastering has also opened up new applications. This capability allows single-experiment mapping of large or multiple features, provides information on surface uniformity over end-use-relevant areas, and offers potential for combinatorial and other screening applications. Examples of these applications are presented.

Multiscale decomposition for heterogeneous land-atmosphere systems

Science.gov (United States)

Liu, Shaofeng; Shao, Yaping; Hintz, Michael; Lennartz-Sassinek, Sabine

2015-02-01

The land-atmosphere system is characterized by pronounced land surface heterogeneity and vigorous atmospheric turbulence both covering a wide range of scales. The multiscale surface heterogeneities and multiscale turbulent eddies interact nonlinearly with each other. Understanding these multiscale processes quantitatively is essential to the subgrid parameterizations for weather and climate models. In this paper, we propose a method for surface heterogeneity quantification and turbulence structure identification. The first part of the method is an orthogonal transform in the probability density function (PDF) domain, in contrast to the orthogonal wavelet transforms which are performed in the physical space. As the basis of the whole method, the orthogonal PDF transform (OPT) is used to asymptotically reconstruct the original signals by representing the signal values with multilevel approximations. The "patch" idea is then applied to these reconstructed fields in order to recognize areas at the land surface or in turbulent flows that are of the same characteristics. A patch here is a connected area with the same approximation. For each recognized patch, a length scale is then defined to build the energy spectrum. The OPT and related energy spectrum analysis, as a whole referred to as the orthogonal PDF decomposition (OPD), is applied to two-dimensional heterogeneous land surfaces and atmospheric turbulence fields for test. The results show that compared to the wavelet transforms, the OPD can reconstruct the original signal more effectively, and accordingly, its energy spectrum represents the signal's multiscale variation more accurately. The method we propose in this paper is of general nature and therefore can be of interest for problems of multiscale process description in other geophysical disciplines.

Absolute Molecular Orientation of Isopropanol at Ceria (100) Surfaces: Insight into Catalytic Selectivity from the Interfacial Structure

Energy Technology Data Exchange (ETDEWEB)

Doughty, Benjamin [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Goverapet Srinivasan, Sriram [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Indian Inst. of Technology (IIT), Rajasthan (India); Bryantsev, Vyacheslav S. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lee, Dongkyu [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lee, Ho Nyung [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Ma, Ying-Zhong [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lutterman, Daniel A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2017-06-12

The initial mechanistic steps underlying heterogeneous chemical catalysis can be described in a framework where the composition, structure, and orientation of molecules adsorbed to reactive interfaces are known. However, extracting this vital information is the limiting step in most cases due in part to challenges in probing the interfacial monolayer with enough chemical specificity to characterize the surface molecular constituents. These challenges are exacerbated at complex or spatially heterogeneous interfaces where competing processes and a distribution of local environments can uniquely drive chemistry. To address these limitations, this work presents a distinctive combination of materials synthesis, surface specific optical experiments, and theory to probe and understand molecular structure at catalytic interfaces. Specifically, isopropanol was adsorbed to surfaces of the model CeO₂ catalyst that were synthesized with only the (100) facet exposed. Vibrational sum-frequency generation was used to probe the molecular monolayer, and with the guidance of density functional theory calculations, was used to extract the structure and absolute molecular orientation of isopropanol at the CeO₂ (100) surface. Our results show that isopropanol is readily deprotonated at the surface, and through the measured absolute molecular orientation of isopropanol, we obtain new insight into the selectivity of the (100) surface to form propylene. Our findings reveal key insight into the chemical and physical phenomena taking place at pristine interfaces thereby pointing to intuitive structural arguments to describe catalytic selectivity in more complex systems.

Chemical trends in ocean islands explained by plume–slab interaction

Science.gov (United States)

Dannberg, Juliane; Gassmöller, Rene

2018-04-01

Earth's surface shows many features, of which the genesis can be understood only through their connection with processes in Earth's deep interior. Recent studies indicate that spatial geochemical patterns at oceanic islands correspond to structures in the lowermost mantle inferred from seismic tomographic models. This suggests that hot, buoyant upwellings can carry chemical heterogeneities from the deep lower mantle toward the surface, providing a window to the composition of the lowermost mantle. The exact nature of this link between surface and deep Earth remains debated and poorly understood. Using computational models, we show that subducted slabs interacting with dense thermochemical piles can trigger the ascent of hot plumes that inherit chemical gradients present in the lowermost mantle. We identify two key factors controlling this process: (i) If slabs induce strong lower-mantle flow toward the edges of these piles where plumes rise, the pile-facing side of the plume preferentially samples material originating from the pile, and bilaterally asymmetric chemical zoning develops. (ii) The composition of the melt produced reflects this bilateral zoning if the overlying plate moves roughly perpendicular to the chemical gradient in the plume conduit. Our results explain some of the observed geochemical trends of oceanic islands and provide insights into how these trends may originate.

Chemical and Enzymatic Strategies for Bacterial and Mammalian Cell Surface Engineering.

Science.gov (United States)

Bi, Xiaobao; Yin, Juan; Chen Guanbang, Ashley; Liu, Chuan-Fa

2018-06-07

The cell surface serves important functions such as the regulation of cell-cell and cell-environment interactions. The understanding and manipulation of the cell surface is important for a wide range of fundamental studies of cellular behavior and for biotechnological and medical applications. With the rapid advance of biology, chemistry and materials science, many strategies have been developed for the functionalization of bacterial and mammalian cell surfaces. Here, we review the recent development of chemical and enzymatic approaches to cell surface engineering with particular emphasis on discussing the advantages and limitations of each of these strategies. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Shape-dependent guidance of active Janus particles by chemically patterned surfaces

Science.gov (United States)

Uspal, W. E.; Popescu, M. N.; Tasinkevych, M.; Dietrich, S.

2018-01-01

Self-phoretic chemically active Janus particles move by inducing—via non-equilibrium chemical reactions occurring on their surfaces—changes in the chemical composition of the solution in which they are immersed. This process leads to gradients in chemical composition along the surface of the particle, as well as along any nearby boundaries, including solid walls. Chemical gradients along a wall can give rise to chemi-osmosis, i.e., the gradients drive surface flows which, in turn, drive flow in the volume of the solution. This bulk flow couples back to the particle, and thus contributes to its self-motility. Since chemi-osmosis strongly depends on the molecular interactions between the diffusing molecular species and the wall, the response flow induced and experienced by a particle encodes information about any chemical patterning of the wall. Here, we extend previous studies on self-phoresis of a sphere near a chemically patterned wall to the case of particles with rod-like, elongated shape. We focus our analysis on the new phenomenology potentially emerging from the coupling—which is inoperative for a spherical shape—of the elongated particle to the strain rate tensor of the chemi-osmotic flow. Via detailed numerical calculations, we show that the dynamics of a rod-like particle exhibits a novel ‘edge-following’ steady state: the particle translates along the edge of a chemical step at a steady distance from the step and with a steady orientation. Moreover, within a certain range of system parameters, the edge-following state co-exists with a ‘docking’ state (the particle stops at the step, oriented perpendicular to the step edge), i.e., a bistable dynamics occurs. These findings are rationalized as a consequence of the competition between the fluid vorticity and the rate of strain by using analytical theory based on the point-particle approximation which captures quasi-quantitatively the dynamics of the system.

Fabrication of Hydrophobic Surface on Wood Veneer via Electroless Nickel Plating Combined with Chemical Corrosion

Directory of Open Access Journals (Sweden)

Zhaojun Tang

2015-12-01

Full Text Available Birch veneers were coated with Ni-P films by a combined process of KBH4 activation and electroless plating. The plated veneers were further chemically corroded to obtain hydrophobic surfaces on wood. The effect of chemical corrosion on the contact angle of the veneers was investigated. The hydrophobic veneers were characterized by X-ray photo electron spectroscopy (XPS, scanning electron microscopy (SEM, and X-ray diffraction (XRD. The surface contact angle of birch veneer before and after it was plated with Ni-P alloy coating was 41º and 121º, respectively. The contact angle reached 136.7º when the nickel-coated veneers were corroded in CuSO4 aqueous solution for 30 min. XPS analysis showed that Cu0 cluster doped with little CuO formed on the corroded surface of Ni-P alloy film after chemical corrosion. SEM and XRD showed that rough copper clusters formed on the surface of the wood veneer and revealed the reason of the surface hydrophobicity. This study provides a new pathway for fabricating hydrophobic wood.

Transfers in heterogeneous environments; Transferts en milieux heterogenes

Energy Technology Data Exchange (ETDEWEB)

Flesselles, J M [Saint-Gobain Recherche, 93 - Aubervilliers (France); Gouesbet, G; Mees, L; Roze, C; Girasole, Th; Grehan, G [Laboratoire d' Electromagnetisme et Systemes Particulaires (LESP), UMR CNRS 6614, CORIA. Universite de Rouen et INSA de Rouen, 76 - Saint-Etienne du Rouvray (France); Goyheneche, J M; Vignoles, G; Coindreau, O [Laboratoire des Composites Thermostructuraux (LCTS), UMR 5801, 33 - Pessac (France); Moyne, Ch [LEMTA (UMR 7563) CNRS-INPL-UHP, 54 - Vandoeuvre les Nancy (France); Coussy, O [Institut Navier - ENPC, 77 - Marne-la-Vallee (France); Lassabatere, Th [Electricite de France Les Renardieres, Dept. Materiaux Mecanique des Composants, 77 - Moret sur Loing (France); Tadrist, L [IUSTI - UMR 6595, 13 - Marseille (France)

2004-07-01

This document gathers the articles and transparencies of the invited talks given at the 2004 French congress of thermal engineering about transfers in heterogeneous environment. Content: transfer phenomena in industrial glass furnaces; simple and multiple scattering diagnosis by femto-second pulsed laser: application to particulate diagnoses; thermal modeling of thermo-structural composites; hybrid mixtures theory, average volumic measurement, periodical or stochastic homogenization: advance in scale change processes; thermo-hydro-chemical-mechanical coupling in porous medium: application to young concrete structures and to clay barriers of disposal facilities; transfers and flows in fluidization: recent advances and future challenges. (J.S.)

Graphene: a promising two-dimensional support for heterogeneous catalysts

Directory of Open Access Journals (Sweden)

Xiaobin eFan

2015-01-01

Full Text Available Graphene has many advantages that make it an attractive two-dimensional (2D support for heterogeneous catalysts. It not only allows the high loading of targeted catalytic species, but also facilitates the mass transfer during the reaction processes. These advantages, along with its unique physical and chemical properties, endow graphene great potential as catalyst support in heterogeneous catalysis.

Theoretical studies of surface enhanced hyper-Raman spectroscopy: The chemical enhancement mechanism

Science.gov (United States)

Valley, Nicholas; Jensen, Lasse; Autschbach, Jochen; Schatz, George C.

2010-08-01

Hyper-Raman spectra for pyridine and pyridine on the surface of a tetrahedral 20 silver atom cluster are calculated using static hyperpolarizability derivatives obtained from time dependent density functional theory. The stability of the results with respect to choice of exchange-correlation functional and basis set is verified by comparison with experiment and with Raman spectra calculated for the same systems using the same methods. Calculated Raman spectra were found to match well with experiment and previous theoretical calculations. The calculated normal and surface enhanced hyper-Raman spectra closely match experimental results. The chemical enhancement factors for hyper-Raman are generally larger than for Raman (102-104 versus 101-102). Integrated hyper-Raman chemical enhancement factors are presented for a set of substituted pyridines. A two-state model is developed to predict these chemical enhancement factors and this was found to work well for the majority of the molecules considered, providing a rationalization for the difference between hyper-Raman and Raman enhancement factors.

Current advances and trends in electro-Fenton process using heterogeneous catalysts - A review.

