Visualising reacting single atoms under controlled conditions: Advances in atomic resolution in situ Environmental (Scanning) Transmission Electron Microscopy (E(S)TEM)

NASA Astrophysics Data System (ADS)

Boyes, Edward D.; Gai, Pratibha L.

2014-02-01

Advances in atomic resolution Environmental (Scanning) Transmission Electron Microscopy (E(S)TEM) for probing gas-solid catalyst reactions in situ at the atomic level under controlled reaction conditions of gas environment and temperature are described. The recent development of the ESTEM extends the capability of the ETEM by providing the direct visualisation of single atoms and the atomic structure of selected solid state heterogeneous catalysts in their working states in real-time. Atomic resolution E(S)TEM provides a deeper understanding of the dynamic atomic processes at the surface of solids and their mechanisms of operation. The benefits of atomic resolution-E(S)TEM to science and technology include new knowledge leading to improved technological processes with substantial economic benefits, improved healthcare, reductions in energy needs and the management of environmental waste generation. xml:lang="fr"

Residual thermal stresses in a solid sphere cast from a thermosetting material

NASA Technical Reports Server (NTRS)

Levitsky, M.; Shaffer, B. W.

1975-01-01

Expressions are developed for the residual thermal stresses in a solid sphere cast from a chemically hardening thermosetting material in a rigid spherical mold. The description of the heat generation rate and temperature variation is derived from a first-order chemical reaction. Solidification is described by the continuous transformation of the material from an inviscid liquidlike state into an elastic solid, with intermediate properties determined by the degree of chemical reaction. Residual stress components are obtained as functions of the parameters of the hardening process and the properties of the hardening material. Variation of the residual stresses with a nondimensionalized reaction rate parameter and the relative compressibility of the hardened material is discussed in detail.

Regeneration of sulfated metal oxides and carbonates

DOEpatents

Hubble, Bill R.; Siegel, Stanley; Cunningham, Paul T.

1978-03-28

Alkali metal or alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate found in dolomite or limestone are employed for removal of sulfur dioxide from combustion exhaust gases. The sulfated carbonates are regenerated to oxides through use of a solid-solid reaction, particularly calcium sulfide with calcium sulfate to form calcium oxide and sulfur dioxide gas. The regeneration is performed by contacting the sulfated material with a reductant gas such as hydrogen within an inert diluent to produce calcium sulfide in mixture with the sulfate under process conditions selected to permit the sulfide-sulfate, solid-state reaction to occur.

A thermodynamic framework for thermo-chemo-elastic interactions in chemically active materials

NASA Astrophysics Data System (ADS)

Zhang, XiaoLong; Zhong, Zheng

2017-08-01

In this paper, a general thermodynamic framework is developed to describe the thermo-chemo-mechanical interactions in elastic solids undergoing mechanical deformation, imbibition of diffusive chemical species, chemical reactions and heat exchanges. Fully coupled constitutive relations and evolving laws for irreversible fluxes are provided based on entropy imbalance and stoichiometry that governs reactions. The framework manifests itself with a special feature that the change of Helmholtz free energy is attributed to separate contributions of the diffusion-swelling process and chemical reaction-dilation process. Both the extent of reaction and the concentrations of diffusive species are taken as independent state variables, which describe the reaction-activated responses with underlying variation of microstructures and properties of a material in an explicit way. A specialized isothermal formulation for isotropic materials is proposed that can properly account for volumetric constraints from material incompressibility under chemo-mechanical loadings, in which inhomogeneous deformation is associated with reaction and diffusion under various kinetic time scales. This framework can be easily applied to model the transient volumetric swelling of a solid caused by imbibition of external chemical species and simultaneous chemical dilation arising from reactions between the diffusing species and the solid.

Chemical degradation of proteins in the solid state with a focus on photochemical reactions.

PubMed

Mozziconacci, Olivier; Schöneich, Christian

2015-10-01

Protein pharmaceuticals comprise an increasing fraction of marketed products but the limited solution stability of proteins requires considerable research effort to prepare stable formulations. An alternative is solid formulation, as proteins in the solid state are thermodynamically less susceptible to degradation. Nevertheless, within the time of storage a large panel of kinetically controlled degradation reactions can occur such as, e.g., hydrolysis reactions, the formation of diketopiperazine, condensation and aggregation reactions. These mechanisms of degradation in protein solids are relatively well covered by the literature. Considerably less is known about oxidative and photochemical reactions of solid proteins. This review will provide an overview over photolytic and non-photolytic degradation reactions, and specially emphasize mechanistic details on how solid structure may affect the interaction of protein solids with light. Copyright © 2014 Elsevier B.V. All rights reserved.

A Solvent-Free Baeyer-Villiger Lactonization for the Undergraduate Organic Laboratory: Synthesis of Gamma-T-Butyl-Epsilon-Caprolactone

ERIC Educational Resources Information Center

Esteb, John J.; Hohman, Nathan J.; Schlamandinger, Diana E.; Wilson, Anne M.

2005-01-01

The solvent-free or solid-state reaction systems like the Baeyer-Villiger rearrangement have become popular in the synthetic organic community and viable option for undergraduate laboratory series to reduce waste and cost and simplify reaction process. The reaction is an efficient method to transform ketones to esters and lactones.

Solid-state reaction synthesis for mixed-phase Eu3+-doped bismuth molybdate and its luminescence properties

NASA Astrophysics Data System (ADS)

Liang, Danyang; Ding, Yu; Wang, Nan; Cai, Xiaomeng; Li, Jia; Han, Linyu; Wang, Shiqi; Han, Yuanyuan; Jia, Guang; Wang, Liyong

2017-09-01

A method for mixed-phase bismuth molybdate doped with Eu3+ ions was developed by solid-state reaction assisting with polyvinyl alcohol (PVA). The results of powder X-ray diffraction showed a mixed-phase structure and the microscopical characterization technology revealed the formation process with the addition of PVA. As a structure inducer, the PVA molecules played a vital role in the formation of phase structure. The as-obtained Eu3+-doped bismuth molybdates were also characterized by using different spectroscopic techniques including FTIR and photoluminescence (PL). The results show that doping concentration, PVA addition and calcination temperature affect photoluminescence properties remarkably.

Peculiarities of methane clathrate hydrate formation and solid-state deformation, including possible superheating of water ice

USGS Publications Warehouse

Stern, L.A.; Kirby, S.H.; Durham, W.B.

1996-01-01

Slow, constant-volume heating of water ice plus methane gas mixtures forms methane clathrate hydrate by a progressive reaction that occurs at the nascent ice/liquid water interface. As this reaction proceeds, the rate of melting of metastable water ice may be suppressed to allow short-lived superheating of ice to at least 276 kelvin. Plastic flow properties measured on clathrate test specimens are significantly different from those of water ice; under nonhydrostatic stress, methane clathrate undergoes extensive strain hardening and a process of solid-state disproportionation or exsolution at conditions well within its conventional hydrostatic stability field.

Emerging applications of spark plasma sintering in all solid-state lithium-ion batteries and beyond

NASA Astrophysics Data System (ADS)

Zhu, Hongzheng; Liu, Jian

2018-07-01

Solid-state batteries have received increasing attention due to their high safety aspect and high energy and power densities. However, the development of solid-state batteries is hindered by inferior solid-solid interfaces between the solid-state electrolyte and electrode, which cause high interfacial resistance, reduced Li-ion and electron transfer rate, and limited battery performance. Recently, spark plasma sintering (SPS) is emerging as a promising technique for fabricating solid-state electrolyte and electrode pellets with clean and intimate solid-solid interfaces. During the SPS process, the unique reaction mechanism through the combination of current, pressure and high heating rate allow the formation of desirable solid-solid interfaces between active material particles. Herein, this work focuses on the overview of the application of SPS for fabricating solid-state electrolyte and electrode in all solid-state Li-ion batteries, and beyond, such as solid-state Li-S and Na-ion batteries. The correlations among SPS parameters, interfacial resistance, and electrochemical properties of solid-state electrolytes and electrodes are discussed for different material systems. In the end, we point out future opportunities and challenges associated with SPS application in the hot area of solid-state batteries. It is expected that this timely review will stimulate more fundamental and applied research in the development of solid-state batteries by SPS.

Determination of outer layer and bulk dehydration kinetics of trehalose dihydrate using atomic force microscopy, gravimetric vapour sorption and near infrared spectroscopy.

PubMed

Jones, Matthew D; Beezer, Anthony E; Buckton, Graham

2008-10-01

Knowledge of the kinetics of solid state reactions is important when considering the stability of many medicines. Potentially, such reactions could follow different kinetics on the surface of particles when compared with their interior, yet solid state processes are routinely followed using only bulk characterisation techniques. Atomic force microscopy (AFM) has previously been shown to be a suitable technique for the investigation of surface processes, but has not been combined with bulk techniques in order to analyse surface and bulk kinetics separately. This report therefore describes the investigation of the outer layer and bulk kinetics of the dehydration of trehalose dihydrate at ambient temperature and low humidity, using AFM, dynamic vapour sorption (DVS) and near infrared spectroscopy (NIR). The use of AFM enabled the dehydration kinetics of the outer layers to be determined both directly and from bulk data. There were no significant differences between the outer layer dehydration kinetics determined using these methods. AFM also enabled the bulk-only kinetics to be analysed from the DVS and NIR data. These results suggest that the combination of AFM and bulk characterisation techniques should enable a more complete understanding of the kinetics of certain solid state reactions to be achieved. (c) 2008 Wiley-Liss, Inc. and the American Pharmacists Association

Growth behavior of LiMn{sub 2}O{sub 4} particles formed by solid-state reactions in air and water vapor

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

Kozawa, Takahiro, E-mail: t-kozawa@jwri.osaka-u.ac.jp; Yanagisawa, Kazumichi; Murakami, Takeshi

Morphology control of particles formed during conventional solid-state reactions without any additives is a challenging task. Here, we propose a new strategy to control the morphology of LiMn{sub 2}O{sub 4} particles based on water vapor-induced growth of particles during solid-state reactions. We have investigated the synthesis and microstructural evolution of LiMn{sub 2}O{sub 4} particles in air and water vapor atmospheres as model reactions; LiMn{sub 2}O{sub 4} is used as a low-cost cathode material for lithium-ion batteries. By using spherical MnCO{sub 3} precursor impregnated with LiOH, LiMn{sub 2}O{sub 4} spheres with a hollow structure were obtained in air, while angulated particlesmore » with micrometer sizes were formed in water vapor. The pore structure of the particles synthesized in water vapor was found to be affected at temperatures below 700 °C. We also show that the solid-state reaction in water vapor is a simple and valuable method for the large-scale production of particles, where the shape, size, and microstructure can be controlled. - Graphical abstract: This study has demonstrated a new strategy towards achieving morphology control without the use of additives during conventional solid-state reactions by exploiting water vapor-induced particle growth. - Highlights: • A new strategy to control the morphology of LiMn{sub 2}O{sub 4} particles is proposed. • Water vapor-induced particle growth is exploited in solid-state reactions. • The microstructural evolution of LiMn{sub 2}O{sub 4} particles is investigated. • The shape, size and microstructure can be controlled by solid-state reactions.« less

Sustainable synthesis of aldehydes, ketones or acids from neat alcohols using nitrogen dioxide gas, and related reactions.

PubMed

Naimi-Jamal, M Reza; Hamzeali, Hamideh; Mokhtari, Javad; Boy, Jürgen; Kaupp, Gerd

2009-01-01

Benzylic alcohols are quantitatively oxidized by gaseous nitrogen dioxide to give pure aromatic aldehydes. The reaction gas mixtures are transformed to nitric acid, which renders the processes free of waste. The exothermic gas-liquid or gas-solid reactions profit from the solubility of nitrogen dioxide in the neat benzylic alcohols. The acid formed impedes further oxidation of the benzaldehydes. The neat isolated benzaldehydes and nitrogen dioxide quantitatively give the benzoic acids. Solid long-chain primary alcohols are directly and quantitatively oxidized with nitrogen dioxide gas to give the fatty acids in the solid state. The oxidations with ubiquitous nitrogen dioxide are extended to solid heterocyclic thioamides, which gives disulfides, and to diphenylamine, which gives tetraphenylhydrazine. These sustainable (green) specific oxidation procedures produce no dangerous residues from the oxidizing agent or from auxiliaries.

Charge and discharge characteristics of lithium-ion graphite electrodes in solid-state cells

NASA Astrophysics Data System (ADS)

Lemont, S.; Billaud, D.

Lithium ions have been electrochemically intercalated into graphite in solid-state cells operating with solid polymer electrolytes based on poly(ethylene oxide) (PEO) complexed with lithium perchlorate (LiClO 4). The working composite electrode is composed of active-divided natural graphite associated with P(EO) 8-LiClO 4 acting as a binder and a Li + ionic conductor. Intercalation and de-intercalation of Li + were performed using galvanostatic or voltammetry techniques. The curves obtained in our solid-state cells were compared with those performed in liquid ethylene carbonate-LiClO 4 electrolyte. It is shown that in solid-state cells, side reactions occur both in the reduction and in the oxidation processes which leads to some uncertainty in the determination of the maximum reversible capacity of the graphite material.

Solid-state 13C NMR studies of a large fossil gymnosperm from the Yallourn Open Cut, Latrobe Valley, Australia

USGS Publications Warehouse

Bates, A.L.; Hatcher, P.G.

1989-01-01

A series of samples taken from the cross section of a 3-m-diameter fossilized gymnospermous log (Araucariaceae) in the Yallourn Seam of the Australian brown coals was examined by solid state 13C nuclear magnetic resonance to delineate chemical changes related to the combined processes of peatification and coalification. The results show that cellulosic materials were degraded and lost on the periphery of the log, however, the degree of such degradation in the central core is substantially less. The lignin is uniformly altered by coalification reactions to a macromolecular substance displaying decreased aryl ether linkages but significantly greater amounts of carbon linkages compared to modern lignin. Changes in the methoxyl carbon contents of lignin in cross section reveal demethylation reactions, but these do not appear to be related to degree of carbon linking. Both the degredation of cellulosic materials and demethylation of lignin appear to be early diagenetic processes occurring during peatification independently of the coalification reactions. ?? 1989.

Computational modeling of chemical reactions and interstitial growth and remodeling involving charged solutes and solid-bound molecules

PubMed Central

Nims, Robert J.; Maas, Steve; Weiss, Jeffrey A.

2014-01-01

Mechanobiological processes are rooted in mechanics and chemistry, and such processes may be modeled in a framework that couples their governing equations starting from fundamental principles. In many biological applications, the reactants and products of chemical reactions may be electrically charged, and these charge effects may produce driving forces and constraints that significantly influence outcomes. In this study, a novel formulation and computational implementation are presented for modeling chemical reactions in biological tissues that involve charged solutes and solid-bound molecules within a deformable porous hydrated solid matrix, coupling mechanics with chemistry while accounting for electric charges. The deposition or removal of solid-bound molecules contributes to the growth and remodeling of the solid matrix; in particular, volumetric growth may be driven by Donnan osmotic swelling, resulting from charged molecular species fixed to the solid matrix. This formulation incorporates the state of strain as a state variable in the production rate of chemical reactions, explicitly tying chemistry with mechanics for the purpose of modeling mechanobiology. To achieve these objectives, this treatment identifies the specific theoretical and computational challenges faced in modeling complex systems of interacting neutral and charged constituents while accommodating any number of simultaneous reactions where reactants and products may be modeled explicitly or implicitly. Several finite element verification problems are shown to agree with closed-form analytical solutions. An illustrative tissue engineering analysis demonstrates tissue growth and swelling resulting from the deposition of chondroitin sulfate, a charged solid-bound molecular species. This implementation is released in the open-source program FEBio (www.febio.org). The availability of this framework may be particularly beneficial to optimizing tissue engineering culture systems by examining the influence of nutrient availability on the evolution of inhomogeneous tissue composition and mechanical properties, the evolution of construct dimensions with growth, the influence of solute and solid matrix electric charge on the transport of cytokines, the influence of binding kinetics on transport, the influence of loading on binding kinetics, and the differential growth response to dynamically loaded versus free-swelling culture conditions. PMID:24558059

Computational modeling of chemical reactions and interstitial growth and remodeling involving charged solutes and solid-bound molecules.

PubMed

Ateshian, Gerard A; Nims, Robert J; Maas, Steve; Weiss, Jeffrey A

2014-10-01

Mechanobiological processes are rooted in mechanics and chemistry, and such processes may be modeled in a framework that couples their governing equations starting from fundamental principles. In many biological applications, the reactants and products of chemical reactions may be electrically charged, and these charge effects may produce driving forces and constraints that significantly influence outcomes. In this study, a novel formulation and computational implementation are presented for modeling chemical reactions in biological tissues that involve charged solutes and solid-bound molecules within a deformable porous hydrated solid matrix, coupling mechanics with chemistry while accounting for electric charges. The deposition or removal of solid-bound molecules contributes to the growth and remodeling of the solid matrix; in particular, volumetric growth may be driven by Donnan osmotic swelling, resulting from charged molecular species fixed to the solid matrix. This formulation incorporates the state of strain as a state variable in the production rate of chemical reactions, explicitly tying chemistry with mechanics for the purpose of modeling mechanobiology. To achieve these objectives, this treatment identifies the specific theoretical and computational challenges faced in modeling complex systems of interacting neutral and charged constituents while accommodating any number of simultaneous reactions where reactants and products may be modeled explicitly or implicitly. Several finite element verification problems are shown to agree with closed-form analytical solutions. An illustrative tissue engineering analysis demonstrates tissue growth and swelling resulting from the deposition of chondroitin sulfate, a charged solid-bound molecular species. This implementation is released in the open-source program FEBio ( www.febio.org ). The availability of this framework may be particularly beneficial to optimizing tissue engineering culture systems by examining the influence of nutrient availability on the evolution of inhomogeneous tissue composition and mechanical properties, the evolution of construct dimensions with growth, the influence of solute and solid matrix electric charge on the transport of cytokines, the influence of binding kinetics on transport, the influence of loading on binding kinetics, and the differential growth response to dynamically loaded versus free-swelling culture conditions.

A new route for the synthesis of submicron-sized LaB{sub 6}

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

Lihong, Bao; Wurentuya,; Wei, Wei

Submicron crystalline LaB{sub 6} has been successfully synthesized by a solid-state reaction of La{sub 2}O{sub 3} with NaBH{sub 4} at 1200 °C. The effects of reaction temperature on the crystal structure, grain size and morphology were investigated by X-ray diffraction, scanning electron microscope and transmission electron microscope. It is found that when the reaction temperature is in the range of 1000–1100 °C, there are ultrafine nanoparticles and nanocrystals that coexist. When the reaction temperature elevated to 1200 °C, the grain morphology transformed from ultrafine nanoparticle to submicron crystals completely. High resolution transmission electron microscope images fully confirm the formation ofmore » LaB{sub 6} cubic structure. - Highlights: • Single-phased LaB{sub 6} have been synthesized by a solid-state reaction in a continuous evacuating process. • The reaction temperature has a important effect on the phase composition. • The grain size increase from nano-size to submicron with increasing reaction temperature.« less

Solid-state reactions to synthesize nanostructured lead selenide semiconductor powders by high-energy milling

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

Rojas-Chavez, H., E-mail: uu_gg_oo@yahoo.com.mx; Reyes-Carmona, F.; Jaramillo-Vigueras, D.

2011-10-15

Highlights: {yields} PbSe synthesized from PbO instead of Pb powder do not require an inert atmosphere. {yields} During high-energy milling oxygen has to be chemically reduced from the lead oxide. {yields} Solid-state and solid-gas chemical reactions promote both solid and gaseous products. -- Abstract: Both solid-solid and gas-solid reactions have been traced during high-energy milling of Se and PbO powders under vial (P, T) conditions in order to synthesize the PbSe phase. Chemical and thermodynamic arguments are postulated to discern the high-energy milling mechanism to transform PbO-Se micropowders onto PbSe-nanocrystals. A set of reactions were evaluated at around room temperature.more » Therefore an experimental campaign was designed to test the nature of reactions in the PbO-Se system during high-energy milling.« less

Mechanism and Influencing Factors of Iron Nuggets Forming in Rotary Hearth Furnace Process at Lower Temperature

NASA Astrophysics Data System (ADS)

Han, Hongliang; Duan, Dongping; Chen, Siming; Yuan, Peng

2015-10-01

In order to improve the efficiency of slag and iron separation, a new idea of "the separation of slag (solid state) and iron (molten state) in rotary hearth furnace process at lower temperature" is put forward. In this paper, the forming process of iron nuggets has been investigated. Based on those results, the forming mechanisms and influencing factors of iron nugget at low temperature are discussed experimentally using an electric resistance furnace simulating a rotary hearth furnace process. Results show that the reduction of iron ore, carburization of reduced iron, and the composition and quantity of slag are very important for producing iron nuggets at lower temperature. Reduction reaction of carbon-containing pellets is mainly at 1273 K and 1473 K (1000 °C and 1200 °C). When the temperature is above 1473 K (1200 °C), the metallization rate of carbon-containing pellets exceeds 93 pct, and the reduction reaction is substantially complete. Direct carburization is the main method for carburization of reduced iron. This reaction occurs above 1273 K (1000 °C), with carburization degree increasing greatly at 1473 K and 1573 K (1200 °C and 1300 °C) after particular holding times. Besides, to achieve the "slag (solid state) and iron (molten state) separation," the melting point of the slag phase should be increased. Slag (solid state) and iron (molten state) separation can be achieved below 1573 K (1300 °C), and when the holding time is 20 minutes, C/O is 0.7, basicity is less than 0.5 and a Na2CO3 level of 3 pct, the recovery rate of iron can reach 90 pct, with a proportion of iron nuggets more than 3.15 mm of nearly 90 pct. This study can provide theoretical and technical basis for iron nugget production.

An optics-based variable-temperature assay system for characterizing thermodynamics of biomolecular reactions on solid support

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

Fei, Yiyan; Landry, James P.; Zhu, X. D., E-mail: xdzhu@physics.ucdavis.edu

A biological state is equilibrium of multiple concurrent biomolecular reactions. The relative importance of these reactions depends on physiological temperature typically between 10 °C and 50 °C. Experimentally the temperature dependence of binding reaction constants reveals thermodynamics and thus details of these biomolecular processes. We developed a variable-temperature opto-fluidic system for real-time measurement of multiple (400–10 000) biomolecular binding reactions on solid supports from 10 °C to 60 °C within ±0.1 °C. We illustrate the performance of this system with investigation of binding reactions of plant lectins (carbohydrate-binding proteins) with 24 synthetic glycans (i.e., carbohydrates). We found that the lectin-glycan reactions in general can be enthalpy-driven,more » entropy-driven, or both, and water molecules play critical roles in the thermodynamics of these reactions.« less

An optics-based variable-temperature assay system for characterizing thermodynamics of biomolecular reactions on solid support

NASA Astrophysics Data System (ADS)

Fei, Yiyan; Landry, James P.; Li, Yanhong; Yu, Hai; Lau, Kam; Huang, Shengshu; Chokhawala, Harshal A.; Chen, Xi; Zhu, X. D.

2013-11-01

A biological state is equilibrium of multiple concurrent biomolecular reactions. The relative importance of these reactions depends on physiological temperature typically between 10 °C and 50 °C. Experimentally the temperature dependence of binding reaction constants reveals thermodynamics and thus details of these biomolecular processes. We developed a variable-temperature opto-fluidic system for real-time measurement of multiple (400-10 000) biomolecular binding reactions on solid supports from 10 °C to 60 °C within ±0.1 °C. We illustrate the performance of this system with investigation of binding reactions of plant lectins (carbohydrate-binding proteins) with 24 synthetic glycans (i.e., carbohydrates). We found that the lectin-glycan reactions in general can be enthalpy-driven, entropy-driven, or both, and water molecules play critical roles in the thermodynamics of these reactions.

Mechanistic insight into formation and changes of nanoparticles in MgF2 sols evidenced by liquid and solid state NMR.

PubMed

Karg, M; Scholz, G; König, R; Kemnitz, E

2012-02-28

The fluorolytic sol-gel reaction of magnesium methoxide with HF in methanol was studied by (19)F, (1)H and (13)C liquid and solid state NMR. In (19)F NMR five different species were identified, three of which belong to magnesium fluoride nanoparticles, i.e. NMR gave access to local structures of solid particles in suspensions. The long-term evolution of (19)F signals was followed and along with (19)F MAS NMR experiments of sols rotating at 13 kHz mechanistic insights into the ageing processes were obtained.

Insights into the discrepant luminescence for BaSiO3 :Eu2+ phosphors prepared by solid-state reaction and precipitation reaction methods.

PubMed

Xu, Jiao; Zhao, Yang; Chen, Jingjing; Mao, Zhiyong; Yang, Yanfang; Wang, Dajian

2017-09-01

Two synthesis routes, solid-state reaction and precipitation reaction, were employed to prepare BaSiO 3 :Eu 2+ phosphors in this study. Discrepancies in the luminescence green emission at 505 nm for the solid-state reaction method sample and in the yellow emission at 570 nm for the sample prepared by the precipitation reaction method, were observed respectively. A detail investigation about the discrepant luminescence of BaSiO 3 :Eu 2+ phosphors was performed by evaluation of X-ray diffraction (XRD), photoluminescence (PL)/photoluminescence excitation (PLE), decay time and thermal quenching properties. The results showed that the yellow emission was generated from the BaSiO 3 :Eu 2+ phosphor, while the green emission was ascribed to a small amount of Ba 2 SiO 4 :Eu 2+ compound that was present in the solid-state reaction sample. This work clarifies the luminescence properties of Eu 2+ ions in BaSiO 3 and Ba 2 SiO 4 hosts. Copyright © 2017 John Wiley & Sons, Ltd.

Hot atoms in cosmic chemistry.

PubMed

Rossler, K; Jung, H J; Nebeling, B

1984-01-01

High energy chemical reactions and atom molecule interactions might be important for cosmic chemistry with respect to the accelerated species in solar wind, cosmic rays, colliding gas and dust clouds and secondary knock-on particles in solids. "Hot" atoms with energies ranging from a few eV to some MeV can be generated via nuclear reactions and consequent recoil processes. The chemical fate of the radioactive atoms can be followed by radiochemical methods (radio GC or HPLC). Hot atom chemistry may serve for laboratory simulation of the reactions of energetic species with gaseous or solid interstellar matter. Due to the effective measurement of 10(8)-10(10) atoms only it covers a low to medium dose regime and may add to the studies of ion implantation which due to the optical methods applied are necessarily in the high dose regime. Experimental results are given for the systems: C/H2O (gas), C/H2O (solid, 77 K), N/CH4 (solid, 77K) and C/NH3 (solid, 77 K). Nuclear reactions used for the generation of 2 to 3 MeV atoms are: N(p,alpha) 11C, 16O(p,alpha pn) 11C and 12C(d,n) 13N with 8 to 45 MeV protons or deuterons from a cyclotron. Typical reactions products are: CO, CO2, CH4, CH2O, CH3OH, HCOOH, NH3, CH3NH2, cyanamide, formamidine, guanidine etc. Products of hot reactions in solids are more complex than in corresponding gaseous systems, which underlines the importance of solid state reactions for the build-up of precursors for biomolecules in space. As one of the major mechanisms for product formation, the simultaneous or fast consecutive reactions of a hot carbon with two target molecules (reaction complex) is discussed.

Room temperature photoluminescence in the visible range from silicon nanowires grown by a solid-state reaction

NASA Astrophysics Data System (ADS)

Anguita, J. V.; Sharma, P.; Henley, S. J.; Silva, S. R. P.

2009-11-01

The solid-liquid-solid method (also known as the solid-state method) is used to produce silicon nanowires at the core of silica nanowires with a support catalyst layer structure of nickel and titanium layers sputtered on oxide-coated silicon wafers. This silane-free process is low cost and large-area compatible. Using electron microscopy and Raman spectroscopy we deduce that the wires have crystalline silicon cores. The nanowires show photoluminescence in the visible range (orange), and we investigate the origin of this band. We further show that the nanowires form a random mesh that acts as an efficient optical trap, giving rise to an optically absorbing medium.

Nanoscale Solid State Batteries Enabled by Thermal Atomic Layer Deposition of a Lithium Polyphosphazene Solid State Electrolyte

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

Pearse, Alexander J.; Schmitt, Thomas E.; Fuller, Elliot J.

Several active areas of research in novel energy storage technologies, including three-dimensional solid state batteries and passivation coatings for reactive battery electrode components, require conformal solid state electrolytes. We describe an atomic layer deposition (ALD) process for a member of the lithium phosphorus oxynitride (LiPON) family, which is employed as a thin film lithium-conducting solid electrolyte. The reaction between lithium tert-butoxide (LiO tBu) and diethyl phosphoramidate (DEPA) produces conformal, ionically conductive thin films with a stoichiometry close to Li 2PO 2N between 250 and 300°C. The P/N ratio of the films is always 1, indicative of a particular polymorph ofmore » LiPON which closely resembles a polyphosphazene. Films grown at 300°C have an ionic conductivity of (6.51 ± 0.36)×10 -7 S/cm at 35°C, and are functionally electrochemically stable in the window from 0 to 5.3V vs. Li/Li +. We demonstrate the viability of the ALD-grown electrolyte by integrating it into full solid state batteries, including thin film devices using LiCoO 2 as the cathode and Si as the anode operating at up to 1 mA/cm 2. The high quality of the ALD growth process allows pinhole-free deposition even on rough crystalline surfaces, and we demonstrate the fabrication and operation of thin film batteries with the thinnest (<40nm) solid state electrolytes yet reported. Finally, we show an additional application of the moderate-temperature ALD process by demonstrating a flexible solid state battery fabricated on a polymer substrate.« less

Nanoscale Solid State Batteries Enabled by Thermal Atomic Layer Deposition of a Lithium Polyphosphazene Solid State Electrolyte

DOE PAGES

Pearse, Alexander J.; Schmitt, Thomas E.; Fuller, Elliot J.; ...

2017-04-10

Several active areas of research in novel energy storage technologies, including three-dimensional solid state batteries and passivation coatings for reactive battery electrode components, require conformal solid state electrolytes. We describe an atomic layer deposition (ALD) process for a member of the lithium phosphorus oxynitride (LiPON) family, which is employed as a thin film lithium-conducting solid electrolyte. The reaction between lithium tert-butoxide (LiO tBu) and diethyl phosphoramidate (DEPA) produces conformal, ionically conductive thin films with a stoichiometry close to Li 2PO 2N between 250 and 300°C. The P/N ratio of the films is always 1, indicative of a particular polymorph ofmore » LiPON which closely resembles a polyphosphazene. Films grown at 300°C have an ionic conductivity of (6.51 ± 0.36)×10 -7 S/cm at 35°C, and are functionally electrochemically stable in the window from 0 to 5.3V vs. Li/Li +. We demonstrate the viability of the ALD-grown electrolyte by integrating it into full solid state batteries, including thin film devices using LiCoO 2 as the cathode and Si as the anode operating at up to 1 mA/cm 2. The high quality of the ALD growth process allows pinhole-free deposition even on rough crystalline surfaces, and we demonstrate the fabrication and operation of thin film batteries with the thinnest (<40nm) solid state electrolytes yet reported. Finally, we show an additional application of the moderate-temperature ALD process by demonstrating a flexible solid state battery fabricated on a polymer substrate.« less

Importance of tunneling in H-abstraction reactions by OH radicals. The case of CH4 + OH studied through isotope-substituted analogs

NASA Astrophysics Data System (ADS)

Lamberts, T.; Fedoseev, G.; Kästner, J.; Ioppolo, S.; Linnartz, H.

2017-03-01

We present a combined experimental and theoretical study focussing on the quantum tunneling of atoms in the reaction between CH4 and OH. The importance of this reaction pathway is derived by investigating isotope substituted analogs. Quantitative reaction rates needed for astrochemical models at low temperature are currently unavailable both in the solid state and in the gas phase. Here, we study tunneling effects upon hydrogen abstraction in CH4 + OH by focusing on two reactions: CH4 + OD → CH3 + HDO and CD4 + OH → CD3 + HDO. The experimental study shows that the solid-state reaction rate RCH4 + OD is higher than RCD4 + OH at 15 K. Experimental results are accompanied by calculations of the corresponding unimolecular and bimolecular reaction rate constants using instanton theory taking into account surface effects. For the work presented here, the unimolecular reactions are particularly interesting as these provide insight into reactions following a Langmuir-Hinshelwood process. The resulting ratio of the rate constants shows that the H abstraction (kCH4 + OD) is approximately ten times faster than D-abstraction (kCD4 + OH) at 65 K. We conclude that tunneling is involved at low temperatures in the abstraction reactions studied here. The unimolecular rate constants can be used by the modeling community as a first approach to describe OH-mediated abstraction reactions in the solid phase. For this reason we provide fits of our calculated rate constants that allow the inclusion of these reactions in models in a straightforward fashion.

A green synthesis of a layered titanate, potassium lithium titanate; lower temperature solid-state reaction and improved materials performance

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

Ogawa, Makoto, E-mail: waseda.ogawa@gmail.com; Department of Earth Sciences, Waseda University, 1-6-1 Nishiwaseda, Shinjuku-ku, Tokyo 169-8050; Morita, Masashi, E-mail: m-masashi@y.akane.waseda.jp

2013-10-15

A layered titanate, potassium lithium titanate, with the size range from 0.1 to 30 µm was prepared to show the effects of the particle size on the materials performance. The potassium lithium titanate was prepared by solid-state reaction as reported previously, where the reaction temperature was varied. The reported temperature for the titanate preparation was higher than 800 °C, though 600 °C is good enough to obtain single-phase potassium lithium titanate. The lower temperature synthesis is cost effective and the product exhibit better performance as photocatalysts due to surface reactivity. - Graphical abstract: Finite particle of a layered titanate, potassiummore » lithium titanate, was prepared by solid-state reaction at lower temperature to show modified materials performance. Display Omitted - Highlights: • Potassium lithium titanate was prepared by solid-state reaction. • Lower temperature reaction resulted in smaller sized particles of titanate. • 600 °C was good enough to obtain single phased potassium lithium titanate. • The product exhibited better performance as photocatalyst.« less

Photochemistry and Transmission Pump-Probe Spectroscopy of 2-Azidobiphenyls in Aqueous Nanocrystalline Suspensions: Simplified Kinetics in Crystalline Solids.

PubMed

Chung, Tim S; Ayitou, Anoklase J-L; Park, Jin H; Breslin, Vanessa M; Garcia-Garibay, Miguel A

2017-04-20

Aqueous nanocrystalline suspensions provide a simple and efficient medium for performing transmission spectroscopy measurements in the solid state. In this Letter we describe the use of laser flash photolysis methods to analyze the photochemistry of 2-azidobiphenyl and several aryl-substituted derivatives. We show that all the crystalline compounds analyzed in this study transform quantitatively into carbazole products via a crystal-to-crystal reconstructive phase transition. While the initial steps of the reaction cannot be followed within the time resolution of our instrument (ca. 8 ns), we detected the primary isocarbazole photoproducts and analyzed the kinetics of their formal 1,5-H shift reactions, which take place in time scales that range from a few nanoseconds to several microseconds. It is worth noting that the high reaction selectivity observed in the crystalline state translates into a clean and simple kinetic process compared to that in solution.

Atomic Scale Dynamics of Contact Formation in the Cross-Section of InGaAs Nanowire Channels

DOE PAGES

Chen, Renjie; Jungjohann, Katherine L.; Mook, William M.; ...

2017-03-23

In the alloyed and compound contacts between metal and semiconductor transistor channels we see that they enable self-aligned gate processes which play a significant role in transistor scaling. At nanoscale dimensions and for nanowire channels, prior experiments focused on reactions along the channel length, but the early stage of reaction in their cross sections remains unknown. We report on the dynamics of the solid-state reaction between metal (Ni) and semiconductor (In 0.53Ga 0.47As), along the cross-section of nanowires that are 15 nm in width. Unlike planar structures where crystalline nickelide readily forms at conventional, low alloying temperatures, nanowires exhibit amore » solid-state amorphization step that can undergo a crystal regrowth step at elevated temperatures. Here, we capture the layer-by-layer reaction mechanism and growth rate anisotropy using in situ transmission electron microscopy (TEM). Our kinetic model depicts this new, in-plane contact formation which could pave the way for engineered nanoscale transistors.« less

Chemical looping combustion: A new low-dioxin energy conversion technology.

PubMed

Hua, Xiuning; Wang, Wei

2015-06-01

Dioxin production is a worldwide concern because of its persistence and carcinogenic, teratogenic, and mutagenic effects. The pyrolysis-chemical looping combustion process of disposing solid waste is an alternative to traditional solid waste incineration developed to reduce the dioxin production. Based on the equilibrium composition of the Deacon reaction, pyrolysis gas oxidized by seven common oxygen carriers, namely, CuO, NiO, CaSO4, CoO, Fe2O3, Mn3O4, and FeTiO3, is studied and compared with the pyrolysis gas directly combusted by air. The result shows that the activity of the Deacon reaction for oxygen carriers is lower than that for air. For four typical oxygen carriers (CuO, NiO, Fe2O3, and FeTiO3), the influences of temperature, pressure, gas composition, and tar on the Deacon reaction are discussed in detail. According to these simulation results, the dioxin production in China, Europe, the United States, and Japan is predicted for solid waste disposal by the pyrolysis-chemical looping combustion process. Thermodynamic analysis results in this paper show that chemical looping combustion can reduce dioxin production in the disposal of solid waste. Copyright © 2015. Published by Elsevier B.V.

Nonthermal effects in photostimulated solid state reaction of Mn doped SrTiO3

NASA Astrophysics Data System (ADS)

Daraselia, D.; Japaridze, D.; Jibuti, Z.; Shengelaya, A.; Müller, K. A.

2017-04-01

The effect of a photostimulated solid state reaction was investigated in Mn doped SrTiO3 samples. Light irradiation was performed by either halogen or UV lamps in order to study the effect of the spectral composition, and the results were compared with samples prepared at the same temperatures in a conventional furnace. The obtained samples were studied by X-ray diffraction for structural characterization and by Electron Paramagnetic Resonance, which provides microscopic information about the local environment as well as the valence state of Mn ions. It was found that light irradiation significantly enhances the solid state reaction rate compared to synthesis in the conventional furnace. Moreover, it was observed that UV lamp irradiation is much more effective compared to halogen lamps. This indicates that the absorption of light with energy larger than the materials band gap plays an important role and points towards the nonthermal mechanism of the photostimulated solid state reaction.

One-step simultaneous differential scanning calorimetry-FTIR microspectroscopy to quickly detect continuous pathways in the solid-state glucose/asparagine Maillard reaction.

PubMed

Hwang, Deng-Fwu; Hsieh, Tzu-Feng; Lin, Shan-Yang

2013-01-01

The stepwise reaction pathway of the solid-state Maillard reaction between glucose (Glc) and asparagine (Asn) was investigated using simultaneous differential scanning calorimetry (DSC)-FTIR microspectroscopy. The color change and FTIR spectra of Glc-Asn physical mixtures (molar ratio = 1:1) preheated to different temperatures followed by cooling were also examined. The successive reaction products such as Schiff base intermediate, Amadori product, and decarboxylated Amadori product in the solid-state Glc-Asn Maillard reaction were first simultaneously evidenced by this unique DSC-FTIR microspectroscopy. The color changed from white to yellow-brown to dark brown, and appearance of new IR peaks confirmed the formation of Maillard reaction products. The present study clearly indicates that this unique DSC-FTIR technique not only accelerates but also detects precursors and products of the Maillard reaction in real time.

Reactive Desorption of CO Hydrogenation Products under Cold Pre-stellar Core Conditions

NASA Astrophysics Data System (ADS)

Chuang, K.-J.; Fedoseev, G.; Qasim, D.; Ioppolo, S.; van Dishoeck, E. F.; Linnartz, H.

2018-02-01

The astronomical gas-phase detection of simple species and small organic molecules in cold pre-stellar cores, with abundances as high as ∼10‑8–10‑9 n H, contradicts the generally accepted idea that at 10 K, such species should be fully frozen out on grain surfaces. A physical or chemical mechanism that results in a net transfer from solid-state species into the gas phase offers a possible explanation. Reactive desorption, i.e., desorption following the exothermic formation of a species, is one of the options that has been proposed. In astronomical models, the fraction of molecules desorbed through this process is handled as a free parameter, as experimental studies quantifying the impact of exothermicity on desorption efficiencies are largely lacking. In this work, we present a detailed laboratory study with the goal of deriving an upper limit for the reactive desorption efficiency of species involved in the CO–H2CO–CH3OH solid-state hydrogenation reaction chain. The limit for the overall reactive desorption fraction is derived by precisely investigating the solid-state elemental carbon budget, using reflection absorption infrared spectroscopy and the calibrated solid-state band-strength values for CO, H2CO and CH3OH. We find that for temperatures in the range of 10 to 14 K, an upper limit of 0.24 ± 0.02 for the overall elemental carbon loss upon CO conversion into CH3OH. This corresponds with an effective reaction desorption fraction of ≤0.07 per hydrogenation step, or ≤0.02 per H-atom induced reaction, assuming that H-atom addition and abstraction reactions equally contribute to the overall reactive desorption fraction along the hydrogenation sequence. The astronomical relevance of this finding is discussed.

Morphology and conductivity study of solid electrolyte Li{sub 3}PO{sub 4}

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

Prayogi, Lugas Dwi, E-mail: ldprayodi@gmail.com; Faisal, Muhamad; Kartini, Evvy, E-mail: kartini@batan.go.id

2016-02-08

The comparison between two different methods of synthesize of solid electrolyte Li{sub 3}PO{sub 4} as precursor material for developing lithium ion battery, has been performed. The first method is to synthesize Li{sub 3}PO{sub 4} prepared by wet chemical reaction from LiOH and H{sub 3}PO{sub 4} which provide facile, abundant available resource, low cost, and low toxicity. The second method is solid state reaction prepared by Li{sub 2}CO{sub 3} and NH{sub 4}H{sub 2}PO{sub 4.} In addition, the possible morphology identification of comparison between two different methods will also be discussed. The composition, morphology, and additional identification phase and another compound ofmore » Li{sub 3}PO{sub 4} powder products from two different reaction are characterized by SEM, EDS, and EIS. The Li{sub 3}PO{sub 4} powder produced from wet reaction and solid state reaction have an average diameter of 0.834 – 7.81 µm and 2.15 – 17.3 µm, respectively. The density of Li{sub 3}PO{sub 4} prepared by wet chemical reaction is 2.238 gr/cm{sup 3}, little bit lower than the sample prepared by solid state reaction which density is 2.3560 gr/cm{sup 3}. The EIS measurement result shows that the conductivity of Li{sub 3}PO{sub 4} is 1.7 x 10{sup −9} S.cm{sup −1} for wet chemical reaction and 1.8 x 10{sup −10} S.cm{sup −1} for solid state reaction. The conductivity of Li{sub 3}PO{sub 4} is not quite different between those two samples even though they were prepared by different method of synthesize.« less

RAPID COMMUNICATION: Formation of MgB2 at ambient temperature with an electrochemical process: a plausible mechanism

NASA Astrophysics Data System (ADS)

Jadhav, A. B.; Subhedar, K. M.; Hyam, R. S.; Talaptra, A.; Sen, Pintu; Bandyopadhyay, S. K.; Pawar, S. H.

2005-06-01

The binary intermetallic MgB2 superconductor has been synthesized by many research groups. However, the mechanism of its formation is not clearly understood. In this communication, a comprehensive mechanism of the formation of MgB2 from Le Chatelier's principle of equilibrium reaction has been explained both for solid-state reaction and electrodeposition methods.

Detonation Reaction Zones in Condensed Explosives

NASA Astrophysics Data System (ADS)

Tarver, Craig M.

2006-07-01

Experimental measurements using nanosecond time resolved embedded gauges and laser interferometric techniques, combined with Non-Equilibrium Zeldovich - von Neumann - Doling (NEZND) theory and Ignition and Growth reactive flow hydrodynamic modeling, have revealed the average pressure/particle velocity states attained in reaction zones of self-sustaining detonation waves in several solid and liquid explosives. The time durations of these reaction zone processes are discussed for explosives based on pentaerythritol tetranitrate (PETN), nitromethane, octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), triaminitrinitrobenzene(TATB) and trinitrotoluene (TNT).

Facile Conversion of Red Phosphorus into Soluble Polyphosphide Anions by Reaction with Potassium Ethoxide.

PubMed

Dragulescu-Andrasi, Alina; Miller, L Zane; Chen, Banghao; McQuade, D Tyler; Shatruk, Michael

2016-03-14

Soluble polyphosphide anions were successfully generated in a number of organic solvents by the reaction between shelf-stable red phosphorus and potassium ethoxide. The species were identified by (31)P NMR spectroscopy in solution and by X-ray crystal-structure determination of (Bu4N)2P16 in the solid state. The reaction was scaled up to gram quantities by using a flow-chemistry process. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Crystal growth of YBCO coated conductors by TFA MOD method

NASA Astrophysics Data System (ADS)

Yoshizumi, M.; Nakanishi, T.; Matsuda, J.; Nakaoka, K.; Sutoh, Y.; Izumi, T.; Shiohara, Y.

2008-09-01

The crystal growth mechanism of TFA (trifluoroacetates)-MOD (metal organic deposition) derived YBa 2Cu 3O y has been investigated to understand the process for higher production rates of the conversion process. YBCO films were prepared by TFA-MOD on CeO 2/Gd 2Zr 2O 7/Hastelloy C276 substrates. The growth rates of YBCO derived from Y:Ba:Cu = 1:2:3 and 1:1.5:3 starting solutions were investigated by XRD and TEM analyses. YBCO growth proceeds in two steps of the epitaxial one from the substrate and solid state reaction. The overall growth rate estimated from the residual amounts of BaF 2 with time measured by XRD is proportional to a square root of P(H 2O). The trend was independent of the composition of starting solutions, however, the growth rate obtained from the 1:1.5:3 starting solutions was high as twice as that of 1:2:3, which could not be explained by the composition of BaF 2 included in the precursor films. On the other hand, the growth rate measured from the thickness of the YBCO quenched film at the same process time showed no difference between the samples of 1:2:3 and 1:1.5:3. The epitaxial growth rate of 1:1.5:3 was also the same as the overall growth rate of that, which means there was no solid state reaction to form YBCO after the epitaxial growth. The YBCO growth mechanism was found to be as follows; YBCO crystals nucleate at the surface of the substrate and epitaxially grow into the precursor by layer-by-layer by a manner with trapping unreacted particles. The amounts of YBCO and the unreacted particles trapped in the YBCO film are independent of the composition of the starting solution in this step. Unreacted particles react with each other to form YBCO and pores by solid state reaction as long as there is BaF 2 left in the film. The Ba-poor starting solution gives little BaF 2 left in the film and so the solid state reaction is completed within a short time, resulting in the fast overall growth rate.

Mechanochemical processing of molybdenum and vanadium sulfides for metal recovery from spent catalysts wastes.

PubMed

Li, Zhao; Chen, Min; Zhang, Qiwu; Liu, Xinzhong; Saito, Fumio

2017-02-01

This work describes the mechanochemical transformations of molybdenum and vanadium sulfides into corresponding molybdate and vanadate, to serve as a new environment-friendly approach for processing hazardous spent hydrodesulphurization (HDS) catalysts solid waste to achieve an easy recovery of not only molybdenum and vanadium but also nickel and cobalt. Co-grinding the molybdenum and vanadium sulfides with oxidants and sodium carbonate stimulates solid-state reactions without any heating aid to form metal molybdates and vanadates. The reactions proceed with an increase in grinding time and were enhanced by using more sodium carbonate and stronger oxidant. The necessary conditions for the successful transformation can be explained on the basis of thermodynamic analyses, namely a negative change in Gibbs free energy. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ohmic contacts to semiconducting diamond

NASA Astrophysics Data System (ADS)

Zeidler, James R.; Taylor, M. J.; Zeisse, Carl R.; Hewett, C. A.; Delahoussaye, Paul R.

1990-10-01

Work was carried out to improve the electron beam evaporation system in order to achieve better deposited films. The basic system is an ion pumped vacuum chamber, with a three-hearth, single-gun e-beam evaporator. Four improvements were made to the system. The system was thoroughly cleaned and new ion pump elements, an e-gun beam adjust unit, and a more accurate crystal monitor were installed. The system now has a base pressure of 3 X 10(exp -9) Torr, and can easily deposit high-melting-temperature metals such as Ta with an accurately controlled thickness. Improved shadow masks were also fabricated for better alignment and control of corner contacts for electrical transport measurements. Appendices include: A Thermally Activated Solid State Reaction Process for Fabricating Ohmic Contacts to Semiconducting Diamond; Tantalum Ohmic Contacts to Diamond by a Solid State Reaction Process; Metallization of Semiconducting Diamond: Mo, Mo/Au, and Mo/Ni/Au; Specific Contact Resistance Measurements of Ohmic Contracts to Diamond; and Electrical Activation of Boron Implanted into Diamond.

Operando Solid-State NMR Observation of Solvent-Mediated Adsorption-Reaction of Carbohydrates in Zeolites

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

Qi, Long; Alamillo, Ricardo; Elliott, William A.

Liquid-phase processing of molecules using heterogeneous catalysts – an important strategy for obtaining renewable chemicals sustainably from biomass – involves reactions that occur at solid-liquid interfaces. In glucose isomerization catalyzed by basic faujasite zeolites, the catalytic activity depends strongly on the solvent composition: initially, it declines precipitously when water is mixed with a small amount of the organic co-solvent γ-valerolactone (GVL), then recovers as the GVL content increases. Using solid-state 13C NMR spectroscopy, we observed glucose isomers located inside the zeolite pores directly, and followed their transformations into fructose and mannose in real time. At low GVL concentrations, glucose ismore » depleted in the zeolite pores relative to the liquid phase, while higher GVL concentrations in solution drive glucose inside the pores, resulting in up to a 32 enhancement in the local glucose concentration. Although their populations exchange rapidly, molecules present at the reactive interface experience a significantly different environment from the bulk solution.« less

End-Member Formulation of Solid Solutions and Reactive Transport

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

Lichtner, Peter C.

2015-09-01

A model for incorporating solid solutions into reactive transport equations is presented based on an end-member representation. Reactive transport equations are solved directly for the composition and bulk concentration of the solid solution. Reactions of a solid solution with an aqueous solution are formulated in terms of an overall stoichiometric reaction corresponding to a time-varying composition and exchange reactions, equivalent to reaction end-members. Reaction rates are treated kinetically using a transition state rate law for the overall reaction and a pseudo-kinetic rate law for exchange reactions. The composition of the solid solution at the onset of precipitation is assumed tomore » correspond to the least soluble composition, equivalent to the composition at equilibrium. The stoichiometric saturation determines if the solid solution is super-saturated with respect to the aqueous solution. The method is implemented for a simple prototype batch reactor using Mathematica for a binary solid solution. Finally, the sensitivity of the results on the kinetic rate constant for a binary solid solution is investigated for reaction of an initially stoichiometric solid phase with an undersaturated aqueous solution.« less

Production of aligned microfibers and nanofibers and derived functional monoliths

DOEpatents

Hu, Michael Z [Knoxville, TN; DePaoli, David W [Knoxville, TN; Kuritz, Tanya [Kingston, TN; Omatete, Ogbemi [New Port Richey, FL

2007-08-14

The present invention comprises a method for producing microfibers and nanofibers and further fabricating derived solid monolithic materials having aligned uniform micro- or nanofibrils. A method for producing fibers ranging in diameter from micrometer-sized to nanometer-sized comprises the steps of producing an electric field and preparing a solid precipitative reaction media wherein the media comprises at least one chemical reactive precursor and a solvent having low electrical conductivity and wherein a solid precipitation reaction process for nucleation and growth of a solid phase occurs within the media. Then, subjecting the media to the electric field to induce in-situ growth of microfibers or nanofibers during the reaction process within the media causing precipitative growth of solid phase particles wherein the reaction conditions and reaction kinetics control the size, morphology and composition of the fibers. The fibers can then be wet pressed while under electric field into a solid monolith slab, dried and consolidated.

On the Maillard reaction of meteoritic amino acids

NASA Astrophysics Data System (ADS)

Kolb, Vera M.; Bajagic, Milica; Liesch, Patrick J.; Philip, Ajish; Cody, George D.

2006-08-01

We have performed the Maillard reaction of a series of meteoritic amino acids with sugar ribose under simulated prebiotic conditions, in the solid state at 65°C and at the room temperature. Many meteoritic amino acids are highly reactive with ribose, even at the room temperature. We have isolated high molecular weight products that are insoluble in water, and have studied their structure by the IR (infrared) and solid-state C-13 NMR (nuclear magnetic resonance) spectroscopic methods. The functional groups and their distribution were similar among these products, and were comparable to the previously isolated insoluble organic materials from the Maillard reaction of the common amino acids with ribose. In addition, there were some similarities with the insoluble organic material that is found on Murchison. Our results suggest that the Maillard products may contribute to the composition of the part of the insoluble organic material that is found on Murchison. We have also studied the reaction of sodium silicate solution with the Maillard mixtures, to elucidate the process by which the organic compounds are preserved under prebiotic conditions.

Thermal Design, Analysis, and Testing of the Quench Module Insert Bread Board

NASA Technical Reports Server (NTRS)

Breeding Shawn; Khodabandeh, Julia; Turner, Larry D. (Technical Monitor)

2001-01-01

The science requirements for materials processing is to provide the desired PI requirements of thermal gradient, solid/liquid interface front velocity for a given processing temperature desired by the PI. Processing is performed by translating the furnace with the sample in a stationary position to minimize any disturbances to the solid/liquid interface front during steady state processing. Typical sample materials for this metals and alloys furnace are lead-tin alloys, lead-antimony alloys, and aluminum alloys. Samples must be safe to process and therefore typically are contained with hermetically sealed cartridge tubes (gas tight) with inner ceramic liners (liquid tight) to prevent contamination and/or reaction of the sample material with the cartridge tube.

Setting the Record Straight: Bottom-Up Carbon Nanostructures via Solid-State Reactions

NASA Astrophysics Data System (ADS)

Jordan, Robert Stanley

Chapter 1 describes the development and spectroscopic investigation of a novel synthetic route to N = 8 armchair graphene nanoribbons from polydiacetylene polymers. Four distinct diphenyl polydiacetylene polymers are produced from the crystal-phase topochemical polymerization of their corresponding diphenyl-1,4-butadiynes. These polydiacetylene polymers are transformed into spectroscopically indistinguishable N = 8 armchair graphene nanoribbons via simple heating in the bulk, solid-state. The stepwise transformation of polydiacetylenes to graphene nanoribbons is examined in detail by the use of complementary spectroscopic methods, namely solid-state nuclear magnetic resonance, infrared, Raman and X-ray photoelectron spectroscopy. The final morphology and width of the nanoribbons is established through the use of high-resolution transmission electron microscopy. Chapter 2 chronicles the implementation of a similar approach to N = 12 armchair graphene nanoribbons from a dinaphthyl substituted polydiacetylene polymer. The mild nature of the process and pristine structure of the nanoribbons is again confirmed with the use of spectroscopic and microscopic methods. The chapter concludes with preliminary electrical measurements of the nanoribbons confirming that they are indeed conductive. Chapter 3 details the development of a synthetic route to diaryl trans-enediynes as structural models of individual reactive units within a polydiacetylene polymer. The trans-enediynes described are found to undergo three distinct annulation reactions depending on reaction conditions. Finally, the synthetic routes developed are utilized to access diethynyl [5]helicenes and phenanthrenes which fueled studies on the mechanism of the Bergman polymerization reaction.

40 CFR 256.63 - Requirements for public participation in the permitting of facilities.

Code of Federal Regulations, 2010 CFR

2010-07-01

... PROTECTION AGENCY (CONTINUED) SOLID WASTES GUIDELINES FOR DEVELOPMENT AND IMPLEMENTATION OF STATE SOLID WASTE... solid waste disposal facility the State shall hold a public hearing to solicit public reaction and...

Electric-field enhanced performance in catalysis and solid-state devices involving gases

DOEpatents

Blackburn, Bryan M.; Wachsman, Eric D.; Van Assche, IV, Frederick Martin

2015-05-19

Electrode configurations for electric-field enhanced performance in catalysis and solid-state devices involving gases are provided. According to an embodiment, electric-field electrodes can be incorporated in devices such as gas sensors and fuel cells to shape an electric field provided with respect to sensing electrodes for the gas sensors and surfaces of the fuel cells. The shaped electric fields can alter surface dynamics, system thermodynamics, reaction kinetics, and adsorption/desorption processes. In one embodiment, ring-shaped electric-field electrodes can be provided around sensing electrodes of a planar gas sensor.

Snapshots of a solid-state transformation: coexistence of three phases trapped in one crystal

DOE PAGES

Aromí, G.; Beavers, C. M.; Sánchez Costa, J.; ...

2016-01-05

Crystal-to-crystal transformations have been crucial in the understanding of solid-state processes, since these may be studied in detail by means of single crystal X-ray diffraction (SCXRD) techniques. The description of the mechanisms and potential intermediates of those processes remains very challenging. In fact, solid-state transient states have rarely been observed, at least to a sufficient level of detail. We have investigated the process of guest extrusion from the non-porous molecular material [Fe(bpp)(H 2L)](ClO 4) 2·1.5C 3H 6O (bpp = 2,6-bis(pyrazol-3-yl)pyridine; H 2L = 2,6-bis(5-(2-methoxyphenyl)-pyrazol-3-yl)pyridine; C 3H 6O = acetone), which occurs through ordered diffusion of acetone in a crystal-to-crystal manner,more » leading to dramatic structural changes. The slow kinetics of the transition allows thermal trapping of the system at various intermediate stages. The transiting single crystal can be then examined at these points through synchrotron SCXRD, offering a window upon the mechanism of the transformation at the molecular scale. These experiments have unveiled the development of an ordered intermediate phase, distinct from the initial and the final states, coexisting as the process advances with either of these two phases or, at a certain moment with both of them. The new intermediate phase has been structurally characterized in full detail by SCXRD, providing insights into the mechanism of this diffusion triggered solid-state phenomenon. Lastly, the process has been also followed by calorimetry, optical microscopy, local Raman spectroscopy and powder X-ray diffraction. The discovery and description of an intermediate ordered state in a molecular solid-state transformation is of great interest and will help to understand the mechanistic details and reaction pathways underlying these transformations.« less

Amorphous and nanocrystalline luminescent Si and Ge obtained via a solid-state chemical metathesis synthesis route

NASA Astrophysics Data System (ADS)

McMillan, Paul F.; Gryko, Jan; Bull, Craig; Arledge, Richard; Kenyon, Anthony J.; Cressey, Barbara A.

2005-03-01

A new solid-state metathesis synthesis route was applied to obtain bulk samples of amorphous or microcrystalline Si and Ge. The method involves reaction of Zintl phases such as NaSi or NaGe, with ammonium or metal (e.g., CuCl, CoBr 2) halides. The driving force for the solid-state reaction is provided by the formation of alkali halides and the transition metals or metal silicides, or gaseous ammonia and hydrogen. The semiconductors were purified by washing to remove other solid products. The amorphous semiconductors were obtained in bulk form from reactions carried out at 200-300 °C. Syntheses at higher temperatures gave rise to microcrystalline semiconductors, or to micro-/nanocrystalline particles contained within the amorphous material. Similar crystalline/amorphous composites were obtained after heat treatment of bulk amorphous materials.

Solid catalyzed isoparaffin alkylation at supercritical fluid and near-supercritical fluid conditions

DOEpatents

Ginosar, Daniel M.; Fox, Robert V.; Kong, Peter C.

2000-01-01

This invention relates to an improved method for the alkylation reaction of isoparaffins with olefins over solid catalysts including contacting a mixture of an isoparaffin, an olefin and a phase-modifying material with a solid acid catalyst member under alkylation conversion conditions at either supercritical fluid, or near-supercritical fluid conditions, at a temperature and a pressure relative to the critical temperature(T.sub.c) and the critical pressure(P.sub.c) of the reaction mixture. The phase-modifying phase-modifying material is employed to promote the reaction's achievement of either a supercritical fluid state or a near-supercritical state while simultaneously allowing for decreased reaction temperature and longer catalyst life.

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

Aromí, G.; Beavers, C. M.; Sánchez Costa, J.

Crystal-to-crystal transformations have been crucial in the understanding of solid-state processes, since these may be studied in detail by means of single crystal X-ray diffraction (SCXRD) techniques. The description of the mechanisms and potential intermediates of those processes remains very challenging. In fact, solid-state transient states have rarely been observed, at least to a sufficient level of detail. We have investigated the process of guest extrusion from the non-porous molecular material [Fe(bpp)(H 2L)](ClO 4) 2·1.5C 3H 6O (bpp = 2,6-bis(pyrazol-3-yl)pyridine; H 2L = 2,6-bis(5-(2-methoxyphenyl)-pyrazol-3-yl)pyridine; C 3H 6O = acetone), which occurs through ordered diffusion of acetone in a crystal-to-crystal manner,more » leading to dramatic structural changes. The slow kinetics of the transition allows thermal trapping of the system at various intermediate stages. The transiting single crystal can be then examined at these points through synchrotron SCXRD, offering a window upon the mechanism of the transformation at the molecular scale. These experiments have unveiled the development of an ordered intermediate phase, distinct from the initial and the final states, coexisting as the process advances with either of these two phases or, at a certain moment with both of them. The new intermediate phase has been structurally characterized in full detail by SCXRD, providing insights into the mechanism of this diffusion triggered solid-state phenomenon. Lastly, the process has been also followed by calorimetry, optical microscopy, local Raman spectroscopy and powder X-ray diffraction. The discovery and description of an intermediate ordered state in a molecular solid-state transformation is of great interest and will help to understand the mechanistic details and reaction pathways underlying these transformations.« less

Surface-Activated Coupling Reactions Confined on a Surface.

PubMed

Dong, Lei; Liu, Pei Nian; Lin, Nian

2015-10-20

Chemical reactions may take place in a pure phase of gas or liquid or at the interface of two phases (gas-solid or liquid-solid). Recently, the emerging field of "surface-confined coupling reactions" has attracted intensive attention. In this process, reactants, intermediates, and products of a coupling reaction are adsorbed on a solid-vacuum or a solid-liquid interface. The solid surface restricts all reaction steps on the interface, in other words, the reaction takes place within a lower-dimensional, for example, two-dimensional, space. Surface atoms that are fixed in the surface and adatoms that move on the surface often activate the surface-confined coupling reactions. The synergy of surface morphology and activity allow some reactions that are inefficient or prohibited in the gas or liquid phase to proceed efficiently when the reactions are confined on a surface. Over the past decade, dozens of well-known "textbook" coupling reactions have been shown to proceed as surface-confined coupling reactions. In most cases, the surface-confined coupling reactions were discovered by trial and error, and the reaction pathways are largely unknown. It is thus highly desirable to unravel the mechanisms, mechanisms of surface activation in particular, of the surface-confined coupling reactions. Because the reactions take place on surfaces, advanced surface science techniques can be applied to study the surface-confined coupling reactions. Among them, scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) are the two most extensively used experimental tools. The former resolves submolecular structures of individual reactants, intermediates, and products in real space, while the latter monitors the chemical states during the reactions in real time. Combination of the two methods provides unprecedented spatial and temporal information on the reaction pathways. The experimental findings are complemented by theoretical modeling. In particular, density-functional theory (DFT) transition-state calculations have been used to shed light on reaction mechanisms and to unravel the trends of different surface materials. In this Account, we discuss recent progress made in two widely studied surface-confined coupling reactions, aryl-aryl (Ullmann-type) coupling and alkyne-alkyne (Glaser-type) coupling, and focus on surface activation effects. Combined experimental and theoretical studies on the same reactions taking place on different metal surfaces have clearly demonstrated that different surfaces not only reduce the reaction barrier differently and render different reaction pathways but also control the morphology of the reaction products and, to some degree, select the reaction products. We end the Account with a list of questions to be addressed in the future. Satisfactorily answering these questions may lead to using the surface-confined coupling reactions to synthesize predefined products with high yield.

Electron transfer from a solid-state electrode assisted by methyl viologen sustains efficient microbial reductive dechlorination of TCE.

PubMed

Aulenta, Federico; Catervi, Alessandro; Majone, Mauro; Panero, Stefania; Reale, Priscilla; Rossetti, Simona

2007-04-01

The ability to transfer electrons, via an extracellular path, to solid surfaces is typically exploited by microorganisms which use insoluble electron acceptors, such as iron-or manganese-oxides or inert electrodes in microbial fuel cells. The reverse process, i.e., the use of solid surfaces or electrodes as electron donors in microbial respirations, although largely unexplored, could potentially have important environmental applications, particularly for the removal of oxidized pollutants from contaminated groundwater or waste streams. Here we show, for the first time, that an electrochemical cell with a solid-state electrode polarized at -500 mV (vs standard hydrogen electrode), in combination with a low-potential redox mediator (methyl viologen), can efficiently transfer electrochemical reducing equivalents to microorganisms which respire using chlorinated solvents. By this approach, the reductive transformation of trichloroethene, a toxic yet common groundwater contaminant, to harmless end-products such as ethene and ethane could be performed. Furthermore, using a methyl-viologen-modified electrode we could even demonstrate that dechlorinating bacteria were able to accept reducing equivalents directly from the modified electrode surface. The innovative concept, based on the stimulation of dechlorination reactions through the use of solid-state electrodes (we propose for this process the acronym BEARD: Bio-Electrochemically Assisted Reductive Dechlorination), holds promise for in situ bioremediation of chlorinated-solvent-contaminated groundwater, and has several potential advantages over traditional approaches based on the subsurface injection of organic compounds. The results of this study raise the possibility that immobilization of selected redox mediators may be a general strategy for stimulating and controlling a range of microbial reactions using insoluble electrodes as electron donors.

Effect of Process Parameter on Barium Titanate Stannate (BTS) Materials Sintered at Low Sintering

NASA Astrophysics Data System (ADS)

Shukla, Alok; Bajpai, P. K.

2011-11-01

Ba(Ti1-xSnx)O3 solid solutions with (x = 0.15, 0.20, 0.30 and 0.40) are synthesized using conventional solid state reaction method. Formation of solid solutions in the range 0 ≤ x ≤0.40 is confirmed using X-ray diffraction technique. Single phase solid solutions with homogeneous grain distribution are observed at relatively low sintering by controlling process parameters viz. sintering time. Composition at optimized temperature (1150 °C) sintered by varying the sintering time, stabilize in cubic perovskite phase. The % experimental density increase with increasing the time of sintering instead of increasing sintering temperature. The lattice parameter increases by increasing the tin composition in the material. This demonstrates that process parameter optimization can lead to single phase at relatively lower sintering-a major advantage for the materials used as capacitor element in MLCC.

Formation of simple nitrogen hydrides NH and NH2 at cryogenic temperatures through N + NH3→ NH + NH2 reaction: dark cloud chemistry of nitrogen.

PubMed

Nourry, Sendres; Krim, Lahouari

2016-07-21

Although NH3 molecules interacting with ground state nitrogen atoms N((4)S) seem not to be a very reactive system without providing additional energy to initiate the chemical process, we show through this study that, in the solid phase, at very low temperature, NH3 + N((4)S) reaction leads to the formation of the amidogen radical NH2. Such a dissociation reaction previously thought to occur exclusively through UV photon or energetic particle irradiation is in this work readily occurring just by stimulating the mobility of N((4)S)-atoms in the 3-10 K temperature range in the solid sample. The N((4)S)-N((4)S) recombination may be the source of metastable molecular nitrogen N2(A), a reactive species which might trigger the NH3 dissociation or react with ground state nitrogen atoms N((4)S) to form excited nitrogen atoms N((4)P/(2)D) through energy transfer processes. Based on our obtained results, it is possible to propose reaction pathways to explain the NH2 radical formation which is the first step in the activation of stable species such as NH3, a chemical induction process that, in addition to playing an important role in the origin of molecular complexity in interstellar space, is known to require external energy supplies to occur in the gas phase.

Experiment and Theory for Nuclear Reactions in Nano-Materials Show e14 - e16 Solid-State Fusion Reactions

NASA Astrophysics Data System (ADS)

George, Russ

2005-03-01

Nano-lattices of deuterium loving metals exhibit coherent behavior by populations of deuterons (d's) occupying a Bloch state. Therein, coherent d-overlap occurs wherein the Bloch condition reduces the Coulomb barrier.Overlap of dd pairs provides a high probability fusion will/must occur. SEM photo evidence showing fusion events is now revealed by laboratories that load or flux d into metal nano-domains. Solid-state dd fusion creates an excited ^4He nucleus entangled in the large coherent population of d's.This contrasts with plasma dd fusion in collision space where an isolated excited ^4He nucleus seeks the ground state via fast particle emission. In momentum limited solid state fusion,fast particle emission is effectively forbidden.Photographed nano-explosive events are beyond the scope of chemistry. Corroboration of the nuclear nature derives from photographic observation of similar events on spontaneous fission, e.g. Cf. We present predictive theory, heat production, and helium isotope data showing reproducible e14 to e16 solid-state fusion reactions.

Apparatus for silicon nitride precursor solids recovery

DOEpatents

Crosbie, Gary M.; Predmesky, Ronald L.; Nicholson, John M.

1995-04-04

Method and apparatus are provided for collecting reaction product solids entrained in a gaseous outflow from a reaction situs, wherein the gaseous outflow includes a condensable vapor. A condensate is formed of the condensable vapor on static mixer surfaces within a static mixer heat exchanger. The entrained reaction product solids are captured in the condensate which can be collected for further processing, such as return to the reaction situs. In production of silicon imide, optionally integrated into a production process for making silicon nitride caramic, wherein reactant feed gas comprising silicon halide and substantially inert carrier gas is reacted with liquid ammonia in a reaction vessel, silicon imide reaction product solids entrained in a gaseous outflow comprising residual carrier gas and vaporized ammonia can be captured by forming a condensate of the ammonia vapor on static mixer surfaces of a static mixer heat exchanger.

Method for silicon nitride precursor solids recovery

DOEpatents

Crosbie, Gary M.; Predmesky, Ronald L.; Nicholson, John M.

1992-12-15

Method and apparatus are provided for collecting reaction product solids entrained in a gaseous outflow from a reaction situs, wherein the gaseous outflow includes a condensable vapor. A condensate is formed of the condensable vapor on static mixer surfaces within a static mixer heat exchanger. The entrained reaction product solids are captured in the condensate which can be collected for further processing, such as return to the reaction situs. In production of silicon imide, optionally integrated into a production process for making silicon nitride caramic, wherein reactant feed gas comprising silicon halide and substantially inert carrier gas is reacted with liquid ammonia in a reaction vessel, silicon imide reaction product solids entrained in a gaseous outflow comprising residual carrier gas and vaporized ammonia can be captured by forming a condensate of the ammonia vapor on static mixer surfaces of a static mixer heat exchanger.

A stochastic model of solid state thin film deposition: Application to chalcopyrite growth

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

Lovelett, Robert J.; Pang, Xueqi; Roberts, Tyler M.

Developing high fidelity quantitative models of solid state reaction systems can be challenging, especially in deposition systems where, in addition to the multiple competing processes occurring simultaneously, the solid interacts with its atmosphere. In this work, we develop a model for the growth of a thin solid film where species from the atmosphere adsorb, diffuse, and react with the film. The model is mesoscale and describes an entire film with thickness on the order of microns. Because it is stochastic, the model allows us to examine inhomogeneities and agglomerations that would be impossible to characterize with deterministic methods. We demonstratemore » the modeling approach with the example of chalcopyrite Cu(InGa)(SeS){sub 2} thin film growth via precursor reaction, which is a common industrial method for fabricating thin film photovoltaic modules. The model is used to understand how and why through-film variation in the composition of Cu(InGa)(SeS){sub 2} thin films arises and persists. We believe that the model will be valuable as an effective quantitative description of many other materials systems used in semiconductors, energy storage, and other fast-growing industries.« less

A stochastic model of solid state thin film deposition: Application to chalcopyrite growth

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

Lovelett, Robert J.; Pang, Xueqi; Roberts, Tyler M.

