Damage accumulation in ion-irradiated Ni-based concentrated solid-solution alloys

DOE PAGES

Ullah, Mohammad W.; Aidhy, Dilpuneet S.; Zhang, Yanwen; ...

2016-03-05

We investigate Irradiation-induced damage accumulation in Ni 0.8Fe 0.2 and Ni 0.8Cr 0.2 alloys by using molecular dynamics simulations to assess possible enhanced radiation-resistance in these face-centered cubic (fcc), single-phase, concentrated solid-solution alloys, as compared with pure fcc Ni.

Preparation and Analysis of Solid Solutions in the Potassium Perchlorate-Permanganate System.

ERIC Educational Resources Information Center

Johnson, Garrett K.

1979-01-01

Describes an experiment, designed for and tested in an advanced inorganic laboratory methods course for college seniors and graduate students, that prepares and analyzes several samples in the nearly ideal potassium perchlorate-permanganate solid solution series. The results are accounted for by a theoretical treatment based upon aqueous…

Welding and brazing of nickel and nickel-base alloys

NASA Technical Reports Server (NTRS)

Mortland, J. E.; Evans, R. M.; Monroe, R. E.

1972-01-01

The joining of four types of nickel-base materials is described: (1) high-nickel, nonheat-treatable alloys, (2) solid-solution-hardening nickel-base alloys, (3) precipitation-hardening nickel-base alloys, and (4) dispersion-hardening nickel-base alloys. The high-nickel and solid-solution-hardening alloys are widely used in chemical containers and piping. These materials have excellent resistance to corrosion and oxidation, and retain useful strength at elevated temperatures. The precipitation-hardening alloys have good properties at elevated temperature. They are important in many aerospace applications. Dispersion-hardening nickel also is used for elevated-temperature service.

Trace element abundances in single presolar silicon carbide grains by synchrotron X-ray fluorescence

NASA Astrophysics Data System (ADS)

Kashiv, Yoav

2004-12-01

Synchrotron x-ray fluorescence (SXRF) was applied to the study of presolar grains for the first time in this study. 41 single SiC grains of the KJF size fraction (mass-weighted median size of 1.86 μm) from the Murchison (CM2) Meteorite were analyzed. The absolute abundances of the following elements were determined (not every element in every grain): S, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Sr, Y, Zr, Nb, Mo, Ru, Os, Ir and Pt (underlined elements were detected here for the first time in single grains). There is good agreement between the heavier trace element abundances in the grains and s-process nucleosynthesis calculations. It suggests that smaller 13C pocket sizes are needed in the parent stars, a free parameter in the stellar models, than is deduced from isotopic analyses of s-, and s-mainly, elements, such as Zr and Mo. In addition, the data confirms the radiogenic nature of the Nb in the grains, due to the in situ decay of 93Zr (t 1/2 = 1.5 × 106 year). The data suggest that the trace elements condensed into the host SiC grains by a combination of condensation in solid solution and incorporation of subgrains. It seems that many of the trace elements reside mainly in subgrains of two solid solution: (1)a TiC based solid solution, and (2)a Mo-Ru carbide based solid solution. The presence of subgrains of an Fe-Ni alloy solid solution is suggested as well. Subgrains of all 3 solid solutions were observed previously in presolar graphite grains.* *This dissertation is a compound document (contains both a paper copy and a CD as part of the dissertation). The CD requires the following system requirements: Adobe Acrobat.

Geochemical modeling of reactions and partitioning of trace metals and radionuclides during titration of contaminated acidic sediments.

PubMed

Zhang, Fan; Luo, Wensui; Parker, Jack C; Spalding, Brian P; Brooks, Scott C; Watson, David B; Jardine, Philip M; Gu, Baohua

2008-11-01

Many geochemical reactions that control aqueous metal concentrations are directly affected by solution pH. However, changes in solution pH are strongly buffered by various aqueous phase and solid phase precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior of the soil-solution system is thus critical to predict metal transport under variable pH conditions. This studywas undertaken to develop a practical generic geochemical modeling approach to predict aqueous and solid phase concentrations of metals and anions during conditions of acid or base additions. The method of Spalding and Spalding was utilized to model soil buffer capacity and pH-dependent cation exchange capacity by treating aquifer solids as a polyprotic acid. To simulate the dynamic and pH-dependent anion exchange capacity, the aquifer solids were simultaneously treated as a polyprotic base controlled by mineral precipitation/ dissolution reactions. An equilibrium reaction model that describes aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange was developed using HydroGeoChem v5.0 (HGC5). Comparison of model results with experimental titration data of pH, Al, Ca, Mg, Sr, Mn, Ni, Co, and SO4(2-) for contaminated sediments indicated close agreement suggesting that the model could potentially be used to predictthe acid-base behavior of the sediment-solution system under variable pH conditions.

The exchange interactions and the state of manganese atoms in the solid solutions in Bi{sub 3}NbO{sub 7} of cubic and tetragonal modifications

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

Chezhina, N.V., E-mail: chezhina@nc2490.spb.edu; Zhuk, N.A.; Korolev, D.A.

2016-01-15

The comparative analysis of magnetic behavior of manganese-containing solid solutions Bi{sub 3}Nb{sub 1−x}Mn{sub x}O{sub 7−δ} (x=0.01−0.10) of cubic and tetragonal modifications was performed. Based on the results of magnetic susceptibility studies paramagnetic manganese atoms in solid solutions of cubic and tetragonal modifications were found to be in the form of Mn(III), Mn(IV) monomers and exchange-coupled dimers of Mn(III)–O–Mn(III), Mn(IV)–O–Mn(IV), Mn(III)–O–Mn(IV). The exchange parameters and the distribution of monomers and dimers in solid solutions as a function of the content of paramagnetic atoms were calculated. - Graphical abstract: Structural transition of cubic to tetragonal Bi{sub 3}NbO{sub 7−δ}.

LEACHING OF TITANIUM FROM MONOSODIUM TITANATE AND MODIFIED MST

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

Taylor-Pashow, K.; Fondeur, F.; Fink, S.

2012-08-01

Analysis of a fouled coalescer and pre-filters from Actinide Removal Process/Modular Caustic Side Solvent Extraction Unit (ARP/MCU) operations showed evidence of Ti containing solids. Based on these results a series of tests were planned to examine the extent of Ti leaching from monosodium titanate (MST) and modified monosodium titanate (mMST) in various solutions. The solutions tested included a series of salt solutions with varying free hydroxide concentrations, two sodium hydroxide concentrations, 9 wt % and 15 wt %, nitric and oxalic acid solutions. Overall, the amount of Ti leached from the MST and mMST was much greater in the acidmore » solutions compared to the sodium hydroxide or salt solutions, which is consistent with the expected trend. The leaching data also showed that increasing hydroxide concentration, whether pure NaOH solution used for filter cleaning in ARP or the waste salt solution, increased the amount of Ti leached from both the MST and mMST. For the respective nominal contact times with the MST solids - for filter cleaning or the normal filter operation, the dissolved Ti concentrations are comparable suggesting either cause may contribute to the increased Ti fouling on the MCU coalescers. Tests showed that Ti containing solids could be precipitated from solution after the addition of scrub acid and a decrease in temperature similar to expected in MCU operations. FTIR analysis of these solids showed some similarity to the solids observed on the fouled coalescer and pre-filters. Although only a cursory study, this information suggests that the practice of increasing free hydroxide in feed solutions to MCU as a mitigation to aluminosilicate formation may be offset by the impact of formation of Ti solids in the overall process. Additional consideration of this finding from MCU and SWPF operation is warranted.« less

Experimental cocrystal screening and solution based scale-up cocrystallization methods.

PubMed

Malamatari, Maria; Ross, Steven A; Douroumis, Dennis; Velaga, Sitaram P

2017-08-01

Cocrystals are crystalline single phase materials composed of two or more different molecular and/or ionic compounds generally in a stoichiometric ratio which are neither solvates nor simple salts. If one of the components is an active pharmaceutical ingredient (API), the term pharmaceutical cocrystal is often used. There is a growing interest among drug development scientists in exploring cocrystals, as means to address physicochemical, biopharmaceutical and mechanical properties and expand solid form diversity of the API. Conventionally, coformers are selected based on crystal engineering principles, and the equimolar mixtures of API and coformers are subjected to solution-based crystallization that are commonly employed in polymorph and salt screening. However, the availability of new knowledge on cocrystal phase behaviour in solid state and solutions has spurred the development and implementation of more rational experimental cocrystal screening as well as scale-up methods. This review aims to provide overview of commonly employed solid form screening techniques in drug development with an emphasis on cocrystal screening methodologies. The latest developments in understanding and the use of cocrystal phase diagrams in both screening and solution based scale-up methods are also presented. Final section is devoted to reviewing the state of the art research covering solution based scale-up cocrystallization process for different cocrystals besides more recent continuous crystallization methods. Copyright © 2017 Elsevier B.V. All rights reserved.

New interpretation of data of the Earth's solid core

NASA Astrophysics Data System (ADS)

Guliyev, H. H.

2017-06-01

The commonly accepted scientific opinions on the inner core as the deformable solid globe are based on the solution of the problem on the distribution of elastic parameters in the inner structures of the Earth. The given solution is obtained within the necessary integral conditions on its self-weight, moment of inertia concerning the axes of rotation and periods of free oscillations of the Earth. It is shown that this solution does not satisfy the mechanics of the deformable solid body with sufficient local conditions following from basic principles concerning the strength, stability and actuality of velocities of propagation of elastic waves. The violation of local conditions shows that the inner core cannot exist in the form of the deformable solid body within the commonly accepted elastic parameters.

Properties of solid solutions, doped film, and nanocomposite structures based on zinc oxide

NASA Astrophysics Data System (ADS)

Lashkarev, G. V.; Shtepliuk, I. I.; Ievtushenko, A. I.; Khyzhun, O. Y.; Kartuzov, V. V.; Ovsiannikova, L. I.; Karpyna, V. A.; Myroniuk, D. V.; Khomyak, V. V.; Tkach, V. N.; Timofeeva, I. I.; Popovich, V. I.; Dranchuk, N. V.; Khranovskyy, V. D.; Demydiuk, P. V.

2015-02-01

A study of the properties of materials based on the wide bandgap zinc oxide semiconductor, which are promising for application in optoelectronics, photovoltaics and nanoplasmonics. The structural and optical properties of solid solution Zn1-xCdxO films with different cadmium content, are studied. The samples are grown using magnetron sputtering on sapphire backing. Low-temperature photoluminescence spectra revealed emission peaks associated with radiative recombination processes in those areas of the film that have varying amounts of cadmium. X-ray phase analysis showed the presence of a cadmium oxide cubic phase in these films. Theoretical studies of the solid solution thermodynamic properties allowed for a qualitative interpretation of the observed experimental phenomena. It is established that the growth of the homogeneous solid solution film is possible only at high temperatures, whereas regions of inhomogeneous composition can be narrowed through elastic deformation, caused by the mismatch of the film-backing lattice constants. The driving forces of the spinodal decomposition of the Zn1-xCdxO system are identified. Fullerene-like clusters of Znn-xCdxOn are used to calculate the bandgap and the cohesive energy of ZnCdO solid solutions. The properties of transparent conductive ZnO films, doped with Group III donor impurities (Al, Ga, In), are examined. It is shown that oxygen vacancies are responsible for the hole trap centers in the zinc oxide photoconductivity process. We also examine the photoluminescence properties of metal-ZnO nanocomposite structures, caused by surface plasmons.

Quantitative experimental determination of the solid solution hardening potential of rhenium, tungsten and molybdenum in single-crystal nickel-based superalloys

DOE PAGES

Fleischmann, Ernst; Miller, Michael K.; Affeldt, Ernst; ...

2015-01-31

Here, the solid-solution hardening potential of the refractory elements rhenium, tungsten and molybdenum in the matrix of single-crystal nickel-based superalloys was experimentally quantified. Single-phase alloys with the composition of the nickel solid-solution matrix of superalloys were cast as single crystals, and tested in creep at 980 °C and 30–75 MPa. The use of single-phase single-crystalline material ensures very clean data because no grain boundary or particle strengthening effects interfere with the solid-solution hardening. This makes it possible to quantify the amount of rhenium, tungsten and molybdenum necessary to reduce the creep rate by a factor of 10. Rhenium is moremore » than two times more effective for matrix strengthening than either tungsten or molybdenum. The existence of rhenium clusters as a possible reason for the strong strengthening effect is excluded as a result of atom probe tomography measurements. If the partitioning coefficient of rhenium, tungsten and molybdenum between the γ matrix and the γ' precipitates is taken into account, the effectiveness of the alloying elements in two-phase superalloys can be calculated and the rhenium effect can be explained.« less

Improvements in geothermal electric power and silica production

DOEpatents

Hill, J.H.; Fulk, M.M.

Electricity is generated from hot geothermal solution by extracting heat therefrom, mineral solids which form in a so cooled geothermal solution are separated to recover minerals and facilitate reinjection of the solution into the ground. The separated solids are treated to recover silica by addition of an acid (amorphous silica precipitates) or a base (other minerals precipitate and soulble silicates are formed which are subsequently precipitated by acid neutralization). If desired, after silica is separated, other minerals can be separated and recovered.

INTERNATIONAL CONFERENCE ON SEMICONDUCTOR INJECTION LASERS SELCO-87: Refractive indices of superlattices made of III-V semiconductor compounds and their solid solutions and semiconductor waveguide laser structures

NASA Astrophysics Data System (ADS)

Unger, K.

1988-11-01

An analysis is made of the theoretical problems encountered in precision calculations of refractive indices of semiconductor materials arising in connection with the use of superlattices as active layers in double-heterostructure lasers and in connection with the use of the impurity-induced disordering effect, i.e., the ability to transform selectively a superlattice into a corresponding solid solution. This can be done by diffusion or ion implantation. A review is given of calculations of refractive indices based on the knowledge of the energy band structure and the role of disorder is considered particularly. An anomaly observed in the (InAl)As system is considered. It is shown that the local field effects and exciton transitions are important. A reasonable approach is clearly a direct calculation of the difference between the refractive indices of superlattices based on compounds and of those based on their solid solutions.

Suppression of vacancy cluster growth in concentrated solid solution alloys

DOE PAGES

Zhao, Shijun; Velisa, Gihan; Xue, Haizhou; ...

2016-12-13

Large vacancy clusters, such as stacking-fault tetrahedra, are detrimental vacancy-type defects in ion-irradiated structural alloys. Suppression of vacancy cluster formation and growth is highly desirable to improve the irradiation tolerance of these materials. In this paper, we demonstrate that vacancy cluster growth can be inhibited in concentrated solid solution alloys by modifying cluster migration pathways and diffusion kinetics. The alloying effects of Fe and Cr on the migration of vacancy clusters in Ni concentrated alloys are investigated by molecular dynamics simulations and ion irradiation experiment. While the diffusion coefficients of small vacancy clusters in Ni-based binary and ternary solid solutionmore » alloys are higher than in pure Ni, they become lower for large clusters. This observation suggests that large clusters can easily migrate and grow to very large sizes in pure Ni. In contrast, cluster growth is suppressed in solid solution alloys owing to the limited mobility of large vacancy clusters. Finally, the differences in cluster sizes and mobilities in Ni and in solid solution alloys are consistent with the results from ion irradiation experiments.« less

Geochemical Modeling of Reactions and Partitioning of Trace Metals and Radionuclides during Titration of Contaminated Acidic Sediments

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

Zhang, Fan; Parker, Jack C.; Luo, Wensui

2008-01-01

Many geochemical reactions that control aqueous metal concentrations are directly affected by solution pH. However, changes in solution pH are strongly buffered by various aqueous phase and solid phase precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior of the soil-solution system is thus critical to predict metal transport under variable pH conditions. This study was undertaken to develop a practical generic geochemical modeling approach to predict aqueous and solid phase concentrations of metals and anions during conditions of acid or base additions. The method of Spalding and Spalding was utilized to model soil buffer capacity and pH-dependent cationmore » exchange capacity by treating aquifer solids as a polyprotic acid. To simulate the dynamic and pH-dependent anion exchange capacity, the aquifer solids were simultaneously treated as a polyprotic base controlled by mineral precipitation/dissolution reactions. An equilibrium reaction model that describes aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange was developed using HydroGeoChem v5.0 (HGC5). Comparison of model results with experimental titration data of pH, Al, Ca, Mg, Sr, Mn, Ni, Co, and SO{sub 4}{sup 2-} for contaminated sediments indicated close agreement, suggesting that the model could potentially be used to predict the acid-base behavior of the sediment-solution system under variable pH conditions.« less

Synthesis of solid solutions of perovskites

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

Dambekalne, M.Y.; Antonova, M.K.; Perro, I.T.

The authors carry out thermographic studies, using a derivatograph, in order to understand the nature of the processes taking place during the synthesis of solid solutions of perovskites. Based on the detailed studies on the phase transformations occurring in the charges of the PSN-PMN solid solutions and on the selection of the optimum conditions for carrying out their synthesis, the authors obtained a powder containing a minimum quantity of the undesirable pyrochlore phase and by sintering it using the hot pressing method, they produced single phase ceramic specimens containing the perovskite phase alone with a density close to the theoreticalmore » value and showing zero apparent porosity and water absorption.« less

Determining mineral weathering rates based on solid and solute weathering gradients and velocities: Application to biotite weathering in saprolites

USGS Publications Warehouse

White, A.F.

2002-01-01

Chemical weathering gradients are defined by the changes in the measured elemental concentrations in solids and pore waters with depth in soils and regoliths. An increase in the mineral weathering rate increases the change in these concentrations with depth while increases in the weathering velocity decrease the change. The solid-state weathering velocity is the rate at which the weathering front propagates through the regolith and the solute weathering velocity is equivalent to the rate of pore water infiltration. These relationships provide a unifying approach to calculating both solid and solute weathering rates from the respective ratios of the weathering velocities and gradients. Contemporary weathering rates based on solute residence times can be directly compared to long-term past weathering based on changes in regolith composition. Both rates incorporate identical parameters describing mineral abundance, stoichiometry, and surface area. Weathering gradients were used to calculate biotite weathering rates in saprolitic regoliths in the Piedmont of Northern Georgia, USA and in Luquillo Mountains of Puerto Rico. Solid-state weathering gradients for Mg and K at Panola produced reaction rates of 3 to 6 x 10-17 mol m-2 s-1 for biotite. Faster weathering rates of 1.8 to 3.6 ?? 10-16 mol m-2 s-1 are calculated based on Mg and K pore water gradients in the Rio Icacos regolith. The relative rates are in agreement with a warmer and wetter tropical climate in Puerto Rico. Both natural rates are three to six orders of magnitude slower than reported experimental rates of biotite weathering. ?? 2002 Elsevier Science B.V. All rights reserved.

Comparative acid-base properties of the surface of components of the CdTe-ZnS system in series of substitutional solid solutions and their analogs

NASA Astrophysics Data System (ADS)

Kirovskaya, I. A.; Kasatova, I. Yu.

2011-07-01

The acid-base properties of the surface of solid solutions and binary components of the CdTe-ZnS system are studied by hydrolytic adsorption, nonaqueous conductometric titration, mechanochemistry, IR spectroscopy, and Raman scattering spectroscopy. The strength, nature, and concentration of acid centers on the original surface and that exposed to CO are determined. The changes in acid-base properties in dependence on the composition of the system under investigation in the series of CdB6, ZnB6 analogs are studied.

Crystal Violet Lactone Salicylaldehyde Hydrazone Zn(II) Complex: a Reversible Photochromic Material both in Solution and in Solid Matrix

PubMed Central

Li, Kai; Li, Yuanyuan; Tao, Jing; Liu, Lu; Wang, Lili; Hou, Hongwei; Tong, Aijun

2015-01-01

Crystal violet lactone (CVL) is a classic halochromic dye which has been widely used as chromogenic reagent in thermochromic and piezochromic systems. In this work, a very first example of CVL-based reversible photochromic compound was developed, which showed distinct color change upon UV-visible light irradiation both in solution and in solid matrix. Moreover, metal complex of CVL salicylaldehyde hydrozone was facilely synthesized, exhibiting reversible photochromic properties with good fatigue resistance. It was served as promising solid material for photo-patterning. PMID:26412101

A multi-scale Lattice Boltzmann model for simulating solute transport in 3D X-ray micro-tomography images of aggregated porous materials

NASA Astrophysics Data System (ADS)

Zhang, Xiaoxian; Crawford, John W.; Flavel, Richard J.; Young, Iain M.

2016-10-01

The Lattice Boltzmann (LB) model and X-ray computed tomography (CT) have been increasingly used in combination over the past decade to simulate water flow and chemical transport at pore scale in porous materials. Because of its limitation in resolution and the hierarchical structure of most natural soils, the X-ray CT tomography can only identify pores that are greater than its resolution and treats other pores as solid. As a result, the so-called solid phase in X-ray images may in reality be a grey phase, containing substantial connected pores capable of conducing fluids and solute. Although modified LB models have been developed to simulate fluid flow in such media, models for solute transport are relatively limited. In this paper, we propose a LB model for simulating solute transport in binary soil images containing permeable solid phase. The model is based on the single-relaxation time approach and uses a modified partial bounce-back method to describe the resistance caused by the permeable solid phase to chemical transport. We derive the relationship between the diffusion coefficient and the parameter introduced in the partial bounce-back method, and test the model against analytical solution for movement of a pulse of tracer. We also validate it against classical finite volume method for solute diffusion in a simple 2D image, and then apply the model to a soil image acquired using X-ray tomography at resolution of 30 μm in attempts to analyse how the ability of the solid phase to diffuse solute at micron-scale affects the behaviour of the solute at macro-scale after a volumetric average. Based on the simulated results, we discuss briefly the danger in interpreting experimental results using the continuum model without fully understanding the pore-scale processes, as well as the potential of using pore-scale modelling and tomography to help improve the continuum models.

First-principles study of band gap engineering via oxygen vacancy doping in perovskite ABB'O₃ solid solutions

DOE PAGES

Qi, Tingting; Curnan, Matthew T.; Kim, Seungchul; ...

2011-12-15

Oxygen vacancies in perovskite oxide solid solutions are fundamentally interesting and technologically important. However, experimental characterization of the vacancy locations and their impact on electronic structure is challenging. We have carried out first-principles calculations on two Zr-modified solid solutions, Pb(Zn 1/3Nb 2/3)O₃ and Pb(Mg 1/3Nb 2/3)O₃, in which vacancies are present. We find that the vacancies are more likely to reside between low-valent cation-cation pairs than high-valent cation-cation pairs. Based on the analysis of our results, we formulate guidelines that can be used to predict the location of oxygen vacancies in perovskite solid solutions. Our results show that vacancies canmore » have a significant impact on both the conduction and valence band energies, in some cases lowering the band gap by ≈0.5 eV. The effects of vacancies on the electronic band structure can be understood within the framework of crystal field theory.« less

Solid solutions of platinum(II) and palladium(II) oxalato-complex salt as precursors of nanoalloys

NASA Astrophysics Data System (ADS)

Zadesenets, A. V.; Asanova, T. I.; Vikulova, E. S.; Filatov, E. Yu.; Plyusnin, P. E.; Baidina, I. A.; Asanov, I. P.; Korenev, S. V.

2013-03-01

A solid solution of platinum (II) and palladium (II) oxalato-complex salt, (NH4)2[Pt0.5Pd0.5(C2O4)2]·2H2O, has been synthesized and studied as a precursor for preparing bimetallic PtPd nanoparticles through its thermal decomposition. The smallest homogenous bimetallic PtPd nanoparticles were found to form in hydrogen and helium atmospheres. The annealing temperature and time have low effect on the bimetallic particles size. Comparative analysis of structural and thermal properties of the solid solution and individual Pt, Pd oxalato-complex salts was performed to investigate a mechanism of thermal decomposition of (NH4)2[Pt0.5Pd0.5(C2O4)2]·2H2O. Based on in situ X-ray photoemission spectroscopy investigation it was proposed a mechanism of formation of bimetallic PtPd nanoparticles from the solid-solution oxalato-complex salt during thermal decomposition.

Design of high-strength refractory complex solid-solution alloys

DOE PAGES

Singh, Prashant; Sharma, Aayush; Smirnov, A. V.; ...

2018-03-28

Nickel-based superalloys and near-equiatomic high-entropy alloys containing molybdenum are known for higher temperature strength and corrosion resistance. Yet, complex solid-solution alloys offer a huge design space to tune for optimal properties at slightly reduced entropy. For refractory Mo-W-Ta-Ti-Zr, we showcase KKR electronic structure methods via the coherent-potential approximation to identify alloys over five-dimensional design space with improved mechanical properties and necessary global (formation enthalpy) and local (short-range order) stability. Deformation is modeled with classical molecular dynamic simulations, validated from our first-principle data. We predict complex solid-solution alloys of improved stability with greatly enhanced modulus of elasticity (3× at 300 K)more » over near-equiatomic cases, as validated experimentally, and with higher moduli above 500 K over commercial alloys (2.3× at 2000 K). We also show that optimal complex solid-solution alloys are not described well by classical potentials due to critical electronic effects.« less

Design of high-strength refractory complex solid-solution alloys

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

Singh, Prashant; Sharma, Aayush; Smirnov, A. V.

Nickel-based superalloys and near-equiatomic high-entropy alloys containing molybdenum are known for higher temperature strength and corrosion resistance. Yet, complex solid-solution alloys offer a huge design space to tune for optimal properties at slightly reduced entropy. For refractory Mo-W-Ta-Ti-Zr, we showcase KKR electronic structure methods via the coherent-potential approximation to identify alloys over five-dimensional design space with improved mechanical properties and necessary global (formation enthalpy) and local (short-range order) stability. Deformation is modeled with classical molecular dynamic simulations, validated from our first-principle data. We predict complex solid-solution alloys of improved stability with greatly enhanced modulus of elasticity (3× at 300 K)more » over near-equiatomic cases, as validated experimentally, and with higher moduli above 500 K over commercial alloys (2.3× at 2000 K). We also show that optimal complex solid-solution alloys are not described well by classical potentials due to critical electronic effects.« less

Elastic constants and pressure derivative of elastic constants of Si1-xGex solid solution

NASA Astrophysics Data System (ADS)

Jivani, A. R.; Baria, J. K.; Vyas, P. S.; Jani, A. R.

2013-02-01

Elastic properties of Si1-xGex solid solution with arbitrary (atomic) concentration (x) are studied using the pseudo-alloy atom model based on the pseudopotential theory and on the higher-order perturbation scheme with the application of our own proposed model potential. We have used local-field correction function proposed by Sarkar et al to study Si-Ge system. The Elastic constants and pressure derivatives of elastic constants of the solid solution is investigated with different concentration x of Ge. It is found in the present study that the calculated numerical values of the aforesaid physical properties of Si-Ge system are function of x. The elastic constants (C11, C12 and C44) decrease linearly with increase in concentration x and pressure derivative of elastic constants (C11, C12 and C44) increase with the concentration x of Ge. This study provides better set of theoretical results for such solid solution for further comparison either with theoretical or experimental results.

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.

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.

Theoretical prediction of morphotropic compositions in Na1/2Bi1/2TiO3-based solid solutions from transition pressures

NASA Astrophysics Data System (ADS)

Gröting, Melanie; Albe, Karsten

2014-02-01

In this article we present a method based on ab initio calculations to predict compositions at morphotropic phase boundaries in lead-free perovskite solid solutions. This method utilizes the concept of flat free energy surfaces and involves the monitoring of pressure-induced phase transitions as a function of composition. As model systems, solid solutions of Na1/2Bi1/2TiO3 with the alkali substituted Li1/2Bi1/2TiO3 and K1/2Bi1/2TiO3 and the alkaline earth substituted CaTiO3 and BaTiO3 are chosen. The morphotropic compositions are identified by determining the composition at which the phase transition pressure equals zero. In addition, we discuss the different effects of hydrostatic pressure (compression and tension) and chemical substitution on the antiphase tilts about the [111] axis (a-a-a-) present in pure Na1/2Bi1/2TiO3 and how they develop in the two solid solutions Na1/2Bi1/2TiO3-CaTiO3 and Na1/2Bi1/2TiO3-BaTiO3. Finally, we discuss the advantages and shortcomings of this simple computational approach.

Solid state RF power: The route to 1W per euro cent

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

Heid, Oliver

2013-04-19

In most particle accelerators RF power is a decisive design constraint due to high costs and relative inflexibility of current electron beam based RF sources, i.e. Klystrons, Magnetrons, Tetrodes etc. At VHF/UHF frequencies the transition to solid state devices promises to fundamentally change the situation. Recent progress brings 1 Watt per Euro cent installed cost within reach. We present a Silicon Carbide semiconductor solution utilising the Solid State Direct Drive technology at unprecedented efficiency, power levels and power densities. The proposed solution allows retrofitting of existing RF accelerators and opens the route to novel particle accelerator concepts.

On the modeling of irradiation-induced homogeneous precipitation in proton-bombarded Ni-Si solid solutions

NASA Astrophysics Data System (ADS)

Lam, Nghi Q.; Janghorban, K.; Ardell, A. J.

1981-10-01

Irradiation-induced solute redistribution leading to precipitation of coherent γ' particles in undersaturated Ni-based solid solutions containing 6 and 8 at.% Si during 400-keV proton bombardment was modeled, based on the concept of solute segregation in concentrated alloys under spatially-dependent defect production conditions. The combined effects of (i) an extremely large difference between the defect production rates in the peak-damage and mid-range regions during irradiation and (ii) a preferential coupling between the interstitial and solute fluxes generate a net transient flux of Si atoms into the mid-range region, which is much larger than the solute flux out of this location. As a result, the Si concentration exceeds the solubility limit and homogeneous precipitation of the γ' phase occurs in this particular region of the irradiated samples. The spatial, compositional and temperature dependences of irradiation-induced homogeneous precipitation derived from the present theoretical calculations are in good qualitative agreement with experimental observations

NEUTRALIZATIONS OF HIGH ALUMINUM LOW URANIUM USED NUCLEAR FUEL SOLUTIONS CONTAINING GADOLINIUM AS A NEUTRON POISON

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

Taylor-Pashow, K.

2011-06-08

H-Canyon will begin dissolving High Aluminum - Low Uranium (High Al/Low U) Used Nuclear Fuel (UNF) following approval by DOE which is anticipated in CY2011. High Al/Low U is an aluminum/enriched uranium UNF with small quantities of uranium relative to aluminum. The maximum enrichment level expected is 93% {sup 235}U. The High Al/Low U UNF will be dissolved in H-Canyon in a nitric acid/mercury/gadolinium solution. The resulting solution will be neutralized and transferred to Tank 39H in the Tank Farm. To confirm that the solution generated could be poisoned with Gd, neutralized, and discarded to the Savannah River Site (SRS)more » high level waste (HLW) system without undue nuclear safety concerns the caustic precipitation of simulant solutions was examined. Experiments were performed with three simulant solutions representative of the H-Canyon estimated concentrations in the final solutions after dissolution. The maximum U, Gd, and Al concentration were selected for testing from the range of solution compositions provided. Simulants were prepared in three different nitric acid concentrations, ranging from 0.5 to 1.5 M. The simulant solutions were neutralized to four different endpoints: (1) just before a solid phase was formed (pH 3.5-4), (2) the point where a solid phase was obtained, (3) 0.8 M free hydroxide, and (4) 1.2 M free hydroxide, using 50 wt % sodium hydroxide (NaOH). The settling behavior of the neutralized solutions was found to be slower compared to previous studies, with settling continuing over a one week period. Due to the high concentration of Al in these solutions, precipitation of solids was observed immediately upon addition of NaOH. Precipitation continued as additional NaOH was added, reaching a point where the mixture becomes almost completely solid due to the large amount of precipitate. As additional NaOH was added, some of the precipitate began to redissolve, and the solutions neutralized to the final two endpoints mixed easily and had expected densities of typical neutralized waste. Based on particle size and scanning electron microscopy analyses, the neutralized solids were found to be homogeneous and less than 20 microns in size. The majority of solids were less than 4 microns in size. Compared to previous studies, a larger percentage of the Gd was found to precipitate in the partially neutralized solutions (at pH 3.5-4). In addition the Gd:U mass ratio was found to be at least 1.0 in all of the solids obtained after partial or full neutralization. The hydrogen to U (H:U) molar ratios for two accident scenarios were also determined. The first was for transient neutralization and agitator failure. Experimentally this scenario was determined by measuring the H:U ratio of the settled solids. The minimum H:U molar ratio for solids from fully neutralized solutions was 388:1. The second accident scenario is for the solids drying out in an unagitiated pump box. Experimentally, this scenario was determined by measuring the H:U molar ratio in centrifuged solids. The minimum H:U atom ratios for centrifuged precipitated solids was 250:1. It was determined previously that a 30:1 H:Pu atom ratio was sufficient for a 1:1 Gd:Pu mass ratio. Assuming a 1:1 equivalence with {sup 239}Pu, the results of these experiments show Gd is a viable poison for neutralizing U/Gd solutions with the tested compositions.« less

Analysis of Ductile-Brittle Transition Temperatures for Controlled-Rolled, Microalloyed, C-Mn Based Steels.

DTIC Science & Technology

1988-05-01

This deformation gives an increase in friction stress without much further reduction in grain size. Solid solution and precipitation strengthening are...finishing temperatures because of the measured effect of Mo on lowering the ferrite transformation temperature (I). The precipitation of NbC in the...unchanged. Very probably, Mo, through its solid solution strengthening of ferrite, particularly at 760°C in the austenite-ferrite region, caused the

Detection of X-ray photons by solution-processed organic-inorganic perovskites

PubMed Central

Yakunin, Sergii; Sytnyk, Mykhailo; Kriegner, Dominik; Shrestha, Shreetu; Richter, Moses; Matt, Gebhard J.; Azimi, Hamed; Brabec, Christoph J.; Stangl, Julian; Kovalenko, Maksym V.; Heiss, Wolfgang

2017-01-01

The evolution of real-time medical diagnostic tools such as angiography and computer tomography from radiography based on photographic plates was enabled by the development of integrated solid-state X-ray photon detectors, based on conventional solid-state semiconductors. Recently, for optoelectronic devices operating in the visible and near infrared spectral regions, solution-processed organic and inorganic semiconductors have also attracted immense attention. Here we demonstrate a possibility to use such inexpensive semiconductors for sensitive detection of X-ray photons by direct photon-to-current conversion. In particular, methylammonium lead iodide perovskite (CH3NH3PbI3) offers a compelling combination of fast photoresponse and a high absorption cross-section for X-rays, owing to the heavy Pb and I atoms. Solution processed photodiodes as well as photoconductors are presented, exhibiting high values of X-ray sensitivity (up to 25 µC mGyair-1 cm-3) and responsivity (1.9×104 carriers/photon), which are commensurate with those obtained by the current solid-state technology. PMID:28553368

Seasonal multiphase equilibria in the atmospheres of Titan and Pluto

NASA Astrophysics Data System (ADS)

Tan, S. P.; Kargel, J. S.

2017-12-01

At the extremely low temperatures in Titan's upper troposphere and on Pluto's surface, the atmospheres as a whole are subject to freeze into solid solutions, not pure ices. The presence of the solid phases introduces conditions with rich phase equilibria upon seasonal changes, even if the temperature undergoes only small changes. For the first time, the profile of atmospheric methane in Titan's troposphere will be reproduced complete with the solid solutions. This means that the freezing point, i.e. the altitude where the first solid phase appears, is determined. The seasonal change will also be evaluated both at the equator and the northern polar region. For Pluto, also for the first time, the seasonal solid-vapor equilibria will be evaluated. The fate of the two solid phases, the methane-rich and carbon-monoxide-rich solid solutions, will be analyzed upon temperature and pressure changes. Such investigations are enabled by the development of a molecular-based thermodynamic model for cryogenic chemical systems, referred to as CRYOCHEM, which includes solid solutions in its phase-equilibria calculations. The atmospheres of Titan and Pluto are modeled as ternary gas mixtures: nitrogen-methane-ethane and nitrogen-methane-carbon monoxide, respectively. Calculations using CRYOCHEM can provide us with compositions not only in two-phase equilibria, but also that in three-phase equilibria. Densities of all phases involved will also be calculated. For Titan, density inversion between liquid and solid phases will be identified and presented. In the inversion, the density of solid phase is less than that in the liquid phase. The method and results of this work will be useful for further investigations and modeling on the atmospheres of Titan, Pluto, and other bodies with similar conditions in the Solar System and beyond.

Metal/Metal Oxide Differential Electrode pH Sensors

NASA Technical Reports Server (NTRS)

West, William; Buehler, Martin; Keymeulen, Didier

2007-01-01

Solid-state electrochemical sensors for measuring the degrees of acidity or alkalinity (in terms of pH values) of liquid solutions are being developed. These sensors are intended to supplant older electrochemical pH sensors that include glass electrode structures and reference solutions. The older sensors are fragile and subject to drift. The present developmental solid-state sensors are more rugged and are expected to be usable in harsh environments. The present sensors are based on a differential-electrode measurement principle. Each sensor includes two electrodes, made of different materials, in equilibrium with the solution of interest.

Molten-salt synthesis and composition-dependent luminescent properties of barium tungsto-molybdate-based solid solution phosphors

NASA Astrophysics Data System (ADS)

Xiang-Hong, He; Zhao-Lian, Ye; Ming-Yun, Guan; Ning, Lian; Jian-Hua, Sun

2016-02-01

Pr3+-activated barium tungsto-molybdate solid solution phosphor Ba(Mo1-zWz)O4:Pr3+ is successfully fabricated via a facile molten-salt approach. The as-synthesized microcrystal is of truncated octahedron and exhibits deep-red-emitting upon blue light excitation. Powder x-ray diffraction and Raman spectroscopy techniques are utilized to investigate the formation of solid solution phosphor. The luminescence behaviors depend on the resulting composition of the microcrystals with fixed Pr3+-doping concentration, while the host lattices remain in a scheelite structure. The forming solid solution via the substitution of [WO4] for [MoO4] can significantly enhance its luminescence, which may be due to the fact that Ba(Mo1-zWz)O4:Pr3+ owns well-defined facets and uniform morphologies. Owing to its properties of high phase purity, well-defined facets, highly uniform morphologies, exceptional chemical and thermal stabilities, and stronger emission intensity, the resulting solid solution phosphor is expected to find potential applications in phosphor-converted white light-emitting diodes (LEDs). Project supported by the Construction Fund for Science and Technology Innovation Group from Jiangsu University of Technology, China, the Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, China (Grant No. KHK1409), the Priority Academic Program Development of Jiangsu Higher Education Institutions, China, and the National Natural Science Foundation of China (Grant No. 21373103).

Incorporation of Cadmium and Nickel into Ferrite Spinel Solid Solution: X-ray Diffraction and X-ray Absorption Fine Structure Analyses.

PubMed

Su, Minhua; Liao, Changzhong; Chan, Tingshan; Shih, Kaimin; Xiao, Tangfu; Chen, Diyun; Kong, Lingjun; Song, Gang

2018-01-16

The feasibility of incorporating Cd and Ni in hematite was studied by investigating the interaction mechanism for the formation of Cd x Ni 1-x Fe 2 O 4 solid solutions (CNFs) from CdO, NiO, and α-Fe 2 O 3 . X-ray diffraction results showed that the CNFs crystallized into spinel structures with increasing lattice parameters as the Cd content in the precursors was increased. Cd 2+ ions were found to occupy the tetrahedral sites, as evidenced by Rietveld refinement and extended X-ray absorption fine structure analyses. The incorporation of Cd and Ni into ferrite spinel solid solution strongly relied on the processing parameters. The incorporation of Cd and Ni into the CNFs was greater at high x values (0.7 < x ≤ 1.0) than at low x values (0.0 ≤ x ≤ 0.7). A feasible treatment technique based on the investigated mechanism of CNF formation was developed, involving thermal treatment of waste sludge containing Cd and Ni. Both of these metals in the waste sludge were successfully incorporated into a ferrite spinel solid solution, and the concentrations of leached Cd and Ni from this solid solution were substantially reduced, stabilizing at low levels. This research offers a highly promising approach for treating the Cd and Ni content frequently encountered in electronic waste and its treatment residues.

Unraveling the Solution-State Supramolecular Structures of Donor-Acceptor Polymers and their Influence on Solid-State Morphology and Charge-Transport Properties.