Science.gov (United States)

Poza-Nogueiras, Verónica; Rosales, Emilio; Pazos, Marta; Sanromán, M Ángeles

2018-06-01

Over the last decades, advanced oxidation processes have often been used alone, or combined with other techniques, for remediation of ground and surface water pollutants. The application of heterogeneous catalysis to electrochemical advanced oxidation processes is especially useful due to its efficiency and environmental safety. Among those processes, electro-Fenton stands out as the one in which heterogeneous catalysis has been broadly applied. Thus, this review has introduced an up-to-date collation of the current knowledge of the heterogeneous electro-Fenton process, highlighting recent advances in the use of different catalysts such as iron minerals (pyrite, magnetite or goethite), prepared catalysts by the load of metals in inorganic and organic materials, nanoparticles, and the inclusion of catalysts on the cathode. The effects of physical-chemical parameters as well as the mechanisms involved are critically assessed. Finally, although the utilization of this process to remediation of wastewater overwhelmingly outnumber other utilities, several applications have been described in the context of regeneration of adsorbent or the remediation of soils as clear examples of the feasibility of the electro-Fenton process to solve different environmental problems. Copyright © 2018 Elsevier Ltd. All rights reserved.

Comparison of reactivity on step and terrace sites of Pd (3 3 2) surface for the dissociative adsorption of hydrogen: A quantum chemical molecular dynamics study

International Nuclear Information System (INIS)

Ahmed, Farouq; Nagumo, Ryo; Miura, Ryuji; Ai, Suzuki; Tsuboi, Hideyuki; Hatakeyama, Nozomu; Endou, Akira; Takaba, Hiromitsu; Kubo, Momoji; Miyamoto, Akira

2011-01-01

The notion of 'active sites' is fundamental to heterogeneous catalysis. However, the exact nature of the active sites, and hence the mechanism by which they act, are still largely a matter of speculation. In this study, we have presented a systematic quantum chemical molecular dynamics (QCMD) calculations for the interaction of hydrogen on different step and terrace sites of the Pd (3 3 2) surface. Finally the dissociative adsorption of hydrogen on step and terrace as well as the influence of surface hydrogen vacancy for the dissociative adsorption of hydrogen has been investigated through QCMD. This is a state-of-the-art method for calculating the interaction of atoms and molecules with metal surfaces. It is found that fully hydrogen covered (saturated) step sites can dissociate hydrogen moderately and that a monovacancy surface is suitable for significant dissociative adsorption of hydrogen. However in terrace site of the surface we have found that dissociation of hydrogen takes place only on Pd sites where the metal atom is not bound to any pre-adsorbed hydrogen atoms. Furthermore, from the molecular dynamics and electronic structure calculations, we identify a number of consequences for the interpretation and modeling of diffusion experiments demonstrating the coverage and directional dependence of atomic hydrogen diffusion on stepped palladium surface.

Population heterogeneity in the surface expression of Ulex europaeus I-lectin (UEA I)-binding sites in cultured malignant and transformed cells

Energy Technology Data Exchange (ETDEWEB)

Virtanen, I.; Lehtonen, E.; Naervaenen, O.; Leivo, I.; Lehto, V.P.

1985-11-01

We studied the binding of fluorochrome-coupled Ulex europaeus I-lectin (UEA-I) to cultured malignant cells: all human malignant and transformed cells and also mouse teratocarcinoma cells examined gave a homogeneous cell membrane-type of surface staining only in some of the cells. Such a population heterogeneity appeared to be independent of the cell cycle. Instead, other lectin conjugates used bound homogeneously to all cell. In permeabilized cells, a juxtanuclear reticular staining of the Golgi apparatus was seen in the UEA-I-positive cells. No staining of the pericellular matrix components, produced by malignant cells grown in serum-free culture medium, could be obtained with TRITC-UEA-I. UEA-I-lectin recognized most polypeptides from A8387 fibrosarcoma cells and HeLa cells, metabolically labelled with (/sup 3/H)fucose. Furthermore, surface labelling of these cells with the neuraminidase-galactose oxidase/sodium borohydride method disclosed that both UEA-I and Ricinus communis agglutinin I revealed the same major surface glycoproteins. Results with metabolically labelled cells showed, in addition, that UEA-I-lectin did not bind to secreted glycoproteins produced by A8387 cells and recognized by other lectins. The results indicate that transformed and malignant cells show a distinct population heterogeneity in their expression of some cell surface-associated fucosyl glycoconjugates. The results also suggest that malignant cells can glycosylate their membrane and secreted glycoproteins in a different manner.

Quantum chemical molecular dynamical investigation of alkyl nitrite photo-dissociated on copper surfaces

International Nuclear Information System (INIS)

Wang Xiaojing; Wang Wei; Han Peilin; Kubo, Momoji; Miyamoto, Akira

2008-01-01

An accelerated quantum chemical molecular dynamical code 'Colors-Excite' was used to investigate the photolysis of alkyl nitrites series, RONO (R=CH 3 and C(CH 3 ) 3 ) on copper surfaces. Our calculations showed that the photo-dissociated processes are associated with the alkyl substituents of RONO when adsorbed on copper surfaces. For R=CH 3 , a two-step photolysis reaction occurred, yielding diverse intermediate products including RO radical, NO, and HNO, consistent with those reported in gas phase. While for R=C(CH 3 ) 3 , only one-step photolysis reaction occurred and gave intermediate products of RO radical and NO. Consequently, pure RO species were achieved to adsorb on metal surfaces by removing the NO species in photolysis reaction. The detailed photo-dissociated behaviors of RONO on copper surfaces with different alkyl substituents which are uncovered by the present simulation can be extended to explain the diverse dissociative mechanism experimentally observed. The quantum chemical molecular dynamical code 'Colors-Excite' is proved to be highly applicable to the photo-dissociations on metal surfaces

Chemical reactivity of α-isosaccharinic acid in heterogeneous alkaline systems

International Nuclear Information System (INIS)

Glaus, M. A.; Loon, L. R. Van

2008-11-01

Cellulose degradation under alkaline conditions is of relevance for the mobility of many radionuclides in the near-field of a cementitious repository for radioactive waste, because metal-binding degradation products may be formed. Among these, α-isosaccharinic acid (α-ISA) is the strongest complexant. The prediction of the equilibrium concentration of α-ISA in cement pore water is therefore an important step in the assessment of the influence of cellulose degradation products on the speciation of radionuclides in such environments. The present report focuses on possible chemical transformation reactions of α-ISA in heterogeneous alkaline model systems containing either Ca(OH) 2 or crushed hardened cement paste. The transformation reactions were monitored by measuring the concentration of α-ISA by high performance anion exchange chromatography and the formation of reaction products by high performance ion exclusion chromatography. The overall loss of organic species from solution was monitored by measuring the concentration of non-purgeable organic carbon. The reactions were examined in diluted and compacted suspensions, either at 25 o C or 90 o C, and under anaerobic atmospheres obtained by various methods. It was found that α-ISA was transformed under all conditions tested to some extent. Reaction products, such as glycolate, formate, lactate and acetate, all compounds with less complexing strength than α-ISA, were detected. The amount of reaction products identified by the chromatographic technique applied was ∼50 % of the amount of α-ISA reacted. Sorption of α-ISA to Ca(OH) 2 contributed only to a minor extent to the loss of α-ISA from the solution phase. As the most important conclusion of the present work it was demonstrated that the presence of oxidising agents had a distinctive influence on the turnover of α-ISA. Under aerobic conditions α-ISA was quantitatively converted to reaction products, whereas under strict anaerobic conditions, only

Chemical reactivity of α-isosaccharinic acid in heterogeneous alkaline systems

International Nuclear Information System (INIS)

Glaus, M. A.; Loon, L. R. Van

2009-05-01

Cellulose degradation under alkaline conditions is of relevance for the mobility of many radionuclides in the near-field of a cementitious repository for radioactive waste, because metal-binding degradation products may be formed. Among these, α- isosaccharinic acid (α-ISA) is the strongest complexant. The prediction of the equilibrium concentration of α-ISA in cement pore water is therefore an important step in the assessment of the influence of cellulose degradation products on the speciation of radionuclides in such environments. The present report focuses on possible chemical transformation reactions of α-ISA in heterogeneous alkaline model systems containing either Ca(OH) 2 or crushed hardened cement paste. The transformation reactions were monitored by measuring the concentration of α-ISA by high performance anion exchange chromatography and the formation of reaction products by high performance ion exclusion chromatography. The overall loss of organic species from solution was monitored by measuring the concentration of non-purgeable organic carbon. The reactions were examined in diluted and compacted suspensions, at either 25 o C or 90 o C, and under anaerobic atmospheres obtained by various methods. It was found that α-ISA was transformed under all conditions tested to some extent. Reaction products, such as glycolate, formate, lactate and acetate, all compounds with less complexing strength than α-ISA, were detected. The amount of reaction products identified by the chromatographic technique applied was ∼ 50 % of the amount of α-ISA reacted. Sorption of α-ISA to Ca(OH) 2 contributed only to a minor extent to the loss of α-ISA from the solution phase. As the most important conclusion of the present work it was demonstrated that the presence of oxidising agents had a distinctive influence on the turnover of α-ISA. Under aerobic conditions α-ISA was quantitatively converted to reaction products, whereas under strict anaerobic conditions, only

Numerical study for Darcy-Forchheimer flow due to a curved stretching surface with Cattaneo-Christov heat flux and homogeneous-heterogeneous reactions

Directory of Open Access Journals (Sweden)

Tasawar Hayat

Full Text Available The current investigation presents Darcy-Forchheimer flow of viscous fluid caused by a curved stretching sheet. Flow for porous space is characterized by Darcy-Forchheimer relation. Concept of homogeneous and heterogeneous reactions is also utilized. Heat transfer for Cattaneo–Christov theory characterizing the feature of thermal relaxation is incorporated. Nonlinear differential systems are derived. Shooting algorithm is employed to construct the solutions for the resulting nonlinear system. The characteristics of various sundry parameters are studied and discussed. Skin friction coefficient and heat transfer rate are numerically described. Keywords: 2D flow, Curved stretching surface, Darcy-Forchheimer porous medium, Cattaneo-Christov heat flux, Homogeneous-heterogeneous reactions

Surface heterogeneity and ionization of Cs promoter in carbon-based ruthenium catalyst for ammonia synthesis

International Nuclear Information System (INIS)

Kotarba, Andrzej; Dmytrzyk, Jaromir; Rarog-Pilecka, Wioletta; Kowalczyk, Zbigniew

2003-01-01

Second-generation ammonia synthesis cesium-doped ruthenium catalyst supported on turbostratic carbon was investigated by the species resolved thermal alkali desorption method (SR-TAD). Energetic barriers for cesium ions (2.86 eV), ground state (1.96 eV) and electronically excited atoms (5.76 eV) desorbing from the Cs-Ru/C catalyst were determined. In the case of ruthenium-free Cs/C system, cesium desorbs as ground state atoms only, with an energy barrier of 2.87 eV. The work functions determined by the thermionic emission of electrons from Cs/C and Cs-Ru/C were of the same value (2.9 eV). It was concluded that ruthenium induces heterogeneous distribution of cesium on the catalyst surface. The promoter stability is reduced on low work function areas and its surface ionization on high work function areas opens the ionic desorption channel. The Cs desorption from the catalyst is discussed in terms of the literature data for the cesium/graphite system

Chemically Tuning the Localized Surface Plasmon Resonances of Gold Nanostructure Arrays

KAUST Repository

Zheng, Yue Bing

2009-04-30

We report on chemical etching of ordered Au nanostructure arrays to continuously tune their localized surface plasmon resonances (LSPR). Real-time extinction spectra were recorded from both Au nanodisks and nanospheres immobilized on glass substrates when immersed in Au etchant. The time-dependent LSPR frequencies, intensities, and bandwidths were studied theoretically with discrete dipole approximations and the Mie solution, and they were correlated with the evolution of the etched Au nanostructures\\' morphology (as examined by atomic force microscopy). Since this chemical etching method can conveniently and accurately tune LSPR, it offers precise control of plasmonic properties and can be useful in applications such as surfaceenhanced Raman spectroscopy and molecular resonance spectroscopy. © 2009 American Chemical Society.