Developing high fidelity quantitative models of solid state reaction systems can be challenging, especially in deposition systems where, in addition to the multiple competing processes occurring simultaneously, the solid interacts with its atmosphere. Here, we develop a model for the growth of a thin solid film where species from the atmosphere adsorb, diffuse, and react with the film. The model is mesoscale and describes an entire film with thickness on the order of microns. Because it is stochastic, the model allows us to examine inhomogeneities and agglomerations that would be impossible to characterize with deterministic methods. We also demonstrate themore » modeling approach with the example of chalcopyrite Cu(InGa)(SeS) 2 thin film growth via precursor reaction, which is a common industrial method for fabricating thin film photovoltaic modules. The model is used to understand how and why through-film variation in the composition of Cu(InGa)(SeS) 2 thin films arises and persists. Finally, we believe that the model will be valuable as an effective quantitative description of many other materials systems used in semiconductors, energy storage, and other fast-growing industries.« less

A stochastic model of solid state thin film deposition: Application to chalcopyrite growth

DOE PAGES

Lovelett, Robert J.; Pang, Xueqi; Roberts, Tyler M.; ...

2016-04-01

Developing high fidelity quantitative models of solid state reaction systems can be challenging, especially in deposition systems where, in addition to the multiple competing processes occurring simultaneously, the solid interacts with its atmosphere. Here, we develop a model for the growth of a thin solid film where species from the atmosphere adsorb, diffuse, and react with the film. The model is mesoscale and describes an entire film with thickness on the order of microns. Because it is stochastic, the model allows us to examine inhomogeneities and agglomerations that would be impossible to characterize with deterministic methods. We also demonstrate themore » modeling approach with the example of chalcopyrite Cu(InGa)(SeS) 2 thin film growth via precursor reaction, which is a common industrial method for fabricating thin film photovoltaic modules. The model is used to understand how and why through-film variation in the composition of Cu(InGa)(SeS) 2 thin films arises and persists. Finally, we believe that the model will be valuable as an effective quantitative description of many other materials systems used in semiconductors, energy storage, and other fast-growing industries.« less

Amorphous and nanocrystalline luminescent Si and Ge obtained via a solid-state chemical metathesis synthesis route

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

McMillan, Paul F.; Gryko, Jan; Bull, Craig

A new solid-state metathesis synthesis route was applied to obtain bulk samples of amorphous or microcrystalline Si and Ge. The method involves reaction of Zintl phases such as NaSi or NaGe, with ammonium or metal (e.g., CuCl, CoBr{sub 2}) halides. The driving force for the solid-state reaction is provided by the formation of alkali halides and the transition metals or metal silicides, or gaseous ammonia and hydrogen. The semiconductors were purified by washing to remove other solid products. The amorphous semiconductors were obtained in bulk form from reactions carried out at 200-300{sup o}C. Syntheses at higher temperatures gave rise tomore » microcrystalline semiconductors, or to micro-/nanocrystalline particles contained within the amorphous material. Similar crystalline/amorphous composites were obtained after heat treatment of bulk amorphous materials.« less

Monolayer Nickel Cobalt Hydroxyl Carbonate for High Performance All-Solid-State Asymmetric Supercapacitors.

PubMed

Zhao, Yufeng; Ma, Hongnan; Huang, Shifei; Zhang, Xuejiao; Xia, Meirong; Tang, Yongfu; Ma, Zi-Feng

2016-09-07

The emergence of atomically thick nanolayer materials, which feature a short ion diffusion channel and provide more exposed atoms in the electrochemical reactions, offers a promising occasion to optimize the performance of supercapacitors on the atomic level. In this work, a novel monolayer Ni-Co hydroxyl carbonate with an average thickness of 1.07 nm is synthesized via an ordinary one-pot hydrothermal route for the first time. This unique monolayer structure can efficiently rise up the exposed electroactive sites and facilitate the surface dependent electrochemical reaction processes, and thus results in outstanding specific capacitance of 2266 F g(-1). Based on this material, an all-solid-state asymmetric supercapacitor is developed adopting alkaline PVA (poly(vinyl alcohol)) gel (PVA/KOH) as electrolyte, which performs remarkable cycling stability (no capacitance fade after 19 000 cycles) together with promising energy density of 50 Wh kg(-1) (202 μWh cm(-2)) and high power density of 8.69 kW kg(-1) (35.1 mW cm(-2)). This as-assembled all-solid-state asymmetric supercapacitor (AASC) holds great potential in the field of portable energy storage devices.

Combinatorial synthesis of phosphors using arc-imaging furnace

PubMed Central

Ishigaki, Tadashi; Toda, Kenji; Yoshimura, Masahiro; Uematsu, Kazuyoshi; Sato, Mineo

2011-01-01

We have applied a novel ‘melt synthesis technique’ rather than a conventional solid-state reaction to rapidly synthesize phosphor materials. During a synthesis, the mixture of oxides or their precursors is melted by light pulses (10–60 s) in an arc-imaging furnace on a water-cooled copper hearth to form a globule of 1–5 mm diameter, which is then rapidly cooled by turning off the light. Using this method, we synthesized several phosphor compounds including Y3Al5O12:Ce(YAG) and SrAl2O4:Eu,Dy. Complex phosphor oxides are difficult to produce by conventional solid-state reaction techniques because of the slow reaction rates among solid oxides; as a result, the oxides form homogeneous compounds or solid solutions. On the other hand, melt reactions are very fast (10–60 s) and result in homogeneous compounds owing to rapid diffusion and mixing in the liquid phase. Therefore, melt synthesis techniques are suitable for preparing multi component homogeneous compounds and solid solutions. PMID:27877432

Combinatorial synthesis of phosphors using arc-imaging furnace

NASA Astrophysics Data System (ADS)

Ishigaki, Tadashi; Toda, Kenji; Yoshimura, Masahiro; Uematsu, Kazuyoshi; Sato, Mineo

2011-10-01

We have applied a novel 'melt synthesis technique' rather than a conventional solid-state reaction to rapidly synthesize phosphor materials. During a synthesis, the mixture of oxides or their precursors is melted by light pulses (10-60 s) in an arc-imaging furnace on a water-cooled copper hearth to form a globule of 1-5 mm diameter, which is then rapidly cooled by turning off the light. Using this method, we synthesized several phosphor compounds including Y3Al5O12:Ce(YAG) and SrAl2O4:Eu,Dy. Complex phosphor oxides are difficult to produce by conventional solid-state reaction techniques because of the slow reaction rates among solid oxides; as a result, the oxides form homogeneous compounds or solid solutions. On the other hand, melt reactions are very fast (10-60 s) and result in homogeneous compounds owing to rapid diffusion and mixing in the liquid phase. Therefore, melt synthesis techniques are suitable for preparing multi component homogeneous compounds and solid solutions.

Chapter 28: Nanomaterials for Energy Applications

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

Hurst, Katherine E; Luther, Joseph M; Ban, Chunmei

2017-01-02

A wide variety of nanomaterials have been applied to energy related applications, including nanofibers, nanocrystalline materials, nanoparticles, and thin film nanocoatings. Solid-state lighting offers significant advantages in energy efficiency compared to traditional lighting technologies. The potential for nanostructured solid-state lighting devices is excellent as it enjoys significant economic drivers in energy efficiency. Fuel cells convert chemical energy to electrical energy through electrochemical reactions at an anode and cathode. The conversion of biomass to fuels and chemicals offers great potential to reduce energy dependence on petroleum and reduce green house gas emissions. Batteries involve the production and storage of electrical charge,more » the transfer of cations and electrical current, each based on electrochemical reactions and chemical reactants. Battery performance relies on the complex processes and factors that affect the transport of charge in the reactants, and across the interface between the chemical phases.« less

Solvent-Free Benzoin and Stetter Reactions with a Small Amount of NHC Catalyst in the Liquid or Semisolid State.

PubMed

Ema, Tadashi; Nanjo, Yoshiko; Shiratori, Sho; Terao, Yuta; Kimura, Ryo

2016-11-04

The intermolecular or intramolecular asymmetric benzoin reaction was catalyzed by a small amount of N-heterocyclic carbene (NHC) (0.2-1 mol %) under solvent-free conditions. The solvent-free intramolecular asymmetric Stetter reaction also proceeded efficiently with NHC (0.2-1 mol %). In some cases, even solid-to-solid or solid-to-liquid conversions took place with low catalyst loading (0.2-1 mol %).

Synthesis of azines in solid state: reactivity of solid hydrazine with aldehydes and ketones.

PubMed

Lee, Byeongno; Lee, Kyu Hyung; Cho, Jaeheung; Nam, Wonwoo; Hur, Nam Hwi

2011-12-16

Highly conjugated azines were prepared by solid state grinding of solid hydrazine and carbonyl compounds such as aldehydes and ketones, using a mortar and a pestle. Complete conversion to the azine product is generally achieved at room temperature within 24 h, without using solvents or additives. The solid-state reactions afford azines as the sole products with greater than 97% yield, producing only water and carbon dioxide as waste.

ORGANIC REACTIONS IN THE SOLID STATE AND IN SOLID SOLUTIONS.

DTIC Science & Technology

on the reactions of phthalic acid and acetanilide , various acyl anilides, and ring-substituted acetanilides . Exploratory experiments were also...performed between ring-substituted acetanilides and succinic, glutaric, maleic and fumaric acids. The influence of imidazole as a catalyst of the...transacylation reaction of phthalic anhydride and acetanilide is also reported. (Author)

Metal Carbonation of Forsterite in Supercritical CO2 and H2O Using Solid State 29Si, 13C NMR Spectroscop

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

Kwak, Ja Hun; Hu, Jian Z.; Hoyt, David W.

2010-03-11

Ex situ solid state NMR was used for the first time to study fundamental mineral carbonation processes and reaction extent relevant to geologic carbon sequestration (GCS) using a model silicate mineral forsterite (Mg2SiO4)+supercriticalCO2 with and without H2O. Run conditions were 80 C and 96 atm. 29Si NMR clearly shows that in the absence of CO2, the role of H2O is to hydrolyze surface Mg-O-Si bonds to produce dissolved Mg2+, and mono- and oligomeric hydroxylated silica species. Surface hydrolysis products contain only Q0 (Si(OH)4) and Q1(Si(OH)3OSi) species. An equilibrium between Q0, Q1 and Mg2+ with a saturated concentration equivalent to lessmore » than 3.2% of the Mg2SiO4 conversion is obtained at a reaction time of up to 7 days. Using scCO2 without H2O, no reaction is observed within 7 days. Using both scCO2 and H2O, the surface reaction products for silica are mainly Q3 (SiOH(OSi)3) species accompanied by a lesser amount of Q2 (Si(OH)2(OSi)2) and Q4 (Si(OSi)4). However, no Q0 and Q1 were detected, indicating the carbonic acid formation/deprotonation and magnesite (MgCO3) precipitation reactions are faster than the forsterite hydrolysis process. Thus it can be concluded that the Mg2SiO4 hydrolysis process is the rate limiting step of the overall mineral carbonation process. 29Si NMR combined with XRD, TEM, SAED and EDX further reveal that the reaction is a surface reaction with the Mg2SiO4 crystallite in the core and with condensed Q2-Q4 species forming amorphous surface layers. 13C MAS NMR identified a possible reaction intermediate as (MgCO3)4-Mg(OH)2-5H2O. However, at long reaction times only crystallite magnesite MgCO3 products are observed.« less

The kinetics and mechanism of nanoconfined molten salt reactions: trimerization of potassium and rubidium dicyanamide.

PubMed

Yancey, Benjamin; Vyazovkin, Sergey

2015-04-21

This study highlights the effect of the aggregate state of a reactant on the reaction kinetics under the conditions of nanoconfinement. Our previous work (Phys. Chem. Chem. Phys., 2014, 16, 11409) has demonstrated considerable deceleration of the solid state trimerization of sodium dicyanamide in organically modified silica nanopores. In the present study we use FTIR, NMR, pXRD, TGA and DSC to analyze the kinetics and mechanism of the liquid state trimerization of potassium and rubidium dicyanamide under similar conditions of nanoconfinement. It is found that nanoconfinement accelerates dramatically the kinetics of the liquid state trimerization, whereas it does not appear to affect the reaction mechanism. Kinetic analysis indicates that the acceleration is associated with an increase in the preexponential factor. Although nanoconfinement has the opposite effects on the respective kinetics of solid and liquid state trimerization, both effects are linked to a change in the preexponential factor. The results obtained are consistent with our hypothesis that the effects differ because nanoconfinement may promote disordering of the solid and ordering of the liquid reaction media.

Solid-State Diffusional Behaviors of Functional Metal Oxides at Atomic Scale.

PubMed

Chen, Jui-Yuan; Huang, Chun-Wei; Wu, Wen-Wei

2018-02-01

Metal/metal oxides have attracted extensive research interest because of their combination of functional properties and compatibility with industry. Diffusion and thermal reliability have become essential issues that require detailed study to develop atomic-scaled functional devices. In this work, the diffusional reaction behavior that transforms piezoelectric ZnO into magnetic Fe 3 O 4 is investigated at the atomic scale. The growth kinetics of metal oxides are systematically studied through macro- and microanalyses. The growth rates are evaluated by morphology changes, which determine whether the growth behavior was a diffusion- or reaction-controlled process. Furthermore, atom attachment on the kink step is observed at the atomic scale, which has important implications for the thermodynamics of functional metal oxides. Faster growth planes simultaneously decrease, which result in the predominance of low surface energy planes. These results directly reveal the atomic formation process of metal oxide via solid-state diffusion. In addition, the nanofabricated method provides a novel approach to investigate metal oxide evolution and sheds light on diffusional reaction behavior. More importantly, the results and phenomena of this study provide considerable inspiration to enhance the material stability and reliability of metal/oxide-based devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Stability of physical state on compound hawthorn dropping pills].

PubMed

Zhang, Wei; Chen, Hong-Yan; Jiang, Jian-Lan

2008-11-01

To evaluate the stability of physical state with accelerate test and dropping in process before and after on compound hawthorn dropping pills. Scanning electron microscope, TG-DTA, FT-IR and XRD were used. The active components presented amorphous, tiny crystal and molecular state in dropping pills, and it had no obvious reaction between PEG 4000 and active components. With time prolonging, a little of active components changed from amorphous state to tiny crystal or molecular state. Solid dispersion improved the stability and dissolution of compound hawthorn dropping pills.

Development of forming and joining technology for TD-NiCr sheet

NASA Technical Reports Server (NTRS)

Torgerson, R. T.

1973-01-01

Forming joining techniques and properties data were developed for thin-gage TD-NiCr sheet in the recrystallized and unrecrystallized conditions. Theoretical and actual forming limit data are presented for several gages of each type of material for five forming processes: brake forming, corrugation forming, joggling, dimpling and beading. Recrystallized sheet can be best formed at room temperature, but unrecrystallized sheet requires forming at elevated temperature. Formability is satisfactory with most processes for the longitudinal orientation but poor for the transverse orientation. Dimpling techniques require further development for both material conditions. Data on joining techniques and joint properties are presented for four joining processes: resistance seam welding (solid-state), resistance spot welding (solid-state), resistance spot welding (fusion) and brazing. Resistance seam welded (solid-state) joints with 5t overlap were stronger than parent material for both material conditions when tested in tensile-shear and stress-rupture. Brazing studies resulted in development of NASA 18 braze alloy (Ni-16Cr-15Mo-8Al-4Si) with several properties superior to baseline TD-6 braze alloy, including lower brazing temperture, reduced reaction with Td-Ni-Cr, and higher stress-rupture properties.

Properties of Poly- and Oligopentacenes Synthesized from Modular Building Blocks

DOE PAGES

Kumarasamy, Elango; Sanders, Samuel N.; Pun, Andrew B.; ...

2016-02-09

Here, we describe a facile route to well-defined, solution-processable pentacene oligomers (2 to 7) and homopolymer using Suzuki–Miyaura cross-coupling reactions. This synthetic strategy leads to regioisomers, regiopure syn- and anti-trimers were also synthesized, revealing minimal changes in solution properties but significant changes in the solid state arising from differing levels of crystallinity. The materials were characterized by steady state absorption spectroscopy and cyclic voltammetry to study their electronic structure. The steady state absorption spectra exhibit a new high-energy transition in the oligomers, which intensifies as a function of oligomer length, thus increasing the range of absorption to include the entiremore » visible spectrum. Density functional theory calculations indicate that the new peak results directly from the oligomerization. Solid state UV–vis suggests that while the monomer is amorphous, bricklayer packing in the higher oligomers significantly alters the solid state absorption relative to solution. The effect of oligomerization on packing was corroborated by GIWAXS analysis, which revealed crystalline domains in the oligomers. These domains, which are most evident in anti-trimer, become more pronounced upon thermal annealing. Photodegradation studies revealed considerable stability enhancement of oligomers toward oxygen and cycloaddition reactions relative to monomer. The synthesis and characterization of the first higher oligomers and homopolymer of pentacene should pave the way to applications in singlet fission, organic field-effect transistors, and organic photovoltaics.« less

Advantages of barium peroxide in the powder synthesis of perovskite superconductors

NASA Technical Reports Server (NTRS)

Hepp, A. F.; Gaier, J. R.; Philipp, W. H.; Warner, J. D.; Garlick, R. G.; Pouch, J. J.

1988-01-01

This paper compares reaction chemistry, material processing, and material characteristics for the solid state reaction using BaCO3 or BaO2 in the synthesis of perovskite superconductors. Results are presented for weight loss and X-ray diffraction, sample morphology and homogeneity as monitored by SEM and EDS, and the superconductivity critical temperature and ac susceptibility. Greater mass density, increased sample homogeneity, lower resistance, and improved reproducibility for material are found when BaO32 is used.

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

Rounaghi, S.A., E-mail: s.a.rounaghi@gmail.com; Kiani Rashid, A.R.; Eshghi, H., E-mail: heshghi@ferdowsi.um.ac.ir

Decomposition of melamine was studied by solid state reaction of melamine and aluminum powders during high energy ball-milling. The milling procedure performed for both pure melamine and melamine/Al mixed powders as the starting materials for various times up to 48 h under ambient atmosphere. The products were characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The results revealed that Al causes melamine deammoniation at the first stages of milling and further milling process leads to the s-triazine ring degradation while nano-crystallite hexagonal aluminum nitride (h-AlN) was the main solid product. Comparison to milling process, the possibility ofmore » the reaction of melamine with Al was also investigated by thermal treatment method using differential scanning calorimeter (DSC) and thermo gravimetric analyzer (TGA). Melamine decomposition occurred by thermal treatment in the range of 270-370 Degree-Sign C, but no reaction between melamine and aluminum was observed. - Graphical Abstract: Mechanochemical reaction of melamine with Al resulted in the formation of nanocrystalline AlN after 7 h milling time Highlights: Black-Right-Pointing-Pointer High energy ball milling of melamine and aluminum results decomposition of melamine with elimination of ammonia. Black-Right-Pointing-Pointer Nano-crystalline AlN was synthesized by the mechanochemical route. Black-Right-Pointing-Pointer Milling process has no conspicuous effect on pure melamine degradation. Black-Right-Pointing-Pointer No reaction takes place by heating melamine and aluminum powder mixture in argon.« less

Solid state laser media driven by remote nuclear powered fluorescence

DOEpatents

Prelas, Mark A.

1992-01-01

An apparatus is provided for driving a solid state laser by a nuclear powered fluorescence source which is located remote from the fluorescence source. A nuclear reaction produced in a reaction chamber generates fluorescence or photons. The photons are collected from the chamber into a waveguide, such as a fiber optic waveguide. The waveguide transports the photons to the remote laser for exciting the laser.

Friction Stir Welding of SiC/Aluminum Metal Matrix Composites

NASA Technical Reports Server (NTRS)

Lee, Jonathan A.

1999-01-01

Friction Stir Welding (FSW) is a new solid state process for joining metals by plasticizing and consolidating materials around the bond line using thermal energy producing from frictional forces. A feasibility study for FSW of Metal Matrix Composites (MMC) was investigated using aluminum 6092 alloy reinforced with 17% SiC particulates. FSW process consists of a special rotating pin tool that is positioned to plunge into the MMC surface at the bond line. As the tool rotates and move forward along the bond line, the material at the bond line is heated up and forced to flow around the rotating tip to consolidate on the tip's backside to form a solid state joint. FSW has the potential for producing sound welds with MMC because the processing temperature occurs well below the melting point of the metal matrix; thereby eliminating the reinforcement-to-matrix solidification defects, reducing the undesirable chemical reactions and porosity problems.

[Fundamentals of plasma chemistry and its application to drug engineering].

PubMed

Kuzuya, M

1996-04-01

In this review, our novel research works in both low temperature plasma chemistry and solid state plasma chemistry were described. As for low temperature plasma, the ESR study on plasma-induced radicals of several selected conventional polymers was shown including the detailed analyses of the radical structure and the mechanism by which the radicals were formed on typical degradable methacrylic polymers and cross-linkable polystyrene. One of the pharmaceutical applications of the plasma processing for drug delivery system (DDS) was also described, which includes the preparations of double-compressed tablet consisting of drugs as a core material and various types of polymers as a wall material followed by plasma-irradiation on such a tablet. As for solid state plasma, the detailed reaction mechanism of solid state mechanochemical polymerization was shown including the solid state single electron transfer and the special feature of the resulting polymers. The structural criteria for polymerizable monomer derived from the quantum chemical considerations were also established. Based on the above findings, we synthesized various polymeric prodrugs by mechanochemical polymerization and studied the nature of hydrolyses (drug release).

High calcination of ferroelectric BaTiO₃ doped Fe nanoceramics prepared by a solid-state sintering method.

PubMed

Samuvel, K; Ramachandran, K

2015-07-05

This study examined the effects of the combination of starting materials on the properties of solid-state reacted BaTiO3 using two different types of BaCO3 and TiO2. In addition, the effect of mechanochemical activation by high energy milling and the Ba/Ti molar ratio on the reaction temperature, particle size and tetragonality were investigated. The TiO2 phase and size plays a major role in increasing the reaction temperature and particle size. With the optimum selection of starting materials and processing conditions, BaTiO3 with a particle size <200 nm (Scherrer's formula) and a tetragonality c/a of approximately 1.007 was obtained. Broadband dielectric spectroscopy is applied to investigate the electrical properties of disordered perovskite-like ceramics in a wide temperature range. From the X-ray diffraction analysis it was found that the newly obtained BaTi0.5Fe0.5O3 ceramics consist of two chemically different phases. The electric modulus M∗ formalism used in the analysis enabled us to distinguish and separate the relaxation processes, dominated by marked conductivity in the ε∗(ω) representation. Interfacial effects on the dielectric properties of the samples have been understood by Cole-Cole plots in complex impedance and modulus formalism. Modulus formalism has identified the effects of both grain and grain boundary microstructure on the dielectric properties, particularly in solid state routed samples. Copyright © 2015 Elsevier B.V. All rights reserved.

High calcination of ferroelectric BaTiO3 doped Fe nanoceramics prepared by a solid-state sintering method

NASA Astrophysics Data System (ADS)

Samuvel, K.; Ramachandran, K.

2015-07-01

This study examined the effects of the combination of starting materials on the properties of solid-state reacted BaTiO3 using two different types of BaCO3 and TiO2. In addition, the effect of mechanochemical activation by high energy milling and the Ba/Ti molar ratio on the reaction temperature, particle size and tetragonality were investigated. The TiO2 phase and size plays a major role in increasing the reaction temperature and particle size. With the optimum selection of starting materials and processing conditions, BaTiO3 with a particle size <200 nm (Scherrer's formula) and a tetragonality c/a of approximately 1.007 was obtained. Broadband dielectric spectroscopy is applied to investigate the electrical properties of disordered perovskite-like ceramics in a wide temperature range. From the X-ray diffraction analysis it was found that the newly obtained BaTi0.5Fe0.5O3 ceramics consist of two chemically different phases. The electric modulus M∗ formalism used in the analysis enabled us to distinguish and separate the relaxation processes, dominated by marked conductivity in the ε∗(ω) representation. Interfacial effects on the dielectric properties of the samples have been understood by Cole-Cole plots in complex impedance and modulus formalism. Modulus formalism has identified the effects of both grain and grain boundary microstructure on the dielectric properties, particularly in solid state routed samples.

Evidence of a Nonphotochemical Mechanism for the Solid-State Formation of Uranyl Peroxide.

PubMed

Kirkegaard, Marie C; Miskowiec, Andrew; Ambrogio, Michael W; Anderson, Brian B

2018-05-21

We have demonstrated the solid-state formation of a uranyl peroxide (UP) species from hydrated uranyl fluoride via a uranyl hydroxide intermediate, the first observation of a UP species formed in a solid-state reaction. Water vapor pressure is shown to be a driving factor of both the loss of fluorine and the subsequent formation of peroxo units. We have ruled out a photochemical mechanism for formation of the UP species by demonstrating that the same reaction occurs in the dark. A radiolytic mechanism is unlikely because of the low radioactivity of the sample material, suggesting the existence of a novel UP formation mechanism.

Oxidation reactions of solid carbonaceous and resinous substances in supercritical water

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

Koda, S.

Recent kinetic studies, particularly those by means of shadowgraphy and X-ray radiography, for supercritical water oxidation of solid carbonaceous and resinous substances have revealed the importance of the O{sub 2} mass transfer process over the intrinsic surface reaction at higher temperatures. The mass transfer processes, internal and external one, should be incorporated in designing SCWO processes for solid substances and related processes such as catalytic SCWO. Some model calculation efforts of late are briefly described. Finally, fundamental information required for future development is itemed.

Solid-State Electrolyte Anchored with a Carboxylated Azo Compound for All-Solid-State Lithium Batteries.

PubMed

Luo, Chao; Ji, Xiao; Chen, Ji; Gaskell, Karen J; He, Xinzi; Liang, Yujia; Jiang, Jianjun; Wang, Chunsheng

2018-05-23

Organic electrode materials are promising for green and sustainable lithium-ion batteries. However, the high solubility of organic materials in the liquid electrolyte results in the shuttle reaction and fast capacity decay. Herein, azo compounds are firstly applied in all-solid-state lithium batteries (ASSLB) to suppress the dissolution challenge. Due to the high compatibility of azobenzene (AB) based compounds to Li 3 PS 4 (LPS) solid electrolyte, the LPS solid electrolyte is used to prevent the dissolution and shuttle reaction of AB. To maintain the low interface resistance during the large volume change upon cycling, a carboxylate group is added into AB to provide 4-(phenylazo) benzoic acid lithium salt (PBALS), which could bond with LPS solid electrolyte via the ionic bonding between oxygen in PBALS and lithium ion in LPS. The ionic bonding between the active material and solid electrolyte stabilizes the contact interface and enables the stable cycle life of PBALS in ASSLB. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formation of sodium bismuth titanate-barium titanate during solid-state synthesis

DOE PAGES

Hou, Dong; Aksel, Elena; Fancher, Chris M.; ...

2017-01-12

Phase formation of sodium bismuth titanate (Na 0.5Bi 0.5TiO 3 or NBT) and its solid solution with barium titanate (BaTiO 3 or BT) during the calcination process is studied using in situ high-temperature diffraction. The reactant powders were mixed and heated to 1000°C, while X-ray diffraction patterns were recorded continuously. Phase evolutions from starting materials to final perovskite products are observed, and different transient phases are identified. The formation mechanism of NBT and NBT–xBT perovskite structures is discussed, and a reaction sequence is suggested based on the observations. The in situ study leads to a new processing approach, which ismore » the use of nano-TiO 2, and gives insights to the particle size effect for solid-state synthesis products. Lastly, it was found that the use of nano-TiO 2 as reactant powder accelerates the synthesis process, decreases the formation of transient phases, and helps to obtain phase-pure products using a lower thermal budget.« less

Moving bed reactor setup to study complex gas-solid reactions.

PubMed

Gupta, Puneet; Velazquez-Vargas, Luis G; Valentine, Charles; Fan, Liang-Shih

2007-08-01

A moving bed scale reactor setup for studying complex gas-solid reactions has been designed in order to obtain kinetic data for scale-up purpose. In this bench scale reactor setup, gas and solid reactants can be contacted in a cocurrent and countercurrent manner at high temperatures. Gas and solid sampling can be performed through the reactor bed with their composition profiles determined at steady state. The reactor setup can be used to evaluate and corroborate model parameters accounting for intrinsic reaction rates in both simple and complex gas-solid reaction systems. The moving bed design allows experimentation over a variety of gas and solid compositions in a single experiment unlike differential bed reactors where the gas composition is usually fixed. The data obtained from the reactor can also be used for direct scale-up of designs for moving bed reactors.

Solid-state reduction of iron in olivine-planetary and meteoritic evolution.

PubMed

Boland, J N; Duba, A

1981-11-12

Iron-nickel metallic particles have been reported in meteorites 1 and lunar 2-5 and terrestrial 6,7 rocks. The origin of these metallic particles is not unique as they may be formed by (1) condensation from a primordial solar nebula 8 ; (2) crystallization from a melt; and (3) subsolidus reduction reactions under low oxygen or sulphur fugacity. We report here an electron microscopy study of the solid-state microstructural development in olivine single crystals (Fo 92 ) in which half of the iron has been reduced to the metallic state by a gas-solid interaction in the temperature range 950-1,500 °C. The reaction, Fo 92 →Fo 96 +metallic Fe(Ni in solid solution)+pyroxene, begins with a homogeneous transformation involving fine-scale metallic precipitates resembling Guinier-Preston zones 9 . The microstructure develops by the growth of the first-formed precipitates during an Ostwald ripening process 9 in which the precipitates located in the dislocation sub-boundaries develop in preference to precipitates in the subgrains. On the other hand, pyroxene is first observed to nucleate heterogeneously at pre-existing dislocations and its coarsening rate is more than an order-of-magnitude faster than that of the metallic phase. Besides the textural similarity of the observed microstructures with that reported for some of the lunar materials 2 , these results have important implications for the physical models of accretion of terrestrial planets, planetesimals and meteorites 10 , especially with respect to the distribution of siderophile elements. The rate of reaction observed here places constraints on models for the formation of the Earth's core by segregation of a metallic phase with or without reduction.

Formation of doubly and triply bonded unsaturated compounds HCN, HNC, and CH2NH via N + CH4 low-temperature solid state reaction: from molecular clouds to solar system objects

NASA Astrophysics Data System (ADS)

Mencos, Alejandro; Krim, Lahouari

2018-06-01

We show in the current study carried out in solid phase at cryogenic temperatures that methane (CH4) ice exposed to nitrogen atoms is a source of two acids HCN, HNC, and their corresponding hydrogenated unsaturated species CH2NH, in addition to CH3, C2H6, CN-, and three nitrogen hydrides NH, NH2, and NH3. The solid state N + CH4 reaction taken in the ground state seems to be strongly temperature dependent. While at temperatures lower than 10 K only CH3, NH, NH2, and NH3 species formation is promoted due to CH bond dissociation and NH bond formation, stable compounds with CN bonds are formed at temperatures ranged between 10 and 40 K. Many of these reaction products, resulting from CH4 + N reaction, have already been observed in N2-rich regions such as the atmospheres of Titan, Kuiper belt objects, and molecular clouds of the interstellar medium. Our results show the power of the solid state N-atom chemistry in the transformation of simple astrochemical relevant species, such as CH4 molecules and N atoms into complex organic molecules which are also potentially prebiotic species.

Prebiotic significance of the Maillard reaction

NASA Astrophysics Data System (ADS)

Kolb, Vera M.; Bajagic, Milica; Zhu, William; Cody, George D.

2005-09-01

The Maillard reaction was studied from a prebiotic point of view. We have shown that the Maillard reaction between ribose and common amino acids occurs readily in the solid state at 65°C. The C-13 NMR spectra of the solid insoluble Maillard products of ribose and serine, or alanine or isoleucine were compared to the spectrum of the insoluble organic carbon on Murchison.

Rydberg phases of Hydrogen and low energy nuclear reactions

NASA Astrophysics Data System (ADS)

Olafsson, Sveinn; Holmlid, Leif

2016-03-01

For over the last 26 years the science of cold fusion/LENR has been researched around the world with slow pace of progress. Modest quantity of excess heat and signatures of nuclear transmutation and helium production have been confirmed in experiments and theoretical work has only resulted in a large flora of inadequate theoretical scenarios. Here we review current state of research in Rydberg matter of Hydrogen that is showing strong signature of nuclear processes. In the presentation experimental behavior of Rydberg matter of hydrogen is described. An extensive collaboration effort of surface physics, catalysis, atomic physics, solid state physics, nuclear physics and quantum information is need to tackle the surprising experimental results that have so far been obtained. Rydberg matter of Hydrogen is the only known state of matter that is able to bring huge collection of protons to so short distances and for so long time that tunneling becomes a reasonable process for making low energy nuclear reactions. Nuclear quantum entanglement can also become realistic process at theses conditions.

Using liquid and solid state NMR and photoluminescence to study the synthesis and solubility properties of amine capped silicon nanoparticles.

PubMed

Giuliani, J R; Harley, S J; Carter, R S; Power, P P; Augustine, M P

2007-08-01

Water soluble silicon nanoparticles were prepared by the reaction of bromine terminated silicon nanoparticles with 3-(dimethylamino)propyl lithium and characterized with liquid and solid state nuclear magnetic resonance (NMR) and photoluminescence (PL) spectroscopies. The surface site dependent 29Si chemical shifts and the nuclear spin relaxation rates from an assortment of 1H-29Si heteronuclear solid state NMR experiments for the amine coated reaction product are consistent with both the 1H and 13C liquid state NMR results and routine transmission electron microscopy, ultra-violet/visible, and Fourier transform infrared measurements. PL was used to demonstrate the pH dependent solubility properties of the amine passivated silicon nanoparticles.

Surface studies relevant to silicon carbide chemical vapor deposition

NASA Technical Reports Server (NTRS)

Stinespring, C. D.; Wormhoudt, J. C.

1989-01-01

Reactions of C2H4, C3H8, and CH4 on the Si(111) surface and C2H4 on the Si(100) surface were investigated for surface temperatures in the range of 1062-1495 K. Results led to the identification of the reaction products, a characterization of the solid-state transport process, a determination of the nucleation mechanism and growth kinetics, and an assessment of orientation effects. Based on these results and on the modeling studies of Stinespring and Wormhoudt (1988) on the associated gas phase chemistry, a physical model for the two-step beta-SiC CVD process is proposed.

In Situ Imaging the Oxygen Reduction Reactions of Solid State Na-O2 Batteries with CuO Nanowires as the Air Cathode.

PubMed

Liu, Qiunan; Yang, Tingting; Du, Congcong; Tang, Yongfu; Sun, Yong; Jia, Peng; Chen, Jingzhao; Ye, Hongjun; Shen, Tongde; Peng, Qiuming; Zhang, Liqiang; Huang, Jianyu

2018-06-13

We report real time imaging of the oxygen reduction reactions (ORRs) in all solid state sodium oxygen batteries (SOBs) with CuO nanowires (NWs) as the air cathode in an aberration-corrected environmental transmission electron microscope under an oxygen environment. The ORR occurred in a distinct two-step reaction, namely, a first conversion reaction followed by a second multiple ORR. In the former, CuO was first converted to Cu 2 O and then to Cu; in the latter, NaO 2 formed first, followed by its disproportionation to Na 2 O 2 and O 2 . Concurrent with the two distinct electrochemical reactions, the CuO NWs experienced multiple consecutive large volume expansions. It is evident that the freshly formed ultrafine-grained Cu in the conversion reaction catalyzed the latter one-electron-transfer ORR, leading to the formation of NaO 2 . Remarkably, no carbonate formation was detected in the oxygen cathode after cycling due to the absence of carbon source in the whole battery setup. These results provide fundamental understanding into the oxygen chemistry in the carbonless air cathode in all solid state Na-O 2 batteries.

Proton conducting ceramics in membrane separations

DOEpatents

Brinkman, Kyle S; Korinko, Paul S; Fox, Elise B; Chen, Frank

2015-04-14

Perovskite materials of the general formula SrCeO.sub.3 and BaCeO.sub.3 are provided having improved conductivity while maintaining an original ratio of chemical constituents, by altering the microstructure of the material. A process of making Pervoskite materials is also provided in which wet chemical techniques are used to fabricate nanocrystalline ceramic materials which have improved grain size and allow lower temperature densification than is obtainable with conventional solid-state reaction processing.

Revealing the reaction mechanisms of Li–O2 batteries using environmental transmission electron microscopy

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

Luo, Langli; Liu, Bin; Song, Shidong

The capacity, Coulombic efficiency, rate, and cyclability of a Li-O2 battery critically depend on the electrode reaction mechanism and the structure/morphology of the reaction product as well as their spatial and temporal evolution1-8, which are all further complicated by the choice of different electrolyte. For the case of aprotic cell, the discharge product, Li2O2, is formed through solution and surface mechanisms9,10, but little is known on the formation mechanism of the perplexing morphology of the reaction product11-15. For the case of Li-O2 battery using solid electrolyte, neither electrode reaction mechanism nor the nature of the reaction production is known. Herein,more » we reveal the full cycle reaction pathway for Li-O2 batteries and its correlation with the nature of the reaction product. Using an aberration-corrected environmental TEM under oxygen environment, we captured, for the first time, the morphology and phase evolution on the carbon nanotube (CNT) cathode of a working solid-state Li-O2 nano-battery16 and directly correlated these features with electrochemical reaction. We found that the oxygen reduction reaction on CNTs initially produces LiO2, which subsequently evolves to Li2O2 and O2 through disproportionation reaction. Surprisingly it is just the releasing of O2 that inflates the particles to a hollow structure with a Li2O outer surface layer and Li2O2 inner-shell, demonstrating that, in general, accommodation of the released O2 coupled with the Li+ ion diffusion and electron transport paths across both spatial and temporal scales critically governs the morphology of the discharging/charging product in Li-O2 system. We anticipate that the direct observation of Li-O2 reaction mechanisms and their correlation with the morphology of the reaction product set foundation for quantitative understanding/modeling of the electrochemical processes in the Li-O2 system, enabling rational design of both solid-state and aprotic Li-O2 batteries.« less

The use of solid-state reactions with volume loss to engineer stress and porosity into the fiber-matrix interface of a ceramic composite

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

Hay, R.S.

The effect of the 11 vol% losing during reaction of yttrium-aluminas garnet (YAG) and zirconia was observed in zirconia coated single-crystal alumina fiber-YAG matrix composites. The reaction caused plastic deformation in the alumina fibers, and possibly a minor amount of porosity at fiber-matrix interfaces that was usually indistinguishable from matrix porosity. The results were analyzed by models for diffusive cavitation modified to use reaction self-stress. Crack-healing, tensile stress states along the reaction front that approach plane stress, and the small volume of self-stressed material make crack-like pores unlikely at the high temperatures required for reaction. Smaller matrix grains might promotemore » formation of smaller cavities but are also incompatible with high temperature. Both modeling and experiment suggest that sufficient porosity for crack deflection and fiber pullout cannot form unless processing methods that form dense composites at lower temperatures are used.« less

A method for phenomenological and chemical kinetics study of autocatalytic reactive dissolution by optical microscopy. The case of uranium dioxide dissolution in nitric acid media

NASA Astrophysics Data System (ADS)

Marc, Philippe; Magnaldo, Alastair; Godard, Jérémy; Schaer, Éric

2018-03-01

Dissolution is a milestone of the head-end of hydrometallurgical processes, as the stabilization rates of the chemical elements determine the process performance and hold-up. This study aims at better understanding the chemical and physico-chemical phenomena of uranium dioxide dissolution reactions in nitric acid media in the Purex process, which separates the reusable materials and the final wastes of the spent nuclear fuels. It has been documented that the attack of sintering-manufactured uranium dioxide solids occurs through preferential attack sites, which leads to the development of cracks in the solids. Optical microscopy observations show that in some cases, the development of these cracks leads to the solid cleavage. It is shown here that the dissolution of the detached fragments is much slower than the process of the complete cleavage of the solid, and occurs with no disturbing phenomena, like gas bubbling. This fact has motivated the measurement of dissolution kinetics using optical microscopy and image processing. By further discriminating between external resistance and chemical reaction, the "true" chemical kinetics of the reaction have been measured, and the highly autocatalytic nature of the reaction confirmed. Based on these results, the constants of the chemical reactions kinetic laws have also been evaluated.

Ambient Mechanochemical Solid-State Reactions of Carbon Nanotubes and Their Reactions via Covalent Coordinate Bond in Solution

NASA Astrophysics Data System (ADS)

Kabbani, Mohamad A.

In its first part, this thesis deals with ambient mechanochemical solid-state reactions of differently functionalized multiple walled carbon nanotubes (MWCNTs) while in its second part it investigates the cross-linking reactions of CNTs in solution via covalent coordinate bonds with transitions metals and carboxylate groups decorating their surfaces. In the first part a series of mechanochemical reactions involving different reactive functionalities on the CNTs such as COOH/OH, COOH/NH2 and COCl/OH were performed. The solid-state unzipping of CNTs leading to graphene formation was confirmed using spectroscopic, thermal and electron microscopy techniques. The non-grapheme products were established using in-situ quadruple mass spectroscopy. The experimental results were confirmed by theoretical simulation calculations using the 'hot spots' protocol. The kinetics of the reaction between MWCNT-COOH and MWCNT-OH was monitored using variable temperature Raman spectroscopy. The low activation energy was discussed in terms of hydrogen bond mediated proton transfer mechanism. The second part involves the reaction of MWCNTII COOH with Zn (II) and Cu (II) to form CNT metal-organic frame (MOFs) products that were tested for their effective use as counter-electrodes in dyes sensitized solar cells (DSSC). The thesis concludes by the study of the room temperature reaction between the functionalized graphenes, GOH and G'-COOH followed by the application of compressive loads. The 3D solid graphene pellet product ( 0.6gm/cc) is conductive and reflective with a 35MPa ultimate strength as compared to 10MPa strength of graphite electrode ( 2.2gm/cc).

Evidence of a Nonphotochemical Mechanism for the Solid-State Formation of Uranyl Peroxide

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

Kirkegaard, Marie C.; Miskowiec, Andrew J.; Ambrogio, Michael W.

Here, we have demonstrated the solid-state formation of a uranyl peroxide (UP) species from hydrated uranyl fluoride via a uranyl hydroxide intermediate, the first observation of a UP species formed in a solid-state reaction. Water vapor pressure is shown to be a driving factor of both the loss of fluorine and the subsequent formation of peroxo units. We have ruled out a photochemical mechanism for formation of the UP species by demonstrating that the same reaction occurs in the dark. A radiolytic mechanism is unlikely because of the low radioactivity of the sample material, suggesting the existence of a novelmore » UP formation mechanism.« less

Evidence of a Nonphotochemical Mechanism for the Solid-State Formation of Uranyl Peroxide

DOE PAGES

Kirkegaard, Marie C.; Miskowiec, Andrew J.; Ambrogio, Michael W.; ...

2018-05-10

Here, we have demonstrated the solid-state formation of a uranyl peroxide (UP) species from hydrated uranyl fluoride via a uranyl hydroxide intermediate, the first observation of a UP species formed in a solid-state reaction. Water vapor pressure is shown to be a driving factor of both the loss of fluorine and the subsequent formation of peroxo units. We have ruled out a photochemical mechanism for formation of the UP species by demonstrating that the same reaction occurs in the dark. A radiolytic mechanism is unlikely because of the low radioactivity of the sample material, suggesting the existence of a novelmore » UP formation mechanism.« less

Coal liquefaction quenching process

DOEpatents

Thorogood, Robert M.; Yeh, Chung-Liang; Donath, Ernest E.

1983-01-01

There is described an improved coal liquefaction quenching process which prevents the formation of coke with a minimum reduction of thermal efficiency of the coal liquefaction process. In the process, the rapid cooling of the liquid/solid products of the coal liquefaction reaction is performed without the cooling of the associated vapor stream to thereby prevent formation of coke and the occurrence of retrograde reactions. The rapid cooling is achieved by recycling a subcooled portion of the liquid/solid mixture to the lower section of a phase separator that separates the vapor from the liquid/solid products leaving the coal reactor.

Solid-State Explosive Reaction for Nanoporous Bulk Thermoelectric Materials.

PubMed

Zhao, Kunpeng; Duan, Haozhi; Raghavendra, Nunna; Qiu, Pengfei; Zeng, Yi; Zhang, Wenqing; Yang, Jihui; Shi, Xun; Chen, Lidong

2017-11-01

High-performance thermoelectric materials require ultralow lattice thermal conductivity typically through either shortening the phonon mean free path or reducing the specific heat. Beyond these two approaches, a new unique, simple, yet ultrafast solid-state explosive reaction is proposed to fabricate nanoporous bulk thermoelectric materials with well-controlled pore sizes and distributions to suppress thermal conductivity. By investigating a wide variety of functional materials, general criteria for solid-state explosive reactions are built upon both thermodynamics and kinetics, and then successfully used to tailor material's microstructures and porosity. A drastic decrease in lattice thermal conductivity down below the minimum value of the fully densified materials and enhancement in thermoelectric figure of merit are achieved in porous bulk materials. This work demonstrates that controlling materials' porosity is a very effective strategy and is easy to be combined with other approaches for optimizing thermoelectric performance. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid-State Reaction Between Fe-Al-Ca Alloy and Al2O3-CaO-FeO Oxide During Heat Treatment at 1473 K (1200 °C)

NASA Astrophysics Data System (ADS)

Liu, Chengsong; Yang, Shufeng; Li, Jingshe; Ni, Hongwei; Zhang, Xueliang

2017-04-01

The aim of this study was to control the physicochemical characteristics of inclusions in steel through appropriate heat treatment. Using a confocal scanning laser microscope (CSLM) and pipe furnace, the solid-state reactions between Fe-Al-Ca alloy and Al2O3-CaO-FeO oxide during heat treatment at 1473 K (1200 °C) and the influence of these reactions on the compositions of and phases in the alloy and oxide were investigated by the diffusion couple method. Suitable pretreatment of the oxide using a CSLM and production of the diffusion couple of Fe-Al-Ca alloy and Al2O3-CaO-FeO oxide gave good contact between the alloy and oxide. The diffusion couple was then sealed in a quartz tube with a piece of Ti foil to lower oxygen partial pressure and a block of Fe-Al-Ca alloy was introduced to conduct heat treatment experiments. Solid-state reactions between the alloy and oxide during heat treatment at 1473 K (1200 °C) were analyzed and discussed. A dynamic model to calculate the width of the particle precipitation zone based on the Wagner model of internal oxidation of metal was proposed. This model was helpful to understand the solid-state reaction mechanism between Fe-Al-Ca alloy and Al2O3-CaO-FeO oxide.

Physico-Geometrical Kinetics of Solid-State Reactions in an Undergraduate Thermal Analysis Laboratory

ERIC Educational Resources Information Center

Koga, Nobuyoshi; Goshi, Yuri; Yoshikawa, Masahiro; Tatsuoka, Tomoyuki

2014-01-01

An undergraduate kinetic experiment of the thermal decomposition of solids by microscopic observation and thermal analysis was developed by investigating a suitable reaction, applicable techniques of thermal analysis and microscopic observation, and a reliable kinetic calculation method. The thermal decomposition of sodium hydrogen carbonate is…

A solid-state pH sensor for nonaqueous media including ionic liquids.

PubMed

Thompson, Brianna C; Winther-Jensen, Orawan; Winther-Jensen, Bjorn; MacFarlane, Douglas R

2013-04-02

We describe a solid state electrode structure based on a biologically derived proton-active redox center, riboflavin (RFN). The redox reaction of RFN is a pH-dependent process that requires no water. The electrode was fabricated using our previously described 'stuffing' method to entrap RFN into vapor phase polymerized poly(3,4-ethylenedioxythiophene). The electrode is shown to be capable of measuring the proton activity in the form of an effective pH over a range of different water contents including nonaqueous systems and ionic liquids (ILs). This demonstrates that the entrapment of the redox center facilitates direct electron communication with the polymer. This work provides a miniaturizable system to determine pH (effective) in nonaqueous systems as well as in ionic liquids. The ability to measure pH (effective) is an important step toward the ability to customize ILs with suitable pH (effective) for catalytic reactions and biotechnology applications such as protein preservation.

Solid-state stability studies of 13-cis-retinoic acid and all-trans-retinoic acid using microcalorimetry and HPLC analysis.

PubMed

Tan, X; Meltzer, N; Lindebaum, S

1992-09-01

The solid-state stabilities of 13-cis-retinoic acid and all-trans-retinoic acid in the presence and absence of oxygen were investigated. The samples were first evaluated using microcalorimetry. The rate laws of different samples under different conditions were deduced from the shapes of the heat flow curves, and the activation energies of the reactions were determined from Arrhenius plots. Under an air atmosphere, the decomposition of 13-cis-retinoic acid is an autocatalytic reaction, while all-trans-retinoic acid undergoes a zero-order process. The degradation of the two compounds at a selected elevated temperature was also determined utilizing HPLC analysis. This technique confirmed the decomposition kinetics. Hence, their half-lives and shelf lives at room temperature could be calculated. Under a nitrogen atmosphere, the microcalorimetric experiment showed a first-order phenomenon for both samples, but HPLC analysis showed no degradation, suggesting that the two samples, in the absence of oxygen, undergo only a physical change.

Substrate milling pretreatment as a key parameter for Solid-State Anaerobic Digestion optimization.

PubMed

Motte, J-C; Escudié, R; Hamelin, J; Steyer, J-P; Bernet, N; Delgenes, J-P; Dumas, C

2014-12-01

The effect of milling pretreatment on performances of Solid-State Anaerobic Digestion (SS-AD) of raw lignocellulosic residue is still controverted. Three batch reactors treating different straw particle sizes (milled 0.25 mm, 1 mm and 10 mm) were followed during 62 days (6 sampling dates). Although a fine milling improves substrate accessibility and conversion rate (up to 30% compared to coarse milling), it also increases the risk of media acidification because of rapid and high acids production during fermentation of the substrate soluble fraction. Meanwhile, a gradual adaptation of microbial communities, were observed according to both reaction progress and methanogenic performances. The study concluded that particle size reduction affected strongly the performances of the reaction due to an increase of substrate bioaccessibility. An optimization of SS-AD processes thanks to particle size reduction could therefore be applied at farm or industrial scale only if a specific management of the soluble compounds is established. Copyright © 2014 Elsevier Ltd. All rights reserved.

An environmentally friendly ball milling process for recovery of valuable metals from e-waste scraps.

PubMed

Zhang, Zhi-Yuan; Zhang, Fu-Shen; Yao, TianQi

2017-10-01

The present study reports a mechanochemical (MC) process for effective recovery of copper (Cu) and precious metals (i.e. Pd and Ag) from e-waste scraps. Results indicated that the mixture of K 2 S 2 O 8 and NaCl (abbreviated as K 2 S 2 O 8 /NaCl hereafter) was the most effective co-milling reagents in terms of high recovery rate. After co-milling with K 2 S 2 O 8 /NaCl, soluble metallic compounds were produced and consequently benefit the subsequent leaching process. 99.9% of Cu and 95.5% of Pd in the e-waste particles could be recovered in 0.5mol/L diluted HCl in 15min. Ag was concentrated in the leaching residue as AgCl and then recovered in 1mol/L NH 3 solution. XRD and XPS analysis indicated that elemental metals in the raw materials were transformed into their corresponding oxidation state during ball milling process at low temperature, implying that solid-solid phase reactions is the reaction mechanism. Based on the results and thermodynamic parameters of the probable reactions, possible reaction pathways during ball milling were proposed. Suggestion on category of e-waste for ball milling process was put forward according to the experiment results. The designed metal recovery process of this study has the advantages of highly recovery rate and quick leaching speed. Thus, this study offers a promising and environmentally friendly method for recovering valuable metals from e-waste. Copyright © 2017 Elsevier Ltd. All rights reserved.

Synthesis of Ti3AuC2, Ti3Au2C2 and Ti3IrC2 by noble metal substitution reaction in Ti3SiC2 for high-temperature-stable Ohmic contacts to SiC

NASA Astrophysics Data System (ADS)

Fashandi, Hossein; Dahlqvist, Martin; Lu, Jun; Palisaitis, Justinas; Simak, Sergei I.; Abrikosov, Igor A.; Rosen, Johanna; Hultman, Lars; Andersson, Mike; Lloyd Spetz, Anita; Eklund, Per

2017-08-01

The large class of layered ceramics encompasses both van der Waals (vdW) and non-vdW solids. While intercalation of noble metals in vdW solids is known, formation of compounds by incorporation of noble-metal layers in non-vdW layered solids is largely unexplored. Here, we show formation of Ti3AuC2 and Ti3Au2C2 phases with up to 31% lattice swelling by a substitutional solid-state reaction of Au into Ti3SiC2 single-crystal thin films with simultaneous out-diffusion of Si. Ti3IrC2 is subsequently produced by a substitution reaction of Ir for Au in Ti3Au2C2. These phases form Ohmic electrical contacts to SiC and remain stable after 1,000 h of ageing at 600 °C in air. The present results, by combined analytical electron microscopy and ab initio calculations, open avenues for processing of noble-metal-containing layered ceramics that have not been synthesized from elemental sources, along with tunable properties such as stable electrical contacts for high-temperature power electronics or gas sensors.

Optimization of processing parameters on the controlled growth of ZnO nanorod arrays for the performance improvement of solid-state dye-sensitized solar cells

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

Lee, Yi-Mu, E-mail: ymlee@nuu.edu.t; Yang, Hsi-Wen

2011-03-15

High-transparency and high quality ZnO nanorod arrays were grown on the ITO substrates by a two-step chemical bath deposition (CBD) method. The effects of processing parameters including reaction temperature (25-95 {sup o}C) and solution concentration (0.01-0.1 M) on the crystal growth, alignment, optical and electrical properties were systematically investigated. It has been found that these process parameters are critical for the growth, orientation and aspect ratio of the nanorod arrays, showing different structural and optical properties. Experimental results reveal that the hexagonal ZnO nanorod arrays prepared under reaction temperature of 95 {sup o}C and solution concentration of 0.03 M possessmore » highest aspect ratio of {approx}21, and show the well-aligned orientation and optimum optical properties. Moreover the ZnO nanorod arrays based heterojunction electrodes and the solid-state dye-sensitized solar cells (SS-DSSCs) were fabricated with an improved optoelectrical performance. -- Graphical abstract: The ZnO nanorod arrays demonstrate well-alignment, high aspect ratio (L/D{approx}21) and excellent optical transmittance by low-temperature chemical bath deposition (CBD). Display Omitted Research highlights: > Investigate the processing parameters of CBD on the growth of ZnO nanorod arrays. > Optimization of CBD process parameters: 0.03 M solution concentration and reaction temperature of 95 {sup o}C. > The prepared ZnO samples possess well-alignment and high aspect ratio (L/D{approx}21). > An n-ZnO/p-NiO heterojunction: great rectifying behavior and low leakage current. > SS-DSSC has J{sub SC} of 0.31 mA/cm{sup 2} and V{sub OC} of 590 mV, and an improved {eta} of 0.059%.« less

Method for producing synthetic fuels from solid waste

DOEpatents

Antal, Jr., Michael J.

1976-11-23

Organic solid wastes represented by the general chemical formula C.sub.X H.sub.Y O.sub.Z are reacted with steam at elevated temperatures to produce H.sub.2 and CO.sub.2. The overall process is represented by the reaction C.sub.X H.sub.Y O.sub.Z + 2(X-Z/2)H.sub.2 O.fwdarw..sup..delta.XCO.sub.2 + [(Y/2) + 2(X-Z/2)] H.sub.2 . (1) reaction (1) is endothermic and requires heat. This heat is supplied by a tower top solar furnace; alternatively, some of the solid wastes can be burned to supply heat for the reaction. The hydrogen produced by reaction (1) can be used as a fuel or a chemical feedstock. Alternatively, methanol can be produced by the commercial process CO.sub.2 + 3H.sub.2 .fwdarw. CH.sub.3 OH + H.sub.2 O . (2) since reaction (1) is endothermic, the system represents a method for storing heat energy from an external source in a chemical fuel produced from solid wastes.

Rapid thermal processing for production of chalcopyrite thin films for solar cells: Design, analysis, and experimental implementation

NASA Astrophysics Data System (ADS)

Lovelett, Robert J.

The direct conversion of solar energy to electricity, or photovoltaic energy conversion, has a number of environmental, social, and economic advantages over conventional electricity generation from fossil fuels. Currently, the most commonly-used material for photovoltaics is crystalline silicon, which is now produced at large scale and silicon-based devices have achieved power conversion efficiencies over 25% However, alternative materials, such as inorganic thin films, offer a number of advantages including the potential for lower manufacturing costs, higher theoretical efficiencies, and better performance in the field. One of these materials is the chalcopyrite Cu(InGa)(SeS) 2, which has demonstrated module efficiencies over 17% and cell efficiencies over 22%. Cu(InGa)(SeS)2 is now in the early stages of commercialization using a precursor reaction process referred to as a "selenization/sulfization" reaction. The precursor reaction process is promising because it has demonstrated high efficiency along with the large area (approximately 1 m2) uniformity that is required for modules. However, some challenges remain that limit the growth of the chalcopyrite solar cell industry including: slow reactions that limit process throughput, a limited understanding of complex reaction kinetics and transport phenomena that affect the through-film composition, and the use of highly toxic H2Se in the reaction process. In this work, I approach each of these challenges. First, to improve process throughput, I designed and implemented a rapid thermal processing (RTP) reactor, whereby the samples are heated by a 1000 W quartz-halogen lamp that is capable of fast temperature ramps and high temperature dwells. With the reactor in place, however, achieving effective temperature control in the thin film material system is complicated by two intrinsic process characteristics: (i) the temperature of the Cu(InGa)(SeS)2 film cannot be measured directly, which leaves the system without complete state feedback; and (ii), the process is significantly nonlinear due to the dominance of radiative heat transfer at high temperatures. Therefore, I developed a novel control system using a first principles-based observer and a specialized temperature controller. Next, to understand the complex kinetics governing the selenization/sulfization processes, a stochastic model of solid state reaction kinetics was developed and applied to the system. The model is capable of predicting several important phenomena observed experimentally, including steep through-film gradients in gallium mole fraction. Furthermore, the model is mathematically general and can be useful for understanding a number of solid state reaction systems. Finally, the RTP system was then used to produce and characterize chalcopyrite films using two general methods: (i) single stage and multi stage reactions in H2Se and H2S, and (ii), reaction of a selenium "capped" precursor in H2S, where selenium was deposited on the precursor by thermal evaporation and the use of toxic H2Se was avoided. It was found that the processing conditions could be used to control material properties including relative sulfur incorporation, crystallinity, and through-film gallium and sulfur profiles. Films produced using the selenium-capped precursor reaction process were used to fabricate solar cell devices using a Mo/Cu(InGa)(SeS)2/CdS/ZnO/ITO substrate device structure, and the devices were tested by measuring the current-voltage characteristic under standard conditions. Devices with approximately 10% efficiency were obtained over a range of compositions and the best device obtained in this work had an efficiency of 12.7%.

Titration of a Solid Acid Monitored by X-Ray Diffraction

ERIC Educational Resources Information Center

Dungey, Keenan E.; Epstein, Paul

2007-01-01

An experiment is described to introduce students to an important class of solid-state reactions while reinforcing concepts of titration by using a pH meter and a powder X-ray diffractometer. The experiment was successful in teaching students the abstract concepts of solid-state structure and diffraction by applying the diffraction concepts learned…

Semiempirical equations for modeling solid-state kinetics based on a Maxwell-Boltzmann distribution of activation energies: applications to a polymorphic transformation under crystallization slurry conditions and to the thermal decomposition of AgMnO4 crystals.

PubMed

Skrdla, Peter J; Robertson, Rebecca T

2005-06-02

Many solid-state reactions and phase transformations performed under isothermal conditions give rise to asymmetric, sigmoidally shaped conversion-time (x-t) profiles. The mathematical treatment of such curves, as well as their physical interpretation, is often challenging. In this work, the functional form of a Maxwell-Boltzmann (M-B) distribution is used to describe the distribution of activation energies for the reagent solids, which, when coupled with an integrated first-order rate expression, yields a novel semiempirical equation that may offer better success in the modeling of solid-state kinetics. In this approach, the Arrhenius equation is used to relate the distribution of activation energies to a corresponding distribution of rate constants for the individual molecules in the reagent solids. This distribution of molecular rate constants is then correlated to the (observable) reaction time in the derivation of the model equation. In addition to providing a versatile treatment for asymmetric, sigmoidal reaction curves, another key advantage of our equation over other models is that the start time of conversion is uniquely defined at t = 0. We demonstrate the ability of our simple, two-parameter equation to successfully model the experimental x-t data for the polymorphic transformation of a pharmaceutical compound under crystallization slurry (i.e., heterogeneous) conditions. Additionally, we use a modification of this equation to model the kinetics of a historically significant, homogeneous solid-state reaction: the thermal decomposition of AgMnO4 crystals. The potential broad applicability of our statistical (i.e., dispersive) kinetic approach makes it a potentially attractive alternative to existing models/approaches.

Thermodynamic interpretation of reactive processes in Ni-Al nanolayers from atomistic simulations

NASA Astrophysics Data System (ADS)

Sandoval, Luis; Campbell, Geoffrey H.; Marian, Jaime

2014-03-01

Metals that can form intermetallic compounds by exothermic reactions constitute a class of reactive materials with multiple applications. Ni-Al laminates of thin alternating layers are being considered as model nanometric metallic multilayers for studying various reaction processes. However, the reaction kinetics at short timescales after mixing are not entirely understood. In this work, we calculate the free energies of Ni-Al alloys as a function of composition and temperature for different solid phases using thermodynamic integration based on state-of-the-art interatomic potentials. We use this information to interpret molecular dynamics (MD) simulations of bilayer systems at 800 K and zero pressure, both in isothermal and isenthalpic conditions. We find that a disordered phase always forms upon mixing as a precursor to a more stable nano crystalline B2 phase. We construe the reactions observed in terms of thermodynamic trajectories governed by the state variables computed. Simulated times of up to 30 ns were achieved, which provides a window to phenomena not previously observed in MD simulations. Our results provide insight into the early experimental reaction timescales and suggest that the path (segregated reactants) → (disordered phase) → (B2 structure) is always realized irrespective of the imposed boundary conditions.

The Synthesis of LiMnxFe1−xPO4/C Cathode Material through Solvothermal Jointed with Solid-State Reaction

PubMed Central

He, Xiangming; Wang, Jixian; Dai, Zhongjia; Wang, Li; Tian, Guangyu

2016-01-01

LiMnxFe1−xPO4/C material has been synthesized through a facile solid-state reaction under the condition of carbon coating, using solvothermal-prepared LiMnPO4 and LiFePO4 as precursors and sucrose as a carbon resource. XRD and element distribution analysis reveal completed solid-state reaction of precursors. LiMnxFe1−xPO4/C composites inherit the morphology of precursors after heat treatment without obvious agglomeration and size increase. LiMnxFe1−xPO4 solid solution forms at low temperature around 350 °C, and Mn2+/Fe2+ diffuse completely within 1 h at 650 °C. The LiMnxFe1−xPO4/C (x < 0.8) composite exhibits a high-discharge capacity of over 120 mAh·g−1 (500 Wh·kg−1) at low C-rates. This paves a way to synthesize the crystal-optimized LiMnxFe1−xPO4/C materials for high performance Li-ion batteries. PMID:28773887

A novel solid state photocatalyst for living radical polymerization under UV irradiation

NASA Astrophysics Data System (ADS)

Fu, Qiang; McKenzie, Thomas G.; Ren, Jing M.; Tan, Shereen; Nam, Eunhyung; Qiao, Greg G.

2016-02-01

This study presents the development of a novel solid state photocatalyst for the photoinduced controlled radical polymerization of methacrylates under mild UV irradiation (λmax ≈ 365 nm) in the absence of conventional photoinitiators, metal-catalysts or dye sensitizers. The photocatalyst design was based on our previous finding that organic amines can act in a synergistic photochemical reaction with thiocarbonylthio compounds to afford well controlled polymethacrylates under UV irradiation. Therefore, in the current contribution an amine-rich polymer was covalently grafted onto a solid substrate, thus creating a heterogeneous catalyst that would allow for facile removal, recovery and recyclability when employed for such photopolymerization reactions. Importantly, the polymethacrylates synthesized using the solid state photocatalyst (ssPC) show similarly excellent chemical and structural integrity as those catalysed by free amines. Moreover, the ssPC could be readily recovered and re-used, with multiple cycles of polymerization showing minimal effect on the integrity of the catalyst. Finally, the ssPC was employed in various photo-“click” reactions, permitting high yielding conjugations under photochemical control.

Non-enzymatic browning kinetics analysed through water-solids interactions and water mobility in dehydrated potato.

PubMed

Acevedo, Nuria C; Schebor, Carolina; Buera, Pilar

2008-06-01

Non-enzymatic browning (NEB) development was studied in dehydrated potato at 70°C. It was related to the macroscopic and molecular properties and to water-solid interactions over a wide range of water activities. Time resolved (1)H NMR, thermal transitions and water sorption isotherms were evaluated. Although non-enzymatic browning could be detected in the glassy state; colour development was higher in the supercooled state. The reaction rate increased up to a water content of 26g/100g of solids (aw=0.84) and then decreased at higher water contents, concomitantly with the increase of water proton mobility. The joint analyses of NEB kinetics, water sorption isotherm and proton relaxation behaviour made it evident that the point at which the reaction rate decreased, after a maximum value, could be related to the appearance of highly mobile water. The results obtained in this work indicate that the prediction of chemical reaction kinetics can be performed through the integrated analysis of water sorption, water and solids mobility and the physical state of the matrix. Copyright © 2007 Elsevier Ltd. All rights reserved.

Beyond the Compositional Threshold of Nanoparticle-Based Materials.

PubMed

Portehault, David; Delacroix, Simon; Gouget, Guillaume; Grosjean, Rémi; Chan-Chang, Tsou-Hsi-Camille

2018-04-17

The design of inorganic nanoparticles relies strongly on the knowledge from solid-state chemistry not only for characterization techniques, but also and primarily for choosing the systems that will yield the desired properties. The range of inorganic solids reported and studied as nanoparticles is however strikingly narrow when compared to the solid-state chemistry portfolio of bulk materials. Efforts to enlarge the collection of inorganic particles are becoming increasingly important for three reasons. First, they can yield materials more performing than current ones for a range of fields including biomedicine, optics, catalysis, and energy. Second, looking outside the box of common compositions is a way to target original properties or to discover genuinely new behaviors. The third reason lies in the path followed to reach these novel nano-objects: exploration and setup of new synthetic approaches. Indeed, willingness to access original nanoparticles faces a synthetic challenge: how to reach nanoparticles of solids that originally belong to the realm of solid-state chemistry and its typical protocols at high temperature? To answer this question, alternative reaction pathways must be sought, which may in turn provide tracks for new, untargeted materials. The corresponding strategies require limiting particle growth by confinement at high temperatures or by decreasing the synthesis temperature. Both approaches, especially the latter, provide a nice playground to discover metastable solids never reported before. The aim of this Account is to raise attention to the topic of the design of new inorganic nanoparticles. To do so, we take the perspective of our own work in the field, by first describing synthetic challenges and how they are addressed by current protocols. We then use our achievements to highlight the possibilities offered by new nanomaterials and to introduce synthetic approaches that are not in the focus of recent literature but hold, in our opinion, great promise. We will span methods of low temperature "chimie douce" aqueous synthesis coupled to microwave heating, sol-gel chemistry and processing coupled to solid state reactions, and then molten salt synthesis. These protocols pave the way to metastable low valence oxyhydroxides, vanadates, perovskite oxides, boron carbon nitrides, and metal borides, all obtained at the nanoscale with structural and morphological features differing from "usual" nanomaterials. These nano-objects show original properties, from sensing, thermoelectricity, charge and spin transports, photoluminescence, and catalysis, which require advanced characterization of surface states. We then identify future trends of synthetic methodologies that will merit further attention in this burgeoning field, by emphasizing the importance of unveiling reaction mechanisms and coupling experiments with modeling.

Electron-rich driven electrochemical solid-state amorphization in Li-Si alloys.

PubMed

Wang, Zhiguo; Gu, Meng; Zhou, Yungang; Zu, Xiaotao; Connell, Justin G; Xiao, Jie; Perea, Daniel; Lauhon, Lincoln J; Bang, Junhyeok; Zhang, Shengbai; Wang, Chongmin; Gao, Fei

2013-09-11

The physical and chemical behaviors of materials used in energy storage devices, such as lithium-ion batteries (LIBs), are mainly controlled by an electrochemical process, which normally involves insertion/extraction of ions into/from a host lattice with a concurrent flow of electrons to compensate charge balance. The fundamental physics and chemistry governing the behavior of materials in response to the ions insertion/extraction is not known. Herein, a combination of in situ lithiation experiments and large-scale ab initio molecular dynamics simulations are performed to explore the mechanisms of the electrochemically driven solid-state amorphization in Li-Si systems. We find that local electron-rich condition governs the electrochemically driven solid-state amorphization of Li-Si alloys. This discovery provides the fundamental explanation of why lithium insertion in semiconductor and insulators leads to amorphization, whereas in metals, it leads to a crystalline alloy. The present work correlates electrochemically driven reactions with ion insertion, electron transfer, lattice stability, and phase equilibrium.

Electron-Rich Driven Electrochemical Solid-State Amorphization in Li-Si Alloys

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

Wang, Zhiguo; Gu, Meng; Zhou, Yungang

2013-08-14

The physical and chemical behaviors of materials used in energy storage devices, such as lithium-ion batteries (LIBs), are mainly controlled by an electrochemical process, which normally involves insertion/extraction of ions into/from a host lattice with a concurrent flow of electrons to compensate charge balance. The fundamental physics and chemistry governing the behavior of materials in response to the ions insertion/extraction is not known. Herein, a combination of in situ lithiation experiments and large-scale ab initio molecular dynamics simulations are performed to explore the mechanisms of the electrochemically driven solid-state amorphization in Li-Si systems. We find that local electron-rich condition governsmore » the electrochemically driven solid-state amorphization of Li-Si alloys. This discovery provides the fundamental explanation of why lithium insertion in semiconductor and insulators leads to amorphization, whereas in metals, it leads to a crystalline alloy. The present work correlates electrochemically driven reactions with ion insertion, electron transfer, lattice stability and phase equilibrium.« less

Redox-Active Hydrogel Polymer Electrolytes with Different pH Values for Enhancing the Energy Density of the Hybrid Solid-State Supercapacitor.

PubMed

Tang, Xiaohui; Lui, Yu Hui; Merhi, Abdul Rahman; Chen, Bolin; Ding, Shaowei; Zhang, Bowei; Hu, Shan

2017-12-27

To enhance the energy density of solid-state supercapacitors, a novel solid-state cell, made of redox-active poly(vinyl alcohol) (PVA) hydrogel electrolytes and functionalized carbon nanotube-coated cellulose paper electrodes, was investigated in this work. Briefly, acidic PVA-[BMIM]Cl-lactic acid-LiBr and neutral PVA-[BMIM]Cl-sodium acetate-LiBr hydrogel polymer electrolytes are used as catholyte and anolyte, respectively. The acidic condition of the catholyte contributes to suppression of the undesired irreversible reaction of Br - and extension of the oxygen evolution reaction potential to a higher value than that of the redox potential of Br - /Br 3 - reaction. The observed Br - /Br 3 - redox activity at the cathode contributes to enhance the cathode capacitance. The neutral condition of the anolyte helps extend the operating voltage window of the supercapacitor by introducing hydrogen evolution reaction overpotential to the anode. The electrosorption of nascent H on the negative electrode also increases the anode capacitance. As a result, the prepared solid-state hybrid supercapacitor shows a broad voltage window of 1.6 V, with a high Coulombic efficiency of 97.6% and the highest energy density of 16.3 Wh/kg with power density of 932.6 W/kg at 2 A/g obtained. After 10 000 cycles of galvanostatic charge and discharge tests at the current density of 10 A/g, it exhibits great cyclic stability with 93.4% retention of the initial capacitance. In addition, a robust capacitive performance can also be observed from the solid-state supercapacitor at different bending angles, indicating its great potential as a flexible energy storage device.

A benign synthesis of alane by the composition-controlled mechanochemical reaction of sodium hydride and aluminum chloride

DOE PAGES

Hlova, Ihor; Goldston, Jennifer F.; Gupta, Shalabh; ...