PubMed

Zheng, Yu-Qing; Yao, Ze-Fan; Lei, Ting; Dou, Jin-Hu; Yang, Chi-Yuan; Zou, Lin; Meng, Xiangyi; Ma, Wei; Wang, Jie-Yu; Pei, Jian

2017-11-01

Polymer self-assembly in solution prior to film fabrication makes solution-state structures critical for their solid-state packing and optoelectronic properties. However, unraveling the solution-state supramolecular structures is challenging, not to mention establishing a clear relationship between the solution-state structure and the charge-transport properties in field-effect transistors. Here, for the first time, it is revealed that the thin-film morphology of a conjugated polymer inherits the features of its solution-state supramolecular structures. A "solution-state supramolecular structure control" strategy is proposed to increase the electron mobility of a benzodifurandione-based oligo(p-phenylene vinylene) (BDOPV)-based polymer. It is shown that the solution-state structures of the BDOPV-based conjugated polymer can be tuned such that it forms a 1D rod-like structure in good solvent and a 2D lamellar structure in poor solvent. By tuning the solution-state structure, films with high crystallinity and good interdomain connectivity are obtained. The electron mobility significantly increases from the original value of 1.8 to 3.2 cm 2 V -1 s -1 . This work demonstrates that "solution-state supramolecular structure" control is critical for understanding and optimization of the thin-film morphology and charge-transport properties of conjugated polymers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Calibration-free quantification of interior properties of porous media with x-ray computed tomography.

PubMed

Hussein, Esam M A; Agbogun, H M D; Al, Tom A

2015-03-01

A method is presented for interpreting the values of x-ray attenuation coefficients reconstructed in computed tomography of porous media, while overcoming the ambiguity caused by the multichromatic nature of x-rays, dilution by void, and material heterogeneity. The method enables determination of porosity without relying on calibration or image segmentation or thresholding to discriminate pores from solid material. It distinguishes between solution-accessible and inaccessible pores, and provides the spatial and frequency distributions of solid-matrix material in a heterogeneous medium. This is accomplished by matching an image of a sample saturated with a contrast solution with that saturated with a transparent solution. Voxels occupied with solid-material and inaccessible pores are identified by the fact that they maintain the same location and image attributes in both images, with voxels containing inaccessible pores appearing empty in both images. Fully porous and accessible voxels exhibit the maximum contrast, while the rest are porous voxels containing mixtures of pore solutions and solid. This matching process is performed with an image registration computer code, and image processing software that requires only simple subtraction and multiplication (scaling) processes. The process is demonstrated in dolomite (non-uniform void distribution, homogeneous solid matrix) and sandstone (nearly uniform void distribution, heterogeneous solid matrix) samples, and its overall performance is shown to compare favorably with a method based on calibration and thresholding. Copyright © 2014 Elsevier Ltd. All rights reserved.

Improving the dissolution rate of poorly water soluble drug by solid dispersion and solid solution: pros and cons.

PubMed

Chokshi, Rina J; Zia, Hossein; Sandhu, Harpreet K; Shah, Navnit H; Malick, Waseem A

2007-01-01

The solid dispersions with poloxamer 188 (P188) and solid solutions with polyvinylpyrrolidone K30 (PVPK30) were evaluated and compared in an effort to improve aqueous solubility and bioavailability of a model hydrophobic drug. All preparations were characterized by differential scanning calorimetry, powder X-ray diffraction, intrinsic dissolution rates, and contact angle measurements. Accelerated stability studies also were conducted to determine the effects of aging on the stability of various formulations. The selected solid dispersion and solid solution formulations were further evaluated in beagle dogs for in vivo testing. Solid dispersions were characterized to show that the drug retains its crystallinity and forms a two-phase system. Solid solutions were characterized to be an amorphous monophasic system with transition of crystalline drug to amorphous state. The evaluation of the intrinsic dissolution rates of various preparations indicated that the solid solutions have higher initial dissolution rates compared with solid dispersions. However, after storage at accelerated conditions, the dissolution rates of solid solutions were lower due to partial reversion to crystalline form. The drug in solid dispersion showed better bioavailability in comparison to solid solution. Therefore, considering physical stability and in vivo study results, the solid dispersion was the most suitable choice to improve dissolution rates and hence the bioavailability of the poorly water soluble drug.

Mechanism of drug release from polymethacrylate-based extrudates and milled strands prepared by hot-melt extrusion.

PubMed

Albers, Jessica; Alles, Rainer; Matthée, Karin; Knop, Klaus; Nahrup, Julia Schulze; Kleinebudde, Peter

2009-02-01

The aim of the study was the formulation of solid dispersions of the poorly water-soluble drug celecoxib and a polymethacrylate carrier by hot-melt extrusion. The objectives were to elucidate the mechanism of drug release from obtained extrudates and milled strands addicted to the solid-state properties of the solid dispersions and to examine and eliminate stability problems occurring under storage, exposure of mechanical stress, and in vitro dissolution. Transparent extrudates containing up to 60% drug could be prepared with a temperature setting below the melting point of celecoxib. XRPD and DSC measurements indicated the formation of a glassy solid solution, where the drug is molecularly dispersed in the carrier. The amorphous state of the glassy solid solution could be maintained during the exposure of mechanical stress in a milling process, and was stable under storage for at least 6 months. Solid-state properties and SEM images of extrudates after dissolution indicated a carrier-controlled dissolution, whereby the drug is molecularly dispersed within the concentrated carrier layer. The glassy solid solution showed a 58-fold supersaturation in 0.1 N HCl within the first 10 min, which was followed by a recrystallization process. Recrystallization could be inhibited by an external addition of HPMC.

Interdiffusion and Intrinsic Diffusion in the Mg-Al System

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

Brennan, Sarah; Bermudez, Katrina; Sohn, Yong Ho

2012-01-01

Solid-to-solid diffusion couples were assembled and annealed to examine the diffusion between pure Mg (99.96%) and Al (99.999%). Diffusion anneals were carried out at 300 , 350 , and 400 C for 720, 360, and 240 hours, respectively. Optical and scanning electron microscopes were utilized to identify the formation of the intermetallic phases, -Al12Mg17 and -Al3Mg2 and absence of the -phase in the diffusion couples. Thicknesses of the -Al12Mg17 and -Al3Mg2 phases were measured and the parabolic growth constants were calculated to determine the activation energies for the growth, 165 and 86 KJ/mole, respectively. Concentration profiles were determined with electronmore » microprobe analysis using pure elemental standards. Composition-dependent interdiffusion coefficients in Mg-solid solution, -Al12Mg17 and - Al3Mg2 and Al-solid solutions were calculated based on the Boltzmann-Matano analysis. Average effective interdiffusion coefficients for each phase were also calculated, and the magnitude was the highest for the -Al3Mg2 phase, followed by -Al12Mg17, Al-solid solution and Mg-solid solution. Intrinsic diffusion coefficients based on Huemann s analysis (e.g., marker plane) were determined for the ~38 at.% Mg in the -Al3Mg2 phase. Activation energies and the pre-exponential factors for the inter- and intrinsic diffusion coefficients were calculated for the temperature range examined. The -Al3Mg2 phase was found to have the lowest activation energies for growth and interdiffusion among all four phases studied. At the marker location in the -Al3Mg2 phase, the intrinsic diffusion of Al was found to be faster than that of Mg. Extrapolations of the impurity diffusion coefficients in the terminal solid solutions were made and compared to the available self- and impurity diffusion data from literature. Thermodynamic factor, tracer diffusion coefficients and atomic mobilities at the marker plane composition were approximated using available literature values of Mg activity in the -Al3Mg2 phase.« less

A decontamination system for chemical weapons agents using a liquid solution on a solid sorbent.

PubMed

Waysbort, Daniel; McGarvey, David J; Creasy, William R; Morrissey, Kevin M; Hendrickson, David M; Durst, H Dupont

2009-01-30

A decontamination system for chemical warfare agents was developed and tested that combines a liquid decontamination reagent solution with solid sorbent particles. The components have fewer safety and environmental concerns than traditional chlorine bleach-based products or highly caustic solutions. The liquid solution, based on Decon Greentrade mark, has hydrogen peroxide and a carbonate buffer as active ingredients. The best solid sorbents were found to be a copolymer of ethylene glycol dimethacrylate and n-lauryl methacrylate (Polytrap 6603 Adsorber); or an allyl methacrylate cross-linked polymer (Poly-Pore E200 Adsorber). These solids are human and environmentally friendly and are commonly used in cosmetics. The decontaminant system was tested for reactivity with pinacolyl methylphosphonofluoridate (Soman, GD), bis(2-chloroethyl)sulfide (Mustard, HD), and S-(2-diisopropylaminoethyl) O-ethyl methylphosphonothioate (VX) by using NMR Spectroscopy. Molybdate ion (MoO(4)(-2)) was added to the decontaminant to catalyze the oxidation of HD. The molybdate ion provided a color change from pink to white when the oxidizing capacity of the system was exhausted. The decontaminant was effective for ratios of agent to decontaminant of up to 1:50 for VX (t(1/2) < or = 4 min), 1:10 for HD (t(1/2) < 2 min with molybdate), and 1:10 for GD (t(1/2) < 2 min). The vapor concentrations of GD above the dry sorbent and the sorbent with decontamination solution were measured to show that the sorbent decreased the vapor concentration of GD. The E200 sorbent had the additional advantage of absorbing aqueous decontamination solution without the addition of an organic co-solvent such as isopropanol, but the rate depended strongly on mixing for HD.

Structural, Electronic, and Optical Properties of BiOX1-xYx (X, Y = F, Cl, Br, and I) Solid Solutions from DFT Calculations.

PubMed

Zhao, Zong-Yan; Liu, Qing-Lu; Dai, Wen-Wu

2016-08-23

Six BiOX1-xYx (X, Y = F, Cl, Br, and I) solid solutions have been systematically investigated by density functional theory calculations. BiOCl1-xBrx, BiOBr1-xIx, and BiOCl1-xIx solid solutions have very small bowing parameters; as such, some of their properties increase almost linearly with increasing x. For BiOF1-xYx solid solutions, the bowing parameters are very large and it is extremely difficult to fit the related calculated data by a single equation. Consequently, BiOX1-xYx (X, Y = Cl, Br, and I) solid solutions are highly miscible, while BiOF1-xYx (Y = Cl, Br, and I) solid solutions are partially miscible. In other words, BiOF1-xYx solid solutions have miscibility gaps or high miscibility temperature, resulting in phase separation and F/Y inhomogeneity. Comparison and analysis of the calculated results and the related physical-chemical properties with different halogen compositions indicates that the parameters of BiOX1-xYx solid solutions are determined by the differences of the physical-chemical properties of the two halogen compositions. In this way, the large deviation of some BiOX1-xYx solid solutions from Vegard's law observed in experiments can be explained. Moreover, the composition ratio of BiOX1-xYx solid solutions can be measured or monitored using optical measurements.

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

Du Hongliang; Zhou Wancheng; Luo Fa

The (1-x)(K{sub 0.5}Na{sub 0.5})NbO{sub 3}-x(Ba{sub 0.5}Sr{sub 0.5})TiO{sub 3} (KNN-BST) solid solution has been synthesized by conventional solid-state sintering in order to search for the new lead-free relaxor ferroelectrics for high temperature applications. The phase structure, dielectric properties, and relaxor behavior of the (1-x)KNN-xBST solid solution are systematically investigated. The phase structure of the (1-x)KNN-xBST solid solution gradually changes from pure perovskite phase with an orthorhombic symmetry to the tetragonal symmetry, then to the pseudocubic phase, and to the cubic phase with increasing addition of BST. The 0.90KNN-0.10BST solid solution shows a broad dielectric peak with permittivity maximum near 2500 andmore » low dielectric loss (<4%) in the temperature range of 100-250 deg. C. The result indicates that this material may have great potential for a variety of high temperature applications. The diffuse phase transition and the temperature of the maximum dielectric permittivity shifting toward higher temperature with increasing frequency, which are two typical characteristics for relaxor ferroelectrics, are observed in the (1-x)KNN-xBST solid solution. The dielectric relaxor behavior obeys a modified Curie-Weiss law and a Vogel-Fulcher relationship. The relaxor nature is attributed to the appearance of polar nanoregions owing to the formation of randon fields including local electric fields and elastic fields. These results confirm that the KNN-based relaxor ferroelectrics can be regarded as an alternative direction for the development of high temperature lead-free relaxor ferroelectrics.« less

EXAFS and electrical studies of new narrow-gap semiconductors: InTe1-xSex and In1-xGaxTe

NASA Astrophysics Data System (ADS)

Lebedev, A. I.; Michurin, A. V.; Sluchinskaya, I. A.; Demin, V. N.; Munro, I. H.

2000-12-01

The local environment of Ga, Se and Tl atoms in InTe-based solid solutions was studied by EXAFS technique. It was shown that all investigated atoms are substitutional impurities, which enter the In(1), Te and In(2) positions in the InTe structure, respectively. The electrical measurements revealed that In1-xGaxTe and InTe1-xSex solid solutions become semiconductors at x>0.24 and >0.15, respectively.

Optimisation of cavity parameters for lasers based on AlGaInAsP/InP solid solutions (λ = 1470 nm)

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

Veselov, D A; Ayusheva, K R; Shashkin, I S

2015-10-31

We have studied the effect of laser cavity parameters on the light–current characteristics of lasers based on the AlGaInAs/GaInAsP/InP solid solution system that emit in the spectral range 1400 – 1600 nm. It has been shown that optimisation of cavity parameters (chip length and front facet reflectivity) allows one to improve heat removal from the laser, without changing other laser characteristics. An increase in the maximum output optical power of the laser by 0.5 W has been demonstrated due to cavity design optimisation. (lasers)

Effect of nitrogen on iron-manganese-based shape memory alloys

NASA Astrophysics Data System (ADS)

Ariapour, Azita

Shape memory effect is due to a reversible martensitic transformation. The major drawback in case of Fe-Mn-based shape memory alloys is their inferior shape memory effect compared to Ni-Ti and Cu-based shape memory alloys and their low strength and corrosion resistance compared to steel alloys. It is known that by increasing the alloy strength the shape memory effect can be improved. Nitrogen in solid solution can increase the strength of steels to a greater extent than other major alloying elements. However, its effect on shape memory effect of Fe-Mn-based alloys is ambiguous. In this work first we investigated the effect of nitrogen addition in solid solution on both shape memory effect (SME) and strength of a Fe-Mn-Cr-Ni-Si shape memory alloy (SMA). It was found that interstitial nitrogen suppressed the shape memory effect in these alloys. As an example addition of 0.24 wt % nitrogen in solid solution to the alloy system suppressed the SME by ˜80% and increased the strength by 20%. A reduction of martensitic phase formation was found to be the dominant factor in suppression of the SME. This was related, experimentally and theoretically to stacking fault energy of the alloy as well as the driving force and friction force during the transformation. The second approach was doping the alloy with both 0.36 wt% of nitrogen and 0.36 wt% of niobium. Niobium has great affinity for nitrogen and thus NbN dispersed particles can be produced in the alloy following hot rolling. Then particles prevent growth of the alloy and increase the strength of the alloy due to reduced grain size, and precipitation hardening. The improvement of SME in this alloy compared to the interstitial containing alloys was due to the large removal of the nitrogen from solid solution. In case of all the alloys studied in this work, the presence of nitrogen in solid solution improved the corrosion resistance of the alloy. This suggests that nitrogen can replace nickel in the alloy. One of the proposed applications for high strength Fe-Mn-based alloys is as tendon rods in prestressed concrete. The advantage of M alloys in this application is the possibility of producing curved structural prestressed concrete.

Thermal properties of spinel based solid solutions

NASA Astrophysics Data System (ADS)

O'Hara, Kelley Rae

Solid solution formation in spinel based systems proved to be a viable approach to decreasing thermal conductivity. Samples with systematically varied additions of MgGa2O4 to MgAl2O 4 were prepared and thermal diffusivity was measured using the laser flash technique. Additionally, heat capacity was measured using differential scanning calorimetry and modeled for the MgAl2O4-MgGa 2O4 system. At 200°C thermal conductivity decreased 24% with a 5 mol% addition of MgGa2O4 to the system. The solid solution continued to decrease the thermal conductivity by 13% up to 1000°C with 5 mol% addition. The decrease in thermal conductivity ultimately resulted in a decrease in heat flux when applied to a theoretical furnace lining, which could lead to energy savings in industrial settings. The MgAl2O4-Al2O3 phase equilibria was investigated to fully understand the system and the thermal properties at elevated temperatures. The solvus line between MgAl2O4 and Al2O3 has been defined at 79.6 wt% Al 2O3 at 1500°C, 83.0 wt% Al2O4 at 1600°C, and 86.5 wt% Al2O3 at 1700°C. A metastable region has been identified at temperatures up to 1700°C which could have significant implications for material processing and properties. The spinel solid solution region has been extended to form an infinite solid solution with Al2O3 at elevated temperatures. A minimum in melting at 1975°C and a chemistry of 96 wt% Al2O3 rather than a eutectic is present. Thermal properties in the MgAl2O4-Al2O 3 system were investigated in both the single phase solid solution region and the two phase region. The thermal diffusivity decreased through the MgAl 2O4 solid solution region and was at a minimum through the entire metastable (nucleation and growth) region. As Al2O 3 became present as a second phase the thermal diffusivity increased with Al2O3 content. There was an 11.7% increase in thermal diffusivity with a change in overall chemistry of 85.20 wt% Al2O 3 to 87.71 wt% Al2O3, due to the drastic change in final chemistry (38.3 wt% Al20 3) caused by the nucleation and growth region in the system.

Chemical effects induced by gamma-irradiation in solid and in aqueous methanol solutions of 4-iodophenol

NASA Astrophysics Data System (ADS)

Mahfouz, R. M.; Siddiqui, M. R. H.; Al-Wassil, A. I.; Al-Resayes, S. I.; Al-Otaibi, A. M.

2005-05-01

The present work is a study on radiolyses of 4-iodophenol in aqueous methanol solutions. The radiolysis products are separated and identified using spectrophotometric and chromatographic techniques. The radiolytic products (I-2, I- and IO3-) formed in aerated solutions at room temperature were identified and the yields are investigated as a function of absorbed gamma-ray dose. The formation of I-2 is mainly dependent on the acidity of solution and produced via the pathway of secondary free radical reactions. Aromatic products of lower and higher molecular weight than the corresponding investigated compound were analysed and separated by HPLC. The results have been discussed in view of mechanisms based on free radicals and ion-molecule interactions. The chemical effects induced by gamma-irradiation in solid 4-iodophenol have also been investigated and the degradation products were identified in solid state by NMR, GC/MS experiments and HPLC after dissolution in aqueous methanol. The results were evaluated and compared with radiolysis data.

Influence of an americium solid phase on americium concentrations in solutions

NASA Astrophysics Data System (ADS)

Rai, Dhanpat; Strickert, R. G.; Moore, D. A.; Serne, R. J.

1981-11-01

Americium-241 concentrations in solutions contacting contaminated sediments for up to 2 yr were measured as a function of pH. Steady-state concentrations were reached within a few days. The solubility-limited Am concentration was found to decrease approximately 10-fold with one unit increase in pH. The log equilibrium constant for the solubility of Am (soil) solid [Am (soil) + H + ⇌ Am (aq complex)+] was found to be -4.12. The predictions based upon thermodynamic data suggest that Am (aq complex)+ is likely to be Am(OH) 2+. Although the chemical formula of Am (soil) was not determined, it does not appear to be Am(OH) 3(a). Published data on sorption coefficients of Am by different rocks, soils, and minerals were critically evaluated. Final Am solution concentrations calculated from the sorption coefficients of a variety of earth materials with several solutions agreed well with the concentrations predicted from the solubility of Am (soil) solid, indicating that the sorption coefficient data are controlled by Am precipitation.

Fluorous tagging strategy for solution-phase synthesis of small molecules, peptides and oligosaccharides

PubMed Central

Zhang, Wei

2005-01-01

The purification of reaction mixtures is a slow process in organic synthesis, especially during the production of large numbers of analogs and compound libraries. Phase-tag methods such as solid-phase synthesis and fluorous synthesis, provide efficient ways of addressing the separation issue. Fluorous synthesis employs functionalized perfluoroalkyl groups attached to substrates or reagents. The separation of the resulting fluorous molecules can be achieved using strong and selective fluorous liquid-liquid extraction, fluorous silica gel-based solid-phase extraction or high-performance liquid chromatography. Fluorous technology is a novel solution-phase method, which has the advantages of fast reaction times in homogeneous environments, being readily adaptable to literature conditions, having easy intermediate analysis, and having flexibility in reaction scale and scope. In principle, any synthetic methods that use a solid-support could be conducted in solution-phase by replacing the polymer linker with a corresponding fluorous tag. This review summarizes the progress of fluorous tags in solution-phase synthesis of small molecules, peptides and oligosaccharides. PMID:15595439

Single crystal structure analyses of scheelite-powellite CaW1-xMoxO4 solidsolutions and unique occurrence in Jisyakuyama skarn deposits

NASA Astrophysics Data System (ADS)

Yamashita, K.; Yoshiasa, A.; Miyazaki, H.; Tokuda, M.; Tobase, T.; Isobe, H.; Nishiyama, T.; Sugiyama, K.; Miyawaki, R.

2017-12-01

Jisyakuyama skarn deposit, Fukuchi, Fukuoka, Japan, shows a simple occurrenceformed by penetration of hot water into limestone cracks. A unique occurrence of scheelite-powellite CaW1-xMoxO4 minerals is observed in the skarn deposit. Many syntheticexperiments for scheelite-powellite solid solutions have been reported as research onfluorescent materials. In this system it is known that a complete continuous solid solution isformed even at room temperature. In this study, we have carried out the chemical analyses,crystal structural refinements and detail description of occurrence on scheelite-powelliteminerals. We have also attempted synthesis of single crystal of solid solution in a widecomposition range. The chemical compositions were determined by JEOL scanningelectron microscope and EDS, INCA system. We have performed the crystal structurerefinements of the scheelite-powellite CaW1-xMoxO4 solid solutions (x=0.0-1.0) byRIGAKU single-crystal structure analysis system RAPID. The R and S values are around0.0s and 1.03. As the result of structural refinements of natural products and many solidsolutions, we confirm that most large natural single crystals have compositions at bothendmembers, and large solid solution crystals are rare. The lattice constants, interatomicdistances and other crystallographic parameters for the solid solution change uniquely withcomposition and it was confirmed as a continuous solid solution. Single crystals of scheeliteendmember + powellite endmember + solid solution with various compositions form anaggregate in the deposit (Figure 1). Crystal shapes of powellite and scheelite arehypidiomorphic and allotriomorphic, respectively. Many solid solution crystals areaccompanied by scheelite endmember and a compositional gap is observed betweenpowellite and solid-solution crystals. The presence of several penetration solutions withsignificantly different W and Mo contents may be assumed. This research can be expectedto lead to giving restrictive conditions to elucidate the mineralization process. Figure1. Scheelite + Powellite + solid solution aggregate

Phase composition and microstructure of WC-Co alloys obtained by selective laser melting

NASA Astrophysics Data System (ADS)

Khmyrov, Roman S.; Shevchukov, Alexandr P.; Gusarov, Andrey V.; Tarasova, Tatyana V.

2018-03-01

Phase composition and microstructure of initial WC, BK8 (powder alloy 92 wt.% WC-8 wt.% Co), Co powders, ball-milled powders with four different compositions (1) 25 wt.% WC-75 wt.% Co, (2) 30 wt.% BK8-70 wt.% Co, (3) 50 wt.% WC-50 wt.% Co, (4) 94 wt.% WC-6 wt.% Co, and bulk alloys obtained by selective laser melting (SLM) from as-milled powders in as-melted state and after heat treatment were investigated by scanning electron microscopy and X-ray diffraction analysis. Initial and ball-milled powders consist of WC, hexagonal α-Co and face-centered cubic β-Co. The SLM leads to the formation of major new phases W3Co3C, W4Co2C and face-centered cubic β-Co-based solid solution. During the heat treatment, there occurs partial decomposition of the face-centered cubic β-Co-based solid solution with the formation of W2C and hexagonal α-Co solid solution. The microstructure of obtained bulk samples, in general, corresponds to the observed phase composition.

Developpement de techniques numeriques pour l'estimation, la modelisation et la prediction de proprietes thermodynamiques et structurales de systems metalliques a fort ordonnancement chimique

NASA Astrophysics Data System (ADS)

Harvey, Jean-Philippe

In this work, the possibility to calculate and evaluate with a high degree of precision the Gibbs energy of complex multiphase equilibria for which chemical ordering is explicitly and simultaneously considered in the thermodynamic description of solid (short range order and long range order) and liquid (short range order) metallic phases is studied. The cluster site approximation (CSA) and the cluster variation method (CVM) are implemented in a new minimization technique of the Gibbs energy of multicomponent and multiphase systems to describe the thermodynamic behaviour of metallic solid solutions showing strong chemical ordering. The modified quasichemical model in the pair approximation (MQMPA) is also implemented in the new minimization algorithm presented in this work to describe the thermodynamic behaviour of metallic liquid solutions. The constrained minimization technique implemented in this work consists of a sequential quadratic programming technique based on an exact Newton’s method (i.e. the use of exact second derivatives in the determination of the Hessian of the objective function) combined to a line search method to identify a direction of sufficient decrease of the merit function. The implementation of a new algorithm to perform the constrained minimization of the Gibbs energy is justified by the difficulty to identify, in specific cases, the correct multiphase assemblage of a system where the thermodynamic behaviour of the equilibrium phases is described by one of the previously quoted models using the FactSage software (ex.: solid_CSA+liquid_MQMPA; solid1_CSA+solid2_CSA). After a rigorous validation of the constrained Gibbs energy minimization algorithm using several assessed binary and ternary systems found in the literature, the CVM and the CSA models used to describe the energetic behaviour of metallic solid solutions present in systems with key industrial applications such as the Cu-Zr and the Al-Zr systems are parameterized using fully consistent thermodynamic an structural data generated from a Monte Carlo (MC) simulator also implemented in the framework of this project. In this MC simulator, the modified embedded atom model in the second nearest neighbour formalism (MEAM-2NN) is used to describe the cohesive energy of each studied structure. A new Al-Zr MEAM-2NN interatomic potential needed to evaluate the cohesive energy of the condensed phases of this system is presented in this work. The thermodynamic integration (TI) method implemented in the MC simulator allows the evaluation of the absolute Gibbs energy of the considered solid or liquid structures. The original implementation of the TI method allowed us to evaluate theoretically for the first time all the thermodynamic mixing contributions (i.e., mixing enthalpy and mixing entropy contributions) of a metallic liquid (Cu-Zr and Al-Zr) and of a solid solution (face-centered cubic (FCC) Al-Zr solid solution) described by the MEAM-2NN. Thermodynamic and structural data obtained from MC and molecular dynamic simulations are then used to parameterize the CVM for the Al-Zr FCC solid solution and the MQMPA for the Al-Zr and the Cu-Zr liquid phase respectively. The extended thermodynamic study of these systems allow the introduction of a new type of configuration-dependent excess parameters in the definition of the thermodynamic function of solid solutions described by the CVM or the CSA. These parameters greatly improve the precision of these thermodynamic models based on experimental evidences found in the literature. A new parameterization approach of the MQMPA model of metallic liquid solutions is presented throughout this work. In this new approach, calculated pair fractions obtained from MC/MD simulations are taken into account as well as configuration-independent volumetric relaxation effects (regular like excess parameters) in order to parameterize precisely the Gibbs energy function of metallic melts. The generation of a complete set of fully consistent thermodynamic, physical and structural data for solid, liquid, and stoichiometric compounds and the subsequent parameterization of their respective thermodynamic model lead to the first description of the complete Al-Zr phase diagram in the range of composition [0 ≤ XZr ≤ 5 / 9] based on theoretical and fully consistent thermodynamic properties. MC and MD simulations are performed for the Al-Zr system to define for the first time the precise thermodynamic behaviour of the amorphous phase for its entire range of composition. Finally, all the thermodynamic models for the liquid phase, the FCC solid solution and the amorphous phase are used to define conditions based on thermodynamic and volumetric considerations that favor the amorphization of Al-Zr alloys.

Mixed oxide solid solutions

DOEpatents

Magno, Scott; Wang, Ruiping; Derouane, Eric

2003-01-01

The present invention is a mixed oxide solid solution containing a tetravalent and a pentavalent cation that can be used as a support for a metal combustion catalyst. The invention is furthermore a combustion catalyst containing the mixed oxide solid solution and a method of making the mixed oxide solid solution. The tetravalent cation is zirconium(+4), hafnium(+4) or thorium(+4). In one embodiment, the pentavalent cation is tantalum(+5), niobium(+5) or bismuth(+5). Mixed oxide solid solutions of the present invention exhibit enhanced thermal stability, maintaining relatively high surface areas at high temperatures in the presence of water vapor.

Analysis of thermoelectric properties of high-temperature complex alloys of nickel-base, iron-base and cobalt-base groups

NASA Technical Reports Server (NTRS)

Holanda, R.

1984-01-01

The thermoelectric properties alloys of the nickel-base, iron-base, and cobalt-base groups containing from 1% to 25% 106 chromium were compared and correlated with the following material characteristics: atomic percent of the principle alloy constituent; ratio of concentration of two constituents; alloy physical property (electrical resistivity); alloy phase structure (percent precipitate or percent hardener content); alloy electronic structure (electron concentration). For solid-solution-type alloys the most consistent correlation was obtained with electron concentration, for precipitation-hardenable alloys of the nickel-base superalloy group, the thermoelectric potential correlated with hardener content in the alloy structure. For solid-solution-type alloys, no problems were found with thermoelectric stability to 1000; for precipitation-hardenable alloys, thermoelectric stability was dependent on phase stability. The effects of the compositional range of alloy constituents on temperature measurement uncertainty are discussed.

Structure of Profiled Crystals Based on Solid Solutions of Bi2Te3 and Their X-Ray Diagnostics

NASA Astrophysics Data System (ADS)

Voronin, A. I.; Bublik, V. T.; Tabachkova, N. Yu.; Belov, Yu. M.

2011-05-01

In this work, we used x-ray structural diagnostic data to reveal the formation of structural regularities in profiled polycrystalline ingots based on Bi and Sb chalcogenide solid solutions. In Bi2Te3 lattice crystals, the solid phase grows such that the cleavage surfaces are perpendicular to the crystallization front. The crystallization singularity determines the nature of the growth texture. Because texture is an important factor determining the anisotropy of properties, which in turn determines the suitability of an ingot for production of modules and the possibility of figure of merit improvement, its diagnostics is an important issue for technology testing. Examples of texture analysis using the method of straight pole figure (SPF) construction for profiled crystals are provided. The structure of the surface layers in the profiled ingots was studied after electroerosion cutting. In addition, the method of estimation of the disturbed layer depth based on the nature of texture changes was used.

Accelerated exploration of multi-principal element alloys with solid solution phases

PubMed Central

Senkov, O.N.; Miller, J.D.; Miracle, D.B.; Woodward, C.

2015-01-01

Recent multi-principal element, high entropy alloy (HEA) development strategies vastly expand the number of candidate alloy systems, but also pose a new challenge—how to rapidly screen thousands of candidate alloy systems for targeted properties. Here we develop a new approach to rapidly assess structural metals by combining calculated phase diagrams with simple rules based on the phases present, their transformation temperatures and useful microstructures. We evaluate over 130,000 alloy systems, identifying promising compositions for more time-intensive experimental studies. We find the surprising result that solid solution alloys become less likely as the number of alloy elements increases. This contradicts the major premise of HEAs—that increased configurational entropy increases the stability of disordered solid solution phases. As the number of elements increases, the configurational entropy rises slowly while the probability of at least one pair of elements favouring formation of intermetallic compounds increases more rapidly, explaining this apparent contradiction. PMID:25739749

Relating hydrogen-bonding interactions with the phase behavior of naproxen/PVP K 25 solid dispersions: evaluation of solution-cast and quench-cooled films.

PubMed

Paudel, Amrit; Nies, Erik; Van den Mooter, Guy

2012-11-05

In this work, we investigated the relationship between various intermolecular hydrogen-bonding (H-bonding) interactions and the miscibility of the model hydrophobic drug naproxen with the hydrophilic polymer polyvinylpyrrolidone (PVP) across an entire composition range of solid dispersions prepared by quasi-equilibrium film casting and nonequilibrium melt quench cooling. The binary phase behavior in solid dispersions exhibited substantial processing method dependence. The solid state solubility of crystalline naproxen in PVP to form amorphous solid dispersions was 35% and 70% w/w naproxen in solution-cast films and quench-cooled films, respectively. However, the presence of a single mixed phase glass transition indicated the amorphous miscibility to be 20% w/w naproxen for the films, beyond which amorphous-amorphous and/or crystalline phase separations were apparent. This was further supported by the solution state interactions data such as PVP globular size distribution and solution infrared spectral profiles. The borderline melt composition showed cooling rate dependence of amorphization. The glass transition and melting point depression profiles of the system were treated with the analytical expressions based on Flory-Huggins mixing theory to interpolate the equilibrium solid solubility. FTIR analysis and subsequent spectral deconvolution revealed composition and miscibility dependent variations in the strength of drug-polymer intermolecular H-bonding. Two types of H-bonded populations were evidenced from 25% w/w and 35% w/w naproxen in solution-cast films and quench-cooled films, respectively, with the higher fraction of strongly H-bonded population in the drug rich domains of phase separated amorphous film compositions and highly drug loaded amorphous quench-cooled dispersions.

Mathematical Analysis of the Solidification Behavior of Plain Steel Based on Solute- and Heat-Transfer Equations in the Liquid-Solid Zone

NASA Astrophysics Data System (ADS)

Fujimura, Toshio; Takeshita, Kunimasa; Suzuki, Ryosuke O.

2018-04-01

An analytical approximate solution to non-linear solute- and heat-transfer equations in the unsteady-state mushy zone of Fe-C plain steel has been obtained, assuming a linear relationship between the solid fraction and the temperature of the mushy zone. The heat transfer equations for both the solid and liquid zone along with the boundary conditions have been linked with the equations to solve the whole equations. The model predictions ( e.g., the solidification constants and the effective partition ratio) agree with the generally accepted values and with a separately performed numerical analysis. The solidus temperature predicted by the model is in the intermediate range of the reported formulas. The model and Neuman's solution are consistent in the low carbon range. A conventional numerical heat analysis ( i.e., an equivalent specific heat method using the solidus temperature predicted by the model) is consistent with the model predictions for Fe-C plain steels. The model presented herein simplifies the computations to solve the solute- and heat-transfer simultaneous equations while searching for a solidus temperature as a part of the solution. Thus, this model can reduce the complexity of analyses considering the heat- and solute-transfer phenomena in the mushy zone.

New insights into the coordination chemistry of Schiff bases derived from amino acids: Planar [Ni4] complexes with tyrosine side-chains

NASA Astrophysics Data System (ADS)

Muche, Simon; Hołyńska, Małgorzata

2017-08-01

Structure and properties of a rare metal complex of the chiral Schiff base ligand derived from ortho-vanillin and L-tyrosine are presented. This study is a continuation of research on ligands containing biologically compatible moieties. The ligand is also fully characterized in form of a sodium salt, in particular in solution, for the first time. The metal complex contains a unique bowl-shaped [Ni4] core. Its structure is investigated both in solution (ESI-MS, NMR) and in solid state (X-ray diffraction studies). Under certain conditions the complex can be isolated as crystalline DMF solvate which is studied in solid state.

Reduction of mixed Mn-Zr oxides: in situ XPS and XRD studies.

PubMed

Bulavchenko, O A; Vinokurov, Z S; Afonasenko, T N; Tsyrul'nikov, P G; Tsybulya, S V; Saraev, A A; Kaichev, V V

2015-09-21

A series of mixed Mn-Zr oxides with different molar ratios Mn/Zr (0.1-9) have been prepared by coprecipitation of manganese and zirconium nitrates and characterized by X-ray diffraction (XRD) and BET methods. It has been found that at concentrations of Mn below 30 at%, the samples are single-phase solid solutions (MnxZr1-xO2-δ) based on a ZrO2 structure. X-ray photoelectron spectroscopy (XPS) measurements showed that manganese in these solutions exists mainly in the Mn(4+) state on the surface. An increase in Mn content mostly leads to an increase in the number of Mn cations in the structure of solid solutions; however, a part of the manganese cations form Mn2O3 and Mn3O4 in the crystalline and amorphous states. The reduction of these oxides with hydrogen was studied by a temperature-programmed reduction technique, in situ XRD, and near ambient pressure XPS in the temperature range from 100 to 650 °C. It was shown that the reduction of the solid solutions MnxZr1-xO2-δ proceeds via two stages. During the first stage, at temperatures between 100 and 500 °C, the Mn cations incorporated into the solid solutions MnxZr1-xO2-δ undergo partial reduction. During the second stage, at temperatures between 500 and 700 °C, Mn cations segregate on the surface of the solid solution. In the samples with more than 30 at% Mn, the reduction of manganese oxides was observed: Mn2O3 → Mn3O4 → MnO.

Effects of drug-carrier interactions on drug dissolution from binary and ternary matrices

NASA Astrophysics Data System (ADS)

Iqbal, Zafar

For nearly five decades, pharmaceutical researchers have studied solid solutions of drugs in polymers as a potential means to enhance the dissolution of drugs with poor aqueous solubility. This has become of greater importance in recent years because most new potential drug compounds (new chemical entities) exhibit poor water solubility and present great challenges to scientists who must design dosage forms from which the drugs are bioavailable. During the formulation of a solid solution, the drug undergoes physical but not chemical alterations that increase its chemical potential in the formulation relative to that of the pure drug in its stable form. This increased chemical potential is responsible for enhanced dissolution as well as physical instabilities, such as amorphous to crystalline conversions and precipitation within the solid state. The chemical potential is derived from the Gibbs free energy, so it is reasonable to explain the behavior of solid solution systems in terms of thermodynamics. Solid solutions and dispersions have been extensively studied by pharmaceutical scientists, both with regard to manufacturing aspects and the proposal of various models in attempts to explain the physical bases for how these systems work. Recently, Dave and Bellantone proposed a model based on the thermodynamic changes resulting from the formulation of binary solid solutions of a drug in the polymer PVP. Their model introduced a modification of the F-H theory, which was used to quantify the drug-polymer interaction energies and calculate the entropy of mixing of the drug and polymer. In this work, the model of Dave and Bellantone was extended to include three-component systems, consisting of one drug mixed in a carrier matrix consisting of mixture of two polymers or a polymer and a surfactant. For this research, solid solutions were formed using various drug weight fractions in the formulations. The study focused on the following points: (1) Prepare solid solution formulations and perform appropriate physical characterizations. (2) Characterize the increase in drug dissolution rates resulting from solid solution formulations. (3) Relate the initial dissolution rates to the drug solubility. (4) Explain the solubility enhancement from solid solution dosage in terms of the drug polymer interactions using the extended thermodynamic model. Two poorly water soluble drugs, levonorgestrel (LEVO) and ethinyl estradiol (EE) were formulated in seven solid solution preparations comprised of four carrier systems. Materials used as carriers included various combinations of the polymers PVP K-30, Copovidone (COP), Poloxamer 182, and the surfactant TweenRTM 20. Additionally, ibuprofen (IBU) was used in three formulations consisting of various combinations of PVP K-30, Copovidone and TweenRTM 20. Formulations with various drug weight fractions (0.5%--30%) were prepared using the solvent evaporation technique. Each formulation was tested for dissolution using intrinsic dissolution apparatus (USP). The solid solutions were compressed into tablets into the sample die that maintained a constant surface area during the dissolution process. DSC, XRD and NIRS scans identified that the crystalline peaks of the drug disappeared with the addition of the polymer for all ratios of EE, indicating the formation of solid solutions (to within the limits of detection of the equipment). This was also observed for the LEVO dispersions up to 10% drug loading. At higher drug loading, solutions were formed but some small degree crystallinity was also present. For each experiment, the initial dissolution rates were obtained from the slope of the mass dissolved vs. time plots taken at early times, and volume normalized initial dissolution rates RV were calculated by dividing the initial dissolution rate by the volume fraction of the drug in the formulation. Comparison of the RV values for the various formulations with a reference RV (typically that of the pure drug or of the formulation with the highest polymer content) allowed calculation of relative volume normalized dissolution rates (RNV). The various RNV were used in the thermodynamic model for data analyses and to determine the interactions between the drug and carrier molecules. It was generally seen that RNV increased with decreased drug fraction, and was adequately modeled by the equations derived from the extended thermodynamic model. It was concluded that the model proposed for the binary and ternary systems successfully represented the mechanism of drug-polymer interaction and the energy changes taken place within the dispersion systems. The dissolution data analysis and subsequent understanding of physical modifications in the dispersion systems characterized by XRD, NIRS and DSC further substantiated the findings. The understanding of the fundamental physical might help scientists to predict the effects of mixing various drugs and polymers, and the effects of varying ratios.