Chemical Controls of Ozone Dry Deposition to the Sea Surface Microlayer

Science.gov (United States)

Carpenter, L.; Chance, R.; Tinel, L.; Saint, A.; Sherwen, T.; Loades, D.; Evans, M. J.; Boxhall, P.; Hamilton, J.; Stolle, C.; Wurl, O.; Ribas-Ribas, M.; Pereira, R.

2017-12-01

Oceanic dry deposition of atmospheric ozone (O3) is both the largest and most uncertain O3 depositional sink, and is widely acknowledged to be controlled largely by chemical reactions in the sea surface microlayer (SML) involving iodide (I-) and dissolved organic material (DOM). These reactions not only determine how quickly O3 can be removed from the atmosphere, but also result in emissions of trace gases including volatile organic compounds and may constitute a source of secondary organic aerosols to the marine atmosphere. Iodide concentrations at the sea surface vary by approximately an order of magnitude spatially, leading to more than fivefold variation in ozone deposition velocities (and volatile iodine fluxes). Sea-surface temperature is a reasonable predictor of [I-], however two recent parameterisations for surface I- differ by a factor of two at low latitudes. The nature and reactivity of marine DOM to O3 is almost completely unknown, although studies have suggested approximately equivalent chemical control of I- and DOM on ozone deposition. Here we present substantial new measurements of oceanic I- in both bulk seawater and the overlying SML, and show improved estimates of the global sea surface iodide distribution. We also present analyses of water-soluble DOM isolated from the SML and bulk seawater, and corresponding laboratory studies of ozone uptake to bulk and SML seawater, with the aim of characterizing the reactivity of O3 towards marine DOM.

Surface characterization of ZnO nanorods grown by chemical bath deposition

Energy Technology Data Exchange (ETDEWEB)

Mbulanga, C.M., E-mail: crispin.mbulanga@nmmu.ac.za [Department of Physics, Nelson Mandela Metropolitan University, P.O. Box 77000, Port Elizabeth 6031 (South Africa); Urgessa, Z.N.; Tankio Djiokap, S.R.; Botha, J.R. [Department of Physics, Nelson Mandela Metropolitan University, P.O. Box 77000, Port Elizabeth 6031 (South Africa); Duvenhage, M.M.; Swart, H.C. [Department of Physics, University of the Free State, P.O Box 77000, Bloemfontein ZA9300 (South Africa)

2016-01-01

The surface composition of as-grown and annealed ZnO nanorods (ZNs) grown by a two-step chemical bath deposition method is investigated by the following surface-sensitive techniques: Time-of-Flight Secondary Ion Mass Spectroscopy (TOF-SIMS), X-ray Photoelectron Spectroscopy (XPS) and Auger Electron Spectroscopy (AES). The presence of H on the surface and throughout the entire thickness of ZNs is confirmed by TOF-SIMS. Based on TOF-SIMS results, the O2 XPS peak mostly observable at ~531.5 is assigned to O bound to H. Furthermore, it is found that the near surface region of as-grown ZNs is Zn-rich, and annealing at high temperature (~850 °C) removes H-related defects from the surface of ZNs and affect the balance of zinc and oxygen concentrations.

The influence of vertical sorbed phase transport on the fate of organic chemicals in surface soils.

Science.gov (United States)

McLachlan, Michael S; Czub, Gertje; Wania, Frank

2002-11-15

Gaseous exchange between surface soil and the atmosphere is an important process in the environmental fate of many chemicals. It was hypothesized that this process is influenced by vertical transport of chemicals sorbed to soil particles. Vertical sorbed phase transport in surface soils occurs by many processes such as bioturbation, cryoturbation, and erosion into cracks formed by soil drying. The solution of the advection/diffusion equation proposed by Jury et al. to describe organic chemical fate in a uniformly contaminated surface soil was modified to include vertical sorbed phase transport This process was modeled using a sorbed phase diffusion coefficient, the value of which was derived from soil carbon mass balances in the literature. The effective diffusivity of the chemical in a typical soil was greater in the modified model than in the model without sorbed phase transport for compounds with log K(OW) > 2 and log K(OA) > 6. Within this chemical partitioning space, the rate of volatilization from the surface soil was larger in the modified model than in the original model by up to a factor of 65. The volatilization rate was insensitive to the value of the sorbed phase diffusion coefficient throughout much of this chemical partitioning space, indicating that the surface soil layer was essentially well-mixed and that the mass transfer coefficient was determined by diffusion through the atmospheric boundary layer only. When this process was included in a non-steady-state regional multimedia chemical fate model running with a generic emissions scenario to air, the predicted soil concentrations increased by upto a factor of 25,whilethe air concentrations decreased by as much as a factor of approximately 3. Vertical sorbed phase transport in the soil thus has a major impact on predicted air and soil concentrations, the state of equilibrium, and the direction and magnitude of the chemical flux between air and soil. It is a key process influencing the environmental

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

Energy Technology Data Exchange (ETDEWEB)

Radisav D. Vidic

2002-05-01

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

Novel ion-molecular surface reaction to result in CH3 adsorbates on (111) surface of chemical vapor deposition diamond from ethane and surface anionic sites

International Nuclear Information System (INIS)

Komatsu, Shojiro; Okada, Katsuyuki; Shimizu, Yoshiki; Moriyoshi, Yusuke

2001-01-01

The existence of CH 3 adsorbates on (111) surface of chemical vapor deposited diamond, which was observed by scanning tunneling microscopy, was explained by the following S N 2 (bimolecular, substitutional, and nucleophilic) type surface reaction; C(s) - +C 2 H 6 ->C(s)-CH 3 +CH 3 - , where C(s) denotes a surface carbon atom. The activation energy was estimated to be 36.78 kcal/mol and the reaction proved to be exothermic with the enthalpy change of -9.250 kcal/mol, according to ab initio molecular orbital calculations at MP2/3-21+G * //RHF/3-21G * level; this result is consistent with typical substrate temperatures, namely about 900 degree C, for chemical vapor deposition of diamond. Charge transfer from the highest occupied molecular orbital of the surface anionic site to the lowest unoccupied molecular orbital of ethane, that is antibonding at the CH 3 - CH 3 bond, has been clearly visualized. A characteristic configuration of an ethane molecule which is associated with an anionic vacant site C(s) - on hydrogenated (111) surface of diamond was also found. [copyright] 2001 American Institute of Physics

Heterogeneous Oxidation of Laboratory-generated Mixed Composition and Biomass Burning Particles

Science.gov (United States)

Lim, C. Y.; Sugrue, R. A.; Hagan, D. H.; Cappa, C. D.; Kroll, J. H.; Browne, E. C.

2016-12-01

Heterogeneous oxidation of organic aerosol (OA) can significantly transform the chemical and physical properties of particulate matter in the atmosphere, leading to changes to the chemical composition of OA and potential volatilization of organic compounds. It has become increasingly apparent that the heterogeneous oxidation kinetics of OA depend on the phase and morphology of the particles. However, most laboratory experiments to date have been performed on single-component, purely organic precursors, which may exhibit fundamentally different behavior than more complex particles in the atmosphere. Here we present laboratory studies of the heterogeneous oxidation of two more complex chemical systems: thin, organic coatings on inorganic seed particles and biomass burning OA. In the first system, squalane (C30H62), a model compound for reduced OA, is coated onto dry ammonium sulfate particles at various thicknesses (10-20 nm) and exposed to hydroxyl radical (OH) in a flow tube reactor. In the second, we use a semi-batch reactor to study the heterogeneous OH-initiated oxidation of biomass burning particles as a part of the 2016 FIREX campaign in Missoula, MT. The resulting changes in chemical composition are monitored with an Aerodyne High Resolution Time-of-flight Aerosol Mass Spectrometer (AMS) and a soot-particle AMS for the non-refractory and refractory systems, respectively. We show that the heterogeneous oxidation kinetics of these multicomponent particles are substantially different than that of the single-component particles. The oxidation of organic coatings is rapid, undergoing dramatic changes to carbon oxidation state and losing a significant amount of organic mass after relatively low OH exposures (equivalent to several days of atmospheric processing). In the case of biomass burning particles, the kinetics are complex, with different components (inferred by aerosol mass spectrometry) undergoing oxidation at different rates.

Anionic co-contaminants and the biogeochemical evolution of aquifer heterogeneity. Final technical report

Energy Technology Data Exchange (ETDEWEB)

Fish, W.

1997-07-01

Adsorption heterogeneity of subsoils may depend on the sorbate and its concentration. Ligands in natural and contaminated subsoils may dissolve substantial metal oxides thereby altering the subsoil heterogeneity. We investigated these hypotheses on sands artificially and naturally coated with various amounts of metal oxides. The adsorbates Cu, oxalate, and mixtures of Cu and oxalate (Cu-Oxalate) were used as probes of the surface. For the concentration range studied, Binding Strength Analysis revealed that the naturally coated samples were heterogeneous at the microscale and the macroscale when oxalate was used as the probe of the surface. Cu revealed a smaller heterogeneity while Cu-Oxalate indicated an intermediate heterogeneity. Various elaborations of homogeneous-site Surface Complexation Models (SCM), calibrated to the surface protonation properties of goethite, modeled accurately the edges of oxalate, Cu, and mixtures of Cu and oxalate. The poorer fits for large concentrations was probably because of the site heterogeneity. The accuracy of SCMs was insensitive to the choice of surface protonation constants (pK{sub a}) and moderately sensitive to the choice of site density. The effective surface complexation constants (K{sup eff}) obtained from individual edges were somewhat different because of the concentration dependent heterogeneity. It was not always possible to use K{sup eff} values for one sorbate concentration to reproduce adsorption of other concentrations of the same sorbate. A modified version of the discrete pK{sub a} spectrum model closely reproduced the acid-base titration curve with two adsorption sites (four pK{sub a}`s). The adsorption of all concentrations of Cu, oxalate, and Cu-Oxalate was often reproduced with only one of those sites. The competition between the dissolved Al and the surface for the oxalate in solution was accurately reproduced with both sites. The dissolution of the oxide coating was often influenced by the pore velocity.

Oxidative regeneration of toluene-saturated natural zeolite by gaseous ozone: The influence of zeolite chemical surface characteristics

Energy Technology Data Exchange (ETDEWEB)

Alejandro, Serguei [Laboratorio de Tecnologías Limpias (F. Ingeniería), Universidad Católica de la Santísima Concepción, Alonso de Ribera 2850, Concepción (Chile); Núcleo de Energías Renovables (F. Ingeniería), Universidad Católica de Temuco, Rudecindo Ortega 02950, Temuco (Chile); Valdés, Héctor, E-mail: hvaldes@ucsc.cl [Laboratorio de Tecnologías Limpias (F. Ingeniería), Universidad Católica de la Santísima Concepción, Alonso de Ribera 2850, Concepción (Chile); Manéro, Marie-Hélène [Université de Toulouse (France); INPT, UPS (France); Laboratoire de Génie Chimique, 4, Allée Emile Monso, F–31030 Toulouse (France); CNRS (France); Laboratoire de Génie Chimique, F–31030 Toulouse (France); Zaror, Claudio A. [Departamento de Ingeniería Química (F. Ingeniería), Universidad de Concepción, Concepción, Correo 3, Casilla 160–C (Chile)

2014-06-01

Highlights: • Surface acidity of modified natural zeolite is related to its chemical reactivity. • Brønsted acid sites are associated to toluene adsorption. • Lewis acid sites could decompose ozone generating surface active oxygen species. • Infrared spectra evidence active atomic oxygen and oxidation by-product formation. • 2NH4Z1 sample shows the highest reactivity toward adsorbed toluene. - Abstract: In this study, the effect of zeolite chemical surface characteristics on the oxidative regeneration of toluene saturated-zeolite samples is investigated. A Chilean natural zeolite (53% clinoptilolite, 40% mordenite and 7% quartz) was chemically modified by acid treatment with hydrochloric acid and by ion-exchange with ammonium sulphate. Thermal pre-treatments at 623 and 823 K were applied and six zeolite samples with different chemical surface characteristics were generated. Chemical modification of natural zeolite followed by thermal out-gassing allows distinguishing the role of acidic surface sites on the regeneration of exhausted zeolites. An increase in Brønsted acid sites on zeolite surface is observed as a result of ammonium-exchange treatment followed by thermal treatment at 623 K, thus increasing the adsorption capacity toward toluene. High ozone consumption could be associated to a high content of Lewis acid sites, since these could decompose ozone into atomic active oxygen species. Then, surface oxidation reactions could take part among adsorbed toluene at Brønsted acid sites and surface atomic oxygen species, reducing the amount of adsorbed toluene after the regenerative oxidation with ozone. Experimental results show that the presence of adsorbed oxidation by-products has a negative impact on the recovery of zeolite adsorption capacity.