2017-05-30

Solid-state mechanochemical synthesis of alane (AlH 3) starting from sodium hydride (NaH) and aluminum chloride (AlCl 3) has been achieved at room temperature. The transformation pathway of this solid-state reaction was controlled by a stepwise addition of AlCl 3 to the initial reaction mixture that contained sodium hydride in excess of stoichiometric amount. As in the case of previously investigated LiH–AlCl 3 system, complete selectivity was achieved whereby formation of unwanted elemental aluminum was fully suppressed, and AlH 3 was obtained in quantitative yield. Reaction progress during each step was investigated by means of solid-state NMR and powder X-ray diffraction,more » which revealed that the overall reaction proceeds through a series of intermediate alanates that may be partially chlorinated. The NaH–AlCl 3 system presents some subtle differences compared to LiH–AlCl 3 system particularly with respect to optimal concentrations needed during one of the reaction stages. Based on the results, we postulate that high local concentrations of NaH may stabilize chlorine-containing derivatives and prevent decomposition into elemental aluminum with hydrogen evolution. As a result, complete conversion with quantitative yield of alane was confirmed by both SSNMR and hydrogen desorption analysis.« less

A benign synthesis of alane by the composition-controlled mechanochemical reaction of sodium hydride and aluminum chloride

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

Hlova, Ihor; Goldston, Jennifer F.; Gupta, Shalabh

Solid-state mechanochemical synthesis of alane (AlH 3) starting from sodium hydride (NaH) and aluminum chloride (AlCl 3) has been achieved at room temperature. The transformation pathway of this solid-state reaction was controlled by a stepwise addition of AlCl 3 to the initial reaction mixture that contained sodium hydride in excess of stoichiometric amount. As in the case of previously investigated LiH–AlCl 3 system, complete selectivity was achieved whereby formation of unwanted elemental aluminum was fully suppressed, and AlH 3 was obtained in quantitative yield. Reaction progress during each step was investigated by means of solid-state NMR and powder X-ray diffraction,more » which revealed that the overall reaction proceeds through a series of intermediate alanates that may be partially chlorinated. The NaH–AlCl 3 system presents some subtle differences compared to LiH–AlCl 3 system particularly with respect to optimal concentrations needed during one of the reaction stages. Based on the results, we postulate that high local concentrations of NaH may stabilize chlorine-containing derivatives and prevent decomposition into elemental aluminum with hydrogen evolution. As a result, complete conversion with quantitative yield of alane was confirmed by both SSNMR and hydrogen desorption analysis.« less

Method of producing particulate-reinforced composites and composites produced thereby

DOEpatents

Han, Qingyou; Liu, Zhiwei

2013-12-24

A process for producing particle-reinforced composite materials through utilization of an in situ reaction to produce a uniform dispersion of a fine particulate reinforcement phase. The process includes forming a melt of a first material, and then introducing particles of a second material into the melt and subjecting the melt to high-intensity acoustic vibration. A chemical reaction initiates between the first and second materials to produce reaction products in the melt. The reaction products comprise a solid particulate phase, and the high-intensity acoustic vibration fragments and/or separates the reaction products into solid particles that are dispersed in the melt and are smaller than the particles of the second material. Also encompassed are particle-reinforced composite materials produced by such a process.

Method of producing particulate-reinforced composites and composites produced thereby

DOEpatents

Han, Qingyou; Liu, Zhiwei

2015-12-29

A process for producing particle-reinforced composite materials through utilization of an in situ reaction to produce a uniform dispersion of a fine particulate reinforcement phase. The process includes forming a melt of a first material, and then introducing particles of a second material into the melt and subjecting the melt to high-intensity acoustic vibration. A chemical reaction initiates between the first and second materials to produce reaction products in the melt. The reaction products comprise a solid particulate phase, and the high-intensity acoustic vibration fragments and/or separates the reaction products into solid particles that are dispersed in the melt and are smaller than the particles of the second material. Also encompassed are particle-reinforced composite materials produced by such a process.

Shockwave Processing of Composite Boron and Titanium Nitride Powders

NASA Astrophysics Data System (ADS)

Beason, Matthew T.; Gunduz, I. Emre; Mukasyan, Alexander S.; Son, Steven F.

2015-06-01

Shockwave processing of powders has been shown to initiate reactions between condensed phase reactants. It has been observed that these reactions can occur at very short timescales, resulting in chemical reactions occurring at a high pressure state. These reactions have the potential to produce metastable phases. Kinetic limitations prevent gaseous reactants from being used in this type of synthesis reaction. To overcome this limitation, a solid source of gaseous reactants must be used. An example of this type of reaction is the nitrogen exchange reaction (e.g. B + TiN, B + Si3N4 etc.). In these reactions nitrogen is ``carried'' by a material that can be then reduced by the second reactant. This work explores the possibility of using nitrogen exchange reactions to synthesize the cubic phase of boron nitride (c-BN) through shockwave processing of ball milled mixtures of boron and titanium nitride. The heating from the passage of the shock wave (pore collapse, plastic work, etc.) combined with thermochemical energy from the reaction may provide a means to synthesize c-BN. This material is based upon work supported by the Department of Energy, National Nuclear Security Administration, under Award Number(s) DE-NA0002377. National Defense Science & Engineering Graduate Fellowship (NDSEG), 32 CFR 168a.

Insights into reaction mechanisms in heterogeneous catalysis revealed by in situ NMR spectroscopy.

PubMed

Blasco, Teresa

2010-12-01

This tutorial review intends to show the possibilities of in situ solid state NMR spectroscopy in the elucidation of reaction mechanisms and the nature of the active sites in heterogeneous catalysis. After a brief overview of the more usual experimental devices used for in situ solid state NMR spectroscopy measurements, some examples of applications taken from the recent literature will be presented. It will be shown that in situ NMR spectroscopy allows: (i) the identification of stable intermediates and transient species using indirect methods, (ii) to prove shape selectivity in zeolites, (iii) the study of reaction kinetics, and (iv) the determination of the nature and the role played by the active sites in a catalytic reaction. The approaches and methodology used to get this information will be illustrated here summarizing the most relevant contributions on the investigation of the mechanisms of a series of reactions of industrial interest: aromatization of alkanes on bifunctional catalysts, carbonylation reaction of methanol with carbon monoxide, ethylbenzene disproportionation, and the Beckmann rearrangement reaction. Special attention is paid to the research carried out on the role played by carbenium ions and alkoxy as intermediate species in the transformation of hydrocarbon molecules on solid acid catalysts.

One-step production of long-chain hydrocarbons from waste-biomass-derived chemicals using bi-functional heterogeneous catalysts.

PubMed

Wen, Cun; Barrow, Elizabeth; Hattrick-Simpers, Jason; Lauterbach, Jochen

2014-02-21

In this study, we demonstrate the production of long-chain hydrocarbons (C8+) from 2-methylfuran (2MF) and butanal in a single step reactive process by utilizing a bi-functional catalyst with both acid and metallic sites. Our approach utilizes a solid acid for the hydroalkylation function and as a support as well as a transition metal as hydrodeoxygenation catalyst. A series of solid acids was screened, among which MCM-41 demonstrated the best combination of activity and stability. Platinum nanoparticles were then incorporated into the MCM-41. The Pt/MCM-41 catalyst showed 96% yield for C8+ hydrocarbons and the catalytic performance was stable over four reaction cycles of 20 hour each. The reaction pathways for the production of long-chain hydrocarbons is probed with a combination of infrared spectroscopy and steady-state reaction experiments. It is proposed that 2MF and butanal go through hydroalkylation first on the acid site followed by hydrodeoxygenation to produce the hydrocarbon fuels.

An infrared study of the nitro—nitrito linkage isomerization in solid nitro- and nitritopentamminecobalt(III) chloride

NASA Astrophysics Data System (ADS)

Heyns, A. M.; de Waal, D.

1989-01-01

The photochemical isomerization reaction of [Co(NH 3) 5NO 2]Cl 2 to [Co(NH 3) 5ONO]Cl 2 has been studied in the solid state by means of i.r. spectroscopy. The reaction is first order with k = 2.53±0.05 × 10 -4s -1 and is much faster ( t1/2=49min) than the well-known spontaneous nitrito → nitro isomerization ( t1/2 = 6 days). The i.r. bands of both the NH 3 and ONO - -groups in the range 4000-50 cm -1 indicate minor differences between the structures of freshly and photochemically prepared [Co(NH 3) 5ONO]Cl 2. The far i.r. spectra indicate the disorder existing in the intermediate products during the isomerization processes.

In situ solid-state electrochemistry of mass-selected ions at well-defined electrode–electrolyte interfaces

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

Prabhakaran, Venkateshkumar; Johnson, Grant E.; Wang, Bingbing

2016-11-07

Molecular-level understanding of electrochemical processes occurring at electrode-electrolyte interfaces (EEI) is key to the rational development of high-performance and sustainable electrochemical technologies. This article reports the development and first application of solid-state in situ electrochemical probes to study redox and catalytic processes occurring at well-defined EEI generated using soft-landing of mass- and charge-selected cluster ions (SL). In situ electrochemical probes with excellent mass transfer properties are fabricated using carefully-designed nanoporous ionic liquid membranes. SL enables deposition of pure active species that are not obtainable with other techniques onto electrode surfaces with precise control over charge state, composition, and kinetic energy.more » SL is, therefore, a unique tool for studying fundamental processes occurring at EEI. For the first time using an aprotic electrochemical probe, the effect of charge state (PMo12O403-/2-) and the contribution of building blocks of Keggin polyoxometalate (POM) clusters to redox processes are characterized by populating EEI with novel POM anions generated by electrospray ionization and gas phase dissociation. Additionally, a proton conducting electrochemical probe has been developed to characterize the reactive electrochemistry (oxygen reduction activity) of bare Pt clusters (Pt40 ~1 nm diameter), thus demonstrating the capability of the probe for studying reactions in controlled gaseous environments. The newly developed in situ electrochemical probes combined with ion SL provide a versatile method to characterize the EEI in solid-state redox systems and reactive electrochemistry at precisely-defined conditions. This capability will advance molecular-level understanding of processes occurring at EEI that are critical to many energy-related technologies.« less

Low-temperature synthesis of actinide tetraborides by solid-state metathesis reactions

DOEpatents

Lupinetti, Anthony J [Los Alamos, NM; Garcia, Eduardo [Los Alamos, NM; Abney, Kent D [Los Alamos, NM

2004-12-14

The synthesis of actinide tetraborides including uranium tetraboride (UB.sub.4), plutonium tetraboride (PuB.sub.4) and thorium tetraboride (ThB.sub.4) by a solid-state metathesis reaction are demonstrated. The present method significantly lowers the temperature required to .ltoreq.850.degree. C. As an example, when UCl.sub.4 is reacted with an excess of MgB.sub.2, at 850.degree. C., crystalline UB.sub.4 is formed. Powder X-ray diffraction and ICP-AES data support the reduction of UCl.sub.3 as the initial step in the reaction. The UB.sub.4 product is purified by washing water and drying.

Formation of the racemic compound of ephedrine base from a physical mixture of its enantiomers in the solid, liquid, solution, or vapor state.

PubMed

Duddu, S P; Grant, D J

1992-08-01

Physical mixtures (conglomerates) of the two enantiomers of ephedrine base, each containing 0.5% (w/w) of water, were observed to be converted to the 1:1 racemic compound in the solid, liquid, solution, or vapor state. From a geometrically mixed racemic conglomerate of particle size 250-300 microns (50-60 mesh), the formation of the racemic compound follows second-order kinetics (first order with respect to each enantiomer), with a rate constant of 392 mol-1 hr-1 at 22 degrees C. The reaction appears to proceed via the vapor phase as indicated by the growth of the crystals of the racemic compound between diametrically separated crystals of the two enantiomers in a glass petri dish. The observed kinetics of conversion in the solid state are explained by a homogeneous reaction model via the vapor and/or liquid states. Formation of the racemic compound from the crystals of ephedrine enantiomers in the solution state may explain why Schmidt et al. (Pharm. Res. 5:391-395, 1988) observed a consistently lower aqueous solubility of the mixture than of the pure enantiomers. The solid phase in equilibrium with the solution at the end of the experiment was found to be the racemic compound, whose melting point and heat of fusion are higher than those of the enantiomers. An association reaction, of measurable rate, between the opposite enantiomers in a binary mixture in the solid, liquid, solution, or vapor state to form the racemic compound may be more common than is generally realized.

Solid-state polymerisation via [2+2] cycloaddition reaction involving coordination polymers.

PubMed

Medishetty, Raghavender; Park, In-Hyeok; Lee, Shim Sung; Vittal, Jagadese J

2016-03-14

Highly crystalline metal ions containing organic polymers are potentially useful to manipulate the magnetic and optical properties to make advanced multifunctional materials. However, it is challenging to synthesise monocrystalline metal complexes of organic polymers and single-phase hybrid materials made up of both coordination and organic polymers by traditional solution crystallisation. This requires an entirely different approach in the solid-state by thermal or photo polymerisation of the ligands. Among the photochemical methods available, [2+2] cycloaddition reaction has been recently employed to generate cyclobutane based coordination polymers from the metal complexes. Cyclobutane polymers have also been integrated into coordination polymers in this way. Recent advancements in the construction of polymeric chains of cyclobutane rings through photo-dimerisation reaction in the monocrystalline solids containing metal complexes, coordination polymers and metal-organic framework structures are discussed here.

Facilitated Oxygen Chemisorption in Heteroatom-Doped Carbon for Improved Oxygen Reaction Activity in All-Solid-State Zinc-Air Batteries.

PubMed

Liu, Sisi; Wang, Mengfan; Sun, Xinyi; Xu, Na; Liu, Jie; Wang, Yuzhou; Qian, Tao; Yan, Chenglin

2018-01-01

Driven by the intensified demand for energy storage systems with high-power density and safety, all-solid-state zinc-air batteries have drawn extensive attention. However, the electrocatalyst active sites and the underlying mechanisms occurring in zinc-air batteries remain confusing due to the lack of in situ analytical techniques. In this work, the in situ observations, including X-ray diffraction and Raman spectroscopy, of a heteroatom-doped carbon air cathode are reported, in which the chemisorption of oxygen molecules and oxygen-containing intermediates on the carbon material can be facilitated by the electron deficiency caused by heteroatom doping, thus improving the oxygen reaction activity for zinc-air batteries. As expected, solid-state zinc-air batteries equipped with such air cathodes exhibit superior reversibility and durability. This work thus provides a profound understanding of the reaction principles of heteroatom-doped carbon materials in zinc-air batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Numerical Modeling of Reactive Multiphase Flow for FCC and Hot Gas Desulfurization Circulating Fluidized Beds

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

Miller, Aubrey L.

2005-07-01

This work was carried out to understand the behavior of the solid and gas phases in a CFB riser. Only the riser is modeled as a straight pipe. A model with linear algebraic approximation to solids viscosity of the form, {musubs} = 5.34{epsisubs}, ({espisubs} is the solids volume fraction) with an appropriate boundary condition at the wall obtained by approximate momentum balance solution at the wall to acount for the solids recirculation is tested against experimental results. The work done was to predict the flow patterns in the CFB risers from available experimental data, including data from a 7.5-cm-ID CFBmore » riser at the Illinois Institute of Technology and data from a 20.0-cm-ID CFB riser at the Particulate Solid Research, Inc., facility. This research aims at modeling the removal of hydrogen sulfide from hot coal gas using zinc oxide as the sorbent in a circulating fluidized bed and in the process indentifying the parameters that affect the performance of the sulfidation reactor. Two different gas-solid reaction models, the unreacted shrinking core (USC) and the grain model were applied to take into account chemical reaction resistances. Also two different approaches were used to affect the hydrodynamics of the process streams. The first model takes into account the effect of micro-scale particle clustering by adjusting the gas-particle drag law and the second one assumes a turbulent core with pseudo-steady state boundary condition at the wall. A comparison is made with experimental results.« less

High temperature lubricating process

DOEpatents

Taylor, R.W.; Shell, T.E.

1979-10-04

It has been difficult to provide adequate lubrication for load bearing, engine components when such engines are operating in excess of about 475/sup 0/C. The present invention is a process for providing a solid lubricant on a load bearing, solid surface, such as in an engine being operated at temperatures in excess of about 475/sup 0/C. The process comprises contacting and maintaining the following steps: a gas phase is provided which includes at least one component reactable in a temperature dependent reaction to form a solid lubricant; the gas phase is contacted with the load bearing surface; the load bearing surface is maintained at a temperature which causes reaction of the gas phase component and the formation of the solid lubricant; and the solid lubricant is formed directly on the load bearing surface. The method is particularly suitable for use with ceramic engines.

High temperature lubricating process

DOEpatents

Taylor, Robert W.; Shell, Thomas E.

1982-01-01

It has been difficult to provide adaquate lubrication for load bearing, engine components when such engines are operating in excess of about 475.degree. C. The present invention is a process for providing a solid lubricant on a load bearing, solid surface (14), such as in an engine (10) being operated at temperatures in excess of about 475.degree. C. The process comprises contacting and maintaining steps. A gas phase (42) is provided which includes at least one component reactable in a temperature dependent reaction to form a solid lubricant. The gas phase is contacted with the load bearing surface. The load bearing surface is maintained at a temperature which causes reaction of the gas phase component and the formation of the solid lubricant. The solid lubricant is formed directly on the load bearing surface. The method is particularly suitable for use with ceramic engines.

Reactive solid surface morphology variation via ionic diffusion.

PubMed

Sun, Zhenchao; Zhou, Qiang; Fan, Liang-Shih

2012-08-14

In gas-solid reactions, one of the most important factors that determine the overall reaction rate is the solid morphology, which can be characterized by a combination of smooth, convex and concave structures. Generally, the solid surface structure varies in the course of reactions, which is classically noted as being attributed to one or more of the following three mechanisms: mechanical interaction, molar volume change, and sintering. Here we show that if a gas-solid reaction involves the outward ionic diffusion of a solid-phase reactant then this outward ionic diffusion could eventually smooth the surface with an initial concave and/or convex structure. Specifically, the concave surface is filled via a larger outward diffusing surface pointing to the concave valley, whereas the height of the convex surface decreases via a lower outward diffusion flux in the vertical direction. A quantitative 2-D continuum diffusion model is established to analyze these two morphological variation processes, which shows consistent results with the experiments. This surface morphology variation by solid-phase ionic diffusion serves to provide a fourth mechanism that supplements the traditionally acknowledged solid morphology variation or, in general, porosity variation mechanisms in gas-solid reactions.

Shape evolution of new-phased lepidocrocite VOOH from single-shelled to double-shelled hollow nanospheres on the basis of programmed reaction-temperature strategy.

PubMed

Wu, Changzheng; Zhang, Xiaodong; Ning, Bo; Yang, Jinlong; Xie, Yi

2009-07-06

Solid templates have been long regarded as one of the most promising ways to achieve single-shelled hollow nanostructures; however, few effective methods for the construction of multishelled hollow objects from their solid template counterparts have been developed. We report here, for the first time, a novel and convenient route to synthesizing double-shelled hollow spheres from the solid templates via programming the reaction-temperature procedures. The programmed temperature strategy developed in this work then provides an essential and general access to multishelled hollow nanostructures based on the designed extension of single-shelled hollow objects, independent of their outside contours, such as tubes, hollow spheres, and cubes. Starting from the V(OH)(2)NH(2) solid templates, we show that the relationship between the hollowing rate and the reaction temperature obey the Van't Hoff rule and Arrhenius activation-energy equation, revealing that it is the chemical reaction rather than the diffusion process that guided the whole hollowing process, despite the fact that the coupled reaction/diffusion process is involved in the hollowing process. Using the double-shelled hollow spheres as the PCM (CaCl(2).6H(2)O) matrix grants much better thermal-storage stability than that for the nanoparticles counterpart, revealing that the designed nanostructures can give rise to significant improvements for the energy-saving performance in future "smart house" systems.

The Origins and Evolution of Molecules in Icy Solids

NASA Technical Reports Server (NTRS)

Hudson, Reggie L.; Moore, Marla H.

2010-01-01

Astronomical observations of the past few decades have revealed the existence of a variety of molecules in extraterrestrial ices. These molecules include H2O, CO, and CO2, and organics such as CH4, CH30H, and C2H6. Some ices are dominated by polar molecules, while non-polar species appear to dominate others. Observations, mainly in the radio and IR regions, have allowed the inference of other solid-phase molecules whose formation remains difficult to explain by gas-phase chemistry alone. Several laboratory research groups have reported on extensive experiments on the solid-phase reaction chemistry of icy materials, generally as initiated by either ionizing radiation or vacuum-UV photons. These experiments not only permit molecular identifications to be made from astronomical observations, but also allow predictions of yet unidentified molecules. This laboratory approach has evolved over more than 30 years with much of the earliest work focusing on complex mixtures thought to represent either cometary or interstellar ices. Although those early experiments documented a rich solid-state photo- and radiation chemistry, they revealed few details of reactions for particular molecules, partly due to the multi-component nature of the samples. Since then, model systems have been examined that allow the chemistry of individual species and specific reactions to be probed. Reactions involving most of the smaller astronomical molecules have now been studied and specific processes identified. Current laboratory work suggests that a variety of reactions occur in extraterrestrial ices, including acid-base processes, radical dimerizations, proton transfers, oxidations, reductions, and isomerizations. This workshop presentation will focus on chemical reactions relevant to solar system and interstellar ices. While most of the work will be drawn from that to which the speaker has contributed, results from other laboratories also will be included. Suggestions for future studies will be made, with an emphasis on some present deficiencies. The speaker's work has been generously supported by these NASA research programs: Cassini Data Analysis, Exobiology, Mars Fundamental Research, Outer Planets Research, Planetary Atmospheres, Planetary Geology and Geophysics, and the NASA Astrobiology Institute.

Esterification of pseudoephedrine hydrochloride by citric acid in a solid dose pharmaceutical preparation.

PubMed

Goel, Alok; Zhao, Zhicheng; Sørensen, Dan; Zhou, Jay; Zhang, Fa

2016-09-10

Esterification of pseudoephedrine hydrochloride (PSE) by citric acid was observed in a solid dose pharmaceutical preparation at room temperature and accelerated stability condition (40°C/75% relative humidity). The esterification of PSE with citric acid was confirmed by a solid-state binary reaction in the presence of minor level of water at elevated temperature to generate three isomeric esters. The structures of the pseudoephedrine citric acid esters were elucidated using high-resolution mass spectrometry and nuclear magnetic resonance spectroscopy (NMR). Occurrence of esterification in solid state, instead of amidation which is generally more favorable than esterification, is likely due to remaining HCl salt form of solid pseudoephedrine hydrochloride to protect its amino group from amidation with citric acid. In contrast, the esterification was not observed from solution reaction between PSE and citric acid. Copyright © 2016 Elsevier B.V. All rights reserved.

Reaction paths and equilibrium end-points in solid-solution aqueous-solution systems

USGS Publications Warehouse

Glynn, P.D.; Reardon, E.J.; Plummer, Niel; Busenberg, E.

1990-01-01

Equations are presented describing equilibrium in binary solid-solution aqueous-solution (SSAS) systems after a dissolution, precipitation, or recrystallization process, as a function of the composition and relative proportion of the initial phases. Equilibrium phase diagrams incorporating the concept of stoichiometric saturation are used to interpret possible reaction paths and to demonstrate relations between stoichiometric saturation, primary saturation, and thermodynamic equilibrium states. The concept of stoichiometric saturation is found useful in interpreting and putting limits on dissolution pathways, but there currently is no basis for possible application of this concept to the prediction and/ or understanding of precipitation processes. Previously published dissolution experiments for (Ba, Sr)SO4 and (Sr, Ca)C??O3orth. solids are interpreted using equilibrium phase diagrams. These studies show that stoichiometric saturation can control, or at least influence, initial congruent dissolution pathways. The results for (Sr, Ca)CO3orth. solids reveal that stoichiometric saturation can also control the initial stages of incongruent dissolution, despite the intrinsic instability of some of the initial solids. In contrast, recrystallisation experiments in the highly soluble KCl-KBr-H2O system demonstrate equilibrium. The excess free energy of mixing calculated for K(Cl, Br) solids is closely modeled by the relation GE = ??KBr??KClRT[a0 + a1(2??KBr-1)], where a0 is 1.40 ?? 0.02, a1, is -0.08 ?? 0.03 at 25??C, and ??KBr and ??KCl are the mole fractions of KBr and KCl in the solids. The phase diagram constructed using this fit reveals an alyotropic maximum located at ??KBr = 0.676 and at a total solubility product, ???? = [K+]([Cl-] + [Br-]) = 15.35. ?? 1990.

Ultrasonic semi-solid coating soldering 6061 aluminum alloys with Sn-Pb-Zn alloys.

PubMed

Yu, Xin-ye; Xing, Wen-qing; Ding, Min

2016-07-01

In this paper, 6061 aluminum alloys were soldered without a flux by the ultrasonic semi-solid coating soldering at a low temperature. According to the analyses, it could be obtained that the following results. The effect of ultrasound on the coating which promoted processes of metallurgical reaction between the components of the solder and 6061 aluminum alloys due to the thermal effect. Al2Zn3 was obtained near the interface. When the solder was in semi-solid state, the connection was completed. Ultimately, the interlayer mainly composed of three kinds of microstructure zones: α-Pb solid solution phases, β-Sn phases and Sn-Pb eutectic phases. The strength of the joints was improved significantly with the minimum shear strength approaching 101MPa. Copyright © 2016. Published by Elsevier B.V.

Analyzing the dependence of oxygen incorporation current density on overpotential and oxygen partial pressure in mixed conducting oxide electrodes.

PubMed

Guan, Zixuan; Chen, Di; Chueh, William C

2017-08-30

The oxygen incorporation reaction, which involves the transformation of an oxygen gas molecule to two lattice oxygen ions in a mixed ionic and electronic conducting solid, is a ubiquitous and fundamental reaction in solid-state electrochemistry. To understand the reaction pathway and to identify the rate-determining step, near-equilibrium measurements have been employed to quantify the exchange coefficients as a function of oxygen partial pressure and temperature. However, because the exchange coefficient contains contributions from both forward and reverse reaction rate constants and depends on both oxygen partial pressure and oxygen fugacity in the solid, unique and definitive mechanistic assessment has been challenging. In this work, we derive a current density equation as a function of both oxygen partial pressure and overpotential, and consider both near and far from equilibrium limits. Rather than considering specific reaction pathways, we generalize the multi-step oxygen incorporation reaction into the rate-determining step, preceding and following quasi-equilibrium steps, and consider the number of oxygen ions and electrons involved in each. By evaluating the dependence of current density on oxygen partial pressure and overpotential separately, one obtains the reaction orders for oxygen gas molecules and for solid-state species in the electrode. We simulated the oxygen incorporation current density-overpotential curves for praseodymium-doped ceria for various candidate rate-determining steps. This work highlights a promising method for studying the exchange kinetics far away from equilibrium.

A Model of Solid State Gas Sensors

NASA Astrophysics Data System (ADS)

Woestman, J. T.; Brailsford, A. D.; Shane, M.; Logothetis, E. M.

1997-03-01

Solid state gas sensors are widely used to measure the concentrations of gases such as CO, CH_4, C_3H_6, H_2, C_3H8 and O2 The applications of these sensors range from air-to-fuel ratio control in combustion processes including those in automotive engines and industrial furnaces to leakage detection of inflammable and toxic gases in domestic and industrial environments. As the need increases to accurately measure smaller and smaller concentrations, problems such as poor selectivity, stability and response time limit the use of these sensors. In an effort to overcome some of these limitations, a theoretical model of the transient behavior of solid state gas sensors has been developed. In this presentation, a model for the transient response of an electrochemical gas sensor to gas mixtures containing O2 and one reducing species, such as CO, is discussed. This model accounts for the transport of the reactive species to the sampling electrode, the catalyzed oxidation/reduction reaction of these species and the generation of the resulting electrical signal. The model will be shown to reproduce the results of published steady state models and to agree with experimental steady state and transient data.

Method of producing particulate-reinforced composites and composties produced thereby

DOEpatents

Han, Qingyou; Liu, Zhiwei

2013-12-24

A process for producing particle-reinforced composite materials through utilization of an in situ reaction to produce a uniform dispersion of a fine particulate reinforcement phase. The process includes forming a melt of a first material, and then introducing particles of a second material into the melt and subjecting the melt to high-intenisty acoustic vibration. A chemical reaction initiates between the first and second materials to produce reaction products in the melt. The reaciton products comprise a solide particulate phase, and the high-intensity acoustic vibration fragments and/or separates the reaction products into solid particles that are dispersed in the melt and are smaller than the particles of the second material. Also encompassed are particles-reinforced composite materials produced by such a process.

Original Synthetic Route To Obtain a SrAl2O4 Phosphor by the Molten Salt Method: Insights into the Reaction Mechanism and Enhancement of the Persistent Luminescence.

PubMed

Rojas-Hernandez, Rocío Estefanía; Rubio-Marcos, Fernando; Gonçalves, Ricardo Henrique; Rodriguez, Miguel Ángel; Véron, Emmanuel; Allix, Mathieu; Bessada, Catherine; Fernandez, José Francisco

2015-10-19

SrAl2O4:Eu(2+), Dy(3+) has been extensively studied for industrial applications in the luminescent materials field, because of its excellent persistent luminescence properties and chemical stability. Traditionally, this strontium aluminate material is synthesized in bulk form and/or fine powder by the classic solid-state method. Here, we report an original synthetic route, a molten salt assisted process, to obtain highly crystalline SrAl2O4 powder with nanometer-scale crystals. The main advantages of salt addition are the increase of the reaction rate and the significant reduction of the synthesis temperature because of much higher mobility of reactants in the liquid medium than in the solid-state method. In particular, the formation mechanism of SrAl2O4, the role of the salt, and the phase's evolution have been explored as a function of temperature and time. Phosphorescent powders based on SrAl2O4:Eu(2+), Dy(3+) with high crystallinity are obtained after 1 h treatment at 900 °C. This work could promote further interest in adopting the molten salt strategy to process high-crystallinity materials with enhanced luminescence to design technologically relevant phosphors.

Shock-induced reaction synthesis of cubic boron nitride

NASA Astrophysics Data System (ADS)

Beason, M. T.; Pauls, J. M.; Gunduz, I. E.; Rouvimov, S.; Manukyan, K. V.; Matouš, K.; Son, S. F.; Mukasyan, A.

2018-04-01

Here, we report ultra-fast (0.1-5 μs) shock-induced reactions in the 3B-TiN system, leading to the direct synthesis of cubic boron nitride, which is extremely rare in nature and is the second hardest material known. Composite powders were produced through high-energy ball milling to provide intimate mixing and subsequently shocked using an explosive charge. High-resolution transmission electron microscopy and X-ray diffraction confirm the formation of nanocrystalline grains of c-BN produced during the metathetical reaction between boron and titanium nitride. Our results illustrate the possibility of rapid reactions enabled by high-energy ball milling possibly occurring in the solid state on incredibly short timescales. This process may provide a route for the discovery and fabrication of advanced compounds.

Two dimensional, transient catalytic combustion of CO-air on platinum

NASA Technical Reports Server (NTRS)

Sinha, N.; Bruno, C.; Bracco, F. V.

1985-01-01

The light off transient of catalytic combustion of lean CO-air mixtures in a platinum coated channel of a honeycomb monolith is studied with a model that resolves transient radial and axial gradients in both the gas and the solid. For the conditions studied it is concluded that: the initial heat release occurs near the entrance at the gas-solid interface and is controlled by heterogeneous reactions; large spatial and temporal temperature gradients occur in the solid near the entrance controlled mostly by the availability of fuel; the temperature of the solid near the entrance achieves almost its steady state value before significant heating of the back; heterogeneous reactions and the gas heated up front and flowing downstream heat the back of the solid; the overall transient time is controlled by the thermal inertia of the solid and by forced convection; radiation significantly influences both transient and steady state particularly near the entrance; the oxidation of CO occurs mostly on the catalyst and becomes diffusion controlled soon into the transient.

First-principles quantum-mechanical investigations of biomass conversion at the liquid-solid interfaces

NASA Astrophysics Data System (ADS)

Dang, Hongli; Xue, Wenhua; Liu, Yingdi; Jentoft, Friederike; Resasco, Daniel; Wang, Sanwu

2014-03-01

We report first-principles density-functional calculations and ab initio molecular dynamics (MD) simulations for the reactions involving furfural, which is an important intermediate in biomass conversion, at the catalytic liquid-solid interfaces. The different dynamic processes of furfural at the water-Cu(111) and water-Pd(111) interfaces suggest different catalytic reaction mechanisms for the conversion of furfural. Simulations for the dynamic processes with and without hydrogen demonstrate the importance of the liquid-solid interface as well as the presence of hydrogen in possible catalytic reactions including hydrogenation and decarbonylation of furfural. Supported by DOE (DE-SC0004600). This research used the supercomputer resources of the XSEDE, the NERSC Center, and the Tandy Supercomputing Center.

Trend-Analysis of Solid-State Structures: Low-Energy Conformational 'Reactions' Involving Directed and Coupled Movements in Half-Sandwich Compounds [CpFe(CO){C(=O)R}PPh3].

PubMed

Brunner, Henri; Tsuno, Takashi

2018-05-01

Invited for this month's cover picture are Prof. Dr. Henri Brunner from the University of Regensburg (Germany) and Prof. Dr. Takashi Tsuno from Nihon University (Japan). The cover picture shows the conformational reaction of JIDLUD→FIHTUL. The order of sample points of solid-state structures reveals information concerning low-energy, directed, and coupled movements in molecules. Read the full text of their Communication at https://doi.org/10.1002/open.201800007.

Surface-mediated nucleation in the solid-state polymorph transformation of terephthalic acid.

PubMed

Beckham, Gregg T; Peters, Baron; Starbuck, Cindy; Variankaval, Narayan; Trout, Bernhardt L

2007-04-18

A molecular mechanism for nucleation for the solid-state polymorph transformation of terephthalic acid is presented. New methods recently developed in our group, aimless shooting and likelihood maximization, are employed to construct a model for the reaction coordinate for the two system sizes studied. The reaction coordinate approximation is validated using the committor probability analysis. The transformation proceeds via a localized, elongated nucleus along the crystal edge formed by fluctuations in the supramolecular synthons, suggesting a nucleation and growth mechanism in the macroscopic system.

Nanointerface-driven reversible hydrogen storage in the nanoconfined Li-N-H system

DOE PAGES

Wood, Brandon C.; Stavila, Vitalie; Poonyayant, Natchapol; ...

2017-01-20

Internal interfaces in the Li 3N/[LiNH 2 + 2LiH] solid-state hydrogen storage system alter the hydrogenation and dehydrogenation reaction pathways upon nanosizing, suppressing undesirable intermediate phases to dramatically improve kinetics and reversibility. Finally, the key role of solid interfaces in determining thermodynamics and kinetics suggests a new paradigm for optimizing complex hydrides for solid-state hydrogen storage by engineering internal microstructure.

Porous-Hybrid Polymers as Platforms for Heterogeneous Photochemical Catalysis.

PubMed

Haikal, Rana R; Wang, Xia; Hassan, Youssef S; Parida, Manas R; Murali, Banavoth; Mohammed, Omar F; Pellechia, Perry J; Fontecave, Marc; Alkordi, Mohamed H

2016-08-10

A number of permanently porous polymers containing Ru(bpy)n photosensitizer or a cobaloxime complex, as a proton-reduction catalyst, were constructed via one-pot Sonogashira-Hagihara (SH) cross-coupling reactions. This process required minimal workup to access porous platforms with control over the apparent surface area, pore volume, and chemical functionality from suitable molecular building blocks (MBBs) containing the Ru or Co complexes, as rigid and multitopic nodes. The cobaloxime molecular building block, generated through in situ metalation, afforded a microporous solid that demonstrated noticeable catalytic activity toward hydrogen-evolution reaction (HER) with remarkable recyclability. We further demonstrated, in two cases, the ability to affect the excited-state lifetime of the covalently immobilized Ru(bpy)3 complex attained through deliberate utilization of the organic linkers of variable dimensions. Overall, this approach facilitates construction of tunable porous solids, with hybrid composition and pronounced chemical and physical stability, based on the well-known Ru(bpy)nor the cobaloxime complexes.

The analysis of magnesium oxide hydration in three-phase reaction system

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

Tang, Xiaojia; Guo, Lin; Chen, Chen

In order to investigate the magnesium oxide hydration process in gas–liquid–solid (three-phase) reaction system, magnesium hydroxide was prepared by magnesium oxide hydration in liquid–solid (two-phase) and three-phase reaction systems. A semi-empirical model and the classical shrinking core model were used to fit the experimental data. The fitting result shows that both models describe well the hydration process of three-phase system, while only the semi-empirical model right for the hydration process of two-phase system. The characterization of the hydration product using X-Ray diffraction (XRD) and scanning electron microscope (SEM) was performed. The XRD and SEM show hydration process in the two-phasemore » system follows common dissolution/precipitation mechanism. While in the three-phase system, the hydration process undergo MgO dissolution, Mg(OH){sub 2} precipitation, Mg(OH){sub 2} peeling off from MgO particle and leaving behind fresh MgO surface. - Graphical abstract: There was existence of a peeling-off process in the gas–liquid–solid (three-phase) MgO hydration system. - Highlights: • Magnesium oxide hydration in gas–liquid–solid system was investigated. • The experimental data in three-phase system could be fitted well by two models. • The morphology analysis suggested that there was existence of a peel-off process.« less

Numerical investigation of the effects of iron oxidation reactions on the fume formation mechanism in arc welding

NASA Astrophysics Data System (ADS)

Sanibondi, Paolo

2015-09-01

Fume formation during arc welding has been modelled using a stochastic approach taking into account iron oxidation reactions. The model includes the nucleation and condensation of Fe and FeO vapours, the reaction of gaseous O2 and O on the nanoparticle surface, the coagulation of the nanoparticles including a sintering time as a function of temperature and composition, assuming chemical equilibrium for species in the gaseous phase. Results suggest that fumes generated in gas metal arc welding with oxidizing shielding mixtures are composed of aggregates of primary particles that are nucleated from gas-phase FeO and further oxidized to Fe3O4 and Fe2O3 in the liquid and solid phase, respectively. The composition of the fumes at the end of the formation process depends on the relative initial concentration of Fe and O2 species in the gas mixture and on the diameter of the primary particles that compose the aggregates: as the oxidation reactions are driven by deposition of oxygen on nanoparticle surface, the oxidation of larger particles is slower than that of smaller particles because of their lower surface to volume ratio. Solid-state diffusion is limiting the oxidation process at temperatures lower than 1500 K, inducing the formation of not fully oxidized particles composed of Fe3O4.

Growth of self-textured Ga3+-substituted Li7La3Zr2O12 ceramics by solid state reaction and their significant enhancement in ionic conductivity

NASA Astrophysics Data System (ADS)

Qin, Shiying; Zhu, Xiaohong; Jiang, Yue; Ling, Ming'en; Hu, Zhiwei; Zhu, Jiliang

2018-03-01

A highly self-textured Ga2O3-substituted Li7La3Zr2O12 (LLZO-Ga) solid electrolyte with a nominal composition of Li6.55Ga0.15La3Zr2O12 is obtained by a simple and low-cost solid-state reaction technique, requiring no seed crystals to achieve grain orientation. The as-prepared self-textured LLZO-Ga shows a strong (420) preferred orientation with a high Lotgering factor of 0.91. Coherently, a terrace-shaped microstructure consisting of many parallel layers, indicating a two-dimensional-like growth mode, is clearly observed in the self-textured sample. As a result, the highly self-textured garnet-type lithium-ion conducting solid electrolyte of LLZO-Ga exhibits an extremely high ionic conductivity, reaching a state-of-the-art level of 2.06 × 10-3 S cm-1 at room temperature (25 °C) and thus shedding light on an important strategy for improving the structure and ionic conductivity of solid electrolytes.

The structure investigations of dehydroacetic acid and 1,8-diaminonaphthalene condensation product by NMR, MS, and X-ray measurements

NASA Astrophysics Data System (ADS)

Kołodziej, B.; Morawiak, M.; Kamieński, B.; Schilf, W.

2016-05-01

A new unexpected product of condensation reaction of 1,8-diaminonaphthalene (DAN) and carbonyl compound (here: dehydroacetic acid (dha)) was synthesized. Discussion about the molecular structure of possible products of this reaction was done on the base of NMR studies. The structure of the titled product in both DMSO solution and in the solid state was resolved by analysis of its spectral data (X-ray structure analysis, multinuclear NMR in solution and solid state spectra) and MS measurements. The presented studies provided clear evidence that the titled product exists in diluted DMSO solution as the mixture of two kinetic free ionic species whereas in concentrated DMSO solution as well as in the solid state this system forms associated ionic pairs bonded together by hydrogen bonds.

Reduction in the Band Gap of Manganese-Doped Zinc Oxide: Role of the Oxidation State

NASA Astrophysics Data System (ADS)

Sharma, Sonia; Ramesh, Pranith; Swaminathan, P.

2015-12-01

Manganese-doped zinc oxide powders were synthesized by solid state reaction of the respective oxides. The high-temperature conditions were chosen such that multiple valence states of manganese were doped in the host zinc oxide lattice. Structural characterization was carried out to confirm the doping and to find the maximum amount of manganese that can be incorporated. Diffuse reflectance spectroscopy was used to measure the optical band gap of the doped sample and the lowering with respect to pure ZnO was attributed to the presence of higher oxidation states of manganese. The presence of these oxidation states was confirmed using x-ray photoelectron spectroscopy. The study shows that a solid state reaction is a viable route for synthesizing doped metal oxides with desired optical properties.

A coupled theory for chemically active and deformable solids with mass diffusion and heat conduction

NASA Astrophysics Data System (ADS)

Zhang, Xiaolong; Zhong, Zheng

2017-10-01

To analyse the frequently encountered thermo-chemo-mechanical problems in chemically active material applications, we develop a thermodynamically-consistent continuum theory of coupled deformation, mass diffusion, heat conduction and chemical reaction. Basic balance equations of force, mass and energy are presented at first, and then fully coupled constitutive laws interpreting multi-field interactions and evolving equations governing irreversible fluxes are constructed according to the energy dissipation inequality and the chemical kinetics. To consider the essential distinction between mass diffusion and chemical reactions in affecting free energy and dissipations of a highly coupled system, we regard both the concentrations of diffusive species and the extent of reaction as independent state variables. This new formulation then distinguishes between the energy contribution from the diffusive species entering the solid and that from the subsequent chemical reactions occurring among these species and the host solid, which not only interact with stresses or strains in different manners and on different time scales, but also induce different variations of solid microstructures and material properties. Taking advantage of this new description, we further establish a specialized isothermal model to predict precisely the transient chemo-mechanical response of a swelling solid with a proposed volumetric constraint that accounts for material incompressibility. Coupled kinetics is incorporated to capture the volumetric swelling of the solid caused by imbibition of external species and the simultaneous dilation arised from chemical reactions between the diffusing species and the solid. The model is then exemplified with two numerical examples of transient swelling accompanied by chemical reaction. Various ratios of characteristic times of diffusion and chemical reaction are taken into account to shed light on the dependency on kinetic time scales of evolution patterns for a diffusion-reaction controlled deformable solid.

Chemical looping fluidized-bed concentrating solar power system and method

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

Ma, Zhiwen

A concentrated solar power (CSP) plant comprises a receiver configured to contain a chemical substance for a chemical reaction and an array of heliostats. Each heliostat is configured to direct sunlight toward the receiver. The receiver is configured to transfer thermal energy from the sunlight to the chemical substance in a reduction reaction. The CSP plant further comprises a first storage container configured to store solid state particles produced by the reduction reaction and a heat exchanger configured to combine the solid state particles and gas through an oxidation reaction. The heat exchanger is configured to transfer heat produced inmore » the oxidation reaction to a working fluid to heat the working fluid. The CSP plant further comprises a power turbine coupled to the heat exchanger, such that the heated working fluid turns the power turbine, and a generator coupled to and driven by the power turbine to generate electricity.« less

Single-Molecule Sensing with Nanopore Confinement: From Chemical Reactions to Biological Interactions.

PubMed

Lin, Yao; Ying, Yi-Lun; Gao, Rui; Long, Yi-Tao

2018-03-25

The nanopore can generate an electrochemical confinement for single-molecule sensing that help understand the fundamental chemical principle in nanoscale dimensions. By observing the generated ionic current, individual bond-making and bond-breaking steps, single biomolecule dynamic conformational changes and electron transfer processes that occur within pore can be monitored with high temporal and current resolution. These single-molecule studies in nanopore confinement are revealing information about the fundamental chemical and biological processes that cannot be extracted from ensemble measurements. In this Concept article, we introduce and discuss the electrochemical confinement effects on single-molecule covalent reactions, conformational dynamics of individual molecules and host-guest interactions in protein nanopores. Then, we extend the concept of nanopore confinement effects to confine electrochemical redox reactions in solid-state nanopores for developing new sensing mechanisms. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The electrochemical reduction processes of solid compounds in high temperature molten salts.

PubMed

Xiao, Wei; Wang, Dihua

2014-05-21

Solid electrode processes fall in the central focus of electrochemistry due to their broad-based applications in electrochemical energy storage/conversion devices, sensors and electrochemical preparation. The electrolytic production of metals, alloys, semiconductors and oxides via the electrochemical reduction of solid compounds (especially solid oxides) in high temperature molten salts has been well demonstrated to be an effective and environmentally friendly process for refractory metal extraction, functional materials preparation as well as spent fuel reprocessing. The (electro)chemical reduction of solid compounds under cathodic polarizations generally accompanies a variety of changes at the cathode/melt electrochemical interface which result in diverse electrolytic products with different compositions, morphologies and microstructures. This report summarizes various (electro)chemical reactions taking place at the compound cathode/melt interface during the electrochemical reduction of solid compounds in molten salts, which mainly include: (1) the direct electro-deoxidation of solid oxides; (2) the deposition of the active metal together with the electrochemical reduction of solid oxides; (3) the electro-inclusion of cations from molten salts; (4) the dissolution-electrodeposition process, and (5) the electron hopping process and carbon deposition with the utilization of carbon-based anodes. The implications of the forenamed cathodic reactions on the energy efficiency, chemical compositions and microstructures of the electrolytic products are also discussed. We hope that a comprehensive understanding of the cathodic processes during the electrochemical reduction of solid compounds in molten salts could form a basis for developing a clean, energy efficient and affordable production process for advanced/engineering materials.

Core-Shell Fe1- xS@Na2.9PS3.95Se0.05 Nanorods for Room Temperature All-Solid-State Sodium Batteries with High Energy Density.

PubMed

Wan, Hongli; Mwizerwa, Jean Pierre; Qi, Xingguo; Liu, Xin; Xu, Xiaoxiong; Li, Hong; Hu, Yong-Sheng; Yao, Xiayin

2018-03-27

High ionic conductivity electrolyte and intimate interfacial contact are crucial factors to realize high-performance all-solid-state sodium batteries. Na 2.9 PS 3.95 Se 0.05 electrolyte with reduced particle size of 500 nm is first synthesized by a simple liquid-phase method and exhibits a high ionic conductivity of 1.21 × 10 -4 S cm -1 , which is comparable with that synthesized with a solid-state reaction. Meanwhile, a general interfacial architecture, that is, Na 2.9 PS 3.95 Se 0.05 electrolyte uniformly anchored on Fe 1- x S nanorods, is designed and successfully prepared by an in situ liquid-phase coating approach, forming core-shell structured Fe 1- x S@Na 2.9 PS 3.95 Se 0.05 nanorods and thus realizing an intimate contact interface. The Fe 1- x S@Na 2.9 PS 3.95 Se 0.05 /Na 2.9 PS 3.95 Se 0.05 /Na all-solid-state sodium battery demonstrates high specific capacity and excellent rate capability at room temperature, showing reversible discharge capacities of 899.2, 795.5, 655.1, 437.9, and 300.4 mAh g -1 at current densities of 20, 50, 100, 150, and 200 mA g -1 , respectively. The obtained all-solid-state sodium batteries show very high energy and power densities up to 910.6 Wh kg -1 and 201.6 W kg -1 based on the mass of Fe 1- x S at current densities of 20 and 200 mA g -1 , respectively. Moreover, the reaction mechanism of Fe 1- x S is confirmed by means of ex situ X-ray diffraction techniques, showing that partially reversible reaction occurs in the Fe 1- x S electrode after the second cycle, which gives the obtained all-solid-state sodium battery an exceptional cycling stability, exhibiting a high capacity of 494.3 mAh g -1 after cycling at 100 mA g -1 for 100 cycles. This contribution provides a strategy for designing high-performance room temperature all-solid-state sodium battery.

Supported organoiridium catalysts for alkane dehydrogenation

DOEpatents

Baker, R. Thomas; Sattelberger, Alfred P.; Li, Hongbo

2013-09-03

Solid supported organoiridium catalysts, a process for preparing such solid supported organoiridium catalysts, and the use of such solid supported organoiridium catalysts in dehydrogenation reactions of alkanes is provided. The catalysts can be easily recovered and recycled.

Synthesis of Y1BaCu3O(x) superconducting powders by intermediate phase reactions

NASA Technical Reports Server (NTRS)

Moure, C.; Fernandez, J. F.; Tartaj, J.; Recio, P.; Duran, P.

1991-01-01

A procedure for synthesizing Y1Ba2Cu3O(x) by solid state reactions was developed. The method is based on the use of barium compounds, previously synthesized, as intermediate phases for the process. The reaction kinetics of this procedure were established between 860 C and 920 C. The crystal structure and the presence of second phases were studied by means of XRD. The sintering behavior and ceramic parameters were also determined. The orthorhombic type-I structure was obtained on the synthesized bodies after a cooling cycle in an air atmosphere. Superconducting transition took place at 91 K. Sintering densities higher than 95 percent D sub th were attained at temperatures below 940 C.

On the implementation of a chain nuclear reaction of thermonuclear fusion on the basis of the p+11B process

NASA Astrophysics Data System (ADS)

Belyaev, V. S.; Krainov, V. P.; Zagreev, B. V.; Matafonov, A. P.

2015-07-01

Various theoretical and experimental schemes for implementing a thermonuclear reactor on the basis of the p+11B reaction are considered. They include beam collisions, fusion in degenerate plasmas, ignition upon plasma acceleration by ponderomotive forces, and the irradiation of a solid-state target from 11B with a proton beam under conditions of a Coulomb explosion of hydrogen microdrops. The possibility of employing ultra-short high-intensity laser pulses to initiate the p+11B reaction under conditions far from thermodynamic equilibrium is discussed. This and some other weakly radioactive thermonuclear reactions are promising owing to their ecological cleanness—there are virtually no neutrons among fusion products. Nuclear reactions that follow the p+11B reaction may generate high-energy protons, sustaining a chain reaction, and this is an advantage of the p+11B option. The approach used also makes it possible to study nuclear reactions under conditions close to those in the early Universe or in the interior of stars.

Lipase production in solid-state fermentation monitoring biomass growth of aspergillus niger using digital image processing.

PubMed

Dutra, Júlio C V; da C Terzi, Selma; Bevilaqua, Juliana Vaz; Damaso, Mônica C T; Couri, Sônia; Langone, Marta A P; Senna, Lilian F

2008-03-01

The aim of this study was to monitor the biomass growth of Aspergillus niger in solid-state fermentation (SSF) for lipase production using digital image processing technique. The strain A. niger 11T53A14 was cultivated in SSF using wheat bran as support, which was enriched with 0.91% (m/v) of ammonium sulfate. The addition of several vegetable oils (castor, soybean, olive, corn, and palm oils) was investigated to enhance lipase production. The maximum lipase activity was obtained using 2% (m/m) castor oil. In these conditions, the growth was evaluated each 24 h for 5 days by the glycosamine content analysis and digital image processing. Lipase activity was also determined. The results indicated that the digital image process technique can be used to monitor biomass growth in a SSF process and to correlate biomass growth and enzyme activity. In addition, the immobilized esterification lipase activity was determined for the butyl oleate synthesis, with and without 50% v/v hexane, resulting in 650 and 120 U/g, respectively. The enzyme was also used for transesterification of soybean oil and ethanol with maximum yield of 2.4%, after 30 min of reaction.

Lipase Production in Solid-State Fermentation Monitoring Biomass Growth of Aspergillus niger Using Digital Image Processing

NASA Astrophysics Data System (ADS)

Dutra, Julio C. V.; da Terzi, Selma C.; Bevilaqua, Juliana Vaz; Damaso, Mônica C. T.; Couri, Sônia; Langone, Marta A. P.; Senna, Lilian F.

The aim of this study was to monitor the biomass growth of Aspergillus niger in solid-state fermentation (SSF) for lipase production using digital image processing technique. The strain A. niger 11T53A14 was cultivated in SSF using wheat bran as support, which was enriched with 0.91% (m/v) of ammonium sulfate. The addition of several vegetable oils (castor, soybean, olive, corn, and palm oils) was investigated to enhance lipase production. The maximum lipase activity was obtained using 2% (m/m) castor oil. In these conditions, the growth was evaluated each 24 h for 5 days by the glycosamine content analysis and digital image processing. Lipase activity was also determined. The results indicated that the digital image process technique can be used to monitor biomass growth in a SSF process and to correlate biomass growth and enzyme activity. In addition, the immobilized esterification lipase activity was determined for the butyl oleate synthesis, with and without 50% v/v hexane, resulting in 650 and 120 U/g, respectively. The enzyme was also used for transesterification of soybean oil and ethanol with maximum yield of 2.4%, after 30 min of reaction.

Further analytical study of hybrid rocket combustion

NASA Technical Reports Server (NTRS)

Hung, W. S. Y.; Chen, C. S.; Haviland, J. K.

1972-01-01

Analytical studies of the transient and steady-state combustion processes in a hybrid rocket system are discussed. The particular system chosen consists of a gaseous oxidizer flowing within a tube of solid fuel, resulting in a heterogeneous combustion. Finite rate chemical kinetics with appropriate reaction mechanisms were incorporated in the model. A temperature dependent Arrhenius type fuel surface regression rate equation was chosen for the current study. The governing mathematical equations employed for the reacting gas phase and for the solid phase are the general, two-dimensional, time-dependent conservation equations in a cylindrical coordinate system. Keeping the simplifying assumptions to a minimum, these basic equations were programmed for numerical computation, using two implicit finite-difference schemes, the Lax-Wendroff scheme for the gas phase, and, the Crank-Nicolson scheme for the solid phase.

Solid electrolyte: The key for high-voltage lithium batteries

DOE PAGES

Li, Juchuan; Ma, Cheng; Chi, Miaofang; ...

2014-10-14

A solid-state high-voltage (5 V) lithium battery is demonstrated to deliver a cycle life of 10 000 with 90% capacity retention. Furthermore, the solid electrolyte enables the use of high-voltage cathodes and Li anodes with minimum side reactions, leading to a high Coulombic efficiency of 99.98+%.

Effect of Ag and Pb Addition on Microstructural and Mechanical Properties of SAC 105 Solders

NASA Astrophysics Data System (ADS)

Molnar, Aliz; Janovszky, Dora; Kardos, Ibolya; Molnar, Istvan; Gacsi, Zoltan

2015-10-01

Melting and crystallization processes of lead-free and lead-contaminated alloys in near-equilibrium state were investigated. In addition, the effect of silver content up to 4 wt.% on the microstructure of Sn-Ag-Cu alloys was studied. The volume fraction of β-Sn decreased by half owing to 4 wt.% Ag content. Furthermore, contamination by lead strongly influences the properties of the solidified microstructure. The Pb grains appear as a result of two processes when the Pb content is equal to 0.5 wt.% or higher: Pb phase solidifies in the quaternary eutectic at 176°C, and Pb grains precipitate from the primary β-Sn solid solution grain during a solid state reaction. The freezing range enlarges to 51°C due to 2 wt.% Pb content owing to quaternary eutectic. Above 1 wt.% Pb content, the mechanical properties also improve due to grains of quaternary eutectic Pb and precipitated Pb grains with a size <1 μm.

PROCESS OF PREPARING ZIRCONIUM OXYCHLORIDE

DOEpatents

Wilhelm, H.A.; Andrews, M.L.

1960-06-28

A process is given for preparing zirconyl chloride by mixing solid zirconyl chloride octahydrate and solid zirconium tetrachloride at room temperature whereby both chlorides are converted to zirconyl chloride trinydrate and hydrogen chloride is formed and volatilized by the reaction heat.

The physics of solid-state neutron detector materials and geometries.

PubMed

Caruso, A N

2010-11-10

Detection of neutrons, at high total efficiency, with greater resolution in kinetic energy, time and/or real-space position, is fundamental to the advance of subfields within nuclear medicine, high-energy physics, non-proliferation of special nuclear materials, astrophysics, structural biology and chemistry, magnetism and nuclear energy. Clever indirect-conversion geometries, interaction/transport calculations and modern processing methods for silicon and gallium arsenide allow for the realization of moderate- to high-efficiency neutron detectors as a result of low defect concentrations, tuned reaction product ranges, enhanced effective omnidirectional cross sections and reduced electron-hole pair recombination from more physically abrupt and electronically engineered interfaces. Conversely, semiconductors with high neutron cross sections and unique transduction mechanisms capable of achieving very high total efficiency are gaining greater recognition despite the relative immaturity of their growth, lithographic processing and electronic structure understanding. This review focuses on advances and challenges in charged-particle-based device geometries, materials and associated mechanisms for direct and indirect transduction of thermal to fast neutrons within the context of application. Calorimetry- and radioluminescence-based intermediate processes in the solid state are not included.

Kinetics of liquid-solid reactions in naphthenic acid conversion and Kraft pulping

NASA Astrophysics Data System (ADS)

Yang, Ling

Two liquid-solid reactions, in which the morphology of the solid changes as the reactions proceeds, were examined. One is the NA conversion in oil by decarboxylation on metal oxides and carbonates, and the other is the Kraft pulping in which lignin removal by delignification reaction. In the study of the NA conversion, CaO was chosen as the catalyst for the kinetic study from the tested catalysts based on NA conversion. Two reaction mixtures, carrier oil plus commercial naphthenic acids and heavy vacuum gas oil (HVGO) from Athabasca bitumen, were applied in the kinetic study. The influence of TAN, temperature, and catalyst loading on the NA conversion and decarboxylation were studied systematically. The results showed that the removal rate of TAN and the decarboxylation of NA were both independent of the concentration of NA over the range studied, and significantly dependent on reaction temperature. The data from analyzing the spent catalyst demonstrated that calcium naphthenate was an intermediate of the decarboxylation reaction of NA, and the decomposition of calcium naphthenate was a rate-determining step. In the study on the delignification of the Kraft pulping, a new mechanism was proposed for the heterogeneous delignification reaction during the Kraft pulping process. In particular, the chemical reaction mechanism took into account the heterogeneous nature of Kraft pulping. Lignin reacted in parallel with sodium hydroxide and sodium sulfide. The mechanism consists of three key kinetic steps: (1) adsorption of hydroxide and hydrosulfide ions on lignin; (2) surface reaction on the solid surface to produce degraded lignin products; and (3) desorption of degradation products from the solid surface. The most important step for the delignification process is the surface reaction, rather than the reactions occurring in the liquid phase. A kinetic model has, thus, been developed based on the proposed mechanism. The derived kinetic model showed that the mechanism could be employed to predict the pulping behavior under a variety of conditions with good accuracy.

Investigation of resonances in 20Mg: Implications for astrophysics and nuclear forces

NASA Astrophysics Data System (ADS)

Randhawa, Jaspreet; Kanungo, Rituparna; Alcorta, Martin; Burbadge, Christina; Burke, Devin; Christian, Greg; Davids, Barry; Even, Julia; Hackman, Greg; Henderson, Jack; Ishimoto, Shigeru; Kaur, Satbir; Keefe, Matthew; Kruecken, Reiner; Lighthall, Jon; Moukaddam, Mohamad; Padilla-Rodal, Elizabeth; Smith, Jenna; Turko, Joseph; Workman, Orry

2016-09-01

18Ne(2p, γ)20Mg provides a possible pathway for breakout from the hot CNO cycles to the rp-process in type I X-ray bursts. This reaction rate is uncertain due to lack of any experimental information on the resonant states in 20Mg above proton emission threshold. Recent calculations using nuclear forces from chiral perturbation theory predict quite a different level structure for 20Mg with and without inclusion of three nucleon forces. These differences make study of 20Mg states important to constraint both nuclear theory and this reaction rate. We have investigated the excited states in 20Mg through inelastic deuteron scattering. The experiment was performed using the IRIS facility at TRIUMF, Canada. The 20Mg beam with an average intensity of 500 pps and energy of 8.5A MeV was directed at novel thin windowless solid deuteron target. Experiment and initial observations will be discussed.

Laser-Induced Fluorescence Measurements for Optical Single Atom Detection for Nuclear Astrophysics

NASA Astrophysics Data System (ADS)

Parzuchowski, Kristen; Singh, Jaideep; Wenzl, Jennifer; Frisbie, Dustin; Johnson, Maegan

2016-09-01

We propose a new highly selective detector to measure rare nuclear reactions relevant for nuclear astrophysics. Our primary interest is the 22Ne(α , n) 25Mg reaction, which is a primary source of neutrons for the s-process. Our proposed detector, in conjunction with a recoil separator, captures the recoil products resulting from the reaction in a cryogenically frozen thin film of solid neon. The fluorescence spectra of the captured atoms is shifted from the absorption spectra by hundreds of nanometers. This allows for the optical detection of individual fluorescence photons against a background of intense excitation light. We will describe our initial studies of laser-induced fluorescence of Yb and Mg in solid Ne. Neon is an attractive medium because it is optically transparent and provides efficient, pure, stable, & chemically inert confinement for a wide variety of atomic and molecular species. Yb is used as a test atom because of its similar atomic structure to Mg and much brighter fluorescence signal. This work is supported by funds from Michigan State University.

Solar photolysis of water

NASA Technical Reports Server (NTRS)

Ryason, P. R. (Inventor)

1978-01-01

A cyclic process is described for the solar photolysis of water, including a first stage in which water is reduced in the presence of a Eu(+2) photooxidizable reagent producing hydrogen and spent oxidized Eu(+3) reagent. The spent reagent Eu(+3) is reduced by means of a transition metal ligand complex reductant, RuL(+3) in a photoexcited state, such as a ruthenium pyridyl complex. Due to competing reactions between the photolysis and regeneration products, the photooxidation reaction must be separated from the regeneration in space and time by supporting the reagent and/or the reductant on solid supports and utilizing pH, wavelength and flow control to maximize hydrogen and oxygen production.

Process for forming a homogeneous oxide solid phase of catalytically active material

DOEpatents

Perry, Dale L.; Russo, Richard E.; Mao, Xianglei

1995-01-01

A process is disclosed for forming a homogeneous oxide solid phase reaction product of catalytically active material comprising one or more alkali metals, one or more alkaline earth metals, and one or more Group VIII transition metals. The process comprises reacting together one or more alkali metal oxides and/or salts, one or more alkaline earth metal oxides and/or salts, one or more Group VIII transition metal oxides and/or salts, capable of forming a catalytically active reaction product, in the optional presence of an additional source of oxygen, using a laser beam to ablate from a target such metal compound reactants in the form of a vapor in a deposition chamber, resulting in the deposition, on a heated substrate in the chamber, of the desired oxide phase reaction product. The resulting product may be formed in variable, but reproducible, stoichiometric ratios. The homogeneous oxide solid phase product is useful as a catalyst, and can be produced in many physical forms, including thin films, particulate forms, coatings on catalyst support structures, and coatings on structures used in reaction apparatus in which the reaction product of the invention will serve as a catalyst.

A new model of reaction-driven cracking: fluid volume consumption and tensile failure during serpentinization

NASA Astrophysics Data System (ADS)

Eichenbaum-Pikser, J. M.; Spiegelman, M. W.; Kelemen, P. B.; Wilson, C. R.

2013-12-01

Reactive fluid flow plays an important role in a wide range of geodynamic processes, such as melt migration, formation of hydrous minerals on fault surfaces, and chemical weathering. These processes are governed by the complex coupling between fluid transport, reaction, and solid deformation. Reaction-driven cracking is a potentially critical feedback mechanism, by which volume change associated with chemical reaction drives fracture in the surrounding rock. It has been proposed to play a role in both serpentinization and carbonation of peridotite, motivating consideration of its application to mineral carbon sequestration. Previous studies of reactive cracking have focused on the increase in solid volume, and as such, have considered failure in compression. However, if the consumption of fluid is considered in the overall volume budget, the reaction can be net volume reducing, potentially leading to failure in tension. To explore these problems, we have formulated and solved a 2-D model of coupled porous flow, reaction kinetics, and elastic deformation using the finite element model assembler TerraFERMA (Wilson et al, G3 2013 submitted). The model is applied to the serpentinization of peridotite, which can be reasonably approximated as the transfer of a single reactive component (H2O) between fluid and solid phases, making it a simple test case to explore the process. The behavior of the system is controlled by the competition between the rate of volume consumption by the reaction, and the rate of volume replacement by fluid transport, as characterized by a nondimensional parameter χ, which depends on permeability, reaction rate, and the bulk modulus of the solid. Large values of χ correspond to fast fluid transport relative to reaction rate, resulting in a low stress, volume replacing regime. At smaller values of χ, fluid transport cannot keep up with the reaction, resulting in pore fluid under-pressure and tensile solid stresses. For the range of χ relevant to the serpentinization of peridotite, these stresses can reach hundreds of MPa, exceeding the tensile strength of peridotite.

Mechanism of Formation of Li 7 P 3 S 11 Solid Electrolytes through Liquid Phase Synthesis

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

Wang, Yuxing; Lu, Dongping; Bowden, Mark

Crystalline Li7P3S11 is a promising solid electrolyte for all solid state lithium/lithium ion batteries. A controllable liquid phase synthesis of Li7P3S11 is more desirable compared to conventional mechanochemical synthesis, but recent attempts suffer from reduced ionic conductivities. Here we elucidate the formation mechanism of crystalline Li7P3S11 synthesized in the liquid phase (acetonitrile, or ACN). We conclude that the crystalline Li7P3S11 forms through a two-step reaction: 1) formation of solid Li3PS4∙ACN and amorphous Li2S∙P2S5 phases in the liquid phase; 2) solid-state conversion of the two phases. The implication of this two-step reaction mechanism to the morphology control and the transport propertiesmore » of liquid phase synthesized Li7P3S11 is identified and discussed.« less

Synthesis and characterization of nanostructured electrodes for solid state ionic devices

NASA Astrophysics Data System (ADS)

Zhang, Yuelan

Solid-state electrochemical energy conversion and storage technologies such as fuel cells and lithium ion batteries will influence the way we use energy and the environment we live in. The demands for advanced power sources with high energy efficiency, minimum environmental impact, and low cost have been the impetus for the development of a new generation of batteries and fuel cells. Currently, lithium ion battery technology's greatest disadvantages are long-term cycling stability and high charge/discharge rate capabilities. On the other hand, fuel cell technology's greatest disadvantage is cost. It is found that these problems could be attenuated by the incorporation of nano-structured materials. But, we are still far away from possessing a solid scientific understanding of what goes on at the nanoscale inside these solid state ionic devices, and what is the relationship between nano-structures and their electrochemical properties, especially between the microstructure and electrode polarization and degradation. Electrode polarization represents a voltage loss in an electrochemical energy conversion process. Such understanding is critical for further progress in solid state ionic devices. This thesis focused on the design, fabrication, and characterization of nanostructured porous electrodes with desired composition and microstructure to minimize electrode polarization losses in the application of fuel cells and lithium ion batteries. Various chemical methods such as sol-gel, hydrothermal, surfactant, colloidal and polymer template-assisted processes have been applied in this work. And various characterization techniques have been used to explore the understanding of the microscopic features with electrochemical interfacial properties of the electrodes. Solid-state diffusion often limits the utilization and rate capability of electrode materials in a lithium-ion battery, especially at high charge/discharge rates. When the fluxes of Li+ insertion or extraction exceeds the diffusion-limited rate of Li+ transport within the bulk phase of an electrode, concentration polarization occurs. Further, large volume changes associated with Li+ insertion or extraction could induce stresses in bulk electrodes, potentially leading to mechanical failure. Porous electrodes with high surface-to-volume ratio would increase the electrochemical reaction surface and suppress the mechanical stress. But porous electrodes also increase the tortuosity of mass transport within solid electrodes. Interconnected porous materials would decrease the percolation threshold for porous electrodes. In this work, electrodes with unique architecture for lithium ion batteries have been fabricated to improve the cycleability, rate capability and capacity retention. Spinel LiMn2O4 with interconnected macropores was created using a glycine-nitrate combustion process. Both microstructure and phase crystallinity were optimized by adjusting the fuel/oxidant ratio. This macroporous LiMn2O4 positive electrode exhibited better capacity retention and rate capability than those with larger particle size prepared by solid state reaction. Detailed electrode kinetic studies indicated that the macroporous microstructure promoted lithium diffusion and the overall reaction process was not controlled by lithium diffusion. Nanostructured tin oxide thin films with columnar grains less than 20 nm were deposited on Au/Si substrate using a combustion CVD method. The microstructure was highly porous and open, and thus was easily accessible to liquid electrolyte. In addition, the microstructure with vertical and radial connectivity of active materials led to decreased tortuosity for mass transport within solid electrodes. Nanoparticles accommodated the large volume change during cycling. These thin film electrodes exhibited highly reversible specific capacity and good capacity retention. It is about 93% after 80 cycles at a charge/discharge rate of 0.3 mA/cm2. When discharged at 0.9 mA/cm2, the obtained capacity retention was about 64% of the capacity at 0.3 mA/cm2. Cathodic interfacial polarization represents the predominant loss in a low-temperature SOFC. In this thesis, several porous nanocomposite electrodes of mixed ionic and electronic conductors (MIEC) with high surface areas were designed and fabricated to improve to minimize the polarization resistance. For the first time, regular, homogeneous and dual porous MIEC electrodes were successfully fabricated using breath figure templating, which is self-assembly of the water droplets in polymer solution. The homogeneous macropores promoted rapid mass transport by decreasing the tortuosity. Further, mesoporous microstructure provided more surface areas for gas adsorption and more TPBs for the electrochemical reactions. The interfacial polarization resistances were 0.94 and 0.39 Ocm 2 at 700 and 750°C, respectively. Furthermore, electrodes consisting of strontium doped lanthanum manganite (LSM) and gadolinium doped ceria (GDC) were developed with a modified sol-gel process for honeycomb SOFCs based on stabilized zirconia electrolytes. The sol gel derived cathodes with fine grain size and large specific surface area, showed much lower interfacial polarization resistances than those prepared by other processing methods. And this process developed strong bonding between the electrode and electrolyte even at low temperatures. The interfacial polarization resistances were 0.65 and 0.16 Ocm 2 at 650 and 750°C, respectively. The mesoscopic regime of overlapping space charge effects had a positive effect on the electrode kinetics. Ceria is a very important catalytic material for fuel reforming in SOFCs and CO poisoning in PEM fuel cells. Especially, the design of a new generation SOFC requires the in-situ reforming of hydrocarbon fuels. In this work, nanostructured ceria was developed via a controlled hydrothermal process in a mixed water-ethanol medium. The microstructure, formation mechanism, and their surface catalytic properties were investigated.

Defect-Induced Luminescence of a Self-Activated Borophosphate Phosphor

NASA Astrophysics Data System (ADS)

Han, Bing; Liu, Beibei; Dai, Yazhou; Zhang, Jie

2018-05-01

A self-activated borophosphate phosphor Ba3BPO7 was prepared via typical solid-state reaction in thermal-carbon reduction atmosphere. The structural and luminescence properties were investigated using x-ray powder diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, and photoluminescence spectroscopy. Upon excitation with ultraviolet (UV) light, the as-prepared phosphor shows bright greenish-yellow emission with a microsecond-level fluorescence lifetime, which could result from the oxygen vacancies produced in the process of solid-state synthesis. The possible luminescence mechanism is proposed. Through the introduction of defects in the host, this work realizes visible luminescence in a pure borophosphate compound that does not contain any rare earth or transition metal activators, so it is helpful to develop defect-related luminescent materials in view of energy conservation and environmental protection for sustainable development.

Nitrosation and nitration of fulvic acid, peat and coal with nitric acid

USGS Publications Warehouse

Thorn, Kevin A.; Cox, Larry G.

2016-01-01

Nitrohumic acids, produced from base extraction of coals and peats oxidized with nitric acid, have received considerable attention as soil ammendments in agriculture. The nitration chemistry however is incompletely understood. Moreover, there is a need to understand the reaction of nitric acid with natural organic matter (NOM) in general, in the context of a variety of environmental and biogeochemical processes. Suwannee River NOM, Suwannee River fulvic acid, and Pahokee Peat fulvic acid were treated with 15N-labeled nitric acid at concentrations ranging from 15% to 22% and analyzed by liquid and solid state 15N NMR spectroscopy. Bulk Pahokee peat and Illinois #6 coal were also treated with nitric acid, at 29% and 40% respectively, and analyzed by solid state 15N NMR spectroscopy. In addition to nitro groups from nitration of aromatic carbon, the 15N NMR spectra of all five samples exhibited peaks attributable to nitrosation reactions. These include nitrosophenol peaks in the peat fulvic acid and Suwannee River samples, from nitrosation of phenolic rings, and N-nitroso groups in the peat samples, from nitrosation of secondary amides or amines, the latter consistent with the peat samples having the highest naturally abundant nitrogen contents. Peaks attributable to Beckmann and secondary reactions of the initially formed oximes were present in all spectra, including primary amide, secondary amide, lactam, and nitrile nitrogens. The degree of secondary reaction product formation resulting from nitrosation reactions appeared to correlate inversely with the 13C aromaticities of the samples. The nitrosation reactions are most plausibly effected by nitrous acid formed from the reduction of nitric acid by oxidizable substrates in the NOM and coal samples.