Two-Dimensional Nanoporous Networks Formed by Liquid-to-Solid Transfer of Hydrogen-Bonded Macrocycles Built from DNA Bases.

PubMed

Bilbao, Nerea; Destoop, Iris; De Feyter, Steven; González-Rodríguez, David

2016-01-11

We present an approach that makes use of DNA base pairing to produce hydrogen-bonded macrocycles whose supramolecular structure can be transferred from solution to a solid substrate. A hierarchical assembly process ultimately leads to two-dimensional nanostructured porous networks that are able to host size-complementary guests. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Saidov, A. S., E-mail: amin@uzsci.net; Usmonov, Sh. N., E-mail: sh-usmonov@rambler.ru; Saidov, M. S.

(Si{sub 2}){sub 1−x−y}(Ge{sub 2}){sub x}(GaAs){sub y} substitutional solid solutions (0 ≤ x ≤ 0.91, 0 ≤ y ≤ 0.94) are grown by liquid-phase epitaxy from a Pb-based solution-melt on Si substrates with the (111) crystallographic orientation. The chemical composition of the epitaxial films is studied by X-rays probe microanalysis, and the distribution profile of solid solution components is determined. Spectral dependences of the photosensitivity and photoluminescence of the n-Si-p(Si{sub 2}){sub 1−x−y}(Ge{sub 2}){sub x}(GaAs){sub y} heterostructures are studied at room and liquid-nitrogen temperatures. Two maxima are found in the photoluminescence spectra of the (Si{sub 2}){sub 1−x−y}(Ge{sub 2}){sub x}(GaAs){sub y} films (0more » ≤ x ≤ 0.91, 0 ≤ y ≤ 0.94) against the background of a broad emission spectrum. The fundamental maximum with an energy of 1.45 eV is caused by the band-to-band recombination of solid solution carriers, and an additional maximum with an energy of 1.33 eV is caused by the recombination of carriers with the participation of impurity levels of the Si-Si bond (Si{sub 2} is covalently coupled with the tetrahedral lattice of the solid solution host)« less

Structural, thermodynamic, and mechanical properties of WCu solid solutions

NASA Astrophysics Data System (ADS)

Liang, C. P.; Wu, C. Y.; Fan, J. L.; Gong, H. R.

2017-11-01

Various properties of Wsbnd Cu solid solutions are systematically investigated through a combined use of first-principles calculation, cluster expansion, special quasirandom structures (SQS), and lattice dynamics. It is shown that SQS are effective to unravel the intrinsic nature of solid solutions, and that BCC and FCC W100-xCux solid solutions are energetically more stable when 0 ≤ x ≤ 70 and 70 < x ≤ 100, respectively. Calculations also reveal that the Debye model should be appropriate to derive thermodynamic properties of Wsbnd Cu, and that the coefficients of thermal expansion of W100-xCux solid solutions are much lower than those of corresponding mechanical mixtures. In addition, the G/B values of W100-xCux solid solutions reach a minimum at x = 50, which is fundamentally due to the softening of phonons as well as strong chemical bonding between W and Cu with a mainly metallic feature.

Roles of Bi, M and VO{sub 4} tetrahedron in photocatalytic properties of novel Bi{sub 0.5}M{sub 0.5}VO{sub 4} (M=La, Eu, Sm and Y) solid solutions for overall water splitting

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

Liu Hui; Research Center for Combustion and Environment Technology, Shanghai Jiao Tong University, shanghai 200240; Faculty of Engineering Sciences, Kyushu University, Fukuoka 816-8580

2012-02-15

Novel Bi{sub 0.5}M{sub 0.5}VO{sub 4} (BMV; M=La, Eu, Sm and Y) solid solutions were prepared and studied in this paper. All the samples were proved to produce H{sub 2} and O{sub 2} simultaneously from pure water under the irradiation of UV light. M-O bond lengths were proved to increase with M cations by refining cell parameters and atomic positions. Besides, band gaps, energy gaps and photocatalytic activities of BMV also changed with M cations. Both of M-O and V-O bond lengths were suggested to account for this phenomenon. Inactive A{sub 0.5}Y{sub 0.5}VO{sub 4} (A=La, Ce) for water splitting proved incorporationmore » of Bi rather than distortion of VO{sub 4} tetrahedron was a critical factor for improving efficiency of overall water splitting by facilitating the generation of electron and hole with lighter effective masses. Replacement of Bi by M cations not only gave indirect effect on band structure but also raised position of conduction band minimum to meet requirement of H{sub 2} production. - Graphical abstract: Novel Bi{sub 0.5}M{sub 0.5}VO{sub 4} (M=La, Eu, Sm and Y) solid solutions showed the high and stable photocatalytic activities for overall water splitting with their crystal radii of M elements. Highlights: Black-Right-Pointing-Pointer BMV solid solutions were novel highly efficient V-based photocatalysts for overall water splitting. Black-Right-Pointing-Pointer Photocatalytic activity of BMV solid solution related to the effective ionic radii of M cations. Black-Right-Pointing-Pointer Incorporation of Bi is one of key factors for the highly efficient activity of BMV solid solution. Black-Right-Pointing-Pointer Incorporation of Y is dispensable for H{sub 2} production.« less

Conversion of depleted uranium hexafluoride to a solid uranium compound

DOEpatents

Rothman, Alan B.; Graczyk, Donald G.; Essling, Alice M.; Horwitz, E. Philip

2001-01-01

A process for converting UF.sub.6 to a solid uranium compound such as UO.sub.2 and CaF. The UF.sub.6 vapor form is contacted with an aqueous solution of NH.sub.4 OH at a pH greater than 7 to precipitate at least some solid uranium values as a solid leaving an aqueous solution containing NH.sub.4 OH and NH.sub.4 F and remaining uranium values. The solid uranium values are separated from the aqueous solution of NH.sub.4 OH and NH.sub.4 F and remaining uranium values which is then diluted with additional water precipitating more uranium values as a solid leaving trace quantities of uranium in a dilute aqueous solution. The dilute aqueous solution is contacted with an ion-exchange resin to remove substantially all the uranium values from the dilute aqueous solution. The dilute solution being contacted with Ca(OH).sub.2 to precipitate CaF.sub.2 leaving dilute NH.sub.4 OH.

Solar-pumped solid state Nd lasers

NASA Technical Reports Server (NTRS)

Williams, M. D.; Zapata, L.

1985-01-01

Solid state neodymium lasers are considered candidates for space-based polar-pumped laser for continuous power transmission. Laser performance for three different slab laser configurations has been computed to show the excellent power capability of such systems if heat problems can be solved. Ideas involving geometries and materials are offered as potential solutions to the heat problem.

Hybrid Circuits with Nanofluidic Diodes and Load Capacitors

NASA Astrophysics Data System (ADS)

Ramirez, P.; Garcia-Morales, V.; Gomez, V.; Ali, M.; Nasir, S.; Ensinger, W.; Mafe, S.

2017-06-01

The chemical and physical input signals characteristic of micro- and nanofluidic devices operating in ionic solutions should eventually be translated into output electric currents and potentials that are monitored with solid-state components. This crucial step requires the design of hybrid circuits showing robust electrical coupling between ionic solutions and electronic elements. We study experimentally and theoretically the connectivity of the nanofluidic diodes in single-pore and multipore membranes with conventional capacitor systems for the cases of constant, periodic, and white-noise input potentials. The experiments demonstrate the reliable operation of these hybrid circuits over a wide range of membrane resistances, electrical capacitances, and solution p H values. The model simulations are based on empirical equations that have a solid physical basis and provide a convenient description of the electrical circuit operation. The results should contribute to advance signal transduction and processing using nanopore-based biosensors and bioelectronic interfaces.

A Finite Length Cylinder Model for Mixed Oxide-Ion and Electron Conducting Cathodes Suited for Intermediate-Temperature Solid Oxide Fuel Cells

DOE PAGES

Jin, Xinfang; Wang, Jie; Jiang, Long; ...

2016-03-25

A physics-based model is presented to simulate the electrochemical behavior of mixed ion and electron conducting (MIEC) cathodes for intermediate-temperature solid oxide fuel cells. Analytic solutions for both transient and impedance models based on a finite length cylinder are derived. These solutions are compared to their infinite length counterparts. The impedance solution is also compared to experimental electrochemical impedance spectroscopy data obtained from both a traditional well-established La 0.6Sr 0.4Co 0.2Fe 0.8O 3-δ (LSCF) cathode and a new SrCo 0.9Nb 0.1O 3-δ (SCN) porous cathode. Lastly, the impedance simulations agree well with the experimental values, demonstrating that the new modelsmore » can be used to extract electro-kinetic parameters of MIEC SOFC cathodes.« less

Effects of Solid Solution Strengthening Elements Mo, Re, Ru, and W on Transition Temperatures in Nickel-Based Superalloys with High γ'-Volume Fraction: Comparison of Experiment and CALPHAD Calculations

NASA Astrophysics Data System (ADS)

Ritter, Nils C.; Sowa, Roman; Schauer, Jan C.; Gruber, Daniel; Goehler, Thomas; Rettig, Ralf; Povoden-Karadeniz, Erwin; Koerner, Carolin; Singer, Robert F.

2018-06-01

We prepared 41 different superalloy compositions by an arc melting, casting, and heat treatment process. Alloy solid solution strengthening elements were added in graded amounts, and we measured the solidus, liquidus, and γ'-solvus temperatures of the samples by DSC. The γ'-phase fraction increased as the W, Mo, and Re contents were increased, and W showed the most pronounced effect. Ru decreased the γ'-phase fraction. Melting temperatures (i.e., solidus and liquidus) were increased by addition of Re, W, and Ru (the effect increased in that order). Addition of Mo decreased the melting temperature. W was effective as a strengthening element because it acted as a solid solution strengthener and increased the fraction of fine γ'-precipitates, thus improving precipitation strengthening. Experimentally determined values were compared with calculated values based on the CALPHAD software tools Thermo-Calc (databases: TTNI8 and TCNI6) and MatCalc (database ME-NI). The ME-NI database, which was specially adapted to the present investigation, showed good agreement. TTNI8 also showed good results. The TCNI6 database is suitable for computational design of complex nickel-based superalloys. However, a large deviation remained between the experiment results and calculations based on this database. It also erroneously predicted γ'-phase separations and failed to describe the Ru-effect on transition temperatures.

One-Dimensional Transport with Equilibrium Chemistry (OTEQ) - A Reactive Transport Model for Streams and Rivers

USGS Publications Warehouse

Runkel, Robert L.

2010-01-01

OTEQ is a mathematical simulation model used to characterize the fate and transport of waterborne solutes in streams and rivers. The model is formed by coupling a solute transport model with a chemical equilibrium submodel. The solute transport model is based on OTIS, a model that considers the physical processes of advection, dispersion, lateral inflow, and transient storage. The equilibrium submodel is based on MINTEQ, a model that considers the speciation and complexation of aqueous species, acid-base reactions, precipitation/dissolution, and sorption. Within OTEQ, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (waterborne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach. The model's ability to simulate pH, precipitation/dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between instream chemistry and hydrologic transport at the field scale. This report details the development and application of OTEQ. Sections of the report describe model theory, input/output specifications, model applications, and installation instructions. OTEQ may be obtained over the Internet at http://water.usgs.gov/software/OTEQ.

Stabilizing Superionic-Conducting Structures via Mixed-Anion Solid Solutions of Monocarba- closo -borate Salts

DOE PAGES

Tang, Wan Si; Yoshida, Koji; Soloninin, Alexei V.; ...

2016-09-01

Solid lithium and sodium closo-polyborate-based salts are capable of superionic conductivities surpassing even liquid electrolytes, but often only at above-ambient temperatures where their entropically driven disordered phases become stabilized. Here we show by X-ray diffraction, quasielastic neutron scattering, differential scanning calorimetry, NMR, and AC impedance measurements that by introducing 'geometric frustration' via the mixing of two different closo-polyborate anions, namely, 1-CB 9H 10- and CB 11H 12-, to form solid-solution anion-alloy salts of lithium or sodium, we can successfully suppress the formation of possible ordered phases in favor of disordered, fast-ion-conducting alloy phases over a broad temperature range from subambientmore » to high temperatures. Finally, this result exemplifies an important advancement for further improving on the remarkable conductive properties generally displayed by this class of materials and represents a practical strategy for creating tailored, ambient-temperature, solid, superionic conductors for a variety of upcoming all-solid-state energy devices of the future.« less

Structural and ferroelectric phase evolution in [KNbO3]1-x[BaNi1/2Nb1/2O3 -δ] x (x =0 ,0.1 )

NASA Astrophysics Data System (ADS)

Hawley, Christopher J.; Wu, Liyan; Xiao, Geoffrey; Grinberg, Ilya; Rappe, Andrew M.; Davies, Peter K.; Spanier, Jonathan E.

2017-08-01

The phase transition evolution for [KNbO3]1-x[BaNi1/2Nb1/2O3 -δ] x(x =0 ,0.1 ) is determined via complementary dielectric permittivity and Raman-scattering measurements. Raman scattering by optical phonons over the range of 100-1000 cm-1 for 83 K

Stabilization of a supersaturated solution of mefenamic acid from a solid dispersion with EUDRAGIT(®) EPO.

PubMed

Kojima, Taro; Higashi, Kenjirou; Suzuki, Toyofumi; Tomono, Kazuo; Moribe, Kunikazu; Yamamoto, Keiji

2012-10-01

The stabilization mechanism of a supersaturated solution of mefenamic acid (MFA) from a solid dispersion with EUDRAGIT(®) EPO (EPO) was investigated. The solid dispersions were prepared by cryogenic grinding method. Powder X-ray diffractometry, in vitro dissolution test, in vivo oral absorption study, infrared spectroscopy, and solid- and solution-state NMR spectroscopies were used to characterize the solid dispersions. Dissolution tests in acetate buffer (pH 5.5) revealed that solid dispersion showed > 200-fold higher concentration of MFA. Supersaturated solution was stable over 1 month and exhibited improved oral bioavailability of MFA in rats, with a 7.8-fold higher area under the plasma concentration-versus-time curve. Solid-state (1)H spin-lattice relaxation time (T(1)) measurement showed that MFA was almost monomolecularly dispersed in the EPO polymer matrix. Intermolecular interaction between MFA and EPO was indicated by solid-state infrared and (13)C-T(1) measurements. Solution-state (1)H-NMR measurement demonstrated that MFA existed in monomolecular state in supersaturated solution. (1)H-T(1) and difference nuclear Overhauser effect measurements indicated that cross relaxation occurred between MFA and EPO due to the small distance between them. The formation and high stability of the supersaturated solution were attributable to the specifically formed intermolecular interactions between MFA and EPO.

Thermodynamics of magnesian calcite solid-solutions at 25°C and 1 atm total pressure

USGS Publications Warehouse

Busenberg, Eurybiades; Plummer, Niel

1989-01-01

The stability of magnesian calcites was reexamined, and new results are presented for 28 natural inorganic, 12 biogenic, and 32 synthetic magnesian calcites. The magnesian calcite solid-solutions were separated into two groups on the basis of differences in stoichiometric solubility and other physical and chemical properties. Group I consists of solids of mainly metamorphic and hydrothermal origin, synthetic calcites prepared at high temperatures and pressures, and synthetic solids prepared at low temperature and very low calcite supersaturations () from artificial sea water or NaClMgCl2CaCl2solutions. Group I solids are essentially binary s of CaCO2 and MgCO2, and are thought to be relatively free of structural defects. Group II solid-solutions are of either biogenic origin or are synthetic magnesian calcites and protodolomites (0–20 and ∼ 45 mole percent MgCO3) prepared at high calcite supersaturations () from NaClNa2SO4MgCl2CaCl2 or NaClMgCl2CaCl2 solutions. Group II solid-solutions are treated as massively defective solids. The defects include substitution foreign ions (Na+ and SO42−) in the magnesian calcite lattice (point defects) and dislocations (~2 · 109 cm−2). Within each group, the excess free energy of mixing, GE, is described by the mixing model , where x is the mole fraction of the end-member Ca0.5Mg0.5CO3 in the solid-solution. The values of A0and A1 for Group I and II solids were evaluated at 25°C. The equilibrium constants of all the solids are closely described by the equation ln , where KC and KD are the equilibrium constants of calcite and Ca0.5Mg0.5CO3. Group I magnesian calcites were modeled as sub-regular solid-solutions between calcite and dolomite, and between calcite and “disordered dolomite”. Both models yield almost identical equilibrium constants for these magnesian calcites. The Group II magnesian calcites were modeled as sub-regular solid-solutions between defective calcite and protodolomite. Group I and II solid-solutions differ significantly in stability. The rate of crystal growth and the chemical composition of the aqueous solutions from which the solids were formed are the main factors controlling stoichiometric solubility of the magnesian calcites and the density of crystal defects. The literature on the occurrence and behavior of magnesian calcites in sea water and other aqueous solutions is also examined.

Chemical weathering rates of a soil chronosequence on granitic alluvium: III. Hydrochemical evolution and contemporary solute fluxes and rates

USGS Publications Warehouse

White, A.F.; Schulz, M.S.; Vivit, D.V.; Blum, A.E.; Stonestrom, David A.; Harden, J.W.

2005-01-01

Although long-term changes in solid-state compositions of soil chronosequences have been extensively investigated, this study presents the first detailed description of the concurrent hydrochemical evolution and contemporary weathering rates in such sequences. The most direct linkage between weathering and hydrology over 3 million years of soil development in the Merced chronosequence in Central California relates decreasing permeability and increasing hydrologic heterogeneity to the development of secondary argillic horizons and silica duripans. In a highly permeable, younger soil (40 kyr old), pore water solutes reflect seasonal to decadal-scale variations in rainfall and evapotranspiration (ET). This climate signal is strongly damped in less permeable older soils (250 to 600 kyr old) where solutes increasingly reflect weathering inputs modified by heterogeneous flow. Elemental balances in the soils are described in terms of solid state, exchange and pore water reservoirs and input/output fluxes from precipitation, ET, biomass, solute discharge and weathering. Solute mineral nutrients are strongly dependent on biomass variations as evidenced by an apparent negative K weathering flux reflecting aggradation by grassland plants. The ratios of solute Na to other base cations progressively increase with soil age. Discharge fluxes of Na and Si, when integrated over geologic time, are comparable to solid-state mass losses in the soils, implying similar past weathering conditions. Similarities in solute and sorbed Ca/Mg ratios reflect short-term equilibrium with the exchange reservoir. Long-term consistency in solute ratios, when contrasted against progressive decreases in solid-state Ca/Mg, requires an additional Ca source, probably from dry deposition. Amorphous silica precipitates from thermodynamically-saturated pore waters during periods of high evapotranspiration and result in the formation of duripans in the oldest soils. The degree of feldspar and secondary gibbsite and kaolinite saturation varies both spatially and temporally due to the seasonality of plant-respired CO2 and a decrease in organically complexed Al. In deeper pore waters, K-feldspar is in equilibrium and plagioclase is about an order of magnitude undersaturated. Hydrologic heterogeneity produces a range of weathering gradients that are constrained by solute distributions and matrix and macropore flow regimes. Plagioclase weathering rates, based on precipitation-corrected Na gradients, vary between 3 and 7 ?? 10-16 mol m-2 s-1. These rates are similar to previously determined solid-state rates but are several orders of magnitude slower than for experimental plagioclase dissolution indicating strong inhibitions to natural weathering, partly due to near-equilibrium weathering reactions. Copyright ?? 2005 Elsevier Ltd.

Single crystals of metal solid solutions

NASA Technical Reports Server (NTRS)

Miller, J. F.; Austin, A. E.; Richard, N.; Griesenauer, N. M.; Moak, D. P.; Mehrabian, M. R.; Gelles, S. H.

1974-01-01

The following definitions were sought in the research on single crystals of metal solid solutions: (1) the influence of convection and/or gravity present during crystallization on the substructure of a metal solid solution; (2) the influence of a magnetic field applied during crystallization on the substructure of a metal solid solution; and (3) requirements for a space flight experiment to verify the results. Growth conditions for the selected silver-zinc alloy system are described, along with pertinent technical and experimental details of the project.

Solid-state and solution /sup 13/C NMR in the conformational analysis of methadone-hydrochloride and related narcotic analgesics

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

Sumner, S.C.J.

1986-01-01

Solid state and solution /sup 13/C NMR have been used to study the conformations of the racemic mixtures and single enantiomers of methadone hydrochloride, alpha and beta methadol hydrochloride, and alpha and beta acetylmethadol hydrochloride. The NMR spectra acquired for the compounds as solids, and in polar and nonpolar solvents are compared, in order to determine the conformation of the molecules in solution. To determine the reliability of assigning solution conformations by comparing solution and solid state chemical shift data, three bond coupling constants measured in solution are compared with those calculated from X-ray data. The conformations of the racemicmore » mixture and plus enantiomer of methadone hydrochloride have been shown to be very similar in the solid state, where minor differences in conformation can be seen by comparing NMR spectra obtained for the solids. Also shown is that the molecules of methadone hydrochloride have conformations in polar and in nonpolar solvents which are very similar to the conformation of the molecules in the solid state.« less

Indirect photopatterning of functionalized organic monolayers via copper-catalyzed "click chemistry"

NASA Astrophysics Data System (ADS)

Williams, Mackenzie G.; Teplyakov, Andrew V.

2018-07-01

Solution-based lithographic surface modification of an organic monolayer on a solid substrate is attained based on selective area photo-reduction of copper (II) to copper (I) to catalyze the azide-alkyne dipolar cycloaddition "click" reaction. X-ray photoelectron spectroscopy is used to confirm patterning, and spectroscopic results are analyzed and supplemented with computational models to confirm the surface chemistry. It is determined that this surface modification approach requires irradiation of the solid substrate with all necessary components present in solution. This method requires only minutes of irradiation to result in spatial and temporal control of the covalent surface functionalization of a monolayer and offers the potential for wavelength tunability that may be desirable in many applications utilizing organic monolayers.

Motion of a Drop on a Solid Surface Due to a Wettability Gradient

NASA Technical Reports Server (NTRS)

Subramanian, R.; Moumen, Nadjoua; McLaughlin, John B.

2005-01-01

The hydrodynamic force experienced by a spherical-cap drop moving on a solid surface is obtained from two approximate analytical solutions and used to predict the quasi-steady speed of the drop in a wettability gradient. One solution is based on approximation of the shape of the drop as a collection of wedges, and the other is based on lubrication theory. Also, asymptotic results from both approximations for small contact angles, as well as an asymptotic result from lubrication theory that is good when the length scale of the drop is large compared with the slip length, are given. The results for the hydrodynamic force also can be used to predict the quasi-steady speed of a drop sliding down an incline.

A Review of RedOx Cycling of Solid Oxide Fuel Cells Anode

PubMed Central

Faes, Antonin; Hessler-Wyser, Aïcha; Zryd, Amédée; Van Herle, Jan

2012-01-01

Solid oxide fuel cells are able to convert fuels, including hydrocarbons, to electricity with an unbeatable efficiency even for small systems. One of the main limitations for long-term utilization is the reduction-oxidation cycling (RedOx cycles) of the nickel-based anodes. This paper will review the effects and parameters influencing RedOx cycles of the Ni-ceramic anode. Second, solutions for RedOx instability are reviewed in the patent and open scientific literature. The solutions are described from the point of view of the system, stack design, cell design, new materials and microstructure optimization. Finally, a brief synthesis on RedOx cycling of Ni-based anode supports for standard and optimized microstructures is depicted. PMID:24958298

What We Have Learned From Our Inspections of Incinerators and Use of Burn Pits in Afghanistan: Final Assessment

DTIC Science & Technology

2015-02-01

In 2004, the Department of Defense (DOD) began introducing new solid waste disposal methods in Afghanistan, including landfills and incineration...base landfills and incinera- tion. Nonetheless, the overall approach to its solid waste disposal in Afghanistan was hap- hazard and reactive. DOD was...contract to have solid waste hauled to a local landfill —a solution that could have eliminat- SIGAR 15-33-AL: Final assessment: incinerators and Burn

Solid Rocket Fuel Constitutive Theory and Polymer Cure

NASA Technical Reports Server (NTRS)

Ream, Robert

2006-01-01

Solid Rocket Fuel is a complex composite material for which no general constitutive theory, based on first principles, has been developed. One of the principles such a relation would depend on is the morphology of the binder. A theory of polymer curing is required to determine this morphology. During work on such a theory an algorithm was developed for counting the number of ways a polymer chain could assemble. The methods used to develop and check this algorithm led to an analytic solution to the problem. This solution is used in a probability distribution function which characterizes the morphology of the polymer.

GOMA 6.0 :

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

Schunk, Peter Randall; Rao, Rekha Ranjana; Chen, Ken S

Goma 6.0 is a finite element program which excels in analyses of multiphysical processes, particularly those involving the major branches of mechanics (viz. fluid/solid mechanics, energy transport and chemical species transport). Goma is based on a full-Newton-coupled algorithm which allows for simultaneous solution of the governing principles, making the code ideally suited for problems involving closely coupled bulk mechanics and interfacial phenomena. Example applications include, but are not limited to, coating and polymer processing flows, super-alloy processing, welding/soldering, electrochemical processes, and solid-network or solution film drying. This document serves as a users guide and reference.

Part 3. a novel stereocontrolled, in situ, solution- and solid-phase, Aza Michael approach for high-throughput generation of tetrahydroaminoquinoline-derived natural-product-like architectures.

PubMed

Prakesch, Michael; Srivastava, Stuti; Leek, Donald M; Arya, Prabhat

2006-01-01

With the goal of rapidly accessing tetrahydroquinoline-based natural-product-like polycyclic architectures, herein, we report an unprecedented, in situ, stereocontrolled Aza Michael approach in solution and on the solid phase. The mild reaction conditions required to reach the desired target are highly attractive for the use of this method in library generation. To our knowledge, this approach has not been used before, and it opens a novel route leading to a wide variety of tetrahydroquinoline-derived bridged tricyclic derivatives.

TANK 26F SUPERNATANT AND 2F EVAPORATOR EDUCTOR PUMP SAMPLE CHARACTERIZATION RESULTS

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

King, W.; Hay, M.; Coleman, C.

2011-08-23

In an effort to understand the reasons for system plugging problems in the SRS 2F evaporator, supernatant samples were retrieved from the evaporator feed tank (Tank 26F) and solids were collected from the evaporator eductor feed pump for characterization. The variable depth supernatant samples were retrieved from Tank 26F in early December of 2010 and samples were provided to SRNL and the F/H Area laboratories for analysis. Inspection and analysis of the samples at SRNL was initiated in early March of 2011. During the interim period, samples were frequently exposed to temperatures as low as 12 C with daily temperaturemore » fluctuations as high as 10 C. The temperature at the time of sample collection from the waste tank was 51 C. Upon opening the supernatant bottles at SRNL, many brown solids were observed in both of the Tank 26F supernatant samples. In contrast, no solids were observed in the supernatant samples sent to the F/H Area laboratories, where the analysis was completed within a few days after receipt. Based on these results, it is believed that the original Tank 26F supernatant samples did not contain solids, but solids formed during the interim period while samples were stored at ambient temperature in the SRNL shielded cells without direct climate control. Many insoluble solids (>11 wt. % for one sample) were observed in the Tank 26F supernatant samples after three months of storage at SRNL which would not dissolve in the supernatant solution in two days at 51 C. Characterization of these solids along with the eductor pump solids revealed the presence of sodium oxalate and clarkeite (uranyl oxyhydroxide) as major crystalline phases. Sodium nitrate was the dominant crystalline phase present in the unwashed Eductor Pump solids. Crystalline sodium nitrate may have formed during the drying of the solids after filtration or may have been formed in the Tank 26F supernatant during storage since the solution was found to be very concentrated (9-12 M Na{sup +}). Concentrated mineral acids and elevated temperature were required to dissolve all of these solids. The refractory nature of some of the solids is consistent with the presence of metal oxides such as aluminosilicates (observed as a minor phase by XRD). Characterization of the water wash solutions and the digested solids confirmed the presence of oxalate salts in both solid samples. Sulfate enrichment was also observed in the Tank 26F solids wash solution, indicating the presence of sulfate precipitates such as burkeite. OLI modeling of the Tank 26F filtered supernatant composition revealed that sodium oxalate has a very low solubility in this solution. The model predicts that the sodium oxalate solubility in the Tank 26F supernatant is only 0.0011 M at 50 C. The results indicate that the highly concentrated nature of the evaporator feed solution and the addition of oxalate anion to the waste stream each contribute to the formation of insoluble solids in the 2F evaporator system.« less

Formation and structure of Al-Zr metallic glasses studied by Monte Carlo simulations

NASA Astrophysics Data System (ADS)

Li, J. H.; Zhao, S. Z.; Dai, Y.; Cui, Y. Y.; Liu, B. X.

2011-06-01

Based on the recently constructed n-body potential, both molecular dynamics and Monte Carlo simulations revealed that the Al-Zr amorphous alloy or metallic glass can be obtained within the composition range of 24-66 at. % Zr. The revealed composition range could be considered the intrinsic glass-forming range and it quantitatively indicates the glass-forming ability of the Al-Zr system. The underlying physics of the finding is that, within the composition range, the amorphous alloys are energetically favored to form. In addition, it is proposed that the energy difference between a solid solution and the amorphous phase could serve as the driving force of the crystalline to amorphous transition and the driving force should be sufficiently large for amorphization to take place. The minimum driving forces for fcc Al-based and hcp Zr-based Al-Zr solid solutions to amorphize are calculated to be about -0.05 and -0.03 eV/atom, respectively, whereas the maximum driving force is found to be -0.23 eV/atom at the alloy stoichiometry of Al60Zr40. A thermodynamics parameter γ¯, defined as the ratio of the driving force to the formation energy of the solid solution, is further proposed to indicate the glass-forming ability of an Al-Zr alloy. Thermodynamics calculations show that the glass-forming ability of the Al56Zr44 alloy is the largest, implying that the Al56Zr44 amorphous alloy is more ready to form than other alloys in the Al-Zr system. Besides, Voronoi analysis found that there exists a strong correlation between the coordinate number and structure. Amorphization could result in increase of coordinate numbers and about 1.5% volume-expansion. The volume-expansion induced by amorphization can be attributed to two factors, i.e., the total bond number of the Al-Zr amorphous phase is greater than that of the corresponding solid solution, and the averaged bond length of the Al-Zr amorphous phase is longer than that of the corresponding solid solution. For the Al-Zr alloys, especially for the Al-Zr amorphous phase, there exists a negative chemical micro-inhomogeneity in the alloys, suggesting that metallic bonds prefer to be formed between the atoms of dissimilar species. Finally, it is found that there is a weak correspondence between the bond-angle distributions of Al-Zr amorphous alloys and the solid solutions. It is further suggested that the configuration of Al-Zr amorphous alloys embodies some hybrid imprint of bcc, fcc, and hcp structures. More interestingly, the short-range order is also observed in the bond-angle distributions.

Efficient sample preparation method based on solvent-assisted dispersive solid-phase extraction for the trace detection of butachlor in urine and waste water samples.

PubMed

Aladaghlo, Zolfaghar; Fakhari, Alireza; Behbahani, Mohammad

2016-10-01

In this work, an efficient sample preparation method termed solvent-assisted dispersive solid-phase extraction was applied. The used sample preparation method was based on the dispersion of the sorbent (benzophenone) into the aqueous sample to maximize the interaction surface. In this approach, the dispersion of the sorbent at a very low milligram level was achieved by inserting a solution of the sorbent and disperser solvent into the aqueous sample. The cloudy solution created from the dispersion of the sorbent in the bulk aqueous sample. After pre-concentration of the butachlor, the cloudy solution was centrifuged and butachlor in the sediment phase dissolved in ethanol and determined by gas chromatography with flame ionization detection. Under the optimized conditions (solution pH = 7.0, sorbent: benzophenone, 2%, disperser solvent: ethanol, 500 μL, centrifuged at 4000 rpm for 3 min), the method detection limit for butachlor was 2, 3 and 3 μg/L for distilled water, waste water, and urine sample, respectively. Furthermore, the preconcentration factor was 198.8, 175.0, and 174.2 in distilled water, waste water, and urine sample, respectively. Solvent-assisted dispersive solid-phase extraction was successfully used for the trace monitoring of butachlor in urine and waste water samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamic Study of Solid-Liquid Equilibrium in NaCl-NaBr-H2O System at 288.15 K

NASA Astrophysics Data System (ADS)

Li, Dan; Meng, Ling-zong; Deng, Tian-long; Guo, Ya-fei; Fu, Qing-Tao

2018-06-01

The solubility data, composition of the solid solution and refractive indices of the NaCl-NaBr-H2O system at 288.15 K were studied with the isothermal equilibrium dissolution method. The solubility diagram and refractive index diagram of this system were plotted at 288.15 K. The solubility diagram consists of two crystallization zones for solid solution Na(Cl,Br) · 2H2O and Na(Cl,Br), one invariant points cosaturated with two solid solution and two univariant solubility isothermal curves. On the basis of Pitzer and Harvie-Weare (HW) chemical models, the composition equations and solubility equilibrium constant equations of the solid solutions at 288.15 K were acquired using the solubility data, the composition of solid solutions, and binary Pitzer parameters. The solubilities calculated using the new method combining the equations are in good agreement with the experimental data.

Synthesis of GaN:ZnO solid solution by solution combustion method and characterization for photocatalytic application

NASA Astrophysics Data System (ADS)

Menon, Sumithra Sivadas; Anitha, R.; Gupta, Bhavana; Baskar, K.; Singh, Shubra

2016-05-01

GaN-ZnO solid solution has emerged as a successful and reproducible photocatalyst for overall water splitting by one-step photoexcitation, with a bandgap in visible region. When the solid solution is formed, some of the Zn and O ions are replaced by Ga and N ions respectively and there is a narrowing of bandgap which is hypothesized as due to Zn3d-N2p repulsion. The traditional method of synthesis of GaN-ZnO solid solution is by nitridation of the starting oxides under constant ammonia flow. Here we report a solution combustion technique for the synthesis of the solid solution at a temperature about 500 ° C in a muffle furnace with metal nitrates as precursors and urea as the fuel. The as prepared samples showed change in color with the increased concentration of ZnO in the solution. The structural, microstructural, morphological and optical properties of the samples were realized by Powder X ray diffraction, Scanning electron microscopy, Energy dispersive X ray analysis, Transmission electron microscopy and Photoluminescence. Finally the hydrogen production efficiency of the GaN-ZnO nanopowders by water splitting was found, using methanol as a scavenger. The apparent quantum yield (AQY) of 0.048% is obtained for GaN-ZnO solid solution.

Ion mobility and conductivity in the M{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} (M=K, Rb) solid solutions with fluorite structure

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

Kavun, V. Ya., E-mail: kavun@ich.dvo.ru; Uvarov, N.F.; Slobodyuk, A.B.

Ionic mobility and conductivity in the K{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} and Rb{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} (x=0.05, 0.09) solid solutions with the fluorite structure have been investigated using the methods of {sup 19}F NMR, X-ray diffraction and impedance spectroscopy. Types of ionic motions in the fluoride sublattice of solid solutions have been established and temperature ranges of their realization have been determined (150–450 K). Diffusion of fluoride ions is a dominating type of ionic motions in the fluoride sublattice of solid solutions under study above 350 K. Due to high ionic conductivity, above 10{sup –3} S/cm at 450 K,more » these solid solutions can be used as solid electrolytes in various electrochemical devices and systems. - Graphical abstract: Temperature dependence of the concentration of mobile (2, 4) and immobile (1, 3) F ions in the K{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} solid solutions. - Highlights: • Studied the ion mobility, conductivity in M{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} solid solutions (M=K, Rb). • An analysis of {sup 19}F NMR spectra made it possible to identify types of ion mobility. • The main type of ion motion above 300 K in solid solutions is a diffusion of ions F{sup –}. • The ionic conductivity of the solid solutions studied more than 10{sup –3} S/cm at 450 K.« less

An added-mass partition algorithm for fluid–structure interactions of compressible fluids and nonlinear solids

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

Banks, J.W., E-mail: banksj3@rpi.edu; Henshaw, W.D., E-mail: henshw@rpi.edu; Kapila, A.K., E-mail: kapila@rpi.edu

We describe an added-mass partitioned (AMP) algorithm for solving fluid–structure interaction (FSI) problems involving inviscid compressible fluids interacting with nonlinear solids that undergo large rotations and displacements. The computational approach is a mixed Eulerian–Lagrangian scheme that makes use of deforming composite grids (DCG) to treat large changes in the geometry in an accurate, flexible, and robust manner. The current work extends the AMP algorithm developed in Banks et al. [1] for linearly elasticity to the case of nonlinear solids. To ensure stability for the case of light solids, the new AMP algorithm embeds an approximate solution of a nonlinear fluid–solidmore » Riemann (FSR) problem into the interface treatment. The solution to the FSR problem is derived and shown to be of a similar form to that derived for linear solids: the state on the interface being fundamentally an impedance-weighted average of the fluid and solid states. Numerical simulations demonstrate that the AMP algorithm is stable even for light solids when added-mass effects are large. The accuracy and stability of the AMP scheme is verified by comparison to an exact solution using the method of analytical solutions and to a semi-analytical solution that is obtained for a rotating solid disk immersed in a fluid. The scheme is applied to the simulation of a planar shock impacting a light elliptical-shaped solid, and comparisons are made between solutions of the FSI problem for a neo-Hookean solid, a linearly elastic solid, and a rigid solid. The ability of the approach to handle large deformations is demonstrated for a problem of a high-speed flow past a light, thin, and flexible solid beam.« less

Czochralski growth of NaNO3-LiNO3 solid solution single crystals using axial vibrational control technique

NASA Astrophysics Data System (ADS)

Avetissov, Igor; Sadovskiy, Andrei; Belov, Stanislav; Kong Khan, Chan; Mozhevitina, Elena; Sukhanova, Ekaterina; Zharikov, Eugeniy

2014-09-01

T-x diagram of LiNO3-NaNO3 quasi-binary system has been improved using an original technique based on Raman measurements of condense phase. (LiNO3)x(NaNO3)1-x solid solution single crystal has been grown at different regimes of axial vibrational control (AVC) technique. Significant difference in segregation coefficient behavior between AVC-CZ and conventional CZ grown crystals has appeared: with AVC intensity increase the segregation coefficient (SC) raises for light molecular weight elements, SC reduces for medium molecular weight elements, and SC remains practically unchangeable for heavy molecular weight elements. Effect of vibrational intensity on vibron and optical characteristics, microhardness of AVC-CZ (LiNO3)x(NaNO3)1-x solid solution single crystals has been studied. For the AVC-CZ crystals has been observed increases in microhardness as well as in optical transmission up to 10 rel% compare to conventional CZ grown crystals.

Strengthening Mechanisms in Thermomechanically Processed NbTi-Microalloyed Steel

NASA Astrophysics Data System (ADS)

Kostryzhev, Andrii G.; Marenych, Olexandra O.; Killmore, Chris R.; Pereloma, Elena V.