Oxidative regeneration of toluene-saturated natural zeolite by gaseous ozone: The influence of zeolite chemical surface characteristics

International Nuclear Information System (INIS)

Alejandro, Serguei; Valdés, Héctor; Manéro, Marie-Hélène; Zaror, Claudio A.

2014-01-01

Highlights: • Surface acidity of modified natural zeolite is related to its chemical reactivity. • Brønsted acid sites are associated to toluene adsorption. • Lewis acid sites could decompose ozone generating surface active oxygen species. • Infrared spectra evidence active atomic oxygen and oxidation by-product formation. • 2NH4Z1 sample shows the highest reactivity toward adsorbed toluene. - Abstract: In this study, the effect of zeolite chemical surface characteristics on the oxidative regeneration of toluene saturated-zeolite samples is investigated. A Chilean natural zeolite (53% clinoptilolite, 40% mordenite and 7% quartz) was chemically modified by acid treatment with hydrochloric acid and by ion-exchange with ammonium sulphate. Thermal pre-treatments at 623 and 823 K were applied and six zeolite samples with different chemical surface characteristics were generated. Chemical modification of natural zeolite followed by thermal out-gassing allows distinguishing the role of acidic surface sites on the regeneration of exhausted zeolites. An increase in Brønsted acid sites on zeolite surface is observed as a result of ammonium-exchange treatment followed by thermal treatment at 623 K, thus increasing the adsorption capacity toward toluene. High ozone consumption could be associated to a high content of Lewis acid sites, since these could decompose ozone into atomic active oxygen species. Then, surface oxidation reactions could take part among adsorbed toluene at Brønsted acid sites and surface atomic oxygen species, reducing the amount of adsorbed toluene after the regenerative oxidation with ozone. Experimental results show that the presence of adsorbed oxidation by-products has a negative impact on the recovery of zeolite adsorption capacity

Characterizing physical properties and heterogeneous chemistry of single particles in air using optical trapping-Raman spectroscopy

Science.gov (United States)

Gong, Z.; Wang, C.; Pan, Y. L.; Videen, G.

2017-12-01

Heterogeneous reactions of solid particles in a gaseous environment are of increasing interest; however, most of the heterogeneous chemistry studies of airborne solids were conducted on particle ensembles. A close examination on the heterogeneous chemistry between single particles and gaseous-environment species is the key to elucidate the fundamental mechanisms of hydroscopic growth, cloud nuclei condensation, secondary aerosol formation, etc., and reduce the uncertainty of models in radiative forcing, climate change, and atmospheric chemistry. We demonstrate an optical trapping-Raman spectroscopy (OT-RS) system to study the heterogeneous chemistry of the solid particles in air at single-particle level. Compared to other single-particle techniques, optical trapping offers a non-invasive, flexible, and stable method to isolate single solid particle from substrates. Benefited from two counter-propagating hollow beams, the optical trapping configuration is adaptive to trap a variety of particles with different materials from inorganic substitution (carbon nanotubes, silica, etc.) to organic, dye-doped polymers and bioaerosols (spores, pollen, etc.), with different optical properties from transparent to strongly absorbing, with different sizes from sub-micrometers to tens of microns, or with distinct morphologies from loosely packed nanotubes to microspheres and irregular pollen grains. The particles in the optical trap may stay unchanged, surface degraded, or optically fragmented according to different laser intensity, and their physical and chemical properties are characterized by the Raman spectra and imaging system simultaneously. The Raman spectra is able to distinguish the chemical compositions of different particles, while the synchronized imaging system can resolve their physical properties (sizes, shapes, morphologies, etc.). The temporal behavior of the trapped particles also can be monitored by the OT-RS system at an indefinite time with a resolution from

Stick-Slip Motion of Moving Contact Line on Chemically Patterned Surfaces

KAUST Repository

Wu, Congmin; Lei, Siulong; Qian, Tiezheng; Wang, Xiaoping

2009-01-01

Based on our continuum hydrodynamic model for immiscible two-phase flows at solid surfaces, the stick-slip motion has been predicted for moving contact line at chemically patterned surfaces [Wang et al., J. Fluid Mech., 605 (2008), pp. 59-78]. In this paper we show that the continuum predictions can be quantitatively verified by molecular dynamics (MD) simulations. Our MD simulations are carried out for two immiscible Lennard-Jones fluids confined by two planar solid walls in Poiseuille flow geometry. In particular, one solid surface is chemically patterned with alternating stripes. For comparison, the continuum model is numerically solved using material parameters directly measured in MD simulations. From oscillatory fluid-fluid interface to intermittent stick-slip motion of moving contact line, we have quantitative agreement between the continuum and MD results. This agreement is attributed to the accurate description down to molecular scale by the generalized Navier boundary condition in our continuum model. Numerical results are also presented for the relaxational dynamics of fluid-fluid interface, in agreement with a theoretical analysis based on the Onsager principle of minimum energy dissipation. © 2010 Global-Science Press.

Structure and chemical composition of layers adsorbed at interfaces with champagne.

Science.gov (United States)

Aguié-Béghin, V; Adriaensen, Y; Péron, N; Valade, M; Rouxhet, P; Douillard, R

2009-11-11

The structure and the chemical composition of the layer adsorbed at interfaces involving champagne have been investigated using native champagne, as well as ultrafiltrate (UFch) and ultraconcentrate (UCch) obtained by ultrafiltration with a 10(4) nominal molar mass cutoff. The layer adsorbed at the air/liquid interface was examined by surface tension and ellipsometry kinetic measurements. Brewster angle microscopy demonstrated that the layer formed on polystyrene by adsorption or drop evaporation was heterogeneous, with a domain structure presenting similarities with the layer adsorbed at the air/liquid interface. The surface chemical composition of polystyrene with the adlayer was determined by X-ray photoelectron spectroscopy (XPS). The contribution of champagne constituents varied according to the liquid (native, UFch, and UCch) and to the procedure of adlayer formation (evaporation, adsorption, and adsorption + rinsing). However, their chemical composition was not significantly influenced either by ultrafiltration or by the procedure of deposition on polystyrene. Modeling this composition in terms of classes of model compounds gave approximately 35% (w/w) of proteins and 65% (w/w) of polysaccharides. In the adlayer, the carboxyl groups or esters represent about 18% of carbon due to nonpolypeptidic compounds, indicating the presence of either uronic acids in the complex structure of pectic polysaccharides or of polyphenolic esters. This structural and chemical information and its relationship with the experimental procedures indicate that proteins alone cannot be used as a realistic model for the macromolecules forming the adsorption layer of champagne. Polysaccharides, the other major macromolecular components of champagne wine, are assembled with proteins at the interfaces, in agreement with the heterogeneous character of the adsorbed layer at interfaces.

Separation of Process Wastewater with Extractive Heterogeneous-Azeotropic Distillation

Directory of Open Access Journals (Sweden)

Tóth András József

2016-10-01

Full Text Available The application of vapour-liquid equilibria-based separation alternatives can be extraordinarily complicated for the treatment of process wastewaters containing heterogeneous-azeotropic. Despite dissimilar successfully tested methods for separation, there is possibility to get better distillation method by enabling the separation of more and more specific process wastewater. Extractive heterogeneous-azeotropic distillation (EHAD is a new advance in treatment of fine chemical wastewater showing special features to cope with the treatment of highly non-ideal mixtures. This method combines the worth of heterogeneous-azeotropic and extractive distillations in one apparatus without addition of any extra materials. The study of the separations of ternary component process wastewater from the fine chemical industry shows both in the modelled and experimental results that EHAD can be successfully applied. The measured and modelled compositions at extreme purities, that is, close to 0% or 100%, can be different because of the inaccuracies of the modelling. This highlights the paramount importance of the experiments if special extra-fine chemicals with almost no impurities, e.g. of pharmacopoeial quality are to be produced by special distillation technique. This study expands the application of EHAD technique, this new field is the separation of process wastewaters.

Cell behavior related to implant surfaces with different microstructure and chemical composition: an in vitro analysis.

Science.gov (United States)

Conserva, Enrico; Lanuti, Anna; Menini, Maria

2010-01-01

This paper reports on an in vitro comparison of osteoblast and mesenchymal stem cell (MSC) adhesion, proliferation, and differentiation related to two different surface treatments applied to the same implant design to determine whether the interaction between cells and implants is influenced by surface structure and chemical composition of the implants. Thirty-nine implants with a sandblasted (SB) surface and 39 implants with a grit-blasted and high-temperature acid-etched (GBAE) surface were used. The implant macrostructures and microstructures were analyzed by high- and low-voltage scanning electron microscopy (SEM) and by stereo-SEM. The surface chemical composition was investigated by energy dispersive analysis and x-ray photoemission spectroscopy. SaOS-2 osteoblasts and human MSCs were used for the evaluation of cell proliferation and alkaline phosphatase enzymatic activity in contact with the two surfaces. The GBAE surface showed fewer contaminants and a very high percentage of titanium (19.7%) compared to the SB surface (14.2%). The two surfaces showed similar mean roughness (Ra), but the depth (Rz) and density (RSm) of the porosity were significantly increased in the GBAE surface. The GBAE surface presented more osteoblast and MSC proliferation than the SB surface. No statistically significant differences in alkaline phosphatase activity were found between surfaces for either cellular line. The GBAE surface showed less surface contaminants and a higher percentage of titanium (19.7%) than the SB surface. The macro/micropore structured design and chemical composition of the GBAE surface allowed greater cell adhesion and proliferation and an earlier cell spreading but did not play an obvious role in in vitro cellular differentiation.

Multifunctional ultra-high vacuum apparatus for studies of the interactions of chemical warfare agents on complex surfaces

International Nuclear Information System (INIS)

Wilmsmeyer, Amanda R.; Morris, John R.; Gordon, Wesley O.; Mantooth, Brent A.; Lalain, Teri A.; Davis, Erin Durke

2014-01-01

A fundamental understanding of the surface chemistry of chemical warfare agents is needed to fully predict the interaction of these toxic molecules with militarily relevant materials, catalysts, and environmental surfaces. For example, rules for predicting the surface chemistry of agents can be applied to the creation of next generation decontaminants, reactive coatings, and protective materials for the warfighter. Here, we describe a multifunctional ultra-high vacuum instrument for conducting comprehensive studies of the adsorption, desorption, and surface chemistry of chemical warfare agents on model and militarily relevant surfaces. The system applies reflection-absorption infrared spectroscopy, x-ray photoelectron spectroscopy, and mass spectrometry to study adsorption and surface reactions of chemical warfare agents. Several novel components have been developed to address the unique safety and sample exposure challenges that accompany the research of these toxic, often very low vapor pressure, compounds. While results of vacuum-based surface science techniques may not necessarily translate directly to environmental processes, learning about the fundamental chemistry will begin to inform scientists about the critical aspects that impact real-world applications

Multifunctional ultra-high vacuum apparatus for studies of the interactions of chemical warfare agents on complex surfaces.