Nitrosation and Nitration of Fulvic Acid, Peat and Coal with Nitric Acid

PubMed Central

Thorn, Kevin A.; Cox, Larry G.

2016-01-01

Nitrohumic acids, produced from base extraction of coals and peats oxidized with nitric acid, have received considerable attention as soil ammendments in agriculture. The nitration chemistry however is incompletely understood. Moreover, there is a need to understand the reaction of nitric acid with natural organic matter (NOM) in general, in the context of a variety of environmental and biogeochemical processes. Suwannee River NOM, Suwannee River fulvic acid, and Pahokee Peat fulvic acid were treated with 15N-labeled nitric acid at concentrations ranging from 15% to 22% and analyzed by liquid and solid state 15N NMR spectroscopy. Bulk Pahokee peat and Illinois #6 coal were also treated with nitric acid, at 29% and 40% respectively, and analyzed by solid state 15N NMR spectroscopy. In addition to nitro groups from nitration of aromatic carbon, the 15N NMR spectra of all five samples exhibited peaks attributable to nitrosation reactions. These include nitrosophenol peaks in the peat fulvic acid and Suwannee River samples, from nitrosation of phenolic rings, and N-nitroso groups in the peat samples, from nitrosation of secondary amides or amines, the latter consistent with the peat samples having the highest naturally abundant nitrogen contents. Peaks attributable to Beckmann and secondary reactions of the initially formed oximes were present in all spectra, including primary amide, secondary amide, lactam, and nitrile nitrogens. The degree of secondary reaction product formation resulting from nitrosation reactions appeared to correlate inversely with the 13C aromaticities of the samples. The nitrosation reactions are most plausibly effected by nitrous acid formed from the reduction of nitric acid by oxidizable substrates in the NOM and coal samples. PMID:27175784

An investigation into the effects of different existing states of aluminum isopropoxide on copper-based catalysts for direct synthesis of dimethyl ether from syngas

NASA Astrophysics Data System (ADS)

Sun, Kai; Wang, Peng; Bian, Zhongkai; Huang, Wei

2018-01-01

Aluminum isopropoxide (AIP) is a vital raw material to produce high surface area alumina catalyst, which is used for catalytic applications, such as hydrocracking, Fischer-Tropsch and STD (syngas to dimethyl ether) reactions. However, the different existing states have an effect on hydrolysis and condensation in the process of precursor preparation. The Cu/Zn/Al slurry catalysts were prepared by aluminum isopropoxide, which were liquid state, crystalline state and solid state, utilizing a complete liquid phase preparation technology. In the dimethyl ether (DME) synthesis reaction, the aluminum resource of crystalline state was prepared for slurry catalyst, which presented high CO conversion and DME selectivity of 54.32% and 69.74%, respectively. Characterization results indicated that different forms of AIP have the variant coordination numbers of Al-O and polymerization degrees, and the catalyst prepared by crystalline state consists amount of tetra-coordinated Al and few hexa-coordinated Al, which can exert different hydrolysis and condensation process compared with other aluminum sources, and finally it contributes to the strong interaction between active site copper species and Zn/Al species, confirming more Cu+ is responsible for the synthesis of DME in the slurry reactor.

Catalytic and electrochemical behaviour of solid oxide fuel cell operated with simulated-biogas mixtures

NASA Astrophysics Data System (ADS)

Dang-Long, T.; Quang-Tuyen, T.; Shiratori, Y.

2016-06-01

Being produced from organic matters of wastes (bio-wastes) through a fermentation process, biogas mainly composed of CH4 and CO2 and can be considered as a secondary energy carrier derived from solar energy. To generate electricity from biogas through the electrochemical process in fuel cells is a state-of-the-art technology possessing higher energy conversion efficiency without harmful emissions compared to combustion process in heat engines. Getting benefits from high operating temperature such as direct internal reforming ability and activation of electrochemical reactions to increase overall system efficiency, solid oxide fuel cell (SOFC) system operated with biogas becomes a promising candidate for distributed power generator for rural applications leading to reductions of environmental issues caused by greenhouse effects and bio-wastes. CO2 reforming of CH4 and electrochemical oxidation of the produced syngas (H2-CO mixture) are two main reaction processes within porous anode material of SOFC. Here catalytic and electrochemical behavior of Ni-ScSZ (scandia stabilized-zirconia) anode in the feed of CH4-CO2 mixtures as simulated-biogas at 800 °C were evaluated. The results showed that CO2 had strong influences on both reaction processes. The increase in CO2 partial pressure resulted in the decrease in anode overvoltage, although open-circuit voltage was dropped. Besides that, the simulation result based on a power-law model for equimolar CH4-CO2 mixture revealed that coking hazard could be suppressed along the fuel flow channel in both open-circuit and closed-circuit conditions.

Functional Nanopores: A Solid-state Concept for Artificial Reaction Compartments and Molecular Factories.

PubMed

Puebla-Hellmann, Gabriel; Mayor, Marcel; Lörtscher, Emanuel

2016-01-01

On the road towards the long-term goal of the NCCR Molecular Systems Engineering to create artificial molecular factories, we aim at introducing a compartmentalization strategy based on solid-state silicon technology targeting zeptoliter reaction volumes and simultaneous electrical contact to ensembles of well-oriented molecules. This approach allows the probing of molecular building blocks under a controlled environment prior to their use in a complex molecular factory. Furthermore, these ultra-sensitive electrical conductance measurements allow molecular responses to a variety of external triggers to be used as sensing and feedback mechanisms. So far, we demonstrate the proof-of-concept by electrically contacting self-assembled mono-layers of alkane-dithiols as an established test system. Here, the molecular films are laterally constrained by a circular dielectric confinement, forming a so-called 'nanopore'. Device yields above 85% are consistently achieved down to sub-50 nm nanopore diameters. This generic platform will be extended to create distributed, cascaded reactors with individually addressable reaction sites, including interconnecting micro-fluidic channels for electrochemical communication among nanopores and sensing sites for reaction control and feedback. In this scientific outlook, we will sketch how such a solid-state nanopore concept can be used to study various aspects of molecular compounds tailored for operation in a molecular factory.

Bridging the gap between homogeneous and heterogeneous catalysis: ortho/para H(2) conversion, hydrogen isotope scrambling, and hydrogenation of olefins by Ir(CO)Cl(PPh(3))(2).

PubMed

Matthes, Jochen; Pery, Tal; Gründemann, Stephan; Buntkowsky, Gerd; Sabo-Etienne, Sylviane; Chaudret, Bruno; Limbach, Hans-Heinrich

2004-07-14

Some transition metal complexes are known to catalyze ortho/para hydrogen conversion, hydrogen isotope scrambling, and hydrogenation reactions in liquid solution. Using the example of Vaska's complex, we present here evidence by NMR that the solvent is not necessary for these reactions to occur. Thus, solid frozen solutions or polycrystalline powdered samples of homogeneous catalysts may become heterogeneous catalysts. Comparative liquid- and solid-state studies provide novel insight into the reaction mechanisms.

A kinetic study of the replacement of calcite marble by fluorite

NASA Astrophysics Data System (ADS)

Trindade Pedrosa, Elisabete; Boeck, Lena; Putnis, Christine V.; Putnis, Andrew

2016-04-01

Replacement reactions are relevant in any situation that involves the reequilibration between a solid and an aqueous fluid phase and are commonly controlled by an interface-coupled dissolution-precipitation mechanism (Putnis and Putnis, 2007). These reactions control many large-scale Earth processes whenever aqueous fluids are available, such as during metamorphism, metasomatism, and weathering. An important consequence of coupled dissolution-precipitation is the generation of porosity in the product phase that then allows the infiltration of the fluid within the mineral being replaced. Understanding the mechanism and kinetics of the replacement of carbonates by fluorite has application in earth sciences and engineering. Fluorite (CaF2) occurs in all kinds of rocks (igneous, sedimentary, and metamorphic) and its origin is commonly associated with hydrothermal fluids. Moreover, calcium carbonate has been suggested as a successful seed material for the sequestration of fluoride from contaminated waters (Waghmare and Arfin, 2015). The aim of the present work is to investigate aspects of the replacement of calcium carbonate by fluorite to better understand the mechanism and kinetics of this reaction. Small cubes (˜ 3 × 3 × 3 mm) of Carrara marble (CaCO3 > 99 %) were cut and reacted with a 4 M ammonium fluoride (NH4F) solution for different times (1 to 48 hours) and temperatures (60, 80, 100, and 140 ° C). The microstructure of the product phases was analysed using SEM. The kinetics of replacement was monitored from the Rietveld analysis of X-ray powder diffraction patterns of the products as a function of temperature and reaction time. After reaction, all samples preserved their size and external morphology (a pseudomorphic replacement) and the product phase (fluorite) was highly porous. The activation energy Ea (kJ/mol) of the replacement reaction was empirically determined by both model-fitting and model-free methods. The isoconversional method yielded an empirical activation energy of 41 kJ/mol, and a statistical approach applied to the model-fitting method revealed that the replacement of Carrara marble by fluorite is better fitted to a diffusion-controlled process. This is consistent with ion diffusion through the fluid phase. These results suggest that the replacement reaction is dependent on the fluid migration rate through the newly formed porosity. Putnis, A., Putnis C.V., 2007. The mechanism of reequilibration of solids in the presence of a fluid phase. Journal of Solid State Chemistry, 180, 1783-1786. Waghmare, S.S., Arfin, T. (2015). Fluoride removal from water by calcium materials: A state-of-the-art review. Int. J. Innov. Res. Sci. Eng. Technol. 4, 8090-8102.

Two-dimensional time-resolved X-ray diffraction study of liquid/solid fraction and solid particle size in Fe-C binary system with an electrostatic levitator furnace

NASA Astrophysics Data System (ADS)

Yonemura, M.; Okada, J.; Watanabe, Y.; Ishikawa, T.; Nanao, S.; Shobu, T.; Toyokawa, H.

2013-03-01

Liquid state provides functions such as matter transport or a reaction field and plays an important role in manufacturing processes such as refining, forging or welding. However, experimental procedures are significantly difficult for an observation of solidification process of iron and iron-based alloys in order to identify rapid transformations subjected to fast temperature evolution. Therefore, in order to study the solidification in iron and iron-based alloys, we considered a combination of high energy X-ray diffraction measurements and an electrostatic levitation method (ESL). In order to analyze the liquid/solid fraction, the solidification of melted spherical specimens was measured at a time resolution of 0.1 seconds during rapid cooling using the two-dimensional time-resolved X-ray diffraction. Furthermore, the observation of particle sizes and phase identification was performed on a trial basis using X-ray small angle scattering with X-ray diffraction.

Skating on thin ice: surface chemistry under interstellar conditions

NASA Astrophysics Data System (ADS)

Fraser, H.; van Dishoeck, E.; Tielens, X.

Solid CO2 has been observed towards both active star forming regions and quiescent clouds (Gerakines et. al. (1999)). The high abundance of CO2 in the solid phase, and its low abundance in the gas phase, support the idea that CO2 is almost exclusively formed in the solid state. Several possible formation mechanisms have been postulated (Ruffle &Herbst (2001): Charnley &Kaufman (2000)), and the detection of CO2 towards quiescent sources such as Elias 16 (Whittet et. al. (1998)) clearly suggests that CO2 can be produced in the absence of UV or electron mediated processes. The most likely route is via the surface reactions between O atoms, or OH radicals, and CO. The tools of modern surface- science offer us the potential to determine many of the physical and chemical attributes of icy interstellar grain mantles under highly controlled conditions, that closely mimic interstellar environments. The Leiden Surface Reaction Simulation Device ( urfreside) combines UHV (UltraS High Vacuum) surface science techniques with an atomic beam to study chemical reactions occurring on the SURFACE and in the BULK of interstellar ice grain mimics. By simultaneously combining two or more surface analysis techniques, the chemical kinetics, reaction mechanisms and activation energies can be determined directly. The experiment is aimed at identifying the key barrierless reactions and desorption pathways on and in H2 O and CO ices under interstellar conditions. The results from traditional HV (high vacuum) and UHV studies of the CO + O and CO + OH reactions will be presented in this paper. Charnley, S.B., & Kaufman, M.J., 2000, ApJ, 529, L111 Gerakines, P.A., 1999, ApJ, 522, 357 Ruffle, D.P., & Herbst, E., 2001, MNRAS, 324, 1054 Whittet, D.C.B., et.al., 1998, ApJ, 498, L159

Tunneling chemical reactions D +H2→DH+H and D +DH→D2+H in solid D2-H2 and HD -H2 mixtures: An electron-spin-resonance study

NASA Astrophysics Data System (ADS)

Kumada, Takayuki

2006-03-01

Tunneling chemical reactions D +H2→DH+H and D +DH→D2+H in solid HD -H2 and D2-H2 mixtures were studied in the temperature range between 4 and 8K. These reactions were initiated by UV photolysis of DI molecules doped in these solids for 30s and followed by measuring the time course of electron-spin-resonance (ESR) intensities of D and H atoms. ESR intensity of D atoms produced by the photolysis decreases but that of H atoms increases with time. Time course of the D and H intensities has the fast and slow processes. The fast process, which finishes within ˜300s after the photolysis, is assigned to the reaction of D atom with one of its nearest-neighboring H2 molecules, D(H2)n(HD)12-n→H(H2)n-1(HD)13-n or D(H2)n(D2)12-n→H(HD )(H2)n-1(D2)12-n for 12⩾n⩾1. Rate constant for the D +H2 reaction between neighboring D atom-H2 molecule pair is determined to be (7.5±0.7)×10-3s-1 in solid HD -H2 and (1.3±0.3)×10-2s-1 in D2-H2 at 4.1K, which is very close to that calculated based on the theory of chemical reaction in gas phase by Hancock et al. [J. Chem. Phys. 91, 3492 (1989)] and Takayanagi and Sato [J. Chem. Phys. 92, 2862 (1990)]. This rate constant was found to be independent of temperature up to 7K within experimental error of ±30%. The slow process is assigned to the reaction of D atom produced in a cage fully surrounded by HD or D2 molecules, D(HD)12 or D(D2)12. This D atom undergoes the D +DH reaction with one of its nearest-neighboring HD molecules in solid HD -H2 or diffuses to the neighbor of H2 molecules to allow the D +H2 reaction in solid HD -H2 and D2-H2. The former is the main channel in solid HD -H2 below 6K where D atoms diffuse very slowly, whereas the latter dominates over the former above 6K. Rate for the reactions in the slow process is independent of temperature below 6K but increases with the increase in temperature above 6K. We found that the increase is due to the increase in hopping rate of D atoms to the neighbor of H2 molecules. Rate constant for the D +DH reaction was found to be independent of temperature up to 7K as well.

Kinetic model of excess activated sludge thermohydrolysis.

PubMed

Imbierowicz, Mirosław; Chacuk, Andrzej

2012-11-01

Thermal hydrolysis of excess activated sludge suspensions was carried at temperatures ranging from 423 K to 523 K and under pressure 0.2-4.0 MPa. Changes of total organic carbon (TOC) concentration in a solid and liquid phase were measured during these studies. At the temperature 423 K, after 2 h of the process, TOC concentration in the reaction mixture decreased by 15-18% of the initial value. At 473 K total organic carbon removal from activated sludge suspension increased to 30%. It was also found that the solubilisation of particulate organic matter strongly depended on the process temperature. At 423 K the transfer of TOC from solid particles into liquid phase after 1 h of the process reached 25% of the initial value, however, at the temperature of 523 K the conversion degree of 'solid' TOC attained 50% just after 15 min of the process. In the article a lumped kinetic model of the process of activated sludge thermohydrolysis has been proposed. It was assumed that during heating of the activated sludge suspension to a temperature in the range of 423-523 K two parallel reactions occurred. One, connected with thermal destruction of activated sludge particles, caused solubilisation of organic carbon and an increase of dissolved organic carbon concentration in the liquid phase (hydrolysate). The parallel reaction led to a new kind of unsolvable solid phase, which was further decomposed into gaseous products (CO(2)). The collected experimental data were used to identify unknown parameters of the model, i.e. activation energies and pre-exponential factors of elementary reactions. The mathematical model of activated sludge thermohydrolysis appropriately describes the kinetics of reactions occurring in the studied system. Copyright © 2012 Elsevier Ltd. All rights reserved.

Composition and structure of acid leached LiMn 2-yTi yO 4 (0.2≤ y≤1.5) spinels

NASA Astrophysics Data System (ADS)

Avdeev, Georgi; Amarilla, José Manuel; Rojo, José María; Petrov, Kostadin; Rojas, Rosa María

2009-12-01

Lithium manganese titanium spinels, LiMn 2-yTi yO 4, (0.2≤ y≤1.5) have been synthesized by solid-state reaction between TiO 2 (anatase), Li 2CO 3 and MnCO 3. Li + was leached from the powdered reaction products by treatment in excess of 0.2 N HCl at 85 °C for 6 h, under reflux. The elemental composition of the acidic solution and solid residues of leaching has been determined by complexometric titration, atomic absorption spectroscopy and X-ray fluorescence analysis. Powder X-ray diffraction was used for structural characterization of the crystalline fraction of the solid residues. It has been found that the amount of Li + leached from LiMn 2-yTi yO 4 decreases monotonically with increasing y in the interval 0.2≤ y≤1.0 and abruptly drops to negligibly small values for y>1.0. The content of Mn and Li in the liquid phase and of Mn and Ti in the solid (amorphous plus crystalline) residue, were related to the composition and cation distribution in the pristine compounds. A new formal chemical equation describing the process of leaching and a mechanism of the structural transformation undergone by the initial solids as a result of Li + removal has been proposed.

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

Harris, J.M.

Chemical phenomena occurring at boundaries between insulating solids and liquids (adsorption, partition, monolayer self-assembly, catalysis, and chemical reactions) are important to energy-related analytical chemistry. These phenomena are central to chromatography, solid-phase extraction, immobilized analytical reagents, and optical sensors. Chemical interactions in these processes cannot generally be identified solely by equilibrium surface concentrations, since the steady-state behavior does not reveal the mechanism or rates of surface reactions. Goal therefore is to develop surface-sensitive spectroscopies by which chemical kinetics at liquid/solid interfaces can be observed on time-scales from nanoseconds to seconds. In the first year, we have used Joule-discharge heating kinetics tomore » study pore structure of silica gels; effects of pore diameter, particle size, and chemical modification on pore connectivity were investigated. Temperature-jump relaxation measurements of sorption/desorption kinetics at liquid/solid interfaces were also carried out using Joule heating; kinetic barriers to sorption of ions from solution were found for both C18 and Cl surfaces. Through a collaboration with Fritz-Haber Institute in Berlin, we were able to acquire laser temperature-jump data on kinetics at liquid/solid interfaces using a colloidal sample. We also quantified the rate of migration of covalently attached ligands on silica surfaces; from the temperature dependence, the large energy barrier to migration was estimated. A review of applications of electronic spectroscopy (absorption and fluorescence) to reversed-phase chromatographic interfaces was published.« less

Process for producing high purity silicon nitride by the direct reaction between elemental silicon and nitrogen-hydrogen liquid reactants

DOEpatents

Pugar, Eloise A.; Morgan, Peter E. D.

1990-01-01

A process is disclosed for producing, at a low temperature, a high purity reaction product consisting essentially of silicon, nitrogen, and hydrogen which can then be heated to produce a high purity alpha silicon nitride. The process comprises: reacting together a particulate elemental high purity silicon with a high purity nitrogen-hydrogen reactant in its liquid state (such as ammonia or hydrazine) having the formula: N.sub.n H.sub.(n+m) wherein: n=1-4 and m=2 when the nitrogen-hydrogen reactant is straight chain, and 0 when the nitrogen-hydrogen reactant is cyclic. High purity silicon nitride can be formed from this intermediate product by heating the intermediate product at a temperature of from about 1200.degree.-1700.degree. C. for a period from about 15 minutes up to about 2 hours to form a high purity alpha silicon nitride product. The discovery of the existence of a soluble Si-N-H intermediate enables chemical pathways to be explored previously unavailable in conventional solid state approaches to silicon-nitrogen ceramics.

Process for producing high purity silicon nitride by the direct reaction between elemental silicon and nitrogen-hydrogen liquid reactants

DOEpatents

Pugar, E.A.; Morgan, P.E.D.

1987-09-15

A process is disclosed for producing, at a low temperature, a high purity reaction product consisting essentially of silicon, nitrogen, and hydrogen which can then be heated to produce a high purity alpha silicon nitride. The process comprises: reacting together a particulate elemental high purity silicon with a high purity nitrogen-hydrogen reactant in its liquid state (such as ammonia or hydrazine) having the formula: N/sub n/H/sub (n+m)/ wherein: n = 1--4 and m = 2 when the nitrogen-hydrogen reactant is straight chain, and 0 when the nitrogen-hydrogen reactant is cyclic. High purity silicon nitride can be formed from this intermediate product by heating the intermediate product at a temperature of from about 1200--1700/degree/C for a period from about 15 minutes up to about 2 hours to form a high purity alpha silicon nitride product. The discovery of the existence of a soluble Si/endash/N/endash/H intermediate enables chemical pathways to be explored previously unavailable in conventional solid-state approaches to silicon-nitrogen ceramics

Methane Post-Processing for Oxygen Loop Closure

NASA Technical Reports Server (NTRS)

Greenwood, Zachary W.; Abney, Morgan B.; Miller, Lee

2016-01-01

State-of-the-art United States Atmospheric Revitalization carbon dioxide (CO2) reduction is based on the Sabatier reaction process, which recovers approximately 50% of the oxygen (O2) from crew metabolic CO2. Oxygen recovery from carbon dioxide is constrained by the limited availability of reactant hydrogen. Post-processing of methane to recover hydrogen with the Umpqua Research Company Plasma Pyrolysis Assembly (PPA) has the potential to further close the Atmospheric Revitalization oxygen loop. The PPA decomposes methane into hydrogen and hydrocarbons, predominantly acetylene, and a small amount of solid carbon. The hydrogen must then be purified before it can be recycled for additional oxygen recovery. Long duration testing and evaluation of a four crew-member sized PPA and a discussion of hydrogen recycling system architectures are presented.

A High-Throughput Process for the Solid-Phase Purification of Synthetic DNA Sequences

PubMed Central

Grajkowski, Andrzej; Cieślak, Jacek; Beaucage, Serge L.

2017-01-01

An efficient process for the purification of synthetic phosphorothioate and native DNA sequences is presented. The process is based on the use of an aminopropylated silica gel support functionalized with aminooxyalkyl functions to enable capture of DNA sequences through an oximation reaction with the keto function of a linker conjugated to the 5′-terminus of DNA sequences. Deoxyribonucleoside phosphoramidites carrying this linker, as a 5′-hydroxyl protecting group, have been synthesized for incorporation into DNA sequences during the last coupling step of a standard solid-phase synthesis protocol executed on a controlled pore glass (CPG) support. Solid-phase capture of the nucleobase- and phosphate-deprotected DNA sequences released from the CPG support is demonstrated to proceed near quantitatively. Shorter than full-length DNA sequences are first washed away from the capture support; the solid-phase purified DNA sequences are then released from this support upon reaction with tetra-n-butylammonium fluoride in dry dimethylsulfoxide (DMSO) and precipitated in tetrahydrofuran (THF). The purity of solid-phase-purified DNA sequences exceeds 98%. The simulated high-throughput and scalability features of the solid-phase purification process are demonstrated without sacrificing purity of the DNA sequences. PMID:28628204

Solid-state reaction of iron on β-SiC

NASA Astrophysics Data System (ADS)

Kaplan, R.; Klein, P. H.; Addamiano, A.

1985-07-01

The solid-state reaction between Fe and β-SiC has been studied using Auger-electron and electron-energy-loss spectroscopies and ion sputter profiling. Fe films from submonolayer coverage to 1000 Å thickness were grown in ultrahigh vacuum, and annealed at temperatures up to 550 °C. Auger line-shape changes occurred even for initial Fe coverage at 190 °C, indicating substantial bond alteration in the SiC substrate. A 1000-Å film was largely consumed by reaction with Si and C diffused from the substrate during a 500 °C anneal, and exhibited both Fe silicide and carbide throughout most of its original volume and free C present as graphite primarily at the surface. As an aid in identifying the reaction products studied in this work, Auger line shapes were first determined for the SiLVV peak in Fe silicide and for the CKLL transition in Fe carbide.

Apparatus and method to keep the walls of a free-space reactor free from deposits of solid materials

NASA Technical Reports Server (NTRS)

Yamakawa, K. A. (Inventor)

1985-01-01

An apparatus and method is disclosed for keeping interior walls of a reaction vessel free of undesirable deposits of solid materials in gas-to-solid reactions. The apparatus includes a movable cleaning head which is configured to be substantially complementary to the interior contour of the walls of the reaction vessel. The head ejects a stream of gas with a relatively high velocity into a narrow space between the head and the walls. The head is moved substantially continuously to at least intermittently blow the stream of gas to substantially the entire surface of the walls wherein undesirable solid deposition is likely to occur. The disclosed apparatus and process is particularly useful for keeping the walls of a free-space silane-gas-to-solid-silicon reactor free of undesirable silicon deposits.

Oxidation process of MoO xC y to MoO 3: kinetics and mechanism

NASA Astrophysics Data System (ADS)

Aleman-Vázquez, L. O.; Torres-García, E.; Rodríguez-Gattorno, G.; Ocotlán-Flores, J.; Camacho-López, M. A.; Cano, J. L.

2004-10-01

A non-isothermal kinetic study of the oxidation of "carbon-modified MoO3" in the temperature range of 150-550°C by simultaneous TGA-DTA was investigated. During the oxidation process, two thermal events were detected, which are associated with the oxidation of carbon in MoOxCy and MoO2 to MoO3. The model-free and model-fitting kinetic approaches have been applied to TGA experimental data. The solid state-kinetics of the oxidation of MoOxCy to MoO3 is governed by F1 (unimolecular decay), which suggests that the reaction is of the first order with respect to oxygen concentration. The constant (Ea)α value (about 115±5 kJ/mol) for this first stage can be related to the nature of the reaction site in the MoO3 matrix. This indicates that oxidation occurs in well-defined lattice position sites (energetically equivalent). On the other hand, for the second stage of oxidation, MoO2 to MoO3, the isoconversional analysis shows a complex (Ea)α dependence on (α) and reveals a typical behavior for competitive reaction. A D2 (two-dimensional diffusion) mechanism with a variable activation energy value in the range 110-200 kJ/mol was obtained. This can be interpreted as an inter-layer oxygen diffusion in the solid bulk, which does not exclude other simultaneous mechanism reactions.

Use of photovoltaic detector for photocatalytic activity estimation

NASA Astrophysics Data System (ADS)

Das, Susanta Kumar; Satapathy, Pravakar; Rao, P. Sai Shruti; Sabar, Bilu; Panda, Rudrashish; Khatua, Lizina

2018-05-01

Photocatalysis is a very important process and have numerous applications. Generally, to estimate the photocatalytic activity of newly grown material, its reaction rate constant w.r.t to some standard commercial TiO2 nanoparticles like Degussa P25 is evaluated. Here a photovoltaic detector in conjunction with laser is used to determine this rate constant. This method is tested using Zinc Orthotitanate (Zn2TiO4) nanoparticles prepared by solid state reaction and it is found that its reaction rate constant is six times higher than that of P25. The value is found to be close to the value found by a conventional system. Our proposed system is much more cost-effective than the conventional one and has the potential to do real time monitoring of the photocatalytic activity.

Detox{sup SM} wet oxidation system studies for engineering scale up

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

Robertson, D.T.; Moslander, J.E.; Zigmond, J.A.

1995-12-31

Catalyzed wet oxidation utilizing iron(III) has been shown to have promise for treating many hazardous and mixed wastes. The reaction occurs at the surface of contact between an aqueous iron(III) solution and organic material. Studies with liquid- and vapor-phase organic waste surrogates have established reaction kinetics and the limits of reaction rate based on organic concentration and iron(III) diffusion. Continuing engineering studies have concentrated on reaction vessel agitator and solids feed configurations, an improved bench scale reflux condenser and reflux condenser calculations, sparging of organic compounds from the process condensate water, filtration of solids from the process solution, and flammabilitymore » limits for volatile organic compounds in the headspace of the reaction vessel under the reaction conditions. Detailed engineering design and fabrication of a demonstration unit for treatment of mixed waste is in progress.« less

Preparing, Characterizing, and Investigating Luminescent Properties of a Series of Long-Lasting Phosphors in a SrO-Al[subscript 2]O[subscript 3] System: An Integrated and Inquiry-Based Experiment in Solid State Chemistry for the Undergraduate Laboratory

ERIC Educational Resources Information Center

Ma, Yan-Zi; Jia, Li; Ma, Kai-Guo; Wang, Hai-Hong; Jing, Xi-Ping

2017-01-01

An integrated and inquiry-based experiment on solid state chemistry is applied to an inorganic chemistry lab course to provide insight into the characteristics of the solid phase reaction. In this experiment, students have the opportunity to synthesize long-lasting phosphors with formula xSrO·yAl[subscript 2]O[subscript 3]:Eu[superscript 2+],…

Probe DNA-Cisplatin Interaction with Solid-State Nanopores

NASA Astrophysics Data System (ADS)

Zhou, Zhi; Hu, Ying; Li, Wei; Xu, Zhi; Wang, Pengye; Bai, Xuedong; Shan, Xinyan; Lu, Xinghua; Nanopore Collaboration

2014-03-01

Understanding the mechanism of DNA-cisplatin interaction is essential for clinical application and novel drug design. As an emerging single-molecule technology, solid-state nanopore has been employed in biomolecule detection and probing DNA-molecule interactions. Herein, we reported a real-time monitoring of DNA-cisplatin interaction by employing solid-state SiN nanopores. The DNA-cisplatin interacting process is clearly classified into three stages by measuring the capture rate of DNA-cisplatin adducts. In the first stage, the negative charged DNA molecules were partially discharged due to the bonding of positive charged cisplatin and forming of mono-adducts. In the second stage, forming of DNA-cisplatin di-adducts with the adjacent bases results in DNA bending and softening. The capture rate increases since the softened bi-adducts experience a lower barrier to thread into the nanopores. In the third stage, complex structures, such as micro-loop, are formed and the DNA-cisplatin adducts are aggregated. The capture rate decreases to zero as the aggregated adduct grows to the size of the pore. The characteristic time of this stage was found to be linear with the diameter of the nanopore and this dynamic process can be described with a second-order reaction model. We are grateful to Laboratory of Microfabrication, Dr. Y. Yao, and Prof. R.C. Yu (Institute of Physics, Chinese Academy of Sciences) for technical assistance.

Low Energy Nuclear Reactions: A Millennium Status Report

NASA Astrophysics Data System (ADS)

Mallove, Eugene F.

2000-03-01

This talk will summarize some of the more convincing recent experiments that show that helium-4, nuclear scale excess energy, tritium, low-level neutron production, and the transmutation of heavy elements can occur near room temperature in relatively simple systems. Despite inappropriate theory-based arguments against it and unethical attacks by people unfamiliar with the supporting experiments, the new field of solid state nuclear reactions is progressing. The physical theory behind the associated phenomena continues to be debated among theorists. The facts of the history of this scientific controversy suggest that it is inadvisable to rush to judgment against allegedly ``impossible" new phenomena when increasingly careful experiments have revealed new vistas in physics. Detailed discussion of evidence for solid state nuclear reactions is available elsewhere (http://www.infinite-energy.com). abstract document

Application of residual polysaccharide-degrading enzymes in dried shiitake mushrooms as an enzyme preparation in food processing.

PubMed

Tatsumi, E; Konishi, Y; Tsujiyama, S

2016-11-01

To examine the activities of residual enzymes in dried shiitake mushrooms, which are a traditional foodstuff in Japanese cuisine, for possible applications in food processing. Polysaccharide-degrading enzymes remained intact in dried shiitake mushrooms and the activities of amylase, β-glucosidase and pectinase were high. A potato digestion was tested using dried shiitake powder. The enzymes reacted with potato tuber specimens to solubilize sugars even under a heterogeneous solid-state condition and that their reaction modes were different at 38 and 50 °C. Dried shiitake mushrooms have a potential use in food processing as an enzyme preparation.

High performance addition-type thermoplastics (ATTs) - Evidence for the formation of a Diels-Alder adduct in the reaction of an acetylene-terminated material and a bismaleimide

NASA Technical Reports Server (NTRS)

Pater, R. H.; Soucek, M. D.; Chang, A. C.; Partos, R. D.

1991-01-01

Recently, the concept and demonstration of a new versatile synthetic reaction for making a large number of high-performance addition-type thermoplastics (ATTs) were reported. The synthesis shows promise for providing polymers having an attractive combination of easy processability, good toughness, respectable high temperature mechanical performance, and excellent thermo-oxidative stability. The new chemistry involves the reaction of an acetylene-terminated material with a bismaleimide or benzoquinone. In order to clarify the reaction mechanism, model compound studies were undertaken in solutions as well as in the solid state. The reaction products were purified by flash chromatography and characterized by conventional analytical techniques including NMR, FT-IR, UV-visible, mass spectroscopy, and high pressure liquid chromatography. The results are presented of the model compound studies which strongly support the formation of a Diels-Alder adduct in the reaction of an acetylene-terminated compound and a bismaleimide or benzoquinone.

Photodesorption of Solid CO2 by Lyα

NASA Astrophysics Data System (ADS)

Bahr, D. A.; Baragiola, R. A.

2012-12-01

We measured desorption of atoms and molecules from films of solid carbon dioxide in an ultrahigh vacuum from 6 to 60 K under irradiation with Lyα (121.6 nm, 10.2 eV) photons, an important process in the balance between gas phase and condensed molecules in the interstellar medium. The measurements use microgravimetry and mass spectrometry during irradiation and temperature programmed desorption after irradiation. At low photon fluences, the desorption flux consists mainly of O atoms and, after ~1017 photons cm-2, it is dominated by CO with smaller amount of O2, C, and CO2, with the presence of O2 indicating solid-state chemical reactions. At high fluences (up to 1018 photons cm-2), the desorption yields saturate at values much higher than in previous studies. The yields (molecules/photon), derived assuming stoichiometric desorption, reach 0.014 at 6 K, growing to ~0.2 at 50 and 60 K. Warming the films during irradiation gives rise to pressure spikes that suggest desorption of trapped species in pores or at defects, possibly assisted by radical-induced reactions. Such an effect could be significant for radiation-processed CO2-coated interstellar grains that are heated by, i.e., cosmic ray impacts or grain-grain collisions. We discuss the experiments considering photochemical mechanisms and compare them to the results of ion irradiation.

The Barium Hydroxide-Ammonium Thiocyanate Reaction: A Titrimetric Continuous Variations Experiment.

ERIC Educational Resources Information Center

Harris, Arlo D.

1979-01-01

Presents an experiment for inorganic, organic, or physical chemistry students utilizing acid-base titrimetry to study the stoichiometric of a solid state reaction. Time involved ranges from one to three, three-hour lab periods. (Author/SA)

Conventional and Microwave Joining of Silicon Carbide Using Displacement Reactions

NASA Technical Reports Server (NTRS)

Kingsley, J.; Yiin, T.; Barmatz, M.

1995-01-01

Microwave heating was used to join Silicon Carbide rods using a thin TiC /Si tape interlayer . Microwaves quickly heated the rods and tape to temperatures where solid-state displacement reactions between TiC and Si occurred.

Reaction mechanism studies towards effective fabrication of lithium-rich anti-perovskites Li 3OX (X=Cl, Br)

DOE PAGES

Li, Shuai; Zhu, Jinlong; Wang, Yonggang; ...

2015-12-10

Lithium-rich Anti-perovskite (LiRAP), with general formula Li 3OX (X = Cl, Br, I), and recently reported as superionic conductors with 3-dimensional Li + migrating channels, is emerging as a promising candidate for solid electrolyte of all-solid-state LIBs. But, it is still difficult to fabricate pure LiRAP due to the difficulty of the phase formation and moisture-sensitive nature of the products. In this work, we thoroughly studied the formation mechanism of Li 3OCl and Li 3OBr in various solid state reaction routes. We developed different experimental strategies in order to improve the syntheses, in purposes of improved phase stability and large-scalemore » production of LiRAP. One feasible method is to use strongly reductive agents Li metal or LiH to eliminate OH species. The results show that LiH is more effective than Li metal because of negatively charged H - and uniform reaction. The other well-established method is using Li 2O and LiX mixture as reagents to preventing OH phase at the beginning, and using protected ball milling to make fine powders and hence active the reaction. Finally, IR spectroscopy, thermal analyses and first-principle calculation were performed to give indications on the reaction pathway.« less

Rapid Solid-State Metathesis Routes to Nanostructured Silicon-Germainum

NASA Technical Reports Server (NTRS)

Rodriguez, Marc (Inventor); Kaner, Richard B. (Inventor); Bux, Sabah K. (Inventor); Fleurial, Jean-Pierre (Inventor)

2014-01-01

Methods for producing nanostructured silicon and silicon-germanium via solid state metathesis (SSM). The method of forming nanostructured silicon comprises the steps of combining a stoichiometric mixture of silicon tetraiodide (SiI4) and an alkaline earth metal silicide into a homogeneous powder, and initating the reaction between the silicon tetraiodide (SiI4) with the alkaline earth metal silicide. The method of forming nanostructured silicon-germanium comprises the steps of combining a stoichiometric mixture of silicon tetraiodide (SiI4) and a germanium based precursor into a homogeneous powder, and initiating the reaction between the silicon tetraiodide (SiI4) with the germanium based precursors.

Synthesisofc-lifepo4 composite by solid state reaction method

NASA Astrophysics Data System (ADS)

Rahayu, I.; Hidayat, S.; Noviyanti, A. R.; Rakhmawaty, D.; Ernawati, E.

2017-02-01

In this research, the enhancement of LiFePO4 conductivity was conducted by doping method with carbon materials. Carbon-based materials were obtained from the mixture of sucrose, and the precursor of LiH2PO4 and α-Fe2O3 was synthesized by solid state reaction. Sintering temperature was varied at 700°C, 800°C, 900°C and 1,000°C. The result showed that C-LiFePO4 could be synthesized by using solid state reaction method. Based on the XRD and FTIR spectrums, C-LiFePO4 can be identified as the type of crystal, characterized by the appearance of sharp signal on (011), (211) and typical peak of LiFePO4 materials. The result of conductivity measurement from C-LiFePO4 at sintering temperature of 900°C and 1,000°C was 2×10-4 S/cm and 4×10-4S/cm, respectively. The conductivity value at sintering temperature of 700°C and 800°C was very small (<10-6 S/cm), which cannot be measured by the existing equipment.

Continuous Flow Aerobic Alcohol Oxidation Reactions Using a Heterogeneous Ru(OH)x/Al2O3 Catalyst

PubMed Central

2015-01-01

Ru(OH)x/Al2O3 is among the more versatile catalysts for aerobic alcohol oxidation and dehydrogenation of nitrogen heterocycles. Here, we describe the translation of batch reactions to a continuous-flow method that enables high steady-state conversion and single-pass yields in the oxidation of benzylic alcohols and dehydrogenation of indoline. A dilute source of O2 (8% in N2) was used to ensure that the reaction mixture, which employs toluene as the solvent, is nonflammable throughout the process. A packed bed reactor was operated isothermally in an up-flow orientation, allowing good liquid–solid contact. Deactivation of the catalyst during the reaction was modeled empirically, and this model was used to achieve high conversion and yield during extended operation in the aerobic oxidation of 2-thiophene methanol (99+% continuous yield over 72 h). PMID:25620869

Hydrothermal carbonization of food waste and associated packaging materials for energy source generation.

PubMed

Li, Liang; Diederick, Ryan; Flora, Joseph R V; Berge, Nicole D

2013-11-01

Hydrothermal carbonization (HTC) is a thermal conversion technique that converts food wastes and associated packaging materials to a valuable, energy-rich resource. Food waste collected from local restaurants was carbonized over time at different temperatures (225, 250 and 275°C) and solids concentrations to determine how process conditions influence carbonization product properties and composition. Experiments were also conducted to determine the influence of packaging material on food waste carbonization. Results indicate the majority of initial carbon remains integrated within the solid-phase at the solids concentrations and reaction temperatures evaluated. Initial solids concentration influences carbon distribution because of increased compound solubilization, while changes in reaction temperature imparted little change on carbon distribution. The presence of packaging materials significantly influences the energy content of the recovered solids. As the proportion of packaging materials increase, the energy content of recovered solids decreases because of the low energetic retention associated with the packaging materials. HTC results in net positive energy balances at all conditions, except at a 5% (dry wt.) solids concentration. Carbonization of food waste and associated packaging materials also results in net positive balances, but energy needs for solids post-processing are significant. Advantages associated with carbonization are not fully realized when only evaluating process energetics. A more detailed life cycle assessment is needed for a more complete comparison of processes. Copyright © 2013 Elsevier Ltd. All rights reserved.

Enhanced ionic conductivity with Li 7O 2Br 3 phase in Li 3OBr anti-perovskite solid electrolyte

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

Zhu, Jinlong; Li, Shuai; Zhang, Yi

Cubic anti-perovskites with general formula Li 3OX (X = Cl, Br, I) were recently reported as superionic conductors with the potential for use as solid electrolytes in all-solid-state lithium ion batteries. These electrolytes are nonflammable, low-cost, and suitable for thermoplastic processing. However, the primary obstacle of its practical implementation is the relatively low ionic conductivity at room temperature. In this work, we synthesized a composite material consisting of two anti-perovskite phases, namely, cubic Li 3OBr and layered Li 7O 2Br 3, by solid state reaction routes. The results indicate that with the phase fraction of Li 7O 2Br 3 increasingmore » to 44 wt. %, the ionic conductivity increased by more than one order of magnitude compared with pure phase Li 3OBr. Formation energy calculations revealed the meta-stable nature of Li 7O 2Br 3, which supports the great difficulty in producing phase-pure Li 7O 2Br 3 at ambient pressure. Here, methods of obtaining phase-pure Li 7O 2Br 3 will continue to be explored, including both high pressure and metathesis techniques.« less

Enhanced ionic conductivity with Li 7O 2Br 3 phase in Li 3OBr anti-perovskite solid electrolyte

DOE PAGES

Zhu, Jinlong; Li, Shuai; Zhang, Yi; ...

2016-09-07

Cubic anti-perovskites with general formula Li 3OX (X = Cl, Br, I) were recently reported as superionic conductors with the potential for use as solid electrolytes in all-solid-state lithium ion batteries. These electrolytes are nonflammable, low-cost, and suitable for thermoplastic processing. However, the primary obstacle of its practical implementation is the relatively low ionic conductivity at room temperature. In this work, we synthesized a composite material consisting of two anti-perovskite phases, namely, cubic Li 3OBr and layered Li 7O 2Br 3, by solid state reaction routes. The results indicate that with the phase fraction of Li 7O 2Br 3 increasingmore » to 44 wt. %, the ionic conductivity increased by more than one order of magnitude compared with pure phase Li 3OBr. Formation energy calculations revealed the meta-stable nature of Li 7O 2Br 3, which supports the great difficulty in producing phase-pure Li 7O 2Br 3 at ambient pressure. Here, methods of obtaining phase-pure Li 7O 2Br 3 will continue to be explored, including both high pressure and metathesis techniques.« less

A nonconjugated radical polymer glass with high electrical conductivity

NASA Astrophysics Data System (ADS)

Joo, Yongho; Agarkar, Varad; Sung, Seung Hyun; Savoie, Brett M.; Boudouris, Bryan W.

2018-03-01

Solid-state conducting polymers usually have highly conjugated macromolecular backbones and require intentional doping in order to achieve high electrical conductivities. Conversely, single-component, charge-neutral macromolecules could be synthetically simpler and have improved processibility and ambient stability. We show that poly(4-glycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl), a nonconjugated radical polymer with a subambient glass transition temperature, underwent rapid solid-state charge transfer reactions and had an electrical conductivity of up to 28 siemens per meter over channel lengths up to 0.6 micrometers. The charge transport through the radical polymer film was enabled with thermal annealing at 80°C, which allowed for the formation of a percolating network of open-shell sites in electronic communication with one another. The electrical conductivity was not enhanced by intentional doping, and thin films of this material showed high optical transparency.

Analysis of Improved Nutritional Composition of Potential Functional Food (Okara) after Probiotic Solid-State Fermentation.

PubMed

Gupta, Sulagna; Lee, Jaslyn J L; Chen, Wei Ning

2018-05-30

Okara is a major agro-waste, generated as a byproduct from the soymilk and tofu industry. Since okara has a high nutritive value, reusing it as a substrate for solid state biofermentation is an economical and environmental friendly option. Rhizopus oligosporus and Lactobacillus plantarum were the probiotic FDA-approved food-grade cultures used in this study. The study revealed that biofermenting okara improves its nutritional composition. It was found that the metabolomic composition (by GC-MS analysis) and antioxidant activity (by DPPH test) improved after the microbial fermentations. Of the two, okara fermented with R. oligosporus showed better results. Further, the metabolites were traced back to their respective biosynthesis pathways, in order to understand the biochemical reactions being triggered during the fermentation processes. The findings of this entire work open up the possibility of employing fermented okara as a potential functional food for animal feed.

Performance of strontium- and magnesium-doped lanthanum gallate electrolyte with lanthanum-doped ceria as a buffer layer for IT-SOFCs

NASA Astrophysics Data System (ADS)

Lee, Dokyol; Han, Ju-Hyeong; Kim, Eun-Gu; Song, Rak-Hyun; Shin, Dong-Ryul

La 0.8Sr 0.2Ga 0.8Mg 0.2O 2.8 (LSGM8080) powder, showing the highest electrical conductivity among LSGMs of various compositions, is synthesized using the glycine nitrate process (GNP) and used as the electrolyte for an intermediate-temperature solid oxide fuel cell (IT-SOFC). The LDC (Ce 0.55La 0.45O 1.775) powder is synthesized by a solid-state reaction and employed as the material for a buffer layer to prevent the reaction between the anode and electrolyte materials. The LDC also serves as the skeleton material for the anode. An anode-supported single cell with an active area of 1 cm 2 is constructed for performance evaluation. A single-cell test is performed at 750 and 800 °C. The maximum power density of the cell 459 and 664 mW cm -2 at 750 and 800 °C, respectively.

5V-class bulk-type all-solid-state rechargeable lithium batteries with electrode-solid electrolyte composite electrodes prepared by aerosol deposition

NASA Astrophysics Data System (ADS)

Iriyama, Yasutoshi; Wadaguchi, Masaki; Yoshida, Koki; Yamamoto, Yuta; Motoyama, Munekazu; Yamamoto, Takayuki

2018-05-01

Composite electrodes (∼9 μm in thickness) composed of 5V-class electrode of LiNi0.5Mn1.5O4 (LNM) and high Li+ conductive crystalline-glass solid electrolyte (LATP, Ohara Inc.) were prepared at room temperature by aerosol deposition (AD) on platinum sheets. The resultant LNM-LATP composite electrodes were combined with LiPON and Li, and 5V-class bulk-type all-solid-state rechargeable lithium batteries (SSBs) were prepared. The crystallnity of the LNM in the LNM-LATP composite electrode was improved by annealing. Both thermogravimetry-mass spectroscopy analysis and XRD analysis clarified that the side reactions between the LNM and the LATP occurred over 500 °C with oxygen release. From these results, annealing temperature of the LNM-LATP composite electrode system was optimized at 500 °C due to the improved crystallinity of the LNM with avoiding the side-reactions. The SSBs with the composite electrodes (9 μm in thickness, 40 vol% of the LNM) annealed at 500 °C delivered 100 mAh g-1 at 10 μA cm-2 at 100 °C. Degradation of the discharge capacity with the repetition of the charge-discharge reactions was observed, which will originate from large volume change of the LNM (∼6.5%) during the reactions.

Development and Characterization of a High-Solids Deacetylation Process

DOE PAGES

Shekiro, III, Joseph; Chen, Xiaowen; Smith, Holly; ...

2016-05-20

Dilute-acid pretreatment has proven to be a robust means of converting herbaceous feedstock to fermentable sugars. However, it also releases acetic acid, a known fermentation inhibitor, from acetyl groups present in the biomass. A mild, dilute alkaline extraction stage was implemented prior to acid pretreatment to separate acetic acid from the hydrolysate sugar stream. This step, termed deacetylation, improved the glucose and xylose yields from enzymatic hydrolysis and ethanol yields from fermentation of the sugars relative to the control experiments using dilute-acid pretreatment of native corn stover without deacetylation. While promising, deacetylation as it was historically practiced is conducted atmore » low solids loadings, and at fixed conditions. Thus, many questions have been left unanswered, including the relationship between sodium hydroxide and solids loading, and acetate and xylan solubilization, as well as the impact of temperature and residence time on the process efficacy. A central composite experiment was designed to evaluate the impact of solids loading, sodium hydroxide loading, reaction time and temperature during deacetylation on the acetate and xylan solubilization of corn stover. Using the ANOVA test, it became apparent that neither of the responses was significantly impacted by the solids loading, while the reaction time was a minor factor - the responses were largely driven by reaction temperature and the sodium hydroxide loading. Based on the results, we successfully demonstrated the ability to transition the low-solids (10 % w/w) deacetylation process to a higher-solids process (30 % w/w) with minimal impact on the ability to extract acetate from biomass. Conditions were selected to minimize xylose loss during deacetylation, while also removing 70 % of acetyl groups. The impact of selected conditions on the enzymatic hydrolysis and fermentation was further investigated. In conclusion, evaluation of the whole-process impact demonstrated that despite the upfront reduction in carbohydrate loss during deacetylation, the overall process sugar yields were depressed by the high-solids, low alkali process relative to the historical control. Consequently, ethanol titers were reduced, though strong fermentation performance was still observed, indicating that 70 % acetate removal is sufficient to depress acetic acid concentrations to a level that does not substantially inhibit ethanol fermentation by rZymomo nas.« less

On the implementation of a chain nuclear reaction of thermonuclear fusion on the basis of the p+{sup 11}B process

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

Belyaev, V. S.; Krainov, V. P., E-mail: vpkrainov@mail.ru; Zagreev, B. V.

2015-07-15

Various theoretical and experimental schemes for implementing a thermonuclear reactor on the basis of the p+{sup 11}B reaction are considered. They include beam collisions, fusion in degenerate plasmas, ignition upon plasma acceleration by ponderomotive forces, and the irradiation of a solid-state target from {sup 11}B with a proton beam under conditions of a Coulomb explosion of hydrogen microdrops. The possibility of employing ultra-short high-intensity laser pulses to initiate the p+{sup 11}B reaction under conditions far from thermodynamic equilibrium is discussed. This and some other weakly radioactive thermonuclear reactions are promising owing to their ecological cleanness—there are virtually no neutrons amongmore » fusion products. Nuclear reactions that follow the p+{sup 11}B reaction may generate high-energy protons, sustaining a chain reaction, and this is an advantage of the p+{sup 11}B option. The approach used also makes it possible to study nuclear reactions under conditions close to those in the early Universe or in the interior of stars.« less

Low-temperature surface formation of NH3 and HNCO: hydrogenation of nitrogen atoms in CO-rich interstellar ice analogues

NASA Astrophysics Data System (ADS)

Fedoseev, G.; Ioppolo, S.; Zhao, D.; Lamberts, T.; Linnartz, H.

2015-01-01

Solid-state astrochemical reaction pathways have the potential to link the formation of small nitrogen-bearing species, like NH3 and HNCO, and prebiotic molecules, specifically amino acids. To date, the chemical origin of such small nitrogen-containing species is still not well understood, despite the fact that ammonia is an abundant constituent of interstellar ices towards young stellar objects and quiescent molecular clouds. This is mainly because of the lack of dedicated laboratory studies. The aim of this work is to experimentally investigate the formation routes of NH3 and HNCO through non-energetic surface reactions in interstellar ice analogues under fully controlled laboratory conditions and at astrochemically relevant temperatures. This study focuses on the formation of NH3 and HNCO in CO-rich (non-polar) interstellar ices that simulate the CO freeze-out stage in dark interstellar cloud regions, well before thermal and energetic processing start to become relevant. We demonstrate and discuss the surface formation of solid HNCO through the interaction of CO molecules with NH radicals - one of the intermediates in the formation of solid NH3 upon sequential hydrogenation of N atoms. The importance of HNCO for astrobiology is discussed.

77 FR 76457 - Howard Hughes Medical Institute, et al.; Notice of Consolidated Decision on Applications for Duty...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-12-28

... chemical state and their catalytic activity in various chemical reactions, by investigating solid... instrument. The unique features of this instrument include its small volume (0.045 L) reaction cell in which...

High Energy Advanced Thermal Storage for Spacecraft Solar Thermal Power and Propulsion Systems

DTIC Science & Technology

2011-10-12

Vol. 108, No. 6, June 1961, pp. 568-572. 38. Storms, E. and Mueller, B., "Phase Relations and Thermodynamic Properties of Transition Metal Borides ...T., and Naka, S., "Formation Process of Tungsten Borides by Solid State Reaction Between Tungsten and Amorphous Boron," Journal of Materials...Molybdenum- Borides ," Journal of Metals, September 1952, pp. 983-988. 41. Ellis, R.C., “Various Preparations of Elemental Boron,” Proceedings of the 1st

Molten Boron Phase-Change Thermal Energy Storage to Augment Solar Thermal Propulsion Systems

DTIC Science & Technology

2011-07-13

Thermodynamic Properties of Transition Metal Borides . I. The Molybdenum-boron system and Elemental Boron," Journal of Physical Chemistry, Vol. 81...February 1977, pp. 318-324. 38Itoh, H., Matsudaira, T., and Naka, S., "Formation Process of Tungsten Borides by Solid State Reaction Between Tungsten...Molybdenum-Boron and Some Properties of The Molybdenum- Borides ," Journal of Metals, September 1952, pp. 983-988. 40Stout, N. D., Mar, R. W., and Boo, W. O

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

Tian, Huajun; Gao, Tao; Li, Xiaogang

Rechargeable magnesium batteries have attracted considerable attention because of their potential high energy density and low cost. However, their development has been severely hindered because of the lack of appropriate cathode materials. Here we report a rechargeable magnesium/iodine battery, in which the soluble iodine reacts with Mg 2+ to form a soluble intermediate and then an insoluble final product magnesium iodide. The liquid–solid two-phase reaction pathway circumvents solid-state Mg 2+ diffusion and ensures a large interfacial reaction area, leading to fast reaction kinetics and high reaction reversibility. As a result, the rechargeable magnesium/iodine battery shows a better rate capability (180more » mAh g –1 at 0.5 C and 140 mAh g –1 at 1 C) and a higher energy density (~400 Wh kg –1) than all other reported rechargeable magnesium batteries using intercalation cathodes. As a result, this study demonstrates that the liquid–solid two-phase reaction mechanism is promising in addressing the kinetic limitation of rechargeable magnesium batteries.« less

High power rechargeable magnesium/iodine battery chemistry

DOE PAGES

Tian, Huajun; Gao, Tao; Li, Xiaogang; ...

2017-01-10

Rechargeable magnesium batteries have attracted considerable attention because of their potential high energy density and low cost. However, their development has been severely hindered because of the lack of appropriate cathode materials. Here we report a rechargeable magnesium/iodine battery, in which the soluble iodine reacts with Mg 2+ to form a soluble intermediate and then an insoluble final product magnesium iodide. The liquid–solid two-phase reaction pathway circumvents solid-state Mg 2+ diffusion and ensures a large interfacial reaction area, leading to fast reaction kinetics and high reaction reversibility. As a result, the rechargeable magnesium/iodine battery shows a better rate capability (180more » mAh g –1 at 0.5 C and 140 mAh g –1 at 1 C) and a higher energy density (~400 Wh kg –1) than all other reported rechargeable magnesium batteries using intercalation cathodes. As a result, this study demonstrates that the liquid–solid two-phase reaction mechanism is promising in addressing the kinetic limitation of rechargeable magnesium batteries.« less

Model study on transesterification of soybean oil to biodiesel with methanol using solid base catalyst.

PubMed

Liu, Xuejun; Piao, Xianglan; Wang, Yujun; Zhu, Shenlin

2010-03-25

Modeling of the transesterification of vegetable oils to biodiesel using a solid base as a catalyst is very important because the mutual solubilities of oil and methanol will increase with the increasing biodiesel yield. The heterogeneous liquid-liquid-solid reaction system would become a liquid-solid system when the biodiesel reaches a certain content. In this work, we adopted a two-film theory and a steady state approximation assumption, then established a heterogeneous liquid-liquid-solid model in the first stage. After the diffusion coefficients on the liquid-liquid interface and the liquid-solid interface were calculated on the basis of the properties of the system, the theoretical value of biodiesel productivity changing with time was obtained. The predicted values were very near the experimental data, which indicated that the proposed models were suitable for the transesterification of soybean oil to biodiesel when solid bases were used as catalysts. Meanwhile, the model indicated that the transesterification reaction was controlled by both mass transfer and reaction. The total resistance will decrease with the increase in biodiesel yield in the liquid-liquid-solid stage. The solid base catalyst exhibited an activation energy range of 9-20 kcal/mol, which was consistent with the reported activation energy range of homogeneous catalysts.

Catalytic and electrochemical behaviour of solid oxide fuel cell operated with simulated-biogas mixtures

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

Dang-Long, T., E-mail: 3TE14098G@kyushu-u.ac.jp; Quang-Tuyen, T., E-mail: tran.tuyen.quang.314@m.kyushu-u.ac.jp; Shiratori, Y., E-mail: shiratori.yusuke.500@m.kyushu-u.ac.jp

2016-06-03

Being produced from organic matters of wastes (bio-wastes) through a fermentation process, biogas mainly composed of CH{sub 4} and CO{sub 2} and can be considered as a secondary energy carrier derived from solar energy. To generate electricity from biogas through the electrochemical process in fuel cells is a state-of-the-art technology possessing higher energy conversion efficiency without harmful emissions compared to combustion process in heat engines. Getting benefits from high operating temperature such as direct internal reforming ability and activation of electrochemical reactions to increase overall system efficiency, solid oxide fuel cell (SOFC) system operated with biogas becomes a promising candidatemore » for distributed power generator for rural applications leading to reductions of environmental issues caused by greenhouse effects and bio-wastes. CO{sub 2} reforming of CH{sub 4} and electrochemical oxidation of the produced syngas (H{sub 2}–CO mixture) are two main reaction processes within porous anode material of SOFC. Here catalytic and electrochemical behavior of Ni-ScSZ (scandia stabilized-zirconia) anode in the feed of CH{sub 4}–CO{sub 2} mixtures as simulated-biogas at 800 °C were evaluated. The results showed that CO{sub 2} had strong influences on both reaction processes. The increase in CO{sub 2} partial pressure resulted in the decrease in anode overvoltage, although open-circuit voltage was dropped. Besides that, the simulation result based on a power-law model for equimolar CH{sub 4}−CO{sub 2} mixture revealed that coking hazard could be suppressed along the fuel flow channel in both open-circuit and closed-circuit conditions.« less

Direct detection and characterization of bioinorganic peroxo moieties in a vanadium complex by 17O solid-state NMR and density functional theory.

PubMed

Gupta, Rupal; Stringer, John; Struppe, Jochem; Rehder, Dieter; Polenova, Tatyana

2018-07-01

Electronic and structural properties of short-lived metal-peroxido complexes, which are key intermediates in many enzymatic reactions, are not fully understood. While detected in various enzymes, their catalytic properties remain elusive because of their transient nature, making them difficult to study spectroscopically. We integrated 17 O solid-state NMR and density functional theory (DFT) to directly detect and characterize the peroxido ligand in a bioinorganic V(V) complex mimicking intermediates non-heme vanadium haloperoxidases. 17 O chemical shift and quadrupolar tensors, measured by solid-state NMR spectroscopy, probe the electronic structure of the peroxido ligand and its interaction with the metal. DFT analysis reveals the unusually large chemical shift anisotropy arising from the metal orbitals contributing towards the magnetic shielding of the ligand. The results illustrate the power of an integrated approach for studies of oxygen centers in enzyme reaction intermediates. Copyright © 2018 Elsevier Inc. All rights reserved.

Transient Numerical Modeling of Catalytic Channels

NASA Technical Reports Server (NTRS)

Struk, Peter M.; Dietrich, Daniel L.; Miller, Fletcher J.; T'ien, James S.

2007-01-01

This paper presents a transient model of catalytic combustion suitable for isolated channels and monolith reactors. The model is a lumped two-phase (gas and solid) model where the gas phase is quasi-steady relative to the transient solid. Axial diffusion is neglected in the gas phase; lateral diffusion, however, is accounted for using transfer coefficients. The solid phase includes axial heat conduction and external heat loss due to convection and radiation. The combustion process utilizes detailed gas and surface reaction models. The gas-phase model becomes a system of stiff ordinary differential equations while the solid phase reduces, after discretization, into a system of stiff ordinary differential-algebraic equations. The time evolution of the system came from alternating integrations of the quasi-steady gas and transient solid. This work outlines the numerical model and presents some sensitivity studies on important parameters including internal transfer coefficients, catalytic surface site density, and external heat-loss (if applicable). The model is compared to two experiments using CO fuel: (1) steady-state conversion through an isothermal platinum (Pt) tube and (2) transient propagation of a catalytic reaction inside a small Pt tube. The model requires internal mass-transfer resistance to match the experiments at lower residence times. Under mass-transport limited conditions, the model reasonably predicted exit conversion using global mass-transfer coefficients. Near light-off, the model results did not match the experiment precisely even after adjustment of mass-transfer coefficients. Agreement improved for the first case after adjusting the surface kinetics such that the net rate of CO adsorption increased compared to O2. The CO / O2 surface mechanism came from a sub-set of reactions in a popular CH4 / O2 mechanism. For the second case, predictions improved for lean conditions with increased external heat loss or adjustment of the kinetics as in the first case. Finally, the results show that different initial surface-species distribution leads to different steady-states under certain conditions. These results demonstrate the utility of a lumped two-phase model of a transient catalytic combustor with detailed chemistry.

Total solids content: a key parameter of metabolic pathways in dry anaerobic digestion

PubMed Central

2013-01-01

Background In solid-state anaerobic digestion (AD) bioprocesses, hydrolytic and acidogenic microbial metabolisms have not yet been clarified. Since these stages are particularly important for the establishment of the biological reaction, better knowledge could optimize the process performances by process parameters adjustment. Results This study demonstrated the effect of total solids (TS) content on microbial fermentation of wheat straw with six different TS contents ranging from wet to dry conditions (10 to 33% TS). Three groups of metabolic behaviors were distinguished based on wheat straw conversion rates with 2,200, 1,600, and 1,400 mmol.kgVS-1 of fermentative products under wet (10 and 14% TS), dry (19 to 28% TS), and highly dry (28 to 33% TS) conditions, respectively. Furthermore, both wet and dry fermentations showed acetic and butyric acid metabolisms, whereas a mainly butyric acid metabolism occurred in highly dry fermentation. Conclusion Substrate conversion was reduced with no changes of the metabolic pathways until a clear limit at 28% TS content, which corresponded to the threshold value of free water content of wheat straw. This study suggested that metabolic pathways present a limit of TS content for high-solid AD. PMID:24261971

Investigation of nutrient feeding strategies in a countercurrent mixed-acid multi-staged fermentation: development of segregated-nitrogen model.

PubMed

Smith, Aaron D; Holtzapple, Mark T

2010-12-01

The MixAlco process is a biorefinery based on the production of carboxylic acids via mixed-culture fermentation. Nitrogen is essential for microbial growth and metabolism, and may exist in soluble (e.g., ammonia) or insoluble forms (e.g., cells). Understanding the dynamics of nitrogen flow in a countercurrent fermentation is necessary to develop control strategies to maximize performance. To estimate nitrogen concentration profiles in a four-stage fermentation train, a mass balance-based segregated-nitrogen model was developed, which uses separate balances for solid- and liquid-phase nitrogen with nitrogen reaction flux between phases assumed to be zero. Comparison of predictions with measured nitrogen profiles from five trains, each with a different nutrient contacting pattern, shows the segregated-nitrogen model captures basic behavior and is a reasonable tool for estimating nitrogen profiles. The segregated-nitrogen model may be used to (1) estimate optimal nitrogen loading patterns, (2) develop a reaction-based model, (3) understand influence of model inputs (e.g., operating parameters, feedstock properties, nutrient loading pattern) on the steady-state nitrogen profile, and (4) determine the direction of the nitrogen reaction flux between liquid and solid phases. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Synthesis of nanostructures in nanowires using sequential catalyst reactions

DOE PAGES

Panciera, F.; Chou, Y. -C.; Reuter, M. C.; ...

2015-07-13

Nanowire growth by the vapour–liquid–solid (VLS) process enables a high level of control over nanowire composition, diameter, growth direction, branching and kinking, periodic twinning, and crystal structure. The tremendous impact of VLS-grown nanowires is due to this structural versatility, generating applications ranging from solid-state lighting and single-photon sources to thermoelectric devices. Here, we show that the morphology of these nanostructures can be further tailored by using the liquid droplets that catalyse nanowire growth as a ‘mixing bowl’, in which growth materials are sequentially supplied to nucleate new phases. Growing within the liquid, these phases adopt the shape of faceted nanocrystalsmore » that are then incorporated into the nanowires by further growth. Furthermore, we demonstrate this concept by epitaxially incorporating metal-silicide nanocrystals into Si nanowires with defect-free interfaces, and discuss how this process can be generalized to create complex nanowire-based heterostructures.« less

Synthesis of nanostructures in nanowires using sequential catalyst reactions

PubMed Central

Panciera, F.; Chou, Y.-C.; Reuter, M.C.; Zakharov, D.; Stach, E.A.; Hofmann, S.; Ross, F.M.

2016-01-01

Nanowire growth by the vapor-liquid-solid process enables a high level of control over nanowire composition, diameter, growth direction, branching and kinking, periodic twinning, and crystal structure. The tremendous impact of VLS-grown nanowires is due to this structural versatility, generating applications ranging from solid state lighting and single photon sources to thermoelectric devices. Here we show that the morphology of these nanostructures can be further tailored by using the liquid droplets that catalyze nanowire growth as a “mixing bowl”, in which growth materials are sequentially supplied to nucleate new phases. Growing within the liquid, these phases adopt the shape of faceted nanocrystals that are then incorporated into the nanowires by further growth. We demonstrate this concept by epitaxially incorporating metal silicide nanocrystals into Si nanowires with defect-free interfaces, and discuss how this process can be generalized to create complex nanowire-based heterostructures. PMID:26168344

Radiolysis of carbohydrates as studied by ESR and spin-trapping—II. Glycerol- d8 xylitol, dulcitol, d-sorbitol and d-mannitol

NASA Astrophysics Data System (ADS)

Kuwabara, M.; Zhang, Z.-Y.; Inanami, O.; Yoshii, G.

Studies concerning the radicals produced in glycerol by reactions with OH radicals have been carried out by investigating deuterated glycerol (glycerol-d 8) by spin-trapping with 2-methyl-2-nitrosopropane. Free radicals produced in linear carbohydrates such as xylitol, dulcitol, D-sorbitol and D-mannitol by reactions with OH radicals as well as by direct γ-radiolysis have been also investigated by spin-trapping. The ESR spectra of the spin-trapped radicals were analysed on the basis of the results from ESR and spin-trapping experiments on glycerol and deuterated glycerol, and the formation of three radical species, CHO-CH-, CH 2-CO- and HO-CH-, due to both OH reactions and direct γ-radiolysis was confirmed for all compounds. The presence of a radical, -CO-CH-, was detected for xylitol, D-sorbitol and D-mannitol. General reactions processes induced by OH reactions or γ-radiolysis in the solid state are discussed.

The influence of physical state on shikimic acid ozonolysis: a case for in situ microspectroscopy

NASA Astrophysics Data System (ADS)

Steimer, S. S.; Lampimäki, M.; Coz, E.; Grzinic, G.; Ammann, M.

2014-03-01

Atmospheric soluble organic aerosol material can become solid or semi-solid. Due to increasing viscosity and decreasing diffusivity, this can impact important processes such as gas uptake and reactivity within aerosols containing such substances. This work explores the dependence of shikimic acid ozonolysis on humidity and thereby viscosity. Shikimic acid, a proxy for oxygenated reactive organic material, reacts with O3 in a Criegee-type reaction. We used an environmental microreactor embedded in a Scanning Transmission X-ray Microscope (STXM) to probe this oxidation process. This technique facilitates in situ measurements with single micron-sized particles and allows to obtain Near Edge X-ray Absorption Fine Structure (NEXAFS) spectra with high spatial resolution. Thus, the chemical evolution of the interior of the particles can be followed under reaction conditions. The experiments show that the overall degradation rate of shikimic acid is depending on the relative humidity in a way that is controlled by the decreasing diffusivity of ozone with decreasing humidity. This decreasing diffusivity is most likely linked to the increasing viscosity of the shikimic acid-water mixture. The degradation rate was also depending on particle size, most congruent with a reacto-diffusion limited kinetic case where the reaction progresses only in a shallow layer within the bulk. No gradient in the shikimic acid concentration was observed within the bulk material at any humidity indicating that the diffusivity of shikimic acid is still high enough to allow its equilibration throughout the particles on the time scale of hours at higher humidity and that the thickness of the oxidized layer under dry conditions, where the particles are solid, is beyond the resolution of STXM.

The influence of physical state on shikimic acid ozonolysis: a case for in situ microspectroscopy

NASA Astrophysics Data System (ADS)

Steimer, S. S.; Lampimäki, M.; Coz, E.; Grzinic, G.; Ammann, M.

2014-10-01

Atmospheric soluble organic aerosol material can become solid or semi-solid. Due to increasing viscosity and decreasing diffusivity, this can impact important processes such as gas uptake and reactivity within aerosols containing such substances. This work explores the dependence of shikimic acid ozonolysis on humidity and thereby viscosity. Shikimic acid, a proxy for oxygenated reactive organic material, reacts with O3 in a Criegee-type reaction. We used an environmental microreactor embedded in a scanning transmission X-ray microscope (STXM) to probe this oxidation process. This technique facilitates in situ measurements with single micron-sized particles and allows to obtain near-edge X-ray absorption fine structure (NEXAFS) spectra with high spatial resolution. Thus, the chemical evolution of the interior of the particles can be followed under reaction conditions. The experiments show that the overall degradation rate of shikimic acid is depending on the relative humidity in a way that is controlled by the decreasing diffusivity of ozone with decreasing humidity. This decreasing diffusivity is most likely linked to the increasing viscosity of the shikimic acid-water mixture. The degradation rate was also depending on particle size, most congruent with a reacto-diffusion limited kinetic case where the reaction progresses only in a shallow layer within the bulk. No gradient in the shikimic acid concentration was observed within the bulk material at any humidity indicating that the diffusivity of shikimic acid is still high enough to allow its equilibration throughout the particles on the timescale of hours at higher humidity and that the thickness of the oxidized layer under dry conditions, where the particles are solid, is beyond the resolution of STXM.

Porous Organic Nanolayers for Coating of Solid-state Devices

PubMed Central

2011-01-01

Background Highly hydrophobic surfaces can have very low surface energy and such low surface energy biological interfaces can be obtained using fluorinated coatings on surfaces. Deposition of biocompatible organic films on solid-state surfaces is attained with techniques like plasma polymerization, biomineralization and chemical vapor deposition. All these require special equipment or harsh chemicals. This paper presents a simple vapor-phase approach to directly coat solid-state surfaces with biocompatible films without any harsh chemical or plasma treatment. Hydrophilic and hydrophobic monomers were used for reaction and deposition of nanolayer films. The monomers were characterized and showed a very consistent coating of 3D micropore structures. Results The coating showed nano-textured surface morphology which can aid cell growth and provide rich molecular functionalization. The surface properties of the obtained film were regulated by varying monomer concentrations, reaction time and the vacuum pressure in a simple reaction chamber. Films were characterized by contact angle analysis for surface energy and with profilometer to measure the thickness. Fourier Transform Infrared Spectroscopy (FTIR) analysis revealed the chemical composition of the coated films. Variations in the FTIR results with respect to different concentrations of monomers showed the chemical composition of the resulting films. Conclusion The presented approach of vapor-phase coating of solid-state structures is important and applicable in many areas of bio-nano interface development. The exposure of coatings to the solutions of different pH showed the stability of the coatings in chemical surroundings. The organic nanocoating of films can be used in bio-implants and many medical devices. PMID:21569579

Formation of III–V ternary solid solutions on GaAs and GaSb plates via solid-phase substitution reactions

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

Vasil’ev, V. I.; Gagis, G. S., E-mail: galina.gagis@gmail.com; Kuchinskii, V. I.