2015-08-01

The effect of deformation temperature on microstructure and mechanical properties was investigated for thermomechanically processed NbTi-microalloyed steel with ferrite-pearlite microstructure. With a decrease in the finish deformation temperature at 1348 K to 1098 K (1075 °C to 825 °C) temperature range, the ambient temperature yield stress did not vary significantly, work hardening rate decreased, ultimate tensile strength decreased, and elongation to failure increased. These variations in mechanical properties were correlated to the variations in microstructural parameters (such as ferrite grain size, solid solution concentrations, precipitate number density and dislocation density). Calculations based on the measured microstructural parameters suggested the grain refinement, solid solution strengthening, precipitation strengthening, and work hardening contributed up to 32 pct, up to 48 pct, up to 25 pct, and less than 3 pct to the yield stress, respectively. With a decrease in the finish deformation temperature, both the grain size strengthening and solid solution strengthening increased, the precipitation strengthening decreased, and the work hardening contribution did not vary significantly.

Development of Automated Monitoring and Management System of Municipal Solid Waste Landfill Based on the Industrial OMRON Controller

NASA Astrophysics Data System (ADS)

Kostarev, S. N.; Sereda, T. G.

2018-01-01

The application of the programmable logic integrated circuits (PLC) for creating the software and hardware complexes of the medium complexity is an economically sound solution. The application of the OMRON controller to solve the monitoring and management tasks of safety of the municipal solid waste (MSW) landfill with the use of technology of the filtrate recirculation and the landfill maps irrigation is shown in the article. The article contains the technical solution connected with the implementation of the 2162059RU invention patent for the municipal solid waste landfill management in the Kurgan region of Russia. The calculation of maps and ponds was made with consideration of the limited sanitary and protection zone. The GRUNDFOS dosing and reactor equipment was proposed to use in the project.

Investigation of compositional segregation during unidirectional solidification of solid solution semiconducting alloys

NASA Technical Reports Server (NTRS)

Wang, J. C.

1982-01-01

Compositional segregation of solid solution semiconducting alloys in the radial direction during unidirectional solidification was investigated by calculating the effect of a curved solid liquid interface on solute concentration at the interface on the solid. The formulation is similar to that given by Coriell, Boisvert, Rehm, and Sekerka except that a more realistic cylindrical coordinate system which is moving with the interface is used. Analytical results were obtained for very small and very large values of beta with beta = VR/D, where V is the velocity of solidification, R the radius of the specimen, and D the diffusivity of solute in the liquid. For both very small and very large beta, the solute concentration at the interface in the solid C(si) approaches C(o) (original solute concentration) i.e., the deviation is minimal. The maximum deviation of C(si) from C(o) occurs for some intermediate value of beta.

Process for recovering chaotropic anions from an aqueous solution also containing other ions

DOEpatents

Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

1999-01-01

A solid/liquid process for the separation and recovery of chaotropic anions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the chaotropic anions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt (lyotrope). A solid/liquid phase admixture of separation particles containing bound chaotropic anions in such an aqueous solution is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture.

Process for recovering chaotropic anions from an aqueous solution also containing other ions

DOEpatents

Rogers, R.; Horwitz, E.P.; Bond, A.H.

1999-03-30

A solid/liquid process for the separation and recovery of chaotropic anions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the chaotropic anions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt (lyotrope). A solid/liquid phase admixture of separation particles containing bound chaotropic anions in such an aqueous solution is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture. 19 figs.

Role of lattice distortion on diffuse phase transition temperatures in Bi0.5Na0.5TiO3-BaTiO3 [BNBTO] solid solutions

NASA Astrophysics Data System (ADS)

Pradhan, Lagen Kumar; Pandey, Rabichandra; Kumar, Sunil; Supriya, Sweety; Kar, Manoranjan

2018-04-01

Effect of lattice distortion on diffuse phase transition in BNBTO solid solutions near Morphotropic phase boundary (MPB) has been investigated. Solid solutions of (Bi0.5Na0.5)1-xBaxTiO3 (with mole % of x= 0.04, 0.05, 0.06, 0.07 and 0.08) were prepared by the planetary ball mill method in ethanol medium. Rietveld refinement technique with rhombohedral (R3c) and tetragonal (P4bm) crystal symmetry has been employed for structural as well as phase analysis of the solid solutions. Both rhombohedral and tetragonal lattice distortion (c/a) tends toward the pseudo-cubic crystal symmetry with the increase of mole fraction of Ba2+ near MPB (x= 6 mole %). Also, the average crystallite size and grain size decrease with increase of mole fraction of Ba2+ in BNT ceramic are due to larger ionic radius of Ba2+ and grain boundary pinning process in the solid solutions respectively. Additionally, depolarization temperature (Td) and maximum temperature (Tm) reduces due to the lattice distortion of both the phases in BNBTO solid solutions, which is explained extensively. Significant increase of dielectric constant has been observed near MPB composition (x=6%) in BNBTO solid solutions.

Preparation of Sic/AIN Solid Solutions Using Organometallic Precursors

DTIC Science & Technology

1989-02-15

pyrolysis of organoaluminum and organosilicon compounds was investigated as a potential source of SiC /AUI solid solutions. Using two different co... pyrolysis methods, homogeneous mixtures of organoaluminum amides and both a vinylic polysilane and a poly- carbosilane were convertec to a preceramic ...solid that transformed to crystalline SiC /AiN solid solutions at 򒸀 C. Moreover, the liquid, polymeric , form of these precursor mixtures provides a

Hydrogen generation by electrolysis of aqueous organic solutions

NASA Technical Reports Server (NTRS)

Jeffries-Nakamura, Barbara (Inventor); Narayanan, Sekharipuram R. (Inventor); Chun, William (Inventor); Valdez, Thomas I. (Inventor)

2006-01-01

A device for electrolysis of an aqueous solution of an organic fuel. The electrolyte is a solid-state polymer membrane with anode and cathode catalysts on both surfaces for electro-oxidization and electro-reduction. A low-cost and portable hydrogen generator can be made based on the device with organic fuels such as methanol.

Subdiffusion kinetics of nanoprecipitate growth and destruction in solid solutions

NASA Astrophysics Data System (ADS)

Sibatov, R. T.; Svetukhin, V. V.

2015-06-01

Based on fractional differential generalizations of the Ham and Aaron-Kotler precipitation models, we study the kinetics of subdiffusion-limited growth and dissolution of new-phase precipitates. We obtain the time dependence of the number of impurities and dimensions of new-phase precipitates. The solutions agree with the Monte Carlo simulation results.

Hydrogen generation by electrolysis of aqueous organic solutions

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram R. (Inventor); Chun, William (Inventor); Jeffries-Nakamura, Barbara (Inventor); Valdez, Thomas I. (Inventor)

2002-01-01

A device for electrolysis of an aqueous solution of an organic fuel. The electrolyte is a solid-state polymer membrane with anode and cathode catalysts on both surfaces for electro-oxidization and electro-reduction. A low-cost and portable hydrogen generator can be made based on the device with organic fuels such as methanol.

Introduction to Solid Supported Membrane Based Electrophysiology

PubMed Central

Bazzone, Andre; Costa, Wagner Steuer; Braner, Markus; Călinescu, Octavian; Hatahet, Lina; Fendler, Klaus

2013-01-01

The electrophysiological method we present is based on a solid supported membrane (SSM) composed of an octadecanethiol layer chemisorbed on a gold coated sensor chip and a phosphatidylcholine monolayer on top. This assembly is mounted into a cuvette system containing the reference electrode, a chlorinated silver wire. After adsorption of membrane fragments or proteoliposomes containing the membrane protein of interest, a fast solution exchange is used to induce the transport activity of the membrane protein. In the single solution exchange protocol two solutions, one non-activating and one activating solution, are needed. The flow is controlled by pressurized air and a valve and tubing system within a faraday cage. The kinetics of the electrogenic transport activity is obtained via capacitive coupling between the SSM and the proteoliposomes or membrane fragments. The method, therefore, yields only transient currents. The peak current represents the stationary transport activity. The time dependent transporter currents can be reconstructed by circuit analysis. This method is especially suited for prokaryotic transporters or eukaryotic transporters from intracellular membranes, which cannot be investigated by patch clamp or voltage clamp methods. PMID:23711952

Introduction to solid supported membrane based electrophysiology.

PubMed

Bazzone, Andre; Costa, Wagner Steuer; Braner, Markus; Călinescu, Octavian; Hatahet, Lina; Fendler, Klaus

2013-05-11

The electrophysiological method we present is based on a solid supported membrane (SSM) composed of an octadecanethiol layer chemisorbed on a gold coated sensor chip and a phosphatidylcholine monolayer on top. This assembly is mounted into a cuvette system containing the reference electrode, a chlorinated silver wire. After adsorption of membrane fragments or proteoliposomes containing the membrane protein of interest, a fast solution exchange is used to induce the transport activity of the membrane protein. In the single solution exchange protocol two solutions, one non-activating and one activating solution, are needed. The flow is controlled by pressurized air and a valve and tubing system within a faraday cage. The kinetics of the electrogenic transport activity is obtained via capacitive coupling between the SSM and the proteoliposomes or membrane fragments. The method, therefore, yields only transient currents. The peak current represents the stationary transport activity. The time dependent transporter currents can be reconstructed by circuit analysis. This method is especially suited for prokaryotic transporters or eukaryotic transporters from intracellular membranes, which cannot be investigated by patch clamp or voltage clamp methods.

Synthesis, structure, and ionic conductivity of solid solution, Li10+δM1+δP2-δS12 (M = Si, Sn).

PubMed

Hori, Satoshi; Suzuki, Kota; Hirayama, Masaaki; Kato, Yuki; Saito, Toshiya; Yonemura, Masao; Kanno, Ryoji

2014-01-01

Solid solutions of the silicon and tin analogous phases of the superionic conductor Li(10)MP(2)S(12) (M = Si, Sn) were synthesized by a conventional solid-state reaction in an evacuated silica tube at 823 K. The ranges of the solid solutions were determined to be 0.20 < δ < 0.43 and -0.25 < δ < -0.01 in Li(10+δ)M(1+δ)P(2-δ)S(12) (0.525 ≤k≤ 0.60 and 0.67 ≤k≤ 0.75 in Li(4-k)M(1-k)PkS(4)) for the Si and Sn systems, respectively. The ionic conductivity of these systems varied as a function of the changing M ions: the Si and Sn systems showed lower conductivity than the Ge system, Li(10+δ)Ge(1+δ)P(2-δ)S(12). The conductivity change for different elements might be due to the lattice size and lithium content affecting the ionic conduction. The relationship between ionic conduction, structure, and lithium concentration is discussed based on the structural and electrochemical information for the silicon, germanium, and tin systems.

Finite element methods for the biomechanics of soft hydrated tissues: nonlinear analysis and adaptive control of meshes.

PubMed

Spilker, R L; de Almeida, E S; Donzelli, P S

1992-01-01

This chapter addresses computationally demanding numerical formulations in the biomechanics of soft tissues. The theory of mixtures can be used to represent soft hydrated tissues in the human musculoskeletal system as a two-phase continuum consisting of an incompressible solid phase (collagen and proteoglycan) and an incompressible fluid phase (interstitial water). We first consider the finite deformation of soft hydrated tissues in which the solid phase is represented as hyperelastic. A finite element formulation of the governing nonlinear biphasic equations is presented based on a mixed-penalty approach and derived using the weighted residual method. Fluid and solid phase deformation, velocity, and pressure are interpolated within each element, and the pressure variables within each element are eliminated at the element level. A system of nonlinear, first-order differential equations in the fluid and solid phase deformation and velocity is obtained. In order to solve these equations, the contributions of the hyperelastic solid phase are incrementally linearized, a finite difference rule is introduced for temporal discretization, and an iterative scheme is adopted to achieve equilibrium at the end of each time increment. We demonstrate the accuracy and adequacy of the procedure using a six-node, isoparametric axisymmetric element, and we present an example problem for which independent numerical solution is available. Next, we present an automated, adaptive environment for the simulation of soft tissue continua in which the finite element analysis is coupled with automatic mesh generation, error indicators, and projection methods. Mesh generation and updating, including both refinement and coarsening, for the two-dimensional examples examined in this study are performed using the finite quadtree approach. The adaptive analysis is based on an error indicator which is the L2 norm of the difference between the finite element solution and a projected finite element solution. Total stress, calculated as the sum of the solid and fluid phase stresses, is used in the error indicator. To allow the finite difference algorithm to proceed in time using an updated mesh, solution values must be transferred to the new nodal locations. This rezoning is accomplished using a projected field for the primary variables. The accuracy and effectiveness of this adaptive finite element analysis is demonstrated using a linear, two-dimensional, axisymmetric problem corresponding to the indentation of a thin sheet of soft tissue. The method is shown to effectively capture the steep gradients and to produce solutions in good agreement with independent, converged, numerical solutions.

Investigation of Different Colloidal Porous Silicon Solutions and Their Composite Solid Matrix Rods by Optical Techniques

NASA Astrophysics Data System (ADS)

Khan, M. Naziruddin; Aldalbahi, Ali; Almohammedi, Abdullah

2018-03-01

Colloidal porous silicon (PSi) in different solvents was synthesized by simple chemical etching. Colloidal solutions were then prepared using different quantities of silicon wafer pieces (Pcs) and chloroplatinic (Pt) acid in catalyst solution. The effect on the properties of the colloidal solutions and composite rods were investigated using various optical characterization techniques. Absorption and photoluminescence (PL) intensity of the colloidal PSi solutions are observed to depend on the quantity of wafer Pcs, the Pt-solution, and the porosity formation on the wafer surface. The morphological structure of the PSi in a solvent and the solid-rod environments were studied using field-emission scanning electron microscopy (FE-SEM) and were observed to have different structures. A mono-oriented structure of PSi exists in tetrahydrofuran, which has stereo orientation in dioxane and dimethylsulfoxide (approximately 5-8 nm as confirmed using high resolution transmission electron microscopy). Subsequently, some colloidal PSi solutions were directly embedded in three types of sol-gel-based matrices, silica, ormosils (or organically modified silica) and polymer, which easily generated solid rods. Spontaneous emission (SE) of the PSi solutions and their composite rods were examined using a high power picosecond 355 nm laser source. The emitted PL and SE signals of the colloidal PSi solutions were dependent on the Pt volume, nature of the solvent, quantity of Si wafer piece, and pumping energy. The response of SE signals from the PSi composites rods is an interesting phenomenon, and such nanocomposites may be used for future research on light amplification.

Investigation of Different Colloidal Porous Silicon Solutions and Their Composite Solid Matrix Rods by Optical Techniques

NASA Astrophysics Data System (ADS)

Khan, M. Naziruddin; Aldalbahi, Ali; Almohammedi, Abdullah

2018-07-01

Colloidal porous silicon (PSi) in different solvents was synthesized by simple chemical etching. Colloidal solutions were then prepared using different quantities of silicon wafer pieces (Pcs) and chloroplatinic (Pt) acid in catalyst solution. The effect on the properties of the colloidal solutions and composite rods were investigated using various optical characterization techniques. Absorption and photoluminescence (PL) intensity of the colloidal PSi solutions are observed to depend on the quantity of wafer Pcs, the Pt-solution, and the porosity formation on the wafer surface. The morphological structure of the PSi in a solvent and the solid-rod environments were studied using field-emission scanning electron microscopy (FE-SEM) and were observed to have different structures. A mono-oriented structure of PSi exists in tetrahydrofuran, which has stereo orientation in dioxane and dimethylsulfoxide (approximately 5-8 nm as confirmed using high resolution transmission electron microscopy). Subsequently, some colloidal PSi solutions were directly embedded in three types of sol-gel-based matrices, silica, ormosils (or organically modified silica) and polymer, which easily generated solid rods. Spontaneous emission (SE) of the PSi solutions and their composite rods were examined using a high power picosecond 355 nm laser source. The emitted PL and SE signals of the colloidal PSi solutions were dependent on the Pt volume, nature of the solvent, quantity of Si wafer piece, and pumping energy. The response of SE signals from the PSi composites rods is an interesting phenomenon, and such nanocomposites may be used for future research on light amplification.

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

Rai, R.N., E-mail: rn_rai@yahoo.co.in; Kant, Shiva; Reddi, R.S.B.

Urea is an attractive material for frequency conversion of high power lasers to UV (for wavelength down to 190 nm), but its usage is hindered due to its hygroscopic nature, though there is no alternative organic NLO crystal which could be transparent up to 190 nm. The hygroscopic character of urea has been modified by making the solid solution (UCNB) of urea (U) and p-chloronitrobenzene (CNB). The formation of the solid solution of CNB in U is explained on the basis of phase diagram, powder XRD, FTIR, elemental analysis and single crystal XRD studies. The solubility of U, CNB andmore » UCNB in ethanol solution is evaluated at different temperatures. Transparent single crystals of UCNB are grown from its saturated solution in ethanol. Optical properties e.g., second harmonic generation (SHG), refractive index and the band gap for UCNB crystal were measured and their values were compared with the parent compounds. Besides modification in hygroscopic nature, UCNB has also shown the higher SHG signal and mechanical hardness in comparison to urea crystal. - Highlights: • The hygroscopic character of urea was modified by making the solid solution • Solid solution formation is support by elemental, powder- and single crystal XRD • Crystal of solid solution has higher SHG signal and mechanical stability. • Refractive index and band gap of solid solution crystal have determined.« less

Solid Solutions of Rare Earth Cations in Mesoporous Anatase Beads and Their Performances in Dye-Sensitized Solar Cells

PubMed Central

Cavallo, Carmen; Salleo, Alberto; Gozzi, Daniele; Di Pascasio, Francesco; Quaranta, Simone; Panetta, Riccardo; Latini, Alessandro

2015-01-01

Solid solutions of the rare earth (RE) cations Pr3+, Nd3+, Sm3+, Gd3+, Er3+ and Yb3+ in anatase TiO2 have been synthesized as mesoporous beads in the concentration range 0.1–0.3% of metal atoms. The solid solutions were have been characterized by XRD, SEM, diffuse reflectance UV-Vis spectroscopy, BET and BJH surface analysis. All the solid solutions possess high specific surface areas, up to more than 100 m2/g. The amount of adsorbed dye in each photoanode has been determined spectrophotometrically. All the samples were tested as photoanodes in dye-sensitized solar cells (DSSCs) using N719 as dye and a nonvolatile, benzonitrile based electrolyte. All the cells were have been tested by conversion efficiency (J–V), quantum efficiency (IPCE), electrochemical impedance spectroscopy (EIS) and dark current measurements. While lighter RE cations (Pr3+, Nd3+) limit the performance of DSSCs compared to pure anatase mesoporous beads, cations from Sm3+ onwards enhance the performance of the devices. A maximum conversion efficiency of 8.7% for Er3+ at a concentration of 0.2% has been achieved. This is a remarkable efficiency value for a DSSC employing N719 dye without co-adsorbents and a nonvolatile electrolyte. For each RE cation the maximum performances are obtained for a concentration of 0.2% metal atoms. PMID:26577287

Mechanism-based selection of stabilization strategy for amorphous formulations: Insights into crystallization pathways.

PubMed

Edueng, Khadijah; Mahlin, Denny; Larsson, Per; Bergström, Christel A S

2017-06-28

We developed a step-by-step experimental protocol using differential scanning calorimetry (DSC), dynamic vapour sorption (DVS), polarized light microscopy (PLM) and a small-scale dissolution apparatus (μDISS Profiler) to investigate the mechanism (solid-to-solid or solution-mediated) by which crystallization of amorphous drugs occurs upon dissolution. This protocol then guided how to stabilize the amorphous formulation. Indapamide, metolazone, glibenclamide and glipizide were selected as model drugs and HPMC (Pharmacoat 606) and PVP (K30) as stabilizing polymers. Spray-dried amorphous indapamide, metolazone and glibenclamide crystallized via solution-mediated nucleation while glipizide suffered from solid-to-solid crystallization. The addition of 0.001%-0.01% (w/v) HPMC into the dissolution medium successfully prevented the crystallization of supersaturated solutions of indapamide and metolazone whereas it only reduced the crystallization rate for glibenclamide. Amorphous solid dispersion (ASD) formulation of glipizide and PVP K30, at a ratio of 50:50% (w/w) reduced but did not completely eliminate the solid-to-solid crystallization of glipizide even though the overall dissolution rate was enhanced both in the absence and presence of HPMC. Raman spectroscopy indicated the formation of a glipizide polymorph in the dissolution medium with higher solubility than the stable polymorph. As a complementary technique, molecular dynamics (MD) simulations of indapamide and glibenclamide with HPMC was performed. It was revealed that hydrogen bonding patterns of the two drugs with HPMC differed significantly, suggesting that hydrogen bonding may play a role in the greater stabilizing effect on supersaturation of indapamide, compared to glibenclamide. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Dissolution of aragonite-strontianite solid solutions in nonstoichiometric Sr (HCO3)2-Ca (HCO3)2-CO2-H2O solutions

USGS Publications Warehouse

Plummer, Niel; Busenberg, E.; Glynn, P.D.; Blum, A.E.

1992-01-01

Synthetic strontianite-aragonite solid-solution minerals were dissolved in CO2-saturated non-stoichiometric solutions of Sr(HCO3)2 and Ca(HCO3)2 at 25??C. The results show that none of the dissolution reactions reach thermodynamic equilibrium. Congruent dissolution in Ca(HCO3)2 solutions either attains or closely approaches stoichiometric saturation with respect to the dissolving solid. In Sr(HCO3)2 solutions the reactions usually become incongruent, precipitating a Sr-rich phase before reaching stoichiometric saturation. Dissolution of mechanical mixtures of solids approaches stoichiometric saturation with respect to the least stable solid in the mixture. Surface uptake from subsaturated bulk solutions was observed in the initial minutes of dissolution. This surficial phase is 0-10 atomic layers thick in Sr(HCO3)2 solutions and 0-4 layers thick in Ca(HCO3)2 solutions, and subsequently dissolves and/or recrystallizes, usually within 6 min of reaction. The initial transient surface precipitation (recrystallization) process is followed by congruent dissolution of the original solid which proceeds to stoichiometric saturation, or until the precipitation of a more stable Sr-rich solid. The compositions of secondary precipitates do not correspond to thermodynamic equilibrium or stoichiometric saturation states. X-ray photoelectron spectroscopy (XPS) measurements indicate the formation of solid solutions on surfaces of aragonite and strontianite single crystals immersed in Sr(HCO3)2 and Ca(HCO3)2 solutions, respectively. In Sr(HCO3)2 solutions, the XPS signal from the outer ~ 60 A?? on aragonite indicates a composition of 16 mol% SrCO3 after only 2 min of contact, and 14-18 mol% SrCO3 after 3 weeks of contact. The strontianite surface averages approximately 22 mol% CaCO3 after 2 min of contact with Ca(HCO3)2 solution, and is 34-39 mol% CaCO3 after 3 weeks of contact. XPS analysis suggests the surface composition is zoned with somewhat greater enrichment in the outer ~25 A?? (as much as 26 mol% SrCO3 on aragonite and 44 mol% CaCO3 on strontianite). The results indicate rapid formation of a solid-solution surface phase from subsaturated aqueous solutions. The surface phase continually adjusts in composition in response to changes in composition of the bulk fluid as net dissolution proceeds. Dissolution rates of the endmembers are greatly reduced in nonstoichiometric solutions relative to dissolution rates observed in stoichiometric solutions. All solids dissolve more slowly in solutions spiked with the least soluble component ((Sr(HCO3)2)) than in solutions spiked with the more soluble component (Ca(HCO3)2), an effect that becomes increasingly significant as stoichiometric saturation is approached. It is proposed that the formation of a non-stoichiometric surface reactive zone significantly decreases dissolution rates. ?? 1992.

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

Solar Metal Sulfate-Ammonia Based Thermochemical Water Splitting Cycle for Hydrogen Production

NASA Technical Reports Server (NTRS)

T-Raissi, Ali (Inventor); Muradov, Nazim (Inventor); Huang, Cunping (Inventor)

2014-01-01

Two classes of hybrid/thermochemical water splitting processes for the production of hydrogen and oxygen have been proposed based on (1) metal sulfate-ammonia cycles (2) metal pyrosulfate-ammonia cycles. Methods and systems for a metal sulfate MSO.sub.4--NH3 cycle for producing H2 and O2 from a closed system including feeding an aqueous (NH3)(4)SO3 solution into a photoctalytic reactor to oxidize the aqueous (NH3)(4)SO3 into aqueous (NH3)(2)SO4 and reduce water to hydrogen, mixing the resulting aqueous (NH3)(2)SO4 with metal oxide (e.g. ZnO) to form a slurry, heating the slurry of aqueous (NH4)(2)SO4 and ZnO(s) in the low temperature reactor to produce a gaseous mixture of NH3 and H2O and solid ZnSO4(s), heating solid ZnSO4 at a high temperature reactor to produce a gaseous mixture of SO2 and O2 and solid product ZnO, mixing the gaseous mixture of SO2 and O2 with an NH3 and H2O stream in an absorber to form aqueous (NH4)(2)SO3 solution and separate O2 for aqueous solution, recycling the resultant solution back to the photoreactor and sending ZnO to mix with aqueous (NH4)(2)SO4 solution to close the water splitting cycle wherein gaseous H2 and O2 are the only products output from the closed ZnSO4--NH3 cycle.

Enhanced photocatalytic degradation of 2-propanol over macroporous GaN/ZnO solid solution prepared by a novel sol-gel method

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

Wang, Lizhong; Ouyang, Shuxin; Ren, Bofan

2015-10-01

Macroporous GaN/ZnO solid solution photocatalyst is synthesized through a novel sol-gel method under mild conditions. The performance of as-synthesized solid solution photocatalyst is evaluated for decomposition of gaseous 2-propanol (IPA). It is found that due to enhancement in both the adsorption to gaseous IPA and the absorbance to visible light, the porous GaN/ZnO solid solution exhibits a good photocatalytic performance for IPA decomposition. Moreover, the mechanism for photocatalytic degradation IPA over porous GaN/ZnO solid solution is also investigated in comparison with those for the two end materials ZnO and GaN. The trapping effects with different scavengers prove that both themore » photoexcited electrons and holes affect the IPA photodegradation process, simultaneously.« less

Synthesis of GaN:ZnO solid solution by solution combustion method and characterization for photocatalytic application

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

Menon, Sumithra Sivadas; Anitha, R.; Baskar, K.

2016-05-23

GaN-ZnO solid solution has emerged as a successful and reproducible photocatalyst for overall water splitting by one-step photoexcitation, with a bandgap in visible region. When the solid solution is formed, some of the Zn and O ions are replaced by Ga and N ions respectively and there is a narrowing of bandgap which is hypothesized as due to Zn3d-N2p repulsion. The traditional method of synthesis of GaN-ZnO solid solution is by nitridation of the starting oxides under constant ammonia flow. Here we report a solution combustion technique for the synthesis of the solid solution at a temperature about 500 °more » C in a muffle furnace with metal nitrates as precursors and urea as the fuel. The as prepared samples showed change in color with the increased concentration of ZnO in the solution. The structural, microstructural, morphological and optical properties of the samples were realized by Powder X ray diffraction, Scanning electron microscopy, Energy dispersive X ray analysis, Transmission electron microscopy and Photoluminescence. Finally the hydrogen production efficiency of the GaN-ZnO nanopowders by water splitting was found, using methanol as a scavenger. The apparent quantum yield (AQY) of 0.048% is obtained for GaN-ZnO solid solution.« less

A facile method to prepare "green" nano-phosphors with a large Stokes-shift and solid-state enhanced photophysical properties based on surface-modified gold nanoclusters.

PubMed

Cheng, C H; Huang, H Y; Talite, M J; Chou, W C; Yeh, J M; Yuan, C T

2017-12-15

Colloidal nano-materials, such as quantum dots (QDs) have been applied to light-conversion nano-phosphors due to their unique tunable emission. However, most of the QDs involve toxic elements and are synthesized in a hazardous solvent. In addition, conventional QD nano-phosphors with a small Stokes shift suffered from reabsorption losses and aggregation-induced quenching in the solid state. Here, we demonstrate a facile, matrix-free method to prepare eco-friendly nano-phosphors with a large Stokes shift based on aqueous thiolate-stabilized gold nanoclusters (GSH-AuNCs) with simple surface modifications. Our method is just to drop GSH-AuNCs solution on the aluminum foil and then surface-modified AuNCs (Al-GSH-AuNCs) can be spontaneously precipitated out of the aqueous solution. Compared with pristine GSH-AuNCs in solution, the Al-GSH-AuNCs exhibit enhanced solid-state PL quantum yields, lengthened PL lifetime, and spectral blue shift, which can be attributed to the aggregation-induced emission enhancement facilitated by surface modifications. Such surface-treatment induced aggregation of AuNCs can restrict the surface-ligand motion, leading to the enhancement of PL properties in the solid state. In addition, the Al-GSH-AuNCs nano-phosphors with a large Stokes shift can mitigate the aggregation-induced PL quenching and reabsorption losses, which would be potential candidates for "green" nano-phosphors. Copyright © 2017 Elsevier Inc. All rights reserved.

Ion mobility and transport properties of bismuth fluoride-containing solid solutions with tysonite-type structure

NASA Astrophysics Data System (ADS)

Kavun, V. Ya.; Uvarov, N. F.; Slobodyuk, A. B.; Merkulov, E. B.; Polyantsev, M. M.

2018-07-01

The ion mobility and conductivity of solid solutions with tysonite-type structure obtained by doping bismuth trifluoride with lead (II) fluoride, and zirconium and bismuth oxides have been studied using 19F NMR, X-ray diffraction analysis, and impedance spectroscopy. The types of ionic motions in the fluoride sublattice of the synthesized solid solutions in the temperature range 150-450 K have been determined and the energy of their activation has been estimated. Due to high ionic conductivity, above 10-2 S/cm at 570 K, these solid solutions can be considered as superionic conductors.

Solid-solution CrCoCuFeNi high-entropy alloy thin films synthesized by sputter deposition

DOE PAGES

An, Zhinan; Jia, Haoling; Wu, Yueying; ...

2015-05-04

The concept of high configurational entropy requires that the high-entropy alloys (HEAs) yield single-phase solid solutions. However, phase separations are quite common in bulk HEAs. A five-element alloy, CrCoCuFeNi, was deposited via radio frequency magnetron sputtering and confirmed to be a single-phase solid solution through the high-energy synchrotron X-ray diffraction, energy-dispersive spectroscopy, wavelength-dispersive spectroscopy, and transmission electron microscopy. The formation of the solid-solution phase is presumed to be due to the high cooling rate of the sputter-deposition process.

First Principle and Experimental Study for Site Preferences of Formability Improved Alloying Elements in Mg Crystal

NASA Astrophysics Data System (ADS)

Zeng, Ying; Jiang, Bin; Shi, Ouling; Quan, Gaofen; Al-Ezzi, Salih; Pan, FuSheng

2018-07-01

Some alloying elements (Al, Er, Gd, Li, Mn, Sn, Y, Zn) were proved recently by calculations or experiments to improve the formability of Mg alloys, but ignoring their site preference in Mg crystals during the calculated process. A crystallographic model was built via first principle calculations to predict the site preferences of these elements. Regularities between doping elements and site preferences were summarized. Meanwhile, in the basis of the crystallographic model, a series of formulas were deduced combining the diffraction law. It predicted that a crystal plane with abnormal XRD peak intensity of the Mg-based solid solutions, compared to that of the pure Mg, prefers to possess solute atoms. Thus, three single-phase solid solution alloys were then prepared through an original In-situ Solution Treatment, and their XRD patterns were compared. Finally, the experiment further described the site preferences of these solute atoms in Mg crystal, verifying the calculation results.

First Principle and Experimental Study for Site Preferences of Formability Improved Alloying Elements in Mg Crystal

NASA Astrophysics Data System (ADS)

Zeng, Ying; Jiang, Bin; Shi, Ouling; Quan, Gaofen; Al-Ezzi, Salih; Pan, FuSheng

2018-03-01

Some alloying elements (Al, Er, Gd, Li, Mn, Sn, Y, Zn) were proved recently by calculations or experiments to improve the formability of Mg alloys, but ignoring their site preference in Mg crystals during the calculated process. A crystallographic model was built via first principle calculations to predict the site preferences of these elements. Regularities between doping elements and site preferences were summarized. Meanwhile, in the basis of the crystallographic model, a series of formulas were deduced combining the diffraction law. It predicted that a crystal plane with abnormal XRD peak intensity of the Mg-based solid solutions, compared to that of the pure Mg, prefers to possess solute atoms. Thus, three single-phase solid solution alloys were then prepared through an original In-situ Solution Treatment, and their XRD patterns were compared. Finally, the experiment further described the site preferences of these solute atoms in Mg crystal, verifying the calculation results.

Impact of soil properties on critical concentrations of cadmium, lead, copper, zinc, and mercury in soil and soil solution in view of ecotoxicological effects.

PubMed

de Vries, Wim; Lofts, Steve; Tipping, Ed; Meili, Markus; Groenenberg, Jan E; Schütze, Gudrun

2007-01-01

Risk assessment for metals in terrestrial ecosystems, including assessments of critical loads, requires appropriate critical limits for metal concentrations in soil and soil solution. This chapter presents an overview of methodologies used to derive critical (i) reactive and total metal concentrations in soils and (ii) free metal ion and total metal concentrations in soil solution for Cd, Pb, Cu, Zn, and Hg, taking into account the effect of soil properties related to ecotoxicological effects. Most emphasis is given to the derivation of critical free and total metal concentrations in soil solution, using available NOEC soil data and transfer functions relating solid-phase and dissolved metal concentrations. This approach is based on the assumption that impacts on test organisms (plants, microorganisms, and soil invertebrates) are mainly related to the soil solution concentration (activity) and not to the soil solid-phase content. Critical Cd, Pb, Cu, Zn, and Hg concentrations in soil solution vary with pH and DOC level. The results obtained are generally comparable to those derived for surface waters based on impacts to aquatic organisms. Critical soil metal concentrations, related to the derived soil solution limits, can be described as a function of pH and organic matter and clay content, and varying about one order of magnitude between different soil types.

Atomistic modeling of crystal-to-amorphous transition and associated kinetics in the Ni-Nb system by molecular dynamics simulations.

PubMed

Dai, X D; Li, J H; Liu, B X

2005-03-17

With the aid of ab initio calculations, an n-body potential of the Ni-Nb system is constructed under the Finnis-Sinclair formalism and the constructed potential is capable of not only reproducing some static physical properties but also revealing the atomistic mechanism of crystal-to-amorphous transition and associated kinetics. With application of the constructed potential, molecular dynamics simulations using the solid solution models reveal that the physical origin of crystal-to-amorphous transition is the crystalline lattice collapsing while the solute atoms are exceeding the critical solid solubilities, which are determined to be 19 atom % Ni and 13 atom % Nb for the Nb- and Ni-based solid solutions, respectively. It follows that an intrinsic glass-forming ability of the Ni-Nb system is within 19-87 atom % Ni, which matches well with that observed in ion beam mixing/solid-state reaction experiments. Simulations using the Nb/Ni/Nb (Ni/Nb/Ni) sandwich models indicate that the amorphous layer at the interfaces grows in a layer-by-layer mode and that, upon dissolving solute atoms, the Ni lattice approaches and exceeds its critical solid solubility faster than the Nb lattice, revealing an asymmetric behavior in growth kinetics. Moreover, an energy diagram is obtained by computing the energetic sequence of the Ni(x)Nb(100)(-)(x) alloy in fcc, bcc, and amorphous structures, respectively, over the entire composition range, and the diagram could serve as a guide for predicting the metastable alloy formation in the Ni-Nb system.

Recovery of gold from computer circuit board scrap using aqua regia.

PubMed

Sheng, Peter P; Etsell, Thomas H

2007-08-01

Computer circuit board scrap was first treated with one part concentrated nitric acid and two parts water at 70 degrees C for 1 h. This step dissolved the base metals, thereby liberating the chips from the boards. After solid-liquid separation, the chips, intermixed with some metallic flakes and tin oxide precipitate, were mechanically crushed to liberate the base and precious metals contained within the protective plastic or ceramic chip cases. The base metals in this crushed product were dissolved by leaching again with the same type of nitric acid-water solution. The remaining solid constituents, crushed chips and resin, plus solid particles of gold, were leached with aqua regia at various times and temperatures. Gold was precipitated from the leachate with ferrous sulphate.

Modelling solid solutions with cluster expansion, special quasirandom structures, and thermodynamic approaches

NASA Astrophysics Data System (ADS)

Saltas, V.; Horlait, D.; Sgourou, E. N.; Vallianatos, F.; Chroneos, A.

2017-12-01

Modelling solid solutions is fundamental in understanding the properties of numerous materials which are important for a range of applications in various fields including nanoelectronics and energy materials such as fuel cells, nuclear materials, and batteries, as the systematic understanding throughout the composition range of solid solutions for a range of conditions can be challenging from an experimental viewpoint. The main motivation of this review is to contribute to the discussion in the community of the applicability of methods that constitute the investigation of solid solutions computationally tractable. This is important as computational modelling is required to calculate numerous defect properties and to act synergistically with experiment to understand these materials. This review will examine in detail two examples: silicon germanium alloys and MAX phase solid solutions. Silicon germanium alloys are technologically important in nanoelectronic devices and are also relevant considering the recent advances in ternary and quaternary groups IV and III-V semiconductor alloys. MAX phase solid solutions display a palette of ceramic and metallic properties and it is anticipated that via their tuning they can have applications ranging from nuclear to aerospace industries as well as being precursors for particular MXenes. In the final part, a brief summary assesses the limitations and possibilities of the methodologies discussed, whereas there is discussion on the future directions and examples of solid solution systems that should prove fruitful to consider.

Investigation of the phase relations in the U-Al-Ge ternary system: Influence of the Al/Ge substitution on the properties of the intermediate phases

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

Moussa, C.; El Sayah, Z.; Chajewski, G.

The phase relations within the U-Al-Ge ternary system were studied for two isothermal sections, at 673 K for the whole Gibbs triangle and at 1173 K for the concentration range 25–100 at% U. The identification of the phases, their composition ranges and stability were determined by x-ray powder diffraction, scanning electron microscopy coupled to energy dispersive spectroscopy and differential thermal analysis. The tie-lines and the solubility domains were determined for the U-Ge and U-Al binaries, the UAl{sub 3}-UGe{sub 3} solid-solution and for the unique ternary intermediate phase U{sub 3}Al{sub 2−x}Ge{sub 3+x}. The experimental isopleth section of the pseudo-binary UAl{sub 3}-UGe{submore » 3} reveals an isomorphous solid solution based on the Cu{sub 3}Au-type below the solidus. The U{sub 3}Al{sub 2−x}Ge{sub 3+x} solid solution extends for −0.1≤x≤1.35 and −0.2≤x≤1.5 at 673 K and 1173 K respectively. It crystallizes in the I-centered tetragonal symmetry. The reciprocal lattice of several compositions of the U{sub 3}Al{sub 2−x}Ge{sub 3+x} solid solution was examined by electron diffraction at room temperature, revealing the presence of a c-glide plane. Their crystal structure was refined by single crystal x-ray diffraction suggesting an isomorphous solid solution best described with the non-centrosymmetric space group I4cm in the paramagnetic domain. The magnetic measurements confirm the ferromagnetic ordering of the solid solution U{sub 3}Al{sub 2−x}Ge{sub 3+x} with an increase of Tc with the Al content. The thermal variation of the specific heat bear out the magnetic transitions with some delocalized character of the uranium 5f electrons. - Graphical abstract: The phase relations within the U-Al-Ge ternary system were experimentally assessed for two isothermal sections, at 673 K for the whole Gibbs triangle and at 1173 K for the concentration range 25–100 at% U. A complete UAl{sub 3}-UGe{sub 3} solid-solution based on the Cu{sub 3}Au-type forms below the solidus. A unique ternary phase showing a large homogeneity domain, U{sub 3}Al{sub 2−x}Ge{sub 3+x} for −0.1≤x≤1.35 and −0.2≤x≤1.5 at 673 K and 1173 K respectively has been evidenced. It is best described with the non-centrosymmetric space group I4cm above room temperature. A linear increase of the ferromagnetic ordering is observed with the Al content. - Highlights: • Isothermal sections of the U-Al-Ge system were investigated for 673 K and 1173 K. • An isomorphous solid-solution UAl{sub 3}-UGe{sub 3} forms for the whole composition range. • U{sub 3}Al{sub 2−x}Ge{sub 3+x} the unique ternary phase to form exists for a large homogeneity domain. • U{sub 3}Al{sub 2−x}Ge{sub 3+x} is best described in I4cm space group above room temperature. • The ferromagnetic transition of U{sub 3}Al{sub 2−x}Ge{sub 3+x} linearly increases with the Al content.« less

High-Capacity Hydrogen-Based Green-Energy Storage Solutions For The Grid Balancing

NASA Astrophysics Data System (ADS)

D'Errico, F.; Screnci, A.