Science.gov (United States)

Wilmsmeyer, Amanda R; Gordon, Wesley O; Davis, Erin Durke; Mantooth, Brent A; Lalain, Teri A; Morris, John R

2014-01-01

A fundamental understanding of the surface chemistry of chemical warfare agents is needed to fully predict the interaction of these toxic molecules with militarily relevant materials, catalysts, and environmental surfaces. For example, rules for predicting the surface chemistry of agents can be applied to the creation of next generation decontaminants, reactive coatings, and protective materials for the warfighter. Here, we describe a multifunctional ultra-high vacuum instrument for conducting comprehensive studies of the adsorption, desorption, and surface chemistry of chemical warfare agents on model and militarily relevant surfaces. The system applies reflection-absorption infrared spectroscopy, x-ray photoelectron spectroscopy, and mass spectrometry to study adsorption and surface reactions of chemical warfare agents. Several novel components have been developed to address the unique safety and sample exposure challenges that accompany the research of these toxic, often very low vapor pressure, compounds. While results of vacuum-based surface science techniques may not necessarily translate directly to environmental processes, learning about the fundamental chemistry will begin to inform scientists about the critical aspects that impact real-world applications.

Multifunctional ultra-high vacuum apparatus for studies of the interactions of chemical warfare agents on complex surfaces

Energy Technology Data Exchange (ETDEWEB)

Wilmsmeyer, Amanda R.; Morris, John R. [Department of Chemistry, Virginia Tech, Blacksburg, Virginia 24061 (United States); Gordon, Wesley O.; Mantooth, Brent A.; Lalain, Teri A. [Research and Technology Directorate, U.S. Army Edgewood Chemical Biological Center, Aberdeen Proving Ground, Maryland 21010 (United States); Davis, Erin Durke [OptiMetrics, Inc., Abingdon, Maryland 21009 (United States)

2014-01-15

A fundamental understanding of the surface chemistry of chemical warfare agents is needed to fully predict the interaction of these toxic molecules with militarily relevant materials, catalysts, and environmental surfaces. For example, rules for predicting the surface chemistry of agents can be applied to the creation of next generation decontaminants, reactive coatings, and protective materials for the warfighter. Here, we describe a multifunctional ultra-high vacuum instrument for conducting comprehensive studies of the adsorption, desorption, and surface chemistry of chemical warfare agents on model and militarily relevant surfaces. The system applies reflection-absorption infrared spectroscopy, x-ray photoelectron spectroscopy, and mass spectrometry to study adsorption and surface reactions of chemical warfare agents. Several novel components have been developed to address the unique safety and sample exposure challenges that accompany the research of these toxic, often very low vapor pressure, compounds. While results of vacuum-based surface science techniques may not necessarily translate directly to environmental processes, learning about the fundamental chemistry will begin to inform scientists about the critical aspects that impact real-world applications.

Climate Implications of the Heterogeneity of Anthropogenic Aerosol Forcing

Science.gov (United States)

Persad, Geeta Gayatri

Short-lived anthropogenic aerosols are concentrated in regions of high human activity, where they interact with radiation and clouds, causing horizontally heterogeneous radiative forcing between polluted and unpolluted regions. Aerosols can absorb shortwave energy in the atmosphere, but deplete it at the surface, producing opposite radiative perturbations between the surface and atmosphere. This thesis investigates climate and policy implications of this horizontal and vertical heterogeneity of anthropogenic aerosol forcing, employing the Geophysical Fluid Dynamics Laboratory's AM2.1 and AM3 models, both at a global scale and using East Asia as a regional case study. The degree of difference between spatial patterns of climate change due to heterogeneous aerosol forcing versus homogeneous greenhouse gas forcing deeply impacts the detection, attribution, and prediction of regional climate change. This dissertation addresses a gap in current understanding of these two forcings' response pattern development, using AM2.1 historical forcing simulations. The results indicate that fast atmospheric and land-surface processes alone substantially homogenize the global pattern of surface energy flux response to heterogeneous aerosol forcing. Aerosols' vertical redistribution of energy significantly impacts regional climate, but is incompletely understood. It is newly identified here, via observations and historical and idealized forcing simulations, that increased aerosol-driven atmospheric absorption may explain half of East Asia's recent surface insolation decline. Further, aerosols' surface and atmospheric effects counteract each other regionally---atmospheric heating enhances summer monsoon circulation, while surface dimming suppresses it---but absorbing aerosols' combined effects reduce summer monsoon rainfall. This thesis constitutes the first vertical decomposition of aerosols' impacts in this high-emissions region and elucidates the monsoonal response to aerosols

Oxidative regeneration of toluene-saturated natural zeolite by gaseous ozone: the influence of zeolite chemical surface characteristics.

Science.gov (United States)

Alejandro, Serguei; Valdés, Héctor; Manéro, Marie-Hélène; Zaror, Claudio A

2014-06-15

In this study, the effect of zeolite chemical surface characteristics on the oxidative regeneration of toluene saturated-zeolite samples is investigated. A Chilean natural zeolite (53% clinoptilolite, 40% mordenite and 7% quartz) was chemically modified by acid treatment with hydrochloric acid and by ion-exchange with ammonium sulphate. Thermal pre-treatments at 623 and 823K were applied and six zeolite samples with different chemical surface characteristics were generated. Chemical modification of natural zeolite followed by thermal out-gassing allows distinguishing the role of acidic surface sites on the regeneration of exhausted zeolites. An increase in Brønsted acid sites on zeolite surface is observed as a result of ammonium-exchange treatment followed by thermal treatment at 623K, thus increasing the adsorption capacity toward toluene. High ozone consumption could be associated to a high content of Lewis acid sites, since these could decompose ozone into atomic active oxygen species. Then, surface oxidation reactions could take part among adsorbed toluene at Brønsted acid sites and surface atomic oxygen species, reducing the amount of adsorbed toluene after the regenerative oxidation with ozone. Experimental results show that the presence of adsorbed oxidation by-products has a negative impact on the recovery of zeolite adsorption capacity. Copyright © 2014 Elsevier B.V. All rights reserved.

Surge-Resistant Nanocomposite Enameled Wire Using Silica Nanoparticles with Binary Chemical Compositions on the Surface

Directory of Open Access Journals (Sweden)

Jeseung Yoo

2015-01-01

Full Text Available We developed polyesterimide (PEI nanocomposite enameled wires using surface-modified silica nanoparticles with binary chemical compositions on the surface. The modification was done using silanes assisted by ultrasound, which facilitated high density modification. Two different trimethoxysilanes were chosen for the modification on the basis of resemblance of chemical compositions on the silica surface to PEI varnish. The surface-modified silica was well dispersed in PEI varnish, which was confirmed by optical observation and viscosity measurement. The glass transition temperature of the silica-PEI nanocomposite increased with the silica content. The silica-dispersed PEI varnish was then used for enameled wire fabrication. The silica-PEI nanocomposite enameled wire exhibited a much longer lifetime compared to that of neat PEI enameled wire in partial discharge conditions.

Chemical surface reactions by click chemistry: coumarin dye modification of 11-bromoundecyltrichlorosilane monolayers

International Nuclear Information System (INIS)

Haensch, Claudia; Hoeppener, Stephanie; Schubert, Ulrich S

2008-01-01

The functionalization of surfaces and the ability to tailor their properties with desired physico-chemical functions is an important field of research with a broad spectrum of applications. These applications range from the modification of wetting properties, over the alteration of optical properties, to the fabrication of molecular electronic devices. In each of these fields, it is of specific importance to be able to control the quality of the layers with high precision. The present study demonstrates an approach that utilizes the 1,3-dipolar cycloaddition of terminal acetylenes to prepare triazole-terminated monolayers on different substrates. The characterization of the precursor monolayers, the optimization of the chemical surface reactions as well as the clicking of a fluorescent dye molecule on such azide-terminated monolayers was carried out. A coumarin 343 derivative was utilized to discuss the aspects of the functionalization approach. Based on this approach, a number of potential surface reactions, facilitated via the acetylene-substituted functional molecules, for a broad range of applications is at hand, thus leading to numerous possibilities where surface modifications are concerned. These modifications can be applied on non-structured surfaces of silicon or glass or can be used on structured surfaces. Various possibilities are discussed

A numerical study of three-dimensional droplets spreading on chemically patterned surfaces

KAUST Repository

Zhong, Hua; Wang, Xiao-Ping; Sun, Shuyu

2016-01-01

We study numerically the three-dimensional droplets spreading on physically flat chemically patterned surfaces with periodic squares separated by channels. Our model consists of the Navier-Stokes-Cahn-Hilliard equations with the generalized Navier

Heterogeneity of activated carbons in adsorption of aniline from aqueous solutions

Science.gov (United States)

Podkościelny, P.; László, K.

2007-08-01

The heterogeneity of activated carbons (ACs) prepared from different precursors is investigated on the basis of adsorption isotherms of aniline from dilute aqueous solutions at various pH values. The APET carbon prepared from polyethyleneterephthalate (PET), as well as, commercial ACP carbon prepared from peat were used. Besides, to investigate the influence of carbon surface chemistry, the adsorption was studied on modified carbons based on ACP carbon. Its various oxygen surface groups were changed by both nitric acid and thermal treatments. The Dubinin-Astakhov (DA) equation and Langmuir-Freundlich (LF) one have been used to model the phenomenon of aniline adsorption from aqueous solutions on heterogeneous carbon surfaces. Adsorption-energy distribution (AED) functions have been calculated by using an algorithm based on a regularization method. Analysis of these functions for activated carbons studied provides important comparative information about their surface heterogeneity.

Impact of chemical polishing on surface roughness and dimensional quality of electron beam melting process (EBM) parts

Science.gov (United States)

Dolimont, Adrien; Rivière-Lorphèvre, Edouard; Ducobu, François; Backaert, Stéphane

2018-05-01

Additive manufacturing is growing faster and faster. This leads us to study the functionalization of the parts that are produced by these processes. Electron Beam melting (EBM) is one of these technologies. It is a powder based additive manufacturing (AM) method. With this process, it is possible to manufacture high-density metal parts with complex topology. One of the big problems with these technologies is the surface finish. To improve the quality of the surface, some finishing operations are needed. In this study, the focus is set on chemical polishing. The goal is to determine how the chemical etching impacts the dimensional accuracy and the surface roughness of EBM parts. To this end, an experimental campaign was carried out on the most widely used material in EBM, Ti6Al4V. Different exposure times were tested. The impact of these times on surface quality was evaluated. To help predicting the excess thickness to be provided, the dimensional impact of chemical polishing on EBM parts was estimated. 15 parts were measured before and after chemical machining. The improvement of surface quality was also evaluated after each treatment.

Chemical changes induced on a TiO2 surface by electron bombardment

International Nuclear Information System (INIS)

Vergara, L.I.; Passeggi, M.C.G.; Ferron, J.