2015-07-15

Processes are considered in which ultrathin layers of III–V ternary solid solutions are formed via the delivery of Group-V element vapors to GaAs and GaSb semiconductor plates, with solid-phase substitution reactions occurring in the surface layers of these plates. This method can form defect-free GaAs{sup 1–x}P{sup x}, GaAs{sup x}Sb{sup 1–x}, and GaP{sup x}Sb{sup 1–x} layers with thicknesses of 10–20 nm and a content x of the embedded components of up to 0.04.

Laser-driven fusion etching process

DOEpatents

Ashby, Carol I. H.; Brannon, Paul J.; Gerardo, James B.

1989-01-01

The surfaces of solid ionic substrates are etched by a radiation-driven chemical reaction. The process involves exposing an ionic substrate coated with a layer of a reactant material on its surface to radiation, e.g. a laser, to induce localized melting of the substrate which results in the occurrance of a fusion reaction between the substrate and coating material. The resultant reaction product and excess reactant salt are then removed from the surface of the substrate with a solvent which is relatively inert towards the substrate. The laser-driven chemical etching process is especially suitable for etching ionic salt substrates, e.g., a solid inorganic salt such as LiNbO.sub.3, such as used in electro-optical/acousto-optic devices. It is also suitable for applications wherein the etching process is required to produce an etched ionic substrate having a smooth surface morphology or when a very rapid etching rate is desired.

Enhanced Multiferroic Properties of YMnO3 Ceramics Fabricated by Spark Plasma Sintering Along with Low-Temperature Solid-State Reaction

PubMed Central

Wang, Meng; Wang, Ting; Song, Shenhua; Ravi, Muchakayala; Liu, Renchen; Ji, Shishan

2017-01-01

Based on precursor powders with a size of 200–300 nm prepared by the low-temperature solid-state reaction method, phase-pure YMnO3 ceramics are fabricated using spark plasma sintering (SPS). X-ray diffraction (XRD) and scanning electron microscopy (SEM) reveal that the high-purity YMnO3 ceramics can be prepared by SPS at 1000 °C for 5 minutes with annealing at 800 °C for 2 h. The relative density of the sample is as high as 97%, which is much higher than those of the samples sintered by other methods. The present dielectric and magnetic properties are much better than those of the samples fabricated by conventional methods and SPS with ball-milling precursors, and the ferroelectric loops at room temperature can be detected. These findings indicate that the YMnO3 ceramics prepared by the low temperature solid reaction method and SPS possess excellent dielectric lossy ferroelectric properties at room temperature, and magnetic properties at low temperature (10 K), making them suitable for potential multiferroic applications. PMID:28772832

Biredox ionic liquids with solid-like redox density in the liquid state for high-energy supercapacitors.

PubMed

Mourad, Eléonore; Coustan, Laura; Lannelongue, Pierre; Zigah, Dodzi; Mehdi, Ahmad; Vioux, André; Freunberger, Stefan A; Favier, Frédéric; Fontaine, Olivier

2017-04-01

Kinetics of electrochemical reactions are several orders of magnitude slower in solids than in liquids as a result of the much lower ion diffusivity. Yet, the solid state maximizes the density of redox species, which is at least two orders of magnitude lower in liquids because of solubility limitations. With regard to electrochemical energy storage devices, this leads to high-energy batteries with limited power and high-power supercapacitors with a well-known energy deficiency. For such devices the ideal system should endow the liquid state with a density of redox species close to the solid state. Here we report an approach based on biredox ionic liquids to achieve bulk-like redox density at liquid-like fast kinetics. The cation and anion of these biredox ionic liquids bear moieties that undergo very fast reversible redox reactions. As a first demonstration of their potential for high-capacity/high-rate charge storage, we used them in redox supercapacitors. These ionic liquids are able to decouple charge storage from an ion-accessible electrode surface, by storing significant charge in the pores of the electrodes, to minimize self-discharge and leakage current as a result of retaining the redox species in the pores, and to raise working voltage due to their wide electrochemical window.

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

Murgia, Fabrizio; Antitomaso, Philippe; Stievano, Lorenzo

The ternary Chevrel phase Cu{sub 2}Mo{sub 6}S{sub 8} was successfully synthetized using a simple and cost-effective solid-state microwave-assisted reaction. While solid-state routes require days of high-temperature treatment under inert atmosphere, highly pure and crystalline Cu{sub 2}Mo{sub 6}S{sub 8} could be obtained in only 400 s from this precursor, the Chevrel binary phase Mo{sub 6}S{sub 8} was then obtained by copper removal through acidic leaching, and was evaluated as a positive electrode material for Mg-battery. The electrochemical performance in half-cell configuration shows reversible capacity exceeding 80 mAh/g, which is comparable to previous works carried out with materials synthesized by conventional high-temperaturemore » solid-state routes. - Graphical abstract: Ultrafast micro-wave synthesis of Chevrel phase Cu{sub 2}Mo{sub 6}S{sub 8} towards Mo{sub 6}S{sub 8} as positive electrode of Mg-battery. - Highlights: • Chevrel phase Cu{sub 2}Mo{sub 6}S{sub 8} is synthesized by fast microwave-assisted solid-state reaction. • Highly-pure and well-crystalline Cu{sub 2}Mo{sub 6}S{sub 8} is obtained. • Mo{sub 6}S{sub 8} obtained from leaching is tested as a positive electrode for Mg batteries.« less

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

Prabhakaran, Venkateshkumar; Johnson, Grant E.; Wang, Bingbing

Molecular-level understanding of electrochemical processes occurring at electrode-electrolyte interfaces (EEI) is key to the rational development of high-performance and sustainable electrochemical technologies. This article reports the development and first application of solid-state in situ electrochemical probes to study redox and catalytic processes occurring at well-defined EEI generated using soft-landing of mass- and charge-selected cluster ions (SL). In situ electrochemical probes with excellent mass transfer properties are fabricated using carefully-designed nanoporous ionic liquid membranes. SL enables deposition of pure active species that are not obtainable with other techniques onto electrode surfaces with precise control over charge state, composition, and kinetic energy.more » SL is, therefore, a unique tool for studying fundamental processes occurring at EEI. For the first time using an aprotic electrochemical probe, the effect of charge state (PMo12O403-/2-) and the contribution of building blocks of Keggin polyoxometalate (POM) clusters to redox processes are characterized by populating EEI with novel POM anions generated by electrospray ionization and gas phase dissociation. Additionally, a proton conducting electrochemical probe has been developed to characterize the reactive electrochemistry (oxygen reduction activity) of bare Pt clusters (Pt40 ~1 nm diameter), thus demonstrating the capability of the probe for studying reactions in controlled gaseous environments. The newly developed in situ electrochemical probes combined with ion SL provide a versatile method to characterize the EEI in solid-state redox systems and reactive electrochemistry at precisely-defined conditions. This capability will advance molecular-level understanding of processes occurring at EEI that are critical to many energy-related technologies.« less

Insights into electrochemical reactions from ambient pressure photoelectron spectroscopy.

PubMed

Stoerzinger, Kelsey A; Hong, Wesley T; Crumlin, Ethan J; Bluhm, Hendrik; Shao-Horn, Yang

2015-11-17

The understanding of fundamental processes in the bulk and at the interfaces of electrochemical devices is a prerequisite for the development of new technologies with higher efficiency and improved performance. One energy storage scheme of great interest is splitting water to form hydrogen and oxygen gas and converting back to electrical energy by their subsequent recombination with only water as a byproduct. However, kinetic limitations to the rate of oxygen-based electrochemical reactions hamper the efficiency in technologies such as solar fuels, fuel cells, and electrolyzers. For these reactions, the use of metal oxides as electrocatalysts is prevalent due to their stability, low cost, and ability to store oxygen within the lattice. However, due to the inherently convoluted nature of electrochemical and chemical processes in electrochemical systems, it is difficult to isolate and study individual electrochemical processes in a complex system. Therefore, in situ characterization tools are required for observing related physical and chemical processes directly at the places where and while they occur and can help elucidate the mechanisms of charge separation and charge transfer at electrochemical interfaces. X-ray photoelectron spectroscopy (XPS), also known as ESCA (electron spectroscopy for chemical analysis), has been used as a quantitative spectroscopic technique that measures the elemental composition, as well as chemical and electronic state of a material. Building from extensive ex situ characterization of electrochemical systems, initial in situ studies were conducted at or near ultrahigh vacuum (UHV) conditions (≤10(-6) Torr) to probe solid-state electrochemical systems. However, through the integration of differential-pumping stages, XPS can now operate at pressures in the torr range, comprising a technique called ambient pressure XPS (AP-XPS). In this Account, we briefly review the working principles and current status of AP-XPS. We use several recent in situ studies on model electrochemical components as well as operando studies performed by our groups at the Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory to illustrate that AP-XPS is both a chemically and an electrically specific tool since photoelectrons carry information on both the local chemistry and electrical potentials. The applications of AP-XPS to oxygen electrocatalysis shown in this Account span well-defined studies of (1) the oxide/oxygen gas interface, (2) the oxide/water vapor interface, and (3) operando measurements of half and full electrochemical cells. Using specially designed model devices, we can expose and isolate the electrode or interface of interest to the incident X-ray beam and AP-XPS analyzer to relate the electrical potentials to the composition/chemical state of the key components and interfaces. We conclude with an outlook on new developments of AP-XPS end stations, which may provide significant improvement in the observation of dynamics over a wide range of time scales, higher spatial resolution, and improved characterization of boundary or interface layers (solid/solid and liquid/solid).

Cationic copper (I) complexes with bulky 1,4-diaza-1,3-butadiene ligands - Synthesis, solid state structure and catalysis

NASA Astrophysics Data System (ADS)

Anga, Srinivas; Kottalanka, Ravi K.; Pal, Tigmansu; Panda, Tarun K.

2013-05-01

We report the full characterization of two glyoxal-based ligands N,N bis(diphenylmethyl)-1,4-diaza-1,3-butadiene ligand (DADPh2, 1) and more bulky N,N bis(triphenylmethyl)-1,4-diaza-1,3-butadiene ligand (DADPh3, 2) by the condensation reaction of glyoxal and diphenylmethanamine and triphenyl-methanamine respectively. The copper (I) complex of composition [Cu(DADPh2)2]PF6 (3) having two neutral bidentate N,N bis(diphenyl-methyl)-1,4-diaza-1,3-butadiene ligand was prepared by the reaction of [Cu(CH3CN)4]PF6 and 1 in 1:2 ratio in dichloromethane. In a similar reaction with N,N bis(triphenylmethyl)-1,4-diaza-1,3-butadiene ligand (2) and [Cu(CH3CN)4]PF6 in dichloromethane yielded corresponding heteroleptic copper (I) complex [Cu(DADPh3)(CH3CN)2]PF6 (4). Another copper (I) complex [Cu(DADPh2)(PPh3)]PF6 (5) can also be obtained by the one pot reaction involving ligand 1, [Cu(CH3CN)4]PF6 and triphenylphosphine. Solid state structures of all the five compounds were established by single crystal X-ray diffraction analysis. The solid state structures of the copper complexes 3-5 reveal a distorted tetrahedral geometry around the copper (I) centers. The copper complexes 3-5 were tested as catalysts for the coupling reaction of o-iodophenol and phenyl acetylene and it was observed that complex 4 exhibits the highest catalytic activity.

Characterization of the relationship of the cure cycle chemistry to cure cycle processing properties

NASA Technical Reports Server (NTRS)

Kranbuehl, D. E.

1986-01-01

Dynamic Dielectric measurements made over a wide range of frequency provide a sensitive and convenient means for monitoring the cure process in thermosets and thermoplastics. The measurement of dielectric relaxation is one of only a few instrumental techniques available for studying molecular properties in both the liquid and solid states. Furthermore, it is probably the only convenient experimental technique for studying the polymerization process of going from a monomeric liquid of varying viscosity to a crosslinked, insoluble, high temperature solid. The objective of the research is to develop on-line dielectric instrumentation for quantitative nondestructive material evaluation and closed loop smart cure cycle control. The key is to relate the chemistry of the cure cycle process to the dielectric properties of the polymer system by correlating the time, temperature, and frequency dependent dielectric measurements with chemical characterization measurements. Measurement of the wide variation in magnitude of the complex permittivity with both frequency and state of cure, coupled with chemical characterization work, have been shown in the laboratory to have the potential to determine: resin quality, composition and age; cure cycle window boundaries; onset of flow and point of maximum flow; extent of and completion of reaction; evolution of volatiles; T sub g; and, crosslinking and molecular weight buildup.

Probing astrophysically important states in the 26Mg nucleus to study neutron sources for the s process

NASA Astrophysics Data System (ADS)

Talwar, R.; Adachi, T.; Berg, G. P. A.; Bin, L.; Bisterzo, S.; Couder, M.; deBoer, R. J.; Fang, X.; Fujita, H.; Fujita, Y.; Görres, J.; Hatanaka, K.; Itoh, T.; Kadoya, T.; Long, A.; Miki, K.; Patel, D.; Pignatari, M.; Shimbara, Y.; Tamii, A.; Wiescher, M.; Yamamoto, T.; Yosoi, M.

2016-05-01

Background: The 22Ne(α ,n )25Mg reaction is the dominant neutron source for the slow neutron capture process (s process) in massive stars, and contributes, together with 13C (α ,n )16O, to the production of neutrons for the s process in asymptotic giant branch (AGB) stars. However, the reaction is endothermic and competes directly with 22Ne(α ,γ )26Mg radiative capture. The uncertainties for both reactions are large owing to the uncertainty in the level structure of 26Mg near the α and neutron separation energies. These uncertainties affect the s -process nucleosynthesis calculations in theoretical stellar models. Purpose: Indirect studies in the past have been successful in determining the energies and the γ -ray and neutron widths of the 26Mg states in the energy region of interest. But, the high Coulomb barrier hinders a direct measurement of the resonance strengths, which are determined by the α widths for these states. The goal of the present experiments is to identify the critical resonance states and to precisely measure the α widths by α -transfer techniques. Methods: The α -inelastic scattering and α -transfer measurements were performed on a solid 26Mg target and a 22Ne gas target, respectively, using the Grand Raiden Spectrometer at the Research Center for Nuclear Physics in Osaka, Japan. The (α ,α') measurements were performed at 0 .45∘ , 4 .1∘ , 8 .6∘ , and 11 .1∘ and the (6Li,d ) measurements at 0∘ and 10∘. The scattered α particles and deuterons were detected by the focal plane detection system consisting of multiwire drift chambers and plastic scintillators. The focal plane energy calibration allowed the study of 26Mg levels from Ex = 7.69-12.06 MeV in the (α ,α') measurement and Ex = 7.36-11.32 MeV in the (6Li,d ) measurement. Results: Six levels (Ex = 10717, 10822, 10951, 11085, 11167, and 11317 keV) were observed above the α threshold in the region of interest (10.61-11.32 MeV). The α widths were calculated for these states from the experimental data. The results were used to determine the α -capture induced reaction rates. Conclusion: The energy range above the α threshold in 26Mg was investigated using a high resolution spectrometer. A number of states were observed for the first time in α -scattering and α -transfer reactions. The excitation energies and spin-parities were determined. Good agreement is observed for previously known levels in 26Mg. From the observed resonance levels the Ex = 10717 keV state has a negligible contribution to the α -induced reaction rates. The rates are dominated in both reaction channels by the resonance contributions of the states at Ex = 10951, 11167, and 11317 keV. The Ex = 11167 keV state has the most appreciable impact on the (α ,γ ) rate and therefore plays an important role in the prediction of the neutron production in s -process environments.

Putting Cocrystal Stoichiometry to Work: A Reactive Hydrogen-Bonded "Superassembly" Enables Nanoscale Enlargement of a Metal-Organic Rhomboid via a Solid-State Photocycloaddition.

PubMed

Chu, Qianli; Duncan, Andrew J E; Papaefstathiou, Giannis S; Hamilton, Tamara D; Atkinson, Manza B J; Mariappan, S V Santhana; MacGillivray, Leonard R

2018-04-11

Enlargement of a self-assembled metal-organic rhomboid is achieved via the organic solid state. The solid-state synthesis of an elongated organic ligand was achieved by a template directed [2 + 2] photodimerization in a cocrystal. Initial cocrystals obtained of resorcinol template and reactant alkene afforded a 1:2 cocrystal with the alkene in a stacked yet photostable geometry. Cocrystallization performed in the presence of excess template resulted in a 3:2 cocrystal composed of novel discrete 10-component hydrogen-bonded "superassemblies" wherein the alkenes undergo a head-to-head [2 + 2] photodimerization. Isolation and reaction of elongated photoproduct with Cu(II) ions afforded a metal-organic rhomboid of nanoscale dimensions that hosts small molecules in the solid state as guests.

Electric, Magnetic, and Magnetoelectric Properties of Yttrium-Containing BaY0.025Ti0.9625O3-SrFe12O19 Composite

NASA Astrophysics Data System (ADS)

Rather, Mehraj ud Din; Samad, Rubiya; Want, Basharat

2018-03-01

The physical properties of BaY0.025Ti0.9625O3, SrFe12O19, and 0.90BaY0.025Ti0.9625O3-0.10 SrFe12O19 composite have been studied. The proposed composite was synthesized by solid-state reaction method from yttrium barium titanate processed by solid-state reaction and strontium hexaferrite obtained by a sol-gel process. Microstructural analysis revealed monophasic grains for yttrium barium titanate phase, while loosely packed biphasic structure was observed for the composite. Powder x-ray analysis showed that the individual phases retained their crystal structure in the composite, without formation of any new additional phase. Measurement of magnetic hysteresis loops at room temperature indicated that the magnetic parameters of the composite were diluted by the presence of the ferroelectric phase. The ferroelectric hysteresis of yttrium barium titanate confirmed the ferroelectric transition at 119°C. Meanwhile, the symmetrical ferroelectric loops observed at different fields established the ferroelectric nature of the composite. Improved dielectric properties and low dielectric losses were observed due to yttrium doping in the composite. The diffuseness of the ferroelectric transitions for the composite was confirmed by the Curie-Weiss law. Activation energy calculations revealed the charge-hopping conduction mechanism in the composite. Magnetodielectric studies confirmed that the overall magnetocapacitance in the composite exhibited combined effects of magnetoresistance and magnetoelectric coupling.

Reactions of Ground State Nitrogen Atoms N(4S) with Astrochemically-Relevant Molecules on Interstellar Dusts

NASA Astrophysics Data System (ADS)

Krim, Lahouari; Nourry, Sendres

2015-06-01

In the last few years, ambitious programs were launched to probe the interstellar medium always more accurately. One of the major challenges of these missions remains the detection of prebiotic compounds and the understanding of reaction pathways leading to their formation. These complex heterogeneous reactions mainly occur on icy dust grains, and their studies require the coupling of laboratory experiments mimicking the extreme conditions of extreme cold and dilute media. For that purpose, we have developed an original experimental approach that combine the study of heterogeneous reactions (by exposing neutral molecules adsorbed on ice to non-energetic radicals H, OH, N...) and a neon matrix isolation study at very low temperatures, which is of paramount importance to isolate and characterize highly reactive reaction intermediates. Such experimental approach has already provided answers to many questions raised about some astrochemically-relevant reactions occurring in the ground state on the surface of dust grain ices in dense molecular clouds. The aim of this new present work is to show the implication of ground state atomic nitrogen on hydrogen atom abstraction reactions from some astrochemically-relevant species, at very low temperatures (3K-20K), without providing any external energy. Under cryogenic temperatures and with high barrier heights, such reactions involving N(4S) nitrogen atoms should not occur spontaneously and require an initiating energy. However, the detection of some radicals species as byproducts, in our solid samples left in the dark for hours at 10K, proves that hydrogen abstraction reactions involving ground state N(4S) nitrogen atoms may occur in solid phase at cryogenic temperatures. Our results show the efficiency of radical species formation stemming from non-energetic N-atoms and astrochemically-relevant molecules. We will then discuss how such reactions, involving nitrogen atoms in their ground states, might be the first key step towards complex organic molecules production in the interstellar medium.

Enhanced photoluminescence of SrWO{sub 4}:Eu{sup 3+} red phosphor synthesized by mechanochemically assisted solid state metathesis reaction method at room temperature

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

Peter, Anthuvan John, E-mail: quantajohn@gmail.com; Banu, I. B. Shameem

2015-06-24

Optically efficient europium activated alkaline earth metal tungstate nano phosphor (SrWO{sub 4}) with different doping concentrations have been synthesized by mechanochemically assisted solid state metathesis reaction at room temperature for the first time. The XRD and Raman spectra results indicated that the prepared powders exhibit a scheelite-type tetragonal structure. FTIR spectra exhibited a high absorption band situated at around 854 cm{sup −1}, which was ascribed to the W–O antisymmetric stretching vibrations into the [WO{sub 4}]{sup 2−} tetrahedron groups. Analysis of the emission spectra with different Eu{sup 3+} concentrations revealed that the optimum dopant concentration for SrWO{sub 4}: x Eu{sup 3+} phosphormore » is about 8 mol% of Eu{sup 3+}.The red emission intensity of the SSM prepared SrWO{sub 4}: 0.08Eu{sup 3+} phosphors are 2 times greater than that of the commercial Y{sub 2}O{sub 2}S: Eu{sup 3+} red phosphor prepared by the conventional solid state reaction method. All the results indicate that the phosphor is a promising red phosphor pumped by NUV InGaN chip for fabricating WLED.« less

Kinetic products in coordination networks: ab initio X-ray powder diffraction analysis.

PubMed

Martí-Rujas, Javier; Kawano, Masaki

2013-02-19

Porous coordination networks are materials that maintain their crystal structure as molecular "guests" enter and exit their pores. They are of great research interest with applications in areas such as catalysis, gas adsorption, proton conductivity, and drug release. As with zeolite preparation, the kinetic states in coordination network preparation play a crucial role in determining the final products. Controlling the kinetic state during self-assembly of coordination networks is a fundamental aspect of developing further functionalization of this class of materials. However, unlike for zeolites, there are few structural studies reporting the kinetic products made during self-assembly of coordination networks. Synthetic routes that produce the necessary selectivity are complex. The structural knowledge obtained from X-ray crystallography has been crucial for developing rational strategies for design of organic-inorganic hybrid networks. However, despite the explosive progress in the solid-state study of coordination networks during the last 15 years, researchers still do not understand many chemical reaction processes because of the difficulties in growing single crystals suitable for X-ray diffraction: Fast precipitation can lead to kinetic (metastable) products, but in microcrystalline form, unsuitable for single crystal X-ray analysis. X-ray powder diffraction (XRPD) routinely is used to check phase purity, crystallinity, and to monitor the stability of frameworks upon guest removal/inclusion under various conditions, but rarely is used for structure elucidation. Recent advances in structure determination of microcrystalline solids from ab initio XRPD have allowed three-dimensional structure determination when single crystals are not available. Thus, ab initio XRPD structure determination is becoming a powerful method for structure determination of microcrystalline solids, including porous coordination networks. Because of the great interest across scientific disciplines in coordination networks, especially porous coordination networks, the ability to determine crystal structures when the crystals are not suitable for single crystal X-ray analysis is of paramount importance. In this Account, we report the potential of kinetic control to synthesize new coordination networks and we describe ab initio XRPD structure determination to characterize these networks' crystal structures. We describe our recent work on selective instant synthesis to yield kinetically controlled porous coordination networks. We demonstrate that instant synthesis can selectively produce metastable networks that are not possible to synthesize by conventional solution chemistry. Using kinetic products, we provide mechanistic insights into thermally induced (573-723 K) (i.e., annealing method) structural transformations in porous coordination networks as well as examples of guest exchange/inclusion reactions. Finally, we describe a memory effect that allows the transfer of structural information from kinetic precursor structures to thermally stable structures through amorphous intermediate phases. We believe that ab initio XRPD structure determination will soon be used to investigate chemical processes that lead intrinsically to microcrystalline solids, which up to now have not been fully understood due to the unavailability of single crystals. For example, only recently have researchers used single-crystal X-ray diffraction to elucidate crystal-to-crystal chemical reactions taking place in the crystalline scaffold of coordination networks. The potential of ab initio X-ray powder diffraction analysis goes beyond single-crystal-to-single-crystal processes, potentially allowing members of this field to study intriguing in situ reactions, such as reactions within pores.

Heterogeneous processes: Laboratory, field, and modeling studies

NASA Technical Reports Server (NTRS)

Poole, Lamont R.; Kurylo, Michael J.; Jones, Rod L.; Wahner, Andreas; Calvert, Jack G.; Leu, M.-T.; Fried, A.; Molina, Mario J.; Hampson, Robert F.; Pitts, M. C.

1991-01-01

The efficiencies of chemical families such as ClO(x) and NO(x) for altering the total abundance and distribution of stratospheric ozone are controlled by a partitioning between reactive (active) and nonreactive (reservoir) compounds within each family. Gas phase thermodynamics, photochemistry, and kinetics would dictate, for example, that only about 1 percent of the chlorine resident in the lower stratosphere would be in the form of active Cl or ClO, the remainder existing in the reservoir compounds HCl and ClONO2. The consistency of this picture was recently challenged by the recognition that important chemical transformations take place on polar regions: the Airborne Antarctic Ozone Experiment (AAOE) and the Airborne Arctic Stratospheric Expedition (AASA). Following the discovery of the Antarctic ozone hole, Solomon et al. suggested that the heterogeneous chemical reaction: ClONO2(g)+HCl(s) yields Cl2(g)+HNO3(s) could play a key role in converting chlorine from inactive forms into a species (Cl2) that would rapidly dissociate in sunlight to liberate atomic chlorine and initiate ozone depletion. The symbols (s) and (g) denote solid phase, or adsorbed onto a solid surface, and gas phase, respectively, and represent the approach by which such a reaction is modeled rather than the microscopic details of the reaction. The reaction was expected to be most important at altitudes where PSC's were most prevalent (10 to 25 km), thereby extending the altitude range over which chlorine compounds can efficiently destroy ozone from the 35 to 45 km region (where concentrations of active chlorine are usually highest) to lower altitudes where the ozone concentration is at its peak. This chapter will briefly review the current state of knowledge of heterogeneous processes in the stratosphere, emphasizing those results obtained since the World Meteorological Organization (WMO) conference. Sections are included on laboratory investigations of heterogeneous reactions, the characteristics and climatology of PSC's, stratospheric sulfate aerosols, and evidence of heterogeneous chemical processing.

Investigation of Fission Product Transport into Zeolite-A for Pyroprocessing Waste Minimization

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

James R. Allensworth; Michael F. Simpson; Man-Sung Yim

Methods to improve fission product salt sorption into zeolite-A have been investigated in an effort to reduce waste associated with the electrochemical treatment of spent nuclear fuel. It was demonstrated that individual fission product chloride salts were absorbed by zeolite-A in a solid-state process. As a result, recycling of LiCl-KCl appears feasible via adding a zone-freezing technique to the current treatment process. Ternary salt molten-state experiments showed the limiting kinetics of CsCl and SrCl2 sorption into the zeolite. CsCl sorption occurred rapidly relative to SrCl2 with no observed dependence on zeolite particle size, while SrCl2 sorption was highly dependent onmore » particle size. The application of experimental data to a developed reaction-diffusion-based sorption model yielded diffusivities of 8.04 × 10-6 and 4.04 × 10-7 cm2 /s for CsCl and SrCl2, respectively. Additionally, the chemical reaction term in the developed model was found to be insignificant compared to the diffusion term.« less

Isothermal Fourier transform infrared microspectrosopic studies on the stability kinetics of solid-state intramolecular cyclization of aspartame sweetener.

PubMed

Cheng, Y D; Lin, S Y

2000-03-01

A novel Fourier transform infrared (FT-IR) microspectrophotometer equipped with differential scanning calorimetry (DSC) was used to investigate the kinetics of intramolecular cyclization of aspartame (APM) sweetener in the solid state under isothermal conditions. The thermal-dependent changes in the peak intensity of IR spectra at 1543, 1283, and 1259 cm(-1) were examined to explore the reaction. The results support that the intramolecular cyclization process in APM proceeded in three steps: the methoxyl group of ester was first thermolyzed to release methanol, then an acyl cation was attacked by the lone pair of electrons available on nitrogen by an S(N)1 pathway, and finally ring-closure occurred. The intramolecular cyclization of APM determined by this microscopic FT-IR/DSC system was found to follow zero-order kinetics after a brief induction period. The bond cleavage energy (259.38 kJ/mol) of thermolysis for the leaving group of -OCH(3), the bond conversion energy (328.88 kJ/mol) for the amide II NH band to DKP NH band, and the CN bond formation energy (326.93 kJ/mol) of cyclization for the DKP in the APM molecule were also calculated from the Arrhenius equation. The total activation energy of the DKP formation via intramolecular cyclization was 261.33 kJ/mol, calculated by the above summation of the bond energy of cleavage, conversion, and formation, which was near to the value determined by the DSC or TGA method. This indicates that the microscopic FT-IR/DSC system is useful as a potential tool not only to investigate the degradation mechanism of drugs in the solid state but also to directly predict the bond energy of the reaction.

When is an imine not an imine? Unusual reactivity of a series of Cu(II) imine-pyridine complexes and their exploitation for the Henry reaction.

PubMed

Cooper, Christine J; Jones, Matthew D; Brayshaw, Simon K; Sonnex, Benjamin; Russell, Mark L; Mahon, Mary F; Allan, David R

2011-04-14

In this paper we report the synthesis and solid-state structures for a series of pyridine based Cu(II) complexes and preliminary data for the asymmetric Henry reaction. Interestingly, the solid-state structures indicate the incorporation of an alcohol into one of the imine groups of the ligand, forming a rare α-amino ether group. The complexes have been studied via single crystal X-ray diffraction, EPR spectroscopy and mass spectrometry. Intriguingly, it has been observed that the alcohol only adds to one of the imine moieties. Density functional theory (DFT) calculations have also been employed to rationalise the observed structures. The Cu(II) complexes have been tested in the asymmetric Henry reaction (benzaldehyde + nitromethane or nitroethane) with ee's up to 84% being achieved as well as high conversions and modest diastereoselectivities. © The Royal Society of Chemistry 2011

Low Energy Nuclear Reactions: Status at the Beginning of the New Millenium

NASA Astrophysics Data System (ADS)

Mallove, Eugene F.

2001-03-01

This talk will summarize some of the more convincing recent experiments that show that ^4He,^3He (including impossible to explain changes in the ^4He/^3He isotopic ratio), nuclear scale excess energy, tritium, low-level neutron production, and the transmutation of heavy elements can occur near room temperature in relatively simple systems. Despite inappropriate theory-based arguments against it and unethical attacks by people unfamiliar with the supporting experiments, the new field of solid state nuclear reactions is progressing. The physical theory behind the associated phenomena continues to be debated among theorists. But progress is being made. The facts of the history of this scientific controversy suggest that it is inadvisable to rush to judgment against allegedly ``impossible" new phenomena when increasingly careful experiments have revealed new vistas in physics. Detailed discussion of evidence for solid state nuclear reactions is available

Quantum State-Resolved Reactive and Inelastic Scattering at Gas-Liquid and Gas-Solid Interfaces

NASA Astrophysics Data System (ADS)

Grütter, Monika; Nelson, Daniel J.; Nesbitt, David J.

2012-06-01

Quantum state-resolved reactive and inelastic scattering at gas-liquid and gas-solid interfaces has become a research field of considerable interest in recent years. The collision and reaction dynamics of internally cold gas beams from liquid or solid surfaces is governed by two main processes, impulsive scattering (IS), where the incident particles scatter in a few-collisions environment from the surface, and trapping-desorption (TD), where full equilibration to the surface temperature (T{TD}≈ T{s}) occurs prior to the particles' return to the gas phase. Impulsive scattering events, on the other hand, result in significant rotational, and to a lesser extent vibrational, excitation of the scattered molecules, which can be well-described by a Boltzmann-distribution at a temperature (T{IS}>>T{s}). The quantum-state resolved detection used here allows the disentanglement of the rotational, vibrational, and translational degrees of freedom of the scattered molecules. The two examples discussed are (i) reactive scattering of monoatomic fluorine from room-temperature ionic liquids (RTILs) and (ii) inelastic scattering of benzene from a heated (˜500 K) gold surface. In the former experiment, rovibrational states of the nascent HF beam are detected using direct infrared absorption spectroscopy, and in the latter, a resonace-enhanced multi-photon-ionization (REMPI) scheme is employed in combination with a velocity-map imaging (VMI) device, which allows the detection of different vibrational states of benzene excited during the scattering process. M. E. Saecker, S. T. Govoni, D. V. Kowalski, M. E. King and G. M. Nathanson Science 252, 1421, 1991. A. M. Zolot, W. W. Harper, B. G. Perkins, P. J. Dagdigian and D. J. Nesbitt J. Chem. Phys 125, 021101, 2006. J. R. Roscioli and D. J. Nesbitt Faraday Disc. 150, 471, 2011.

Hydrothermal carbonization of food waste for nutrient recovery and reuse.

PubMed

Idowu, Ifeolu; Li, Liang; Flora, Joseph R V; Pellechia, Perry J; Darko, Samuel A; Ro, Kyoung S; Berge, Nicole D

2017-11-01

Food waste represents a rather large and currently underutilized source of potentially available and reusable nutrients. Laboratory-scale experiments evaluating the hydrothermal carbonization of food wastes collected from restaurants were conducted to understand how changes in feedstock composition and carbonization process conditions influence primary and secondary nutrient fate. Results from this work indicate that at all evaluated reaction times and temperatures, the majority of nitrogen, calcium, and magnesium remain integrated within the solid-phase, while the majority of potassium and sodium reside in the liquid-phase. The fate of phosphorus is dependent on reaction times and temperatures, with solid-phase integration increasing with higher reaction temperature and longer time. A series of leaching experiments to determine potential solid-phase nutrient availability were also conducted and indicate that, at least in the short term, nitrogen release from the solids is small, while almost all of the phosphorus present in the solids produced from carbonizing at 225 and 250°C is released. At a reaction temperature of 275°C, smaller fractions of the solid-phase total phosphorus are released as reaction times increase, likely due to increased solids incorporation. Using these data, it is estimated that up to 0.96% and 2.30% of nitrogen and phosphorus-based fertilizers, respectively, in the US can be replaced by the nutrients integrated within hydrochar and liquid-phases generated from the carbonization of currently landfilled food wastes. Copyright © 2017 Elsevier Ltd. All rights reserved.

The Mechanochemical Reaction of Palladium(II) Chloride with a Bidentate Phosphine

ERIC Educational Resources Information Center

Berry, David E.; Carrie, Philippa; Fawkes, Kelli L.; Rebner, Bruce; Xing, Yao

2010-01-01

This experiment describes the reaction of palladium(II) chloride with 1,5-bis(diphenylphosphino)pentane by grinding the two powders together in the solid state. The product is the precursor for the metalation reaction at one of the methylene carbon atoms of the ligand's backbone. The final product is known to be a catalyst for Suzuki-Miyaura…

A Microwave-Assisted Reduction of Cyclohexanone Using Solid-State-Supported Sodium Borohydride

ERIC Educational Resources Information Center

White, Lori L.; Kittredge, Kevin W.

2005-01-01

The reduction of carbonyl groups by sodium borohydride though is a well-known reaction in most organic lab texts, a difficulty for an instructor adopting this reaction in a student lab is that it is too long. Using a microwave assisted organic synthesis solves this difficulty and one such reaction, which is the microwave-assisted reduction of…

Continuous Heterogeneous Photocatalysis in Serial Micro-Batch Reactors.

PubMed

Pieber, Bartholomäus; Shalom, Menny; Antonietti, Markus; Seeberger, Peter H; Gilmore, Kerry

2018-01-29

Solid reagents, leaching catalysts, and heterogeneous photocatalysts are commonly employed in batch processes but are ill-suited for continuous-flow chemistry. Heterogeneous catalysts for thermal reactions are typically used in packed-bed reactors, which cannot be penetrated by light and thus are not suitable for photocatalytic reactions involving solids. We demonstrate that serial micro-batch reactors (SMBRs) allow for the continuous utilization of solid materials together with liquids and gases in flow. This technology was utilized to develop selective and efficient fluorination reactions using a modified graphitic carbon nitride heterogeneous catalyst instead of costly homogeneous metal polypyridyl complexes. The merger of this inexpensive, recyclable catalyst and the SMBR approach enables sustainable and scalable photocatalysis. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tunneling chemical reactions D+H{sub 2}{yields}DH+H and D+DH{yields}D{sub 2}+H in solid D{sub 2}-H{sub 2} and HD-H{sub 2} mixtures: An electron-spin-resonance study

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

Kumada, Takayuki

2006-03-07

Tunneling chemical reactions D+H{sub 2}{yields}DH+H and D+DH{yields}D{sub 2}+H in solid HD-H{sub 2} and D{sub 2}-H{sub 2} mixtures were studied in the temperature range between 4 and 8 K. These reactions were initiated by UV photolysis of DI molecules doped in these solids for 30 s and followed by measuring the time course of electron-spin-resonance (ESR) intensities of D and H atoms. ESR intensity of D atoms produced by the photolysis decreases but that of H atoms increases with time. Time course of the D and H intensities has the fast and slow processes. The fast process, which finishes within {approx}300more » s after the photolysis, is assigned to the reaction of D atom with one of its nearest-neighboring H{sub 2} molecules, D(H{sub 2}){sub n}(HD){sub 12-n}{yields}H(H{sub 2}){sub n-1}(HD){sub 13-n} or D(H{sub 2}){sub n}(D{sub 2}){sub 12-n}{yields}H(HD)(H{sub 2}){sub n-1}(D{sub 2}){sub 12-n} for 12{>=}n{>=}1. Rate constant for the D+H{sub 2} reaction between neighboring D atom-H{sub 2} molecule pair is determined to be (7.5{+-}0.7)x10{sup -3} s{sup -1} in solid HD-H{sub 2} and (1.3{+-}0.3)x10{sup -2} s{sup -1} in D{sub 2}-H{sub 2} at 4.1 K, which is very close to that calculated based on the theory of chemical reaction in gas phase by Hancock et al. [J. Chem. Phys. 91, 3492 (1989)] and Takayanagi and Sato [J. Chem. Phys. 92, 2862 (1990)]. This rate constant was found to be independent of temperature up to 7 K within experimental error of {+-}30%. The slow process is assigned to the reaction of D atom produced in a cage fully surrounded by HD or D{sub 2} molecules, D(HD){sub 12} or D(D{sub 2}){sub 12}. This D atom undergoes the D+DH reaction with one of its nearest-neighboring HD molecules in solid HD-H{sub 2} or diffuses to the neighbor of H{sub 2} molecules to allow the D+H{sub 2} reaction in solid HD-H{sub 2} and D{sub 2}-H{sub 2}. The former is the main channel in solid HD-H{sub 2} below 6 K where D atoms diffuse very slowly, whereas the latter dominates over the former above 6 K. Rate for the reactions in the slow process is independent of temperature below 6 K but increases with the increase in temperature above 6 K. We found that the increase is due to the increase in hopping rate of D atoms to the neighbor of H{sub 2} molecules. Rate constant for the D+DH reaction was found to be independent of temperature up to 7 K as well.« less

Rechargeable quasi-solid state lithium battery with organic crystalline cathode

PubMed Central

Hanyu, Yuki; Honma, Itaru

2012-01-01

Utilization of metal-free low-cost high-capacity organic cathodes for lithium batteries has been a long-standing goal, but critical cyclability problems owing to dissolution of active materials into the electrolyte have been an inevitable obstacle. For practical utilisation of numerous cathode-active compounds proposed over the past decades, a novel battery construction strategy is required. We have designed a solid state cell that accommodates organic cathodic reactions in solid phase. The cell was successful at achieving high capacity exceeding 200 mAh/g with excellent cycleability. Further investigations confirmed that our strategy is effective for numerous other redox-active organic compounds. This implies hundreds of compounds dismissed before due to low cycleability would worth a re-visit under solid state design. PMID:22693655

Synthesis and hydration behavior of calcium zirconium aluminate (Ca{sub 7}ZrAl{sub 6}O{sub 18}) cement

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

Kang, Eun-Hee; Yoo, Jun-Sang; Kim, Bo-Hye

2014-02-15

Calcium zirconium aluminate (Ca{sub 7}ZrAl{sub 6}O{sub 18}) cements were prepared by solid state reaction and polymeric precursor methods, and their phase evolution, morphology, and hydration behavior were investigated. In polymeric precursor method, a nearly single phase Ca{sub 7}ZrAl{sub 6}O{sub 18} was obtained at relatively lower temperature (1200 °C) whereas in solid state reaction, a small amount of CaZrO{sub 3} coexisted with Ca{sub 7}ZrAl{sub 6}O{sub 18} even at higher temperature (1400 °C). Unexpectedly, Ca{sub 7}ZrAl{sub 6}O{sub 18} synthesized by polymeric precursor process was the large-sized and rough-shaped powder. The planetary ball milling was employed to control the particle size and shape.more » The hydration behavior of Ca{sub 7}ZrAl{sub 6}O{sub 18} was similar to that of Ca{sub 3}Al{sub 2}O{sub 6} (C3A), but the hydration products were Ca{sub 3}Al{sub 2}O{sub 6}·6H{sub 2}O (C3AH6) and several intermediate products. Thus, Zr (or ZrO{sub 2}) stabilized the intermediate hydration products of C3A.« less

Optical Fluorescence Microscopy for Spatially Characterizing Electron Transfer across a Solid-Liquid Interface on Heterogeneous Electrodes.

PubMed

Choudhary, Eric; Velmurugan, Jeyavel; Marr, James M; Liddle, James A; Szalai, Veronika

2016-01-01

Heterogeneous catalytic materials and electrodes are used for (electro)chemical transformations, including those important for energy storage and utilization. 1, 2 Due to the heterogeneous nature of these materials, activity measurements with sufficient spatial resolution are needed to obtain structure/activity correlations across the different surface features (exposed facets, step edges, lattice defects, grain boundaries, etc.). These measurements will help lead to an understanding of the underlying reaction mechanisms and enable engineering of more active materials. Because (electro)catalytic surfaces restructure with changing environments, 1 it is important to perform measurements in operando . Sub-diffraction fluorescence microscopy is well suited for these requirements because it can operate in solution with resolution down to a few nm. We have applied sub-diffraction fluorescence microscopy to a thin cell containing an electrocatalyst and a solution containing the redox sensitive dye p-aminophenyl fluorescein to characterize reaction at the solid-liquid interface. Our chosen dye switches between a nonfluorescent reduced state and a one-electron oxidized bright state, a process that occurs at the electrode surface. This scheme is used to investigate the activity differences on the surface of polycrystalline Pt, in particular to differentiate reactivity at grain faces and grain boundaries. Ultimately, this method will be extended to study other dye systems and electrode materials.

Advances in Solid State Joining of High Temperature Alloys

NASA Technical Reports Server (NTRS)

Ding, Jeff; Schneider, Judy

2011-01-01

Many of the metals used in the oil and gas industry are difficult to fusion weld including Titanium and its alloys. Solid state joining processes are being pursued as an alternative process to produce robust structures more amenable to high pressure applications. Various solid state joining processes include friction stir welding (FSW) and a patented modification termed thermal stir welding (TSW). The configuration of TSWing utilizes an induction coil to preheat the material minimizing the burden on the weld tool extending its life. This provides the ability to precisely select and control the temperature to avoid detrimental changes to the microstructure. The work presented in this presentation investigates the feasibility of joining various titanium alloys using the solid state welding processes of FSW and TSW. Process descriptions and attributes of each weld process will be presented. Weld process set ]up and welding techniques will be discussed leading to the challenges experienced. Mechanical property data will also be presented.

Mechanochemical stabilization and sintering of nanocrystalline the (ZrO2)0.97 (Y2O3)0.03 solid solution from pure oxides

NASA Astrophysics Data System (ADS)

Rendtorff, N. M.; Suárez, G.; Sakka, Y.; Aglietti, E. F.

2011-10-01

The mechanochemical activation processing has proved to be an effective technique to enhance a solid-state reaction at relatively low temperatures. In such a process, the mechanical effects of milling, such as reduction of particle size and mixture homogenization, are accompanied by chemical effects, such as partial decomposition of salts or hydroxides resulting in very active reactants. The objective of the present work is to obtain (ZrO2)0.97(Y2O3)0.03 nanocrystalline tetragonal solid solution powders directly using a high energy milling on a mixture of the pure oxides. A second objective is to evaluate the efficiency of the processing proposed and to characterize both textural and structural evolution of the mixtures during the milling processes and throughout posterior low temperature treatments. The Textural and structural evolution were studied by XRD analysis, specific area measurements (BET) and SEM. Firstly a decrease of the crystallinity of the reactants was observed, followed by the disappearance of Y2O3 diffraction peaks and the partial appearance of the tetragonal phase at room temperature. The solid solution proportion was increased with the high energy milling time, obtaining complete stabilization of the tetragonal solid solution with long milling treatments (60 min).The obtained powders were uniaxially pressed and sintered at different temperatures (600-1400°C) the influence of the milling time was correlated with the sinterization degree and final crystalline composition of the materials. Finally, fully stabilized nanocrystalline zirconia materials were obtained satisfactorily by the proposed method.

Characterization of milled solid residue from cypress liquefaction in sub- and super ethanol.

PubMed

Liu, Hua-Min; Liu, Yu-Lan

2014-01-01

Cypress liquefaction in sub- and super ethanol was carried out in an autoclave at various temperatures. Milled solid residue (MSR) was isolated from solid residue remaining from the liquefaction process, and its chemical characteristics was comparatively investigated with milled wood lignin (MWL) of cypress by sugar analysis, elemental analysis, FT-IR analysis, gel permeation chromatography, and NMR analysis. Results showed that there were two reactions (de-polymerization and re-polymerization) during the cypress liquefaction in sub- and super ethanol and the re-polymerization reactions were the main reaction at 220-260°C. Considering the stability of side-chain, the stability of lignin side-chain in cypress during liquefaction process in ethanol could be sequenced as follows: β-5>β-β'>β-O-4'. The MSR were mainly from the decomposition and re-polymerization of lignin. This study suggests that characterization of MSR provides a promising method to investigate the mechanisms of cypress liquefaction in ethanol. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

Role of Precursor-Conversion Chemistry in the Crystal-Phase Control of Catalytically Grown Colloidal Semiconductor Quantum Wires.

PubMed

Wang, Fudong; Buhro, William E

2017-12-26

Crystal-phase control is one of the most challenging problems in nanowire growth. We demonstrate that, in the solution-phase catalyzed growth of colloidal cadmium telluride (CdTe) quantum wires (QWs), the crystal phase can be controlled by manipulating the reaction chemistry of the Cd precursors and tri-n-octylphosphine telluride (TOPTe) to favor the production of either a CdTe solute or Te, which consequently determines the composition and (liquid or solid) state of the Bi x Cd y Te z catalyst nanoparticles. Growth of single-phase (e.g., wurtzite) QWs is achieved only from solid catalysts (y ≪ z) that enable the solution-solid-solid growth of the QWs, whereas the liquid catalysts (y ≈ z) fulfill the solution-liquid-solid growth of the polytypic QWs. Factors that affect the precursor-conversion chemistry are systematically accounted for, which are correlated with a kinetic study of the composition and state of the catalyst nanoparticles to understand the mechanism. This work reveals the role of the precursor-reaction chemistry in the crystal-phase control of catalytically grown colloidal QWs, opening the possibility of growing phase-pure QWs of other compositions.

Global distribution of secondary organic aerosol particle phase state

NASA Astrophysics Data System (ADS)

Shiraiwa, M.; Li, Y., Sr.; Tsimpidi, A.; Karydis, V.; Berkemeier, T.; Pandis, S. N.; Lelieveld, J.; Koop, T.; Poeschl, U.

2016-12-01

Secondary organic aerosols (SOA) account for a large fraction of submicron particles in the atmosphere and play a key role in aerosol effects on climate, air quality and public health. The formation and aging of SOA proceed through multiple steps of chemical reaction and mass transport in the gas and particle phases, which is challenging for the interpretation of field measurements and laboratory experiments as well as accurate representation of SOA evolution in atmospheric aerosol models. SOA particles can adopt liquid, semi-solid and amorphous solid (glassy) phase states depending on chemical composition, relative humidity and temperature. The particle phase state is crucial for various atmospheric gas-particle interactions, including SOA formation, heterogeneous and multiphase reactions and ice nucleation. We found that organic compounds with a wide variety of functional groups fall into molecular corridors, characterized by a tight inverse correlation between molar mass and volatility. Based on the concept of molecular corridors, we develop a method to estimate glass transition temperatures based on the molar mass and molecular O:C ratio of SOA components, which is a key property for determination of particle phase state. We use the global chemistry climate model EMAC with the organic aerosol module ORACLE to predict the atmospheric SOA phase state. For the planetary boundary layer, global simulations indicate that SOA is mostly liquid in tropical and polar air with high relative humidity, semi-solid in the mid-latitudes, and solid over dry lands. We find that in the middle and upper troposphere (>500 hPa) SOA should be mostly in a glassy solid phase state. Thus, slow diffusion of water, oxidants, and organic molecules could kinetically limit gas-particle interactions of SOA in the free and upper troposphere, promote ice nucleation and facilitate long-range transport of reactive and toxic organic pollutants embedded within SOA.

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

Shekiro, III, Joseph; Chen, Xiaowen; Smith, Holly

Dilute-acid pretreatment has proven to be a robust means of converting herbaceous feedstock to fermentable sugars. However, it also releases acetic acid, a known fermentation inhibitor, from acetyl groups present in the biomass. A mild, dilute alkaline extraction stage was implemented prior to acid pretreatment to separate acetic acid from the hydrolysate sugar stream. This step, termed deacetylation, improved the glucose and xylose yields from enzymatic hydrolysis and ethanol yields from fermentation of the sugars relative to the control experiments using dilute-acid pretreatment of native corn stover without deacetylation. While promising, deacetylation as it was historically practiced is conducted atmore » low solids loadings, and at fixed conditions. Thus, many questions have been left unanswered, including the relationship between sodium hydroxide and solids loading, and acetate and xylan solubilization, as well as the impact of temperature and residence time on the process efficacy. A central composite experiment was designed to evaluate the impact of solids loading, sodium hydroxide loading, reaction time and temperature during deacetylation on the acetate and xylan solubilization of corn stover. Using the ANOVA test, it became apparent that neither of the responses was significantly impacted by the solids loading, while the reaction time was a minor factor - the responses were largely driven by reaction temperature and the sodium hydroxide loading. Based on the results, we successfully demonstrated the ability to transition the low-solids (10 % w/w) deacetylation process to a higher-solids process (30 % w/w) with minimal impact on the ability to extract acetate from biomass. Conditions were selected to minimize xylose loss during deacetylation, while also removing 70 % of acetyl groups. The impact of selected conditions on the enzymatic hydrolysis and fermentation was further investigated. In conclusion, evaluation of the whole-process impact demonstrated that despite the upfront reduction in carbohydrate loss during deacetylation, the overall process sugar yields were depressed by the high-solids, low alkali process relative to the historical control. Consequently, ethanol titers were reduced, though strong fermentation performance was still observed, indicating that 70 % acetate removal is sufficient to depress acetic acid concentrations to a level that does not substantially inhibit ethanol fermentation by rZymomo nas.« less

Effects of Drying Process on an IgG1 Monoclonal Antibody Using Solid-State Hydrogen Deuterium Exchange with Mass Spectrometric Analysis (ssHDX-MS).

PubMed

Moussa, Ehab M; Wilson, Nathan E; Zhou, Qi Tony; Singh, Satish K; Nema, Sandeep; Topp, Elizabeth M

2018-01-03

Lyophilization and spray drying are widely used to manufacture solid forms of therapeutic proteins. Lyophilization is used to stabilize proteins vulnerable to degradation in solution, whereas spray drying is mainly used to prepare inhalation powders or as an alternative to freezing for storing bulk drug substance. Both processes impose stresses that may adversely affect protein structure, stability and bioactivity. Here, we compared lyophilization with and without controlled ice nucleation, and spray drying for their effects on the solid-state conformation and matrix interactions of a model IgG1 monoclonal antibody (mAb). Solid-state conformation and matrix interactions of the mAb were probed using solid-state hydrogen-deuterium exchange with mass spectrometric analysis (ssHDX-MS), and solid-state Fourier transform infrared (ssFTIR) and solid-state fluorescence spectroscopies. mAb conformation and/or matrix interactions were most perturbed in mannitol-containing samples and the distribution of states was more heterogeneous in sucrose and trehalose samples that were spray dried. The findings demonstrate the sensitivity of ssHDX-MS to changes weakly indicated by spectroscopic methods, and support the broader use of ssHDX-MS to probe formulation and process effects on proteins in solid samples.

Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

DOEpatents

Bamberger, C.E.; Robinson, P.R.

A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cyclic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

DOEpatents

Bamberger, Carlos E.; Robinson, Paul R.

1980-01-01

A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cylic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

Solid-to-solid oxidation of a vanadium(IV) to a vanadium(V) compound: chemisty of a sulfur-containing siderophore.

PubMed

Chatterjee, Pabitra B; Crans, Debbie C

2012-09-03

Visible light facilitates a solid-to-solid photochemical aerobic oxidation of a hunter-green microcrystalline oxidovanadium(IV) compound (1) to form a black powder of cis-dioxidovanadium(V) (2) at ambient temperature. The siderophore ligand pyridine-2,6-bis(thiocarboxylic acid), H(2)L, is secreted by a microorganism from the Pseudomonas genus. This irreversible transformation of a metal monooxo to a metal dioxo complex in the solid state in the absence of solvent is unprecedented. It serves as a proof-of-concept reaction for green chemistry occurring in solid matrixes.

Science Update: Inorganic Chemistry.

ERIC Educational Resources Information Center

Rawls, Rebecca

1981-01-01

Describes areas of inorganic chemistry which have changed dramatically in the past year or two, including photochemistry, electrochemistry, organometallic complexes, inorganic reaction theory, and solid state chemistry. (DS)

Production of reducing sugar from Enteromorpha intestinalis by hydrothermal and enzymatic hydrolysis.

PubMed

Kim, Dong-Hyun; Lee, Sang-Bum; Jeong, Gwi-Taek

2014-06-01

In this work, to evaluate the efficacy of marine macro-algae Enteromorpha intestinalis as a potential bioenergy resource, the effects of reaction conditions (solid-to-liquid ratio, reaction temperature, and reaction time) on sugars produced by a combined process of hydrothermal and enzymatic hydrolysis were investigated. As a result of the hydrothermal hydrolysis, a 7.3g/L (8% yield) total reducing sugar was obtained under conditions including solid-to-liquid ratio of 1:10, reaction temperature of 170°C, and reaction time of 60min. By subsequent (post-hydrothermal) enzymatic hydrolysis of samples treated at 170°C for 30min, a 20.1g/L (22% yield) was achieved. Copyright © 2014 Elsevier Ltd. All rights reserved.

The Application of High-Resolution Electron Microscopy to Problems in Solid State Chemistry: The Exploits of a Peeping TEM.

ERIC Educational Resources Information Center

Eyring, LeRoy

1980-01-01

Describes methods for using the high-resolution electron microscope in conjunction with other tools to reveal the identity and environment of atoms. Problems discussed include the ultimate structure of real crystalline solids including defect structure and the mechanisms of chemical reactions. (CS)

Fabrication, characterization and applications of iron selenide

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

Hussain, Raja Azadar, E-mail: hussainazadar@yahoo.com; Badshah, Amin; Lal, Bhajan

This review article presents fabrication of FeSe by solid state reactions, solution chemistry routes, chemical vapor deposition, spray pyrolysis and chemical vapor transport. Different properties and applications such as crystal structure and phase transition, band structure, spectroscopy, superconductivity, photocatalytic activity, electrochemical sensing, and fuel cell activity of FeSe have been discussed. - Graphical abstract: Iron selenide can be synthesized by solid state reactions, chemical vapor deposition, solution chemistry routes, chemical vapor transport and spray pyrolysis. - Highlights: • Different fabrication methods of iron selenide (FeSe) have been reviewed. • Crystal structure, band structure and spectroscopy of FeSe have been discussed.more » • Superconducting, catalytic and fuel cell application of FeSe have been presented.« less

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

PubMed

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

2013-09-09

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

InP/ZnS nanocrystals: coupling NMR and XPS for fine surface and interface description.

PubMed

Virieux, Héloïse; Le Troedec, Marianne; Cros-Gagneux, Arnaud; Ojo, Wilfried-Solo; Delpech, Fabien; Nayral, Céline; Martinez, Hervé; Chaudret, Bruno

2012-12-05

Advanced (1)H, (13)C, and (31)P solution- and solid-state NMR studies combined with XPS were used to probe, at the molecular scale, the composition (of the core, the shell, and the interface) and the surface chemistry of InP/ZnS core/shell quantum dots prepared via a non-coordinating solvent strategy. The interface between the mismatched InP and ZnS phases is composed of an amorphous mixed oxide phase incorporating InPO(x) (with x = 3 and predominantly 4), In(2)O(3), and InO(y)(OH)(3-2y) (y = 0, 1). Thanks to the analysis of the underlying reaction mechanisms, we demonstrate that the oxidation of the upper part of the InP core is the consequence of oxidative conditions brought by decarboxylative coupling reactions (ketonization). These reactions occur during both the core preparation and the coating process, but according to different mechanisms.

Preparation of actinide boride materials via solid-state metathesis reactions and actinide dicarbollide precursors

NASA Astrophysics Data System (ADS)

Lupinetti, Anthony J.; Fife, Julie; Garcia, Eduardo; Abney, Kent D.

2000-07-01

Information gaps exist in the knowledge base needed for choosing among the alternate processes to be used in the safe conversion of fissile materials to optimal forms for safe interim storage, long-term storage, and ultimate disposition. The current baseline storage technology for various wastes uses borosilicate glasses.1 The focus of this paper is the synthesis of actinide-containing ceramic materials at low and moderate temperatures (200 °C-1000 °C) using molecular and polymeric actinide borane and carborane complexes.

A Thermally Activated Solid State Reaction Process for Fabricating Ohmic Contacts to Semiconducting Diamond

DTIC Science & Technology

1990-09-01

due to Ken Regan. Dr. Howard Rast, Dr. Carl Zeisse, Maureen O * Brien , Dr. Don Mullin, Richard Nguyen, Paul Thibado. Dr. Charlesý Kewett, and Dr. Alan...Standard form 298 (FRONT) 1!NCL-ASSIFIED 21a. NAME OF RESPONS’OLL NOWVfOUAý J. R. Zeidler 69)55" 1 - I~ C( 7 ci) NMH 7540-01 .2$ O -8600 SIA,~afre tO~m...boron nitride could extend the operating temperature of devices to temperatures in excess of 1000*C. TABLE I. Selected properties of semiconductors

In Situ Investigation of a Self-Accelerated Cocrystal Formation by Grinding Pyrazinamide with Oxalic Acid.

PubMed

Kulla, Hannes; Greiser, Sebastian; Benemann, Sigrid; Rademann, Klaus; Emmerling, Franziska

2016-07-14

A new cocrystal of pyrazinamide with oxalic acid was prepared mechanochemically and characterized by PXRD, Raman spectroscopy, solid-state NMR spectroscopy, DTA-TG, and SEM. Based on powder X-ray diffraction data the structure was solved. The formation pathway of the reaction was studied in situ using combined synchrotron PXRD and Raman spectroscopy. Using oxalic acid dihydrate the initially neat grinding turned into a rapid self-accelerated liquid-assisted grinding process by the release of crystallization water. Under these conditions, the cocrystal was formed directly within two minutes.

Research program in nuclear and solid state physics. [including pion absorption spectra and muon spin precession

NASA Technical Reports Server (NTRS)

1974-01-01

The survey of negative pion absorption reactions on light and medium nuclei was continued. Muon spin precession was studied using an iron target. An impulse approximation model of the pion absorption process implied that the ion will absorb almost exclusively on nucleon pairs, single nucleon absorption being suppressed by energy and momentum conservation requirements. For measurements on both paramagnetic and ferromagnetic iron, the external magnetic field was supplied by a large C-type electromagnet carrying a current of about 100 amperes.

The Journal of Physical Chemistry A. Time-Dependent Quantum Molecular Dynamics Workshop, Brian Head, Utah, March 13-17, 1999. Volume 103, Number 47

DTIC Science & Technology

1999-11-25

reactions the situation is more complicated since many of the modes are in the process of changing from free rotors to nearly harmonic bending motions ...are dihedral angles between the CH3 planes and the CC axis (see text). Heavy solid contours denote repulsive regions ( energies higher than that of...while vi is the source term describing the rate of formation of ethane in energy state i from the free methyl radicals. The effective bimolecular

Comparison of solid-state and submerged-state fermentation for the bioprocessing of switchgrass to ethanol and acetate by Clostridium phytofermentans.

PubMed

Jain, Abhiney; Morlok, Charles K; Henson, J Michael

2013-01-01

The conversion of sustainable energy crops using microbiological fermentation to biofuels and bioproducts typically uses submerged-state processes. Alternatively, solid-state fermentation processes have several advantages when compared to the typical submerged-state processes. This study compares the use of solid-state versus submerged-state fermentation using the mesophilic anaerobic bacterium Clostridium phytofermentans in the conversion of switchgrass to the end products of ethanol, acetate, and hydrogen. A shift in the ratio of metabolic products towards more acetate and hydrogen production than ethanol production was observed when C. phytofermentans was grown under solid-state conditions as compared to submerged-state conditions. Results indicated that the end product concentrations (in millimolar) obtained using solid-state fermentation were higher than using submerged-state fermentation. In contrast, the total fermentation products (in weight of product per weight of carbohydrates consumed) and switchgrass conversion were higher for submerged-state fermentation. The conversion of xylan was greater than glucan conversion under both fermentation conditions. An initial pH of 7 and moisture content of 80 % resulted in maximum end products formation. Scanning electron microscopy study showed the presence of biofilm formed by C. phytofermentans growing on switchgrass under submerged-state fermentation whereas bacterial cells attached to surface and no apparent biofilm was observed when grown under solid-state fermentation. To our knowledge, this is the first study reporting consolidated bioprocessing of a lignocellulosic substrate by a mesophilic anaerobic bacterium under solid-state fermentation conditions.

Prion Infected Meat-and-Bone Meal Is Still Infectious after Biodiesel Production

PubMed Central

Bruederle, Cathrin E.; Hnasko, Robert M.; Kraemer, Thomas; Garcia, Rafael A.; Haas, Michael J.; Marmer, William N.; Carter, John Mark

2008-01-01

The epidemic of bovine spongiform encephalopathy (BSE) has led to a world-wide drop in the market for beef by-products, such as Meat-and-Bone Meal (MBM), a fat-containing but mainly proteinaceaous product traditionally used as an animal feed supplement. While normal rendering is insufficient, the production of biodiesel from MBM has been suggested to destroy infectivity from transmissible spongiform encephalopathies (TSEs). In addition to producing fuel, this method simultaneously generates a nutritious solid residue. In our study we produced biodiesel from MBM under defined conditions using a modified form of alkaline methanolysis. We evaluated the presence of prion in the three resulting phases of the biodiesel reaction (Biodiesel, Glycerol and Solid Residue) in vitro and in vivo. Analysis of the reaction products from 263K scrapie infected MBM led to no detectable immunoreactivity by Western Blot. Importantly, and in contrast to the biochemical results the solid MBM residue from the reaction retained infectivity when tested in an animal bioassay. Histochemical analysis of hamster brains inoculated with the solid residue showed typical spongiform degeneration and vacuolation. Re-inoculation of these brains into a new cohort of hamsters led to onset of clinical scrapie symptoms within 75 days, suggesting that the specific infectivity of the prion protein was not changed during the biodiesel process. The biodiesel reaction cannot be considered a viable prion decontamination method for MBM, although we observed increased survival time of hamsters and reduced infectivity greater than 6 log orders in the solid MBM residue. Furthermore, results from our study compare for the first time prion detection by Western Blot versus an infectivity bioassay for analysis of biodiesel reaction products. We could show that biochemical analysis alone is insufficient for detection of prion infectivity after a biodiesel process. PMID:18698417

In Situ Monitoring of Chemical Reactions at a Solid-Water Interface by Femtosecond Acoustics.

PubMed

Shen, Chih-Chiang; Weng, Meng-Yu; Sheu, Jinn-Kong; Yao, Yi-Ting; Sun, Chi-Kuang

2017-11-02

Chemical reactions at a solid-liquid interface are of fundamental importance. Interfacial chemical reactions occur not only at the very interface but also in the subsurface area, while existing monitoring techniques either provide limited spatial resolution or are applicable only for the outmost atomic layer. Here, with the aid of the time-domain analysis with femtosecond acoustics, we demonstrate a subatomic-level-resolution technique to longitudinally monitor chemical reactions at solid-water interfaces, capable of in situ monitoring even the subsurface area under atmospheric conditions. Our work was proven by monitoring the already-known anode oxidation process occurring during photoelectrochemical water splitting. Furthermore, whenever the oxide layer thickness equals an integer  number of the effective atomic layer thickness, the measured acoustic echo will show higher signal-to-noise ratios with reduced speckle noise, indicating the quantum-like behavior of this coherent-phonon-based technique.

Simulation of the infiltration process of a ceramic open-pore body with a metal alloy in semi-solid state to design the manufacturing of interpenetrating phase composites

NASA Astrophysics Data System (ADS)

Schomer, Laura; Liewald, Mathias; Riedmüller, Kim Rouven

2018-05-01

Metal-ceramic Interpenetrating Phase Composites (IPC) belong to a special subcategory of composite materials and reveal enhanced properties compared to conventional composite materials. Currently, IPC are produced by infiltration of a ceramic open-pore body with liquid metal applying high pressure and I or high temperature to avoid residual porosity. However, these IPC are not able to gain their complete potential, because of structural damages and interface reactions occurring during the manufacturing process. Compared to this, the manufacturing of IPC using the semi-solid forming technology offers great perspectives due to relative low processing temperatures and reduced mechanical pressure. In this context, this paper is focusing on numerical investigations conducted by using the FLOW-3D software for gaining a deeper understanding of the infiltration of open-pore bodies with semi-solid materials. For flow simulation analysis, a geometric model and different porous media drag models have been used. They have been adjusted and compared to get a precise description of the infiltration process. Based on these fundamental numerical investigations, this paper also shows numerical investigations that were used for basically designing a semi-solid forming tool. Thereby, the development of the flow front and the pressure during the infiltration represent the basis of the evaluation. The use of an open and closed tool cavity combined with various geometries of the upper die shows different results relating to these evaluation arguments. Furthermore, different overflows were designed and its effects on the pressure at the end of the infiltration process were investigated. Thus, this paper provides a general guideline for a tool design for manufacturing of metal-ceramic IPC using semi-solid forming.

Enzymatic Pretreatment Coupled with the Addition of p-Hydroxyanisole Increased Levulinic Acid Production from Steam-Exploded Rice Straw Short Fiber.

PubMed

Ma, Li-Tong; Zhao, Zhi-Min; Yu, Bin; Chen, Hong-Zhang

2016-11-01

Levulinic acid production, directly from lignocellulosic biomass, resulted in low yields due to the poor substrate accessibility and occurrence of side reactions. The effects of reaction conditions, enzymatic pretreatment, and inhibitor addition on the conversion of steam-exploded rice straw (SERS) short fiber to levulinic acid catalyzed by solid superacid were investigated systematically. The results indicated that the optimal reaction conditions were temperature, time, and solid superacid concentration combinations of 200 °C, 15 min, and 7.5 %. Enzymatic pretreatment improved the substrate accessibility to solid superacid catalyst, and p-hydroxyanisole inhibitor reduced the side reactions during reaction processes, which helped to increase levulinic acid yield. The levulinic acid yield reached 25.2 % under the optimal conditions, which was 61.5 % higher than that without enzymatic pretreatment and inhibitor addition. Therefore, enzymatic pretreatment coupled with the addition of p-hydroxyanisole increased levulinic acid production effectively, which contributed to the value-added utilization of lignocellulosic biomass.

An advanced model framework for solid electrolyte intercalation batteries.

PubMed

Landstorfer, Manuel; Funken, Stefan; Jacob, Timo

2011-07-28

Recent developments of solid electrolytes, especially lithium ion conductors, led to all solid state batteries for various applications. In addition, mathematical models sprout for different electrode materials and battery types, but are missing for solid electrolyte cells. We present a mathematical model for ion flux in solid electrolytes, based on non-equilibrium thermodynamics and functional derivatives. Intercalated ion diffusion within the electrodes is further considered, allowing the computation of the ion concentration at the electrode/electrolyte interface. A generalized Frumkin-Butler-Volmer equation describes the kinetics of (de-)intercalation reactions and is here extended to non-blocking electrodes. Using this approach, numerical simulations were carried out to investigate the space charge region at the interface. Finally, discharge simulations were performed to study different limitations of an all solid state battery cell. This journal is © the Owner Societies 2011

Advances in simultaneous DSC-FTIR microspectroscopy for rapid solid-state chemical stability studies: some dipeptide drugs as examples.

PubMed

Lin, Shan-Yang; Wang, Shun-Li

2012-04-01

The solid-state chemistry of drugs has seen growing importance in the pharmaceutical industry for the development of useful API (active pharmaceutical ingredients) of drugs and stable dosage forms. The stability of drugs in various solid dosage forms is an important issue because solid dosage forms are the most common pharmaceutical formulation in clinical use. In solid-state stability studies of drugs, an ideal accelerated method must not only be selected by different complicated methods, but must also detect the formation of degraded product. In this review article, an analytical technique combining differential scanning calorimetry and Fourier-transform infrared (DSC-FTIR) microspectroscopy simulates the accelerated stability test, and simultaneously detects the decomposed products in real time. The pharmaceutical dipeptides aspartame hemihydrate, lisinopril dihydrate, and enalapril maleate either with or without Eudragit E were used as testing examples. This one-step simultaneous DSC-FTIR technique for real-time detection of diketopiperazine (DKP) directly evidenced the dehydration process and DKP formation as an impurity common in pharmaceutical dipeptides. DKP formation in various dipeptides determined by different analytical methods had been collected and compiled. Although many analytical methods have been applied, the combined DSC-FTIR technique is an easy and fast analytical method which not only can simulate the accelerated drug stability testing but also at the same time enable to explore phase transformation as well as degradation due to thermal-related reactions. This technique offers quick and proper interpretations. Copyright © 2012 Elsevier B.V. All rights reserved.

Reaction-diffusion controlled growth of complex structures

NASA Astrophysics Data System (ADS)

Noorduin, Willem; Mahadevan, L.; Aizenberg, Joanna

2013-03-01

Understanding how the emergence of complex forms and shapes in biominerals came about is both of fundamental and practical interest. Although biomineralization processes and organization strategies to give higher order architectures have been studied extensively, synthetic approaches to mimic these self-assembled structures are highly complex and have been difficult to emulate, let alone replicate. The emergence of solution patterns has been found in reaction-diffusion systems such as Turing patterns and the BZ reaction. Intrigued by this spontaneous formation of complexity we explored if similar processes can lead to patterns in the solid state. We here identify a reaction-diffusion system in which the shape of the solidified products is a direct readout of the environmental conditions. Based on insights in the underlying mechanism, we developed a toolbox of engineering strategies to deterministically sculpt patterns and shapes, and combine different morphologies to create a landscape of hierarchical multi scale-complex tectonic architectures with unprecedented levels of complexity. These findings may hold profound implications for understanding, mimicking and ultimately expanding upon nature's morphogenesis strategies, allowing the synthesis of advanced highly complex microscale materials and devices. WLN acknowledges the Netherlands Organization for Scientific Research for financial support

High capacity and stable all-solid-state Li ion battery using SnO2-embedded nanoporous carbon.