One of the current main challenges in green-power storage and smart grids is the lack of effective solutions for accommodating the unbalance between renewable energy sources, that offer intermittent electricity supply, and a variable electricity demand. Energy management systems have to be foreseen for the near future, while they still represent a major challenge. Integrating intermittent renewable energy sources, by safe and cost-effective energy storage systems based on solid state hydrogen is today achievable thanks to recently some technology breakthroughs. Optimized solid storage method made of magnesium-based hydrides guarantees a very rapid absorption and desorption kinetics. Coupled with electrolyzer technology, high-capacity storage of green-hydrogen is therefore practicable. Besides these aspects, magnesium has been emerging as environmentally friend energy storage method to sustain integration, monitoring and control of large quantity of GWh from high capacity renewable generation in the EU.

High-Capacity Hydrogen-Based Green-Energy Storage Solutions for the Grid Balancing

NASA Astrophysics Data System (ADS)

D'Errico, F.; Screnci, A.

One of the current main challenges in green-power storage and smart grids is the lack of effective solutions for accommodating the unbalance between renewable energy sources, that offer intermittent electricity supply, and a variable electricity demand. Energy management systems have to be foreseen for the near future, while they still represent a major challenge. Integrating intermittent renewable energy sources, by safe and cost-effective energy storage systems based on solid state hydrogen is today achievable thanks to recently some technology breakthroughs. Optimized solid storage method made of magnesium-based hydrides guarantees a very rapid absorption and desorption kinetics. Coupled with electrolyzer technology, high-capacity storage of green-hydrogen is therefore practicable. Besides these aspects, magnesium has been emerging as environmentally friend energy storage method to sustain integration, monitoring and control of large quantity of GWh from high capacity renewable generation in the EU.

Quench-age method for the fabrication of niobium-aluminum superconductors

DOEpatents

Pickus, Milton R.; Ciardella, Robert L.

1978-01-01

A flexible Nb.sub.3 Al superconducting wire is fabricated from a niobium-aluminum composite wire by heating to form a solid solution which is retained at room temperature as a metastable solid solution by quenching. The metastable solid solution is then transformed to the stable superconducting A-15 phase by low temperature aging. The transformation induced by aging can be controlled to yield either a multifilamentary or a solid A-15 core surrounded by ductile niobium.

Recent developments and future trends in solid phase microextraction techniques towards green analytical chemistry.

PubMed

Spietelun, Agata; Marcinkowski, Łukasz; de la Guardia, Miguel; Namieśnik, Jacek

2013-12-20

Solid phase microextraction find increasing applications in the sample preparation step before chromatographic determination of analytes in samples with a complex composition. These techniques allow for integrating several operations, such as sample collection, extraction, analyte enrichment above the detection limit of a given measuring instrument and the isolation of analytes from sample matrix. In this work the information about novel methodological and instrumental solutions in relation to different variants of solid phase extraction techniques, solid-phase microextraction (SPME), stir bar sorptive extraction (SBSE) and magnetic solid phase extraction (MSPE) is presented, including practical applications of these techniques and a critical discussion about their advantages and disadvantages. The proposed solutions fulfill the requirements resulting from the concept of sustainable development, and specifically from the implementation of green chemistry principles in analytical laboratories. Therefore, particular attention was paid to the description of possible uses of novel, selective stationary phases in extraction techniques, inter alia, polymeric ionic liquids, carbon nanotubes, and silica- and carbon-based sorbents. The methodological solutions, together with properly matched sampling devices for collecting analytes from samples with varying matrix composition, enable us to reduce the number of errors during the sample preparation prior to chromatographic analysis as well as to limit the negative impact of this analytical step on the natural environment and the health of laboratory employees. Copyright © 2013 Elsevier B.V. All rights reserved.

Interdiffusion in Ternary Magnesium Solid Solutions of Aluminum and Zinc

DOE PAGES

Kammerer, Catherine; Kulkarni, Nagraj S; Warmack, Robert J Bruce; ...

2016-01-11

Al and Zn are two of the most common alloying elements in commercial Mg alloys, which can improve the physical properties through solid solution strengthening and precipitation hardening. Diffusion plays a key role in the kinetics of these and other microstructural design relevant to Mg-alloy development. However, there is a lack of multicomponent diffusion data available for Mg alloys. Through solid-to-solid diffusion couples, diffusional interactions of Al and Zn in ternary Mg solid-solution at 400° and 450 °C were examined by an extension of the Boltzmann-Matano analysis based on Onsager s formalism. Concentration profiles of Mg-Al-Zn ternary alloys were determinedmore » by electron probe microanalysis, and analyzed to determine the ternary interdiffusion coefficients as a function of composition. Zn was determined to interdiffuse the fastest, followed by Mg and Al. Appreciable diffusional interactions among Mg, Al, and Zn were observed by variations in sign and magnitude of cross interdiffusion coefficients. In particular, Zn was found to significantly influence the interdiffusion of Mg and Al significantly: the and ternary cross interdiffusion coefficients were both negative, and large in magnitude, in comparison to and , respectively. Al and Mg were observed influence the interdiffusion of Mg and Al, respectively, with positive and interdiffusion coefficients, but their influence on the Zn interdiffusion was negligible.« less

Disappearance of superconductivity in the solid solution between (Ca4Al2O6)(Fe2As2) and (Ca4Al2O6)(Fe2P2) superconductors.

PubMed

Shirage, Parasharam M; Kihou, Kunihiro; Lee, Chul-Ho; Takeshita, Nao; Eisaki, Hiroshi; Iyo, Akira

2012-09-19

The effect of alloying the two perovskite-type iron-based superconductors (Ca(4)Al(2)O(6))(Fe(2)As(2)) and (Ca(4)Al(2)O(6))(Fe(2)P(2)) was examined. While the two stoichiometric compounds possess relatively high T(c)'s of 28 and 17 K, respectively, their solid solutions of the form (Ca(4)Al(2)O(6))(Fe(2)(As(1-x)P(x))(2)) do not show superconductivity over a wide range from x = 0.50 to 0.95. The resultant phase diagram is thus completely different from those of other typical iron-based superconductors such as BaFe(2)(As,P)(2) and LaFe(As,P)O, in which superconductivity shows up when P is substituted for As in the non-superconducting "parent" compounds. Notably, the solid solutions in the non-superconducting range exhibit resistivity anomalies at temperatures of 50-100 K. The behavior is reminiscent of the resistivity kink commonly observed in various non-superconducting parent compounds that signals the onset of antiferromagnetic/orthorhombic long-range order. The similarity suggests that the suppression of the superconductivity in the present case also has a magnetic and/or structural origin.

Electrochemical Deposition of Niobium onto the Surface of Copper Using a Novel Choline Chloride-Based Ionic Liquid

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

Wixtroma, Alex I.; Buhlera, Jessica E.; Reece, Charles E.

2013-06-01

Recent research has shown that choline chloride-based solutions can be used to replace acid-based electrochemical polishing solutions. In this study niobium metal was successfully deposited on the surface of copper substrate via electrochemical deposition using a novel choline chloride-based ionic liquid. The niobium metal used for deposition on the Cu had been dissolved in the solution from electrochemical polishing of a solid niobium piece prior to the deposition. The visible coating on the surface of the Cu was analyzed using scanning electron microscopy (SEM) and electron dispersive x-ray spectroscopy (EDX). This deposition method effectively recycles previously dissolved niobium from electrochemicalmore » polishing.« less

Neutralization of Plutonium and Enriched Uranium Solutions Containing Gadolinium as a Neutron Poison

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

BRONIKOWSKI, MG.

2004-04-01

Materials currently being dissolved in the HB-Line Facility will result in an accumulated solution containing an estimated uranium:plutonium (U:Pu) ratio of 4.3:1 and an 235U enrichment estimated at 30 per cent The U:Pu ratio and the enrichment are outside the evaluated concentration range for disposition to high level waste (HLW) using gadolinium (Gd) as a neutron poison. To confirm that the solution generated during the current HB-Line dissolving campaign can be poisoned with Gd, neutralized and discarded to the Savannah River Site (SRS) high level waste (HLW) system without undue nuclear safety concerns the caustic precipitation of surrogate solutions wasmore » examined. Experiments were performed with a U/Pu/Gd solution representative of the HB-Line estimated concentration ratio and also a U/Gd solution. Depleted U was used in the experiments as the enrichment of the U will not affect the chemical behavior during neutralization, but will affect the amount of Gd added to the solution. Settling behavior of the neutralized solutions was found to be comparable to previous studies. The neutralized solutions mixed easily and had expected densities of typical neutralized waste. The neutralized solids were found to be homogeneous and less than 20 microns in size. Partially neutralized solids were more amorphous than the fully neutralized solids. Based on the results of these experiments, Gd was found to be a viable poison for neutralizing a U/Pu/Gd solution with a U:Pu mass ratio of 4.3:1 thus extending the U:Pu mass ratio from the previously investigated 0-3:1 to 4.3:1. However, further work is needed to allow higher U concentrations or U:Pu ratios greater than investigated in this work.« less

Water-enhanced solvation of organics

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

Lee, Jane H.

1993-07-01

Water-enhanced solvation (WES) was explored for Lewis acid solutes in Lewis base organic solvents, to develop cheap extract regeneration processes. WES for solid solutes was determined from ratios of solubilities of solutes in water-sat. and low-water solvent; both were determined from solid-liquid equilibrium. Vapor-headspace analysis was used to determine solute activity coefficients as function of organic phase water concentration. WES magnitudes of volatile solutes were normalized, set equal to slope of log γ s vs x w/x s curve. From graph shape Δ(log γ s) represents relative change in solute activity coefficient. Solutes investigated by vapor-headspace analysis were acetic acid,more » propionic acid, ethanol, 1,2-propylene glycol, 2,3-butylene glycol. Monocarboxylic acids had largest decrease in activity coefficient with water addition followed by glycols and alcohols. Propionic acid in cyclohexanone showed greatest water-enhancement Δ(log γ acid)/Δ(x w/x acid) = -0.25. In methylcyclohexanone, the decrease of the activity coefficient of propionic acid was -0.19. Activity coefficient of propionic acid in methylcyclohexanone stopped decreasing once the water reached a 2:1 water to acid mole ratio, implying a stoichiometric relation between water, ketone, and acid. Except for 2,3-butanediol, activity coefficients of the solutes studied decreased monotonically with water content. Activity coefficient curves of ethanol, 1,2-propanediol and 2,3-butanediol did not level off at large water/solute mole ratio. Solutes investigated by solid-liquid equilibrium were citric acid, gallic acid, phenol, xylenols, 2-naphthol. Saturation concentration of citric acid in anhydrous butyl acetate increased from 0.0009 to 0.087 mol/L after 1.3 % (g/g) water co-dissolved into organic phase. Effect of water-enhanced solvation for citric acid is very large but very small for phenol and its derivatives.« less

Raman spectroscopic investigation of thorium dioxide-uranium dioxide (ThO₂-UO₂) fuel materials.

PubMed

Rao, Rekha; Bhagat, R K; Salke, Nilesh P; Kumar, Arun

2014-01-01

Raman spectroscopic investigations were carried out on proposed nuclear fuel thorium dioxide-uranium dioxide (ThO2-UO2) solid solutions and simulated fuels based on ThO2-UO2. Raman spectra of ThO2-UO2 solid solutions exhibited two-mode behavior in the entire composition range. Variations in mode frequencies and relative intensities of Raman modes enabled estimation of composition, defects, and oxygen stoichiometry in these compounds that are essential for their application. The present study shows that Raman spectroscopy is a simple, promising analytical tool for nondestructive characterization of this important class of nuclear fuel materials.

Determination of thermophysical characteristics of solid materials by electrical modelling of the solutions to the inverse problems in nonsteady heat conduction

NASA Technical Reports Server (NTRS)

Kozdoba, L. A.; Krivoshei, F. A.

1985-01-01

The solution of the inverse problem of nonsteady heat conduction is discussed, based on finding the coefficient of the heat conduction and the coefficient of specific volumetric heat capacity. These findings are included in the equation used for the electrical model of this phenomenon.

Correlation of Solid State and Solution Coordination Numbers with Infrared Spectroscopy in Five-, Six-, and Eight-Coordinate Transition Metal Complexes of DOTAM.

PubMed

Nagata, Maika K C T; Brauchle, Paul S; Wang, Sen; Briggs, Sarah K; Hong, Young Soo; Laorenza, Daniel W; Lee, Andrea G; Westmoreland, T David

2016-08-16

Three new DOTAM (1,4,7,10-tetrakis(acetamido)-1,4,7,10-tetraazacyclododecane) complexes have been synthesized and characterized by X-ray crystallography: [Co(DOTAM)]Cl 2 •3H 2 O, [Ni(DOTAM)]Cl 2 •4H 2 O, and [Cu(DOTAM)](ClO 4 ) 2 •H 2 O. Solid state and solution IR spectroscopic features for a series of [M(DOTAM)] 2+ complexes (M=Mn, Co, Cu, Ni, Ca, Zn) correlate with solid state and solution coordination numbers. [Co(DOTAM)] 2+ , [Ni(DOTAM)] 2+ , and [Zn(DOTAM)] 2+ are demonstrated to be six-coordinate in both the solid state and in solution, while [Mn(DOTAM)] 2+ and [Ca(DOTAM)] 2+ are eight-coordinate in the solid state and remain so in solution. [Cu(DOTAM)] 2+ , which is five-coordinate by X-ray crystallography, is shown to increase its coordination number in solution to six-coordinate.

Solid/liquid interfacial free energies in binary systems

NASA Technical Reports Server (NTRS)

Nason, D.; Tiller, W. A.

1973-01-01

Description of a semiquantitative technique for predicting the segregation characteristics of smooth interfaces between binary solid and liquid solutions in terms of readily available thermodynamic parameters of the bulk solutions. A lattice-liquid interfacial model and a pair-bonded regular solution model are employed in the treatment with an accommodation for liquid interfacial entropy. The method is used to calculate the interfacial segregation and the free energy of segregation for solid-liquid interfaces between binary solutions for the (111) boundary of fcc crystals. The zone of compositional transition across the interface is shown to be on the order of a few atomic layers in width, being moderately narrower for ideal solutions. The free energy of the segregated interface depends primarily upon the solid composition and the heats of fusion of the component atoms, the composition difference of the solutions, and the difference of the heats of mixing of the solutions.

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.

Quantitative Characterization of Magnetic Mobility of Nanoparticle in Solution-Based Condition.

PubMed

Rodoplu, Didem; Boyaci, Ismail H; Bozkurt, Akif G; Eksi, Haslet; Zengin, Adem; Tamer, Ugur; Aydogan, Nihal; Ozcan, Sadan; Tugcu-Demiröz, Fatmanur

2015-01-01

Magnetic nanoparticles are considered as the ideal substrate to selectively isolate target molecules or organisms from sample solutions in a wide variety of applications including bioassays, bioimaging and environmental chemistry. The broad array of these applications in fields requires the accurate magnetic characterization of nanoparticles for a variety of solution based-conditions. Because the freshly synthesized magnetic nanoparticles demonstrated a perfect magnetization value in solid form, they exhibited a different magnetic behavior in solution. Here, we present simple quantitative method for the measurement of magnetic mobility of nanoparticles in solution-based condition. Magnetic mobility of the nanoparticles was quantified with initial mobility of the particles using UV-vis absorbance spectroscopy in water, ethanol and MES buffer. We demonstrated the efficacy of this method through a systematic characterization of four different core-shell structures magnetic nanoparticles over three different surface modifications. The solid nanoparticles were characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD) and saturation magnetization (Ms). The surfaces of the nanoparticles were functionalized with 11-mercaptoundecanoic acid and bovine serum albumin BSA was selected as biomaterial. The effect of the surface modification and solution media on the stability of the nanoparticles was monitored by zeta potentials and hydrodynamic diameters of the nanoparticles. Results obtained from the mobility experiments indicate that the initial mobility was altered with solution media, surface functionalization, size and shape of the magnetic nanoparticle. The proposed method easily determines the interactions between the magnetic nanoparticles and their surrounding biological media, the magnetophoretic responsiveness of nanoparticles and the initial mobilities of the nanoparticles.

IN SITU SOURCE TREATMENT OF CR(VI) USING A FE(II)-BASED REDUCTANT BLEND: LONG-TERM MONITORING AND EVALUATION

EPA Science Inventory

The long-term effectiveness of a FeSO4 + Na2S2O4 reductant solution blend for in situ saturated zone treatment of dissolved and solid phase Cr(VI) in a high pH chromite ore processing solid waste (COPSW) fill material was investigated. Two field pilot injection studies were cond...

System and process for dissolution of solids

DOEpatents

Liezers, Martin; Farmer, III, Orville T.

2017-10-10

A system and process are disclosed for dissolution of solids and "difficult-to-dissolve" solids. A solid sample may be ablated in an ablation device to generate nanoscale particles. Nanoparticles may then swept into a coupled plasma device operating at atmospheric pressure where the solid nanoparticles are atomized. The plasma exhaust may be delivered directly into an aqueous fluid to form a solution containing the atomized and dissolved solids. The composition of the resulting solution reflects the composition of the original solid sample.

Analytical solution for the transient wave propagation of a buried cylindrical P-wave line source in a semi-infinite elastic medium with a fluid surface layer

NASA Astrophysics Data System (ADS)

Shan, Zhendong; Ling, Daosheng

2018-02-01

This article develops an analytical solution for the transient wave propagation of a cylindrical P-wave line source in a semi-infinite elastic solid with a fluid layer. The analytical solution is presented in a simple closed form in which each term represents a transient physical wave. The Scholte equation is derived, through which the Scholte wave velocity can be determined. The Scholte wave is the wave that propagates along the interface between the fluid and solid. To develop the analytical solution, the wave fields in the fluid and solid are defined, their analytical solutions in the Laplace domain are derived using the boundary and interface conditions, and the solutions are then decomposed into series form according to the power series expansion method. Each item of the series solution has a clear physical meaning and represents a transient wave path. Finally, by applying Cagniard's method and the convolution theorem, the analytical solutions are transformed into the time domain. Numerical examples are provided to illustrate some interesting features in the fluid layer, the interface and the semi-infinite solid. When the P-wave velocity in the fluid is higher than that in the solid, two head waves in the solid, one head wave in the fluid and a Scholte wave at the interface are observed for the cylindrical P-wave line source.

Solid lipid nanoparticles suspension versus commercial solutions for dermal delivery of minoxidil.

PubMed

Padois, Karine; Cantiéni, Céline; Bertholle, Valérie; Bardel, Claire; Pirot, Fabrice; Falson, Françoise

2011-09-15

Solid lipid nanoparticles have been reported as possible carrier for skin drug delivery. Solid lipid nanoparticles are produced from biocompatible and biodegradable lipids. Solid lipid nanoparticles made of semi-synthetic triglycerides stabilized with a mixture of polysorbate and sorbitan oleate were loaded with 5% of minoxidil. The prepared systems were characterized for particle size, pH and drug content. Ex vivo skin penetration studies were performed using Franz-type glass diffusion cells and pig ear skin. Ex vivo skin corrosion studies were realized with a method derived from the Corrositex(®) test. Solid lipid nanoparticles suspensions were compared to commercial solutions in terms of skin penetration and skin corrosion. Solid lipid nanoparticles suspensions have been shown as efficient as commercial solutions for skin penetration; and were non-corrosive while commercial solutions presented a corrosive potential. Solid lipid nanoparticles suspensions would constitute a promising formulation for hair loss treatment. Copyright © 2011 Elsevier B.V. All rights reserved.

Role of the chemical substitution on the luminescence properties of solid solutions Ca{sub (1−x)}Cd{sub (x)}WO{sub 4} (0 ≤ x ≤1)

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

Taoufyq, A.; Laboratoire Matériaux et Environnement LME, Faculté des Sciences, Université Ibn Zohr, BP 8106, Cité Dakhla, Agadir; CEA, DEN, Département d'Etudes des Réacteurs, Service de Physique Expérimentale, Laboratoire Dosimétrie Capteurs Instrumentation, 13108 Saint-Paul-lez-Durance

2015-10-15

Highlights: • Luminescence can be modified by chemical substitution in solid solutions Ca{sub 1−x}Cd{sub x}WO{sub 4}. • The various emission spectra (charge transfer) were obtained under X-ray excitation. • Scheelite or wolframite solid solutions presented two types of emission spectra. • A luminescence component depended on cadmium substitution in each solid solution. • A component was only characteristic of oxyanion symmetry in each solid solution. - Abstract: We have investigated the chemical substitution effects on the luminescence properties under X-ray excitation of the solid solutions Ca{sub (1−x)}Cd{sub (x)}WO{sub 4} with 0 ≤ x ≤ 1. Two types of wide spectralmore » bands, associated with scheelite-type or wolframite-type solid solutions, have been observed at room temperature. We decomposed each spectral band into several spectral components characterized by energies and intensities varying with composition x. One Gaussian component was characterized by an energy decreasing regularly with the composition x, while the other Gaussian component was only related to the tetrahedral or octahedral configurations of tungstate groups WO{sub 4}{sup 2−} or WO{sub 6}{sup 6−}. The luminescence intensities exhibited minimum values in the composition range x < 0.5 corresponding to scheelite-type structures, then, they regularly increased for cadmium compositions x > 0.5 corresponding to wolframite-type structures.« less

PuS: Reflectivity

NASA Astrophysics Data System (ADS)

Troć, R.

This document is part of subvolume B6bβ`Actinide Monochalcogenides' of Volume 27 `Magnetic properties of non-metallic inorganic compounds based on transition elements' of Landolt-Börnstein - Group III `Condensed Matter'. The volume presents magnetic and related properties of monochalcogenides based on actinides and their solid solutions.

Growth of Solid Solution Crystals

NASA Technical Reports Server (NTRS)

Lehoczky, S. L.; Szofran, F. R.; Holland, L. R.

1985-01-01

The major objective of this program is to determine the conditions under which single crystals of solid solutions can be grown from the melt in a Bridgman configuration with a high degree of chemical homogeneity. The central aim is to assess the role of gravity in the growth process and to explore the possible advantages for growth in the absence of gravity. The alloy system being investigated is the solid solution semiconductor with x-values appropriate for infrared detector applications in Hg sub (1-x) Cd sub x Te the 8 to 14 micro m wavelength region. Both melt and Te-solvent growth are being considered. The study consists of an extensive ground-based experimental and theoretical research effort followed by flight experimentation where appropriate. Experimental facilities have been established for the purification, casting, and crystal growth of the alloy system. Facilities have been also established for the metallurgical, compositional, electric and optical characterization of the alloys. Crystals are being grown by the Bridgman-Stockbarger method and are analyzed by various experimental techniques to evaluate the effects of growth conditions on the longitudinal and radial compositional variations and defect densities in the crystals.

Immobilization of lambda exonuclease onto polymer micropillar arrays for the solid-phase digestion of dsDNAs.

PubMed

Oliver-Calixte, Nyoté J; Uba, Franklin I; Battle, Katrina N; Weerakoon-Ratnayake, Kumuditha M; Soper, Steven A

2014-05-06

The process of immobilizing enzymes onto solid supports for bioreactions has some compelling advantages compared to their solution-based counterpart including the facile separation of enzyme from products, elimination of enzyme autodigestion, and increased enzyme stability and activity. We report the immobilization of λ-exonuclease onto poly(methylmethacrylate) (PMMA) micropillars populated within a microfluidic device for the on-chip digestion of double-stranded DNA. Enzyme immobilization was successfully accomplished using 3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS) coupling to carboxylic acid functionalized PMMA micropillars. Our results suggest that the efficiency for the catalysis of dsDNA digestion using λ-exonuclease, including its processivity and reaction rate, were higher when the enzyme was attached to a solid support compared to the free solution digestion. We obtained a clipping rate of 1.0 × 10(3) nucleotides s(-1) for the digestion of λ-DNA (48.5 kbp) by λ-exonuclease. The kinetic behavior of the solid-phase reactor could be described by a fractal Michaelis-Menten model with a catalytic efficiency nearly 17% better than the homogeneous solution-phase reaction. The results from this work will have important ramifications in new single-molecule DNA sequencing strategies that employ free mononucleotide identification.

Development and evaluation of die and container materials. Low cost silicon solar array project

NASA Technical Reports Server (NTRS)

Wills, R. R.; Niesx, D. E.

1979-01-01

Specific compositions of high purity silicon aluminum oxynitride (Sialon) and silicon beryllium oxynitride (Sibeon) solid solutions were shown to be promising refractory materials for handling and manipulating solar grade silicon into silicon ribbon. Evaulation of the interaction of these materials in contact with molten silicon indicated that solid solutions based upon beta-Si3N4 were more stable than those based on Si2N2O. Sibeon was more resistant to molten silicon attack than Sialon. Both materials should preferably be used in an inert atmosphere rather than under vacuum conditions because removal of oxygen from the silicon melt occurs as SiO enhances the dissolution of aluminum and beryllium. The wetting angles of these materials were low enough for these materials to be considered as both die and container materials.

Use of a screening method to determine excipients which optimize the extent and stability of supersaturated drug solutions and application of this system to solid formulation design.

PubMed

Vandecruys, Roger; Peeters, Jef; Verreck, Geert; Brewster, Marcus E

2007-09-05

Assessing the effect of excipients on the ability to attain and maintain supersaturation of drug-based solution may provide useful information for the design of solid formulations. Judicious selection of materials that affect either the extent or stability of supersaturating drug delivery systems may be enabling for poorly soluble drug candidates or other difficult-to-formulate compounds. The technique suggested herein is aimed at providing a screening protocol to allow preliminary assessment of these factors based on small to moderate amounts of drug substance. A series of excipients were selected that may, by various mechanisms, affect supersaturation including pharmaceutical polymers such as HMPC and PVP, surfactants such as Polysorbate 20, Cremophor RH40 and TPGS and hydrophilic cyclodextrins such as HPbetaCD. Using a co-solvent based method and 25 drug candidates, the data suggested, on the whole, that the surfactants and the selected cyclodextrin seemed to best augment the extent of supersaturation but had variable benefits as stabilizers, while the pharmaceutical polymers had useful effect on supersaturation stability but were less helpful in increasing the extent of supersaturation. Using these data, a group of simple solid dosage forms were prepared and tested in the dog for one of the drug candidates. Excipients that gave the best extent and stability for the formed supersaturated solution in the screening assay also gave the highest oral bioavailability in the dog.

Shape optimization of three-dimensional stamped and solid automotive components

NASA Technical Reports Server (NTRS)

Botkin, M. E.; Yang, R.-J.; Bennett, J. A.

1987-01-01

The shape optimization of realistic, 3-D automotive components is discussed. The integration of the major parts of the total process: modeling, mesh generation, finite element and sensitivity analysis, and optimization are stressed. Stamped components and solid components are treated separately. For stamped parts a highly automated capability was developed. The problem description is based upon a parameterized boundary design element concept for the definition of the geometry. Automatic triangulation and adaptive mesh refinement are used to provide an automated analysis capability which requires only boundary data and takes into account sensitivity of the solution accuracy to boundary shape. For solid components a general extension of the 2-D boundary design element concept has not been achieved. In this case, the parameterized surface shape is provided using a generic modeling concept based upon isoparametric mapping patches which also serves as the mesh generator. Emphasis is placed upon the coupling of optimization with a commercially available finite element program. To do this it is necessary to modularize the program architecture and obtain shape design sensitivities using the material derivative approach so that only boundary solution data is needed.

Solution and solid trinitrotoluene (TNT) photochemistry: persistence of TNT-like ultraviolet (UV) resonance Raman bands.

PubMed

Gares, Katie L; Bykov, Sergei V; Godugu, Bhaskar; Asher, Sanford A

2014-01-01

We examined the 229 nm deep-ultraviolet resonance Raman (DUVRR) spectra of solution and solid-state trinitrotoluene (TNT) and its solution and solid-state photochemistry. Although TNT photodegrades with a solution quantum yield of ϕ ∼ 0.015, the initial photoproducts show DUVRR spectra extraordinarily similar to pure TNT, due to the similar photoproduct enhancement of the -NO2 stretching vibrations. This results in TNT-like DUVRR spectra even after complete TNT photolysis. These ultraviolet resonance Raman spectral bands enable DUVRR of trace as well as DUVRR standoff TNT detection. We determined the structure of various initial TNT photoproducts by using liquid chromatography-mass spectrometry and tandem mass spectrometry. Similar TNT DUVRR spectra and photoproducts are observed in the solution and solid states.

Application of ANP and DEMATEL to evaluate the decision-making of municipal solid waste management in Metro Manila.

PubMed

Tseng, Ming-Lang

2009-09-01

A municipal solid waste management (MSW) expert group was consulted in order to mirror how government officials might reach an effective solution regarding municipal solid waste management in Metro Manila. A critical issue regarding this is how the expert group can better evaluate and select a favorable MSW management solution using a series of criteria. MSW management solution selection is a multiple criteria decision-making (MCDM) problem, which requires the consideration of a large number of complex criteria. A robust MCDM method should consider the interactions among these criteria. The analytic network process (ANP) is a relatively new MCDM method which can deal with all kinds of interactions systematically. The Decision Making Trial and Evaluation Laboratory (DEMATEL) not only can convert the relations between cause and effect of criteria into a structural model, but also can be used as a way to handle the inner dependences within a set of criteria. Hence, this paper applies an effective solution based on a combined ANP and DEMATEL method to assist the expert group evaluating different MSW management solutions. According to the results, the best solution is for each city to have its own type of thermal process technology and resource recovery facility before landfill rather than entering a joint venture with enterprises or going into build-operate-transfer projects in order to be able to construct thermal process technologies and resource recovery facilities.

Evolution of ion emission yield of alloys with the nature of the solute. 2: Interpretation

NASA Technical Reports Server (NTRS)

Blaise, G.; Slodzian, G.

1977-01-01

Solid solutions of transition elements in copper, nickel, cobalt, iron, and aluminum matrices were analyzed by observing secondary ion emissions under bombardment with 6.2-keV argon ions. Enchancement of the production of solute-element ions was observed. An ion emission model is proposed according to which the ion yield is governed by the probability of an atom leaving the metal in a preionized state. The energy distribution of the valence electrons of the solute atoms is the bases of the probability calculation.

Development of advanced high strength tantalum base alloys. Part 1: Screening investigation

NASA Technical Reports Server (NTRS)

Buckman, R. W., Jr.

1971-01-01

Five experimental tantalum alloy compositions containing 13-18% W+Re+Hf solid solution solute additions with dispersed phase strengthening achieved by carbon or nitrogen additions were prepared as 1.4 inch diameter ingot processed to 3/8 inch diameter rod and evaluated. Elevated temperature tensile and creep strength increased monotonically with increasing solute content. Room temperature elongation decreased for 20% to less than 2% as the solute content was increased above 16%. Phase identification indicated that the precipitating phase in the carbide containing alloys was Ta2C.

Binning and filtering: the six-color solution

NASA Astrophysics Data System (ADS)

Ashdown, Ian; Robinson, Shane; Salsbury, Marc

2006-08-01

The use of LED backlighting for LCD displays requires careful binning of red, green, and blue LEDs by dominant wavelength to maintain the color gamuts as specified by NTSC, SMPTE, and EBU/ITU standards. This problem also occurs to a lesser extent with RGB and RGBA assemblies for solid-state lighting, where color gamut consistency is required for color-changing luminaires. In this paper, we propose a "six-color solution," based on Grassman's laws, that does not require color binning, but nevertheless guarantees a fixed color gamut that subsumes the color gamuts of carefully-binned RGB assemblies. A further advantage of this solution is that it solves the problem of peak wavelength shifts with varying junction temperatures. The color gamut can thus remain fixed over the full range of LED intensities and ambient temperatures. A related problem occurs with integrated circuit (IC) colorimeters used for optical feedback with LED backlighting and RGB(A) solid-state lighting, wherein it can be difficult to distinguish between peak wavelength shifts and changes in LED intensity. We apply our six-color solution to the design of a novel colorimeter for LEDs that independently measures changes in peak wavelength and intensity. The design is compatible with current manufacturing techniques for tristimulus colorimeter ICs. Together, the six-color solution for LEDs and colorimeters enables less expensive LED backlighting and solid-state lighting systems with improved color stability.

High-temperature solution growth and characterization of (1-x)PbTiO3-xBi(Zn2/3Nb1/3)O3 piezo-/ferroelectric single crystals

NASA Astrophysics Data System (ADS)

Paterson, Alisa R.; Zhao, Jinyan; Liu, Zenghui; Wu, Xiaoqing; Ren, Wei; Ye, Zuo-Guang

2018-03-01

Complex perovskite PbTiO3-Bi(Me‧Me″)O3 solid solutions represent new materials systems that possess a higher Curie temperature (TC) than the relaxor-PbTiO3 solid solutions, and are useful for potential applications. To this end, novel ferroelectric single crystals of the (1-x)PbTiO3-xBi(Zn2/3Nb1/3)O3 (PT-BZN) solid solution were successfully grown by the high-temperature solution growth (HTSG) method. Powder X-ray diffraction shows that the symmetry of the grown crystals is tetragonal. The dielectric permittivity and optical domain structures were characterized by dielectric measurements and polarized light microscopy, respectively, as a function of temperature, revealing a first-order ferroelectric-paraelectric phase transition at a TC of 436 ± 2 °C. Based on the TC, the average composition of the crystal platelet was estimated to be 0.58PT-0.42BZN. Piezoresponse force microscopy measurements of the phase and amplitude as a function of voltage reveal the complex polar domain structure and demonstrate the ferroelectric switching behaviour of these materials. These results suggest that the PT-BZN single crystals indeed form a new family of high TC piezo-/ferroelectric materials which are potentially useful for the fabrication of electromechanical transducers for high-temperature applications.

Nonlinear effects on electrophoresis of a charged dielectric nanoparticle in a charged hydrogel medium

NASA Astrophysics Data System (ADS)

Bhattacharyya, S.; De, Simanta

2016-09-01

The impact of the solid polarization of a charged dielectric particle in gel electrophoresis is studied without imposing a weak-field or a thin Debye length assumption. The electric polarization of a dielectric particle due to an external electric field creates a non-uniform surface charge density, which in turn creates a non-uniform Debye layer at the solid-gel interface. The solid polarization of the particle, the polarization of the double layer, and the electro-osmosis of mobile ions within the hydrogel medium create a nonlinear effect on the electrophoresis. We have incorporated those nonlinear effects by considering the electrokinetics governed by the Stokes-Brinkman-Nernst-Planck-Poisson equations. We have computed the governing nonlinear coupled set of equations numerically by adopting a finite volume based iterative algorithm. Our numerical method is tested for accuracy by comparing with several existing results on free-solution electrophoresis as well as results based on the Debye-Hückel approximation. Our computed result shows that the electrophoretic velocity decreases with the rise of the particle dielectric permittivity constant and attains a saturation limit at large values of permittivity. A significant impact of the solid polarization is found in gel electrophoresis compared to the free-solution electrophoresis.

Development of a Reduced-Order Model for Reacting Gas-Solids Flow using Proper Orthogonal Decomposition

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

McDaniel, Dwayne; Dulikravich, George; Cizmas, Paul

2017-11-27

This report summarizes the objectives, tasks and accomplishments made during the three year duration of this research project. The report presents the results obtained by applying advanced computational techniques to develop reduced-order models (ROMs) in the case of reacting multiphase flows based on high fidelity numerical simulation of gas-solids flow structures in risers and vertical columns obtained by the Multiphase Flow with Interphase eXchanges (MFIX) software. The research includes a numerical investigation of reacting and non-reacting gas-solids flow systems and computational analysis that will involve model development to accelerate the scale-up process for the design of fluidization systems by providingmore » accurate solutions that match the full-scale models. The computational work contributes to the development of a methodology for obtaining ROMs that is applicable to the system of gas-solid flows. Finally, the validity of the developed ROMs is evaluated by comparing the results against those obtained using the MFIX code. Additionally, the robustness of existing POD-based ROMs for multiphase flows is improved by avoiding non-physical solutions of the gas void fraction and ensuring that the reduced kinetics models used for reactive flows in fluidized beds are thermodynamically consistent.« less

Investigation of ZrO/sub 2//mullite solid solution by energy dispersive X-ray spectroscopy and electron diffraction

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

Dinger, T.R.; Krishnam, K.M.; Moya, J.S.

1984-10-01

A mullite/15 vol.%ZrO/sub 2/ composite was analyzed using the techniques of microdiffraction and energy dispersive X-ray spectroscopy (EDXS). The EDXS results indicate that there is a significantly high solid solubility of mullite in zirconia and zirconia in mullite; microdiffraction results suggest that ordering occurs in the ZrO/sub 2/(ss) phase based on the presence of forbidden reflections for the P 2/sub 1//c space group of monoclinic zirconia. The presence of a secondary phase at the grain boundaries, either amorphous or crystalline, has not been generally detected throughout the bulk. The results provide experimental evidence for the hypothesis of Moya and Osendimore » that the increased toughness and flexural strength of these composites are related to solid solution effects rather than to transformation or microcrack toughening mechanisms.« less

Allantoin as a solid phase adsorbent for removing endotoxins.

PubMed

Vagenende, Vincent; Ching, Tim-Jang; Chua, Rui-Jing; Gagnon, Pete

2013-10-04

In this study we present a simple and robust method for removing endotoxins from protein solutions by using crystals of the small-molecule compound 2,5-dioxo-4-imidazolidinyl urea (allantoin) as a solid phase adsorbent. Allantoin crystalline powder is added to a protein solution at supersaturated concentrations, endotoxins bind and undissolved allantoin crystals with bound endotoxins are removed by filtration or centrifugation. This method removes an average of 99.98% endotoxin for 20 test proteins. The average protein recovery is ∼80%. Endotoxin binding is largely independent of pH, conductivity, reducing agent and various organic solvents. This is consistent with a hydrogen-bond based binding mechanism. Allantoin does not affect protein activity and stability, and the use of allantoin as a solid phase adsorbent provides better endotoxin removal than anion exchange, polymixin affinity and biological affinity methods for endotoxin clearance. Copyright © 2013 Elsevier B.V. All rights reserved.

Solid Solution Characterization in Metal by Original Tomographic Scanning Microwave Microscopy Technique

NASA Astrophysics Data System (ADS)

Bourillot, Eric; Vitry, Pauline; Optasanu, Virgil; Plassard, Cédric; Lacroute, Yvon; Montessin, Tony; Lesniewska, Eric

A general challenge in metallic components is the need for materials research to improve the service lifetime of the structural tanks or tubes subjected to harsh environments or the storage medium for the products. One major problem is the formation of lightest chemical elements bubbles or different chemical association, which can have a significant impact on the mechanical properties and structural stability of materials. The high migration mobility of these light chemical elements in solids presents a challenge for experimental characterization. Here, we present work relating to an original non-destructive, with high spatial resolution, tomographic technique based on Scanning Microwave Microscopy (SMM), which is used to visualize in-depth chemical composition of solid solution of a light chemical element in a metal. The experiments showed the capacity of SMM to detect volume. Measurements realized at different frequencies give access to a tomographic study of the sample.

Process for recovering pertechnetate ions from an aqueous solution also containing other ions

DOEpatents

Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

1997-01-01

A solid/liquid process for the separation and recovery of TcO.sub.4.sup.-1 ions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups; whereas the aqueous solution from which the TcO.sub.4.sup.-1 ions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt. A solid/liquid phase admixture of separation particles containing bound TcO.sub.4.sup.-1 ions in such an aqueous solution that is free from MoO.sub.4.sup.-2 ions is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture.

1H, 13C, 15N NMR analysis of sildenafil base and citrate (Viagra) in solution, solid state and pharmaceutical dosage forms.

PubMed

Wawer, Iwona; Pisklak, Maciej; Chilmonczyk, Zdzisław

2005-08-10

Sildenafil citrate (SC) (Viagra) and sildenafil base in pure form are easily and unequivocally characterized by multinuclear NMR spectroscopy. Analysis of chemical shifts indicates that: (i) N6-H forms intramolecular hydrogen bonds, (ii) N25 is protonated in the salt and (iii) intermolecular OH...N hydrogen bonds involving N2 and N4 are present in the solid sildenafil citrate. 13C CPMAS NMR method has been proposed for the identification and quantitation of Viagra in its pharmaceutical formulations.