2007-01-01

We study the TiO 2 (Ti 4+ ) chemical reduction induced by electron bombardment using Auger electron spectroscopy and factor analysis. We show that the electron irradiation of a TiO 2 sample is characterized by the appearance of a lower Ti oxidation state, Ti 2 O 3 (Ti 3+ ), followed by a further deposition of carbon, which is present inevitably in the environment even under ultra-high vacuum conditions. The appearance of C over the surface is found to be a complex mechanism which affects the reduction process through passivation of the electron-induced oxygen desorption and formation of titanium carbide. For very high irradiation doses, we also found that the chemical changes on the surface are stopped due to the deposition of carbon in a graphitic form

Simulation of the evolution of fused silica's surface defect during wet chemical etching

Science.gov (United States)

Liu, Taixiang; Yang, Ke; Li, Heyang; Yan, Lianghong; Yuan, Xiaodong; Yan, Hongwei

2017-08-01

Large high-power-laser facility is the basis for achieving inertial confinement fusion, one of whose missions is to make fusion energy usable in the near future. In the facility, fused silica optics plays an irreplaceable role to conduct extremely high-intensity laser to fusion capsule. But the surface defect of fused silica is a major obstacle limiting the output power of the large laser facility and likely resulting in the failure of ignition. To mitigate, or event to remove the surface defect, wet chemical etching has been developed as a practical way. However, how the surface defect evolves during wet chemical etching is still not clearly known so far. To address this problem, in this work, the three-dimensional model of surface defect is built and finite difference time domain (FDTD) method is developed to simulate the evolution of surface defect during etching. From the simulation, it is found that the surface defect will get smooth and result in the improvement of surface quality of fused silica after etching. Comparatively, surface defects (e.g. micro-crack, scratch, series of pinholes, etc.) of a typical fused silica at different etching time are experimentally measured. It can be seen that the simulation result agrees well with the result of experiment, indicating the FDTD method is valid for investigating the evolution of surface defect during etching. With the finding of FDTD simulation, one can optimize the treatment process of fused silica in practical etching or even to make the initial characterization of surface defect traceable.

Directed transport by surface chemical potential gradients for enhancing analyte collection in nanoscale sensors.

Science.gov (United States)

Sitt, Amit; Hess, Henry

2015-05-13

Nanoscale detectors hold great promise for single molecule detection and the analysis of small volumes of dilute samples. However, the probability of an analyte reaching the nanosensor in a dilute solution is extremely low due to the sensor's small size. Here, we examine the use of a chemical potential gradient along a surface to accelerate analyte capture by nanoscale sensors. Utilizing a simple model for transport induced by surface binding energy gradients, we study the effect of the gradient on the efficiency of collecting nanoparticles and single and double stranded DNA. The results indicate that chemical potential gradients along a surface can lead to an acceleration of analyte capture by several orders of magnitude compared to direct collection from the solution. The improvement in collection is limited to a relatively narrow window of gradient slopes, and its extent strongly depends on the size of the gradient patch. Our model allows the optimization of gradient layouts and sheds light on the fundamental characteristics of chemical potential gradient induced transport.

A novel surface cleaning method for chemical removal of fouling lead layer from chromium surfaces

International Nuclear Information System (INIS)

Gholivand, Kh.; Khosravi, M.; Hosseini, S.G.; Fathollahi, M.

2010-01-01

Most products especially metallic surfaces require cleaning treatment to remove surface contaminations that remain after processing or usage. Lead fouling is a general problem which arises from lead fouling on the chromium surfaces of bores and other interior parts of systems which have interaction with metallic lead in high temperatures and pressures. In this study, a novel chemical solution was introduced as a cleaner reagent for removing metallic lead pollution, as a fouling metal, from chromium surfaces. The cleaner aqueous solution contains hydrogen peroxide (H 2 O 2 ) as oxidizing agent of lead layer on the chromium surface and acetic acid (CH 3 COOH) as chelating agent of lead ions. The effect of some experimental parameters such as acetic acid concentration, hydrogen peroxide concentration and temperature of the cleaner solution during the operation on the efficiency of lead cleaning procedure was investigated. The results of scanning electron microscopy (SEM) showed that using this procedure, the lead pollution layer could be completely removed from real chromium surfaces without corrosion of the original surface. Finally, the optimum conditions for the complete and fast removing of lead pollution layer from chromium surfaces were proposed. The experimental results showed that at the optimum condition (acetic acid concentration 28% (V/V), hydrogen peroxide 8% (V/V) and temperature 35 deg. C), only 15-min time is needed for complete removal of 3 g fouling lead from a chromium surface.

On the topography of sputtered or chemically etched crystals: surface energies minimised

International Nuclear Information System (INIS)

Chadderton, L.T.; Cope, J.O.

1984-01-01

The sputtering of single or polycrystalline metal surfaces by heavy ions gives rise to the characteristic topographical features of etch pits, ripples, and cones (pyramids). For cones and pyramids, in particular, no completely satisfactory explanation exists as to the origin of the basic geometry. Scanning electron micrographs are shown. It is proposed that for topographical features of both chemical etch and ion beam origin on single crystal surfaces, the presence of facets on cones and pyramids in particular, is due to the minimization of surface energy. (U.K.)

Assessing chemical exposure and ecological impacts of environmental surface waters using cell culture-based metabolomic

Science.gov (United States)

Waste water treatment plants (WWTPs), as well as industrial and agricultural operations release complex mixtures of anthropogenic chemicals that negatively affect surface water quality. Previous studies have shown that exposure to such complex chemical mixtures can produce adver...

Chemical treatment of the intra-canal dentin surface: a new approach to modify dentin hydrophobicity

Directory of Open Access Journals (Sweden)

Cesar GAITAN-FONSECA

2013-01-01

Full Text Available Objective This study evaluated the hydrophobicity of dentin surfaces that were modified through chemical silanization with octadecyltrichlorosilane (OTS. Material and Methods An in vitro experimental study was performed using 40 human permanent incisors that were divided into the following two groups: non-silanized and silanized. The specimens were pretreated and chemically modified with OTS. After the chemical modification, the dentin hydrophobicity was examined using a water contact angle measurement (WCA. The effectiveness of the modification of hydrophobicity was verified by the fluid permeability test (FPT. Results and Conclusions Statistically significant differences were found in the values of WCA and FPT between the two groups. After silanization, the hydrophobic intraradicular dentin surface exhibited in vitro properties that limit fluid penetration into the sealed root canal. This chemical treatment is a new approach for improving the sealing of the root canal system.

Numerical tackling for viscoelastic fluid flow in rotating frame considering homogeneous-heterogeneous reactions

Directory of Open Access Journals (Sweden)

Najwa Maqsood

Full Text Available This study provides a numerical treatment for rotating flow of viscoelastic (Maxwell fluid bounded by a linearly deforming elastic surface. Mass transfer analysis is carried out in the existence of homogeneous-heterogeneous reactions. By means of usual transformation, the governing equations are changed into global similarity equations which have been tackled by an expedient shooting approach. A contemporary numerical routine bvp4c of software MATLAB is also opted to develop numerical approximations. Both methods of solution are found in complete agreement in all the cases. Velocity and concentration profiles are computed and elucidated for certain range of viscoelastic fluid parameter. The solutions contain a rotation-strength parameter λ that has a considerable impact on the flow fields. For sufficiently large value of λ, the velocity fields are oscillatory decaying function of the non-dimensional vertical distance. Concentration distribution at the surface is found to decrease upon increasing the strengths of chemical reactions. A comparison of present computations is made with those of already published ones and such comparison appears convincing. Keywords: Maxwell fluid, Similarity solution, Numerical method, Chemical reaction, Stretching sheet

Study of heat-moisture treatment of potato starch granules by chemical surface gelatinization.

Science.gov (United States)

Bartz, Josiane; da Rosa Zavareze, Elessandra; Dias, Alvaro Renato Guerra

2017-08-01

Native potato starch was subjected to heat-moisture treatment (HMT) at 12%, 15%, 18%, 21%, and 24% of moisture content at 110 °C for 1 h, and the effects on morphology, structure, and thermal and physicochemical properties were investigated. To reveal the internal structure, 30% and 50% of the granular surface were removed by chemical surface gelatinization in concentrated LiCl solution. At moisture contents of 12% and 15%, HTM reduced the gelatinization temperatures and relative crystallinity of the starches, while at moisture contents of 21% and 24 % both increased. The alterations on morphology, X-ray pattern, physicochemical properties, and increase of amylose content were more intense with the increase of moisture content of HMT. The removal of granular layers showed that the changes promoted by HMT occur throughout the whole granule and were pronounced at the core or peripheral region, depending of the moisture content applied during HMT. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Graphene-Based Nanomaterials as Heterogeneous Acid Catalysts: A Comprehensive Perspective

Directory of Open Access Journals (Sweden)

Bhaskar Garg

2014-09-01

Full Text Available Acid catalysis is quite prevalent and probably one of the most routine operations in both industrial processes and research laboratories worldwide. Recently, “graphene”, a two dimensional single-layer carbon sheet with hexagonal packed lattice structure, imitative of nanomaterials, has shown great potential as alternative and eco-friendly solid carbocatalyst for a variety of acid-catalyzed reactions. Owing to their exceptional physical, chemical, and mechanical properties, graphene-based nanomaterials (G-NMs offer highly stable Brønsted acidic sites, high mass transfer, relatively large surface areas, water tolerant character, and convenient recoverability as well as recyclability, whilst retaining high activity in acid-catalyzed chemical reactions. This comprehensive review focuses on the chemistry of G-NMs, including their synthesis, characterization, properties, functionalization, and up-to-date applications in heterogeneous acid catalysis. In line with this, in certain instances readers may find herein some criticisms that should be taken as constructive and would be of value in understanding the scope and limitations of current approaches utilizing graphene and its derivatives for the same.

Chemical reactivity of {alpha}-isosaccharinic acid in heterogeneous alkaline systems

Energy Technology Data Exchange (ETDEWEB)

Glaus, M. A.; Loon, L. R. Van

2009-05-15

Cellulose degradation under alkaline conditions is of relevance for the mobility of many radionuclides in the near-field of a cementitious repository for radioactive waste, because metal-binding degradation products may be formed. Among these, {alpha}- isosaccharinic acid ({alpha}-ISA) is the strongest complexant. The prediction of the equilibrium concentration of {alpha}-ISA in cement pore water is therefore an important step in the assessment of the influence of cellulose degradation products on the speciation of radionuclides in such environments. The present report focuses on possible chemical transformation reactions of {alpha}-ISA in heterogeneous alkaline model systems containing either Ca(OH){sub 2} or crushed hardened cement paste. The transformation reactions were monitored by measuring the concentration of {alpha}-ISA by high performance anion exchange chromatography and the formation of reaction products by high performance ion exclusion chromatography. The overall loss of organic species from solution was monitored by measuring the concentration of non-purgeable organic carbon. The reactions were examined in diluted and compacted suspensions, at either 25 {sup o}C or 90 {sup o}C, and under anaerobic atmospheres obtained by various methods. It was found that {alpha}-ISA was transformed under all conditions tested to some extent. Reaction products, such as glycolate, formate, lactate and acetate, all compounds with less complexing strength than {alpha}-ISA, were detected. The amount of reaction products identified by the chromatographic technique applied was {approx} 50 % of the amount of {alpha}-ISA reacted. Sorption of {alpha}-ISA to Ca(OH){sub 2} contributed only to a minor extent to the loss of {alpha}-ISA from the solution phase. As the most important conclusion of the present work it was demonstrated that the presence of oxidising agents had a distinctive influence on the turnover of {alpha}-ISA. Under aerobic conditions {alpha}-ISA was

Chemical films and monolayers on the water surface and their interactions with ultraviolet radiation: a pilot investigation

International Nuclear Information System (INIS)

Schouten, Peter; Lemckert, Charles; Underhill, Ian; Turner, Geoff; Turnbull, David; Parisi, Alfio; Downs, Nathan