PubMed

Notohara, Hiroo; Urita, Koki; Yamamura, Hideyuki; Moriguchi, Isamu

2018-06-08

Extensive research efforts are devoted to development of high performance all-solid-state lithium ion batteries owing to their potential in not only improving safety but also achieving high stability and high capacity. However, conventional approaches based on a fabrication of highly dense electrode and solid electrolyte layers and their close contact interface is not always applicable to high capacity alloy- and/or conversion-based active materials such as SnO 2 accompanied with large volume change in charging-discharging. The present work demonstrates that SnO 2 -embedded nanoporous carbons without solid electrolyte inside the nanopores are a promising candidate for high capacity and stable anode material of all-solid-state battery, in which the volume change reactions are restricted in the nanopores to keep the constant electrode volume. A prototype all-solid-state full cell consisting of the SnO 2 -based anode and a LiNi 1/3 Co 1 / 3 Mn 1/3 O 2 -based cathode shows a good performance of 2040 Wh/kg at 268.6 W/kg based on the anode material weight.

Polycarbonate-based polyurethane as a polymer electrolyte matrix for all-solid-state lithium batteries

NASA Astrophysics Data System (ADS)

Bao, Junjie; Shi, Gaojian; Tao, Can; Wang, Chao; Zhu, Chen; Cheng, Liang; Qian, Gang; Chen, Chunhua

2018-06-01

Four kinds of polycarbonate-based polyurethane with 8-14 wt% hard segments content are synthesized via reactions of polycarbonatediol, hexamethylene diisocyanate and diethylene glycol. The mechanical strength of the polyurethanes increase with the increase of hard segments content. Solid polymer electrolytes composed of the polycarbonate-based polyurethanes and LiTFSI exhibits fascinating characteristics for all-solid-state lithium batteries with a high ionic conductivity of 1.12 × 10-4 S cm-1 at 80 °C, an electrochemical stability window up to 4.5 V (vs. Li+/Li), excellent mechanical strength and superior interfacial stability against lithium metal. The all-solid-state batteries using LiFePO4 cathode can deliver high discharge capacities (161, 158, 134 and 93 mAh g-1 at varied rates of 0.2, 0.5, 1 and 2 C) at 80 °C and excellent cycling performance (with 91% capacity retention after 600 cycles at 1 C). All the results indicate that such a polyurethane-based solid polymer electrolyte can be a promising candidate for all-solid-state lithium batteries.

Vapour-induced solid-state C-H bond activation for the clean synthesis of an organopalladium biothiol sensor.

PubMed

Monas, Andrea; Užarević, Krunoslav; Halasz, Ivan; Kulcsár, Marina Juribašić; Ćurić, Manda

2016-10-27

Room-temperature accelerated aging in the solid state has been applied for atom- and energy-efficient activation of either one or two C-H bonds of azobenzene and methyl orange by palladium(ii) acetate. Organopalladium complexes are prepared in quantitative reactions without potentially harmful side products. Dicyclopalladated methyl orange is water-soluble and is a selective chromogenic biothiol sensor at physiologically-relevant micromolar concentrations in buffered aqueous media.

Observation of Spontaneous C=C Bond Breaking in the Reaction between Atomic Boron and Ethylene in Solid Neon.

PubMed

Jian, Jiwen; Lin, Hailu; Luo, Mingbiao; Chen, Mohua; Zhou, Mingfei

2016-07-11

A ground-state boron atom inserts into the C=C bond of ethylene to spontaneously form the allene-like compound H2 CBCH2 on annealing in solid neon. This compound can further isomerize to the propyne-like HCBCH3 isomer under UV light excitation. The observation of this unique spontaneous C=C bond insertion reaction is consistent with theoretical predictions that the reaction is thermodynamically exothermic and kinetically facile. This work demonstrates that the stronger C=C bond, rather than the less inert C-H bond, can be broken to form organoboron species from the reaction of a boron atom with ethylene even at cryogenic temperatures. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bioethanol production: an integrated process of low substrate loading hydrolysis-high sugars liquid fermentation and solid state fermentation of enzymatic hydrolysis residue.

PubMed

Chu, Qiulu; Li, Xin; Ma, Bin; Xu, Yong; Ouyang, Jia; Zhu, Junjun; Yu, Shiyuan; Yong, Qiang

2012-11-01

An integrated process of enzymatic hydrolysis and fermentation was investigated for high ethanol production. The combination of enzymatic hydrolysis at low substrate loading, liquid fermentation of high sugars concentration and solid state fermentation of enzymatic hydrolysis residue was beneficial for conversion of steam explosion pretreated corn stover to ethanol. The results suggested that low substrate loading hydrolysis caused a high enzymatic hydrolysis yield; the liquid fermentation of about 200g/L glucose by Saccharomyces cerevisiae provided a high ethanol concentration which could significantly decrease cost of the subsequent ethanol distillation. A solid state fermentation of enzymatic hydrolysis residue was combined, which was available to enhance ethanol production and cellulose-to-ethanol conversion. The results of solid state fermentation demonstrated that the solid state fermentation process accompanied by simultaneous saccharification and fermentation. Copyright © 2012 Elsevier Ltd. All rights reserved.

NO ICE HYDROGENATION: A SOLID PATHWAY TO NH{sub 2}OH FORMATION IN SPACE

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

Congiu, Emanuele; Dulieu, Francois; Chaabouni, Henda

2012-05-01

Icy dust grains in space act as catalytic surfaces onto which complex molecules form. These molecules are synthesized through exothermic reactions from precursor radicals and, mostly, hydrogen atom additions. Among the resulting products are species of biological relevance, such as hydroxylamine-NH{sub 2}OH-a precursor molecule in the formation of amino acids. In this Letter, laboratory experiments are described that demonstrate NH{sub 2}OH formation in interstellar ice analogs for astronomically relevant temperatures via successive hydrogenation reactions of solid nitric oxide (NO). Inclusion of the experimental results in an astrochemical gas-grain model proves the importance of a solid-state NO+H reaction channel as amore » starting point for prebiotic species in dark interstellar clouds and adds a new perspective to the way molecules of biological importance may form in space.« less

Very Tiny Rocks: Site-Specific, Size-Dependent Reaction Kinetics at Nanoparticle-Water Interfaces

NASA Astrophysics Data System (ADS)

Rustad, J. R.

2008-12-01

One of the most fundamental challenges in geochemistry is to be able to understand the rates and mechanisms of elementary reactions that describe chemical processes occurring at mineral-water interfaces. One of the reasons for the primitive conceptual state of reaction kinetics in solid earth geochemistry is that it is very difficult to identify defensible elementary reactions where theoretical predictions can be made and the results can tested experimentally at the same length and time scale of the prediction. For example, the most fundamental predictor of complexation kinetics in aqueous solution is the characteristic water exchange rate, which are well known for the aquo ions and vary by 20 orders of magnitude even for simple trivalent ions. In contrast, for interfacial reactions, it was not even known whether water exchange rates were faster or slower than equivalent metal sites in solution, prohibiting any quantitive understanding of mineral reaction kinetics at the molecular level. Recent advances in synthesis and characterization of materials at nanometer length scales has been able to bridge the gap in scale, and nanometer-sized minerals have given us our first quantitative understanding of elementary reaction rates for fundamental processes involving water and hydroxide exchange reactions. I describe the results of molecular dynamics calculation and experimental measurement of the rates of water, hydroxide, and proton exchange reactions on nanoparticle surfaces. The calculations already show that transition state theory is completely inadequate to understand the rates of even the simplest elementary reactions. Furthermore, the mechanistic implications of rate parameters such as activation volume and activation enthalpy may be different in moving from aquo ions to interfaces. Is a molecular understanding of geochemical processes really needed? One might have asked a biologist at the turn of the century whether studying the structure of proteins would ever be useful for curing disease. True molecular level understanding of interfacial interactions has the potential to revolutionize geology, allowing unprecedented detail and accuracy in such important contexts as climate reconstruction and tectonic history. Geology has an inevitable molecular future.

New insights into pre-lithiation kinetics of graphite anodes via nuclear magnetic resonance spectroscopy

NASA Astrophysics Data System (ADS)

Holtstiege, Florian; Schmuch, Richard; Winter, Martin; Brunklaus, Gunther; Placke, Tobias

2018-02-01

Pre-lithiation of anode materials can be an effective method to compensate active lithium loss which mainly occurs in the first few cycles of a lithium ion battery (LIB), due to electrolyte decomposition and solid electrolyte interphase (SEI) formation at the surface of the anode. There are many different pre-lithiation methods, whereas pre-lithiation using metallic lithium constitutes the most convenient and widely utilized lab procedure in literature. In this work, for the first time, solid state nuclear magnetic resonance spectroscopy (NMR) is applied to monitor the reaction kinetics of the pre-lithiation process of graphite with lithium. Based on static 7Li NMR, we can directly observe both the dissolution of lithium metal and parallel formation of LiCx species in the obtained NMR spectra with time. It is also shown that the degree of pre-lithiation as well as distribution of lithium metal on the electrode surface have a strong impact on the reaction kinetics of the pre-lithiation process and on the remaining amount of lithium metal. Overall, our findings are highly important for further optimization of pre-lithiation methods for LIB anode materials, both in terms of optimized pre-lithiation time and appropriate amounts of lithium metal.

A study of suppressed formation of low-conductivity phases in doped Li 7La 3Zr 2O 12 garnets by in situ neutron diffraction

DOE PAGES

Chen, Yan; Rangasamy, Ezhiylmurugan; dela Cruz, Clarina R.; ...

2015-09-28

Doped Li 7La 3Zr 2O 12 garnets, oxide-based solids with good Li + conductivity and compatibility, show great potential as leading electrolyte material candidates for all-solid-state lithium ion batteries. Still yet, the conductive bulk usually suffers from the presence of secondary phases and the transition towards a low-conductivity tetragonal phase during synthesis. Dopants are designed to stabilize the high-conductive cubic phase and suppress the formation of the low-conductivity phases. In situ neutron diffraction enables a direct observation of the doping effects by monitoring the phase evolutions during garnet synthesis. It reveals the reaction mechanism involving the temporary presence of intermediatemore » phases. The off-stoichiometry due to the liquid Li 2CO 3 evaporation leads to the residual of the low-conductivity intermediate phase in the as-synthesized bulk. Appropriate doping of an active element may alter the component of the intermediate phases and promote the completion of the reaction. While the dopants aid to stabilize most of the cubic phase, a small amount of tetragonal phase tends to form under a diffusion process. Lastly, the in situ observations provide the guideline of process optimization to suppress the formation of unwanted low-conductivity phases.« less

Phosphate Reactions as Mechanisms of High-Temperature Lubrication

NASA Technical Reports Server (NTRS)

Nagarajan, Anitha; Garrido, Carolina; Gatica, Jorge E.; Morales, Wilfredo

2006-01-01

One of the major problems preventing the operation of advanced gas turbine engines at higher temperatures is the inability of currently used liquid lubricants to survive at these higher temperatures under friction and wear conditions. Current state-of-the-art organic liquid lubricants rapidly degrade at temperatures above 300 C; hence some other form of lubrication is necessary. Vapor-phase lubrication is a promising new technology for high-temperature lubrication. This lubrication method employs a liquid phosphate ester that is vaporized and delivered to bearings or gears; the vapor reacts with the metal surfaces, generating a solid lubricious film that has proven very stable at high temperatures. In this study, solid lubricious films were grown on cast-iron foils in order to obtain reaction and diffusion rate data to help characterize the growth mechanism. A phenomenological mathematical model of the film deposition process was derived incorporating transport and kinetic parameters that were coupled to the experimental data. This phenomenological model can now be reliably used as a predictive and scale-up tool for future vapor-phase lubrication studies.

Solid State Welding Development at Marshall Space Flight Center

NASA Technical Reports Server (NTRS)

Ding, Robert J.; Walker, Bryant

2012-01-01

What is TSW and USW? TSW is a solid state weld process consisting of an induction coil heating source, a stir rod, and non-rotating containment plates Independent heating, stirring and forging controls Decouples the heating, stirring and forging process elements of FSW. USW is a solid state weld process consisting of an induction coil heating source, a stir rod, and a non-rotating containment plate; Ultrasonic energy integrated into non-rotating containment plate and stir rod; Independent heating, stirring and forging controls; Decouples the heating, stirring and forging process elements of FSW.

Sequestration of flue gas CO₂ by direct gas-solid carbonation of air pollution control system residues.

PubMed

Tian, Sicong; Jiang, Jianguo

2012-12-18

Direct gas-solid carbonation reactions of residues from an air pollution control system (APCr) were conducted using different combinations of simulated flue gas to study the impact on CO₂ sequestration. X-ray diffraction analysis of APCr determined the existence of CaClOH, whose maximum theoretical CO₂ sequestration potential of 58.13 g CO₂/kg APCr was calculated by the reference intensity ratio method. The reaction mechanism obeyed a model of a fast kinetics-controlled process followed by a slow product layer diffusion-controlled process. Temperature is the key factor in direct gas-solid carbonation and had a notable influence on both the carbonation conversion and the CO₂ sequestration rate. The optimal CO₂ sequestrating temperature of 395 °C was easily obtained for APCr using a continuous heating experiment. CO₂ content in the flue gas had a definite influence on the CO₂ sequestration rate of the kinetics-controlled process, but almost no influence on the final carbonation conversion. Typical concentrations of SO₂ in the flue gas could not only accelerate the carbonation reaction rate of the product layer diffusion-controlled process, but also could improve the final carbonation conversion. Maximum carbonation conversions of between 68.6% and 77.1% were achieved in a typical flue gas. Features of rapid CO₂ sequestration rate, strong impurities resistance, and high capture conversion for direct gas-solid carbonation were proved in this study, which presents a theoretical foundation for the applied use of this encouraging technology on carbon capture and storage.

One-dimensional carbon-sulfur composite fibers for Na-S rechargeable batteries operating at room temperature.

PubMed

Hwang, Tae Hoon; Jung, Dae Soo; Kim, Joo-Seong; Kim, Byung Gon; Choi, Jang Wook

2013-09-11

Na-S batteries are one type of molten salt battery and have been used to support stationary energy storage systems for several decades. Despite their successful applications based on long cycle lives and low cost of raw materials, Na-S cells require high temperatures above 300 °C for their operations, limiting their propagation into a wide range of applications. Herein, we demonstrate that Na-S cells with solid state active materials can perform well even at room temperature when sulfur-containing carbon composites generated from a simple thermal reaction were used as sulfur positive electrodes. Furthermore, this structure turned out to be robust during repeated (de)sodiation for ~500 cycles and enabled extraordinarily high rate performance when one-dimensional morphology is adopted using scalable electrospinning processes. The current study suggests that solid-state Na-S cells with appropriate atomic configurations of sulfur active materials could cover diverse battery applications where cost of raw materials is critical.

2-and 1-D coordination polymers of Dy(III) and Ho(III) with near infrared and visible luminescence by efficient charge-transfer antenna ligand

NASA Astrophysics Data System (ADS)

Oylumluoglu, Gorkem; Coban, Mustafa Burak; Kocak, Cagdas; Aygun, Muhittin; Kara, Hulya

2017-10-01

Two new lanthanide-based coordination complexes, [Dy(2-stp).2(H2O)]n (1) and {[Ho(2-stp).3(H2O)]·(H2O)}n (2) [2-stp = 2-sulfoterephthalic acid] were synthesized by hydrothermal reaction and characterized by elemental analysis, UV, IR, single crystal X-ray diffraction and solid state photoluminescence. DyIII and HoIII atoms are eight-coordinated and adopt a distorted square-antiprismatic geometry in complexes 1 and 2, respectively. In compound 1, Dy atoms are coordinated by four bridging 2-stp ligands forming two-dimensional (2D) layer, while Ho atoms by three bridging 2-stp ligands creating one dimensional (1D) double chains in 2. In addition, complexes 1 and 2 display in the solid state and at room temperature an intense yellow emission, respectively; this photoluminescence is achieved by an indirect process (antenna effect). The excellent luminescent performances make these complexes very good candidates for potential luminescence materials.

Novel symmetrical coralloid Cu 3D superstructures: Solid-state synthesis from a Cu-carboxylate MOF and their in-situ thermal conversion

NASA Astrophysics Data System (ADS)

Chen, Lingyun; Shen, Yongming; Bai, Junfeng; Wang, Chunzhao

2009-08-01

We describe here a one-step solid-state process for the synthesis of metal three-dimensional (3D) superstructures from a metal-organic framework (MOF). Novel symmetrical coralloid Cu 3D superstructures with surface interspersed with clusters of Cu nanoparticles were successfully synthesized by thermolysis of the [Cu 3( btc) 2] ( btc=benzene-1,3,5-tricarboxylato) MOF in a one-end closed horizontal tube furnace (OCTF). The obtained products were characterized by TGA, FT-IR, XRD, EDX, SEM, TEM, HRTEM and SAED. Different reaction conditions were discussed. Furthermore, the synthesized Cu samples were converted into CuO microstructures by in-situ calcination in the air. In addition, the possible formation mechanism was also proposed. This method is a simple and facile route, which builds a direct linkage between metal-carboxylate MOF crystals and metal nano- or microstructures and also opens a new application field of MOFs.

Photolysis of Pure Solid O3 and O2 Films at 193nm

NASA Technical Reports Server (NTRS)

Raut, U.; Loeffler, M. J.; Fama, M.; Baragiola, R. A.

2011-01-01

We studied quantitatively the photochemistry of solid O3 and O2 films at 193 nm and 22 K with infrared spectroscopy and microgravimetry. Photolysis of pure ozone destroyed O3, but a small amount of ozone remained in the film at high fluence. Photolysis of pure O2 produced O3 in an amount that increased with photon fluence to a stationary level. For both O2 and O3 films, the O3:O2 ratio at large fluences is ?0.07, about two orders of magnitude larger than those obtained in gas phase photolysis. This enhancement is attributed to the increased photodissociation of O2 due to photoabsorption by O2 dimers, a process significant at solid-state densities. We obtain initial quantum yield for ozone synthesis from solid oxygen, phi (O3) = 0.24 0.06, and quantum yields for destruction of O3 and O2 in their parent solids, phi(-O3) = 1.0 0.2 and phi(-O2) = 0.36 0.1. Combined with known photoabsorption cross sections, we estimate probabilities for geminate recombination of 0.5 0.1 for O3 fragments and 0.88 0.03 for oxygen atoms from O2 dissociation. Using a single parameter kinetic model, we deduce the ratio of reaction cross sections for an O atom with O2 vs. O3 to be 0.1 0.2. The general good agreement of the model with the data suggests the validity of the central assumption of efficient energy and spin relaxation of photofragments in the solid prior to their reactions with other species.

Photolysis of pure solid O{sub 3} and O{sub 2} films at 193 nm

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

Raut, U.; Loeffler, M. J.; Fama, M.

2011-05-21

We studied quantitatively the photochemistry of solid O{sub 3} and O{sub 2} films at 193 nm and 22 K with infrared spectroscopy and microgravimetry. Photolysis of pure ozone destroyed O{sub 3}, but a small amount of ozone remained in the film at high fluence. Photolysis of pure O{sub 2} produced O{sub 3} in an amount that increased with photon fluence to a stationary level. For both O{sub 2} and O{sub 3} films, the O{sub 3}:O{sub 2} ratio at large fluences is {approx}0.07, about two orders of magnitude larger than those obtained in gas phase photolysis. This enhancement is attributed tomore » the increased photodissociation of O{sub 2} due to photoabsorption by O{sub 2} dimers, a process significant at solid-state densities. We obtain initial quantum yield for ozone synthesis from solid oxygen, {Phi}(O{sub 3}) = 0.24 {+-} 0.06, and quantum yields for destruction of O{sub 3} and O{sub 2} in their parent solids, {Phi}(-O{sub 3}) = 1.0 {+-} 0.2 and {Phi}(-O{sub 2}) = 0.36 {+-} 0.1. Combined with known photoabsorption cross sections, we estimate probabilities for geminate recombination of 0.5 {+-} 0.1 for O{sub 3} fragments and 0.88 {+-} 0.03 for oxygen atoms from O{sub 2} dissociation. Using a single parameter kinetic model, we deduce the ratio of reaction cross sections for an O atom with O{sub 2} vs. O{sub 3} to be 0.1-0.2. The general good agreement of the model with the data suggests the validity of the central assumption of efficient energy and spin relaxation of photofragments in the solid prior to their reactions with other species.« less

Deuterium and carbon-13 NMR of the solid polymorphism of benzenehexoyl hexa-n-hexanoate

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

Lifshitz, E.; Goldfarb,, D.; Vega, S.

Deuterium and carbon-13 NMR of specifically labeled benzenehexoyl hexa-n-hexanoate in the various solid-state phases are reported. The spectra exhibit dynamic line shapes which change discontinuously at the phase transitions. The results are interpreted in terms of sequential melting of the side chains on going from the low-temperature solid phases IV, III, etc., toward the liquid. In phase IV the molecules are very nearly static, except for fast rotation of the methyl groups about their C/sub 3/ axes. The results in phase III were quantitatively interpreted in terms of a two-site isomerization process involving simultaneous rotation by 95/sup 0/ about C/submore » 1/-C/sub 2/ and transition from gtg to g'g't (or equivalently g'tg' to ggt) for the rest of the chain. The specific rate of this reaction at 0/sup 0/C is approx. 10/sup 5/s/sup -1/. In phase II additional chain isomerization processes set-in which were, however, not analyzed quantitatively. Further motional modes, involving reorientation of whole chains about their C/sup ar/-O bonds, appear on going to phase I. In all solid phases the benzene ring remains static.« less

Modeling microbiological and chemical processes in municipal solid waste bioreactor, Part II: Application of numerical model BIOKEMOD-3P.

PubMed

Gawande, Nitin A; Reinhart, Debra R; Yeh, Gour-Tsyh

2010-02-01

Biodegradation process modeling of municipal solid waste (MSW) bioreactor landfills requires the knowledge of various process reactions and corresponding kinetic parameters. Mechanistic models available to date are able to simulate biodegradation processes with the help of pre-defined species and reactions. Some of these models consider the effect of critical parameters such as moisture content, pH, and temperature. Biomass concentration is a vital parameter for any biomass growth model and often not compared with field and laboratory results. A more complex biodegradation model includes a large number of chemical and microbiological species. Increasing the number of species and user defined process reactions in the simulation requires a robust numerical tool. A generalized microbiological and chemical model, BIOKEMOD-3P, was developed to simulate biodegradation processes in three-phases (Gawande et al. 2009). This paper presents the application of this model to simulate laboratory-scale MSW bioreactors under anaerobic conditions. BIOKEMOD-3P was able to closely simulate the experimental data. The results from this study may help in application of this model to full-scale landfill operation.

Thermal Stir Welding Development at Marshall Space Flight Center

NASA Technical Reports Server (NTRS)

Ding, Robert J.

2008-01-01

Solid state welding processes have become the focus of welding process development at NASA's Marshall Space Flight Center. Unlike fusion weld processes such as tungsten inert gas (TIG), variable polarity plasma arc (VPPA), electron beam (EB), etc., solid state welding processes do not melt the material during welding. The resultant microstructure can be characterized as a dynamically recrystallized morphology much different than the casted, dentritic structure typical of fusion weld processes. The primary benefits of solid state processes over fusion weld processes include superior mechanic properties and the elimination of thermal distortion and residual stresses. These solid state processes attributes have profoundly influenced the direction of advanced welding research and development within the NASA agency. Thermal Stir Welding (TSW) is a new solid state welding process being developed at the Marshall Space Flight Center. Unlike friction stir welding, the heating, stirring and forging elements of the weld process can be decoupled for independent control. An induction coil induces energy into a workpiece to attain a desired plastic temperature. An independently controlled stir rod, captured within non-rotating containment plates, then stirs the plasticized material followed by forging plates/rollers that work the stirred weld joint. The independent control (decoupling) of heating, stirring and forging allows, theoretically, for the precision control of microstructure morphology. The TSW process is being used to evaluate the solid state joining of Haynes 230 for ARES J-2X applications. It is also being developed for 500-in (12.5 mm) thick commercially pure grade 2 titanium for navy applications. Other interests include Inconel 718 and stainless steel. This presentation will provide metallurgical and mechanical property data for these high melting temperature alloys.

Effect of bioaugmented inoculation on microbiota dynamics during solid-state fermentation of Daqu starter using autochthonous of Bacillus, Pediococcus, Wickerhamomyces and Saccharomycopsis.

PubMed

Li, Pan; Lin, Weifeng; Liu, Xiong; Wang, Xiaowen; Gan, Xing; Luo, Lixin; Lin, Wei-Tie

2017-02-01

Daqu, a traditional fermentation starter that is used for Chinese liquor and vinegar production, is still manufactured through a traditional spontaneous solid-state fermentation process with no selected microorganisms are intentionally inoculated. The aim of this work was to analyze the microbiota dynamics during the solid-state fermentation process of Daqu using a traditional and bioaugmented inoculation with autochthonous of Bacillus, Pediococcus, Saccharomycopsis and Wickerhamomyces at an industrial scale. Highly similar dynamics of physicochemical parameters, enzymatic activities and microbial communities were observed during the traditional and bioaugmented solid-state fermentation processes. Both in the two cases, groups of Streptophyta, Rickettsiales and Xanthomonadales only dominated the first two days, but Bacillales and Eurotiales became predominant members after 2 and 10 days fermentation, respectively. Phylotypes of Enterobacteriales, Lactobacillales, Saccharomycetales and Mucorales dominated the whole fermentation process. No significant difference (P > 0.05) in microbial structure was observed between the traditional and bioaugmented fermentation processes. However, slightly higher microbial richness was found during the bioaugmented fermentation process after 10 days fermentation. Our results reinforced the microbiota dynamic stability during the solid-state fermentation process of Daqu, and might aid in controlling the traditional Daqu manufacturing process. Copyright © 2016 Elsevier Ltd. All rights reserved.

Reactions of vanadium dioxide molecules with acetylene: infrared spectra of VO2(η(2)-C2H2)(x) (x = 1, 2) and OV(OH)CCH in solid neon.

PubMed

Zhou, Xiaojie; Chen, Mohua; Zhou, Mingfei

2013-07-03

Reactions of vanadium dioxide molecules with acetylene have been studied by matrix isolation infrared spectroscopy. Reaction intermediates and products are identified on the basis of isotopic substitutions as well as density functional frequency calculations. Ground state vanadium dioxide molecule reacts with acetylene in forming the side-on-bonded VO2(η(2)-C2H2) and VO2(η(2)-C2H2)2 complexes spontaneously on annealing in solid neon. The VO2(η(2)-C2H2) complex is characterized to have a (2)B2 ground state with C2v symmetry, whereas the VO2(η(2)-C2H2)2 complex has a (2)A ground state with C2 symmetry. The VO2(η(2)-C2H2) and VO2(η(2)-C2H2)2 complexes are photosensitive. The VO2(η(2)-C2H2) complex rearranges to the OV(OH)CCH molecule upon UV-vis light excitation.

Simple synthetic route to manganese-containing nanowires with the spinel crystal structure

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

Yu, Lei; Zhang, Yan; Hudak, Bethany M.

This report describes a new route to synthesize single-crystalline manganese-containing spinel nanowires (NWs) by a two-step hydrothermal and solid-state synthesis. Interestingly, a nanowire or nanorod morphology is maintained during conversion from MnO{sub 2}/MnOOH to CuMn{sub 2}O{sub 4}/Mg{sub 2}MnO{sub 4}, despite the massive structural rearrangement this must involve. Linear sweep voltammetry (LSV) curves of the products give preliminary demonstration that CuMn{sub 2}O{sub 4} NWs are catalytically active towards the oxygen evolution reaction (OER) in alkaline solution, exhibiting five times the magnitude of current density found with pure carbon black. - Highlights: • Synthesis of single-crystalline manganese-containing spinel nanowires. • Binary oxidemore » nanowire converted to ternary oxide wire through solid state reaction. • Approach to structure conversion with shape retention could be generally applicable. • Copper and Manganese display multiple oxidation states with potential for catalysis. • CuMn{sub 2}O{sub 4} nanowires show promise as catalysts for the oxygen evolution reaction.« less

Low-temperature crystallization of anodized TiO2 nanotubes at the solid-gas interface and their photoelectrochemical properties

NASA Astrophysics Data System (ADS)

Liu, Jing; Liu, Zhaoyue; Zhang, Tierui; Zhai, Jin; Jiang, Lei

2013-06-01

TiO2 nanotubular arrays formed by electrochemical anodization have attracted significant attention for photoelectrochemical applications that utilize solar energy. However, the as-anodized TiO2 nanotubes are amorphous, and need to be crystallized by high-temperature thermal annealing. Herein, we describe a low-temperature hydrothermal solid-gas route to crystallize TiO2 nanotubes. In this process, the as-anodized TiO2 hydroxo nanotubes are dehydrated to yield anatase phase via solid-gas interface reaction in an autoclave at a temperature of less than 180 °C. The solid-gas interface reaction alleviates the collapse of as-anodized TiO2 nanotubes during hydrothermal process efficiently. Compared with the common thermal annealing at the same temperature but at atmospheric pressure, the hydrothermal route improves the photocurrent density of TiO2 nanotubes by ~10 times in KOH electrolyte. The duration of the hydrothermal reaction has a substantial effect on the photoelectrochemical properties of TiO2 nanotubes, which is ascribed to the synergetic effect between the crystallization and structural evolution. Electron donors can further suppress the charge recombination in the low-temperature crystallized TiO2 nanotubes and boost the photocurrent density by ~120%.TiO2 nanotubular arrays formed by electrochemical anodization have attracted significant attention for photoelectrochemical applications that utilize solar energy. However, the as-anodized TiO2 nanotubes are amorphous, and need to be crystallized by high-temperature thermal annealing. Herein, we describe a low-temperature hydrothermal solid-gas route to crystallize TiO2 nanotubes. In this process, the as-anodized TiO2 hydroxo nanotubes are dehydrated to yield anatase phase via solid-gas interface reaction in an autoclave at a temperature of less than 180 °C. The solid-gas interface reaction alleviates the collapse of as-anodized TiO2 nanotubes during hydrothermal process efficiently. Compared with the common thermal annealing at the same temperature but at atmospheric pressure, the hydrothermal route improves the photocurrent density of TiO2 nanotubes by ~10 times in KOH electrolyte. The duration of the hydrothermal reaction has a substantial effect on the photoelectrochemical properties of TiO2 nanotubes, which is ascribed to the synergetic effect between the crystallization and structural evolution. Electron donors can further suppress the charge recombination in the low-temperature crystallized TiO2 nanotubes and boost the photocurrent density by ~120%. Electronic supplementary information (ESI) available: Morphology images of TiO2 nanotubular arrays crystallized by hydrothermal solid-liquid reaction at 130 °C, 160 °C and 180 °C for 4 h. Cross-sectional image of TiO2 nanotubular arrays prepared by anodizing Ti foil at 20 V for 20 min in 0.5 wt% HF solution followed by drying in air at 100 °C for 1 h; Photocurrent density-potential curves of TiO2 nanotubular arrays crystallized by thermal annealing at 450 °C and atmospheric pressure for 4 h. See DOI: 10.1039/c3nr01286g

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

Chen, L. X.; Zhang, X.; Lockard, J. V.

Transient molecular structures along chemical reaction pathways are important for predicting molecular reactivity, understanding reaction mechanisms, as well as controlling reaction pathways. During the past decade, X-ray transient absorption spectroscopy (XTA, or LITR-XAS, laser-initiated X-ray absorption spectroscopy), analogous to the commonly used optical transient absorption spectroscopy, has been developed. XTA uses a laser pulse to trigger a fundamental chemical process, and an X-ray pulse(s) to probe transient structures as a function of the time delay between the pump and probe pulses. Using X-ray pulses with high photon flux from synchrotron sources, transient electronic and molecular structures of metal complexes havemore » been studied in disordered media from homogeneous solutions to heterogeneous solution-solid interfaces. Several examples from the studies at the Advanced Photon Source in Argonne National Laboratory are summarized, including excited-state metalloporphyrins, metal-to-ligand charge transfer (MLCT) states of transition metal complexes, and charge transfer states of metal complexes at the interface with semiconductor nanoparticles. Recent developments of the method are briefly described followed by a future prospective of XTA. It is envisioned that concurrent developments in X-ray free-electron lasers and synchrotron X-ray facilities as well as other table-top laser-driven femtosecond X-ray sources will make many breakthroughs and realise dreams of visualizing molecular movies and snapshots, which ultimately enable chemical reaction pathways to be controlled.« less

Rapid solid-state metathesis route to transition-metal doped titanias

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

Coleman, Nathaniel; Perera, Sujith; Gillan, Edward G., E-mail: edward-gillan@uiowa.edu

2015-12-15

Rapid solid-state metathesis (SSM) reactions are often short-lived highly exothermic reactions that yield a molten alkali halide salt that aids in product growth and crystallization. SSM reactions may also produce kinetically stabilized structures due to the short (seconds) reaction times. This report describes the investigation of rapid SSM reactions in the synthesis of transition-metal doped titanias (M–TiO{sub 2}). The dopant targeted compositions were ten mol percent and based on elemental analysis, many of the M–TiO{sub 2} samples were close to this targeted level. Based on surface analysis, some samples showed large enrichment in surface dopant content, particularly chromium and manganesemore » doped samples. Due to the highly exothermic nature of these reactions, rutile structured TiO{sub 2} was observed in all cases. The M–TiO{sub 2} samples are visible colored and show magnetic and optical properties consistent with the dopant in an oxide environment. UV and visible photocatalytic experiments with these visibly colored rutile M–TiO{sub 2} powders showed that many of them are strongly absorbent for methylene blue dye and degrade the dye under both UV and visible light illumination. This work may open up SSM reactions as an alternate non-thermodynamic reaction strategy for dopant incorporation into a wide range of oxide and non-oxides.« less

A solid-state nuclear magnetic resonance study of post-plasma reactions in organosilicone microwave plasma-enhanced chemical vapor deposition (PECVD) coatings.

PubMed

Hall, Colin J; Ponnusamy, Thirunavukkarasu; Murphy, Peter J; Lindberg, Mats; Antzutkin, Oleg N; Griesser, Hans J

2014-06-11

Plasma-polymerized organosilicone coatings can be used to impart abrasion resistance and barrier properties to plastic substrates such as polycarbonate. Coating rates suitable for industrial-scale deposition, up to 100 nm/s, can be achieved through the use of microwave plasma-enhanced chemical vapor deposition (PECVD), with optimal process vapors such as tetramethyldisiloxane (TMDSO) and oxygen. However, it has been found that under certain deposition conditions, such coatings are subject to post-plasma changes; crazing or cracking can occur anytime from days to months after deposition. To understand the cause of the crazing and its dependence on processing plasma parameters, the effects of post-plasma reactions on the chemical bonding structure of coatings deposited with varying TMDSO-to-O2 ratios was studied with (29)Si and (13)C solid-state magic angle spinning nuclear magnetic resonance (MAS NMR) using both single-pulse and cross-polarization techniques. The coatings showed complex chemical compositions significantly altered from the parent monomer. (29)Si MAS NMR spectra revealed four main groups of resonance lines, which correspond to four siloxane moieties (i.e., mono (M), di (D), tri (T), and quaternary (Q)) and how they are bound to oxygen. Quantitative measurements showed that the ratio of TMDSO to oxygen could shift the chemical structure of the coating from 39% to 55% in Q-type bonds and from 28% to 16% for D-type bonds. Post-plasma reactions were found to produce changes in relative intensities of (29)Si resonance lines. The NMR data were complemented by Fourier transform infrared (FTIR) spectroscopy. Together, these techniques have shown that the bonding environment of Si is drastically altered by varying the TMDSO-to-O2 ratio during PECVD, and that post-plasma reactions increase the cross-link density of the silicon-oxygen network. It appears that Si-H and Si-OH chemical groups are the most susceptible to post-plasma reactions. Coatings produced at a low TMDSO-to-oxygen ratio had little to no singly substituted moieties, displayed a highly cross-linked structure, and showed less post-plasma reactions. However, these chemically more stable coatings are less compatible mechanically with plastic substrates, because of their high stiffness.

A kinetico-mechanistic study on the C-H bond activation of primary benzylamines; cooperative and solid-state cyclopalladation on dimeric complexes.

PubMed

Font, Helena; Font-Bardia, Mercè; Gómez, Kerman; González, Gabriel; Granell, Jaume; Macho, Israel; Martínez, Manuel

2014-09-28

The cyclometallation reactions of dinuclear μ-acetato complexes of the type [Pd(AcO)(μ-AcO)L]2 (L = 4-RC6H4CH2NH2, R = H, Cl, F, CF3), a process found to occur readily even in the solid state, have been studied from a kinetico-mechanistic perspective. Data indicate that the dinuclear acetato bridged derivatives are excellent starting materials to activate carbon-hydrogen bonds in a facile way. In all cases the established concerted ambiphilic proton abstraction by a coordinated acetato ligand has been proved. The metallation has also been found to occur in a cooperative manner, with the metallation of the first palladium unit of the dimeric complex being rate determining; no intermediate mono-metallated compounds are observed in any of the processes. The kinetically favoured bis-cyclopalladated compound obtained after complete C-H bond activation does not correspond to the final isolated XRD-characterized complexes. This species, bearing the classical open-book dimeric form, has a much more complex structure than the final isolated compound, with different types of acetato ligands.

Twinning, Epitaxy and Domain Switching in Ferroelastic Inclusion Compounds

NASA Technical Reports Server (NTRS)

Hollingsworth, Mark D.; Peterson, Matthew L.

2003-01-01

Our research is in the area of solid-state organic chemistry, which lies at the interface between physical organic chemistry and materials science. We use crystalline solids as models to probe fundamental issues about physical processes, molecular interactions and chemical reactions that are important for fabrication, stabilization and application of technological materials. Much of our most recent work has focused on the phenomena of ferroelastic and ferroelectric domain switching, in which application of an external force or electric field to a crystal causes the molecules inside the crystal to reorient, in tandem, to a new orientational state. To better understand and control the domain switching process, we have designed and synthesized over twenty closely related, ferroelastic organic crystals. Our approach has been to use crystalline inclusion compounds, in which one molecule (the guest) is trapped within the crystalline framework of a second molecule (the host). By keeping the host constant and varying the proportions and kinds of guests, it has been possible to tailor these materials so that domain switching is rapid and reversible (which is desirable for high technology applications). Inclusion compounds therefore serve as powerful systems for understanding the specific molecular mechanisms that control domain switching.

Syntheses, structure and magnetic properties of two vanadate garnets Ca{sub 5}M{sub 4}V{sub 6}O{sub 24} (M=Co, Ni)

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

Wang, Nannan; College of Materials Science and Engineering, Fuzhou University, Fuzhou, Fujian 350108; He, Zhangzhen, E-mail: hcz1988@hotmail.com

2015-08-15

Two vanadate compounds Ca{sub 5}M{sub 4}V{sub 6}O{sub 24} (M=Co, Ni) have been synthesized by a high-temperature solid-state reaction. The compounds are found to crystallize in the cubic system with a space group Ia-3d, which exhibit a typical garnet structural framework. Magnetic measurements show that Ca{sub 5}M{sub 4}V{sub 6}O{sub 24} (M=Co, Ni) exhibit similar magnetic behaviors, in which Ca{sub 5}Co{sub 4}V{sub 6}O{sub 24} possesses an antiferromagnetic ordering at T{sub N}=~6 K while Ca{sub 5}Ni{sub 4}V{sub 6}O{sub 24} shows an antiferromagnetic ordering at T{sub N}=~7 K. - Graphical abstract: Garnet vanadate compounds Ca{sub 5}M{sub 4}V{sub 6}O{sub 24} (M=Co, Ni) have been synthesizedmore » by a high-temperature solid-state reaction. Structural features and magnetic behaviors are also investigated. - Highlights: • New type of garnet vanadates Ca{sub 5}M{sub 4}V{sub 6}O{sub 24} (M=Co, Ni) are synthesized by a high-temperature solid-state reaction. • Structural features are confirmed by single crystal samples. • Magnetic behaviors are firstly investigated in the systems.« less

Synthesis and Characterization of AlCl3 Impregnated Molybdenum Oxide as Heterogeneous Nano-Catalyst for the Friedel-Crafts Acylation Reaction in Ambient Condition.

PubMed

Jadhav, Arvind H; Chinnappan, Amutha; Hiremath, Vishwanath; Seo, Jeong Gil

2015-10-01

Aluminum trichloride (AlCl3) impregnated molybdenum oxide heterogeneous nano-catalyst was prepared by using simple impregnation method. The prepared heterogeneous catalyst was characterized by powder X-ray diffraction, FT-IR spectroscopy, solid-state NMR spectroscopy, SEM imaging, and EDX mapping. The catalytic activity of this protocol was evaluated as heterogeneous catalyst for the Friedel-Crafts acylation reaction at room temperature. The impregnated MoO4(AlCl2)2 catalyst showed tremendous catalytic activity in Friedel-Crafts acylation reaction under solvent-free and mild reaction condition. As a result, 84.0% yield of acyl product with 100% consumption of reactants in 18 h reaction time at room temperature was achieved. The effects of different solvents system with MoO4(AlCl2)2 catalyst in acylation reaction was also investigated. By using optimized reaction condition various acylated derivatives were prepared. In addition, the catalyst was separated by simple filtration process after the reaction and reused several times. Therefore, heterogeneous MoO4(AlCl2)2 catalyst was found environmentally benign catalyst, very convenient, high yielding, and clean method for the Friedel-Crafts acylation reaction under solvent-free and ambient reaction condition.

Separation of uranium from (U, Th)O 2 and (U, Pu)O 2 by solid state reactions route

NASA Astrophysics Data System (ADS)

Keskar, Meera; Mudher, K. D. Singh; Venugopal, V.

2005-01-01

Solid state reactions of UO 2, ThO 2, PuO 2 and their mixed oxides (U, Th)O 2 and (U, Pu)O 2 were carried out with sodium nitrate upto 900 °C, to study the formation of various phases at different temperatures, which are amenable for easy dissolution and separation of the actinide elements in dilute acid. Products formed by reacting unsintered as well as sintered UO 2 with NaNO 3 above 500 °C were readily soluble in 2 M HNO 3, whereas ThO 2 and PuO 2 did not react with NaNO 3 to form any soluble products. Thus reactions of mixed oxides (U, Th)O 2 and (U, Pu)O 2 with NaNO 3 were carried out to study the quantitative separation of U from (U, Th)O 2 and (U, Pu)O 2. X-ray diffraction, X-ray fluorescence, thermal analysis and chemical analysis techniques were used for the characterization of the products formed during the reactions.

Recent Advances in Fast Ion Conducting Materials and Devices - Proceedings of the 2nd Asian Conference on Solid State Ionics

NASA Astrophysics Data System (ADS)

Chowdari, B. V. R.; Liu, Qingguo; Chen, Liquan

The Table of Contents for the book is as follows: * Preface * Invited Papers * Recent Trends in Solid State Ionics * Theoretical Aspects of Fast Ion Conduction in Solids * Chemical Bonding and Intercalation Processes in Framework Structures * Extra-Large Near-Electrode Regions and Diffusion Length on the Solid Electrolyte-Electrode Interface as Studied by Photo-EMF Method * Frequency Response of Glasses * XPS Studies on Ion Conducting Glasses * Characterization of New Ambient Temperature Lithium Polymer-Electrolyte * Recent Development of Polymer Electrolytes: Solid State Voltammetry in Polymer Electrolytes * Secondary Solid State Batteries: From Material Properties to Commercial Development * Silver Vanadium Oxide Bronze and its Applications for Electrochemical Devices * Study on β''-Alumina Solid Electrolyte and β Battery in SIC * Materials for Solid Oxide Fuel Cells * Processing for Super Superionic Ceramics * Hydrogen Production Using Oxide Ionic or Protonic Conductor * Ionically Conductive Sulfide-Based Lithium Glasses * Relation of Conductivity to Structure and Structural Relaxation in Ion-Conducting Glasses * The Mechanism of Ionic Conductivity in Glass * The Role of Synthesis and Structure in Solid State Ionics - Electrodes to Superconductors * Electrochromism in Spin-Coated Thin Films from Peroxo-Poly tungstate Solutions * Electrochemical Studies on High Tc Superconductors * Multivalence Fast Ionic Conductors - Montmorillonites * Contributed Papers * Volt-Ampere Characteristics and Interface Charge Transport in Solid Electrolytes * Internal Friction of Silver Chalcogenides * Thermal Expansion of Ionic and Superionic Solids * Improvement of PEO-LiCF3SO3 Complex Electrolytes Using Additives * Ionic Conductivity of Modified Poly (Methoxy Polyethylene Glycol Methacrylate) s-Lithium Salt Complexes * Solid Polymer Electrolytes of Crosslinked Polyethylene Glycol and Lithium Salts * Single Ionic Conductors Prepared by in Situ Polymerization of Methacrylic Acid Alkali Metal Salts in Polyethylene Oxide * Redox Behavior of Alkyl Viologens in Ion Conductive Polymer Solid * Ionic Conductivity of Interpenetrating Polymer Networks Containing LiClO4 * Electrochemical Behaviors of Porphyrins Incorporated into Solid Polymer Electrolytes * Lithium Ion Conducting Polymer Electrolytes * Electrochemical Synthesis of Polyaniline Thin Film * Electrochemical Aspect of Polyaniline Electrode in Aqueous Electrolyte * Mixed Cation Effect in Epoxy Resin - PEO-IPN Containing Perchlorate Salts * Conductivity, Raman and IR Studies on the Doped PEO-PPG Polymer Blends * Proton Conducting Polymeric Electrolytes from Poly (Ethyleneoxide) System * Surface Structure of Polymer Solid Ionic Conductors Based on Segmented Polyether Polyurethaneureas * Study on Addition Products of LiI and Diethylene Glycol etc. * Solid State Rechargeable Battery Using Paper Form Copper Ion Conductive Solid Electrolyte * Characterization of Electrode/Electrolyte Interfaces in Battery Li/PVAC-Li-Mont./Li1+xV3O8 by AC Impedance Method * Investigation on Reversibility of Vanadium Oxide Cathode Materials in Solid-State Battery * Preparation and Characterization of Silver Boromolybdate Solid State Batteries * The Electric Properties of the Trinary Cathode Material and its Application in Magnisium Solid State Cell * Electrical Properties and Phase Relation of Na2Mo0.1S0.9O4 Doped with Rare Earth Sulfate * New Electrochemical Probe for Rapid Determination of Silicon Concentration in Hot Metals * A New Theoretical EMF Expression for SOx(x = 2, 3) Sensors Based on Na2SO4 Solid Electrolyte * Evaluation of the Electrochemical SOx(x = 2, 3) Sensor with a Tubular Nasicon Electrolyte * The Response Time of a Modified Oxygen Sensor Using Zirconia Electrolyte * Preparation, Characteristics and Sintering Behavior of MgO-PSZ Powder * Reaction between La0.9MnO3 and Yttria Doped Zirconia * Development of the Extended-Life Oxygen Sensor of Caβ''-Al2O3 * Caβ''-Al2O3 Ultra-Low Oxygen Sensor * Measurement of Sulfur Concentration with Zirconia-Based Electrolyte Cell in Molten Iron * Influence of SO2 on the Conductivity of Calcia Stabilized Zirconia * Reactions between YSZ and La1-xCaxMnO3 as a Cathode for SOFC * Preparation and Electrical Properties of Lithium β''-Alumina * Influence of Lithia Content on Properties of β''-Alumina Ceramics * Electrical Conductivity of Solid Solutions of Na2SO4 with Na2SeO4 * Effect of Antagonist XO42- = MoO42- and WO42- Ion Substitution on the Electrical Conductivity of Li2SO4 : Li2CO3 Eutectic System * Study on the Electrical Properties and Structure of Multicrystal Materials Li5+xGe1-xCrxV3O12 * Preliminary Study on Synthesis of Silver Zirconium Silicophosphates by Sol - Gel Process * Sodium Ion Conduction in Iron(III) Exchanged Y Zeolite * Electrical Properties of V5O9+x (x = 0, 1) and CuxV5O9.1 * Electrical Properties of the Tetragonal ZrO2 Stabilized with CeO2, CeO2 + Gd2O3 * Study of Preparation and Ionic Conduction of Doped Barium Cerate Perovskite * Preparing Fine Alumina Powder by Homogeneous Precipitation Method for Fabricating β''-Al2O3 * Amorphous Lithium Ion Conductors in Li2S-SiS2-LiBO2 System * Mixed Alkali Effect of Glass Super Ionic Conductors * Electrical Property and Phase Separation, Crystallization Behavior of A Cu+-Conducting Glass * Investigation of Phase Separation and Crystallization for 0.4CuI-0.3 Cu2O-0.3P2O5 Glass by SEM and XRD * Study on the Lithium Solid Electrolytes of Li3N-LiX(X = F, Cl, Br, I)-B2O3 Ternary Systems * Synthesis and Characterization of the Li2O : P2O5 : WO3 Glasses * The Electrochromic Properties of Electrodeposited Ni-O Films in Nonaqueous Electrolytes * All Solid-State WO3-MnO2 Based Electrochromic Window * Electrochromism in Nickel Oxide Films * E S R of X-Irradiated Melt Quenched Li2SO4 * Mixed-Alkali Effect in the Li2O-Na2O-TeO2 Glass System * Electrical and Thermal Studies on Silver Tellurite Glasses * Late Entries (Invited Papers) * Proton Conducting Polymers * Light Scattering Studies on Superionic Conductor YSZ * Development of Thin Film Surface Modified Solid State Electrochemical Gas Sensors * Author Index * List of Participants

Operando characterization of cathodic reactions in a liquid-state lithium-oxygen micro-battery by scanning transmission electron microscopy.

PubMed

Liu, Pan; Han, Jiuhui; Guo, Xianwei; Ito, Yoshikazu; Yang, Chuchu; Ning, Shoucong; Fujita, Takeshi; Hirata, Akihiko; Chen, Mingwei

2018-02-16

Rechargeable non-aqueous lithium-oxygen batteries with a large theoretical capacity are emerging as a high-energy electrochemical device for sustainable energy strategy. Despite many efforts made to understand the fundamental Li-O 2 electrochemistry, the kinetic process of cathodic reactions, associated with the formation and decomposition of a solid Li 2 O 2 phase during charging and discharging, remains debate. Here we report direct visualization of the charge/discharge reactions on a gold cathode in a non-aqueous lithium-oxygen micro-battery using liquid-cell aberration-corrected scanning transmission electron microscopy (STEM) combining with synchronized electrochemical measurements. The real-time and real-space characterization by time-resolved STEM reveals the electrochemical correspondence of discharge/charge overpotentials to the nucleation, growth and decomposition of Li 2 O 2 at a constant current density. The nano-scale operando observations would enrich our knowledge on the underlying reaction mechanisms of lithium-oxygen batteries during round-trip discharging and charging and shed lights on the strategies in improving the performances of lithium-oxygen batteries by tailoring the cathodic reactions.

Room-Temperature Performance of Poly(Ethylene Ether Carbonate)-Based Solid Polymer Electrolytes for All-Solid-State Lithium Batteries.

PubMed

Jung, Yun-Chae; Park, Myung-Soo; Kim, Duck-Hyun; Ue, Makoto; Eftekhari, Ali; Kim, Dong-Won

2017-12-13

Amorphous poly(ethylene ether carbonate) (PEEC), which is a copolymer of ethylene oxide and ethylene carbonate, was synthesized by ring-opening polymerization of ethylene carbonate. This route overcame the common issue of low conductivity of poly(ethylene oxide)(PEO)-based solid polymer electrolytes at low temperatures, and thus the solid polymer electrolyte could be successfully employed at the room temperature. Introducing the ethylene carbonate units into PEEC improved the ionic conductivity, electrochemical stability and lithium transference number compared with PEO. A cross-linked solid polymer electrolyte was synthesized by photo cross-linking reaction using PEEC and tetraethyleneglycol diacrylate as a cross-linking agent, in the form of a flexible thin film. The solid-state Li/LiNi 0.6 Co 0.2 Mn 0.2 O 2 cell assembled with solid polymer electrolyte based on cross-linked PEEC delivered a high initial discharge capacity of 141.4 mAh g -1 and exhibited good capacity retention at room temperature. These results demonstrate the feasibility of using this solid polymer electrolyte in all-solid-state lithium batteries that can operate at ambient temperatures.

Synthesis and Characterization of a Perovskite Barium Zirconate (BaZrO[subscript 3]): An Experiment for an Advanced Inorganic Chemistry Laboratory

ERIC Educational Resources Information Center

Thananatthanachon, Todsapon

2016-01-01

In this experiment, the students explore the synthesis of a crystalline solid-state material, barium zirconate (BaZrO3) by two different synthetic methods: (a) the wet chemical method using BaCl[subscript 2]·2H[subscript 2]O and ZrOCl[subscript 2]·8H[subscript 2]O as the precursors, and (b) the solid-state reaction from BaCO[subscript 3] and…

Synthesis of Sr2Si5N8:Ce3+ phosphors for white LEDs via an efficient chemical deposition

PubMed Central

Yang, Che-Yuan; Som, Sudipta; Das, Subrata; Lu, Chung-Hsin

2017-01-01

Novel chemical vapor deposition (CVD) process was successfully developed for the growth of Sr2Si5N8:Ce3+ phosphors with elevated luminescent properties. Metallic strontium was used as a vapor source for producing Sr3N2 vapor to react with Si3N4 powder via a homogeneous gas-solid reaction. The phosphors prepared via the CVD process showed high crystallinity, homogeneous particle size ranging from 8 to 10 μm, and high luminescence properties. In contrast, the phosphors prepared via the conventional solid-state reaction process exhibited relative low crystallinity, non-uniform particle size in the range of 0.5–5 μm and relatively lower luminescent properties than the phosphors synthesized via the CVD process. Upon the blue light excitation, Sr2−xCexSi5N8 phosphors exhibited a broad yellow band. A red shift of the emission band from 535 to 556 nm was observed with the increment in the doping amount of Ce3+ ions from x = 0.02 to x = 0.10. The maximum emission was observed at x = 0.06, and the external and internal quantum efficiencies were calculated to be 51% and 71%, respectively. Furthermore, the CVD derived optimum Sr1.94Ce0.06Si5N8 phosphor exhibited sufficient thermal stability for blue-LEDs and the activation energy was calculated to be 0.33 eV. The results demonstrate a potential synthesis process for nitride phosphors suitable for light emitting diodes. PMID:28361999

Synthesis of Sr2Si5N8:Ce3+ phosphors for white LEDs via an efficient chemical deposition

NASA Astrophysics Data System (ADS)

Yang, Che-Yuan; Som, Sudipta; Das, Subrata; Lu, Chung-Hsin

2017-03-01

Novel chemical vapor deposition (CVD) process was successfully developed for the growth of Sr2Si5N8:Ce3+ phosphors with elevated luminescent properties. Metallic strontium was used as a vapor source for producing Sr3N2 vapor to react with Si3N4 powder via a homogeneous gas-solid reaction. The phosphors prepared via the CVD process showed high crystallinity, homogeneous particle size ranging from 8 to 10 μm, and high luminescence properties. In contrast, the phosphors prepared via the conventional solid-state reaction process exhibited relative low crystallinity, non-uniform particle size in the range of 0.5-5 μm and relatively lower luminescent properties than the phosphors synthesized via the CVD process. Upon the blue light excitation, Sr2-xCexSi5N8 phosphors exhibited a broad yellow band. A red shift of the emission band from 535 to 556 nm was observed with the increment in the doping amount of Ce3+ ions from x = 0.02 to x = 0.10. The maximum emission was observed at x = 0.06, and the external and internal quantum efficiencies were calculated to be 51% and 71%, respectively. Furthermore, the CVD derived optimum Sr1.94Ce0.06Si5N8 phosphor exhibited sufficient thermal stability for blue-LEDs and the activation energy was calculated to be 0.33 eV. The results demonstrate a potential synthesis process for nitride phosphors suitable for light emitting diodes.

Relationship between fabrication method and chemical stability of Ni-BaZr0.8Y0.2O3-δ membrane

NASA Astrophysics Data System (ADS)

Fang, Shumin; Wang, Siwei; Brinkman, Kyle S.; Su, Qing; Wang, Haiyan; Chen, Fanglin

2015-03-01

NiO effectively promotes the sintering of highly refractory Y-doped BaZrO3 (BZY) through the formation of BaY2NiO5, providing a simple and cost-effective method for the fabrication of dense BZY electrolyte and Ni-BZY hydrogen separation membrane at ∼1400 °C. Unfortunately, insulating BaCO3 and Y2O3 phases formed on the surface of BZY and Ni-BZY prepared by solid state reaction method with NiO after annealing in wet CO2. Ni-BZY membranes prepared from different methods suffered different degree of performance loss in wet H2 at 900 °C. The chemical instability of Ni-BZY is attributed to the formation of a secondary phase (BaY2O4) generated from the reduction of BaY2NiO5 in H2 during the sintering process. Both BaY2O4 and BaY2NiO5 react with H2O, and CO2 at elevated temperatures, generating insulating Ba(OH)2 and BaCO3 phases, respectively. The less BaY2O4 is formed in the fabrication process, the better chemical stability the Ni-BZY membranes possess. Therefore, a new Ni-BZY membrane is prepared through a judicial combination of BZY powders prepared from combined EDTA-citric and solid state reaction methods, and demonstrates exceptional chemical stability in H2O and CO2, enabling stable and even improved hydrogen flux in wet 50% CO2 at 900 °C.

Solid-State Metalized Reduction of Magnesium-Rich Low-Nickel Oxide Ores Using Coal as the Reductant Based on Thermodynamic Analysis

NASA Astrophysics Data System (ADS)

Ma, Baozhong; Xing, Peng; Yang, Weijiao; Wang, Chengyan; Chen, Yongqiang; Wang, Hua

2017-08-01

The solid-state metalized reduction of magnesium-rich low-nickel oxide ore using coal as a reductant was studied based on thermodynamic analysis. The major constituent minerals of the ore were silicates and goethite. The former was the main nickel-bearing mineral, and the latter was the main iron-bearing mineral. Single factor tests were conducted to investigate the effects of reduction temperature, duration, and coal dosage on the beneficiation of nickel and iron such that optimal conditions were achieved. Considering the low recoveries of nickel and iron (Ni, 13.9 pct; Fe, 30.3 pct) under the obtained optimal conditions, an improved process, adding CaF2 before the reaction, was proposed to modify the solid-state metalized process. The results showed that the recoveries of nickel and iron reached to 96.5 and 73.4 pct, respectively, and that the grades of nickel and iron in the concentrate increased from 2.5 and 62.6 wt pct to 6.9 and 71.4 wt pct, respectively. Nickel and iron in the absence of CaF2 were metalized; nevertheless, the size of ferronickel particles was only 1 μm. Furthermore, alloys in the presence of CaF2 aggregated and exhibited bands with a length greater than 200 µm. These observations suggested that CaF2 could effectively reduce the surface tension of the newly generated alloy interface and promote the migration and polymerization of the alloy particles, which improves the beneficiation of nickel and iron by magnetic separation.

Optimization of Aluminium-to-Magnesium Ultrasonic Spot Welding

NASA Astrophysics Data System (ADS)

Panteli, A.; Chen, Y.-C.; Strong, D.; Zhang, Xiaoyun; Prangnell, P. B.

2012-03-01

The ability to join dissimilar materials in the automotive industry will result in more efficient multimaterial structures. However, welding of aluminium (Al) to magnesium (Mg) alloys is problematic because of the rapid formation of brittle intermetallic phases at the weld interface. Ultrasonic welding (USW) is a solid-state joining technology that may offer a potential solution, but USW of Al to Mg is currently not well understood. Here, we have investigated the effect of process variables and energy input on joint formation between Al-6111 and Mg-AZ31 alloys, and we report on the optimum welding conditions, heat generation, and the formation of a significant intermetallic reaction layer. Furthermore, the factors influencing the interface reaction rate and the advantages of precoating the Mg with Al are discussed.

Kinetic analysis of non-isothermal solid-state reactions: multi-stage modeling without assumptions in the reaction mechanism.

PubMed

Pomerantsev, Alexey L; Kutsenova, Alla V; Rodionova, Oxana Ye

2017-02-01

A novel non-linear regression method for modeling non-isothermal thermogravimetric data is proposed. Experiments for several heating rates are analyzed simultaneously. The method is applicable to complex multi-stage processes when the number of stages is unknown. Prior knowledge of the type of kinetics is not required. The main idea is a consequent estimation of parameters when the overall model is successively changed from one level of modeling to another. At the first level, the Avrami-Erofeev functions are used. At the second level, the Sestak-Berggren functions are employed with the goal to broaden the overall model. The method is tested using both simulated and real-world data. A comparison of the proposed method with a recently published 'model-free' deconvolution method is presented.

Microemulsion and Sol-Gel Synthesized ZrO₂-MgO Catalysts for the Liquid-Phase Dehydration of Xylose to Furfural.

PubMed

Parejas, Almudena; Montes, Vicente; Hidalgo-Carrillo, Jesús; Sánchez-López, Elena; Marinas, Alberto; Urbano, Francisco J

2017-12-18

Two series of catalysts were prepared by sol-gel and microemulsion synthetic procedure (SG and ME, respectively). Each series includes both pure Mg and Zr solids as well as Mg-Zr mixed solids with 25%, 50% and 75% nominal Zr content. The whole set of catalysts was characterized from thermal, structural and surface chemical points of view and subsequently applied to the liquid-phase xylose dehydration to furfural. Reactions were carried out in either a high-pressure autoclave or in an atmospheric pressure multi-reactor under a biphasic (organic/water) reaction mixture. Butan-2-ol and toluene were essayed as organic solvents. Catalysts prepared by microemulsion retained part of the surfactant used in the synthetic procedure, mainly associated with the Zr part of the solid. The MgZr-SG solid presented the highest surface acidity while the Mg3Zr-SG one exhibited the highest surface basicity among mixed systems. Xylose dehydration in the high-pressure system and with toluene/water solvent mixture led to the highest furfural yield. Moreover, the yield of furfural increases with the Zr content of the catalyst. Therefore, the catalysts constituted of pure ZrO₂ (especially Zr-SG) are the most suitable to carry out the process under study although MgZr mixed solids could be also suitable for overall processes with additional reaction steps.

Comparisons of predicted steady-state levels in rooms with extended- and local-reaction bounding surfaces

NASA Astrophysics Data System (ADS)

Hodgson, Murray; Wareing, Andrew

2008-01-01

A combined beam-tracing and transfer-matrix model for predicting steady-state sound-pressure levels in rooms with multilayer bounding surfaces was used to compare the effect of extended- and local-reaction surfaces, and the accuracy of the local-reaction approximation. Three rooms—an office, a corridor and a workshop—with one or more multilayer test surfaces were considered. The test surfaces were a single-glass panel, a double-drywall panel, a carpeted floor, a suspended-acoustical ceiling, a double-steel panel, and glass fibre on a hard backing. Each test surface was modeled as of extended or of local reaction. Sound-pressure levels were predicted and compared to determine the significance of the surface-reaction assumption. The main conclusions were that the difference between modeling a room surface as of extended or of local reaction is not significant when the surface is a single plate or a single layer of material (solid or porous) with a hard backing. The difference is significant when the surface consists of multilayers of solid or porous material and includes a layer of fluid with a large thickness relative to the other layers. The results are partially explained by considering the surface-reflection coefficients at the first-reflection angles.

Advanced fusion welding processes, solid state joining and a successful marriage. [production of aerospace structures

NASA Technical Reports Server (NTRS)

Miller, F. R.

1972-01-01

Joining processes for aerospace systems combine fusion welding and solid state joining during production of metal structures. Detailed characteristics of electron beam welding, plasma arc welding, diffusion welding, inertia welding and weldbond processes are discussed.

Energy-saving approaches to solid state street lighting

NASA Astrophysics Data System (ADS)

Vitta, Pranciškus; Stanikūnas, Rytis; Tuzikas, Arūnas; Reklaitis, Ignas; Stonkus, Andrius; Petrulis, Andrius; Vaitkevičius, Henrikas; Žukauskas, Artūras

2011-10-01

We consider the energy-saving potential of solid-state street lighting due to improved visual performance, weather sensitive luminance control and tracking of pedestrians and vehicles. A psychophysical experiment on the measurement of reaction time with a decision making task was performed under mesopic levels of illumination provided by a highpressure sodium (HPS) lamp and different solid-state light sources, such as daylight and warm-white phosphor converted light-emitting diodes (LEDs) and red-green-blue LED clusters. The results of the experiment imply that photopic luminances of road surface provided by solid-state light sources with an optimized spectral power distribution might be up to twice as low as those provided by the HPS lamp. Dynamical correction of road luminance against road surface conditions typical of Lithuanian climate was estimated to save about 20% of energy in comparison with constant-level illumination. The estimated energy savings due to the tracking of pedestrians and vehicles amount at least 25% with the cumulative effect of intelligent control of at least 40%. A solid-state street lighting system with intelligent control was demonstrated using a 300 m long test ground consisting of 10 solid-state street luminaires, a meteorological station and microwave motion sensor network operated via power line communication.

Lateral spreading of Au contacts on InP

NASA Technical Reports Server (NTRS)

Fatemi, Navid S.; Weizer, Victor G.

1990-01-01

The contact spreading phenomenon observed when small area Au contacts on InP are annealed at temperatures above about 400 C was investigated. It was found that the rapid lateral expansion of the contact metallization which consumes large quantities of InP during growth is closely related to the third stage in the series of solid state reactions that occur between InP and Au, i.e., to the Au3In-to-Au9In4 transition. Detailed descriptions are presented of both the spreading process and the Au3In-to-Au9In4 transition along with arguments that the two processes are manifestations of the same basic phenomenon.

Highly efficient red-emitting BaMgBO3F:Eu3+,R+ (R: Li, Na, K, Rb) phosphor for near-UV excitation synthesized via glass precursor solid-state reaction

NASA Astrophysics Data System (ADS)

Shinozaki, Kenji; Akai, Tomoko

2017-09-01

Eu3+-doped fluoroborate crystals of BaMgBO3F were synthesized by a solid-state reaction using a glassy precursor material, and their photoluminescence (PL) was investigated. To compensate for the incorporation of Eu3+ into Ba2+ sites, samples codoped with alkali ions (Li+, Na+, K+, Rb+) were also prepared. The Eu3+-doped sample showed red PL with a quantum yield (QY) of 65% caused by near-UV excitation (λ = 393 nm), and PL intensity and QY increased with the codoping of Eu3+ and alkali ions. It was found that the Eu3+,Li+-codoped sample showed the highest PL intensity and a QY of 83%.

Two-stage, acetic acid-aqueous ammonia, fractionation of empty fruit bunches for increased lignocellulosic biomass utilization.

PubMed

Kim, Dong Young; Kim, Young Soo; Kim, Tae Hyun; Oh, Kyeong Keun

2016-01-01

Fractionation of EFB was conducted in two consecutive steps using a batch reaction system: hemicellulose hydrolysis using acetic acid (AA; 3.0-7.0 wt.%) at 170-190°C for 10-20 min in the first stage, and lignin solubilization using ammonium hydroxide (5-20 wt.%) at 140-220°C for 5-25 min in the second stage. The two-stage process effectively fractionated empty fruit bunches (EFB) in terms of hemicellulose hydrolysis (53.6%) and lignin removal (59.5%). After the two-stage treatment, the fractionated solid contained 65.3% glucan. Among three investigated process parameters, reaction temperature and ammonia concentration had greater impact on the delignification reaction in the second stage than reaction time. The two-stage fractionation processing improved the enzymatic digestibility to 72.9% with 15 FPU of cellulase/g of glucan supplemented with 70 pNPG of β-glycosidase (Novozyme 188)/g-glucan, which was significantly enhanced from the equivalent digestibility of 28.3% for untreated EFB and 45.7% for AAH-fractionated solid. Copyright © 2015 Elsevier Ltd. All rights reserved.

Hallmarks of mechanochemistry: from nanoparticles to technology.

PubMed

Baláž, Peter; Achimovičová, Marcela; Baláž, Matej; Billik, Peter; Cherkezova-Zheleva, Zara; Criado, José Manuel; Delogu, Francesco; Dutková, Erika; Gaffet, Eric; Gotor, Francisco José; Kumar, Rakesh; Mitov, Ivan; Rojac, Tadej; Senna, Mamoru; Streletskii, Andrey; Wieczorek-Ciurowa, Krystyna

2013-09-21

The aim of this review article on recent developments of mechanochemistry (nowadays established as a part of chemistry) is to provide a comprehensive overview of advances achieved in the field of atomistic processes, phase transformations, simple and multicomponent nanosystems and peculiarities of mechanochemical reactions. Industrial aspects with successful penetration into fields like materials engineering, heterogeneous catalysis and extractive metallurgy are also reviewed. The hallmarks of mechanochemistry include influencing reactivity of solids by the presence of solid-state defects, interphases and relaxation phenomena, enabling processes to take place under non-equilibrium conditions, creating a well-crystallized core of nanoparticles with disordered near-surface shell regions and performing simple dry time-convenient one-step syntheses. Underlying these hallmarks are technological consequences like preparing new nanomaterials with the desired properties or producing these materials in a reproducible way with high yield and under simple and easy operating conditions. The last but not least hallmark is enabling work under environmentally friendly and essentially waste-free conditions (822 references).

Experiment Automation with a Robot Arm using the Liquids Reflectometer Instrument at the Spallation Neutron Source

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

Zolnierczuk, Piotr A; Vacaliuc, Bogdan; Sundaram, Madhan

The Liquids Reflectometer instrument installed at the Spallation Neutron Source (SNS) enables observations of chemical kinetics, solid-state reactions and phase-transitions of thin film materials at both solid and liquid surfaces. Effective measurement of these behaviors requires each sample to be calibrated dynamically using the neutron beam and the data acquisition system in a feedback loop. Since the SNS is an intense neutron source, the time needed to perform the measurement can be the same as the alignment process, leading to a labor-intensive operation that is exhausting to users. An update to the instrument control system, completed in March 2013, implementedmore » the key features of automated sample alignment and robot-driven sample management, allowing for unattended operation over extended periods, lasting as long as 20 hours. We present a case study of the effort, detailing the mechanical, electrical and software modifications that were made as well as the lessons learned during the integration, verification and testing process.« less

Variable diffusion rates during exsolution coarsening in the presence of fluids.

NASA Astrophysics Data System (ADS)

Putnis, Andrew; Prent, Alexander

2017-04-01

The scale of exsolution textures in mineral solid solutions has long been used as an indicator of thermal history during cooling. The theory of spinodal decomposition in an anisotropic solid and subsequent coarsening of exsolution textures as a function of temperature and cooling rate is well developed (see Petrishcheva et al., 2009 and Abart et al., 2009 for a review of the Cahn-Hilliard theory). For the case of exsolution in the alkali feldspar solid solution [(Na,K)AlSi3O8] the characteristic texture shows compositional fluctuations in Na,K with a wavelength that depends on the cooling rate. The cooling rate is determined from knowledge of the Na-K interdiffusion coefficient, assuming that the unmixing is simply due to the interdiffusion of Na and K in an otherwise fixed tetrahedral Al,Si framework. Cryptoperthites and mesoperthites with a periodic lamellar microstructure are considered to be the end-result of such a solid-state exsolution process. Later-stage fluid infiltration results in patch perthites that are formed at a sharp replacement front by a dissolution-precipitation mechanism (Parsons et al., 2015). Patch perthites have an easily recognizable texture and are clear indicators of a reaction with an aqueous solution. The distinction is thus drawn between crypto- and meso-perthite showing periodic lamellae, associated with a solid-state exsolution process, and the patch perthite showing irregular domains of Na-rich and K-rich feldspars associated with a fluid mediated reprecipitation process. However, the presence of fluids can also enhance the coarsening of lamellar exsolution textures, retaining an apparently solid-state microstructure but with a length scale that is dependent on local recrystallization driven by fluid infiltration. Examples will be given from alkali feldspars in granitic rocks where it is clearly demonstrable that cooling rates cannot be inferred from such exsolution textures. The variability in Na,K diffusion rates and thus different length scales of exsolution are likely to be due to the efficiency of diffusional transport through a fluid phase, which is influenced by differences in fluid-induced micro- and nano-porosity. Abart R. et al. (2009) Am. J. Sci. 309, 450-475. Petrishcheva E. and Abart R. (2009) Am. J. Sci, 309, 431-449. Parsons I. et al., (2015) Am. Min. 100, 1277-1303.

Distinguishing solid bitumens formed by thermochemical sulfate reduction and thermal chemical alteration

USGS Publications Warehouse

Kelemen, S.R.; Walters, C.C.; Kwiatek, P.J.; Afeworki, M.; Sansone, M.; Freund, H.; Pottorf, R.J.; Machel, H.G.; Zhang, T.; Ellis, G.S.; Tang, Y.; Peters, K.E.