PuS: Thermoelectric Power

NASA Astrophysics Data System (ADS)

Troć, R.

This document is part of subvolume B6bβ`Actinide Monochalcogenides' of Volume 27 `Magnetic properties of non-metallic inorganic compounds based on transition elements' of Landolt-Börnstein - Group III `Condensed Matter'. The volume presents magnetic and related properties of monochalcogenides based on actinides and their solid solutions.

Synthesis and characterization of the LDH hydrotalcite-pyroaurite solid-solution series

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

Rozov, K., E-mail: urs.berner@psi.c; Rock-Water Interaction Group, Institute of Geological Sciences, University of Bern, Baltzerstrasse 3, CH-3012; Berner, U.

2010-08-15

A layered double hydroxide (LDH) hydrotalcite-pyroaurite solid-solution series Mg{sub 3}(Al{sub x}Fe{sub 1-x})(CO{sub 3}){sub 0.5}(OH){sub 8} with 1 - x = 0.0, 0.1...1.0 was prepared by co-precipitation at 23 {+-} 2 {sup o}C and pH = 11.40 {+-} 0.03. The compositions of the solids and the reaction solutions were determined using ICP-OES (Mg, Al, Fe, and Na) and TGA techniques (CO{sub 3}{sup 2-}, OH{sup -}, and H{sub 2}O). Powder X-ray diffraction was employed for phase identification and determination of the unit cell parameters a{sub o} and c{sub o} from peak profile analysis. The parameter a{sub o} = b{sub o} was foundmore » to be a linear function of the composition. This dependency confirms Vegard's law and indicates the presence of a continuous solid-solution series in the hydrotalcite-pyroaurite system. TGA data show that the temperatures at which interlayer H{sub 2}O molecules and CO{sub 3}{sup 2-} anions are lost, and at which dehydroxylation of the layers occurs, all decrease with increasing mole fraction of iron within the hydroxide layers. Features of the Raman spectra also depend on the iron content. The absence of Raman bands for Fe-rich members (x{sub Fe} > 0.5) is attributed to possible fluorescence phenomena. Based on chemical analysis of both the solids and the reaction solutions after synthesis, preliminary Gibbs free energies of formation have been estimated. Values of {Delta}G{sup o}{sub f}(hydrotalcite) = - 3773.3 {+-} 51.4 kJ/mol and {Delta}G{sup o}{sub f}(pyroaurite) = - 3294.5 {+-} 95.8 kJ/mol were found at 296.15 K. The formal uncertainties of these formations constants are very high. Derivation of more precise values would require carefully designed solubility experiments and improved analytical techniques.« less

Fluoride-selective optical sensor based on the dipyrrolyl-tetrathiafulvalene chromophore.

PubMed

Rivadehi, Shadi; Reid, Ellen F; Hogan, Conor F; Bhosale, Sheshanath V; Langford, Steven J

2012-01-28

A chemosensor bearing dipyrrolyl motifs as recognition sites and a tetrathiafulvalene redox tag has been evaluated as an optical and redox sensor for a series of anions (F(-), Cl(-), Br(-), HSO(4)(-), CH(3)COO(-), and H(2)PO(4)(-)) in DCM solution. The receptor shows specific optical signaling for fluoride but little electrochemical effect in solution. The solid-state performance of the sensor leads to measurable changes in water. Design implications towards better systems based on these results and other examples are discussed.

The Synthesis of Polymer Precursors and Exploratory Research Based on Acetylene Displacement Reaction

DTIC Science & Technology

1980-10-01

the addition of solids, a soluble base, potassium 2,6-dimethylphenoxide was tried. It was felt that the two ortho -methyl groups would sterically...was obtained, but as a mixture of all three nitro -isomers. Moreover, direct crystallization from the nitration media could not be induced even by...transferred to a dropping funnel. This solution was added dropwise over ca. 1 hr to a solution of 1220 g 4- nitro - benzil in 5.1 1 DMSO in a 22-1 pot held

Corner wetting during the vapor-liquid-solid growth of faceted nanowires

NASA Astrophysics Data System (ADS)

Spencer, Brian; Davis, Stephen

2016-11-01

We consider the corner wetting of liquid drops in the context of vapor-liquid-solid growth of nanowires. Specifically, we construct numerical solutions for the equilibrium shape of a liquid drop on top of a faceted nanowire by solving the Laplace-Young equation with a free boundary determined by mixed boundary conditions. A key result for nanowire growth is that for a range of contact angles there is no equilibrium drop shape that completely wets the corner of the faceted nanowire. Based on our numerical solutions we determine the scaling behavior for the singular surface behavior near corners of the nanowire in terms of the Young contact angle and drop volume.

Calculation of the solvus temperature of metastable phases in the Al-Mg-Si alloys

NASA Astrophysics Data System (ADS)

Vasilyev, A. A.; Gruzdev, A. S.; Kuz'min, N. L.

2011-09-01

A procedure has been proposed for the self-consistent calculation of the solvus temperatures of metastable phase precipitates in Al-Mg-Si alloys and the specific energy of their interface with the aluminum matrix. The procedure is based on the results of experimental studies on the kinetics of formation of these precipitates during decomposition of supersaturated solid solutions of quenched Al-Mg-Si alloys, which were carried out by measuring the Young's modulus and electrical resistivity. On the basis of the obtained set of solvus temperatures of the β″-phase, an empirical formula has been proposed for calculating this temperature as a function of the chemical composition of the initial solid solution.

Solid lithium ion conducting electrolytes and methods of preparation

DOEpatents

Narula, Chaitanya K; Daniel, Claus

2013-05-28

A composition comprised of nanoparticles of lithium ion conducting solid oxide material, wherein the solid oxide material is comprised of lithium ions, and at least one type of metal ion selected from pentavalent metal ions and trivalent lanthanide metal ions. Solution methods useful for synthesizing these solid oxide materials, as well as precursor solutions and components thereof, are also described. The solid oxide materials are incorporated as electrolytes into lithium ion batteries.

Solid lithium ion conducting electrolytes and methods of preparation

DOEpatents

Narula, Chaitanya K.; Daniel, Claus

2015-11-19

A composition comprised of nanoparticles of lithium ion conducting solid oxide material, wherein the solid oxide material is comprised of lithium ions, and at least one type of metal ion selected from pentavalent metal ions and trivalent lanthanide metal ions. Solution methods useful for synthesizing these solid oxide materials, as well as precursor solutions and components thereof, are also described. The solid oxide materials are incorporated as electrolytes into lithium ion batteries.

INTERNATIONAL CONFERENCE ON SEMICONDUCTOR INJECTION LASERS SELCO-87: Simple formula for the thermal conductivity of a quaternary solid solution

NASA Astrophysics Data System (ADS)

Nakwaski, W.

1988-11-01

An analysis is made of the thermal conductivity of quaternary solid solutions (alloys) allowing for their disordered structure on the basis of a phenomenological analysis proposed by Abeles. This method is applied to a quaternary solid solution In1 - xGaxAsyP1 - y. A simple analytic expression is derived for the thermal conductivity of this material.

Lattice Parameter Behavior with Different Nd and O Concentrations in (U 1-yNd y)O 2±x Solid Solution

DOE PAGES

Lee, Seung Min; Knight, Travis W.; Voit, Stwart L.; ...

2016-02-02

The solid solution of (U1-yFPy)O- 2±x, has the same fluorite structure as UO 2±x lambda, and the lattice parameter is affected by dissolved fission product and oxygen concentrations. We investigated the relation between the lattice parameter and the concentrations of neodymium and oxygen in the fluorite structure of (U 1-yNd y)O 2±x using X-ray diffraction. Moreover, the lattice parameter behavior in the (U 1-yNd y)O 2±x, solid solution shows a linear change as a function of the oxygen-to-metal ratio and solubility of neodymium. The lattice parameter depends on the radii of ions forming the fluorite structure and also can bemore » expressed by a particular rule (modified Vegard's law). Furthermore, the numerical analyses of the lattice parameters for the stoichiometric and nonstoichionietric solid solutions were conducted, and the lattice parameter model for the (U1-yNdy)O 2±x, solid solution was assessed. There is a very linear relationship between the lattice parameter and the Nd and O concentration for the stoichiometry and nonstoichiometry of the (U 1-yNd y)O 2±x solid solution was verified.« less

Revisiting HgCl 2: A solution- and solid-state 199Hg NMR and ZORA-DFT computational study

NASA Astrophysics Data System (ADS)

Taylor, R. E.; Carver, Colin T.; Larsen, Ross E.; Dmitrenko, Olga; Bai, Shi; Dybowski, C.

2009-07-01

The 199Hg chemical-shift tensor of solid HgCl 2 was determined from spectra of polycrystalline materials, using static and magic-angle spinning (MAS) techniques at multiple spinning frequencies and field strengths. The chemical-shift tensor of solid HgCl 2 is axially symmetric ( η = 0) within experimental error. The 199Hg chemical-shift anisotropy (CSA) of HgCl 2 in a frozen solution in dimethylsulfoxide (DMSO) is significantly smaller than that of the solid, implying that the local electronic structure in the solid is different from that of the material in solution. The experimental chemical-shift results (solution and solid state) are compared with those predicted by density functional theory (DFT) calculations using the zeroth-order regular approximation (ZORA) to account for relativistic effects. 199Hg spin-lattice relaxation of HgCl 2 dissolved in DMSO is dominated by a CSA mechanism, but a second contribution to relaxation arises from ligand exchange. Relaxation in the solid state is independent of temperature, suggesting relaxation by paramagnetic impurities or defects.

Effect of dope solution temperature on the membrane structure and membrane distillation performance

NASA Astrophysics Data System (ADS)

Nawi, N. I. M.; Bilad, M. R.; Nordin, N. A. H. M.

2018-04-01

Membrane distillation (MD) is a non-isothermal process applicable to purify water using hydrophobic membrane. Membrane in MD is hydrophobic, permeable to water vapor but repels liquid water. MD membrane is expected to pose high flux, high fouling and scaling resistances and most importantly high wetting resistance. This study develops flat-sheet polyvinylidene fluoride (PVDF) membrane by exploring both liquid-liquid and liquid-solid phase inversion technique largely to improve its wetting resistance and flux performance. We hypothesize that temperature of dope solution play roles in solid-liquid separation during membrane formation and an optimum balance between liquid-liquid and liquid-solid (crystallization) separation leads to highly performance PVDF membrane. Findings obtained from differential scanning calorimeter test show that increasing dope solution temperature reduces degree of PVDF crystallinity and suppresses formation of crystalline structure. The morphological images of the resulting membranes show that at elevated dope solution temperature (40, 60, 80 and 100°C), the spherulite-like structures are formed across the thickness of membranes ascribed from due to different type of crystals. The performance of direct-contact MD shows that the obtained flux of the optimum dope temperature (60°C) of 10.8 L/m2h is comparable to commercial PTFE-based MD membrane.

Molecular interactions in high conductive gel electrolytes based on low molecular weight gelator.

PubMed

Bielejewski, Michał; Łapiński, Andrzej; Demchuk, Oleg

2017-03-15

Organic ionic gel (OIG) electrolytes, also known as gel electrolytes or ionogels are one example of modern functional materials with the potential to use in wide range of electrochemical applications. The functionality of OIGs arises from the thermally reversible solidification of electrolytes or ionic liquids and their superior ionic conductivity. To understand and to predict the properties of these systems it is important to get the knowledge about the interactions on molecular level between the solid gelator matrix and the electrolyte solution. This paper reports the spectroscopic studies (FT-IR, UV-Vis and Raman) of the gel electrolyte based on low molecular weight gelator methyl-4,6-O-(p-nitrobenzylidene)-α-d-glucopyranoside and solution of quaternary ammonium salt, tetramethylammonium bromide. The solidification process was based on sol-gel technique. Below characteristic temperature, defined as gel to sol phase transition temperature, T gs , the samples were solid-like and showed high conductivity values of the same order as observed for pure liquid electrolytes. The investigations were performed for a OIGs in a wide range of molar concentrations of the electrolyte solution. Copyright © 2016 Elsevier Inc. All rights reserved.

Magnetism and Solid Solution Effects in NiAI (40% AI) Alloys

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

Liu, Chain T; Fu, Chong Long; Chisholm, Matthew F

2007-01-01

The solid solution effects of ternary additions of transition elements in intermetallic Ni-40% Al were investigated by both experimental studies and theoretical calculations. Co solute atoms when sitting at Ni sublattice sites do not affect the lattice parameter and hardening behavior of Ni-40Al. On the other hand, Fe, Mn, and Cr solutes, which are mainly on Al sublattice sites, substantially expand the lattice parameter and produce an unusual solid solution softening effect. First-principles calculations predict that these solute atoms with large unfilled d-band electrons develop large magnetic moments and effectively expand the lattice parameter when occupying Al sublattice sites. Themore » theoretical predictions were verified by both electron loss-energy spectroscopy (EELS) analyses and magnetic susceptibility measurements. The observed softening behavior can be explained quantitatively by the replacement of Ni anti-site defects (potent hardeners) by Fe, Mn, and Cr anti-site defects with smaller atom size mismatch between solute and Al atoms. This study has led to the identification of magnetic interaction as an important physical parameter affecting the solid solution hardening in intermetallic alloys containing transition elements.« less

Applications of inductively coupled plasma mass spectrometry and laser ablation inductively coupled plasma mass spectrometry in materials science

NASA Astrophysics Data System (ADS)

Becker, Johanna Sabine

2002-12-01

Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) have been applied as the most important inorganic mass spectrometric techniques having multielemental capability for the characterization of solid samples in materials science. ICP-MS is used for the sensitive determination of trace and ultratrace elements in digested solutions of solid samples or of process chemicals (ultrapure water, acids and organic solutions) for the semiconductor industry with detection limits down to sub-picogram per liter levels. Whereas ICP-MS on solid samples (e.g. high-purity ceramics) sometimes requires time-consuming sample preparation for its application in materials science, and the risk of contamination is a serious drawback, a fast, direct determination of trace elements in solid materials without any sample preparation by LA-ICP-MS is possible. The detection limits for the direct analysis of solid samples by LA-ICP-MS have been determined for many elements down to the nanogram per gram range. A deterioration of detection limits was observed for elements where interferences with polyatomic ions occur. The inherent interference problem can often be solved by applying a double-focusing sector field mass spectrometer at higher mass resolution or by collision-induced reactions of polyatomic ions with a collision gas using an ICP-MS fitted with collision cell. The main problem of LA-ICP-MS is quantification if no suitable standard reference materials with a similar matrix composition are available. The calibration problem in LA-ICP-MS can be solved using on-line solution-based calibration, and different procedures, such as external calibration and standard addition, have been discussed with respect to their application in materials science. The application of isotope dilution in solution-based calibration for trace metal determination in small amounts of noble metals has been developed as a new calibration strategy. This review discusses new analytical developments and possible applications of ICP-MS and LA-ICP-MS for the quantitative determination of trace elements and in surface analysis for materials science.

Ab initio assessment of Bi1-xRExCuOS (RE = La, Gd, Y, Lu) solid solutions as a semiconductor for photochemical water splitting.

PubMed

Lardhi, Sheikha; Curutchet, Antton; Cavallo, Luigi; Harb, Moussab; Le Bahers, Tangui

2017-05-17

The investigation of the BiCuOCh (Ch = S, Se and Te) semiconductor family for thermoelectric or photovoltaic materials is a topic of increasing research interest. These materials can also be considered for photochemical water splitting if one representative having a bandgap, E g , at around 2 eV can be developed. With this aim, we simulated the solid solutions Bi 1-x RE x CuOS (RE = Y, La, Gd and Lu) from pure BiCuOS (E g ∼ 1.1 eV) to pure RECuOS compositions (E g ∼ 2.9 eV) by DFT calculations based on the HSE06 range-separated hybrid functional with the inclusion of spin-orbit coupling. Starting from the thermodynamic stability of the solid solution, several properties were computed for each system including bandgaps, dielectric constants, effective masses and exciton binding energies. We discussed the variation of these properties based on the relative organization of Bi and RE atoms in their common sublattice to offer a physical understanding of the influence of the RE doping of BiCuOS. Some compositions were found to give appropriate properties for water splitting applications. Furthermore, we found that at low RE fractions the transport properties of BiCuOS are improved that can find applications beyond water splitting.

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

Bradley, D. J.

The activity coefficient of carbon in nickel, nickel-titanium, nickel-titanium-chromium, nickel-titanium-molybdenum and nickel-titanium-molybdenum-chromium alloys has been measured at 900, 1100 and 1215/sup 0/C. The results indicate that carbon obeys Henry's Law over the range studied (0 to 2 at. percent). The literature for the nickel-carbon and iron-carbon systems are reviewed and corrected. For the activity of carbon in iron as a function of composition, a new relationship based on re-evaluation of the thermodynamics of the CO/CO/sub 2/ equilibrium is proposed. Calculations using this relationship reproduce the data to within 2.5 percent, but the accuracy of the calibrating standards used by manymore » investigators to analyze for carbon is at best 5 percent. This explains the lack of agreement between the many precise sets of data. The values of the activity coefficient of carbon in the various solid solutions are used to calculate a set of parameters for the Kohler-Kaufman equation. The calculations indicate that binary interaction energies are not sufficient to describe the thermodynamics of carbon in some of the nickel-based solid solutions. The results of previous workers for carbon in nickel-iron alloys are completely described by inclusion of ternary terms in the Kohler-Kaufman equation. Most of the carbon solid solution at high temperatures in nickel and nickel-titantium alloys precipitates from solution on quenching in water. The precipitate is composed of very small particles (greater than 2.5 nm) of elemental carbon. The results of some preliminary thermomigration experiments are discussed and recommendations for further work are presented.« less

Controlling mechanisms of metals release form cement-based waste form in acetic acid solution

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

Cheng, Kuang Ye.

1991-01-01

The purpose of this dissertation is to identify the individual leaching mechanisms of metals by knowing the pH profile within the leached specimen and the physical and chemical properties of the leached material. Leaching of cement-based waste form in acetic acid solutions with different acidic strengths has been investigated in this work. The pH profile along the acid penetration route in the cement-based waste form was identified by various pH color indicators. The pH in the surface altered layer varies from 5.0 to 6.0, which is very close to the pH in the bulk leachate. A reacting zone, where themore » pH abruptly changes from 6 to 12, sharply divides the altered surface layer from the remaining unleached waste form or kernel. Leaching of metals is controlled by the acidity available in the leachant. Dissolution of alkaline materials leaves a silica-rich layer on the surface of the cement-based waste form. This surface layer exhibits different properties than those of the unleached material. The surface layer has a higher water content, is lighter weight, and is soft and friable. Furthermore, the abundant silicate content on the solid surface detains portion of the leached metals, while they are moving through the leached layer into bulk solution. The leaching of metals is a consequence of acid penetration. The distance from the solid/solution interface to the front of the leaching boundary can be regarded as the depth of leaching zone, where the metals dissolve and diffuse out of the waste form. The metal ions diffuse through the leached layer may be retarded on the solid surface by the pH-dependent adsorption reactions. It is found that the leaching process through the leached layer is diffusion-controlled for calcium and cadmium, whereas diffusion and adsorption occur simultaneously in the leached layer for lead and arsenic.« less

Solid surface dependent layering of self-arranged structures with fibril-like assemblies of alpha-synuclein

NASA Astrophysics Data System (ADS)

Bukauskas, V.; Šetkus, A.; Šimkienė, I.; Tumėnas, S.; Kašalynas, I.; Rėza, A.; Babonas, J.; Časaitė, V.; Povilonienė, S.; Meškys, R.

2012-03-01

In present work the formation of hybrid constructions composed of alpha-synuclein-based colloidal solutions on various solid surfaces (silica coated Si, mica, CaF2 and KBr) is investigated by scanning probe microscopy, spectrocopic ellipsometry, Fourier transformed infrared spectroscopy and vibrational circular dichroism. Prior to the modification of the solids, the proteins were intentionally fibrilled under special conditions. It is proved that the multi-component coatings are self-arranged on the solid substrates. Depending on the substrate material, the interface films consisting of individual biomolecules can be detected on the solid surfaces. The coatings with fibril-like alpha-synuclein objects can be obtained on solid surfaces with negligible or comparatively thick interface films. The results are interpreted in terms of the charged surface-controlled electrostatic interaction between the substrate and the biomolecules. Solubility of solids is considered in this interpretation.

Process for recovering pertechnetate ions from an aqueous solution also containing other ions

DOEpatents

Rogers, R.; Horwitz, E.P.; Bond, A.H.

1997-02-18

A solid/liquid process for the separation and recovery of TcO{sub 4}{sup {minus}1} ions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups; whereas the aqueous solution from which the TcO{sub 4}{sup {minus}1} ions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt. A solid/liquid phase admixture of separation particles containing bound TcO{sub 4}{sup {minus}1} ions in such an aqueous solution that is free from MoO{sub 4}{sup {minus}2} ions is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture. 15 figs.

Influence of carbonate ion in the crystallization medium on the formation and chemical composition of CaHA-SrHA solid solutions

NASA Astrophysics Data System (ADS)

Nikolaev, Anton; Kuz'mina, Maria; Frank-Kamenetskaya, Olga; Zorina, Maina

2015-06-01

The study of the influence of carbonate ions in a solution to Sr-distribution in system «solution-crystal» and to ion substitutions and the non-stoichiometry of formed CaHA-SrHA solid solutions was carried out. The CaHA-SrHA solid solutions were synthesized by precipitation from aqueous solutions with the atomic C/P ratio equal to 0, 0.05 and 0.1 at T = 90 °C. Resulting precipitates were studied using various methods including X-ray powder diffraction, infrared spectroscopy and different chemical analyses. The results of the study have shown that in the range of values of (Ca + Sr)/P in the water solution from 40% to 85%, the presence of carbonate ions (C/P = 0.05-0.1) promotes the incorporation of strontium in the apatite. Crystalline apatite solid solutions formed from water solutions of such composition are more defective compared to apatites that are mainly calcium or strontium. They are characterized by a smaller size coherence scattering domain length along [0 0 1] direction and a greater number of carbonate ions, water molecules and vacancies at the Ca-sites.

Solid-state NMR and IR for the analysis of pharmaceutical solids: polymorphs of fosinopril sodium.

PubMed

Brittain, H G; Morris, K R; Bugay, D E; Thakur, A B; Serajuddin, A T

1993-01-01

The two polymorphic modifications of fosinopril sodium have been characterized as to their differences in melting behaviour, powder X-ray diffraction patterns, Fourier transform infrared spectra (FTIR), and solid-state 31P- and 13C-NMR spectra. The polymorphs were found to be enantiotropically related based upon melting point, heat of fusion, and solution mediated transformation data. Analysis of the solid-state FTIR and 13C-NMR data indicated that the environment of the acetal side chain of fosinopril sodium differed in two polymorphs, and that there might be cis-trans isomerization about the C6-N peptide bond. These conformational differences are postulated as the origin of the observed polymorphism.

Reclamation of niobium compounds from ionic liquid electrochemical polishing of superconducting radio frequency cavities

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

Wixtrom, Alex I.; Buhler, Jessica E.; Reece, Charles E.

2013-06-01

Recent research has shown that choline chloride (vitamin B4)-based solutions can be used as a greener alternative to acid-based electrochemical polishing solutions. This study demonstrated a successful method for electrochemical deposition of niobium compounds onto the surface of copper substrates using a novel choline chloride-based ionic liquid. Niobium ions present in the ionic liquid solution were dissolved into the solution prior to deposition via electrochemical polishing of solid niobium. A black coating was clearly visible on the surface of the Cu following deposition. This coating was analyzed using scanning electron microscopy (SEM), electron dispersive X-ray spectroscopy (EDX), atomic force microscopymore » (AFM), and X-ray fluorescence spectroscopy (XRF). This ionic liquid-based electrochemical deposition method effectively recycles previously dissolved niobium from electrochemical polishing of superconducting radio frequency (SRF) cavities.« less

Intermediate Valence Tuning and Seebeck Coefficient Optimization in Yb-based Low-Temperature Thermoelectric Materials

NASA Astrophysics Data System (ADS)

Lehr, Gloria; Morelli, Donald; Jin, Hyungyu; Heremans, Joseph

2014-03-01

Several Yb-based intermediate valence compounds have unique thermoelectric properties at low temperatures. These materials are interesting to study for niche applications such as cryogenic Peltier cooling of infrared sensors on satellites. Elements of different sizes, which form isostructural compounds, are used to form solid solutions creating a chemical pressure (smaller atoms - Sc) or relaxation (larger atoms - La) to alter the volume of the unit cell and thereby manipulate the average Yb valence. Magnetic susceptibility measurements show a strong correlation between the Seebeck coefficient and the ratio of trivalent to divalent Yb in these compounds. Two different Yb-based solid solution systems, Yb1-xScxAl2 and Yb1-xLaxCu2Si2, demonstrate that the concentration of Yb can be used to tune both the magnitude of the Seebeck coefficient as well as the temperature at which its absolute maximum occurs. This work is supported by Michigan State University and AFOSR-MURI ``Cryogenic Peltier Cooling'' Contract #FA9550-10-1-0533.

High degree of polymerization in a fullerene-containing supramolecular polymer.

PubMed

Isla, Helena; Pérez, Emilio M; Martín, Nazario

2014-05-26

Supramolecular polymers based on dispersion forces typically show lower molecular weights (MW) than those based on hydrogen bonding or metal-ligand coordination. We present the synthesis and self-assembling properties of a monomer featuring two complementary units, a C60 derivative and an exTTF-based macrocycle, that interact mainly through π-π, charge-transfer, and van der Waals interactions. Thanks to the preorganization in the host part, a remarkable log K(a)=5.1±0.5 in CHCl3 at room temperature is determined for the host-guest couple. In accordance with the large binding constant, the monomer self-assembles in the gas phase, in solution, and in the solid state to form linear supramolecular polymers with a very high degree of polymerization. A MW above 150 kDa has been found experimentally in solution, while in the solid state the monomer forms extraordinarily long, straight, and uniform fibers with lengths reaching several microns. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An overview of the sustainability of solid waste management at military installations

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

Borglin, S.; Shore, J.; Worden, H.

2009-08-15

Sustainable municipal solid waste management at military solutions necessitates a combined approach that includes waste reduction, alternative disposal techniques, and increased recycling. Military installations are unique because they often represent large employers in the region in which they are located, thereby making any practices they employ impact overall waste management strategies of the region. Solutions for waste sustainability will be dependent on operational directives and base location, availability of resources such as water and energy, and size of population. Presented in this paper are descriptions of available waste strategies that can be used to support sustainable waste management. Results presentedmore » indicate source reduction and recycling to be the most sustainable solutions. However, new waste-to-energy plants and composting have potential to improve on these well proven techniques and allow military installations to achieve sustainable waste management.« less

Nanocellular foam with solid flame retardant

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

Chen, Liang; Kelly-Rowley, Anne M.; Bunker, Shana P.

Prepare nanofoam by (a) providing an aqueous solution of a flame retardant dissolved in an aqueous solvent, wherein the flame retardant is a solid at 23.degree. C. and 101 kiloPascals pressure when in neat form; (b) providing a fluid polymer composition selected from a solution of polymer dissolved in a water-miscible solvent or a latex of polymer particles in a continuous aqueous phase; (c) mixing the aqueous solution of flame retardant with the fluid polymer composition to form a mixture; (d) removing water and, if present, solvent from the mixture to produce a polymeric composition having less than 74 weight-percentmore » flame retardant based on total polymeric composition weight; (e) compound the polymeric composition with a matrix polymer to form a matrix polymer composition; and (f) foam the matrix polymer composition into nanofoam having a porosity of at least 60 percent.« less

The study of the antimicrobial activity of colloidal solutions of silver nanoparticles prepared using food stabilizers.

PubMed

Balandin, G V; Suvorov, O A; Shaburova, L N; Podkopaev, D O; Frolova, Yu V; Ermolaeva, G A

2015-06-01

The bactericidal effect of colloidal solutions of silver nanoparticles based on food stabilizers, gum arabic and chitosan, against bacterial cultures of microorganisms in food production is described. The antibacterial activity of nanotechnology products containing different amounts of stabilizing additives when applied to solid pH-neutral substrates is studied. For its evaluation a method making it possible to take into account the capability of nanoparticles to diffuse in solid media was applied. Minimal inhibitory concentrations of nanoparticles used against Erwinia herbicola, Pseudomonas fluorescens, Bacillus subtilis, Sarcina flava were found. A suggestion was made concerning the influence of the spatial structure of bacteria on the antibacterial activity of colloidal solutions of silver nanoparticles. The data concerning the antibacterial activity and minimal inhibiting concentrations of nanoparticles may be used for development of products suppressing activity of microorganisms hazardous for food production.

Solid-phase assays for small molecule screening using sol-gel entrapped proteins.

PubMed

Lebert, Julie M; Forsberg, Erica M; Brennan, John D

2008-04-01

With compound libraries exceeding one million compounds, the ability to quickly and effectively screen these compounds against relevant pharmaceutical targets has become crucial. Solid-phase assays present several advantages over solution-based methods. For example, a higher degree of miniaturization can be achieved, functional- and affinity-based studies are possible, and a variety of detection methods can be used. Unfortunately, most protein immobilization methods are either too harsh or require recombinant proteins and thus are not amenable to delicate proteins such as kinases and membrane-bound receptors. Sol-gel encapsulation of proteins in an inorganic silica matrix has emerged as a novel solid-phase assay platform. In this minireview, we discuss the development of sol-gel derived protein microarrays and sol-gel based monolithic bioaffinity columns for the high-throughput screening of small molecule libraries and mixtures.

New strategy and easy fabrication of solid-state supercapacitor based on polypyrrole and nitrile rubber.

PubMed

Lee, Sangyool; Lee, Youngkwan; Cho, Mi-Suk; Nam, Jae-Do

2008-09-01

Solid state redox supercapacitors were fabricated using a solid polymer electrolyte, nitrile butadiene rubber (NBR)-KCI and chemically deposited polypyrrole (PPy) as the conducting polymer electrodes on both surfaces of a NBR film. The optimal conditions for the preparation of the PPy/NBR electrode were confirmed as functions of the uptake of pyrrole monomer into the NBR matrix as well as the immersion time in an oxidant solution. The morphology of the PPy-NBR-KCI capacitor was observed using scanning electron microscopy. The performance of the capacitors was characterized using a galvanostatic charge-discharge technique.

ZrB 2-HfB 2 solid solutions as electrode materials for hydrogen reaction in acidic and basic solutions

DOE PAGES

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

2016-11-09

Spark plasma sintered transition metal diborides such as HfB 2, ZrB 2 and their solid solutions were investigated as electrode materials for electrochemical hydrogen evolutions reactions (HER) in 1 M H 2SO 4 and 1 M NaOH electrolytes. HfB 2 and ZrB 2 formed complete solid solutions when mixed in 1:1, 1:4, and 4:1 ratios and they were stable in both electrolytes. The HER kinetics of the diborides were slower in the basic solution than in the acidic solutions. The Tafel slopes in 1 M H 2SO 4 were in the range of 0.15 - 0.18 V/decade except for puremore » HfB 2 which showed a Tafel slope of 0.38 V/decade. In 1 M NaOH the Tafel slopes were in the range of 0.12 - 0.27 V/decade. The composition of Hf xZr 1-xB 2 solid solutions with x = 0.2 - 0.8, influenced the exchange current densities, overpotentials and Tafel slopes of the HER. As a result, the EIS data were fitted with a porous film equivalent circuit model in order to better understand the HER behavior. In addition, modeling calculations, using density functional theory approach, were carried out to estimate the density of states and band structure of the boride solid solutions.« less

Calculation of open and closed system elastic coefficients for multicomponent solids

NASA Astrophysics Data System (ADS)

Mishin, Y.

2015-06-01

Thermodynamic equilibrium in multicomponent solids subject to mechanical stresses is a complex nonlinear problem whose exact solution requires extensive computations. A few decades ago, Larché and Cahn proposed a linearized solution of the mechanochemical equilibrium problem by introducing the concept of open system elastic coefficients [Acta Metall. 21, 1051 (1973), 10.1016/0001-6160(73)90021-7]. Using the Ni-Al solid solution as a model system, we demonstrate that open system elastic coefficients can be readily computed by semigrand canonical Monte Carlo simulations in conjunction with the shape fluctuation approach. Such coefficients can be derived from a single simulation run, together with other thermodynamic properties needed for prediction of compositional fields in solid solutions containing defects. The proposed calculation approach enables streamlined solutions of mechanochemical equilibrium problems in complex alloys. Second order corrections to the linear theory are extended to multicomponent systems.

On the Formulation of Weakly Singular Displacement/Traction Integral Equations; and Their Solution by the MLPG Method

NASA Technical Reports Server (NTRS)

Atluri, Satya N.; Shen, Shengping

2002-01-01

In this paper, a very simple method is used to derive the weakly singular traction boundary integral equation based on the integral relationships for displacement gradients. The concept of the MLPG method is employed to solve the integral equations, especially those arising in solid mechanics. A moving Least Squares (MLS) interpolation is selected to approximate the trial functions in this paper. Five boundary integral Solution methods are introduced: direct solution method; displacement boundary-value problem; traction boundary-value problem; mixed boundary-value problem; and boundary variational principle. Based on the local weak form of the BIE, four different nodal-based local test functions are selected, leading to four different MLPG methods for each BIE solution method. These methods combine the advantages of the MLPG method and the boundary element method.

Microstructural Evolution and Phase Formation in 2nd-Generation Refractory-Based High Entropy Alloys

PubMed Central

Eshed, Eyal; Larianovsky, Natalya; Kovalevsky, Alexey; Popov, Vladimir; Gorbachev, Igor; Popov, Vladimir; Katz-Demyanetz, Alexander

2018-01-01

Refractory-based high entropy alloys (HEAs) of the 2nd-generation type are new intensively-studied materials with a high potential for structural high-temperature applications. This paper presents investigation results on microstructural evolution and phase formation in as-cast and subsequently heat-treated HEAs at various temperature-time regimes. Microstructural examination was performed by means of scanning electron microscopy (SEM) combined with the energy dispersive spectroscopy (EDS) mode of electron probe microanalysis (EPMA) and qualitative X-ray diffraction (XRD). The primary evolutionary trend observed was the tendency of Zr to gradually segregate as the temperature rises, while all the other elements eventually dissolve in the BCC solid solution phase once the onset of Laves phase complex decomposition is reached. The performed thermodynamic modelling was based on the Calculation of Phase Diagrams method (CALPHAD). The BCC A2 solid solution phase is predicted by the model to contain increasing amounts of Cr as the temperature rises, which is in perfect agreement with the actual results obtained by SEM. However, the model was not able to predict the existence of the Zr-rich phase or the tendency of Zr to segregate and form its own solid solution—most likely as a result of the Zr segregation trend not being an equilibrium phenomenon. PMID:29360763

Antimony leaching and chemical species analyses in an industrial solid waste: Surface and bulk speciation using ToF-SIMS and XANES.

PubMed

Kappen, P; Ferrando-Miguel, G; Reichman, S M; Innes, L; Welter, E; Pigram, P J

2017-05-05

The surface chemistry and bulk chemical speciation of solid industrial wastes containing 8wt-% antimony (Sb) were investigated using synchrotron X-ray Absorption Near Edge Structure (XANES) and Time-of-Flight Ion Secondary Mass Spectrometry (ToF-SIMS). Leaching experiments were conducted in order to better understand the behavior of Sb in waste streams and to inform regulatory management of antimony-containing wastes. The experiments also demonstrate how a combination of XANES and ToF-SIMS adds value to the field of waste investigations. Leaching treatments (acid and base) were performed at a synchrotron over 24h time periods. Surface analyses of the wastes before leaching showed the presence of Sb associated with S and O. Bulk analyses revealed Sb to be present, primarily, as trivalent sulfide species. Both acid and base leaching did not change the antimony speciation on the solid. Leaching transferred about 1% of the total Sb into solution where Sb was found to be present as Sb(V). XANES data showed similarities between leachate and FeSbO 4 . During base leaching, the Sb content in solution gradually increased over time, and potential desorption mechanisms are discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

A novel surfactant-free lipid-based formulation for improving oral bioavailability of loratadine using colloidal silicon dioxide as emulsifier and solid carrier.

PubMed

Huang, Ri; Tan, Yonggang; Shen, Lao; Wang, Tao; Quan, Dongqin

2018-05-08

The purpose of this study was to develop an innovative surfactant-free lipid-based formulation (LF) for improving oral bioavailability of loratadine based on using solid particles colloidal silicon dioxide (CSD) as emulsifier and solid carrier. Loratadine was dissolved in oil solution with the aid of co-solvent and LF were prepared by a simple adsorption and milling technique. The LF Powder was evaluated in terms of angle of repose and X-ray powder diffraction. After dispersing and emulsifying in water, the particle size and morphology were also characterized. In vitro dissolution and pharmacokinetic behavior in vivo were also studied. Orthogonal design indicated that the amount of CSD in formulations had a major and significant influence on emulsification. The optimal formulation showed LF with good flowability and without crystallization or deposition of loratadine in it. After dispersing in water, an emulsion with mean droplet size of 1.2μm was obtained. Although the dissolution of drug from LF was slower in vitro in acidic aqueous solution, pharmacokinetic studies in vivo showed that the bioavailability of loratadine increased 2.49-fold by CF compared to commercial tablet. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Surface Defects Enhanced Visible Light Photocatalytic H2 Production for Zn-Cd-S Solid Solution.

PubMed

Zhang, Xiaoyan; Zhao, Zhao; Zhang, Wanwan; Zhang, Guoqiang; Qu, Dan; Miao, Xiang; Sun, Shaorui; Sun, Zaicheng

2016-02-10

In order to investigate the defect effect on photocatalytic performance of the visible light photocatalyst, Zn-Cd-S solid solution with surface defects is prepared in the hydrazine hydrate. X-ray photoelectron spectra and photoluminescence results confirm the existence of defects, such as sulfur vacancies, interstitial metal, and Zn and Cd in the low valence state on the top surface of solid solutions. The surface defects can be effectively removed by treating with sulfur vapor. The solid solution with surface defect exhibits a narrower band gap, wider light absorption range, and better photocatalytic perfomance. The optimized solid solution with defects exhibits 571 μmol h(-1) for 50 mg photocatalyst without loading Pt as cocatalyst under visible light irradiation, which is fourfold better than that of sulfur vapor treated samples. The wavelength dependence of photocatalytic activity discloses that the enhancement happens at each wavelength within the whole absorption range. The theoretical calculation shows that the surface defects induce the conduction band minimum and valence band maximum shift downward and upward, respectively. This constructs a type I junction between bulk and surface of solid solution, which promotes the migration of photogenerated charges toward the surface of nanostructure and leads to enhanced photocatalytic activity. Thus a new method to construct highly efficient visible light photocatalysts is opened. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Raman scattering study of the structural ordering in Bi1- x La x FeO3 ceramic ferroelectromagnetics

NASA Astrophysics Data System (ADS)

Teplyakova, N. A.; Titov, S. V.; Verbenko, I. A.; Sidorov, N. V.; Reznichenko, L. A.

2015-09-01

Based on Raman spectra, we have studied structural ordering processes in ceramics of ferroelectromagnetics Bi1- x La x FeO3 ( x = 0.075-0.20). It has been found that the structure of Bi1- x La x FeO3 is close to the structure of the crystal BiFeO3. However, lines in Raman spectra of Bi1- x La x FeO3 are considerably broadened compared to lines in the Raman spectrum of the BiFeO3 single crystal, which indicates that the structure of solid solutions is much more disordered. In Raman spectra of Bi1- x La x FeO3, in the range of librational vibrations of octahedra as a whole (50-90 cm-1), several groups of lines are observed in frequency ranges 59-69, 72-77, and 86-92 cm-1 (depending on the composition of solid solution). This confirms X-ray data that examined solid solutions are not single-phase. At a La content x = 0.120, Raman lines in the low-frequency spectral range narrow, which indicates that the ordering of structural units in cationic sublattices somewhat increases. Upon an increase in the content of La in the Bi1- x La x FeO3 structure, no unambiguous dependence of parameters of spectral lines is observed. It is likely that this is explained by the fact that, as the value of x increases, the character of the incorporation of La into the structure of the solid solution changes.