2011-01-01

Over the past 50 years numerous types of chemical films and monolayers have been deployed on top of a wide variety of water reserves in an endeavour to reduce evaporation. To date very little knowledge has been assimilated on how these chemical films and monolayers, once applied to a water surface, influence the underwater UV light field and, in turn, the delicate ecosystems that exist in aquatic environments. This manuscript presents underwater UV exposure profiles weighted to the DNA damage action spectrum measured under an octadecanol/hexadecanol/lime chemical film mixture, a silicone-based chemical film and an octadecanol monolayer applied to the water surface. UV transmission and absorption properties were also evaluated for each of these chemical films and monolayers. From this it was found that when chemical films/monolayers are applied to surface water they can reduce the penetration of biologically effective UV into the water column by up to 85% at a depth as small as 1 cm. This could have a positive influence on the aquatic ecosystem, as harmful UV radiation may be prevented from reaching and consequently damaging a variety of life forms or it could have a negative effect by potentially stopping aquatic organisms from adapting to solar ultraviolet radiation over extended application intervals. Additionally, there is currently no readily applicable system or technique available to readily detect or visualize chemical films and monolayers on the water surface. To overcome this problem a new method of monolayer and chemical film visualization, using a UV camera system, is detailed and tested and its applicability for usage in both laboratory-based trials and real-world operations is evaluated

Chemical films and monolayers on the water surface and their interactions with ultraviolet radiation: a pilot investigation

Science.gov (United States)

Schouten, Peter; Lemckert, Charles; Turnbull, David; Parisi, Alfio; Downs, Nathan; Underhill, Ian; Turner, Geoff

2011-06-01

Over the past 50 years numerous types of chemical films and monolayers have been deployed on top of a wide variety of water reserves in an endeavour to reduce evaporation. To date very little knowledge has been assimilated on how these chemical films and monolayers, once applied to a water surface, influence the underwater UV light field and, in turn, the delicate ecosystems that exist in aquatic environments. This manuscript presents underwater UV exposure profiles weighted to the DNA damage action spectrum measured under an octadecanol/hexadecanol/lime chemical film mixture, a silicone-based chemical film and an octadecanol monolayer applied to the water surface. UV transmission and absorption properties were also evaluated for each of these chemical films and monolayers. From this it was found that when chemical films/monolayers are applied to surface water they can reduce the penetration of biologically effective UV into the water column by up to 85% at a depth as small as 1 cm. This could have a positive influence on the aquatic ecosystem, as harmful UV radiation may be prevented from reaching and consequently damaging a variety of life forms or it could have a negative effect by potentially stopping aquatic organisms from adapting to solar ultraviolet radiation over extended application intervals. Additionally, there is currently no readily applicable system or technique available to readily detect or visualize chemical films and monolayers on the water surface. To overcome this problem a new method of monolayer and chemical film visualization, using a UV camera system, is detailed and tested and its applicability for usage in both laboratory-based trials and real-world operations is evaluated.

Device and method for enhanced collection and assay of chemicals with high surface area ceramic

Science.gov (United States)

Addleman, Raymond S.; Li, Xiaohong Shari; Chouyyok, Wilaiwan; Cinson, Anthony D.; Bays, John T.; Wallace, Krys

2016-02-16

A method and device for enhanced capture of target analytes is disclosed. This invention relates to collection of chemicals for separations and analysis. More specifically, this invention relates to a solid phase microextraction (SPME) device having better capability for chemical collection and analysis. This includes better physical stability, capacity for chemical collection, flexible surface chemistry and high affinity for target analyte.

Enhancement of Biomass and Lipid Productivities of Water Surface-Floating Microalgae by Chemical Mutagenesis.

Science.gov (United States)

Nojima, Daisuke; Ishizuka, Yuki; Muto, Masaki; Ujiro, Asuka; Kodama, Fumito; Yoshino, Tomoko; Maeda, Yoshiaki; Matsunaga, Tadashi; Tanaka, Tsuyoshi

2017-05-27

Water surface-floating microalgae have great potential for biofuel applications due to the ease of the harvesting process, which is one of the most problematic steps in conventional microalgal biofuel production. We have collected promising water surface-floating microalgae and characterized their capacity for biomass and lipid production. In this study, we performed chemical mutagenesis of two water surface-floating microalgae to elevate productivity. Floating microalgal strains AVFF007 and FFG039 (tentatively identified as Botryosphaerella sp. and Chlorococcum sp., respectively) were exposed to ethyl methane sulfonate (EMS) or 1-methyl-3-nitro-1-nitrosoguanidine (MNNG), and pale green mutants (PMs) were obtained. The most promising FFG039 PM formed robust biofilms on the surface of the culture medium, similar to those formed by wild type strains, and it exhibited 1.7-fold and 1.9-fold higher biomass and lipid productivities than those of the wild type. This study indicates that the chemical mutation strategy improves the lipid productivity of water surface-floating microalgae without inhibiting biofilm formation and floating ability.

Physical adsorption vs. chemical binding of undecylenic acid on porous silicon surface: a comparative study of differently functionalized materials

Energy Technology Data Exchange (ETDEWEB)

Salonen, J.; Lehto, V.P. [University of Turku (Finland). Department of Physics; Chirvony, V.; Matveeva, E. [Nanophotonics Technology Center, Technical University of Valencia (Spain); Pastor, E.

2009-07-15

To imply miscibility to porous silicon (PSi) used for biomedical purposes a number of functionalization methods are employed. In order to distinguish between a non-specific surfactant-like interaction (physical sorption) and chemical binding of unsaturated chemicals (undecylenic acid, UD) to H-terminated PSi surface we studied the two differently treated materials. Differential scanning calorimetry (DSC) and thermogravimetry (TGA), BET and FTIR measurements were performed with the PSi powder samples (n+ doped). Changes in surface area, weight loss, calorific effect and chemical composition that accompanied the thermal treatment have shown that the physisorbed UD molecules undergo a chemical process (binding) with the Si-H{sub x} surface groups at about 150 C in both, N{sub 2} inert atmosphere and in a synthetic air, oxidative atmosphere. Controlled conversion of physically sorbed molecules to the chemically attached ones is discussed with respect to methods of surface modification of PSi materials for increasing their biocompatibility. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Sea spray aerosol chemical composition: elemental and molecular mimics for laboratory studies of heterogeneous and multiphase reactions.

Science.gov (United States)

Bertram, Timothy H; Cochran, Richard E; Grassian, Vicki H; Stone, Elizabeth A

2018-04-03

Sea spray aerosol particles (SSA), formed through wave breaking at the ocean surface, contribute to natural aerosol particle concentrations in remote regions of Earth's atmosphere, and alter the direct and indirect effects of aerosol particles on Earth's radiation budget. In addition, sea spray aerosol serves as suspended surface area that can catalyze trace gas reactions. It has been shown repeatedly that sea spray aerosol is heavily enriched in organic material compared to the surface ocean. The selective enrichment of organic material complicates the selection of representative molecular mimics of SSA for laboratory or computational studies. In this review, we first provide a short introduction to SSA formation processes and discuss chemical transformations of SSA that occur in polluted coastal regions and remote pristine air. We then focus on existing literature of the chemical composition of nascent SSA generated in controlled laboratory experiments and field investigations. We combine the evidence on the chemical properties of nascent SSA with literature measurements of SSA water uptake to assess SSA molecular composition and liquid water content. Efforts to speciate SSA organic material into molecular classes and specific molecules have led to the identification of saccharides, alkanes, free fatty acids, anionic surfactants, dicarboxylic acids, amino acids, proteinaceous matter, and other large macromolecules. However to date, less than 25% of the organic mass of nascent SSA has been quantified at a molecular level. As discussed here, quantitative measurements of size resolved elemental ratios, combined with determinations of water uptake properties, provides unique insight on the concentration of ions within SSA as a function of particle size, pointing to a controlling role for relative humidity and the hygroscopicity of SSA organic material at small particle diameters.

AFM assessment of the surface nano/microstructure on chemically damaged historical and model glasses

International Nuclear Information System (INIS)

Carmona, Noemi; Kowal, Andrzej; Rincon, Jesus-Maria; Villegas, Maria-Angeles

2010-01-01

Surface chemical damage on selected historical glasses from 13th to 19th centuries was evaluated by means of atomic force microscopy (AFM). Nano- and microstructure, roughness and topography of ancient glass samples have been compared with those of model glasses prepared by conventional melting at the laboratory with similar compositions to those most frequently found in historical glass pieces. The results obtained allow discussing the chemical degradation mechanisms in terms of the acid and/or basic chemical attack carried out by the combination of gaseous pollutants and environmental humidity. Even though deep corrosion features escape to the observation order of magnitude of the AF microscope used, the AFM technique proves to be quite useful for the study and evaluation of the most common surface pathologies of historical glasses with different compositions once submitted to natural weathering.

AFM assessment of the surface nano/microstructure on chemically damaged historical and model glasses

Energy Technology Data Exchange (ETDEWEB)

Carmona, Noemi [Centro Nacional de Investigaciones Metalurgicas, CSIC, Avda. Gregorio del Amo, 8, 28040 Madrid (Spain); Kowal, Andrzej [Institute of Catalysis and Surface Chemistry, PAN, ul. Niezapominajek 8, 30239 Cracow (Poland); Rincon, Jesus-Maria [Instituto Eduardo Torroja de Ciencias de la Construccion, CSIC, C. Serrano Galvache s/n, 28033 Madrid (Spain); Villegas, Maria-Angeles, E-mail: mariangeles.villegas@cchs.csic.es [Centro Nacional de Investigaciones Metalurgicas, CSIC, Avda. Gregorio del Amo, 8, 28040 Madrid (Spain); Instituto de Historia, Centro de Ciencias Humanas y Sociales, CSIC, C. Albasanz, 26-28, 28037 Madrid (Spain)

2010-01-15

Surface chemical damage on selected historical glasses from 13th to 19th centuries was evaluated by means of atomic force microscopy (AFM). Nano- and microstructure, roughness and topography of ancient glass samples have been compared with those of model glasses prepared by conventional melting at the laboratory with similar compositions to those most frequently found in historical glass pieces. The results obtained allow discussing the chemical degradation mechanisms in terms of the acid and/or basic chemical attack carried out by the combination of gaseous pollutants and environmental humidity. Even though deep corrosion features escape to the observation order of magnitude of the AF microscope used, the AFM technique proves to be quite useful for the study and evaluation of the most common surface pathologies of historical glasses with different compositions once submitted to natural weathering.

Influences of chemical aging on the surface morphology and crystallization behavior of basaltic glass fibers

DEFF Research Database (Denmark)

Lund, Majbritt Deichgræber; Yue, Yuanzheng

2008-01-01

The impact of aging in high humidity and water on the surface morphology and crystallization behavior of basaltic glass fibers has been studied using scanning electron microscopy, transmission electron microscopy, calorimetry and X-ray diffraction. The results show that interaction between...... the fibers and the surrounding media (high humidity or water at 70 C) leads to chemical changes strongly affecting the surface morphology. The crystallization peak temperature of the basaltic glass fibers are increased without changing the onset temperature, this may be caused by a chemical depletion...

Magnetic properties and macroscopic heterogeneity of FeCoNbB Hitperms

Science.gov (United States)

Butvin, Pavol; Butvinová, Beata; Sitek, Jozef; Degmová, Jarmila; Vlasák, Gabriel; Švec, Peter; Janičkovič, Dušan

Nanocrystalline ribbons of Fe 81-xCo xNb 7B 12 (where x ranges from 0 to 40.5 at%) Hitperm alloys have been investigated as to their basic magnetic properties and the influence of the macroscopic heterogeneity. Different crystalline share at surfaces compared with the volume average is observed by conversion electron Mössbauer spectroscopy (CEMS) and Mössbauer spectroscopy (MS), respectively. This marks the presence of macroscopic heterogeneity in these Hitperms. The heterogeneity is generally more significant in Ar-annealed samples than in the vacuum-annealed ones. The characteristic slant hysteresis loops (hard-ribbon-axis) are seen as a rule with few exceptions. An inspection of hysteresis loop response of resin potted samples shows that the surfaces bi-axially squeeze the ribbon interior in heterogeneous Hitperms when the ribbons cool down after annealing. Certain compositions show macroscopic viscous flow prior to crystallization so the heterogeneity gets another chance to induce anisotropy during annealing. The induction attains 1.5 T but saturates poorly due to the heterogeneity and the ensuing anisotropy. Moreover the heterogeneity appears to hamper the crystallization within the ribbon interior. Unlike Finemets, the density of these Hitperms show no pronounced trend with annealing.