2008-01-01

Insoluble solid bitumens are organic residues that can form by the thermal chemical alteration (TCA) or thermochemical sulfate reduction (TSR) of migrated petroleum. TCA may actually encompass several low temperature processes, such as biodegradation and asphaltene precipitation, followed by thermal alteration. TSR is an abiotic redox reaction where petroleum is oxidized by sulfate. It is difficult to distinguish solid bitumens associated with TCA of petroleum from those associated with TSR when both processes occur at relatively high temperature. The focus of the present work was to characterize solid bitumen samples associated with TCA or TSR using X-ray photoelectron spectroscopy (XPS). XPS is a surface analysis conducted on either isolated or in situ (>25 ??m diameter) solid bitumen that can provide the relative abundance and chemical speciation of carbon, organic and inorganic heteroatoms (NSO). In this study, naturally occurring solid bitumens from three locations, Nisku Fm. Brazeau River area (TSR-related), LaBarge Field Madison Fm. (TSR-related), and the Alaskan Brooks range (TCA-related), are compared to organic solids generated during laboratory simulation of the TSR and TCA processes. The abundance and chemical nature of organic nitrogen and sulfur in solid bitumens can be understood in terms of the nature of (1) petroleum precursor molecules, (2) the concentration of nitrogen by way of thermal stress and (3) the mode of sulfur incorporation. TCA solid bitumens originate from polar materials that are initially rich in sulfur and nitrogen. Aromaticity and nitrogen increase as thermal stress cleaves aliphatic moieties and condensation reactions take place. Organic sulfur in TCA organic solids remains fairly constant with increasing maturation (3.5 to ???17 sulfur per 100 carbons) into aromatic structures and to the low levels of nitrogen in their hydrocarbon precursors. Hence, XPS results provide organic chemical composition information that helps to distinguish whether solid bitumen, either in situ or removed and concentrated from the rock matrix, was formed via the TCA or TRS process. ?? 2008 Elsevier Ltd.

Critical considerations for the qualitative and quantitative determination of process-induced disorder in crystalline solids.

PubMed

Newman, Ann; Zografi, George

2014-09-01

Solid-state instabilities in crystalline solids arise during processing primarily because a certain level of structural disorder has been introduced into the crystal. Many physical instabilities appear to be associated with the recrystallization of molecules from these disordered regions, while chemical instabilities arise from sufficient molecular mobility to allow solid-state chemical reactivity. In this Commentary we discuss the various forms of structural disorder, processing which can produce disorder, the quantitative analysis of process-induced order, and strategies to limit disorder and its effects. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

All-solid-state lithium-ion and lithium metal batteries - paving the way to large-scale production

NASA Astrophysics Data System (ADS)

Schnell, Joscha; Günther, Till; Knoche, Thomas; Vieider, Christoph; Köhler, Larissa; Just, Alexander; Keller, Marlou; Passerini, Stefano; Reinhart, Gunther

2018-04-01

Challenges and requirements for the large-scale production of all-solid-state lithium-ion and lithium metal batteries are herein evaluated via workshops with experts from renowned research institutes, material suppliers, and automotive manufacturers. Aiming to bridge the gap between materials research and industrial mass production, possible solutions for the production chains of sulfide and oxide based all-solid-state batteries from electrode fabrication to cell assembly and quality control are presented. Based on these findings, a detailed comparison of the production processes for a sulfide based all-solid-state battery with conventional lithium-ion cell production is given, showing that processes for composite electrode fabrication can be adapted with some effort, while the fabrication of the solid electrolyte separator layer and the integration of a lithium metal anode will require completely new processes. This work identifies the major steps towards mass production of all-solid-state batteries, giving insight into promising manufacturing technologies and helping stakeholders, such as machine engineering, cell producers, and original equipment manufacturers, to plan the next steps towards safer batteries with increased storage capacity.

Characterization of the Kinetics of NF3-Fluorination of NpO2

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

Casella, Andrew M.; Scheele, Randall D.; McNamara, Bruce K.

2015-12-23

The exploitation of selected actinide and fission product fluoride volatilities has long been considered as a potentially attractive compact method for recycling used nuclear fuels to avoid generating the large volumes of radioactive waste arising from aqueous reprocessing [1-7]. The most developed process uses the aggressive and hazardous fluorinating agents hydrogen fluoride (HF) and/or molecular fluorine (F2) at high temperatures to volatilize the greatest fraction of the used nuclear fuel into a single gas stream. The volatilized fluorides are subsequently separated using a series of fractionation and condensation columns to recover the valuable fuel constituents and fission products. In pursuitmore » of a safer and less complicated approach, we investigated an alternative fluoride volatility-based process using the less hazardous fluorinating agent nitrogen trifluoride (NF3) and leveraging its less aggressive nature to selectively evolve fission product and actinide fluorides from the solid phase based on their reaction temperatures into a single recycle stream [8-15]. In this approach, successive isothermal treatments using NF3 will first evolve the more thermally susceptible used nuclear fuel constituents leaving the other constituents in the residual solids until subsequent isothermal temperature treatments cause these others to volatilize. During investigation of this process, individual neat used fuel components were treated with isothermal NF3 in an attempt to characterize the kinetics of each fluorination reaction to provide input into the design of a new volatile fluoride separations approach. In these directed investigations, complex behavior was observed between NF3 and certain solid reactants such as the actinide oxides of uranium, plutonium, and neptunium. Given the similar thermal reaction susceptibilities of neptunium oxide (NpO2) and uranium dioxide (UO2) and the importance of Np and U, we initially focused our efforts on determining the reaction kinetic parameters for NpO2. Characterizing the NF3 fluorination of NpO2 using established models for gas-solid reactions [16] proved unsuccessful so we developed a series of successive fundamental reaction mechanisms to characterize the observed successive fluorination reactions leading to production of the volatile neptunium hexafluoride (NpF6).« less

Subnanosecond measurements of detonation fronts in solid high explosives

NASA Astrophysics Data System (ADS)

Sheffield, S. A.; Bloomquist, D. D.; Tarver, C. M.

1984-04-01

Detonation fronts in solid high explosives have been examined through measurements of particle velocity histories resulting from the interaction of a detonation wave with a thin metal foil backed by a water window. Using a high time resolution velocity-interferometer system, experiments were conducted on three explosives—a TATB (1,3,5-triamino-trinitrobenzene)-based explosive called PBX-9502, TNT (2,4,6-Trinitrotoluene), and CP (2-{5-cyanotetrazolato} pentaamminecobalt {III} perchlorate). In all cases, detonation-front rise times were found to be less than the 300 ps resolution of the interferometer system. The thermodynamic state in the front of the detonation wave was estimated to be near the unreacted state determined from an extrapolation of low-pressure unreacted Hugoniot data for both TNT and PBX-9502 explosives. Computer calculations based on an ignition and growth model of a Zeldovich-von Neumann-Doering (ZND) detonation wave show good agreement with the measurements. By using the unreacted Hugoniot and a JWL equation of state for the reaction products, we estimated the initial reaction rate in the high explosive after the detonation wave front interacted with the foil to be 40 μs-1 for CP, 60 μs-1 for TNT, and 80 μs-1 for PBX-9502. The shape of the profiles indicates the reaction rate decreases as reaction proceeds.

Entropy Analyses of Four Familiar Processes.

ERIC Educational Resources Information Center

Craig, Norman C.

1988-01-01

Presents entropy analysis of four processes: a chemical reaction, a heat engine, the dissolution of a solid, and osmosis. Discusses entropy, the second law of thermodynamics, and the Gibbs free energy function. (MVL)

Preparation and properties of a MnCo2O4 for ceramic interconnect of solid oxide fuel cell via glycine nitrate process

NASA Astrophysics Data System (ADS)

Yoon, Mi Young; Lee, Eun Jung; Song, Rak Hyun; Hwang, Hae Jin

2011-12-01

MnCo2O4 powder was prepared by a wet chemistry method using metal nitrates and glycine in an aqueous solution. The phase stability, sintering behavior, thermal expansion and electrical conductivity were examined to characterize powder suitability as an interconnect material in solid oxide fuel cells (SOFCs). X-ray diffraction indicated that the MnCo2O4 spinel synthesized by the glycine nitrate process was stable until 1100 °C and it was possible to obtain a fully densified single phase spinel. On the other hand, the MnCo2O4 synthesized by a solid state reaction decomposed into a cubic spinel and CoO after being sintered at 1100 °C. This might be associated with the reduction of Co3+ in the octahedral site of the cubic spinel phase. MnCo2O4 showed a thermal expansion coefficient comparable to that of other SOFCs components, as well as good electrical conductivity. Therefore, MnCo2O4 is a potential candidate for the ceramic interconnects in SOFCs, provided the phase instability under reducing environments can be improved.

A Specific Nucleophilic Ring-Opening Reaction of Aziridines as a Unique Platform for the Construction of Hydrogen Polysulfides Sensors

DOE PAGES

Chen, Wei; Rosser, Ethan W.; Zhang, Di; ...

2015-05-11

Hydrogen polysulfides (H 2S n, n>1) have been recently suggested to be the actual signalling molecules that involved in sulfur-related redox biology. However the exact mechanisms of H 2S n are still poorly understood and a major hurdle in this field is the lack of reliable and convenient methods for H 2S n detection. In this work we report a unique ring-opening reaction of N-sulfonylaziridine by Na 2S 2 under mild conditions. Based on this reaction a novel H 2S n-specific fluorescent probe (AP) was developed. The probe showed high sensitivity and selectivity for H 2S n. Notably, the fluorescentmore » turn-on product, i.e. compound 1, exhibited excellent two-photon photophysical properties and a large Stokes shift. Moreover, the high solid state luminescent efficiency of compound 1 makes it a potential candidate for organic emitters and solid-state lighting devices.« less

Online investigations on ozonation products of pyrene and benz[ a]anthracene particles with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer

NASA Astrophysics Data System (ADS)

Gao, Shaokai; Zhang, Yang; Meng, Junwang; Shu, Jinian

The reaction products of ozone with pyrene and benz[ a]anthracene absorbed on azelaic acid particles under the pseudo-first-order reaction conditions have been investigated with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). The pyrene and benz[ a]anthracene particles with the initial concentrations of ˜1 mg m -3 are respectively exposed to ˜22 ppm ozone in a reaction chamber with a volume of ˜180 L. The time-of-flight mass spectra of the particulate ozonides are obtained. The assignments of the mass spectra reveal that 4-carboxy-5-phenanthrene-carboxyaldehyde (71%) and hydroxypyrene (23%) are the main solid state ozonides of pyrene, while 2-(2-formyl)phenyl-3-naphthoic acid (35%), hydroxybenz[ a]anthrone (30%), and benz[ a]anthracene-7,12-dione (18%) are the main solid state ozonides of benz[ a]anthracene. The pathways of the ozonations are proposed in the paper.

Fabrication of Ni-silicide/Si heterostructured nanowire arrays by glancing angle deposition and solid state reaction.

PubMed

Hsu, Hsun-Feng; Huang, Wan-Ru; Chen, Ting-Hsuan; Wu, Hwang-Yuan; Chen, Chun-An

2013-05-10

This work develops a method for growing Ni-silicide/Si heterostructured nanowire arrays by glancing angle Ni deposition and solid state reaction on ordered Si nanowire arrays. Samples of ordered Si nanowire arrays were fabricated by nanosphere lithography and metal-induced catalytic etching. Glancing angle Ni deposition deposited Ni only on the top of Si nanowires. When the annealing temperature was 500°C, a Ni3Si2 phase was formed at the apex of the nanowires. The phase of silicide at the Ni-silicide/Si interface depended on the diameter of the Si nanowires, such that epitaxial NiSi2 with a {111} facet was formed at the Ni-silicide/Si interface in Si nanowires with large diameter, and NiSi was formed in Si nanowires with small diameter. A mechanism that is based on flux divergence and a nucleation-limited reaction is proposed to explain this phenomenon of size-dependent phase formation.

Fabrication of Ni-silicide/Si heterostructured nanowire arrays by glancing angle deposition and solid state reaction

PubMed Central

2013-01-01

This work develops a method for growing Ni-silicide/Si heterostructured nanowire arrays by glancing angle Ni deposition and solid state reaction on ordered Si nanowire arrays. Samples of ordered Si nanowire arrays were fabricated by nanosphere lithography and metal-induced catalytic etching. Glancing angle Ni deposition deposited Ni only on the top of Si nanowires. When the annealing temperature was 500°C, a Ni3Si2 phase was formed at the apex of the nanowires. The phase of silicide at the Ni-silicide/Si interface depended on the diameter of the Si nanowires, such that epitaxial NiSi2 with a {111} facet was formed at the Ni-silicide/Si interface in Si nanowires with large diameter, and NiSi was formed in Si nanowires with small diameter. A mechanism that is based on flux divergence and a nucleation-limited reaction is proposed to explain this phenomenon of size-dependent phase formation. PMID:23663726

Graphite Carbon-Supported Mo2C Nanocomposites by a Single-Step Solid State Reaction for Electrochemical Oxygen Reduction.

PubMed

Huang, K; Bi, K; Liang, C; Lin, S; Wang, W J; Yang, T Z; Liu, J; Zhang, R; Fan, D Y; Wang, Y G; Lei, M

2015-01-01

Novel graphite-molybdenum carbide nanocomposites (G-Mo2C) are synthesized by a typical solid state reaction with melamine and MoO3 as precursors under inert atmosphere. The characterization results indicate that G-Mo2C composites are composed of high crystallization and purity of Mo2C and few layers of graphite carbon. Mo2C nanoparticles with sizes ranging from 5 to 50 nm are uniformly supported by surrounding graphite layers. It is believed that Mo atom resulting from the reduction of MoO3 is beneficial to the immobilization of graphite carbon. Moreover, the electrocatalytic performances of G-Mo2C for ORR in alkaline medium are investigated by cyclic voltammetry (CV), rotating disk electrode (RDE) and chronoamperometry test with 3M methanol. The results show that G-Mo2C has a considerable catalytic activity and superior methanol tolerance performance for the oxygen reduction reaction (ORR) benefiting from the chemical interaction between the carbide nanoparticles and graphite carbon.

Fluidized-bed combustion reduces atmospheric pollutants

NASA Technical Reports Server (NTRS)

Jonke, A. A.

1972-01-01

Method of reducing sulfur and nitrogen oxides released during combustion of fossil fuels is described. Fuel is burned in fluidized bed of solids with simultaneous feeding of crushed or pulverized limestone to control emission. Process also offers high heat transfer rates and efficient contacting for gas-solid reactions.

Influence of cobalt and manganese content on the dehydrogenation capacity and kinetics of air-exposed LaNi 5+ x-type alloys in solid gas and electrochemical reactions

NASA Astrophysics Data System (ADS)

Raekelboom, E.; Cuevas, F.; Knosp, B.; Percheron-Guégan, A.

The effect of cobalt and manganese content on the dehydrogenation properties of air-exposed MmB 5+ x-type (Mm = mischmetal; B = Ni, Al, Co and Mn) alloys was investigated both in solid gas and electrochemical reactions. The cobalt and manganese content were varied separately while keeping constant the plateau pressure of the hydrides. The increase of the cobalt content leads to a decrease of the hydrogen capacity whereas the manganese content has no much effect. In solid gas reactions, the kinetics were found to be limited by the hydrogen diffusion through the surface oxidation layer. As for the electrochemistry, the kinetics are limited by a corrosion layer formed in alkaline medium. The desorption rates for both processes increase as the cobalt or manganese content decreases. This is thought to be due to an enhancement of the hydrogen diffusivity through the oxidation layer. As a result, a low cobalt or manganese content in MmB 5+ x alloys is found to be beneficial for the hydrogen desorption kinetics in both processes.

Advances in bioleaching for recovery of metals and bioremediation of fuel ash and sewage sludge.

PubMed

Gu, Tingyue; Rastegar, Seyed Omid; Mousavi, Seyyed Mohammad; Li, Ming; Zhou, Minghua

2018-08-01

Bioleaching has been successfully used in commercial metal mining for decades. It uses microbes to biosolubilize metal-containing inorganic compounds such as metal oxides and sulfides. There is a growing interest in using bioleaching for bioremediation of solid wastes by removing heavy metals from ash and sewage sludge. This review presents the state of the art in bioleaching research for recovery of metals and bioremediation of solid wastes. Various process parameters such as reaction time, pH, temperature, mass transfer rate, nutrient requirement, pulp density and particle size are discussed. Selections of more effective microbes are assessed. Pretreatment methods that enhance bioleaching are also discussed. Critical issues in bioreactor scale-up are analyzed. The potential impact of advances in biofilm and microbiome is explained. Copyright © 2018 Elsevier Ltd. All rights reserved.

Sintering of BaCe(sub 0.85)Y(sub 0.15)O(sub 3-delta) with/without SrTiO3 Dopant

NASA Technical Reports Server (NTRS)

Dynys, F.; Sayir, A.; Heimann, P. J.

2004-01-01

The perovskite composition, BaCe(sub 0.85)Y(sub 0.15)O(sub 3-delta), displays excellent protonic conduction at high temperatures making it a desirable candidate for hydrogen separation membranes. This paper reports on the sintering behavior of BaCe(sub 0.85)Y(sub 0.15)O(sub 3-delta) powders doped with SrTiO3. Two methods were used to synthesize BaCe(sub 0.85)Y(sub 0.15)O(sub 3-delta) powders: (1) solid state reaction and (2) wet chemical co-precipitation. Co-precipitated powder crystallized into the perovskite phase at 1000 C for 4 hrs. Complete reaction and crystallization of the perovskite phase by solid state was achieved by calcining at 1200 C for 24 hrs. Solid state synthesis produced a coarser powder with an average particle size of 1.3 microns and surface area of 0.74 sq m/g. Co-precipitation produced a finer powder with a average particle size of 65 nm and surface area of 14.9 sq m/g. Powders were doped with 1, 2, 5, and 10 mole % SrTiO3. Samples were sintered at 1450 C, 1550 C and 1650 C. SrTiO3 enhances sintering, optimal dopant level is different for powders synthesized by solid state and co-precipitation. Both powders exhibit similar grain growth behavior. Dopant levels of 5 and 10 mole % SrTiO3 significantly enhances the grain size.

Mapping Ionic Currents and Reactivity on the Nanoscale: Electrochemical Strain Microscopy

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

Kalinin, S.V.

2010-10-19

Solid-state electrochemical processes in oxides underpin a broad spectrum of energy and information storage devices, ranging from Li-ion and Li-air batteries, to solid oxide fuel cells (SOFC) to electroresistive and memristive systems. These functionalities are controlled by the bias-driven diffusive and electromigration transport of mobile ionic species, as well as intricate a set of electrochemical and defect-controlled reactions at interfaces and in bulk. Despite the wealth of device-level and atomistic studies, little is known on the mesoscopic mechanisms of ion diffusion and electronic transport on the level of grain clusters, individual grains, and extended defects. The development of the capabilitymore » for probing ion transport on the nanometer scale is a key to deciphering complex interplay between structure, functionality, and performance in these systems. Here we introduce Electrochemical Strain Microscopy, a scanning probe microscopy technique based on strong strain-bias coupling in the systems in which local ion concentrations are changed by electrical fields. The imaging capability, as well as time- and voltage spectroscopies analogous to traditional current based electrochemical characterization methods are developed. The reversible intercalation of Li and mapping electrochemical activity in LiCoO2 is demonstrated, illustrating higher Li diffusivity at non-basal planes and grain boundaries. In Si-anode device structure, the direct mapping of Li diffusion at extended defects and evolution of Li-activity with charge state is explored. The electrical field-dependence of Li mobility is studied to determine the critical bias required for the onset of electrochemical transformation, allowing reaction and diffusion processes in the battery system to be separated at each location. Finally, the applicability of ESM for probing oxygen vacancy diffusion and oxygen reduction/evolution reactions is illustrated, and the high resolution ESM maps are correlated with aberration corrected scanning transmission electron microscopy imaging. The future potential for deciphering mechanisms of electrochemical transformations on an atomically-defined single-defect level is discussed.« less

Repercussion of Solid state vs. Liquid state synthesized p-n heterojunction RGO-copper phosphate on proton reduction potential in water.

PubMed

Samal, Alaka; Das, Dipti P; Madras, Giridhar

2018-02-13

The same copper phosphate catalysts were synthesized by obtaining the methods involving solid state as well as liquid state reactions in this work. And then the optimised p-n hybrid junction photocatalysts have been synthesized following the same solid/liquid reaction pathways. The synthesized copper phosphate photocatalyst has unique rod, flower, caramel-treat-like morphology. The Mott-Schottky behavior is in accordance with the expected behavior of n-type semiconductor and the carrier concentration was calculated using the M-S analysis for the photocatalyst. And for the p-n hybrid junction of 8RGO-Cu 3 (PO 4 ) 2 -PA (PA abbreviated for photoassisted synthesis method), 8RGO-Cu 3 (PO 4 ) 2 -EG(EG abbreviated for Ethylene Glycol based synthesis method), 8RGO-Cu 3 (PO 4 ) 2 -PEG (PEG abbreviated for Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol based synthesis method)the amount of H 2 synthesized was 7500, 6500 and 4500 µmol/h/g, respectively. The excited electrons resulting after the irradiation of visible light on the CB of p-type reduced graphene oxide (RGO) migrate easily to n-type Cu 3 (PO 4 ) 2 via. the p-n junction interfaces and hence great charge carrier separation was achieved.

Enhanced ionic conductivity with Li{sub 7}O{sub 2}Br{sub 3} phase in Li{sub 3}OBr anti-perovskite solid electrolyte

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

Zhu, Jinlong, E-mail: jlzhu04@physics.unlv.edu, E-mail: yusheng.zhao@unlv.edu, E-mail: zhaoys@sustc.edu.cn; Li, Shuai; Zhang, Yi

Cubic anti-perovskites with general formula Li{sub 3}OX (X = Cl, Br, I) were recently reported as superionic conductors with the potential for use as solid electrolytes in all-solid-state lithium ion batteries. These electrolytes are nonflammable, low-cost, and suitable for thermoplastic processing. However, the primary obstacle of its practical implementation is the relatively low ionic conductivity at room temperature. In this work, we synthesized a composite material consisting of two anti-perovskite phases, namely, cubic Li{sub 3}OBr and layered Li{sub 7}O{sub 2}Br{sub 3,} by solid state reaction routes. The results indicate that with the phase fraction of Li{sub 7}O{sub 2}Br{sub 3} increasing to 44 wt.more » %, the ionic conductivity increased by more than one order of magnitude compared with pure phase Li{sub 3}OBr. Formation energy calculations revealed the meta-stable nature of Li{sub 7}O{sub 2}Br{sub 3}, which supports the great difficulty in producing phase-pure Li{sub 7}O{sub 2}Br{sub 3} at ambient pressure. Methods of obtaining phase-pure Li{sub 7}O{sub 2}Br{sub 3} will continue to be explored, including both high pressure and metathesis techniques.« less

All-solid-state lithium organic battery with composite polymer electrolyte and pillar[5]quinone cathode.

PubMed

Zhu, Zhiqiang; Hong, Meiling; Guo, Dongsheng; Shi, Jifu; Tao, Zhanliang; Chen, Jun

2014-11-26

The cathode capacity of common lithium ion batteries (LIBs) using inorganic electrodes and liquid electrolytes must be further improved. Alternatively, all-solid-state lithium batteries comprising the electrode of organic compounds can offer much higher capacity. Herein, we successfully fabricated an all-solid-state lithium battery based on organic pillar[5]quinone (C35H20O10) cathode and composite polymer electrolyte (CPE). The poly(methacrylate) (PMA)/poly(ethylene glycol) (PEG)-LiClO4-3 wt % SiO2 CPE has an optimum ionic conductivity of 0.26 mS cm(-1) at room temperature. Furthermore, pillar[5]quinine cathode in all-solid-state battery rendered an average operation voltage of ∼2.6 V and a high initial capacity of 418 mAh g(-1) with a stable cyclability (94.7% capacity retention after 50 cycles at 0.2C rate) through the reversible redox reactions of enolate/quinonid carbonyl groups, showing favorable prospect for the device application with high capacity.

Process for desulfurizing petroleum feedstocks

DOEpatents

Gordon, John Howard; Alvare, Javier

2014-06-10

A process for upgrading an oil feedstock includes reacting the oil feedstock with a quantity of an alkali metal, wherein the reaction produces solid materials and liquid materials. The solid materials are separated from the liquid materials. The solid materials may be washed and heat treated by heating the materials to a temperature above 400.degree. C. The heat treating occurs in an atmosphere that has low oxygen and water content. Once heat treated, the solid materials are added to a solution comprising a polar solvent, where sulfide, hydrogen sulfide or polysulfide anions dissolve. The solution comprising polar solvent is then added to an electrolytic cell, which during operation, produces alkali metal and sulfur.

Solid-state transformation of Fe-rich intermetallic phases in Al–5.0Cu–0.6Mn squeeze cast alloy with variable Fe contents during solution heat treatment

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

Lin, Bo; School of Mechanical Engineering, Gui Zhou University, Guiyang 550000; Zhang, Weiwen, E-mail: mewzhang@scut.edu.cn

2015-06-15

The Al–5.0 wt.% Cu–0.6 wt.% Mn alloys with a variable Fe content were prepared by squeeze casting. Optical microscopy (OM), Deep etching technique, scanning electron microscopy(SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to examine the solid-state transformation of Fe-rich intermetallics during the solution heat treatment. The results showed that the Chinese script-like α-Fe, Al{sub 6}(FeMn) and needle-like Al{sub 3}(FeMn) phases transform to a new Cu-rich β-Fe (Al{sub 7}Cu{sub 2}(FeMn)) phase during solution heat treatment. The possible reaction and overall transformation kinetics of the solid-state phase transformation for the Fe-rich intermetallics were investigated. - Graphical abstract: Displaymore » Omitted - Highlights: • The α-Fe, Al{sub 6}(FeMn) and Al{sub 3}(FeMn) phases change to the β-Fe phases. • Possible reactions of Fe phases during solution heat treatment are discussed. • The overall fractional transformation rate follows an Avrami curve.« less

Dual fluidized bed design for the fast pyrolysis of biomass

USDA-ARS?s Scientific Manuscript database

A mechanism for the transport of solids between fluidised beds in dual fluidised bed systems for the fast pyrolysis of biomass process was selected. This mechanism makes use of an overflow standpipe to transport solids from the fluidised bed used for the combustion reactions to a second fluidised be...

APPARATUS FOR SHORT TIME MEASUREMENTS IN A FIXED-BED, GAS/SOLID REACTOR

EPA Science Inventory

An apparatus for exposure of a solid to reactive process gas is described which makes possible short time (≥ 0.3 to 15 s) exposures in a fixed-bed reactor. Operating conditions for differential reaction with respect to the gas concentration and rapid quench for arresting hi...

Consequences of acid strength for isomerization and elimination catalysis on solid acids.

PubMed

Macht, Josef; Carr, Robert T; Iglesia, Enrique

2009-05-13

We address here the manner in which acid catalysis senses the strength of solid acids. Acid strengths for Keggin polyoxometalate (POM) clusters and zeolites, chosen because of their accurately known structures, are described rigorously by their deprotonation energies (DPE). Mechanistic interpretations of the measured dynamics of alkane isomerization and alkanol dehydration are used to obtain rate and equilibrium constants and energies for intermediates and transition states and to relate them to acid strength. n-Hexane isomerization rates were limited by isomerization of alkoxide intermediates on bifunctional metal-acid mixtures designed to maintain alkane-alkene equilibrium. Isomerization rate constants were normalized by the number of accessible protons, measured by titration with 2,6-di-tert-butylpyridine during catalysis. Equilibrium constants for alkoxides formed by protonation of n-hexene increased slightly with deprotonation energies (DPE), while isomerization rate constants decreased and activation barriers increased with increasing DPE, as also shown for alkanol dehydration reactions. These trends are consistent with thermochemical analyses of the transition states involved in isomerization and elimination steps. For all reactions, barriers increased by less than the concomitant increase in DPE upon changes in composition, because electrostatic stabilization of ion-pairs at the relevant transition states becomes more effective for weaker acids, as a result of their higher charge density at the anionic conjugate base. Alkoxide isomerization barriers were more sensitive to DPE than for elimination from H-bonded alkanols, the step that limits 2-butanol and 1-butanol dehydration rates; the latter two reactions showed similar DPE sensitivities, despite significant differences in their rates and activation barriers, indicating that slower reactions are not necessarily more sensitive to acid strength, but instead reflect the involvement of more unstable organic cations at their transition states. These compensating effects from electrostatic stabilization depend on how similar the charge density in these organic cations is to that in the proton removed. Cations with more localized charge favor strong electrostatic interactions with anions and form more stable ionic structures than do cations with more diffuse charges. Ion-pairs at elimination transition states contain cations with higher local charge density at the sp(2) carbon than for isomerization transition states; as a result, these ion-pairs recover a larger fraction of the deprotonation energy, and, consequently, their reactions become less sensitive to acid strength. These concepts lead us to conclude that the energetic difficulty of a catalytic reaction, imposed by gas-phase reactant proton affinities in transition state analogues, does not determine its sensitivity to the acid strength of solid catalysts.

Density of Trap States and Auger-mediated Electron Trapping in CdTe Quantum-Dot Solids.

PubMed

Boehme, Simon C; Azpiroz, Jon Mikel; Aulin, Yaroslav V; Grozema, Ferdinand C; Vanmaekelbergh, Daniël; Siebbeles, Laurens D A; Infante, Ivan; Houtepen, Arjan J

2015-05-13

Charge trapping is an ubiquitous process in colloidal quantum-dot solids and a major limitation to the efficiency of quantum dot based devices such as solar cells, LEDs, and thermoelectrics. Although empirical approaches led to a reduction of trapping and thereby efficiency enhancements, the exact chemical nature of the trapping mechanism remains largely unidentified. In this study, we determine the density of trap states in CdTe quantum-dot solids both experimentally, using a combination of electrochemical control of the Fermi level with ultrafast transient absorption and time-resolved photoluminescence spectroscopy, and theoretically, via density functional theory calculations. We find a high density of very efficient electron traps centered ∼0.42 eV above the valence band. Electrochemical filling of these traps increases the electron lifetime and the photoluminescence quantum yield by more than an order of magnitude. The trapping rate constant for holes is an order of magnitude lower that for electrons. These observations can be explained by Auger-mediated electron trapping. From density functional theory calculations we infer that the traps are formed by dicoordinated Te atoms at the quantum dot surface. The combination of our unique experimental determination of the density of trap states with the theoretical modeling of the quantum dot surface allows us to identify the trapping mechanism and chemical reaction at play during charge trapping in these quantum dots.

Addition of a Second Metal (Co) to Molybdenum Carbide: Effect of the Doping Route.

PubMed

Araujo, C P B; Frota, A V V M; Souza, C P de; Souto, M V M; Barbosa, C M

2018-03-01

Molybdenum carbide is an interesting and versatile material, which has important applications in the metal matrix industry as a reinforcement material, as well as in the catalytic field. Though many papers suggest different methodologies for adding cobalt to the carbide structure aiming either to increase catalytic activity or enhancing mechanical proprieties such as ductility, etc. no straightforward evaluation is available. In the present paper two doping methodologies were studied: via solid state mixture of powders and via wet impregnation. Ammonium molybdate [(NH4)2MoO4] and cobalt nitrate [Co(NO3)2·6H2O] were used as starting materials and the doping process was carried out before carburization reaction. Those materials were characterized by FT-IR, SEM, XRF and XRD. The carbo-reduction products' were evaluated on XRD and XRF basis. Doped precursors' evaluation showed that the wet impregnated doped materials presented smaller particle sizes, were more homogeneous and retained more cobalt than the solid state doped ones. However, final products' assessment indicated that the solid state methodology was able to retain a greater dopant percentage according to XRF evaluation, and XRD data indicated a more intrinsic addition of the dopant to the carbide structure. In addition, no significant changes on particle size could be attributed to any of the methodologies, both producing Mo2C of approximately 30 nm.

Interfacial Reactivity Benchmarking of the Sodium Ion Conductors Na3PS4 and Sodium β-Alumina for Protected Sodium Metal Anodes and Sodium All-Solid-State Batteries.

PubMed

Wenzel, Sebastian; Leichtweiss, Thomas; Weber, Dominik A; Sann, Joachim; Zeier, Wolfgang G; Janek, Jürgen

2016-10-05

The interfacial stability of solid electrolytes at the electrodes is crucial for an application of all-solid-state batteries and protected electrodes. For instance, undesired reactions between sodium metal electrodes and the solid electrolyte form charge transfer hindering interphases. Due to the resulting large interfacial resistance, the charge transfer kinetics are altered and the overvoltage increases, making the interfacial stability of electrolytes the limiting factor in these systems. Driven by the promising ionic conductivities of Na 3 PS 4 , here we explore the stability and viability of Na 3 PS 4 as a solid electrolyte against metallic Na and compare it to that of Na-β″-Al 2 O 3 (sodium β-alumina). As expected, Na-β″-Al 2 O 3 is stable against sodium, whereas Na 3 PS 4 decomposes with an increasing overall resistance, making Na-β″-Al 2 O 3 the electrolyte of choice for protected sodium anodes and all-solid-state batteries.

Solid state synthesis of layered sodium manganese oxide for sodium-ion battery by in-situ high energy X-ray diffraction and X-ray absorption near edge spectroscopy [Solid state synthesis of layered sodium manganese oxide for sodium-ion battery by in-situ HEXRD and XANES

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

Ma, Tianyuan; Xu, Gui -Liang; Zeng, Xiaoqiao

In situ high energy X-ray diffraction (HEXRD) and in situ X-ray absorption near edge spectroscopy (XANES) were carried out to understand the soild state synthesis of Na xMnO 2, with particular interest on the synthesis of P2 type Na 2/3MnO 2. It was found that there were multi intermediate phases formed before NaMnO 2 appeared at about 600 °C. And the final product after cooling process is a combination of O'3 NaMnO 2 with P2 Na 2/3MnO 2. A P2 type Na 2/3MnO 2 was synthesized at reduced temperature (600 °C). The influence of Na 2CO 3 impurity on themore » electrochemical performance of P2 Na 2/3MnO 2 was thoroughly investigated in our work. It was found that the content of Na 2CO 3 can be reduced by optimizing Na 2CO 3/MnCO 3 ratio during the solid state reaction or other post treatment such as washing with water. Lastly, we expected our results could provide a good guide for future development of high performance cathode materials for sodium-ion batteries.« less

Solid state synthesis of layered sodium manganese oxide for sodium-ion battery by in-situ high energy X-ray diffraction and X-ray absorption near edge spectroscopy [Solid state synthesis of layered sodium manganese oxide for sodium-ion battery by in-situ HEXRD and XANES

DOE PAGES

Ma, Tianyuan; Xu, Gui -Liang; Zeng, Xiaoqiao; ...

2016-12-07

In situ high energy X-ray diffraction (HEXRD) and in situ X-ray absorption near edge spectroscopy (XANES) were carried out to understand the soild state synthesis of Na xMnO 2, with particular interest on the synthesis of P2 type Na 2/3MnO 2. It was found that there were multi intermediate phases formed before NaMnO 2 appeared at about 600 °C. And the final product after cooling process is a combination of O'3 NaMnO 2 with P2 Na 2/3MnO 2. A P2 type Na 2/3MnO 2 was synthesized at reduced temperature (600 °C). The influence of Na 2CO 3 impurity on themore » electrochemical performance of P2 Na 2/3MnO 2 was thoroughly investigated in our work. It was found that the content of Na 2CO 3 can be reduced by optimizing Na 2CO 3/MnCO 3 ratio during the solid state reaction or other post treatment such as washing with water. Lastly, we expected our results could provide a good guide for future development of high performance cathode materials for sodium-ion batteries.« less

Facile synthesis of highly efficient and recyclable magnetic solid acid from biomass waste

PubMed Central

Liu, Wu-Jun; Tian, Ke; Jiang, Hong; Yu, Han-Qing

2013-01-01

In this work, sawdust, a biomass waste, is converted into a magnetic porous carbonaceous (MPC) solid acid catalyst by an integrated fast pyrolysis–sulfonation process. The resultant magnetic solid acid has a porous structure with high surface area of 296.4 m2 g−1, which can be attributed to the catalytic effect of Fe. The catalytic activity and recyclability of the solid acid catalyst are evaluated during three typical acid-catalyzed reactions: esterification, dehydration, and hydrolysis. The favorable catalytic performance in all three reactions is attributed to the acid's high strength with 2.57 mmol g−1 of total acid sites. Moreover, the solid acid can be reused five times without a noticeable decrease in catalytic activity, indicating the stability of the porous carbon (PC)–sulfonic acid group structure. The findings in the present work offer effective alternatives for environmentally friendly utilization of abundant biomass waste. PMID:23939253

Laboratory Studies on the Formation of Carbon-Bearing Molecules in Extraterrestrial Environments: From the Gas Phase to the Solid State

NASA Technical Reports Server (NTRS)

Jamieson, C. S.; Guo, Y.; Gu, X.; Zhang, F.; Bennett, C. J.; Kaiser, R. I.

2006-01-01

A detailed knowledge of the formation of carbon-bearing molecules in interstellar ices and in the gas phase of the interstellar medium is of paramount interest to understand the astrochemical evolution of extraterrestrial environments (1). This research also holds strong implications to comprehend the chemical processing of Solar System environments such as icy planets and their moons together with the atmospheres of planets and their satellites (2). Since the present composition of each interstellar and Solar System environment reflects the matter from which it was formed and the processes which have changed the chemical nature since the origin (solar wind, planetary magnetospheres, cosmic ray exposure, photolysis, chemical reactions), a detailed investigation of the physicochemical mechanisms altering the pristine environment is of paramount importance to grasp the contemporary composition. Once these underlying processes have been unraveled, we can identify those molecules, which belonged to the nascent setting, distinguish molecular species synthesized in a later stage, and predict the imminent chemical evolution of, for instance, molecular clouds. Laboratory experiments under controlled physicochemical conditions (temperature, pressure, chemical composition, high energy components) present ideal tools for simulating the chemical evolution of interstellar and Solar System environments. Here, laboratory experiments can predict where and how (reaction mechanisms; chemicals necessary) in extraterrestrial environments and in the interstellar medium complex, carbon bearing molecules can be formed on interstellar grains and in the gas phase. This paper overviews the experimental setups utilized in our laboratory to mimic the chemical processing of gas phase and solid state (ices) environments. These are a crossed molecular beams machine (3) and a surface scattering setup (4). We also present typical results of each setup (formation of amino acids, aldehydes, epoxides; synthesis of hydrogen terminated carbon chains as precursors to complex PAHs and to carbonaceous dust grains in general; nitriles as precursor to amino acids).

Nanoscaled Na3PS4 Solid Electrolyte for All-Solid-State FeS2/Na Batteries with Ultrahigh Initial Coulombic Efficiency of 95% and Excellent Cyclic Performances.

PubMed

Wan, Hongli; Mwizerwa, Jean Pierre; Qi, Xingguo; Xu, Xiaoxiong; Li, Hong; Zhang, Qiang; Cai, Liangting; Hu, Yong-Sheng; Yao, Xiayin

2018-04-18

Nanosized Na 3 PS 4 solid electrolyte with an ionic conductivity of 8.44 × 10 -5 S cm -1 at room temperature is synthesized by a liquid-phase reaction. The resultant all-solid-state FeS 2 /Na 3 PS 4 /Na batteries show an extraordinary high initial Coulombic efficiency of 95% and demonstrate high energy density of 611 Wh kg -1 at current density of 20 mA g -1 at room temperature. The outstanding performances of the battery can be ascribed to good interface compatibility and intimate solid-solid contact at FeS 2 electrode/nanosized Na 3 PS 4 solid electrolytes interface. Meanwhile, excellent cycling stability is achieved for the battery after cycling at 60 mA g -1 for 100 cycles, showing a high capacity of 287 mAh g -1 with the capacity retention of 80%.

Solid-state chelation of metal ions by ethylenediaminetetraacetate intercalated in a layered double hydroxide.

PubMed

Tarasov, Konstantin A; O'Hare, Dermot; Isupov, Vitaly P

2003-03-24

The solid-state chelation of transition metal ions (Co(2+), Ni(2+), and Cu(2+)) from aqueous solutions into the lithium aluminum layered double hydroxide ([LiAl(2)(OH)(6)]Cl x 0.5H(2)O or LDH) which has been pre-intercalated with EDTA (ethylenediaminetetraacetate) ligand has been investigated. The intercalated metal cations form [M(edta)](2)(-) complexes between the LDH layers as indicated by elemental analysis, powder X-ray diffraction, and IR and UV-vis spectroscopies. If metal chloride or nitrate salts are used in the reaction with the LDH then co-intercalation of either the Cl(-) or NO(3)(-) anions is observed. In the case of metal acetate salts the cations intercalate without the accompanying anion. This can be explained by the different intercalation selectivity of the anions in relation to the LDH. In the latter case the introduction of the positive charge into LDH structure was compensated for by the release from the solid of the equivalent quantity of lithium and hydrogen cations. Time-resolved in-situ X-ray diffraction measurements have revealed that the chelation/intercalation reactions proceed very quickly. The rate of the reaction found for nickel acetate depends on concentration as approximately k[Ni(Ac)(2)](3).

Microstructure and growth kinetics of nickel silicide ultra-thin films synthesized by solid-state reactions

NASA Astrophysics Data System (ADS)

Coia, Cedrik

The objective of the thesis is to develop a detailed fundamental understanding of the thermally induced solid-state reactions that lead to the formation of the NiSi. We use in situ synchrotron x-ray diffraction as well as wafer curvature measurements to monitor reactions as they occur during the annealing treatment. These analyses are complemented by ex situ transmission electron microscopy, Rutherford backscattering spectroscopy, and secondary ions mass spectroscopy. The solid-state reactions between 4 to 500 nm-thick Ni films and Si (001) are considerably more complex than previously believed. In addition to the commonly observed phases listed above, we observe the formation of three additional compounds---θ-Ni2Si, Ni31Si12 and Ni3Si2---before the complete transformation of the reacted film into NiSi. These compounds are found to co-exist laterally (within the same layer) with delta-Ni2Si and/or NiSi. The metastable compound θ-Ni2Si, which formation results from texture inheritance and rapid growth through vacancy diffusion, is present in all samples and forms at the same temperature (300+/-10°C) regardless of the initial Ni thickness. Indeed, this compound forms rapidly during ramps anneals, apparently consuming all the delta-Ni2Si for initial Ni films thickness of up to 10 nm. Its disappearance is also rapid and is correlated to both the growth of NiSi and to a surprising return of the orthorhombic delta-Ni 2Si. The formation sequence is therefore not monotonic in composition in contrast to what is usually expected in solid-state reactions. An investigation of the effect of alloying elements (Pt and Co) and impurities (B, P, As, F, N) on the Ni-Si reactions enables us to determine that nucleation plays a limiting role in the growth of metastable θ-Ni2Si and that the template provided by delta-Ni2Si is crucial in promoting this nucleation. Furthermore, reactions with amorphized and amorphous substrates indicate that the possibility of epitaxy with the Si substrate is not a necessary condition for θ-Ni2Si to form. Activated CMOS dopants and alloying impurities delay the growth of all Ni-rich compounds and eventually suppress the formation of θ-Ni2Si possibly because of a limited solubility. Impurities implanted without subsequent re-crystallization anneals stabilize the compound partly through the presence of an amorphous interface, at least at the beginning of the reaction. A quantitative investigation of the growth kinetics of θ-Ni 2Si on undoped Si(001) reveals two distinct stages which are well described by a model incorporating 2D nucleation-controlled growth at the silicide/Si interface and the non-planar diffusion-controlled penetration of θ-Ni 2Si in the overlying delta-Ni2Si grains. Despite the very good fit of the model to our data, we cannot rule out the possibility that the second stage consists of a 1D diffusion-controlled planar growth during which the composition of the non-stoichiometric θ-Ni2Si changes. In F-doped samples, the second stage corresponds to a 1D diffusion-controlled growth in the absence of delta-Ni2Si and Ni, suggesting a possible compositional change during growth. The results presented in this thesis show that thanks to the use of powerful in situ monitoring techniques we have observed the kinetic competition between different growing compounds in the early stages of their growth. This competition has been predicted by many growth models, yet to our knowledge it has not been observed so far. We also have shown that this competition can lead to the lateral co-existence of several compounds in the same layer whereas most solid-state reaction models assume or require a layer-by-layer co-existence scheme. Finally, we show that the combination of (i) strong interfacial concentration gradients, (ii) structural similarities between delta-Ni 2Si, NiSi and θ-Ni2Si, and (iii) the ability of the latter to sustain vacancies and to nucleate in concentration gradients lead to a very peculiar reaction pathway, which results in a striking non-sequential succession of compounds. Our results therefore bear an important interest on the fundamental material science point of view in addition to the technological points of view given their pertinence for the SALICIDE process used to implement the Ni-Si contact metallurgy in the CMOS technology. (Abstract shortened by UMI.)

Room temperature magnetoelectric coupling and electrical properties of Ni doped Co - ferrite - PZT nanocomposites

NASA Astrophysics Data System (ADS)

Chakraborty, Sarit; Mandal, S. K.; Dey, P.; Saha, B.

2018-04-01

Multiferroic magnetoelectric materials are very interesting for the researcher for the potential application in device preparation. We have prepared 0.3Ni0.5Co0.5Fe2O4 - 0.7PbZr0.58Ti0.42O3 magnetoelectric nanocomposites through chemical pyrophoric reaction process followed by solid state reaction and represented magnetoelectric coupling coefficient, thermally and magnetically tunable AC electrical properties. For the structural characterization XRD pattern and SEM micrograph have been analyzed. AC electrical properties reveal that the grain boundaries resistances are played dominating role in the conduction process in the system. Dielectric studies are represents that the dielectric polarization is decreased with frequency as well as magnetic field where it increases with increasing temperature. The dielectric profiles also represents the electromechanical resonance at a frequency of ˜183 kHz. High dielectric constant and low dielectric loss at room temperature makes the material very promising for the application of magnetic field sensor devices.

Influence of surface diffusion on the formation of hollow nanostructures induced by the Kirkendall effect: the basic concept.

PubMed

Fan, Hong Jin; Knez, Mato; Scholz, Roland; Hesse, Dietrich; Nielsch, Kornelius; Zacharias, Margit; Gösele, Ulrich

2007-04-01

The Kirkendall effect has been widely applied for fabrication of nanoscale hollow structures, which involves an unbalanced counterdiffusion through a reaction interface. Conventional treatment of this process only considers the bulk diffusion of growth species and vacancies. In this letter, a conceptual extension is proposed: the development of the hollow interior undergoes two main stages. The initial stage is the generation of small Kirkendall voids intersecting the compound interface via a bulk diffusion process; the second stage is dominated by surface diffusion of the core material (viz., the fast-diffusing species) along the pore surface. This concept applies to spherical as well as cylindrical nanometer and microscale structures, and even to macroscopic bilayers. As supporting evidence, we show the results of a spinel-forming solid-state reaction of core-shell nanowires, as well as of a planar bilayer of ZnO-Al2O3 to illustrate the influence of surface diffusion on the morphology evolution.

CONFERENCES AND SYMPOSIA: Microscopics of fluctuations of the energy of atoms in solids

NASA Astrophysics Data System (ADS)

Slutsker, A. I.; Mihailin, A. I.; Slutsker, I. A.

1994-04-01

Internal atomic-molecular vibrational dynamics of solids gives rise to short-lived localised states of atoms with a much higher energy or amplitude of vibrations, i.e., it gives rise to fluctuations. These fluctuations play the dominant role in a variety of physical processes, which include diffusion, evaporation, plastic deformation, highly elastic deformation of polymers, fracture, chemical reactions, electronic transi-tions, biological functions, and many others. The essentials of the fluctuation origin of these processes are given in the classical papers of Ya I Frenkel'. The microscopics of fluctuations of the energy of atoms has begun to develop successfully. The present paper provides a brief historical introduction, which is followed by the first results (obtained by computer simulation) that can account for the detailed characteristics of fluctuations: the lifetime of a fluctuation state of atoms, the size of a fluctuation region, and migration of fluctuations. Special attention is given to the mechanism of formation of energy fluctuations. Investigations of fluctuation dynamics in condensed media, regarded as a new and to some extent independent part of the physics of liquids and solids, have been given a decisive start by the fundamental work of Yakov Il'ich Frenkel'. He began his investigations back in the twenties and continued them with outstanding success throughout his life. The study reported below represents the attempt by the present authors to continue the development of the fruitful ideas of Yakov Il'ich.

Solid-State Fermentation vs Submerged Fermentation for the Production of l-Asparaginase.

PubMed

Doriya, K; Jose, N; Gowda, M; Kumar, D S

l-Asparaginase, an enzyme that catalyzes l-asparagine into aspartic acid and ammonia, has relevant applications in the pharmaceutical and food industry. So, this enzyme is used in the treatment of acute lymphoblastic leukemia, a malignant disorder in children. This enzyme is also able to reduce the amount of acrylamide found in carbohydrate-rich fried and baked foods which is carcinogenic to humans. The concentration of acrylamide in food can be reduced by deamination of asparagine using l-Asparaginase. l-Asparaginase is present in plants, animals, and microbes. Various microorganisms such as bacteria, yeast, and fungi are generally used for the production of l-Asparaginase as it is difficult to obtain the same from plants and animals. l-Asparaginase from bacteria causes anaphylaxis and other abnormal sensitive reactions. To overcome this, eukaryotic organisms such as fungi can be used for the production of l-Asparaginase. l-Asparaginase can be produced either by solid-state fermentation (SSF) or by submerged fermentation (SmF). SSF is preferred over SmF as it is cost effective, eco-friendly and it delivers high yield of enzyme. SSF process utilizes agricultural and industrial wastes as solid substrate. The contamination level is substantially reduced in SSF through low moisture content. Current chapter will discuss in detail the chemistry and applications of l-Asparaginase enzyme and various methods available for the production of the enzyme, especially focusing on the advantages and limitations of SSF and SmF processes. © 2016 Elsevier Inc. All rights reserved.

Mathematical model to analyze the dissolution behavior of metastable crystals or amorphous drug accompanied with a solid-liquid interface reaction.

PubMed

Hirai, Daiki; Iwao, Yasunori; Kimura, Shin-Ichiro; Noguchi, Shuji; Itai, Shigeru

2017-04-30

Metastable crystals and the amorphous state of poorly water-soluble drugs in solid dispersions (SDs), are subject to a solid-liquid interface reaction upon exposure to a solvent. The dissolution behavior during the solid-liquid interface reaction often shows that the concentration of drugs is supersaturated, with a high initial drug concentration compared with the solubility of stable crystals but finally approaching the latter solubility with time. However, a method for measuring the precipitation rate of stable crystals and/or the potential solubility of metastable crystals or amorphous drugs has not been established. In this study, a novel mathematical model that can represent the dissolution behavior of the solid-liquid interface reaction for metastable crystals or amorphous drug was developed and its validity was evaluated. The theory for this model was based on the Noyes-Whitney equation and assumes that the precipitation of stable crystals at the solid-liquid interface occurs through a first-order reaction. Moreover, two models were developed, one assuming that the surface area of the drug remains constant because of the presence of excess drug in the bulk and the other that the surface area changes in time-dependency because of agglomeration of the drug. SDs of Ibuprofen (IB)/polyvinylpyrrolidone (PVP) were prepared and their dissolution behaviors under non-sink conditions were fitted by the models to evaluate improvements in solubility. The model assuming time-dependent surface area showed good agreement with experimental values. Furthermore, by applying the model to the dissolution profile, parameters such as the precipitation rate and the potential solubility of the amorphous drug were successfully calculated. In addition, it was shown that the improvement in solubility with supersaturation was able to be evaluated quantitatively using this model. Therefore, this mathematical model would be a useful tool to quantitatively determine the supersaturation concentration of a metastable drug from solid dispersions. Copyright © 2017 Elsevier B.V. All rights reserved.

From laser particle acceleration to the synthesis of extremely neutron rich isotopes via the novel fission-fusion mechanism

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

Thirolf, P. G., E-mail: Peter.Thirolf@lmu.de

2015-02-24

High-power, short pulse lasers have emerged in the last decade as attractive tools for accelerating charged particles (electrons, ions) to high energies over mm-scale acceleration lengths, thus promising to rival conventional acceleration techniques in the years ahead. In the first part of the article, the principles of laser-plasma interaction as well as the techniques and the current status of the acceleration of electron and ion beams will be briefly introduced. In particular with the upcoming next generation of multi-PW class laser systems, such as the one under construction for the ELI-Nuclear Physics project in Bucharest (ELI-NP), very efficient acceleration mechanismsmore » for brilliant ion beams like radiation pressure acceleration (RPA) come into reach. Here, ultra-dense ion beams reaching solid-state density can be accelerated from thin target foils, exceeding the density of conventionally accelerated ion beams by about 14 orders of magnitude. This unique property of laser-accelerated ion beams can be exploited to explore the scenario of a new reaction mechanism called ‘fission-fusion’, which will be introduced in the second part of the article. Accelerating fissile species (e.g. {sup 232}Th) towards a second layer of the same material will lead to fission both of the beam-like and target-like particles. Due to the close to solid-state density of the accelerated ion bunches, fusion may occur between neutron-rich (light) fission products. This may open an access path towards extremely neutron-rich nuclides in the vicinity of the N=126 waiting point of the astrophysical r process. ‘Waiting points’ at closed nucleon shells play a crucial role in controlling the reaction rates. However, since most of the pathway of heavy-element formation via the rapid-neutron capture process (r-process) runs in ‘terra incognita’ of the nuclear landscape, in particular the waiting point at N=126 is yet unexplored and will remain largely inaccessible to conventional nuclear reaction schemes even at next-generation radioactive beam facilities, underlining the attractive perspectives offered, e.g., by ELI-NP.« less

Maximum production of fermentable sugars from barley straw using optimized soaking in aqueous ammonia (SAA) pretreatment

USDA-ARS?s Scientific Manuscript database

Soaking in aqueous ammonia (SAA) pretreatment was investigated to improve enzymatic digestibility and consequently to increase total fermentable sugar production from barley straw. Various effects of pretreatment process parameters, such as reaction temperature, reaction time, solid:liquid ratio, an...

Transient Kinetics and Quantum Yield Studies of Nanocrystalline α-Phenyl-Substituted Ketones: Sorting Out Reactions from Singlet and Triplet Excited States.

PubMed

Park, Jin H; Chung, Tim S; Hipwell, Vince M; Rivera, Edris A; Garcia-Garibay, Miguel A

2018-06-11

Recent work has shown that diarylmethyl radicals generated by pulsed laser excitation in nanocrystalline (NC) suspensions of tetraarylacetones constitute a valuable probe for the detailed mechanistic analysis of the solid-state photodecarbonylation reaction. Using a combination of reaction quantum yields and laser flash photolysis in nanocrystalline suspensions of ketones with different substituents on one of the α-carbons we are able to suggest with confidence that a significant fraction of the initial α-cleavage reaction takes place from the ketone singlet excited state, that the originally formed diarylmethyl-acyl radical pair loses CO in the crystal with time constants in the sub-nanosecond regime, and that the secondary bis(diarylmethyl) triplet radical pair has a lifetime limited by the rate of intersystem crossing of ca. 70 ns.

Synthesis and structural characterization of Co2+ ions doped ZnO nanopowders by solid state reaction through sonication

NASA Astrophysics Data System (ADS)

Babu, B.; Rama Krishna, Ch.; Venkata Reddy, Ch.; Pushpa Manjari, V.; Ravikumar, R. V. S. S. N.

2013-05-01

Cobalt ions doped zinc oxide nanopowder was prepared at room temperature by a novel and simple one step solid-state reaction method through sonication in the presence of a suitable surfactant Sodium Lauryl Sulphate (SLS). The prepared powder was characterized by various spectroscopic techniques. Powder XRD data revealed that the crystal structure belongs to hexagonal and its average crystallite size was evaluated. From optical absorption data, crystal fields (Dq), inter-electronic repulsion parameters (B, C) were evaluated. By correlating optical and EPR spectral data, the site symmetry of Co2+ ion in the host lattice was determined as octahedral. Photoluminescence spectra exhibited the emission bands in ultraviolet and blue regions. The CIE chromaticity coordinates are also evaluated from the emission spectrum. FT-IR spectra showed the characteristic vibrational bands of Znsbnd O.

Complex impedance analyses and magnetoelectric effect in ferrite ferroelectric composite ceramics

NASA Astrophysics Data System (ADS)

Patankar, K. K.; Kanade, S. A.; Padalkar, D. S.; Chougule, B. K.

2007-02-01

Magnetoelectric (ME) composites yBa0.8Pb0.2TiO3 (1-y)CuFe2O4 are prepared by ceramic method. The component phases are prepared from two different routes, viz. CuFe2O4 (ferrite phase) is prepared by oxalate precursor route and Ba0.8Pb0.2TiO3 (ferroelectric phase) by solid-state reaction route. No intermediate phases are observed in the composites containing these ferrite and ferroelectric phases. ME conversion factor (measure of ME effect) is found to be enhanced compared to those reported in the composites, in which the component phases were prepared by only one route, i.e. solid-state reaction route. The results on ME conversion are well accounted by measuring the complex impedance and analyzing their Nyquist plots.

A promising red-emitting phosphor for white-light-emitting diodes prepared by a modified solid-state reaction

NASA Astrophysics Data System (ADS)

Ren, Fuqiang; Chen, Donghua

2010-02-01

Using urea, boric acid and polyethylene glycol (PEG) as auxiliary reagents, the novel red-emitting phosphors Ca 19Zn 2 (PO 4) 14:Eu 3+ have been successfully synthesized by a modified solid-state reaction. Thermogravimetric (TG) analysis, X-ray diffraction (XRD), transmission electron microscopy (TEM) and photoluminescence (PL) spectra were used to characterize the resulting phosphors. The dependence of the photoluminescence properties of Ca 19Zn 2 (PO 4) 14:Eu 3+ phosphors upon urea, boric acid and PEG concentration and the quadric-sintered temperature were investigated. Luminescent measurements showed that the phosphors can be efficiently excited by ultraviolet (UV) to visible region, emitting a red light with a peak wavelength of 616 nm. The material has potential application as a fluorescent material for ultraviolet light-emitting diodes (UV-LEDs).

LiCoPO4 cathode from a CoHPO4·xH2O nanoplate precursor for high voltage Li-ion batteries

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

Choi, Daiwon; Li, Xiaolin; Henderson, Wesley A.

2016-02-01

Highly crystalline LiCoPO4/C cathode has been synthesized without any impurities via single step solid-state reaction using CoHPO4xH2O nanoplates as a precursor obtained by simple precipitation route. The electrochemical test shows specific capacity as high as 125mAh/g at charge/discharge rate of C/10. Synthesis approach for obtaining CoHPO4xH2O nanoplate precursor and final LiCoPO4/C cathode using single step solid-state reaction have been characterized using X-ray diffraction, thermos gravimetric analyses (TGA) – differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The electrochemical test and cycling stability using different electrolytes, additive and separator have been investigated.

A new chemical route to a hybrid nanostructure: room-temperature solid-state reaction synthesis of Ag@AgCl with efficient photocatalysis.

PubMed

Hu, Pengfei; Cao, Yali

2012-08-07

The room-temperature solid-state chemical reaction technique has been used to synthesize the silver nanoparticle-loaded semiconductor silver@silver chloride for the first time. It has the advantages of convenient operation, lower cost, less pollution, and mass production. This simple technique created a wide array of nanosized silver particles which had a strong surface plasmon resonance effect in the visible region, and built up an excellent composite structure of silver@silver chloride hybrid which exhibited high photocatalytic activity and stability towards decomposition of organic methyl orange under visible-light illumination. Moreover, this work achieved the control of composition of the silver@silver chloride composite simply by adjusting the feed ratio of reactants. It offers an alternative method for synthesising metal@semiconductor composites.

A Rechargeable Al/S Battery with an Ionic-Liquid Electrolyte.

PubMed

Gao, Tao; Li, Xiaogang; Wang, Xiwen; Hu, Junkai; Han, Fudong; Fan, Xiulin; Suo, Liumin; Pearse, Alex J; Lee, Sang Bok; Rubloff, Gary W; Gaskell, Karen J; Noked, Malachi; Wang, Chunsheng

2016-08-16

Aluminum metal is a promising anode material for next generation rechargeable batteries owing to its abundance, potentially dendrite-free deposition, and high capacity. The rechargeable aluminum/sulfur (Al/S) battery is of great interest owing to its high energy density (1340 Wh kg(-1) ) and low cost. However, Al/S chemistry suffers poor reversibility owing to the difficulty of oxidizing AlSx . Herein, we demonstrate the first reversible Al/S battery in ionic-liquid electrolyte with an activated carbon cloth/sulfur composite cathode. Electrochemical, spectroscopic, and microscopic results suggest that sulfur undergoes a solid-state conversion reaction in the electrolyte. Kinetics analysis identifies that the slow solid-state sulfur conversion reaction causes large voltage hysteresis and limits the energy efficiency of the system. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid-state chemistry and particle engineering with supercritical fluids in pharmaceutics.

PubMed

Pasquali, Irene; Bettini, Ruggero; Giordano, Ferdinando

2006-03-01

The present commentary aims to review the modern and innovative strategies in particle engineering by the supercritical fluid technologies and it is principally concerned with the aspects of solid-state chemistry. Supercritical fluids based processes for particle production have been proved suitable for controlling solid-state, morphology and particle size of pharmaceuticals, in some cases on an industrial scale. Supercritical fluids should be considered in a prominent position in the development processes of drug products for the 21st century. In this respect, this innovative technology will help in meeting the more and more stringent requirements of regulatory authorities in terms of solid-state characterisation and purity, and environmental acceptability.

Feedbacks between microphysics and photochemical aging in viscous aerosol

NASA Astrophysics Data System (ADS)

Dou, Jing; Corral Arroyo, Pablo; Alpert, Peter A.; Ammann, Markus; Peter, Thomas; Krieger, Ulrich K.

2017-04-01

Fe(III)-citrate complex photochemistry, which plays an important role in aerosol aging, especially in lower troposphere, has been widely recognized in both solution and solid states. It can get excited by light below about 500 nm, inducing the oxidation of carboxylate ligands and the production of peroxides (e.g., OH•, HO2•), which have a significant impact on the climate, air quality and health. Recently, there is literature reporting that aqueous aerosol particles may attain highly viscous, semi-solid or even glassy physical states under a wide range of atmospheric conditions. However, systematic studies on the effect of high viscosity on photochemical processes are scarce. In this research, mass and size changes of a single, aqueous Fe(III)-citrate/citric acid particle levitated in an electrodynamic balance (EDB) are tracked during photochemical processing. We observe an overall mass loss during photochemical processing due to evaporation of volatile (e.g., CO2) and semi-volatile (e.g., ketones) compounds. It is known that relative humidity and temperature strongly effects the viscosity of citric acid. Hence, under light intensities large enough not limiting photochemical processing (at a wavelength of either 375 nm or 473 nm), the quasi-steady state evaporation rate in our experiments depends on relative humidity and temperature. The same holds true for the characteristic time scale for reaching thermodynamic equilibrium after switching off the light source. We are focusing on the high viscosity case (i.e., reduced molecular mobility and low water content), which slows down the transport of products but can also affect chemical reaction rates (e.g., initial absorption process, charge and energy transfer). Data are compared to kinetic modeling and diffusivities for semi-volatile compounds are estimated aiming at a more detailed understanding of the feedbacks between microphysics and photochemical aging.

State-of-technology for joining TD-NiCr sheet

NASA Technical Reports Server (NTRS)

Holko, K. H.; Moore, T. J.; Gyorgak, C. A.

1972-01-01

At the current state-of-technology there are many joining processes that can be used to make sound welds in TD-NiCr sheet. Some of these that are described in this report are electron beam welding, gas-tungsten arc welding, diffusion welding, resistance spot welding, resistance seam welding, and brazing. The strengths of the welds made by the various processes show considerable variation, especially at elevated temperatures. Most of the fusion welding processes tend to give weak welds at elevated temperatures (with the exception of fusion-type resistance spotwelds). However, solid-state welds have been made with parent metal properties. The process used for a specific application will be dictated by the specific joint requirements. In highly stressed joints at elevated temperatures, one of the solid-state processes, such as DFW, RSW (solid-state or fusion), and RSEW, offer the most promise.

Prediction of crosslink density of solid propellant binders. [curing of elastomers

NASA Technical Reports Server (NTRS)

Marsh, H. E., Jr.

1976-01-01

A quantitative theory is outlined which allows calculation of crosslink density of solid propellant binders from a small number of predetermined parameters such as the binder composition, the functionality distributions of the ingredients, and the extent of the curing reaction. The parameter which is partly dependent on process conditions is the extent of reaction. The proposed theoretical model is verified by independent measurement of effective chain concentration and sol and gel fractions in simple compositions prepared from model compounds. The model is shown to correlate tensile data with composition in the case of urethane-cured polyether and certain solid propellants. A formula for the branching coefficient is provided according to which if one knows the functionality distributions of the ingredients and the corresponding equivalent weights and can measure or predict the extent of reaction, he can calculate the branching coefficient of such a system for any desired composition.

Solid anaerobic digestion: State-of-art, scientific and technological hurdles.

PubMed

André, Laura; Pauss, André; Ribeiro, Thierry

2018-01-01

In this paper, a state-of-art about solid anaerobic digestion (AD), focused on recent progress and trends of research is proposed. Solid anaerobic digestion should be the most appropriate process for degradation of by-products with high total solid (TS) content, especially lignocellulosic materials like agricultural waste (straw, manure), household waste and food waste. Solid AD is already widely used in waste water treatment plant for treating plant for sewage sludge but could be more developed for lignocellulosic materials with high TS content. Many research works were carried out in Europe on solid AD, focused on current hurdles (BMP, codigestion, inhibition, microbial population, rheology, water transfers, inoculum, etc.) in order to optimize the solid AD process. In conclusion, hurdles of solid AD process should and must be solved in order to propose better productivity and profitability of such system operating with high TS content (>15%), favouring reliable industrial processes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effects of gravity reduction on phase equilibria. Part 1: Unary and binary isostructural solids

NASA Technical Reports Server (NTRS)

Larson, D. J., Jr.

1975-01-01

Analysis of the Skylab II M553 Experiment samples resulted in the hypothesis that the reduced gravity environment was altering the melting and solidification reactions. A theoretical study was conducted to define the conditions under which such alteration of phase relations is feasible, determine whether it is restricted to space processing, and, if so, ascertain which alloy systems or phase reactions are most likely to demonstrate such effects. Phase equilibria of unary and binary systems with a single solid phase (unary and isomorphous) were considered.

Sol-gel analogous aminolysis-ammonolysis of chlorosilanes to chlorine-free Si/(C)/N-materials.

PubMed

Wiltzsch, Conny; Wagler, Jörg; Roewer, Gerhard; Kroke, Edwin

2009-07-28

Large amounts of chlorosilanes, especially SiCl4 and CH3SiCl3, are produced as side-products of the industrial fabrication of solar or electronic grade silicon and the Müller-Rochow process. It was a goal of the present study to transform these compounds into useful chlorine-free precursors for Si/(C)/N ceramics via a sol-gel analogous liquid processing route. Chlorine substitution of the chlorosilanes (mixtures) with diethylamine did not yield chlorine-free products, complete reactions are only possible with lithium diethylamide. However, aminolyses with n-propylamine were successful. Transamination with ammonia was not possible with diethylaminosilanes but was with n-propylaminosilanes in various solvents. This result was attributed to steric reasons and polar interactions of the N-H groups. Colourless solid or liquid polysilazanes were obtained, depending on the silane (mixture) and the solvent. Transamination reactions of CH3Si(NH-n-Pr)3 in chloroform reproducibly yielded a cage-like oligosilazane of the composition (CH3)9Si9(NH)12N. Single crystal X-ray structure analysis revealed a seven-cyclic cluster containing four six- and three ten-membered silazane rings. This unique silazane cage as well as the other aminosilanes and the silazanes were comprehensively characterised using multi-nuclear solid state and solution NMR, elemental analyses and thermal gravimetry (TGA).

Exploration and exploitation of homologous series of bis(acrylamido)alkanes containing pyridyl and phenyl groups: β-sheet versus two-dimensional layers in solid-state photochemical [2 + 2] reactions.

PubMed

Garai, Mousumi; Biradha, Kumar

2015-09-01

The homologous series of phenyl and pyridyl substituted bis(acrylamido)alkanes have been synthesized with the aim of systematic analysis of their crystal structures and their solid-state [2 + 2] reactivities. The changes in the crystal structures with respect to a small change in the molecular structure, that is by varying alkyl spacers between acrylamides and/or by varying the end groups (phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl) on the C-terminal of the amide, were analyzed in terms of hydrogen-bonding interference (N-H⋯Npy versus N-H⋯O=C) and network geometries. In this series, a greater tendency towards the formation of N-H⋯O hydrogen bonds (β-sheets and two-dimensional networks) over N-H⋯N hydrogen bonds was observed. Among all the structures seven structures were found to have the required alignments of double bonds for the [2 + 2] reaction such that the formations of single dimer, double dimer and polymer are facilitated. However, only four structures were found to exhibit such a solid-state [2 + 2] reaction to form a single dimer and polymers. The two-dimensional hydrogen-bonding layer via N-H⋯O hydrogen bonds was found to promote solid-state [2 + 2] photo-polymerization in a single-crystal-to-single-crystal manner. Such two-dimensional layers were encountered only when the spacer between acryl amide moieties is butyl. Only four out of the 16 derivatives were found to form hydrates, two each from 2-pyridyl and 4-pyridyl derivatives. The water molecules in these structures govern the hydrogen-bonding networks by the formation of an octameric water cluster and one-dimensional zigzag water chains. The trends in the melting points and densities were also analyzed.

A new process for converting SO2 to sulfur without generating secondary pollutants through reactions involving CaS and CaSO4.

PubMed

Sohn, H Y; Kim, Byung-Su

2002-07-01

Nonferrous smelters and coal gasification processes generate environmentally harmful sulfur dioxide streams, most of which are treated to produce sulfuric acid with the accompanying problems of market shortage and transportation difficulties. Some sulfur dioxide streams are scrubbed with an alkali solution or a solid substance such as limestone or dolomite, which in turn generates wastes that pose other pollution problems. While the conversion of sulfur dioxide to elemental sulfur has many environmental advantages, no processes exist that are environmentally acceptable and economically viable. A new method for converting sulfur dioxide to elemental sulfur by a cyclic process involving calcium sulfide and calcium sulfate without generating solid wastes has been developed. In this process, calcium sulfate pellets as the starting raw material are reduced by a suitable reducing agent such as hydrogen to produce calcium sulfide pellets, which are used to reduce sulfur dioxide producing elemental sulfur vapor and calcium sulfate. The latter is then reduced to regenerate calcium sulfide. Thermodynamic analysis and experimental results indicated that the CaS-SO2 reaction produces mainly sulfur vapor and solid calcium sulfate and that the gaseous product from the CaSO4-H2 reaction is mainly water vapor. The rates of the two reactions are reasonably rapid in the temperature range 1000-1100 K, and, importantly, the physical strengths and reactivities of the pellets are maintained largely unchanged up to the tenth cycle, the last cycle tested in this work. Sulfur dioxide-containing streams from certain sources, such as the regenerator off-gas from an integrated gasification combined cycle desulfurization unit and new sulfide smelting plants, contain much higher partial pressures of SO2. In these cases, the rate of the first reaction is expected to be proportionally higher than in the test conditions reported in this paper.

Atomic insights into nanoparticle formation of hydroxyfluorinated anatase featuring titanium vacancies

DOE PAGES

Li, Wei; Body, Monique; Legein, Christophe; ...

2016-06-28

Anatase TiO 2 with exposed highly reactive (001) surface is commonly prepared using solution-based synthesis in the presence of a fluorinating agent acting as a structure directing agent. Here, the solvothermal reaction of titanium tetraisopropoxide in the presence of aqueous HF has resulted in the stabilization of an oxyhydroxyfluorinated anatase phase featuring cationic vacancies. In the present work, we have studied its formation mechanism, revealing a solid-state transformation of a highly defective anatase phase having a hydroxyfluoride composition that subsequently evolves through an oxolation reaction into an oxyhydroxyfluoride phase. Importantly, this work confirms that titanium alkoxide precursors can react withmore » HF via a fluorolysis process yielding fluorinated molecular precursors, which further condense to produce new composition and structural features deviating from a well ordered anatase network.« less

Shape-selective synthesis of non-micellar cobalt oxide (CoO) nanomaterials by microwave irradiations

NASA Astrophysics Data System (ADS)

Kundu, Subrata; Jayachandran, M.