Aluminum-doped ceria-zirconia solid solutions with enhanced thermal stability and high oxygen storage capacity.

PubMed

Dong, Qiang; Yin, Shu; Guo, Chongshen; Sato, Tsugio

2012-10-01

A facile solvothermal method to synthesize aluminum-doped ceria-zirconia (Ce0.5Zr0.5-xAlxO2-x/2, x = 0.1 to 0.4) solid solutions was carried out using Ce(NH4)2(NO3)6, Zr(NO3)3·2H2O Al(NO3)3·9H2O, and NH4OH as the starting materials at 200°C for 24 h. The obtained solid solutions from the solvothermal reaction were calcined at 1,000°C for 20 h in air atmosphere to evaluate the thermal stability. The synthesized Ce0.5Zr0.3Al0.2O1.9 particle was characterized for the oxygen storage capacity (OSC) in automotive catalysis. For the characterization, X-ray diffraction, transmission electron microscopy, and the Brunauer-Emmet-Teller (BET) technique were employed. The OSC values of all samples were measured at 600°C using thermogravimetric-differential thermal analysis. Ce0.5Zr0.3Al0.2O1.9 solid solutions calcined at 1,000°C for 20 h with a BET surface area of 18 m2 g-1 exhibited a considerably high OSC of 427 μmol-O g-1 and good OSC performance stability. The same synthesis route was employed for the preparation of the CeO2 and Ce0.5Zr0.5O2. The incorporation of aluminum ion in the lattice of ceria-based catalyst greatly enhanced the thermal stability and OSC.

Silicate-catalyzed chemical grouting compositions

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

Not Available

1972-09-28

Chemical grouting compositions for stabilizing earth, sand, and other porous particulate formations or agglomerates of solids are described. The composition for producing a chemically grouting structure consists of an aqueous base solution of: (1) vegetative polyphenolic material consisting of condensed type tannins, and an aqueous catalyst solution of (2) a water-soluble alkali metal silicate. The polyphenolic material is present in an amount from 5% to 40% based on the weight of the base solution, and the water- soluble alkali metal silicate is present in an amount to provide from 1% to 15% SiOD2U in the silicate compound based on themore » weight of the polyphenolic material. These grouting compositions are completely safe to operating personnel and to surrounding environment, since the potassium or sodium silicate catalysts are nontoxic. (15 claims)« less

Evolution of Microstructure in Brazed Joints of Austenitic-Martensitic Stainless Steel with Pure Silver Obtained with Ag-27Cu-5Sn Brazing Filler Material

NASA Astrophysics Data System (ADS)

Gangadharan, S.; Sivakumar, D.; Venkateswaran, T.; Kulkarni, Kaustubh

2016-12-01

Brazing of an austenitic-martensitic stainless steel (AMSS) with pure silver was carried out at 1053 K, 1073 K, and 1093 K (780 °C, 800 °C, and 820 °C) with Ag-27Cu-5Sn (wt pct) as brazing filler material (BFM). Wettability of the liquid BFM over base AMSS surface was found to be poor. Application of nickel coating to the steel was observed to enhance the wettability and to enable the formation of a good bond between BFM and the steel. The mechanism responsible for enhanced metallurgical bonding of the BFM with AMSS in the presence of nickel coating was explained based on diffusional interactions and uphill diffusion of iron, chromium and nickel observed in the brazed microstructure. Good diffusion-assisted zone was observed to form on silver side at all three temperatures. Four phases were encountered within the joint including silver solid solution, copper solid solution, Cu3Sn intermetallic and Ni-Fe solid solution. The Cu3Sn intermetallic was present in small amounts in the joints brazed at 1053 K and 1073 K (780 °C and 800 °C). The joint formed at 1093 K (820 °C) exhibited the absence of Cu3Sn, fewer defects and larger diffusion-assisted zone. Hardness of base AMSS was found to reduce during brazing due to austenite reversion and post-brazing sub-zero treatment for 2.5 hours was found suitable to recover the hardness.

Stabilized antiferroelectricity in xBiScO3-(1-x)NaNbO3 lead-free ceramics with established double hysteresis loops

NASA Astrophysics Data System (ADS)

Gao, Lisheng; Guo, Hanzheng; Zhang, Shujun; Randall, Clive A.

2018-02-01

We previously reported various solid solution systems that demonstrated the stabilized antiferroelectric (P) phases in NaNbO3 through lowering the tolerance factor. However, all those reported modifications were achieved by adding A2+B4+O3 type solid solutions. A lead-free antiferroelectric (AFE) solid solution xBiScO3-(1-x)NaNbO3 was rationalized by adopting the tolerance factor design rule. Specifically, adding BiScO3 was found to effectively stabilize the AFE phase without changing the crystal symmetry of NaNbO3. Microstructure and electron zone axis diffraction patterns from transmission electron microscopy revealed the stabilized AFE (P) phase in this solid solution. Besides, the electric-field-induced polarization with a double-hysteresis loop was observed. The present results pointed out that the strategy could also be applied while adding A3+B3+O3 type solid solutions. In addition, it expanded the compositional design that can be applied to antiferroelectric materials.

Fluid-solid interaction: benchmarking of an external coupling of ANSYS with CFX for cardiovascular applications.

PubMed

Hose, D R; Lawford, P V; Narracott, A J; Penrose, J M T; Jones, I P

2003-01-01

Fluid-solid interaction is a primary feature of cardiovascular flows. There is increasing interest in the numerical solution of these systems as the extensive computational resource required for such studies becomes available. One form of coupling is an external weak coupling of separate solid and fluid mechanics codes. Information about the stress tensor and displacement vector at the wetted boundary is passed between the codes, and an iterative scheme is employed to move towards convergence of these parameters at each time step. This approach has the attraction that separate codes with the most extensive functionality for each of the separate phases can be selected, which might be important in the context of the complex rheology and contact mechanics that often feature in cardiovascular systems. Penrose and Staples describe a weak coupling of CFX for computational fluid mechanics to ANSYS for solid mechanics, based on a simple Jacobi iteration scheme. It is important to validate the coupled numerical solutions. An extensive analytical study of flow in elastic-walled tubes was carried out by Womersley in the late 1950s. This paper describes the performance of the coupling software for the straight elastic-walled tube, and compares the results with Womersley's analytical solutions. It also presents preliminary results demonstrating the application of the coupled software in the context of a stented vessel.

Piezoelectric Ceramics of the (1 − x)Bi0.50Na0.50TiO3–xBa0.90Ca0.10TiO3 Lead-Free Solid Solution: Chemical Shift of the Morphotropic Phase Boundary, a Case Study for x = 0.06

PubMed Central

Vivar-Ocampo, Rodrigo; Pardo, Lorena; Ávila, David; Morán, Emilio; González, Amador M.; Bucio, Lauro; Villafuerte-Castrejón, María-Elena

2017-01-01

Research and development of lead-free piezoelectric materials are still the hottest topics in the field of piezoelectricity. One of the most promising lead-free family of compounds to replace lead zirconate–titanate for actuators is that of Bi0.50Na0.50TiO3 (BNT) based solid solutions. The pseudo-binary (1 − x)Bi0.50Na0.50TiO3–xBa1 − yCayTiO3 system has been proposed for high temperature capacitors and not yet fully explored as piezoelectric material. In this work, the solid solution with x = 0.06 and y = 0.10 was obtained by two different synthesis routes: solid state and Pechini, aiming at using reduced temperatures, both in synthesis (<800 °C) and sintering (<1150 °C), while maintaining appropriated piezoelectric performance. Crystal structure, ceramic grain size, and morphology depend on the synthesis route and were analyzed by X-ray diffraction, together with scanning and transmission electron microscopy. The effects of processing and ceramic microstructure on the structural, dielectric, ferroelectric, and piezoelectric properties were discussed in terms of a shift of the Morphotropic Phase Boundary, chemically induced by the synthesis route. PMID:28773096

Piezoelectric Ceramics of the (1 - x)Bi0.50Na0.50TiO₃-xBa0.90Ca0.10TiO₃ Lead-Free Solid Solution: Chemical Shift of the Morphotropic Phase Boundary, a Case Study for x = 0.06.

PubMed

Vivar-Ocampo, Rodrigo; Pardo, Lorena; Ávila, David; Morán, Emilio; González, Amador M; Bucio, Lauro; Villafuerte-Castrejón, María-Elena

2017-07-01

Research and development of lead-free piezoelectric materials are still the hottest topics in the field of piezoelectricity. One of the most promising lead-free family of compounds to replace lead zirconate-titanate for actuators is that of Bi 0.50 Na 0.50 TiO₃ (BNT) based solid solutions. The pseudo-binary (1 - x )Bi 0.50 Na 0.50 TiO₃- x Ba 1 - y Ca y TiO₃ system has been proposed for high temperature capacitors and not yet fully explored as piezoelectric material. In this work, the solid solution with x = 0.06 and y = 0.10 was obtained by two different synthesis routes: solid state and Pechini, aiming at using reduced temperatures, both in synthesis (<800 °C) and sintering (<1150 °C), while maintaining appropriated piezoelectric performance. Crystal structure, ceramic grain size, and morphology depend on the synthesis route and were analyzed by X-ray diffraction, together with scanning and transmission electron microscopy. The effects of processing and ceramic microstructure on the structural, dielectric, ferroelectric, and piezoelectric properties were discussed in terms of a shift of the Morphotropic Phase Boundary, chemically induced by the synthesis route.

Solution-mediated phase transformation of haloperidol mesylate in the presence of sodium lauryl sulfate.

PubMed

Greco, Kristyn; Bogner, Robin

2011-09-01

Forming a salt is a common way to increase the solubility of a poorly soluble compound. However, the solubility enhancement gained by salt formation may be lost due to solution-mediated phase transformation (SMPT) during dissolution. The SMPT of a salt can occur due to a supersaturated solution near the dissolving surface caused by pH or other solution conditions. In addition to changes in pH, surfactants are also known to affect SMPT. In this study, SMPT of a highly soluble salt, haloperidol mesylate, at pH 7 in the presence of a commonly used surfactant, sodium lauryl sulfate (SLS), was investigated. Dissolution experiments were performed using a flow-through dissolution apparatus with solutions containing various concentrations of SLS. Compacts of haloperidol mesylate were observed during dissolution in the flow-through apparatus using a stereomicroscope. Raman microscopy was used to characterize solids. The dissolution of haloperidol mesylate was significantly influenced by the addition of sodium lauryl sulfate. In conditions where SMPT was expected, the addition of SLS at low concentrations (0.1-0.2 mM) reduced the dissolution of haloperidol mesylate. In solutions containing concentrations of SLS above the critical micelle concentration (CMC) (10-15 mM), the dissolution of haloperidol mesylate increased compared to below the CMC. The solids recovered from solubility experiments of haloperidol mesylate indicated that haloperidol free base precipitated at all concentrations of SLS. Above 5 mM of SLS, Raman microscopy suggested a new form, perhaps the estolate salt. The addition of surfactant in solids that undergo solution-mediated phase transformation can add complexity to the dissolution profiles and conversion.

Feasible way of Human Solid and Liquid Wastes' Inclusion Into Intersystem Mass Exchange of Biological-Technical Life Support Systems

NASA Astrophysics Data System (ADS)

Ushakova, Sofya; Tikhomirov, Alexander A.; Tikhomirova, Natalia; Kudenko, Yurii; Griboskaya, Illiada; Gros, Jean-Bernard; Lasseur, Christophe

The basic objective arising at use of mineralized human solid and liquid wastes serving as the source of mineral elements for plants cultivation in biological-technical life support systems appears to be NaCl presence in them. The given work is aimed at feasibility study of mineralized human metabolites' utilization for nutrient solutions' preparation for their further employment at a long-term cultivation of uneven-aged wheat and Salicornia europaea L. cenosis in a conveyer regime. Human solid and liquid wastes were mineralized by the "wet incineration" method developed by Yu. Kudenko. On their base the solutions were prepared which were used for cultivation of 5-aged wheat conveyer with the time step-interval of 14 days. Wheat was cultivated by hydroponics method on expanded clay aggregate. For partial demineralization of nutrient solution every two weeks after regular wheat harvesting 12 L of solution was withdrawn from the wheat irrigation tank and used for Salicornia europaea cultivation by the water culture method in a conveyer regime. The Salicornia europaea conveyer was represented by 2 ages with the time step-interval of 14 days. Resulting from repeating withdrawal of the solution used for wheat cultivation, sodium concentration in the wheat irrigation solution did not exceed 400 mg/l, and mineral elements contained in the taken solution were used for Salicornia europaea cultivation. The experiment lasted 7 months. Total wheat biomass productivity averaged 30.1 g*m-2*day-1 at harvest index equal to 36.8The work was carried out under support of SB RAS grant 132 and INTAS 05-1000008-8010

Chemical Disposition of Plutonium in Hanford Site Tank Wastes

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

Delegard, Calvin H.; Jones, Susan A.

2015-05-07

This report examines the chemical disposition of plutonium (Pu) in Hanford Site tank wastes, by itself and in its observed and potential interactions with the neutron absorbers aluminum (Al), cadmium (Cd), chromium (Cr), iron (Fe), manganese (Mn), nickel (Ni), and sodium (Na). Consideration also is given to the interactions of plutonium with uranium (U). No consideration of the disposition of uranium itself as an element with fissile isotopes is considered except tangentially with respect to its interaction as an absorber for plutonium. The report begins with a brief review of Hanford Site plutonium processes, examining the various means used tomore » recover plutonium from irradiated fuel and from scrap, and also examines the intermediate processing of plutonium to prepare useful chemical forms. The paper provides an overview of Hanford tank defined-waste–type compositions and some calculations of the ratios of plutonium to absorber elements in these waste types and in individual waste analyses. These assessments are based on Hanford tank waste inventory data derived from separately published, expert assessments of tank disposal records, process flowsheets, and chemical/radiochemical analyses. This work also investigates the distribution and expected speciation of plutonium in tank waste solution and solid phases. For the solid phases, both pure plutonium compounds and plutonium interactions with absorber elements are considered. These assessments of plutonium chemistry are based largely on analyses of idealized or simulated tank waste or strongly alkaline systems. The very limited information available on plutonium behavior, disposition, and speciation in genuine tank waste also is discussed. The assessments show that plutonium coprecipitates strongly with chromium, iron, manganese and uranium absorbers. Plutonium’s chemical interactions with aluminum, nickel, and sodium are minimal to non-existent. Credit for neutronic interaction of plutonium with these absorbers occurs only if they are physically proximal in solution or the plutonium present in the solid phase is intimately mixed with compounds or solutions of these absorbers. No information on the potential chemical interaction of plutonium with cadmium was found in the technical literature. Definitive evidence of sorption or adsorption of plutonium onto various solid phases from strongly alkaline media is less clear-cut, perhaps owing to fewer studies and to some well-attributed tests run under conditions exceeding the very low solubility of plutonium. The several studies that are well-founded show that only about half of the plutonium is adsorbed from waste solutions onto sludge solid phases. The organic complexants found in many Hanford tank waste solutions seem to decrease plutonium uptake onto solids. A number of studies show plutonium sorbs effectively onto sodium titanate. Finally, this report presents findings describing the behavior of plutonium vis-à-vis other elements during sludge dissolution in nitric acid based on Hanford tank waste experience gained by lab-scale tests, chemical and radiochemical sample characterization, and full-scale processing in preparation for strontium-90 recovery from PUREX sludges.« less

Materials research for passive solar systems: Solid-state phase-change materials

NASA Astrophysics Data System (ADS)

Benson, D. K.; Webb, J. D.; Burrows, R. W.; McFadden, J. D. O.; Christensen, C.

1985-03-01

A set of solid-state phase-change materials is being evaluated for possible use in passive solar thermal energy storage systems. The most promising materials are organic solid solutions of pentaerythritol (C5H12O4), pentaglycerinve (C5H12O3), and neopentyl glycol (C5H12O2). Solid solution mixtures of these compounds can be tailored so that they exhibit solid-to-solid phase transformations at any desired temperature between 25 C and 188 C, and have latent heats of transformation etween 20 and 70 cal/g. Transformation temperatures, specific heats, and latent heats of transformation have been measured for a number of these materials. Limited cyclic experiments suggest that the solid solutions are stable. These phase-change materials exhibit large amounts of undercooling; however, the addition of certain nucleating agents as particulate dispersions in the solid phase-change material greatly reduces this effect. Computer simulations suggest that the use of an optimized solid-state phase-change material in a Trombe wall could provide better performance than a concrete Trombe wall four times thicker and nine times heavier.

Solid phase extraction and spectrophotometric determination of Au(III) with 5-(2-hydroxy-5-nitrophenylazo)thiorhodanine.

PubMed

Hu, Qiufen; Chen, Xiubin; Yang, Xiangjun; Huang, Zhangjie; Chen, Jing; Yang, Guangyu

2006-04-01

A new chromogenic reagent, 5-(2-hydroxy-5-nitrophenylazo)thiorhodanine (HNATR) was synthesized. A highly sensitive, selective and rapid method for the determination microg l(-1) level of Au(III) based on the rapid reaction of Au(III) with HNATR and the solid phase extraction of the colored complex with a reversed phase polymer-based C(18) cartridge have been developed. The HNATR reacted with Au(III) to form a red complex of a molar ratio 1:2 (Au(III) to HNATR) in the presence of 0.05 - 0.5 mol l(-1) of phosphoric acid solution and emulsifier-OP medium. This complex was enriched by the solid phase extraction with a polymer-based C(18) cartridge. The enrichment factor of 100 was achieved. The molar absorptivity of the complex is 1.37 x 10(5) l mol(-1) cm(-1) at 520 nm in the measured solution. The system obeys Beer's law in the range of 0.01 - 3 microg ml(-1). The relative standard deviation for eleven replicates sample of 0.5 microg l(-1) level is 2.18%. The detection limit, based on the three times of standard deviation is 0.02 microg l(-1) in the original sample. This method was applied to the determination of gold in water and ore with good results.

Electrolyte for batteries with regenerative solid electrolyte interface

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

Xiao, Jie; Lu, Dongping; Shao, Yuyan

2017-08-01

An energy storage device comprising: an anode; and a solute-containing electrolyte composition wherein the solute concentration in the electrolyte composition is sufficiently high to form a regenerative solid electrolyte interface layer on a surface of the anode only during charging of the energy storage device, wherein the regenerative layer comprises at least one solute or solvated solute from the electrolyte composition.

Design principles for radiation-resistant solid solutions

NASA Astrophysics Data System (ADS)

Schuler, Thomas; Trinkle, Dallas R.; Bellon, Pascal; Averback, Robert

2017-05-01

We develop a multiscale approach to quantify the increase in the recombined fraction of point defects under irradiation resulting from dilute solute additions to a solid solution. This methodology provides design principles for radiation-resistant materials. Using an existing database of solute diffusivities, we identify Sb as one of the most efficient solutes for this purpose in a Cu matrix. We perform density-functional-theory calculations to obtain binding and migration energies of Sb atoms, vacancies, and self-interstitial atoms in various configurations. The computed data informs the self-consistent mean-field formalism to calculate transport coefficients, allowing us to make quantitative predictions of the recombined fraction of point defects as a function of temperature and irradiation rate using homogeneous rate equations. We identify two different mechanisms according to which solutes lead to an increase in the recombined fraction of point defects; at low temperature, solutes slow down vacancies (kinetic effect), while at high temperature, solutes stabilize vacancies in the solid solution (thermodynamic effect). Extension to other metallic matrices and solutes are discussed.

Towards medicinal mechanochemistry: evolution of milling from pharmaceutical solid form screening to the synthesis of active pharmaceutical ingredients (APIs).

PubMed

Tan, Davin; Loots, Leigh; Friščić, Tomislav

2016-06-14

This overview highlights the emergent area of mechanochemical reactions for making active pharmaceutical ingredients (APIs), and covers the latest advances in the recently established area of mechanochemical screening and synthesis of pharmaceutical solid forms, specifically polymorphs, cocrystals, salts and salt cocrystals. We also provide an overview of the most recent developments in pharmaceutical uses of mechanochemistry, including real-time reaction monitoring, techniques for polymorph control and approaches for continuous manufacture using twin screw extrusion, and more. Most importantly, we show how the overlap of previously unrelated areas of mechanochemical screening for API solid forms, organic synthesis by milling, and mechanochemical screening for molecular recognition, enables the emergence of a new research discipline in which different aspects of pharmaceutical and medicinal chemistry are addressed through mechanochemistry rather than through conventional solution-based routes. The emergence of such medicinal mechanochemistry is likely to have a strong impact on future pharmaceutical and medicinal chemistry, as it offers not only access to materials and reactivity that are sometimes difficult or even impossible to access from solution, but can also provide a general answer to the demands of the pharmaceutical industry for cleaner, safer and efficient synthetic solutions.

Room-temperature ferromagnetism in Fe-based perovskite solid solution in lead-free ferroelectric Bi0.5Na0.5TiO3 materials

NASA Astrophysics Data System (ADS)

Hung, Nguyen The; Bac, Luong Huu; Trung, Nguyen Ngoc; Hoang, Nguyen The; Van Vinh, Pham; Dung, Dang Duc

2018-04-01

The integration of ferromagnetism in lead-free ferroelectric materials is important to fabricate smart materials for electronic devices. In this work, (1 - x)Bi0.5Na0.5TiO3 + xMgFeO3-δ materials (x = 0-9 mol%) were prepared through sol-gel method. X-ray diffraction characterization indicated that MgFeO3-δ materials existed as a well solid solution in lead-free ferroelectric Bi0.5Na0.5TiO3 materials. The rhombohedral structure of Bi0.5Na0.5TiO3 materials was distorted due to the random distribution of Mg and Fe cations into the host lattice. The reduced optical band gap and the induced room-temperature ferromagnetism were due to the spin splitting of transition metal substitution at the B-site of perovskite Bi0.5Na0.5TiO3 and the modification by A-site co-substitution. This work elucidates the role of secondary phase as solid solution in Bi0.5Na0.5TiO3 material for development of lead-free multiferroelectric materials.

On the nature of the excess heat capacity of mixing

NASA Astrophysics Data System (ADS)

Benisek, Artur; Dachs, Edgar

2011-03-01

The excess vibrational entropy (Δ S {vib/ex}) of several silicate solid solutions are found to be linearly correlated with the differences in end-member volumes (Δ V i ) and end-member bulk moduli (Δκ i ). If a substitution produces both, larger and elastically stiffer polyhedra, then the substituted ion will find itself in a strong enlarged structure. The frequency of its vibration is decreased because of the increase in bond lengths. Lowering of frequencies produces larger heat capacities, which give rise to positive excess vibrational entropies. If a substitution produces larger but elastically softer polyhedra, then increase and decrease of mean bond lengths may be similar in magnitude and their effect on the vibrational entropy tends to be compensated. The empirical relationship between Δ S {vib/ex}, Δ V i and Δκ i , as described by Δ S {vib/ex} = (Δ V i + mΔκ i ) f, was calibrated on six silicate solid solutions (analbite-sanidine, pyrope-grossular, forsterite-fayalite, analbite-anorthite, anorthite-sanidine, CaTs-diopside) yielding m = 0.0246 and f = 2.926. It allows the prediction of Δ S {vib/ex} behaviour of a solid solution based on its volume and bulk moduli end-member data.

A solid dielectric gated graphene nanosensor in electrolyte solutions.

PubMed

Zhu, Yibo; Wang, Cheng; Petrone, Nicholas; Yu, Jaeeun; Nuckolls, Colin; Hone, James; Lin, Qiao

2015-03-23

This letter presents a graphene field effect transistor (GFET) nanosensor that, with a solid gate provided by a high- κ dielectric, allows analyte detection in liquid media at low gate voltages. The gate is embedded within the sensor and thus is isolated from a sample solution, offering a high level of integration and miniaturization and eliminating errors caused by the liquid disturbance, desirable for both in vitro and in vivo applications. We demonstrate that the GFET nanosensor can be used to measure pH changes in a range of 5.3-9.3. Based on the experimental observations and quantitative analysis, the charging of an electrical double layer capacitor is found to be the major mechanism of pH sensing.

Design of robotic cells based on relative handling modules with use of SolidWorks system

NASA Astrophysics Data System (ADS)

Gaponenko, E. V.; Anciferov, S. I.

2018-05-01

The article presents a diagramed engineering solution for a robotic cell with six degrees of freedom for machining of complex details, consisting of the base with a tool installation module and a detail machining module made as parallel structure mechanisms. The output links of the detail machining module and the tool installation module can move along X-Y-Z coordinate axes each. A 3D-model of the complex is designed in the SolidWorks system. It will be used further for carrying out engineering calculations and mathematical analysis and obtaining all required documentation.

Lipid immiscibility and biophysical properties: Molecular order within and among unit cell volumes

USDA-ARS?s Scientific Manuscript database

Saturated and unsaturated fatty acids clearly have a discrete chemical structure in the solid state. In a saturated solution, the solid state and solution state are in chemical equilibrium. The lipid stearic acid packs in unit cell volumes in the liquid state as well as in the solid state. Normal...

Multiferroic properties in NdFeO3-PbTiO3 solid solutions

NASA Astrophysics Data System (ADS)

Kumar, Sunil; Pal, Jaswinder; Kaur, Shubhpreet; Agrawal, P.; Singh, Mandeep; Singh, Anupinder

2018-05-01

The x(NdFeO3) - 1-x(PbTiO3) where x = 0.2 solid solution was prepared using solid state reaction route. The X-ray diffraction (XRD) data reveals the single phase formation. The microstructure shows grain growth with lesser porosity. The energy dispersive analysis confirms the presence of elements in stochiometric proportion. The polarization vs. Electric field loop estabilished a ferroelectric type behavior but lossy in nature. This lossy nature may be due to the presence of large leakage current in solid solution. The Magnetization vs. Magnetic field plot exhibits a unsaturated hysteriss loop indicates that the sample is not purely ferromagnetic.

Study of low-temperature active rare-earth oxide catalysts for automotive exhaust clean-up.

DOT National Transportation Integrated Search

2014-02-01

We report a facile onepot synthesis of CexZr1-xO2 (0x1) solid solution nanocrystals using hydrothermal reactions. A direct formation of oxide solid solutions in aqueous solution under pressure at low temperatures was clearly revealed by X-ra...

SSM-based electrophysiology.

PubMed

Schulz, Patrick; Garcia-Celma, Juan J; Fendler, Klaus

2008-10-01

An assay technique for the electrical characterization of electrogenic transport proteins on solid supported membranes is presented. Membrane vesicles, proteoliposomes or membrane fragments containing the transporter are adsorbed to the solid supported membrane and are activated by providing a substrate or a ligand via a rapid solution exchange. This technique opens up new possibilities where conventional electrophysiology fails like transporters or ion channels from bacteria and from intracellular compartments. Its rugged design and potential for automation make it suitable for drug screening.

Experimental research of solid waste drying in the process of thermal processing

NASA Astrophysics Data System (ADS)

Bukhmirov, V. V.; Kolibaba, O. B.; Gabitov, R. N.

2015-10-01

The convective drying process of municipal solid waste layer as a polydispersed multicomponent porous structure is studied. On the base of the experimental data criterial equations for calculating heat transfer and mass transfer processes in the layer, depending on the humidity of the material, the speed of the drying agent and the layer height are obtained. These solutions are used in the thermal design of reactors for the thermal processing of multicomponent organic waste.

Regeneration of carboxylic acid-laden basic sorbents by leaching with a volatile base in an organic solvent

DOEpatents

King, C. Judson; Husson, Scott M.

1999-01-01

Carboxylic acids are sorbed from aqueous feedstocks onto a solid adsorbent. The acids are freed from the sorbent phase by treating it with an organic solution of alkylamine thus forming an alkylamine/carboxylic acid complex which is decomposed with improved efficiency to the desired carboxylic acid and the alkylamine. Carbon dioxide addition can be used to improve the adsorption or the carboxylic acids by the solid phase sorbent.

Solid-solution thermodynamics in Al-Li alloys

NASA Astrophysics Data System (ADS)

Alekseev, A. A.; Lukina, E. A.

2016-05-01

The relative equilibrium concentrations of lithium atoms distributed over different electron-structural states has been estimated. The possibility of the existence of various nonequilibrium electron-structural states of Li atoms in the solid solution in Al has been substantiated thermodynamically. Upon the decomposition of the supersaturated solid solution, the supersaturation on three electron-structural states of Li atoms that arises upon the quenching of the alloy can lead to the formation of lithium-containing phases in which the lithium atoms enter in one electron-structural state.

Concentration Dependent Physical Properties of Ge1-xSnx Solid Solution

NASA Astrophysics Data System (ADS)

Jivani, A. R.; Jani, A. R.

2011-12-01

Our own proposed potential is used to investigate few physical properties like total energy, bulk modulus, pressure derivative of bulk modulus, elastic constants, pressure derivative of elastic constants, Poisson's ratio and Young's modulus of Ge1-xSnx solid solution with x is atomic concentration of α-Sn. The potential combines linear plus quadratic types of electron-ion interaction. First time screening function proposed by Sarkar et al is used to investigate the properties of the Ge-Sn solid solution system.

New anatase-type Til-2xNbxAlxO2 solid solution nanoparticles: direct formation, phase stability, and photocatalytic performance.

PubMed

Hirano, Masanori; Ito, Takaharu

2006-12-01

New anatase-type titania solid solutions co-doped with niobium and aluminum (Til-2xNbxAIlxO2 (X = 0 -0.20)) were synthesized as nanoparticles from precursor solutions of TiOSO4, NbCl5, and Al(NO3)3 under mild hydrothermal conditions at 180 degrees C for 5 h using the hydrolysis of urea. The lattice parameters a0 and c0 of anatase slightly and gradually increased, when the content of niobium and aluminum increased from X = 0 to 0.20. The crystallite size of anatase increased from 12 to 28 nm with increasing the value of X from 0 to 0.20. Their photocatalytic activity and adsorptivity were evaluated separately by the measurement of the concentration of methylene blue (MB) remained in the solution in the dark or under UV-light irradiation. The adsorptivity of TiO2 was improved by the formation of anatase-type Til-2xNbxAlxO2 solid solutions. The photocatalytic activity of anatase-type Til-2xNbxAlxO2 solid solutions was superior to that of commercially available anatase-type pure TiO2 (ST-01) and anatase-type pure TiO2 hydrothermally prepared. The new anatase phase of Til-2xNbxAlxO2 (X = 0-0.20) solid solutions existed stably up to 850 0C during heat treatment in air. In comparison with hydrothermal pure TiO2, the starting temperature of anatase-to-rutile phase transformation was delayed by the formation of Ti1-2xNbxAlxO, (X = 0-0.20) solid solutions, although its completing temperature was accelerated.

Solid Waste Management Solutions for a Rapidly Urbanizing Area in Thailand: Recommendations Based on Stakeholder Input.

PubMed

Yukalang, Nachalida; Clarke, Beverley; Ross, Kirstin

2018-06-21

Municipal solid waste is a significant problem, particularly in developing countries that lack sufficient infrastructure and useable land mass to process it in an appropriate manner. Some developing nations are experiencing a combination of issues that prevent proper management of solid waste. This paper reviews the management of municipal solid waste in northeast Thailand, using the Tha Khon Yang Sub-district Municipality (TKYSM) in Maha Sarakham Province as a case study. The combination of rapid population and economic growth and its associated affluence has led to an increase in the use of consumer items and a concomitant increase in the production of municipal solid waste. In the TKYSM there is pressure on local government to establish a suitable waste management program to resolve the escalating waste crisis. The aim of this study is to provide viable solutions to waste management challenges in the TKYSM, and potentially to offer guidance to other similar localities also facing the same challenges. It is well established that successful changes to waste management require an understanding of local context and consideration of specific issues within a region. Therefore, extensive community consultation and engagement with local experts was undertaken to develop an understanding of the particular waste management challenges of the TKYSM. Research methods included observations, one-on-one interviews and focus groups with a range of different stakeholders. The outcomes of this research highlight a number of opportunities to improve local infrastructure and operational capacity around solid waste management. Waste management in rural and urban areas needs to be approached differently. Solutions include: development of appropriate policy and implementation plans (based around the recommendations of this paper); reduction of the volume of waste going to landfill by establishing a waste separation system; initiation of a collection service that supports waste separation at source; educating the citizens of the municipality; and the local government staff, and for the local government to seek external support from the local temples and expertise from the nearby university.

Molecularly imprinted solid-phase extraction coupled to liquid chromatography for determination of Sudan dyes in preserved beancurds.

PubMed

Yan, Hongyuan; Qiao, Jindong; Pei, Yuning; Long, Tao; Ding, Wen; Xie, Kun

2012-05-01

New molecularly imprinted microspheres synthesized by suspension polymerisation using phenylamine and naphthol as mimic template were successfully applied as selective sorbents for the solid-phase extraction used for the simultaneous determination of four Sudan dyes from preserved beancurd products. The obtained imprinted microspheres showed good recognition and selectivity to the four Sudan dyes in aqueous solution and the affinity could be easily controlled by adjusting the property of the solution. Under the selected experimental condition, the recoveries of the Sudan dyes in preserved beancurds at three spiked levels were ranged between 90.2-104.5% with the relative standard deviation of less than 6.8%. The limit of detection (LOD) and limit of quantification (LOQ) based on a signal-to-noise of 3 and 10 were in the range of 0.005-0.009μgg(-1) and 0.015-0.030μgg(-1), respectively. Comparing with alumina and C18-based extraction, the selectivity and repeatability of molecularly imprinted solid-phase extraction (MISPE) were obviously improved. This method could be potentially applied for the determination of Sudan dyes in complicated food samples. Copyright © 2011 Elsevier Ltd. All rights reserved.

La-Sr-Ni-Co-O based perovskite-type solid solutions as catalyst precursors in the CO 2 reforming of methane

NASA Astrophysics Data System (ADS)

Valderrama, Gustavo; Kiennemann, Alain; Goldwasser, Mireya R.

La 1- xSr xNi 0.4Co 0.6O 3 and La 0.8Sr 0.2Ni 1- yCo yO 3 solid solutions with perovskite-type structure were synthesized by the sol-gel resin method and used as catalytic precursors in the dry reforming of methane with CO 2 to syngas, between 873 and 1073 K at atmospheric pressure under continuous flow of reactant gases with CH 4/CO 2 = 1 ratio. These quaternary oxides were characterized by X-ray diffraction (XRD), BET specific surface area and temperature-programmed reduction (TPR) techniques. XRD analyses of the more intense diffraction peaks and cell parameter measurements showed formation of La-Sr-Ni-Co-O solid solutions with La 0.9Sr 0.1CoO 3 and/or La 0.9Sr 0.1NiO 3 as the main crystallographic phases present on the solids depending on the degree of substitution. TPR analyses showed that Sr doping decreases the temperature of reduction via formation of intermediary species producing Ni 0, Co 0 with particle sizes in the range of nanometers over the SrO and La 2O 3 phases. These metallic nano particles highly dispersed in the solid matrix are responsible for the high activity shown during the reaction and avoid carbon formation. The presence of Sr in doping quantities also promotes the secondary reactions of carbon formation and water-gas shift in a very small extension during the dry reforming reaction.

Methods for the preparation and analysis of solids and suspended solids for total mercury

USGS Publications Warehouse

Olund, Shane D.; DeWild, John F.; Olson, Mark L.; Tate, Michael T.

2004-01-01

The methods documented in this report are utilized by the Wisconsin District Mercury Lab for analysis of total mercury in solids (soils and sediments) and suspended solids (isolated on filters). Separate procedures are required for the different sample types. For solids, samples are prepared by room-temperature acid digestion and oxidation with aqua regia. The samples are brought up to volume with a 5 percent bromine monochloride solution to ensure complete oxidation and heated at 50?C in an oven overnight. Samples are then analyzed with an automated flow injection system incorporating a cold vapor atomic fluorescence spectrometer. A method detection limit of 0.3 ng of mercury per digestion bomb was established using multiple analyses of an environmental sample. Based on the range of masses processed, the minimum sample reporting limit varies from 0.6 ng/g to 6 ng/g. Suspended solids samples are oxidized with a 5 percent bromine monochloride solution and held at 50?C in an oven for 5 days. The samples are then analyzed with an automated flow injection system incorporating a cold vapor atomic fluorescence spectrometer. Using a certified reference material as a surrogate for an environmental sample, a method detection limit of 0.059 ng of mercury per filter was established. The minimum sample reporting limit varies from 0.059 ng/L to 1.18 ng/L, depending on the volume of water filtered.

Effect of varying Ga content in ZnO:GaN solid solution synthesized by solution combustion technique for photocatalytic applications

NASA Astrophysics Data System (ADS)

Menon, Sumithra Sivadas; Janani, R.; Baskar, K.; Gupta, Bhavana; Singh, Shubra

2017-05-01

ZnO:GaN (oxy)nitride solid solution has been established as the most efficient non-oxide photocatalyst for water splitting under visible irradiation with one step photoexcitation and also boasts a band gap tunability from 2.8 eV to 2.5 eV[1]. The solid solution of GaN in ZnO is formed by the intersubstitution of few of Zn/O ions by Ga/N ions, and this results in the introduction of new defect levels above the valence band which narrows the effective band gap enabling activity under visible region of spectra. In this work, we report the synthesis of ZnO:GaN solid solution by a solution combustion technique where metal nitrates and urea are used as precursors. The Zn/Ga ratio was varied from 16 to 1 in the precursors. The as synthesized samples were characterized as phase pure by X-ray diffraction, where the wurtzite structure was retained up to Zn/Ga ratio of 5. The Diffuse reflectance spectroscopy studies revealed that as the Ga content in the solid solution increases there is a reduction in band gap, from 2.9 eV to 2.4 eV. The reduced band gap of the samples facilitates its photocatalytic activity under visible region of the spectra as evaluated by photoelectrochemical measurements.

Method of fabricating lipid bilayer membranes on solid supports

NASA Technical Reports Server (NTRS)

Cho, Nam-Joon (Inventor); Frank, Curtis W. (Inventor); Glenn, Jeffrey S. (Inventor); Cheong, Kwang Ho (Inventor)

2012-01-01

The present invention provides a method of producing a planar lipid bilayer on a solid support. With this method, a solution of lipid vesicles is first deposited on the solid support. Next, the lipid vesicles are destabilized by adding an amphipathic peptide solution to the lipid vesicle solution. This destabilization leads to production of a planar lipid bilayer on the solid support. The present invention also provides a supported planar lipid bilayer, where the planar lipid bilayer is made of naturally occurring lipids and the solid support is made of unmodified gold or titanium oxide. Preferably, the supported planar lipid bilayer is continuous. The planar lipid bilayer may be made of any naturally occurring lipid or mixture of lipids, including, but not limited to phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylinsitol, cardiolipin, cholesterol, and sphingomyelin.

Preparation of UO2, ThO2 and (Th,U)O2 pellets from photochemically-prepared nano-powders

NASA Astrophysics Data System (ADS)

Pavelková, Tereza; Čuba, Václav; de Visser-Týnová, Eva; Ekberg, Christian; Persson, Ingmar

2016-02-01

Photochemically-induced preparation of nano-powders of crystalline uranium and/or thorium oxides and their subsequent pelletizing has been investigated. The preparative method was based on the photochemically induced formation of amorphous solid precursors in aqueous solution containing uranyl and/or thorium nitrate and ammonium formate. The EXAFS analyses of the precursors shown that photon irradiation of thorium containing solutions yields a compound with little long-range order but likely "ThO2 like" and the irradiation of uranium containing solutions yields the mixture of U(IV) and U(VI) compounds. The U-containing precursors were carbon free, thus allowing direct heat treatment in reducing atmosphere without pre-treatment in the air. Subsequent heat treatment of amorphous solid precursors at 300-550 °C yielded nano-crystalline UO2, ThO2 or solid (Th,U)O2 solutions with high purity, well-developed crystals with linear crystallite size <15 nm. The prepared nano-powders of crystalline oxides were pelletized without any binder (pressure 500 MPa), the green pellets were subsequently sintered at 1300 °C under an Ar:H2 (20:1) mixture (UO2 and (Th,U)O2 pellets) or at 1600 °C in ambient air (ThO2 pellets). The theoretical density of the sintered pellets varied from 91 to 97%.