Efficacy of liquid and foam decontamination technologies for chemical warfare agents on indoor surfaces.

Science.gov (United States)

Love, Adam H; Bailey, Christopher G; Hanna, M Leslie; Hok, Saphon; Vu, Alex K; Reutter, Dennis J; Raber, Ellen

2011-11-30

Bench-scale testing was used to evaluate the efficacy of four decontamination formulations on typical indoor surfaces following exposure to the liquid chemical warfare agents sarin (GB), soman (GD), sulfur mustard (HD), and VX. Residual surface contamination on coupons was periodically measured for up to 24h after applying one of four selected decontamination technologies [0.5% bleach solution with trisodium phosphate, Allen Vanguard Surface Decontamination Foam (SDF™), U.S. military Decon Green™, and Modec Inc. and EnviroFoam Technologies Sandia Decontamination Foam (DF-200)]. All decontamination technologies tested, except for the bleach solution, performed well on nonporous and nonpermeable glass and stainless-steel surfaces. However, chemical agent residual contamination typically remained on porous and permeable surfaces, especially for the more persistent agents, HD and VX. Solvent-based Decon Green™ performed better than aqueous-based bleach or foams on polymeric surfaces, possibly because the solvent is able to penetrate the polymer matrix. Bleach and foams out-performed Decon Green for penetrating the highly polar concrete surface. Results suggest that the different characteristics needed for an ideal and universal decontamination technology may be incompatible in a single formulation and a strategy for decontaminating a complex facility will require a range of technologies. Copyright © 2011 Elsevier B.V. All rights reserved.

Dynamical, structural and chemical heterogeneities in a binary metallic glass-forming liquid

Science.gov (United States)

Puosi, F.; Jakse, N.; Pasturel, A.

2018-04-01

As it approaches the glass transition, particle motion in liquids becomes highly heterogeneous and regions with virtually no mobility coexist with liquid-like domains. This complex dynamic is believed to be responsible for different phenomena including non-exponential relaxation and the breakdown of the Stokes-Einstein relation. Understanding the relationships between dynamical heterogeneities and local structure in metallic liquids and glasses is a major scientific challenge. Here we use classical molecular dynamics simulations to study the atomic dynamics and microscopic structure of Cu50Zr50 alloy in the supercooling regime. Dynamical heterogeneities are identified via an isoconfigurational analysis. We demonstrate the transition from isolated to clustering low mobility with decreasing temperature. These slow clusters, whose sizes grow upon cooling, are also associated with concentration fluctuations, characterized by a Zr-enriched phase, with a composition CuZr2 . In addition, a structural analysis of slow clusters based on Voronoi tessellation evidences an increase with respect of the bulk system of the fraction of Cu atoms having a local icosahedral order. These results are in agreement with the consolidated scenario of the relevant role played by icosahedral order in the dynamic slowing-down in supercooled metal alloys.

The mineralogic evolution of the Martian surface through time: Implications from chemical reaction path modeling studies

Science.gov (United States)

Plumlee, G. S.; Ridley, W. I.; Debraal, J. D.; Reed, M. H.

1993-01-01

Chemical reaction path calculations were used to model the minerals that might have formed at or near the Martian surface as a result of volcano or meteorite impact driven hydrothermal systems; weathering at the Martian surface during an early warm, wet climate; and near-zero or sub-zero C brine-regolith reactions in the current cold climate. Although the chemical reaction path calculations carried out do not define the exact mineralogical evolution of the Martian surface over time, they do place valuable geochemical constraints on the types of minerals that formed from an aqueous phase under various surficial and geochemically complex conditions.

Glassy aerosols with a range of compositions nucleate ice heterogeneously at cirrus temperatures

Directory of Open Access Journals (Sweden)

T. W. Wilson

2012-09-01

Full Text Available Atmospheric secondary organic aerosol (SOA is likely to exist in a semi-solid or glassy state, particularly at low temperatures and humidities. Previously, it has been shown that glassy aqueous citric acid aerosol is able to nucleate ice heterogeneously under conditions relevant to cirrus in the tropical tropopause layer (TTL. In this study we test if glassy aerosol distributions with a range of chemical compositions heterogeneously nucleate ice under cirrus conditions. Three single component aqueous solution aerosols (raffinose, 4-hydroxy-3-methoxy-DL-mandelic acid (HMMA and levoglucosan and one multi component aqueous solution aerosol (raffinose mixed with five dicarboxylic acids and ammonium sulphate were studied in both the liquid and glassy states at a large cloud simulation chamber. The investigated organic compounds have similar functionality to oxidised organic material found in atmospheric aerosol and have estimated temperature/humidity induced glass transition thresholds that fall within the range predicted for atmospheric SOA. A small fraction of aerosol particles of all compositions were found to nucleate ice heterogeneously in the deposition mode at temperatures relevant to the TTL (<200 K. Raffinose and HMMA, which form glasses at higher temperatures, nucleated ice heterogeneously at temperatures as high as 214.6 and 218.5 K respectively. We present the calculated ice active surface site density, n_s, of the aerosols tested here and also of glassy citric acid aerosol as a function of relative humidity with respect to ice (RH_i. We also propose a parameterisation which can be used to estimate heterogeneous ice nucleation by glassy aerosol for use in cirrus cloud models up to ~220 K. Finally, we show that heterogeneous nucleation by glassy aerosol may compete with ice nucleation on mineral dust particles in mid-latitudes cirrus.

Heterogeneously catalyzed reactive extraction for biomass valorization into chemicals and fuels

NARCIS (Netherlands)

Ordomskiy, V.; Khodakov, A.Y.; Nijhuis, T.A.; Schouten, J.C.

2015-01-01

This paper focuses on the heterogeneously catalyzed reactive extraction and separation in reaction steps in organic and aqueous phases during the transformation of biomass derived products. Two approaches are demonstrated for decomposing and preserving routes for biomass transformation into valuable

Applying Nightingale charts to evaluate the heterogeneity of biomedical waste in a Hospital

Directory of Open Access Journals (Sweden)

Janini Cristina Paiz

2014-12-01

Full Text Available OBJECTIVES: to evaluate the heterogeneity of biomedical waste (BW using Nightingale charts.METHOD: cross-sectional study consisting of data collection on wastes (direct observation of receptacles, physical characterisation, and gravimetric composition, development of a Management Information System, and creation of statistical charts.RESULTS: the wastes with the greatest degree of heterogeneity are, in order, recyclable, infectious, and organic wastes; chemical waste had the most efficient segregation; Nightingale charts are useful for quick visualisation and systematisation of information on heterogeneity.CONCLUSION: the development of a management information system and the use of Nightingale charts allows for the identification and correction of errors in waste segregation, which increase health risks and contamination by infectious and chemical wastes and reduce the sale and profit from recyclables.

Spatial heterogeneity of soils of the Cerrado-Pantanal ecotone

OpenAIRE

Lucena, Isabela Codolo de; Amorim, Ricardo Santos Silva; Lobo, Francisco de Almeida; Baldoni, Raquel Negrão; Matos, Dalva Maria da Silva

2014-01-01

In areas of the Cerrado-Pantanal ecotone in Brazil, the soil displays features which are inherent to the processes of soil formation, both of the Central Plateau and the Pantanal Plain. Given this premise, the area should be noteworthy for its high level of edaphic heterogeneity. The present study aimed to determine the physical, chemical and physico-hydric attributes that best explain the heterogeneity of soils in areas of the Cerrado-Pantanal ecotone, and to assess whether these attributes ...

Heterogeneous Nucleation and Growth of Nanoparticles at Environmental Interfaces.

Science.gov (United States)

Jun, Young-Shin; Kim, Doyoon; Neil, Chelsea W

2016-09-20

Mineral nucleation is a phase transformation of aqueous components to solids with an accompanying creation of new surfaces. In this evolutional, yet elusive, process, nuclei often form at environmental interfaces, which provide remarkably reactive sites for heterogeneous nucleation and growth. Naturally occurring nucleation processes significantly contribute to the biogeochemical cycles of important components in the Earth's crust, such as iron and manganese oxide minerals and calcium carbonate. However, in recent decades, these cycles have been significantly altered by anthropogenic activities, which affect the aqueous chemistry and equilibrium of both surface and subsurface systems. These alterations can trigger the dissolution of existing minerals and formation of new nanoparticles (i.e., nucleation and growth) and consequently change the porosity and permeability of geomedia in subsurface environments. Newly formed nanoparticles can also actively interact with components in natural and engineered aquatic systems, including those posing a significant hazard such as arsenic. These interactions can bilaterally influence the fate and transport of both newly formed nanoparticles and aqueous components. Due to their importance in natural and engineered processes, heterogeneous nucleation at environmental interfaces has started to receive more attention. However, a lack of time-resolved in situ analyses makes the evaluation of heterogeneous nucleation challenging because the physicochemical properties of both the nuclei and surfaces significantly and dynamically change with time and aqueous chemistry. This Account reviews our in situ kinetic studies of the heterogeneous nucleation and growth behaviors of iron(III) (hydr)oxide, calcium carbonate, and manganese (hydr)oxide minerals in aqueous systems. In particular, we utilized simultaneous small-angle and grazing incidence small-angle X-ray scattering (SAXS/GISAXS) to investigate in situ and in real-time the effects of

Eddy covariance measurement of the spatial heterogeneity of surface energy exchanges over Heron Reef, Great Barrier Reef, Australia

Science.gov (United States)

MacKellar, M.; McGowan, H. A.; Phinn, S. R.

2011-12-01

Coral reefs cover 2.8 to 6.0 x 105 km2 of the Earth's surface and are warm, shallow regions that are believed to contribute enhanced sensible and latent heat to the atmosphere, relative to the surrounding ocean. To predict the impact of climate variability on coral reefs and their weather and climate including cloud, winds, rainfall patterns and cyclone genesis, accurate parameterisation of air-sea energy exchanges over coral reefs is essential. This is also important for the parameterisation and validation of regional to global scale forecast models to improve prediction of tropical and sub-tropical marine and coastal weather. Eddy covariance measurements of air-sea fluxes over coral reefs are rare due to the complexities of installing instrumentation over shallow, tidal water. Consequently, measurements of radiation and turbulent flux data for coral reefs have been captured remotely (satellite data) or via single measurement sites downwind of coral reefs (e.g. terrestrial or shipboard instrumentation). The resolution of such measurements and those that have been made at single locations on reefs may not capture the spatial heterogeneity of surface-atmosphere energy exchanges due to the different geomorphic and biological zones on coral reefs. Accordingly, the heterogeneity of coral reefs with regard to substrate, benthic communities and hydrodynamic processes are not considered in the characterization of the surface radiation energy flux transfers across the water-atmosphere interface. In this paper we present a unique dataset of concurrent in situ eddy covariance measurements made on instrumented pontoons of the surface energy balance over different geomorphic zones of a coral reef (shallow reef flat, shallow and deep lagoons). Significant differences in radiation transfers and air-sea turbulent flux exchanges over the reef were highlighted, with higher Bowen ratios over the shallow reef flat. Increasing wind speed was shown to increase flux divergence between

Chemical imaging and solid state analysis at compact surfaces using UV imaging

DEFF Research Database (Denmark)

Wu, Jian X.; Rehder, Sönke; van den Berg, Frans

2014-01-01

and excipients in a non-invasive way, as well as mapping the glibenclamide solid state form. An exploratory data analysis supported the critical evaluation of the mapping results and the selection of model parameters for the chemical mapping. The present study demonstrated that the multi-wavelength UV imaging......Fast non-destructive multi-wavelength UV imaging together with multivariate image analysis was utilized to visualize distribution of chemical components and their solid state form at compact surfaces. Amorphous and crystalline solid forms of the antidiabetic compound glibenclamide...