2013-04-01

Shape-selective formation of CoO nanoparticles has been developed using a simple one-step in situ non-micellar microwave (MW) heating method. CoO NPs were synthesized by mixing aqueous CoCl2·6H2O solution with poly (vinyl) alcohol (PVA) in the presence of sodium hydroxide (NaOH). The reaction mixture was irradiated using MW for a total time of 2 min. This process exclusively generated different shapes like nanosphere, nanosheet, and nanodendrite structures just by tuning the Co(II) ion to PVA molar ratios and controlling other reaction parameters. The proposed synthesis method is efficient, straightforward, reproducible, and robust. Other than in catalysis, these cobalt oxide nanomaterials can be used for making pigments, battery materials, for developing solid state sensors, and also as an anisotropy source for magnetic recording.

Irradiation resistance of silicon carbide joint at light water reactor–relevant temperature

DOE PAGES

Koyanagi, T.; Katoh, Y.; Kiggans, J. O.; ...

2017-03-10

We fabricated and irradiated monolithic silicon carbide (SiC) to SiC plate joints with neutrons at 270–310 °C to 8.7 dpa for SiC. The joining methods included solid state diffusion bonding using titanium and molybdenum interlayers, SiC nanopowder sintering, reaction sintering with a Ti-Si-C system, and hybrid processing of polymer pyrolysis and chemical vapor infiltration (CVI). All the irradiated joints exhibited apparent shear strength of more than 84 MPa on average. Significant irradiation-induced cracking was found in the bonding layers of the Ti and Mo diffusion bonds and Ti-Si-C reaction sintered bond. Furthermore, the SiC-based bonding layers of the SiC nanopowdermore » sintered and hybrid polymer pyrolysis and CVI joints all showed stable microstructure following the irradiation.« less

Multistep Reduction Kinetics of Fine Iron Ore with Carbon Monoxide in a Micro Fluidized Bed Reaction Analyzer

NASA Astrophysics Data System (ADS)

Chen, Hongsheng; Zheng, Zhong; Chen, Zhiwei; Yu, Wenzhou; Yue, Junrong

2017-04-01

The reduction kinetics of Brazilian hematite by CO is investigated in a Micro Fluidized Bed Reaction Analyzer (MFBRA) using an analyzing method based on Johnson-Mehl-Avrami (JMA) model at temperatures of 973 K (700 °C), 1023 K (750 °C), 1073 K (800 °C), and 1123 K (850 °C). The solid products at different reduction stages are evaluated by SEM/EDS and XRD technologies. Results indicate that the reduction process is better to be discussed in terms of a parallel reaction model that consists of the reactions of hematite to wüstite and wüstite to iron, rather than a stepwise route. Meanwhile, the controlling mechanism of the reduction process is found to vary with temperature and the degree of conversion. The overall process is controlled by the gas-solid reaction occurring at the iron/wüstite interface in the initial stages, and then is limited by the nucleation of wüstite, and finally shifts to diffusion control. Moreover, the reactions of hematite to wüstite and wüstite to iron take place simultaneously but with different time dependences, and the apparent activation energies of hematite to wüstite and wüstite to iron are determined as 83.61 and 80.40 KJ/mol, respectively.

Detection of different oxidation states of individual manganese porphyrins during their reaction with oxygen at a solid/liquid interface.

PubMed

den Boer, Duncan; Li, Min; Habets, Thomas; Iavicoli, Patrizia; Rowan, Alan E; Nolte, Roeland J M; Speller, Sylvia; Amabilino, David B; De Feyter, Steven; Elemans, Johannes A A W

2013-07-01

Manganese porphyrins have been extensively investigated as model systems for the natural enzyme cytochrome P450 and as synthetic oxidation catalysts. Here, we report single-molecule studies of the multistep reaction of manganese porphyrins with molecular oxygen at a solid/liquid interface, using a scanning tunnelling microscope (STM) under environmental control. The high lateral resolution of the STM, in combination with its sensitivity to subtle differences in the electronic properties of molecules, allowed the detection of at least four distinct reaction species. Real-space and real-time imaging of reaction dynamics enabled the observation of active sites, immobile on the experimental timescale. Conversions between the different species could be tuned by the composition of the atmosphere (argon, air or oxygen) and the surface bias voltage. By means of extensive comparison of the results to those obtained by analogous solution-based chemistry, we assigned the observed species to the starting compound, reaction intermediates and products.

Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations

DOE PAGES

Zhu, Yizhou; He, Xingfeng; Mo, Yifei

2015-10-06

First-principles calculations were performed to investigate the electrochemical stability of lithium solid electrolyte materials in all-solid-state Li-ion batteries. The common solid electrolytes were found to have a limited electrochemical window. Our results suggest that the outstanding stability of the solid electrolyte materials is not thermodynamically intrinsic but is originated from kinetic stabilizations. The sluggish kinetics of the decomposition reactions cause a high overpotential leading to a nominally wide electrochemical window observed in many experiments. The decomposition products, similar to the solid-electrolyte-interphases, mitigate the extreme chemical potential from the electrodes and protect the solid electrolyte from further decompositions. With the aidmore » of the first-principles calculations, we revealed the passivation mechanism of these decomposition interphases and quantified the extensions of the electrochemical window from the interphases. We also found that the artificial coating layers applied at the solid electrolyte and electrode interfaces have a similar effect of passivating the solid electrolyte. Our newly gained understanding provided general principles for developing solid electrolyte materials with enhanced stability and for engineering interfaces in all-solid-state Li-ion batteries.« less

Polymerization of phenol by using discharged plasma under hydrothermal state

NASA Astrophysics Data System (ADS)

Mitsugi, M.; Yoshida, A.; Watanabe, H.; Kiyan, T.; Takade, M.; Miyaji, K.; Namihira, T.; Kuwahara, Y.; Akiyama, H.; Hara, M.; Sasaki, M.; Goto, M.

2010-03-01

Supercritical fluid with plasma is a type of green processing media because this technique does not use catalyst and toxic solvents. In this study, we carried out experiments of organic materials in the presence of discharged plasma in sub- and supercritical water to evaluate the possibility for new reactions. For this purpose, we used SUS316 reactor that generates plasma at temperature and pressure up to 573K and 30MPa, respectively. 100 mmol/L aqueous phenol solution was used as starting material. The reactions were carried out at temperature of 523K and under pressure of 25MPa. After a series of reactions, water-soluble, water-insoluble (oily products), solid residue and gaseous product were obtained. For the analysis of these products, HPLC, GC-MS, TOC, GC-TCD and TOF-MS were used. The highest phenol conversion was 16.96% obtained at 523K, 25MPa and with 4000 times discharged plasma. Polymerized phenol was obtained as a product.

In–situ Spatiotemporal Chemical Reactions at Water-Solid Interfacial Processes using Microelectrode Techniques: from Biofilm to Metal Corrosion

EPA Science Inventory

Recent developments in microscale sensors allows the non-destructive and in–situ measurement of both the absolute and changes in chemical concentrations in engineered and natural aquatic systems. Microelectrodes represent a unique tool for studying in–situ chemical reactions in b...

Solid state synthesis of Mn{sub 5}Ge{sub 3} in Ge/Ag/Mn trilayers: Structural and magnetic studies

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

Myagkov, V.G.; Bykova, L.E.; Matsynin, A.A.

The thin-film solid-state reaction between elemental Ge and Mn across chemically inert Ag layers with thicknesses of (0, 0.3, 1 and 2.2 µm) in Ge/Ag/Mn trilayers was studied for the first time. The initial samples were annealed at temperatures between 50 and 500 °C at 50 °C intervals for 1 h. The initiation temperature of the reaction for Ge/Mn (without a Ag barrier layer) was ~ 120 °C and increased slightly up to ~ 250 °C when the Ag barrier layer thickness increased up to 2.2 µm. In spite of the Ag layer, only the ferromagnetic Mn{sub 5}Ge{sub 3} compoundmore » and the Nowotny phase were observed in the initial stage of the reaction after annealing at 500 °C. The cross-sectional studies show that during Mn{sub 5}Ge{sub 3} formation the Ge is the sole diffusing species. The magnetic and cross-sectional transmission electron microscopy (TEM) studies show an almost complete transfer of Ge atoms from the Ge film, via a 2.2 µm Ag barrier layer, into the Mn layer. We attribute the driving force of the long-range transfer to the long-range chemical interactions between reacting Mn and Ge atoms. - Graphical abstract: The direct visualization of the solid state reaction between Mn and Ge across a Ag buffer layer at 500 °C. - Highlights: • The migration of Ge, via an inert 2.2 µm Ag barrier, into a Mn layer. • The first Mn{sub 5}Ge{sub 3} phase was observed in reactions with different Ag layers. • The Ge is the sole diffusing species during Mn{sub 5}Ge{sub 3} formation • The long-range chemical interactions control the Ge atomic transfer.« less

Hydrolysis of ferric chloride in solution

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

Lussiez, G.; Beckstead, L.

1996-11-01

The Detox{trademark} process uses concentrated ferric chloride and small amounts of catalysts to oxidize organic compounds. It is under consideration for oxidizing transuranic organic wastes. Although the solution is reused extensively, at some point it will reach the acceptable limit of radioactivity or maximum solubility of the radioisotopes. This solution could be cemented, but the volume would be increased substantially because of the poor compatibility of chlorides and cement. A process has been developed that recovers the chloride ions as HCl and either minimizes the volume of radioactive waste or permits recycling of the radioactive chlorides. The process involves amore » two-step hydrolysis at atmospheric pressure, or preferably under a slight vacuum, and relatively low temperature, about 200{degrees}C. During the first step of the process, hydrolysis occurs according to the reaction below: FeCl{sub 3 liquid} + H{sub 2}O {r_arrow} FeOCl{sub solid} + 2 HCl{sub gas} During the second step, the hot, solid, iron oxychloride is sprayed with water or placed in contact with steam, and hydrolysis proceeds to the iron oxide according to the following reaction: 2 FeOCl{sub solid} + H{sub 2}O {r_arrow} Fe{sub 2}O{sub 3 solid} + 2 HCl{sub gas}. The iron oxide, which contains radioisotopes, can then be disposed of by cementation or encapsulation. Alternately, these chlorides can be washed off of the solids and can then either be recycled or disposed of in some other way.« less

Solid-state optical refrigeration to sub-100 Kelvin regime

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

Melgaard, Seth D.; Albrecht, Alexander R.; Hehlen, Markus P.

We report that since the first demonstration of net cooling twenty years ago, optical refrigeration of solids has progressed to outperform all other solid-state cooling processes. It has become the first and only solid-state refrigerator capable of reaching cryogenic temperatures, and now the first solid-state cooling below 100 K. Such substantial progress required a multi-disciplinary approach of pump laser absorption enhancement, material characterization and purification, and thermal management. Here we present the culmination of two decades of progress, the record cooling to ≈91K from room temperature.

Solid-state optical refrigeration to sub-100 Kelvin regime

DOE PAGES

Melgaard, Seth D.; Albrecht, Alexander R.; Hehlen, Markus P.; ...

2016-02-05

We report that since the first demonstration of net cooling twenty years ago, optical refrigeration of solids has progressed to outperform all other solid-state cooling processes. It has become the first and only solid-state refrigerator capable of reaching cryogenic temperatures, and now the first solid-state cooling below 100 K. Such substantial progress required a multi-disciplinary approach of pump laser absorption enhancement, material characterization and purification, and thermal management. Here we present the culmination of two decades of progress, the record cooling to ≈91K from room temperature.

Solid-state optical refrigeration to sub-100 Kelvin regime

PubMed Central

Melgaard, Seth D.; Albrecht, Alexander R.; Hehlen, Markus P.; Sheik-Bahae, Mansoor

2016-01-01

Since the first demonstration of net cooling twenty years ago, optical refrigeration of solids has progressed to outperform all other solid-state cooling processes. It has become the first and only solid-state refrigerator capable of reaching cryogenic temperatures, and now the first solid-state cooling below 100 K. Such substantial progress required a multi-disciplinary approach of pump laser absorption enhancement, material characterization and purification, and thermal management. Here we present the culmination of two decades of progress, the record cooling to ≈ 91 K from room temperature. PMID:26847703

Modeling of Blast Furnace with Layered Cohesive Zone

NASA Astrophysics Data System (ADS)

Dong, X. F.; Yu, A. B.; Chew, S. J.; Zulli, P.

2010-04-01

An ironmaking blast furnace (BF) is a moving bed reactor involving counter-, co-, and cross-current flows of gas, powder, liquids, and solids, coupled with heat exchange and chemical reactions. The behavior of multiple phases directly affects the stability and productivity of the furnace. In the present study, a mathematical model is proposed to describe the behavior of fluid flow, heat and mass transfer, as well as chemical reactions in a BF, in which gas, solid, and liquid phases affect each other through interaction forces, and their flows are competing for the space available. Process variables that characterize the internal furnace state, such as reduction degree, reducing gas and burden concentrations, as well as gas and condensed phase temperatures, have been described quantitatively. In particular, different treatments of the cohesive zone (CZ), i.e., layered, isotropic, and anisotropic nonlayered, are discussed, and their influence on simulation results is compared. The results show that predicted fluid flow and thermochemical phenomena within and around the CZ and in the lower part of the BF are different for different treatments. The layered CZ treatment corresponds to the layered charging of burden and naturally can predict the CZ as a gas distributor and liquid generator.

Highly time-resolved imaging of combustion and pyrolysis product concentrations in solid fuel combustion: NO formation in a burning cigarette.

PubMed

Zimmermann, Ralf; Hertz-Schünemann, Romy; Ehlert, Sven; Liu, Chuan; McAdam, Kevin; Baker, Richard; Streibel, Thorsten

2015-02-03

The highly dynamic, heterogeneous combustion process within a burning cigarette was investigated by a miniaturized extractive sampling probe (microprobe) coupled to photoionization mass spectrometry using soft laser single photon ionization (SPI) for online real-time detection of molecular ions of combustion and pyrolysis products. Research cigarettes smoked by a smoking machine are used as a reproducible model system for solid-state biomass combustion, which up to now is not addressable by current combustion-diagnostic tools. By combining repetitively recorded online measurement sequences from different sampling locations in an imaging approach, highly time- and space-resolved quantitative distribution maps of, e.g., nitrogen monoxide, benzene, and oxygen concentrations were obtained at a near microscopic level. The obtained quantitative distribution maps represent a time-resolved, movie-like imaging of the respective compound's formation and destruction zones in the various combustion and pyrolysis regions of a cigarette during puffing. Furthermore, spatially resolved kinetic data were ascertainable. The here demonstrated methodology can also be applied to various heterogenic combustion/pyrolysis or reaction model systems, such as fossil- or biomass-fuel pellet combustion or to a positional resolved analysis of heterogenic catalytic reactions.

Energy transfer and radiative recombination processes in (Gd, Lu)3Ga3Al2O12:Pr3+ scintillators

NASA Astrophysics Data System (ADS)

Wu, Yuntao; Ren, Guohao

2013-10-01

(GdxLu3-x)Ga3Al2O12:0.3 at.%Pr (x = 0.025, 0.05, 0.1, 0.2, 0.4, 0.6) (GLGAG:Pr) polycrystalline powders are prepared by solid-state reaction method. To better understand the luminescence mechanism, the optical diffuse reflectance, photoluminescence emission and excitation, X-ray excited luminescence spectra and decay kinetics of GLGAG:Pr were investigated in detailed, allowing the determination of energy transfer from 5d state of Pr3+ to 4f state of Gd3+, and the non-radiative relaxation from 5d to 4f state of Pr3+. Besides, the former process plays more negative role in the emission quenching of GLGAG:Pr than later one. Pr3+ ion is regarded as an ineffective activation ion in Gd-based multicomponent aluminate garnets. In addition, the wavelength-resolved thermoluminescence spectra of GLGAG:Pr were studied after UV and X-ray irradiation. It is revealed that the localized recombination processes from electron traps to lower lying 4f levels of Pr3+ occurs without populating the higher 5d levels of Pr3+.

Evolution of material properties during free radical photopolymerization

NASA Astrophysics Data System (ADS)

Wu, Jiangtao; Zhao, Zeang; Hamel, Craig M.; Mu, Xiaoming; Kuang, Xiao; Guo, Zaoyang; Qi, H. Jerry

2018-03-01

Photopolymerization is a widely used polymerization method in many engineering applications such as coating, dental restoration, and 3D printing. It is a complex chemical and physical process, through which a liquid monomer solution is rapidly converted to a solid polymer. In the most common free-radical photopolymerization process, the photoinitiator in the solution is exposed to light and decomposes into active radicals, which attach to monomers to start the polymerization reaction. The activated monomers then attack Cdbnd C double bonds of unsaturated monomers, which leads to the growth of polymer chains. With increases in the polymer chain length and the average molecular weight, polymer chains start to connect and form a network structure, and the liquid polymer solution becomes a dense solid. During this process, the material properties of the cured polymer change dramatically. In this paper, experiments and theoretical modeling are used to investigate the free-radical photopolymerization reaction kinetics, material property evolution and mechanics during the photopolymerization process. The model employs the first order chemical reaction rate equations to calculate the variation of the species concentrations. The degree of monomer conversion is used as an internal variable that dictates the mechanical properties of the cured polymer at different curing states, including volume shrinkage, glass transition temperature, and nonlinear viscoelastic properties. To capture the nonlinear behavior of the cured polymer under low temperature and finite deformation, a multibranch nonlinear viscoelastic model is developed. A phase evolution model is used to describe the mechanics of the coupling between the crosslink network evolution and mechanical loading during the curing process. The comparison of the model and the experimental results indicates that the model can capture property changes during curing. The model is further applied to investigate the internal stress of a thick sample caused by volume shrinkage during photopolymerization. Changes in the conversion degree gradient and the internal stress during photopolymerization are determined using FEM simulation. The model can be extended to many photocuring processes, such as photopolymerization 3D printing, surface coating and automotive part curing processes.

Dynamics and control of gold-encapped gallium arsenide nanowires imaged by 4D electron microscopy

PubMed Central

Chen, Bin; Fu, Xuewen; Tang, Jau; Lysevych, Mykhaylo; Tan, Hark Hoe; Jagadish, Chennupati; Zewail, Ahmed H.

2017-01-01

Eutectic-related reaction is a special chemical/physical reaction involving multiple phases, solid and liquid. Visualization of a phase reaction of composite nanomaterials with high spatial and temporal resolution provides a key understanding of alloy growth with important industrial applications. However, it has been a rather challenging task. Here, we report the direct imaging and control of the phase reaction dynamics of a single, as-grown free-standing gallium arsenide nanowire encapped with a gold nanoparticle, free from environmental confinement or disturbance, using four-dimensional (4D) electron microscopy. The nondestructive preparation of as-grown free-standing nanowires without supporting films allows us to study their anisotropic properties in their native environment with better statistical character. A laser heating pulse initiates the eutectic-related reaction at a temperature much lower than the melting points of the composite materials, followed by a precisely time-delayed electron pulse to visualize the irreversible transient states of nucleation, growth, and solidification of the complex. Combined with theoretical modeling, useful thermodynamic parameters of the newly formed alloy phases and their crystal structures could be determined. This technique of dynamical control aided by 4D imaging of phase reaction processes on the nanometer-ultrafast time scale opens new venues for engineering various reactions in a wide variety of other systems. PMID:29158393

Calcination and solid state reaction of ceramic-forming components to provide single-phase superconducting materials having fine particle size

DOEpatents

Balachandran, Uthamalingam; Poeppel, Roger B.; Emerson, James E.; Johnson, Stanley A.

1992-01-01

An improved method for the preparation of single phase, fine grained ceramic materials from precursor powder mixtures where at least one of the components of the mixture is an alkali earth carbonate. The process consists of heating the precursor powders in a partial vacuum under flowing oxygen and under conditions where the partial pressure of CO.sub.2 evolved during the calcination is kept to a very low level relative to the oxygen. The process has been found particularly suitable for the preparation of high temperature copper oxide superconducting materials such as YBa.sub.2 Cu.sub.3 O.sub.x "123" and YBa.sub.2 Cu.sub.4 O.sub.8 "124".

Enzymatic lignocellulose hydrolysis: Improved cellulase productivity by insoluble solids recycling

PubMed Central

2013-01-01

Background It is necessary to develop efficient methods to produce renewable fuels from lignocellulosic biomass. One of the main challenges to the industrialization of lignocellulose conversion processes is the large amount of cellulase enzymes used for the hydrolysis of cellulose. One method for decreasing the amount of enzyme used is to recycle the enzymes. In this study, the recycle of enzymes associated with the insoluble solid fraction after the enzymatic hydrolysis of cellulose was investigated for pretreated corn stover under a variety of recycling conditions. Results It was found that a significant amount of cellulase activity could be recovered by recycling the insoluble biomass fraction, and the enzyme dosage could be decreased by 30% to achieve the same glucose yields under the most favorable conditions. Enzyme productivity (g glucose produced/g enzyme applied) increased between 30 and 50% by the recycling, depending on the reaction conditions. While increasing the amount of solids recycled increased process performance, the methods applicability was limited by its positive correlation with increasing total solids concentrations, reaction volumes, and lignin content of the insoluble residue. However, increasing amounts of lignin rich residue during the recycle did not negatively impact glucose yields. Conclusions To take advantage of this effect, the amount of solids recycled should be maximized, based on a given processes ability to deal with higher solids concentrations and volumes. Recycling of enzymes by recycling the insoluble solids fraction was thus shown to be an effective method to decrease enzyme usage, and research should be continued for its industrial application. PMID:23336604

Introduction of oxygen vacancies and fluorine into TiO{sub 2} nanoparticles by co-milling with PTFE

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

Senna, Mamoru, E-mail: senna@applc.keio.ac.jp; Sepelak, Vladimir; Shi, Jianmin

2012-03-15

Solid-state processes of introducing oxygen vacancies and transference of fluorine to n-TiO{sub 2} nanoparticles by co-milling with poly(tetrafluoroethylene) (PTFE) powder were examined by diffuse reflectance spectroscopy (DRS) of UV, visual, near- and mid-IR regions, thermal analyses (TG-DTA), energy-dispersive X-ray spectroscopy (EDXS), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD). The broad absorption peak at around 8800 cm{sup -1} (1140 nm) was attributed to the change in the electronic states, viz. electrons trapped at the oxygen vacancies (Vo) and d-d transitions of titanium ions. Incorporation of fluorine into n-TiO{sub 2} was concentrated at the near surfacemore » region and amounted to ca. 40 at% of the total fluorine in PTFE, after co-milling for 3 h, as confirmed by the F1s XPS spectrum. The overall atomic ratio, F/Ti, determined by EDXS was 0.294. By combining these analytical results, a mechanism of the present solid state processes at the boundary between PTFE and n-TiO{sub 2} was proposed. The entire process is triggered by the partial oxidative decomposition of PTFE. This is accompanied by the abstraction of oxygen atoms from the n-TiO{sub 2} lattices. Loss of the oxygen atoms results in the formation of the diverse states of locally distorted coordination units of titania, i.e. TiO{sub 6-n}Vo{sub n}, located at the near surface region. This leads subsequent partial ligand exchange between F and O, to incorporate fluorine preferentially to the near surface region of n-TiO{sub 2} particles, where local non-crystalline states predominate. - Graphical abstract: Scheme of the reaction processes: (a) pristine mixture, (b) oxygen abstraction from TiO{sub 2} and (c) fluorine migration from PTFE to TiO{sub 2}. Highlights: Transfer of fluorine from PTFE to n-TiO{sub 2} in a dry solid state process was confirmed. Black-Right-Pointing-Pointer 40% of F in PTFE was incorporated to the near surface region of n-TiO{sub 2} nanoparticles. Black-Right-Pointing-Pointer The transfer process is triggered by the oxidative decomposition of PTFE. Black-Right-Pointing-Pointer Fluorine incorporation is mediated by the formation of oxygen vacancies. Black-Right-Pointing-Pointer The sequential mechanisms are verified by XPS, EDXS, HRTEM, TG and DRS.« less

Three-Dimensional Modeling of Flow and Thermochemical Behavior in a Blast Furnace

NASA Astrophysics Data System (ADS)

Shen, Yansong; Guo, Baoyu; Chew, Sheng; Austin, Peter; Yu, Aibing

2015-02-01

An ironmaking blast furnace (BF) is a complex high-temperature moving bed reactor involving counter-, co- and cross-current flows of gas, liquid and solid, coupled with heat and mass exchange and chemical reactions. Two-dimensional (2D) models were widely used for understanding its internal state in the past. In this paper, a three-dimensional (3D) CFX-based mathematical model is developed for describing the internal state of a BF in terms of multiphase flow and the related thermochemical behavior, as well as process indicators. This model considers the intense interactions between gas, solid and liquid phases, and also their competition for the space. The model is applied to a BF covering from the burden surface at the top to the liquid surface in the hearth, where the raceway cavity is considered explicitly. The results show that the key in-furnace phenomena such as flow/temperature patterns and component distributions of solid, gas and liquid phases can be described and characterized in different regions inside the BF, including the gas and liquids flow circumferentially over the 3D raceway surface. The in-furnace distributions of key performance indicators such as reduction degree and gas utilization can also be predicted. This model offers a cost-effective tool to understand and control the complex BF flow and performance.

Prospects of Optical Single Atom Detection in Noble Gas Solids for Measurements of Rare Nuclear Reactions

NASA Astrophysics Data System (ADS)

Singh, Jaideep; Bailey, Kevin G.; Lu, Zheng-Tian; Mueller, Peter; O'Connor, Thomas P.; Xu, Chen-Yu; Tang, Xiaodong

2013-04-01

Optical detection of single atoms captured in solid noble gas matrices provides an alternative technique to study rare nuclear reactions relevant to nuclear astrophysics. I will describe the prospects of applying this approach for cross section measurements of the ^22Ne,,),25Mg reaction, which is the crucial neutron source for the weak s process inside of massive stars. Noble gas solids are a promising medium for the capture, detection, and manipulation of atoms and nuclear spins. They provide stable and chemically inert confinement for a wide variety of guest species. Because noble gas solids are transparent at optical wavelengths, the guest atoms can be probed using lasers. We have observed that ytterbium in solid neon exhibits intersystem crossing (ISC) which results in a strong green fluorescence (546 nm) under excitation with blue light (389 nm). Several groups have observed ISC in many other guest-host pairs, notably magnesium in krypton. Because of the large wavelength separation of the excitation light and fluorescence light, optical detection of individual embedded guest atoms is feasible. This work is supported by DOE, Office of Nuclear Physics, under contract DE-AC02-06CH11357.

Short residence time coal liquefaction process including catalytic hydrogenation

DOEpatents

Anderson, R.P.; Schmalzer, D.K.; Wright, C.H.

1982-05-18

Normally solid dissolved coal product and a distillate liquid product are produced by continuously passing a feed slurry comprising raw feed coal and a recycle solvent oil and/or slurry together with hydrogen to a preheating-reaction zone, the hydrogen pressure in the preheating-reaction zone being at least 1,500 psig (105 kg/cm[sup 2]), reacting the slurry in the preheating-reaction zone at a temperature in the range of between about 455 and about 500 C to dissolve the coal to form normally liquid coal and normally solid dissolved coal. A total slurry residence time is maintained in the reaction zone ranging from a finite value from about 0 to about 0.2 hour, and reaction effluent is continuously and directly contacted with a quenching fluid to substantially immediately reduce the temperature of the reaction effluent to below 425 C to substantially inhibit polymerization so that the yield of insoluble organic matter comprises less than 9 weight percent of said feed coal on a moisture-free basis. The reaction is performed under conditions of temperature, hydrogen pressure and residence time such that the quantity of distillate liquid boiling within the range C[sub 5]-454 C is an amount at least equal to that obtainable by performing the process under the same condition except for a longer total slurry residence time, e.g., 0.3 hour. Solvent boiling range liquid is separated from the reaction effluent and recycled as process solvent. The amount of solvent boiling range liquid is sufficient to provide at least 80 weight percent of that required to maintain the process in overall solvent balance. 6 figs.

Short residence time coal liquefaction process including catalytic hydrogenation

DOEpatents

Anderson, Raymond P.; Schmalzer, David K.; Wright, Charles H.

1982-05-18

Normally solid dissolved coal product and a distillate liquid product are produced by continuously passing a feed slurry comprising raw feed coal and a recycle solvent oil and/or slurry together with hydrogen to a preheating-reaction zone (26, alone, or 26 together with 42), the hydrogen pressure in the preheating-reaction zone being at least 1500 psig (105 kg/cm.sup.2), reacting the slurry in the preheating-reaction zone (26, or 26 with 42) at a temperature in the range of between about 455.degree. and about 500.degree. C. to dissolve the coal to form normally liquid coal and normally solid dissolved coal. A total slurry residence time is maintained in the reaction zone ranging from a finite value from about 0 to about 0.2 hour, and reaction effluent is continuously and directly contacted with a quenching fluid (40, 68) to substantially immediately reduce the temperature of the reaction effluent to below 425.degree. C. to substantially inhibit polymerization so that the yield of insoluble organic matter comprises less than 9 weight percent of said feed coal on a moisture-free basis. The reaction is performed under conditions of temperature, hydrogen pressure and residence time such that the quantity of distillate liquid boiling within the range C.sub.5 -454.degree. C. is an amount at least equal to that obtainable by performing the process under the same condition except for a longer total slurry residence time, e.g., 0.3 hour. Solvent boiling range liquid is separated from the reaction effluent (83) and recycled as process solvent (16). The amount of solvent boiling range liquid is sufficient to provide at least 80 weight percent of that required to maintain the process in overall solvent balance.

Synthesis of potassium ferrate using residual ferrous sulfate as iron bearing material

NASA Astrophysics Data System (ADS)

Kanari, N.; Filippov, L.; Diot, F.; Mochón, J.; Ruiz-Bustinza, I.; Allain, E.; Yvon, J.

2013-03-01

This paper summarizes the results obtained during potassium ferrate (K2FeVIO4) synthesis which is a high added value material. This compound that contains iron in the rare hexavalent state is becoming a substance of growing importance for the water and effluent treatment industries. This is due to its multi-functional nature (oxidation, flocculation, elimination of heavy metals, decomposition of organic matter, etc.). The most well known synthesis methods for potassium ferrate synthesis are those involving the chemical and/or electrochemical oxidation of iron (II) and (III) from aqueous solutions having a high alkali concentration. These methods are generally characterized by a low FeVI efficiency due to the reaction of the potassium ferrate with water, leading to the reduction of FeVI into FeIII. Concerning the work pertinent to this paper, the synthesis of K2FeVIO4 was achieved by a simultaneous reaction of two solids (iron sulfate and KOH) and one gaseous oxidant (chlorine). The synthesis process is performed in a rotary reactor at room temperature and the global synthesis reaction is exothermic. The effects of different experimental parameters on the potassium ferrate synthesis are investigated to determine the optimal conditions for the process.

A study of hydriding kinetics of metal hydrides using a physically based model

NASA Astrophysics Data System (ADS)

Voskuilen, Tyler G.

The reaction of hydrogen with metals to form metal hydrides has numerous potential energy storage and management applications. The metal hydrogen system has a high volumetric energy density and is often reversible with a high cycle life. The stored hydrogen can be used to produce energy through combustion, reaction in a fuel cell, or electrochemically in metal hydride batteries. The high enthalpy of the metal-hydrogen reaction can also be used for rapid heat removal or delivery. However, improving the often poor gravimetric performance of such systems through the use of lightweight metals usually comes at the cost of reduced reaction rates or the requirement of pressure and temperature conditions far from the desired operating conditions. In this work, a 700 bar Sievert system was developed at the Purdue Hydrogen Systems Laboratory to study the kinetic and thermodynamic behavior of high pressure hydrogen absorption under near-ambient temperatures. This system was used to determine the kinetic and thermodynamic properties of TiCrMn, an intermetallic metal hydride of interest due to its ambient temperature performance for vehicular applications. A commonly studied intermetallic hydride, LaNi5, was also characterized as a base case for the phase field model. The analysis of the data obtained from such a system necessitate the use of specialized techniques to decouple the measured reaction rates from experimental conditions. These techniques were also developed as a part of this work. Finally, a phase field model of metal hydride formation in mass-transport limited interstitial solute reactions based on the regular solution model was developed and compared with measured kinetics of LaNi5 and TiCrMn. This model aided in the identification of key reaction features and was used to verify the proposed technique for the analysis of gas-solid reaction rates determined volumetrically. Additionally, the phase field model provided detailed quantitative predictions of the effects of multidimensional phase growth and transitions between rate-limiting processes on the experimentally determined reaction rates. Unlike conventional solid state reaction analysis methods, this model relies fully on rate parameters based on the physical mechanisms occurring in the hydride reaction and can be extended to reactions in any dimension.

KENNEDY SPACE CENTER, FLA. - Workers in KSC's Vertical Processing Facility prepare a solid state recorder for installation in a protective enclosure as part of the prelaunch preparations for STS-82, the second Hubble Space Telescope servicing mission. The digital solid state recorder will replace one of three engineering/science tape recorders on Hubble. The solid state recorder has no moving parts to wear out. It also is more flexible than a reel-to-reel recorder and can store 10 times as much data. Liftoff aboard Discovery is targeted Feb. 11 with a crew of seven.

NASA Image and Video Library

1997-01-16

KENNEDY SPACE CENTER, FLA. - Workers in KSC's Vertical Processing Facility prepare a solid state recorder for installation in a protective enclosure as part of the prelaunch preparations for STS-82, the second Hubble Space Telescope servicing mission. The digital solid state recorder will replace one of three engineering/science tape recorders on Hubble. The solid state recorder has no moving parts to wear out. It also is more flexible than a reel-to-reel recorder and can store 10 times as much data. Liftoff aboard Discovery is targeted Feb. 11 with a crew of seven.

KENNEDY SPACE CENTER, FLA. - Workers in KSC's Vertical Processing Facility install a solid state recorder into a transport assembly in its protective enclosure as part of the prelaunch preparations for STS-82, the second Hubble Space Telescope servicing mission. The digital solid state recorder will replace one of three engineering/science tape recorders on Hubble. The solid state recorder has no moving parts to wear out. It also is more flexible than a reel-to-reel recorder and can store 10 times as much data. Liftoff aboard Discovery is targeted Feb. 11 with a crew of seven.

NASA Image and Video Library

1997-01-16

KENNEDY SPACE CENTER, FLA. - Workers in KSC's Vertical Processing Facility install a solid state recorder into a transport assembly in its protective enclosure as part of the prelaunch preparations for STS-82, the second Hubble Space Telescope servicing mission. The digital solid state recorder will replace one of three engineering/science tape recorders on Hubble. The solid state recorder has no moving parts to wear out. It also is more flexible than a reel-to-reel recorder and can store 10 times as much data. Liftoff aboard Discovery is targeted Feb. 11 with a crew of seven.

Characterization of Pharmaceutical Cocrystals and Salts by Dynamic Nuclear Polarization-Enhanced Solid-State NMR Spectroscopy

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

Zhao, Li; Hanrahan, Michael P.; Chakravarty, Paroma

Multicomponent solids such as cocrystals have emerged as a way to control and engineer the stability, solubility and manufacturability of solid active pharmaceutical ingredients (APIs). Cocrystals are typically formed by solution- or solid-phase reactions of APIs with suitable cocrystal coformers, which are often weak acids. One key structural question about a given multicomponent solid is whether it should be classified as a salt, where the basic API is protonated by the acid, or as a cocrystal, where the API and coformer remain neutral and engage in hydrogen bonding interactions. It has previously been demonstrated that solid-state NMR spectroscopy is amore » powerful probe of structure in cocrystals and salts of APIs, however, the poor sensitivity of solid-state NMR spectroscopy usually restricts the types of experiments that can be performed. Here relayed dynamic nuclear polarization (DNP) was applied to reduce solid-state NMR experiments by one to two orders of magnitude for salts and cocrystals of a complex API. The large sensitivity gains from DNP facilitates rapid acquisition of natural isotopic abundance 13C and 15N solid-state NMR spectra. Critically, DNP enables double resonance 1H-15N solid-state NMR experiments such as 2D 1H-15N HETCOR, 1H-15N CP-build up, 15N{1H} J-resolved/attached proton tests, 1H-15N DIPSHIFT and 1H-15N PRESTO. The latter two experiments allow 1H-15N dipolar coupling constants and H-N bond lengths to be accurately measured, providing an unambiguous assignment of nitrogen protonation state and definitive classification of the multi-component solids as cocrystals or salts. In conclusion, these types of measurements should also be extremely useful in the context of polymorph discrimination, NMR crystallography structure determination and for probing hydrogen bonding in a variety of organic materials.« less

Characterization of Pharmaceutical Cocrystals and Salts by Dynamic Nuclear Polarization-Enhanced Solid-State NMR Spectroscopy

DOE PAGES

Zhao, Li; Hanrahan, Michael P.; Chakravarty, Paroma; ...

2018-02-15

Multicomponent solids such as cocrystals have emerged as a way to control and engineer the stability, solubility and manufacturability of solid active pharmaceutical ingredients (APIs). Cocrystals are typically formed by solution- or solid-phase reactions of APIs with suitable cocrystal coformers, which are often weak acids. One key structural question about a given multicomponent solid is whether it should be classified as a salt, where the basic API is protonated by the acid, or as a cocrystal, where the API and coformer remain neutral and engage in hydrogen bonding interactions. It has previously been demonstrated that solid-state NMR spectroscopy is amore » powerful probe of structure in cocrystals and salts of APIs, however, the poor sensitivity of solid-state NMR spectroscopy usually restricts the types of experiments that can be performed. Here relayed dynamic nuclear polarization (DNP) was applied to reduce solid-state NMR experiments by one to two orders of magnitude for salts and cocrystals of a complex API. The large sensitivity gains from DNP facilitates rapid acquisition of natural isotopic abundance 13C and 15N solid-state NMR spectra. Critically, DNP enables double resonance 1H-15N solid-state NMR experiments such as 2D 1H-15N HETCOR, 1H-15N CP-build up, 15N{1H} J-resolved/attached proton tests, 1H-15N DIPSHIFT and 1H-15N PRESTO. The latter two experiments allow 1H-15N dipolar coupling constants and H-N bond lengths to be accurately measured, providing an unambiguous assignment of nitrogen protonation state and definitive classification of the multi-component solids as cocrystals or salts. In conclusion, these types of measurements should also be extremely useful in the context of polymorph discrimination, NMR crystallography structure determination and for probing hydrogen bonding in a variety of organic materials.« less

Realization of reliable solid-state quantum memory for photonic polarization qubit.

PubMed

Zhou, Zong-Quan; Lin, Wei-Bin; Yang, Ming; Li, Chuan-Feng; Guo, Guang-Can

2012-05-11

Faithfully storing an unknown quantum light state is essential to advanced quantum communication and distributed quantum computation applications. The required quantum memory must have high fidelity to improve the performance of a quantum network. Here we report the reversible transfer of photonic polarization states into collective atomic excitation in a compact solid-state device. The quantum memory is based on an atomic frequency comb (AFC) in rare-earth ion-doped crystals. We obtain up to 0.999 process fidelity for the storage and retrieval process of single-photon-level coherent pulse. This reliable quantum memory is a crucial step toward quantum networks based on solid-state devices.

Energy transfer mechanism of Sm3+/Eu3+ co-doped 2CaO-B2O3-P2O5 phosphors

NASA Astrophysics Data System (ADS)

Prasad, V. Reddy; Damodaraiah, S.; Ratnakaram, Y. C.

2018-04-01

Sm3+/Eu3+ co-doped calcium borophosphate phosphors were synthesized by solid state reaction method. 2CaO-B2O3-P2O5: Sm3+/Eu3+ co-doped phosphors were characterized by XRD, SEM, 31P solid state NMR, excitation, photoluminescence (PL) and decay profiles.. XRD profiles showed that the prepared phosphors exhibit a hexagonal phase in crystal structure and SEM results showed that the particles are more irregular morphologies. From 31P NMR spectra of Sm3+/Eu3+ co-doped 2CaO-B2O3-P2O5 phosphors, the chemical shifts located in the positive frequency region indicating the presence of mono-phosphate complexes Q0-(PO43 - ) . Photoluminescence spectra of Sm3+/Eu3+ co-doped 2CaO-B2O3-P2O5 phosphors show enhancement in emission intensity of Eu3+ ion due to co-doping with Sm3+ ions through energy transfer process. The energy level mechanism between Sm3+ and Eu3+ ions has been clearly explained. The energy transfer process has also been evidenced by lifetime decay profiles. These results suggest that the prepared phosphors are potential red luminescent optical materials.

Nuclear conversion theory: molecular hydrogen in non-magnetic insulators

NASA Astrophysics Data System (ADS)

Ilisca, Ernest; Ghiglieno, Filippo

2016-09-01

The hydrogen conversion patterns on non-magnetic solids sensitively depend upon the degree of singlet/triplet mixing in the intermediates of the catalytic reaction. Three main `symmetry-breaking' interactions are brought together. In a typical channel, the electron spin-orbit (SO) couplings introduce some magnetic excitations in the non-magnetic solid ground state. The electron spin is exchanged with a molecular one by the electric molecule-solid electron repulsion, mixing the bonding and antibonding states and affecting the molecule rotation. Finally, the magnetic hyperfine contact transfers the electron spin angular momentum to the nuclei. Two families of channels are considered and a simple criterion based on the SO coupling strength is proposed to select the most efficient one. The denoted `electronic' conversion path involves an emission of excitons that propagate and disintegrate in the bulk. In the other denoted `nuclear', the excited electron states are transients of a loop, and the electron system returns to its fundamental ground state. The described model enlarges previous studies by extending the electron basis to charge-transfer states and `continui' of band states, and focuses on the broadening of the antibonding molecular excited state by the solid conduction band that provides efficient tunnelling paths for the hydrogen conversion. After working out the general conversion algebra, the conversion rates of hydrogen on insulating and semiconductor solids are related to a few molecule-solid parameters (gap width, ionization and affinity potentials) and compared with experimental measures.

Nuclear conversion theory: molecular hydrogen in non-magnetic insulators

PubMed Central

Ghiglieno, Filippo

2016-01-01

The hydrogen conversion patterns on non-magnetic solids sensitively depend upon the degree of singlet/triplet mixing in the intermediates of the catalytic reaction. Three main ‘symmetry-breaking’ interactions are brought together. In a typical channel, the electron spin–orbit (SO) couplings introduce some magnetic excitations in the non-magnetic solid ground state. The electron spin is exchanged with a molecular one by the electric molecule–solid electron repulsion, mixing the bonding and antibonding states and affecting the molecule rotation. Finally, the magnetic hyperfine contact transfers the electron spin angular momentum to the nuclei. Two families of channels are considered and a simple criterion based on the SO coupling strength is proposed to select the most efficient one. The denoted ‘electronic’ conversion path involves an emission of excitons that propagate and disintegrate in the bulk. In the other denoted ‘nuclear’, the excited electron states are transients of a loop, and the electron system returns to its fundamental ground state. The described model enlarges previous studies by extending the electron basis to charge-transfer states and ‘continui’ of band states, and focuses on the broadening of the antibonding molecular excited state by the solid conduction band that provides efficient tunnelling paths for the hydrogen conversion. After working out the general conversion algebra, the conversion rates of hydrogen on insulating and semiconductor solids are related to a few molecule–solid parameters (gap width, ionization and affinity potentials) and compared with experimental measures. PMID:27703681

Novel polyoxometalate silica nano-sized spheres: efficient catalysts for olefin oxidation and the deep desulfurization process.

PubMed

Nogueira, Lucie S; Ribeiro, Susana; Granadeiro, Carlos M; Pereira, Eulália; Feio, Gabriel; Cunha-Silva, Luís; Balula, Salete S

2014-07-07

A novel method to prepare silica nano-sized particles incorporating polyoxometalates was developed leading to a new efficient heterogeneous oxidative catalyst. Zinc-substituted polyoxotungstate [PW11Zn(H2O)O39](5-) (PW11Zn) was encapsulated into silica nanoparticles using a cross-linked organic-inorganic core, performed through successive spontaneous reactions in water. The potassium salt of PW11Zn and the composite formed, PW11Zn-APTES@SiO2, were characterized by a myriad of solid-state methods such as FT-IR, FT-Raman, (31)P and (13)C CP/MAS solid-state NMR, elemental analysis and SEM-EDS, confirming the integrity of the PW11Zn structure immobilized in the silica nanoparticles. The new composite has shown to be a versatile catalyst for the oxidation of olefins and also to catalyze the desulfurization of a model oil using H2O2 as the oxidant and acetonitrile as the solvent. The novel composite material was capable of being recycled without significant loss of activity and maintaining its structural stability for consecutive desulfurization and olefin oxidative cycles.

Analysis of minerals containing dissolved traces of the fluid phase components water and carbon dioxide

NASA Technical Reports Server (NTRS)

Freund, Friedemann

1991-01-01

Substantial progress has been made towards a better understanding of the dissolution of common gas/fluid phase components, notably H2O and CO2, in minerals. It has been shown that the dissolution mechanisms are significantly more complex than currently believed. By judiciously combining various solid state analytical techniques, convincing evidence was obtained that traces of dissolved gas/fluid phase components undergo, at least in part, a redox conversion by which they split into reduced H2 and and reduced C on one hand and oxidized oxygen, O(-), on the other. Analysis for 2 and C as well as for any organic molecules which may form during the process of co-segregation are still impeded by the omnipresent danger of extraneous contamination. However, the presence of O(-), an unusual oxidized form of oxygen, has been proven beyond a reasonable doubt. The presence of O(-) testifies to the fact that a redox reaction must have taken place in the solid state involving the dissolved traces of gas/fluid phase components. Detailed information on the techniques used and the results obtained are given.

Visualising substrate-fingermark interactions: Solid-state NMR spectroscopy of amino acid reagent development on cellulose substrates.

PubMed

Spindler, Xanthe; Shimmon, Ronald; Roux, Claude; Lennard, Chris

2015-05-01

Most spectroscopic studies of the reaction products formed by ninhydrin, 1,2-indanedione-zinc (Ind-Zn) and 1,8-diazafluoren-9-one (DFO) when reacted with amino acids or latent fingermarks on paper substrates are focused on visible absorption or luminescence spectroscopy. In addition, structural elucidation studies are typically limited to solution-based mass spectrometry or liquid nuclear magnetic resonance (NMR) spectroscopy, which does not provide an accurate representation of the fingermark development process on common paper substrates. The research presented in this article demonstrates that solid-state carbon-13 magic angle spinning NMR ((13)C-MAS-NMR) is a technique that can not only be utilised for structural studies of fingermark enhancement reagents, but is a promising technique for characterising the effect of paper chemistry on fingermark deposition and enhancement. The latter opens up a research area that has been under-explored to date but has the potential to improve our understanding of how fingermark secretions and enhancement reagents interact with paper substrates. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Optimization of fed-batch enzymatic hydrolysis from alkali-pretreated sugarcane bagasse for high-concentration sugar production.

PubMed

Gao, Yueshu; Xu, Jingliang; Yuan, Zhenhong; Zhang, Yu; Liu, Yunyun; Liang, Cuiyi

2014-09-01

Fed-batch enzymatic hydrolysis process from alkali-pretreated sugarcane bagasse was investigated to increase solids loading, produce high-concentration fermentable sugar and finally to reduce the cost of the production process. The optimal initial solids loading, feeding time and quantities were examined. The hydrolysis system was initiated with 12% (w/v) solids loading in flasks, where 7% fresh solids were fed consecutively at 6h, 12h, 24h to get a final solids loading of 33%. All the requested cellulase loading (10 FPU/g substrate) was added completely at the beginning of hydrolysis reaction. After 120 h of hydrolysis, the maximal concentrations of cellobiose, glucose and xylose obtained were 9.376 g/L, 129.50 g/L, 56.03 g/L, respectively. The final total glucan conversion rate attained to 60% from this fed-batch process. Copyright © 2014. Published by Elsevier Ltd.

The size effect to O2- -Ce4+ charge transfer emission and band gap structure of Sr2 CeO4.

PubMed

Wang, Wenjun; Pan, Yu; Zhang, Wenying; Liu, Xiaoguang; Li, Ling

2018-04-24

Sr 2 CeO 4 phosphors with different crystalline sizes were synthesized by the sol-gel method or the solid-state reaction. Their crystalline size, luminescence intensity of O 2- -Ce 4+ charge transfer and energy gaps were obtained through the characterization by X-ray diffraction, photoluminescence spectra, as well as UV-visible diffuse reflectance measurements. An inverse relationship between photoluminescence (PL) spectra and crystalline size was observed when the heating temperature was from 1000°C to 1300°C. In addition, band energy calculated for all samples showed that a reaction temperature of 1200°C for the solid-state method and 1100°C for sol-gel method gave the largest values, which corresponded with the smallest crystalline size. Correlation between PL intensity and crystalline size showed an inverse relationship. Band structure, density of states and partial density of states of the crystal were calculated to analyze the mechanism using the cambrige sequential total energy package (CASTEP) module integrated with Materials Studio software. Copyright © 2018 John Wiley & Sons, Ltd.

Review—Practical Challenges Hindering the Development of Solid State Li Ion Batteries

DOE PAGES

Kerman, Kian; Luntz, Alan; Viswanathan, Venkatasubramanian; ...

2017-06-09

Solid state electrolyte systems boasting Li+ conductivity of >10 mS cm -1 at room temperature have opened the potential for developing a solid state battery with power and energy densities that are competitive with conventional liquid electrolyte systems. The primary focus of this review is twofold. First, differences in Li penetration resistance in solid state systems are discussed, and kinetic limitations of the solid state interface are highlighted. Second, technological challenges associated with processing such systems in relevant form factors are elucidated, and architectures needed for cell level devices in the context of product development are reviewed. Specific research vectorsmore » that provide high value to advancing solid state batteries are outlined and discussed.« less

Precipitation in Al–Mg solid solution prepared by solidification under high pressure

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

Jie, J.C., E-mail: jiejc@dlut.edu.cn; School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001; Wang, H.W.

2014-01-15

The precipitation in Al–Mg solid solution containing 21.6 at.% Mg prepared by solidification under 2 GPa was investigated. The results show that the γ-Al{sub 12}Mg{sub 17} phase is formed and the β′ phase cannot be observed in the solid solution during ageing process. The precipitation of γ and β phases takes place in a non-uniform manner during heating process, i.e. the γ and β phases are first formed in the interdendritic region, which is caused by the inhomogeneous distribution of Mg atoms in the solid solution solidified under high pressure. Peak splitting of X-ray diffraction patterns of Al(Mg) solid solutionmore » appears, and then disappears when the samples are aged at 423 K for different times, due to the non-uniform precipitation in Al–Mg solid solution. The direct transformation from the γ to β phase is observed after ageing at 423 K for 24 h. It is considered that the β phase is formed through a peritectoid reaction of α + γ → β which needs the diffusion of Mg atoms across the interface of α/γ phases. - Highlights: • The γ phase is formed and the β′ phase is be observed in Al(Mg) solid solution. • Peak splitting of XRD pattern of Al(Mg) solid solution appears during aged at 150 °C. • The β phase is formed through a peritectoid reaction of α + γ → β.« less

Sustainable Engineering and Improved Recycling of PET for High-Value Applications: Transforming Linear PET to Lightly Branched PET with a Novel, Scalable Process

NASA Astrophysics Data System (ADS)

Pierre, Cynthia; Torkelson, John

2009-03-01

A major challenge for the most effective recycling of poly(ethylene terephthalate) concerns the fact that initial melt processing of PET into a product leads to substantial degradation of molecular weight. Thus, recycled PET has insufficient melt viscosity for reuse in high-value applications such as melt-blowing of PET bottles. Academic and industrial research has tried to remedy this situation by synthesis and use of ``chain extenders'' that can lead to branched PET (with higher melt viscosity than the linear recycled PET) via condensation reactions with functional groups on the PET. Here we show that simple processing of PET via solid-state shear pulverization (SSSP) leads to enhanced PET melt viscosity without need for chemical additives. We hypothesize that this branching results from low levels of chain scission accompanying SSSP, leading to formation of polymeric radicals that participate in chain transfer and combination reactions with other PET chains and thereby to in situ branch formation. The pulverized PET exhibits vastly enhanced crystallization kinetics, eliminating the need to employ cold crystallization to achieve maximum PET crystallinity. Results of SSSP processing of PET will be compared to results obtained with poly(butylene terephthalate).

Hydrogen generation systems utilizing sodium silicide and sodium silica gel materials

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

Wallace, Andrew P.; Melack, John M.; Lefenfeld, Michael

Systems, devices, and methods combine reactant materials and aqueous solutions to generate hydrogen. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Multiple inlets of varied placement geometries deliver aqueous solution to the reaction. The reactant materials and aqueous solution are churned to control the state of the reaction. The aqueous solution can be recycled and returned to the reaction. One systemmore » operates over a range of temperatures and pressures and includes a hydrogen separator, a heat removal mechanism, and state of reaction control devices. The systems, devices, and methods of generating hydrogen provide thermally stable solids, near-instant reaction with the aqueous solutions, and a non-toxic liquid by-product.« less

Hydrogen generation systems utilizing sodium silicide and sodium silica gel materials

DOEpatents

Wallace, Andrew P.; Melack, John M.; Lefenfeld, Michael

2015-07-14

Systems, devices, and methods combine reactant materials and aqueous solutions to generate hydrogen. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Multiple inlets of varied placement geometries deliver aqueous solution to the reaction. The reactant materials and aqueous solution are churned to control the state of the reaction. The aqueous solution can be recycled and returned to the reaction. One system operates over a range of temperatures and pressures and includes a hydrogen separator, a heat removal mechanism, and state of reaction control devices. The systems, devices, and methods of generating hydrogen provide thermally stable solids, near-instant reaction with the aqueous solutions, and a non-toxic liquid by-product.

Variational transition state theory: theoretical framework and recent developments.

PubMed

Bao, Junwei Lucas; Truhlar, Donald G

2017-12-11

This article reviews the fundamentals of variational transition state theory (VTST), its recent theoretical development, and some modern applications. The theoretical methods reviewed here include multidimensional quantum mechanical tunneling, multistructural VTST (MS-VTST), multi-path VTST (MP-VTST), both reaction-path VTST (RP-VTST) and variable reaction coordinate VTST (VRC-VTST), system-specific quantum Rice-Ramsperger-Kassel theory (SS-QRRK) for predicting pressure-dependent rate constants, and VTST in the solid phase, liquid phase, and enzymes. We also provide some perspectives regarding the general applicability of VTST.

Controlled short residence time coal liquefaction process

DOEpatents

Anderson, Raymond P.; Schmalzer, David K.; Wright, Charles H.

1982-05-04

Normally solid dissolved coal product and a distillate liquid product are produced by continuously passing a feed slurry comprising raw feed coal and a recycle solvent oil and/or slurry together with hydrogen to a preheating-reaction zone (26, alone, or 26 together with 42), the hydrogen pressure in the preheating-reaction zone being at least 1500 psig (105 kg/cm.sup.2), reacting the slurry in the preheating-reaction zone (26, or 26 with 42) at a temperature in the range of between about 455.degree. and about 500.degree. C. to dissolve the coal to form normally liquid coal and normally solid dissolved coal. A total slurry residence time is maintained in the reaction zone ranging from a finite value from about 0 to about 0.2 hour, and reaction effluent is continuously and directly contacted with a quenching fluid (40, 68) to substantially immediately reduce the temperature of the reaction effluent to below 425.degree. C. to substantially inhibit polymerization so that the yield of insoluble organic matter comprises less than 9 weight percent of said feed coal on a moisture-free basis. The reaction is performed under conditions of temperature, hydrogen pressure and residence time such that the quantity of distillate liquid boiling within the range C.sub.5 -455.degree. C. is an amount at least equal to that obtainable by performing the process under the same conditions except for a longer total slurry residence time, e.g., 0.3 hour. Solvent boiling range liquid is separated from the reaction effluent and recycled as process solvent.

Temperature-Jump Relaxation Kinetics at Liquid/Solid Interfaces: Fluorescence Thermometry of Porous Silica Heated by a Joule Discharge

DTIC Science & Technology

1991-05-22

for understanding reaction mechanisms responsible for the steady-state behavior and determining the dispersion of rates in cases where inhomogeneities...derivatized by the following procedure. Three grams of the silica was placed in a dry reaction vessel consisting of a three neck flask, addition funnel...to the reaction vessel , taking care to avoid contact with the air. A five-fold molar equivalent excess of ODS (based on the silanol 8 density of the

Rapid, cool sintering of wet processed yttria-stabilized zirconia ceramic electrolyte thin films.

PubMed

Park, Jun-Sik; Kim, Dug-Joong; Chung, Wan-Ho; Lim, Yonghyun; Kim, Hak-Sung; Kim, Young-Beom

2017-09-29

Here we report a photonic annealing process for yttria-stabilized zirconia films, which are one of the most well-known solid-state electrolytes for solid oxide fuel cells (SOFCs). Precursor films were coated using a wet-chemical method with a simple metal-organic precursor solution and directly annealed at standard pressure and temperature by two cycles of xenon flash lamp irradiation. The residual organics were almost completely decomposed in the first pre-annealing step, and the fluorite crystalline phases and good ionic conductivity were developed during the second annealing step. These films showed properties comparable to those of thermally annealed films. This process is much faster than conventional annealing processes (e.g. halogen furnaces); a few seconds compared to tens of hours, respectively. The significance of this work includes the treatment of solid-state electrolyte oxides for SOFCs and the demonstration of the feasibility of other oxide components for solid-state energy devices.

Lowering the synthesis temperature of Y3Fe5O12 by surfactant assisted solid state reaction

NASA Astrophysics Data System (ADS)

Xue, Fenghua; Huang, Ju; Li, Tianrui; Wang, Zifan; Zhou, Xiaochao; Wei, Lujun; Gao, Baizhi; Zhai, Ya; Li, Qi; Xu, Qingyu; Du, Jun

2018-01-01

There is an urgent technical requirement of lowering the sintering temperature of Y3Fe5O12 (YIG) for its practical applications. In this paper, a modified solid state reaction method is reported by adding the surfactant of cetyltrimethylammonium bromide (CTAB). A high sintering temperature of 1200 °C is required for the formation of YIG phase without adding CTAB, which is effectively decreased to 1050 °C by adding CTAB. The morphology studies show that the sintering temperature plays the main role in the crystal growth and excludes the possible contribution of CTAB. The prepared YIG ceramic samples show soft ferromagnetic properties, with coercivity of only 21.2 Oe for the sample prepared with CTAB at 1050 °C, which decreases with increasing sintering temperature. The main role of adding CTAB is preventing the agglomeration of ball milled ultrafine source particles, which may facilitate the interdiffusion among them and promote the reaction at lower temperatures. Furthermore, the Gilbert damping constant is significantly reduced for YIG prepared by adding CTAB, which is one order smaller than that without CTAB.

Precise non-steady-state characterization of solid active materials with no preliminary mechanistic assumptions

DOE PAGES

Constales, Denis; Yablonsky, Gregory S.; Wang, Lucun; ...

2017-04-25

This paper presents a straightforward and user-friendly procedure for extracting a reactivity characterization of catalytic reactions on solid materials under non-steady-state conditions, particularly in temporal analysis of products (TAP) experiments. The kinetic parameters derived by this procedure can help with the development of detailed mechanistic understanding. The procedure consists of the following two major steps: 1) Three “Laplace reactivities” are first determined based on the moments of the exit flow pulse response data; 2) Depending on a select kinetic model, kinetic constants of elementary reaction steps can then be expressed as a function of reactivities and determined accordingly. In particular,more » we distinguish two calculation methods based on the availability and reliability of reactant and product data. The theoretical results are illustrated using a reverse example with given parameters as well as an experimental example of CO oxidation over a supported Au/SiO 2 catalyst. The procedure presented here provides an efficient tool for kinetic characterization of many complex chemical reactions.« less

Activities of the Solid State Physics Research Institute

NASA Technical Reports Server (NTRS)

1985-01-01

Topics addressed include: muon spin rotation; annealing problems in gallium arsenides; Hall effect in semiconductors; computerized simulation of radiation damage; single-nucleon removal from Mg-24; and He-3 reaction at 200 and 400 MeV.

The alcohol-sensing behaviour of SnO2 nanorods prepared by a facile solid state reaction

NASA Astrophysics Data System (ADS)

Gao, F.; Ren, X. P.; Wan, W. J.; Zhao, Y. P.; Li, Y. H.; Zhao, H. Y.

2017-02-01

SnO2 nanorods with the range of 12-85 nm in diameter were fabricated by a facile solid state reaction in the medium of NaCl-KCl mixture at room temperature and calcined at 600, 680, 760 and 840 oC, respectively. The XRD, TEM and XPS were employed to characterize the structure and morphology of the SnO2 nanorods. The influence of the calcination temperature on the gas sensing behaviour of the SnO2 nanorods with different diameter was investigated. The result showed that all the sensors had good response to alcohol. The response of the gracile nanorods prepared at a low calcined temperature demonstrated significantly better than the thick nanorods prepared at a high calcined temperature. The mechanism was attributed to the nonstoichiometric ratio of Sn/O and larger surface area of the gracile nanorods to enhance the oxygen surface adsorption.

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

Chen, Wei; Rosser, Ethan W.; Zhang, Di

Hydrogen polysulfides (H 2S n, n>1) have been recently suggested to be the actual signalling molecules that involved in sulfur-related redox biology. However the exact mechanisms of H 2S n are still poorly understood and a major hurdle in this field is the lack of reliable and convenient methods for H 2S n detection. In this work we report a unique ring-opening reaction of N-sulfonylaziridine by Na 2S 2 under mild conditions. Based on this reaction a novel H 2S n-specific fluorescent probe (AP) was developed. The probe showed high sensitivity and selectivity for H 2S n. Notably, the fluorescentmore » turn-on product, i.e. compound 1, exhibited excellent two-photon photophysical properties and a large Stokes shift. Moreover, the high solid state luminescent efficiency of compound 1 makes it a potential candidate for organic emitters and solid-state lighting devices.« less

Spectroscopic and Electrochemical Properties of Lithium-Rich LiFePO4 Cathode Synthesized by Solid-State Reaction

NASA Astrophysics Data System (ADS)

Rosaiah, P.; Hussain, O. M.; Zhu, Jinghui; Qiu, Yejun

2017-08-01

Lithium iron phosphate (Li x FePO4) is synthesized by a solid-state reaction method. The structural, electrical and electrochemical properties are studied in detail. It is found that the increment of lithium concentration (up to x = 1.05) does not affect the structure of LiFePO4 but improves its electrical conductivity as well as electrochemical performance. Surface morphological studies exhibited the formation of rod-like nanoparticles with small size. Electric and dielectric properties are also investigated over a frequency range of 1 Hz-1 MHz at different temperatures. The conductivity increased with increasing temperature, which follows the Arrhenius relation with the activation energy of about 0.31 eV. And the electrochemical tests found that the Li1.05FePO4 cathode possessed improved discharge capacity with better cycling performance.

Zr doping effect with low-cost solid-state reaction method to synthesize submicron Li4Ti5O12 anode material

NASA Astrophysics Data System (ADS)

Seo, Inseok; Lee, Cheul-Ro; Kim, Jae-Kwang

2017-09-01

To improve the electrochemical properties, fine Zr-doping Li4Ti5O12 anode materials for rechargeable lithium batteries with a uniform particle size distribution were synthesized by a modified solid-state reaction using fine Li2CO3 and TiO2 (anatase) powders as precursors with a Li:Ti molar ratio of 4:5. The use of fine Li2CO3 and TiO2 (anatase) powders as precursors prevented the formation of ZrO2 at 0.1 mol Zr-doping. XRD analysis revealed that the substitution of Zr for Ti leads to the increase of lattice parameters, allowing improved Li diffusion. The discharge capacity retention increased slightly with Zr-doping and the 0.1 mol Zr-doped Li4Ti5O12 electrode achieved 99% retention of discharge capacity.

Coherent diffractive imaging of solid state reactions in zinc oxide crystals

NASA Astrophysics Data System (ADS)

Leake, Steven J.; Harder, Ross; Robinson, Ian K.

2011-11-01

We investigated the doping of zinc oxide (ZnO) microcrystals with iron and nickel via in situ coherent x-ray diffractive imaging (CXDI) in vacuum. Evaporated thin metal films were deposited onto the ZnO microcrystals. A single crystal was selected and tracked through annealing cycles. A solid state reaction was observed in both iron and nickel experiments using CXDI. A combination of the shrink wrap and guided hybrid-input-output phasing methods were applied to retrieve the electron density. The resolution was 33 nm (half order) determined via the phase retrieval transfer function. The resulting images are nevertheless sensitive to sub-angstrom displacements. The exterior of the microcrystal was found to degrade dramatically. The annealing of ZnO microcrystals coated with metal thin films proved an unsuitable doping method. In addition the observed defect structure of one crystal was attributed to the presence of an array of defects and was found to change upon annealing.

Study of structural, spectroscopic and dielectric properties of multiferroic cadmium doped Samarium manganite synthesized by solid state reaction method

NASA Astrophysics Data System (ADS)

Gupta, Vandana; Raina, Bindu; Verma, Seema; Bamzai, K. K.

2018-05-01

Samarium manganite doped with cadmium having general formula Sm1-xCdxMnO3 for x = 0.05, 0.15 were synthesized by solid state reaction technique. These compositions were characterized by various techniques like X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and dielectric. XRD analysis confirms the single phase formation with pervoskites structure having orthorhombic phase. Densities were determined and compared with the results obtained by Archimedes principle. The scanning electron micrograph shows that the particle size distribution is almost homogeneous and spherical in shape. FTIR analysis confirms the presence of various atomic bonds within a molecule. A very large value of dielectric constant was observed at low frequencies due to the presence of grains and interfaces. The dielectric constant value decreases with increase in cadmium doping at samarium site.

JAGUAR Procedures for Detonation Behavior of Silicon Containing Explosives

NASA Astrophysics Data System (ADS)

Stiel, Leonard; Baker, Ernest; Capellos, Christos; Poulos, William; Pincay, Jack

2007-06-01

Improved relationships for the thermodynamic properties of solid and liquid silicon and silicon oxide for use with JAGUAR thermo-chemical equation of state routines were developed in this study. Analyses of experimental melting temperature curves for silicon and silicon oxide indicated complex phase behavior and that improved coefficients were required for solid and liquid thermodynamic properties. Advanced optimization routines were utilized in conjunction with the experimental melting point data to establish volumetric coefficients for these substances. The new property libraries resulted in agreement with available experimental values, including Hugoniot data at elevated pressures. Detonation properties were calculated with JAGUAR using the revised property libraries for silicon containing explosives. Constants of the JWLB equation of state were established for varying extent of silicon reaction. Supporting thermal heat transfer analyses were conducted for varying silicon particle sizes to establish characteristic times for melting and silicon reaction.

Reactive-brittle dynamics in peridotite alteration

NASA Astrophysics Data System (ADS)

Evans, O.; Spiegelman, M. W.; Kelemen, P. B.

2017-12-01

The interactions between reactive fluids and brittle solids are critical in Earth dynamics. Implications of such processes are wide-ranging: from earthquake physics to geologic carbon sequestration and the cycling of fluids and volatiles through subduction zones. Peridotite alteration is a common feature in many of these processes, which - despite its obvious importance - is relatively poorly understood from a geodynamical perspective. In particular, alteration reactions are thought to be self-limiting in nature, contradicting observations of rocks that have undergone 100% hydration/carbonation. One potential explanation of this observation is the mechanism of "reaction-driven cracking": that volume changes associated with these reactions are large enough to fracture the surrounding rock, leading to a positive feedback where new reactive surfaces are exposed and fluid pathways are created. The purpose of this study is to investigate the relative roles of reaction, elastic stresses and surface tension in alteration reactions. In this regard we derive a system of equations describing reactive fluid flow in an elastically deformable porous media, and explore them via a combination of analytic and numerical solutions. Using this model we show that the final stress state of a dry peridotite that has undergone reaction depends strongly on the rates of reaction versus fluid transport: significant fluid flow driven by pressure and/or surface tension gradients implies higher fractions of serpentinization, leaving behind a highly stressed residuum of partially reacted material. Using a model set-up that mimics a cylindrical triaxial apparatus we predict that the resulting stresses would lead to tensile failure and the generation of radially oriented cracks.

High speed real-time wavefront processing system for a solid-state laser system

NASA Astrophysics Data System (ADS)

Liu, Yuan; Yang, Ping; Chen, Shanqiu; Ma, Lifang; Xu, Bing

2008-03-01

A high speed real-time wavefront processing system for a solid-state laser beam cleanup system has been built. This system consists of a core2 Industrial PC (IPC) using Linux and real-time Linux (RT-Linux) operation system (OS), a PCI image grabber, a D/A card. More often than not, the phase aberrations of the output beam from solid-state lasers vary fast with intracavity thermal effects and environmental influence. To compensate the phase aberrations of solid-state lasers successfully, a high speed real-time wavefront processing system is presented. Compared to former systems, this system can improve the speed efficiently. In the new system, the acquisition of image data, the output of control voltage data and the implementation of reconstructor control algorithm are treated as real-time tasks in kernel-space, the display of wavefront information and man-machine conversation are treated as non real-time tasks in user-space. The parallel processing of real-time tasks in Symmetric Multi Processors (SMP) mode is the main strategy of improving the speed. In this paper, the performance and efficiency of this wavefront processing system are analyzed. The opened-loop experimental results show that the sampling frequency of this system is up to 3300Hz, and this system can well deal with phase aberrations from solid-state lasers.

Chemical surface deposition of ultra-thin semiconductors

DOEpatents

McCandless, Brian E.; Shafarman, William N.

2003-03-25

A chemical surface deposition process for forming an ultra-thin semiconducting film of Group IIB-VIA compounds onto a substrate. This process eliminates particulates formed by homogeneous reactions in bath, dramatically increases the utilization of Group IIB species, and results in the formation of a dense, adherent film for thin film solar cells. The process involves applying a pre-mixed liquid coating composition containing Group IIB and Group VIA ionic species onto a preheated substrate. Heat from the substrate causes a heterogeneous reaction between the Group IIB and VIA ionic species of the liquid coating composition, thus forming a solid reaction product film on the substrate surface.

Mechanochemical synthesis of nanostructured Sr(Ti{sub 1-x}Fe{sub x})O{sub 3-{delta}} solid-solution powders and their surface photovoltage responses

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

Chen Xiaofeng; Luo Qiong; GlobalFoundries Singapore Pte Ltd, 60 Woodlands Industrial Park D Street 2, Singapore 738406

2012-05-15

A series of nanostructure Sr(Ti{sub 1-x}Fe{sub x})O{sub 3-{delta}} (STFx, x=0.4, 0.6, 0.8) solid-solution powders were synthesized by mechanochemical approach milling from the mixture of SrO, Fe{sub 2}O{sub 3} and TiO{sub 2} metal oxides at room temperature. The XRD results revealed that the perovskite STFx nanoparticles were finally formed with few residual {alpha}-Fe{sub 2}O{sub 3} detected dependent on the milling conditions. The structure evolution suggested that the mechanochemical synthesis underwent via a solid-state reaction route to initially form Ti-rich perovskite and then incorporate with the residual {alpha}-Fe{sub 2}O{sub 3} to achieve the estimated composition. The synthesized STF08 powders exhibited the significantmore » Surface Photovoltage (SPV) spectrum response both in UV and in visible-light region with p-type semiconductor behavior. This finding suggested that the synthesized STF nanopowders could potentially utilize more solar spectrum energy effectively for photo-oxidation and photo-catalysis applications. - Graphical abstract: It is demonstrated that Sr(Ti{sub 1-x}Fe{sub x})O{sub 3-{delta}} perovskite nanopowders were successfully synthesized by mechanochemical reaction approach at room temerpature, and the synthesized STF08 powders showed the significant SPV response in UV-VIS region with p-type semiconductor behaviors. Highlights: Black-Right-Pointing-Pointer Sr(Ti{sub 1-x}Fe{sub x})O{sub 3-{delta}} nanopowders synthesized by mechanochemical reaction approach. Black-Right-Pointing-Pointer The reaction process was shorten by introduce high impact energy. Black-Right-Pointing-Pointer Synthesized STF08 powders show the significant SPV response in UV-VIS region. Black-Right-Pointing-Pointer Synthesized STFx powders show p-type semiconductor behaviors.« less