Sample Results from MCU Solids Outage

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

Peters, T.; Washington, A.; Oji, L.

2014-09-22

Savannah River National Laboratory (SRNL) has received several solid and liquid samples from MCU in an effort to understand and recover from the system outage starting on April 6, 2014. SRNL concludes that the presence of solids in the Salt Solution Feed Tank (SSFT) is the likely root cause for the outage, based upon the following discoveries: A solids sample from the extraction contactor #1 proved to be mostly sodium oxalate; A solids sample from the scrub contactor#1 proved to be mostly sodium oxalate; A solids sample from the Salt Solution Feed Tank (SSFT) proved to be mostly sodium oxalate;more » An archived sample from Tank 49H taken last year was shown to contain a fine precipitate of sodium oxalate; A solids sample from ; A liquid sample from the SSFT was shown to have elevated levels of oxalate anion compared to the expected concentration in the feed. Visual inspection of the SSFT indicated the presence of precipitated or transferred solids, which were likely also in the Salt Solution Receipt Tank (SSRT). The presence of the solids coupled with agitation performed to maintain feed temperature resulted in oxalate solids migration through the MCU system and caused hydraulic issues that resulted in unplanned phase carryover from the extraction into the scrub, and ultimately the strip contactors. Not only did this carryover result in the Strip Effluent (SE) being pushed out of waste acceptance specification, but it resulted in the deposition of solids into several of the contactors. At the same time, extensive deposits of aluminosilicates were found in the drain tube in the extraction contactor #1. However it is not known at this time how the aluminosilicate solids are related to the oxalate solids. The solids were successfully cleaned out of the MCU system. However, future consideration must be given to the exclusion of oxalate solids into the MCU system. There were 53 recommendations for improving operations recently identified. Some additional considerations or additional details are provided below as recommendations. From this point on, IC-Anions analyses of the DSSHT should be part of the monthly routine analysis in order to spot negative trends in the oxalate leaving the MCU system. Care must be taken to monitor the oxalate content to watch for sudden precipitation of oxalate salts in the system; Conduct a study to optimize the cleaning strategy at ARP-MCU through decreasing the concentration or entirely eliminating the oxalic acid; The contents of the SSFT should remain unagitated. Routine visual observation should be maintained to ensure there is not a large buildup of solids. As water with agitation provided sufficient removal of the solids in the feed tank, it should be considered as a good means for dissolving oxalate solids if they are found in the future; Conduct a study to improve prediction of oxalate solubility in salt batch feed materials. As titanium and mercury have been found in various solids in this report, evaluate if either element plays a role in oxalate solubility during processing; Salt batch characterization focuses primarily on characterization and testing of unaltered Tank 21H material; however, non-typical feeds are developed through cleaning, washing, and/or sump transfers. As these solutions are processed through MCU, they may precipitate solids or reduce performance. Salt batch characterization and testing should be expanded to encompass a broader range of feeds that may be processed through ARPMCU.« less

Conformal Electroplating of Azobenzene-Based Solar Thermal Fuels onto Large-Area and Fiber Geometries.

PubMed

Zhitomirsky, David; Grossman, Jeffrey C

2016-10-05

There is tremendous growth in fields where small functional molecules and colloidal nanomaterials are integrated into thin films for solid-state device applications. Many of these materials are synthesized in solution and there often exists a significant barrier to transition them into the solid state in an efficient manner. Here, we develop a methodology employing an electrodepositable copolymer consisting of small functional molecules for applications in solar energy harvesting and storage. We employ azobenzene solar thermal fuel polymers and functionalize them to enable deposition from low concentration solutions in methanol, resulting in uniform and large-area thin films. This approach enables conformal deposition on a variety of conducting substrates that can be either flat or structured depending on the application. Our approach further enables control over film growth via electrodepsition conditions and results in highly uniform films of hundreds of nanometers to microns in thickness. We demonstrate that this method enables superior retention of solar thermal fuel properties, with energy densities of ∼90 J/g, chargeability in the solid state, and exceptional materials utilization compared to other solid-state processing approaches. This novel approach is applicable to systems such as photon upconversion, photovoltaics, photosensing, light emission, and beyond, where small functional molecules enable solid-state applications.

COMPUTATIONAL MODELING OF CIRCULATING FLUIDIZED BED REACTORS

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

Ibrahim, Essam A

2013-01-09

Details of numerical simulations of two-phase gas-solid turbulent flow in the riser section of Circulating Fluidized Bed Reactor (CFBR) using Computational Fluid Dynamics (CFD) technique are reported. Two CFBR riser configurations are considered and modeled. Each of these two riser models consist of inlet, exit, connecting elbows and a main pipe. Both riser configurations are cylindrical and have the same diameter but differ in their inlet lengths and main pipe height to enable investigation of riser geometrical scaling effects. In addition, two types of solid particles are exploited in the solid phase of the two-phase gas-solid riser flow simulations tomore » study the influence of solid loading ratio on flow patterns. The gaseous phase in the two-phase flow is represented by standard atmospheric air. The CFD-based FLUENT software is employed to obtain steady state and transient solutions for flow modulations in the riser. The physical dimensions, types and numbers of computation meshes, and solution methodology utilized in the present work are stated. Flow parameters, such as static and dynamic pressure, species velocity, and volume fractions are monitored and analyzed. The differences in the computational results between the two models, under steady and transient conditions, are compared, contrasted, and discussed.« less

Method for characterizing and choosing the solid mixed fuel for microthrusters of microelectromechanical systems

NASA Astrophysics Data System (ADS)

Futko, S. I.; Bondarenko, V. P.; Dolgii, L. N.

2012-05-01

We propose a method for characterizing and choosing solid mixed fuels for use as the solid-fuel charge of microthrusters of microelectromechanical systems. The method is based on the solution of the problem on the dependence of impulse responses of such a microthruster on the diameter of the outlet cross-section of its combustion chamber and the microkinetic parameters of the fuel. The variants of choosing the above fuels have been illustrated using glycidyl azide polymer/RDX as the example of a solid fuel mixture. The paper presents the characteristic criteria determining the composition of mixed fuels for the microthruster of a microelectromechanical system and considers the main types of "direct" and "inverse" problems arising in characterizing and choosing such fuels.

Minoxidil (Mx) as a prophylaxis of doxorubicin--induced alopecia.

PubMed

Rodriguez, R; Machiavelli, M; Leone, B; Romero, A; Cuevas, M A; Langhi, M; Romero Acuña, L; Romero Acuña, J; Amato, S; Barbieri, M

1994-10-01

Minoxidil (Mx) is known to induce hair growth in men with male-pattern baldness. Based on this potential, the effectiveness of Mx 2% topical solution was evaluated in cancer patients (pts) to prevent doxorubicin-induced alopecia. 48 female pts with different types of solid tumors treated with doxorubicin-based chemotherapy in a dose range of 50-60 mg/m2/cycle were randomly assigned to receive Mx 2% topical solution or placebo. 88% and 92% of pts in both arms showed severe alopecia (p = ns). No adverse effects were observed. In this study Mx 2% topical solution was non-toxic but was not effective in the prevention of chemotherapy-induced alopecia.

Planet Patrol. An Educational Unit on Solid Waste Solutions for Grades 4-6.

ERIC Educational Resources Information Center

Shively, Patti J.; And Others

This educational unit on solid waste solutions is intended to convey to students an understanding of the four methods of solid waste handling, in priority order, as recommended by the Environmental Protection Agency: (1) reduction in the volume of waste produced; (2) recycling and composting; (3) waste combustion, i.e., incineration of waste; and…

Solid-phase extraction microfluidic devices for matrix removal in trace element assay of actinide materials

DOE PAGES

Gao, Jun; Manard, Benjamin Thomas; Castro, Alonso; ...

2017-02-02

Advances in sample nebulization and injection technology have significantly reduced the volume of solution required for trace impurity analysis in plutonium and uranium materials. Correspondingly, we have designed and tested a novel chip-based microfluidic platform, containing a 100-µL or 20-µL solid-phase microextraction column, packed by centrifugation, which supports nuclear material mass and solution volume reductions of 90% or more compared to standard methods. Quantitative recovery of 28 trace elements in uranium was demonstrated using a UTEVA chromatographic resin column, and trace element recovery from thorium (a surrogate for plutonium) was similarly demonstrated using anion exchange resin AG MP-1. Of ninemore » materials tested, compatibility of polyvinyl chloride (PVC), polypropylene (PP), and polytetrafluoroethylene (PTFE) chips with the strong nitric acid media was highest. Finally, the microcolumns can be incorporated into a variety of devices and systems, and can be loaded with other solid-phase resins for trace element assay in high-purity metals.« less

Sensitivity enhancement for nitrophenols using cationic surfactant-modified activated carbon for solid-phase extraction surface-assisted laser desorption/ionization mass spectrometry.

PubMed

Chen, Y C; Tsai, M F

2000-01-01

Previous work has demonstrated that a combination of solid-phase extraction with surface-assisted laser desorption/ionization (SPE-SALDI) mass spectrometry can be applied to the determination of trace nitrophenols in water. An improved method to lower the detection limit of this hyphenated technique is described in this present study. Activated carbon powder is used as both the SPE adsorbent and the SALDI solid in the analysis by SPE-SALDI. The surface of the activated carbon is modified by passing an aqueous solution of a cationic surfactant through the SPE cartridge. The results demonstrate that the sensitivity for nitrophenols in the analysis by SPE-SALDI can be improved by using cationic surfactants to modify the surface of the activated carbon. The detection limit for nitrophenols is about 25 ppt based on a signal-to-noise ratio of 3 by sampling from 100 mL of solution. Copyright 2000 John Wiley & Sons, Ltd.

Solid-phase extraction microfluidic devices for matrix removal in trace element assay of actinide materials

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

Gao, Jun; Manard, Benjamin Thomas; Castro, Alonso

Advances in sample nebulization and injection technology have significantly reduced the volume of solution required for trace impurity analysis in plutonium and uranium materials. Correspondingly, we have designed and tested a novel chip-based microfluidic platform, containing a 100-µL or 20-µL solid-phase microextraction column, packed by centrifugation, which supports nuclear material mass and solution volume reductions of 90% or more compared to standard methods. Quantitative recovery of 28 trace elements in uranium was demonstrated using a UTEVA chromatographic resin column, and trace element recovery from thorium (a surrogate for plutonium) was similarly demonstrated using anion exchange resin AG MP-1. Of ninemore » materials tested, compatibility of polyvinyl chloride (PVC), polypropylene (PP), and polytetrafluoroethylene (PTFE) chips with the strong nitric acid media was highest. Finally, the microcolumns can be incorporated into a variety of devices and systems, and can be loaded with other solid-phase resins for trace element assay in high-purity metals.« less

The solid-solution region for the langasite-type Ca3TaGa3Si2O14 crystal as determined by a lever rule

NASA Astrophysics Data System (ADS)

Zhao, Hengyu; Uda, Satoshi; Maeda, Kensaku; Nozawa, Jun; Koizumi, Haruhiko; Fujiwara, Kozo

2015-04-01

A lever rule was applied to data concerning the compositions and proportions of secondary phases coexisting with a Ca3TaGa3Si2O14 (CTGS) matrix to determine the boundary compositions of the solid-solution region for CTGS at 1320 °C, as a means of ascertaining the solid-solution for the langasite-type phase in the quaternary CaO-Ta2O5-Ga2O3-SiO2 system. The compositions and proportions of secondary phases were assessed by electron probe micro-analysis as well as through back-scattered electron images. The experimental results showed that the narrow solid-solution region for CTGS is located in a Ta-poor, Ga-poor and Si-rich region relative to its stoichiometric composition.

Dynamics of Re(2,2'-bipyridine)(CO)3Cl MLCT formation and decay after picosecond pulsed X-ray excitation and femtosecond UV excitation.

PubMed

Zhao, Liyan; Odaka, Hideho; Ono, Hiroshi; Kajimoto, Shinji; Hatanaka, Koji; Hobley, Jonathan; Fukumura, Hiroshi

2005-01-01

The dynamics of Re(2,2'-bipyridine)(CO)3Cl MLCT state formation and decay were determined after femtosecond UV laser excitation and picosecond pulsed X-ray excitation, in an N,N-dimethylformamide (DMF) solution as well as in its solid form. At room temperature, after UV excitation, this MLCT excited state emits both in DMF solution and in the solid form. Transient absorption spectra were measured in solution at various delay times following excitation by a 160 fs, 390 nm laser pulse. There was a prompt absorption increase at around 460 nm occurring within the pump probe convolution (<1 ps), which was assigned to the formation of the 3MLCT state. This transient absorbance was constant over 100 ps. In contrast to the solution state, in the solid state, the emission maximum slightly red-shifts with increasing time after laser excitation. In both solid and solution the emission rises within the system response time. The solid sample exhibited a 1.4 ns emission decay that was not observed for the solution sample. The emission rise from a solid sample after 20 ps pulsed X-ray excitation was significantly slower than the system's time resolution. It is proposed that kinetically energetic electrons are ejected following X-ray induced ionisation, creating ionised tracks in which energetic cations and electrons take time to recombine yielding delayed 3MLCT states that emit.

Ab initio calculation of excess properties of La{sub 1−x}(Ln,An){sub x}PO{sub 4} solid solutions

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

Li, Yan; JARA High-Performance Computing, Schinkelstrasse 2, 52062 Aachen; Kowalski, Piotr M., E-mail: p.kowalski@fz-juelich.de

2014-12-15

We used ab initio computational approach to predict the excess enthalpy of mixing and the corresponding regular/subregular model parameters for La{sub 1−x}Ln{sub x}PO{sub 4} (Ln=Ce,…, Tb) and La{sub 1−x}An{sub x}PO{sub 4} (An=Pu, Am and Cm) monazite-type solid solutions. We found that the regular model interaction parameter W computed for La{sub 1−x}Ln{sub x}PO{sub 4} solid solutions matches the few existing experimental data. Within the lanthanide series W increases quadratically with the volume mismatch between LaPO{sub 4} and LnPO{sub 4} endmembers (ΔV=V{sub LaPO{sub 4}}−V{sub LnPO{sub 4}}), so that W(kJ/mol)=0.618(ΔV(cm{sup 3}/mol)){sup 2}. We demonstrate that this relationship also fits the interaction parameters computedmore » for La{sub 1−x}An{sub x}PO{sub 4} solid solutions. This shows that lanthanides can be used as surrogates for investigation of the thermodynamic mixing properties of actinide-bearing solid solutions. - Highlights: • The excess enthalpies of mixing for monazite-type solid solutions are computed. • The excess enthalpies increase with the endmembers volume mismatch. • The relationship derived for lanthanides is transferable to La{sub 1−x}An{sub x}PO{sub 4} systems.« less

X-ray absorption investigation of local structural disorder in Ni 1-xFe x (x=0.10, 0.20, 0.35, and 0.50) alloys

DOE PAGES

Zhang, Fuxiang X.; Jin, Ke; Zhao, Shijun; ...

2017-04-27

Defect energetics in structural materials has long been recognized to be affected by specific alloy compositions. Significantly enhanced radiation resistance has recently been observed in concentrated solid-solution alloys. However, the link between local structural disorder and modified defect dynamics in solid solutions remains unclear. To reveal the atomic-level lattice distortion, the local structures of Ni and Fe in Ni 1-xFe x (x=0.1, 0.2, 0.35 and 0.5) solid solution alloys were measured with extended X-ray absorption fine structure (EXAFS) technique. The lattice constant and the first-neighbor distances increase with the increase of Fe content in the solid solutions. EXAFS measurements havemore » revealed that the bond length of Fe with surrounding atoms is 0.01-0.03 larger than that of Ni in the alloy systems. Debye-Waller factor of the Fe-Fe bonds in all the systems is also slightly larger than that of the Ni-Ni bond. EXAFS fitting suggests that the local structural disorder is enhanced with the addition of Fe elements in the solid solution. The local bonding environments from ab initio calculation are in good agreement with the experimental results, which suggest that the Fe has a larger first-neighbor bonding distance than that of Ni, and thus Ni atom inside the Ni-Fe solid solution alloys undergoes compressive strain.« less

X-ray absorption investigation of local structural disorder in Ni 1-xFe x (x=0.10, 0.20, 0.35, and 0.50) alloys

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

Zhang, Fuxiang X.; Jin, Ke; Zhao, Shijun

Defect energetics in structural materials has long been recognized to be affected by specific alloy compositions. Significantly enhanced radiation resistance has recently been observed in concentrated solid-solution alloys. However, the link between local structural disorder and modified defect dynamics in solid solutions remains unclear. To reveal the atomic-level lattice distortion, the local structures of Ni and Fe in Ni 1-xFe x (x=0.1, 0.2, 0.35 and 0.5) solid solution alloys were measured with extended X-ray absorption fine structure (EXAFS) technique. The lattice constant and the first-neighbor distances increase with the increase of Fe content in the solid solutions. EXAFS measurements havemore » revealed that the bond length of Fe with surrounding atoms is 0.01-0.03 larger than that of Ni in the alloy systems. Debye-Waller factor of the Fe-Fe bonds in all the systems is also slightly larger than that of the Ni-Ni bond. EXAFS fitting suggests that the local structural disorder is enhanced with the addition of Fe elements in the solid solution. The local bonding environments from ab initio calculation are in good agreement with the experimental results, which suggest that the Fe has a larger first-neighbor bonding distance than that of Ni, and thus Ni atom inside the Ni-Fe solid solution alloys undergoes compressive strain.« less

New laser media based on microporous glasses

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

Altshuler, G.B.; Bakanov, V.A.; Dulneva, E.G.

The results of the investigation of new class of the laser media based on dye solutions impregnated microporous glasses are presented. Based on such media highly effective active elements of tunable dye lasers and passive modulators for solid-state lasers are created. This article is devoted to laser media of the new type - the heterogenous solid-liquid media on the basis of the impregnated by the solutions of the dyes of the microporous glasses. The microporous glasses represent themselves the products of the leaching of heat - treated sodium borosilicate glasses of a certain composition range. As a result of heatmore » treatment is realized the phase separated glass. It consists of two interconnected phases: the silica rich phase and the chemical unstable sodium - borate - rich phase. If we place this glass in the acid then the ions of sodium and borate will be transfered to the solution. As a result we obtain the porous glass and this process produces the continuous claster. Therefore it could be easily impregnated by liquids and gases. We now have the technology that permits us to obtain the samples with the volume porosity from ten to fifty percent and the size of this poroses could be varied from twenty angstroms up to one thousand angstroms.« less

Injection and swirl driven flowfields in solid and liquid rocket motors

NASA Astrophysics Data System (ADS)

Vyas, Anand B.

In this work, we seek approximate analytical solutions to describe the bulk flow motion in certain types of solid and liquid rocket motors. In the case of an idealized solid rocket motor, a cylindrical double base propellant grain with steady regression rate is considered. The well known inviscid profile determined by Culick is extended here to include the effects of viscosity and steady grain regression. The approximate analytical solution for the cold flow is obtained from similarity principles, perturbation methods and the method of variation of parameters. The velocity, vorticity, pressure gradient and the shear stress distributions are determined and interpreted for different rates of wall regression and injection Reynolds number. The liquid propellant rocket engine considered here is based on a novel design that gives rise to a cyclonic flow. The resulting bidirectional motion is triggered by the tangential injection of an oxidizer just upstream of the chamber nozzle. Velocity, vorticity and pressure gradient distributions are determined for the bulk gas dynamics using a non-reactive inviscid model. Viscous corrections are then incorporated to explain the formation of a forced vortex near the core. Our results compare favorably with numerical simulations and experimental measurements obtained by other researchers. They also indicate that the bidirectional vortex in a cylindrical chamber is a physical solution of the Euler equations. In closing, we investigate the possibility of multi-directional flow behavior as predicted by Euler's equation and as reported recently in laboratory experiments.

Structure of a bimetallic strip produced by plasma spraying of a TiAl powder on a niobium sheet

NASA Astrophysics Data System (ADS)

Povarova, K. B.; Antonova, A. V.; Burmistrov, V. I.; Safronov, B. V.; Perfilov, L. S.; Chukanov, A. P.

2007-10-01

Ti-48 at % Al alloy granules produced by centrifugal spraying are milled into a powder with a particle size of 40 100 μm, and are applied onto a niobium foil using plasma spraying in an argon atmosphere. The fabricated TiAl/Nb bimetallic strip consists of a 100-μm-thick niobium layer and a porous 300-to 400-μm-thick TiAl layer formed by flattened particles. Directly after the preparation of the bimetallic strip, the surface of the TiAl porous layer is rough. Vacuum annealing at 1000, 1100, and 1200°C for 0.5 1.5 h leads to intense pore healing. After deposition and annealing, the interlayer adhesion is strong. The preparation of TiAl granules and spraying of the powder is accompanied by aluminum depletion of the Ti-48 at % Al alloy to 42 45 at % and an increase in the fraction of the α2-Ti3Al phase in the deposited layer. The prepared material has a duplex structure. An intermediate diffuse layer characterized by a variable composition and thickness is formed at the interface. This layer consists of two solid solutions; one of them, which is formed at the TiAl layer, is an α2-Ti3Al-based solid solution of niobium and the other, which is formed at the niobium foil, is a niobium-based solid solution of titanium and aluminum.

Solid-water detoxifying reagents for chemical and biological agents

DOEpatents

Hoffman, Dennis M [Livermore, CA; Chiu, Ing Lap [Castro Valley, CA

2006-04-18

Formation of solid-water detoxifying reagents for chemical and biological agents. Solutions of detoxifying reagent for chemical and biological agents are coated using small quantities of hydrophobic nanoparticles by vigorous agitation or by aerosolization of the solution in the presence of the hydrophobic nanoparticles to form a solid powder. For example, when hydrophobic fumed silica particles are shaken in the presence of IN oxone solution in approximately a 95:5-weight ratio, a dry powder results. The hydrophobic silica forms a porous coating of insoluble fine particles around the solution. Since the chemical or biological agent tends to be hydrophobic on contact with the weakly encapsulated detoxifying solution, the porous coating breaks down and the detoxifying reagent is delivered directly to the chemical or biological agent for maximum concentration at the point of need. The solid-water (coated) detoxifying solutions can be blown into contaminated ventilation ducting or other difficult to reach sites for detoxification of pools of chemical or biological agent. Once the agent has been detoxified, it can be removed by flushing the area with air or other techniques.

Influence of isotopic disorder on solid state amorphization and polyamorphism in solid H2O -D2O solutions

NASA Astrophysics Data System (ADS)

Gromnitskaya, E. L.; Danilov, I. V.; Lyapin, A. G.; Brazhkin, V. V.

2015-10-01

We present a low-temperature and high-pressure ultrasonic study of elastic properties of isotopic H2O-D2O solid solutions, comparing their properties with those of the isotopically pure H2O and D2O ices. Measurements were carried out for solid state amorphization (SSA) from 1h to high-density amorphous (HDA) ice upon compression up to 1.8 GPa at 77 K and for the temperature-induced (77 -190 K ) u-HDA (unrelaxed HDA) → e-HDA (expanded HDA) → low-density amorphous (LDA )→1 c cascade of ice transformations near room pressure. There are many similarities in the elasticity behaviour of H2O ,D2O , and H2O-D2O solid solutions, including the softening of the shear elastic modulus as a precursor of SSA and the HDA →LDA transition. We have found significant isotopic effects during H/D substitution, including elastic softening of H2O -D2O solid solutions with respect to the isotopically pure ices in the case of the bulk moduli of ices 1c and 1h and for both bulk and shear elastic moduli of HDA ice at high pressures (>1 GPa ) . This softening is related to the configurational isotopic disorder in the solid solutions. At low pressures, the isotope concentration dependence of the elastic moduli of u-HDA ice changes remarkably and becomes monotonic with pronounced change of the bulk modulus (≈20 %) .

Analysis of 2H-Evaporator Acid Cleaning Samples

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

Hay, M.; Diprete, D.; Edwards, T.

The 2H-Evaporator acid cleaning solution samples were analyzed by SRNL to determine a composition for the scale present in the evaporator before recent acid cleaning. Composite samples were formed from the solution samples from the two acid cleaning cycles. The solution composition was converted to a weight percent scale solids basis under an assumed chemical composition. The scale composition produced from the acid cleaning solution samples indicates a concentration of 6.85 wt% uranium. An upper bound, onesided 95% confidence interval on the weight percent uranium value may be given as 6.9 wt% + 1.645 × 0.596 wt% = 7.9 wt%.more » The comparison of the composition from the current acid cleaning solutions with the composition of recent scale samples along with the thermodynamic modeling results provides reasonable assurance that the sample results provide a good representation of the overall scale composition in the evaporator prior to acid cleaning. The small amount of scale solids dissolved in the 1.5 M nitric acid during the evaporator cleaning process likely produced only a small amount of precipitation based on modeling results and the visual appearance of the samples.« less

Lessons learned: from dye-sensitized solar cells to all-solid-state hybrid devices.

PubMed

Docampo, Pablo; Guldin, Stefan; Leijtens, Tomas; Noel, Nakita K; Steiner, Ullrich; Snaith, Henry J

2014-06-25

The field of solution-processed photovoltaic cells is currently in its second spring. The dye-sensitized solar cell is a widely studied and longstanding candidate for future energy generation. Recently, inorganic absorber-based devices have reached new record efficiencies, with the benefits of all-solid-state devices. In this rapidly changing environment, this review sheds light on recent developments in all-solid-state solar cells in terms of electrode architecture, alternative sensitizers, and hole-transporting materials. These concepts are of general applicability to many next-generation device platforms. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigations on Mg-borate kinetics and mechanisms during evaporation, dilution and crystallization by Raman spectroscopy

NASA Astrophysics Data System (ADS)

Peng, Jiaoyu; Chen, Jing; Dong, Yaping; Li, Wu

2018-06-01

Raman spectra of boron-concentrated, diluted, and corresponding mother solutions of brine were recorded at 298.15 K. The main polyborate anions present and their interactions in brine during evaporation and dilution were proposed according to the Raman spectra. The polyborate anions B(OH)3, B3O3(OH)4-, B5O6(OH)4-, and B6O7(OH)62- were found to be the main forms in boron-concentrated brine with B3O3(OH)4- ion being the principal form. Diluting brines with water accelerated depolymerization of B5O6(OH)4- and B6O7(OH)62- anions into B(OH)3 and B3O3(OH)4- ions and generated OH- ions, causing the pH of the solutions to increase from 4.2 to almost 8.0. Mg-borates precipitated from all diluted solutions could be classified as either hexaborates or triborates. A mechanism of solid phase transformation was also proposed and discussed based on Raman spectra analysis and solid species and solution pH data.

Stresses due to Relative Sliding between Particles Surrounded by an Electrolyte Solution with Application to Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Zhang, Cong; Conlisk, A. T.

2013-11-01

Mechanical stresses in the solid phase of the electrodes within lithium-ion batteries have been the subject of much work recently with the emphasis on the stresses induced by lithium insertion to or extraction from the active solid material. The particles within lithium-ion battery electrodes can undergo relative motion with relative velocities of different magnitudes and directions. One mode of the relative motion, resembling the slider bearing motion, manifests itself as two particles sliding relative to each other within an electrolyte solution. The electrolyte solution within the narrow pores between the particles is the medium through which the particles interact with each other. The effect of the electrolyte solution is not conventionally considered. The relative motion of the particles induces significant pressures. The primary objective of this work is to develop a model based on the lubrication approximation to investigate the magnitude and direction of the stresses induced by this sliding motion. Other applications in the biomedical field are also discussed. Supported by DOE Graduate Automotive Technology Education (GATE) and OSU Center for Automotive Research.

Coatable Li4 SnS4 Solid Electrolytes Prepared from Aqueous Solutions for All-Solid-State Lithium-Ion Batteries.

PubMed

Choi, Young Eun; Park, Kern Ho; Kim, Dong Hyeon; Oh, Dae Yang; Kwak, Hi Ram; Lee, Young-Gi; Jung, Yoon Seok

2017-06-22

Bulk-type all-solid-state lithium-ion batteries (ASLBs) for large-scale energy-storage applications have emerged as a promising alternative to conventional lithium-ion batteries (LIBs) owing to their superior safety. However, the electrochemical performance of bulk-type ASLBs is critically limited by the low ionic conductivity of solid electrolytes (SEs) and poor ionic contact between the active materials and SEs. Herein, highly conductive (0.14 mS cm -1 ) and dry-air-stable SEs (Li 4 SnS 4 ) are reported, which are prepared using a scalable aqueous-solution process. An active material (LiCoO 2 ) coated by solidified Li 4 SnS 4 from aqueous solutions results in a significant improvement in the electrochemical performance of ASLBs. Side-effects of the exposure of LiCoO 2 to aqueous solutions are minimized by using predissolved Li 4 SnS 4 solution. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fluidized bed gasification of extracted coal

DOEpatents

Aquino, Dolores C.; DaPrato, Philip L.; Gouker, Toby R.; Knoer, Peter

1986-01-01

Coal or similar carbonaceous solids are extracted by contacting the solids in an extraction zone (12) with an aqueous solution having a pH above 12.0 at a temperature between 65.degree. C. and 110.degree. C. for a period of time sufficient to remove bitumens from the coal into said aqueous solution and the extracted solids are then gasified at an elevated pressure and temperature in a fluidized bed gasification zone (60) wherein the density of the fluidized bed is maintained at a value above 160 kg/m.sup.3. In a preferred embodiment of the invention, water is removed from the aqueous solution in order to redeposit the extracted bitumens onto the solids prior to the gasification step.

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

Lee, Seung Min; Knight, Travis W.; Voit, Stwart L.

The solid solution of (U1-yFPy)O- 2±x, has the same fluorite structure as UO 2±x lambda, and the lattice parameter is affected by dissolved fission product and oxygen concentrations. We investigated the relation between the lattice parameter and the concentrations of neodymium and oxygen in the fluorite structure of (U 1-yNd y)O 2±x using X-ray diffraction. Moreover, the lattice parameter behavior in the (U 1-yNd y)O 2±x, solid solution shows a linear change as a function of the oxygen-to-metal ratio and solubility of neodymium. The lattice parameter depends on the radii of ions forming the fluorite structure and also can bemore » expressed by a particular rule (modified Vegard's law). Furthermore, the numerical analyses of the lattice parameters for the stoichiometric and nonstoichionietric solid solutions were conducted, and the lattice parameter model for the (U1-yNdy)O 2±x, solid solution was assessed. There is a very linear relationship between the lattice parameter and the Nd and O concentration for the stoichiometry and nonstoichiometry of the (U 1-yNd y)O 2±x solid solution was verified.« less

Processing of solid solution, mixed uranium/refractory metal carbides for advanced space nuclear power and propulsion systems

NASA Astrophysics Data System (ADS)

Knight, Travis Warren

Nuclear thermal propulsion (NTP) and space nuclear power are two enabling technologies for the manned exploration of space and the development of research outposts in space and on other planets such as Mars. Advanced carbide nuclear fuels have been proposed for application in space nuclear power and propulsion systems. This study examined the processing technologies and optimal parameters necessary to fabricate samples of single phase, solid solution, mixed uranium/refractory metal carbides. In particular, the pseudo-ternary carbide, UC-ZrC-NbC, system was examined with uranium metal mole fractions of 5% and 10% and corresponding uranium densities of 0.8 to 1.8 gU/cc. Efforts were directed to those methods that could produce simple geometry fuel elements or wafers such as those used to fabricate a Square Lattice Honeycomb (SLHC) fuel element and reactor core. Methods of cold uniaxial pressing, sintering by induction heating, and hot pressing by self-resistance heating were investigated. Solid solution, high density (low porosity) samples greater than 95% TD were processed by cold pressing at 150 MPa and sintering above 2600 K for times longer than 90 min. Some impurity oxide phases were noted in some samples attributed to residual gases in the furnace during processing. Also, some samples noted secondary phases of carbon and UC2 due to some hyperstoichiometric powder mixtures having carbon-to-metal ratios greater than one. In all, 33 mixed carbide samples were processed and analyzed with half bearing uranium as ternary carbides of UC-ZrC-NbC. Scanning electron microscopy, x-ray diffraction, and density measurements were used to characterize samples. Samples were processed from powders of the refractory mono-carbides and UC/UC 2 or from powders of uranium hydride (UH3), graphite, and refractory metal carbides to produce hypostoichiometric mixed carbides. Samples processed from the constituent carbide powders and sintered at temperatures above the melting point of UC showed signs of liquid phase sintering and were shown to be largely solid solutions. Pre-compaction of mixed carbide powders prior to sintering was shown to be necessary to achieve high densities. Hypostoichiometric, samples processed at 2500 K exhibited only the initial stage of sintering and solid solution formation. Based on these findings, a suggested processing methodology is proposed for producing high density, solid solution, mixed carbide fuels. Pseudo-binary, refractory carbide samples hot pressed at 3100 K and 6 MPa showed comparable densities (approximately 85% of the theoretical value) to samples processed by cold pressing and sintering at temperatures of 2800 K.

Pressure-coupled combustion response model for solid propellants based on Zeldovich-Novozhilov approach

NASA Technical Reports Server (NTRS)

Harstad, K. G.; Strand, L. D.

1987-01-01

An exact analytical solution is given to the problem of long-time propellant thermal response to a specified pressure oscillation. Coupling to the gas phase is made using the quasisteady Zeldovich-Novozhilov approximation. Explicit linear and lowest order (quadratic) nonlinear expressions for propellant response are obtained from the implicit nonlinear solutions. Using these expressions, response curves are presented for an ammonium perchlorate composite propellant and HMX monopropellant.

The vibrational spectra and structure of 4-methyl oxaloacetate (carbomethoxypyruvic acid)

NASA Astrophysics Data System (ADS)

Schiering, David W.; Katon, J. E.

1986-04-01

The vibrational spectra of solid 4-methyl oxalocetate have been recorded. Infrared spectra were collected at ambient and liquid nitrogen temperatures; Raman spectra were collected at ambient temperature only. A tentative vibrational assignment of the solid is proposed based on a dimer structure composed of two enolic monomer units hydrogen bonded through the carboxylic acid group. 4-Methyl oxaloacetate was found to undergo keto—enol tautomerization in solution, and the solvent dependency of this equilibrium was demonstrated.

Transformation of meta-stable calcium silicate hydrates to tobermorite: reaction kinetics and molecular structure from XRD and NMR spectroscopy

PubMed Central

2009-01-01

Understanding the integrity of well-bore systems that are lined with Portland-based cements is critical to the successful storage of sequestered CO2 in gas and oil reservoirs. As a first step, we investigate reaction rates and mechanistic pathways for cement mineral growth in the absence of CO2 by coupling water chemistry with XRD and NMR spectroscopic data. We find that semi-crystalline calcium (alumino-)silicate hydrate (Al-CSH) forms as a precursor solid to the cement mineral tobermorite. Rate constants for tobermorite growth were found to be k = 0.6 (± 0.1) × 10-5 s-1 for a solution:solid of 10:1 and 1.6 (± 0.8) × 10-4 s-1 for a solution:solid of 5:1 (batch mode; T = 150°C). This data indicates that reaction rates for tobermorite growth are faster when the solution volume is reduced by half, suggesting that rates are dependent on solution saturation and that the Gibbs free energy is the reaction driver. However, calculated solution saturation indexes for Al-CSH and tobermorite differ by less than one log unit, which is within the measured uncertainty. Based on this data, we consider both heterogeneous nucleation as the thermodynamic driver and internal restructuring as possible mechanistic pathways for growth. We also use NMR spectroscopy to characterize the site symmetry and bonding environment of Al and Si in a reacted tobermorite sample. We find two [4]Al coordination structures at δiso = 59.9 ppm and 66.3 ppm with quadrupolar product parameters (PQ) of 0.21 MHz and 0.10 MHz (± 0.08) from 27Al 3Q-MAS NMR and speculate on the Al occupancy of framework sites by probing the protonation environment of Al metal centers using 27Al{1H}CP-MAS NMR. PMID:19144195

Computer simulation of concentrated solid solution strengthening

NASA Technical Reports Server (NTRS)

Kuo, C. T. K.; Arsenault, R. J.

1976-01-01

The interaction forces between a straight edge dislocation moving through a three-dimensional block containing a random array of solute atoms were determined. The yield stress at 0 K was obtained by determining the average maximum solute-dislocation interaction force that is encountered by edge dislocation, and an expression relating the yield stress to the length of the dislocation and the solute concentration is provided. The magnitude of the solid solution strengthening due to solute atoms can be determined directly from the numerical results, provided the dislocation line length that moves as a unit is specified.

Dynamic fields near a crack tip growing in an elastic-perfectly-plastic solid

NASA Technical Reports Server (NTRS)

Nemat-Nasser, S.; Gao, Y. C.

1983-01-01

A full asymptotic solution is presented for the fields in the neighborhood of the tip of a steadily advancing crack in an incompressible elastic-perfectly-plastic solid. There are four findings for mode I crack growth in the plane strain condition. The first is that the entire crack tip in steady crack growth is surrounded by a plastic region and that no elastic unloading is predicted by the complete dynamic asymptotic solution. The second is that, in contrast to the quasi-static solution, the dynamic solution yields strain fields with a logarithmic singularity everywhere near the crack tip. The third is that whereas the stress field varies throughout the entire crack tip neighborhood, it does not exhibit behavior that can be approximated by a constant field followed by an essentially centered-fan field and then by another constant field, especially for small crack growth speeds. The fourth finding is that there are two shock fronts emanating from the crack tip across which certain stress and strain components undergo jump discontinuities. After reviewing the mode III steady-state crack growth, it is concluded that ductile fracture criteria for nonstationary cracks must be based on solutions that include the inertia effects and that for this purpose quasi-static solutions may be inadequate.

Supercritical fluid molecular spray film deposition and powder formation

DOEpatents

Smith, Richard D.

1986-01-01

Solid films are deposited, or fine powders formed, by dissolving a solid material into a supercritical fluid solution at an elevated pressure and then rapidly expanding the solution through a short orifice into a region of relatively low pressure. This produces a molecular spray which is directed against a substrate to deposit a solid thin film thereon, or discharged into a collection chamber to collect a fine powder. Upon expansion and supersonic interaction with background gases in the low pressure region, any clusters of solvent are broken up and the solvent is vaporized and pumped away. Solute concentration in the solution is varied primarily by varying solution pressure to determine, together with flow rate, the rate of deposition and to control in part whether a film or powder is produced and the granularity of each. Solvent clustering and solute nucleation are controlled by manipulating the rate of expansion of the solution and the pressure of the lower pressure region. Solution and low pressure region temperatures are also controlled.

Plasma synthesis of lithium based intercalation powders for solid polymer electrolyte batteries

DOEpatents

Kong, Peter C [Idaho Falls, ID; Pink, Robert J [Pocatello, ID; Nelson, Lee O [Idaho Falls, ID

2005-01-04

The invention relates to a process for preparing lithium intercalation compounds by plasma reaction comprising the steps of: forming a feed solution by mixing lithium nitrate or lithium hydroxide or lithium oxide and the required metal nitrate or metal hydroxide or metal oxide and between 10-50% alcohol by weight; mixing the feed solution with O.sub.2 gas wherein the O.sub.2 gas atomizes the feed solution into fine reactant droplets, inserting the atomized feed solution into a plasma reactor to form an intercalation powder; and if desired, heating the resulting powder to from a very pure single phase product.

Gd Ba Cu O bulk superconductors fabricated by a seeded infiltration growth technique under reduced oxygen partial pressure

NASA Astrophysics Data System (ADS)

Iida, K.; Babu, N. H.; Shi, Y. H.; Cardwell, D. A.; Murakami, M.

2006-06-01

Single-grain Gd-Ba-Cu-O (GdBCO) bulk superconductors have been grown by a seeded infiltration and growth (SIG) technique under a 1% O2+N2 atmosphere using a generic MgO-doped Nd-Ba-Cu-O (MgO-NdBCO) seed placed on the sample surface at room temperature (the so-called the cold-seeding method). Partial melting of the MgO-NdBCO seeds fabricated in air under notionally identical thermal processing conditions, however, limited the reliability of this bulk GdBCO single-grain process. The observed seed decomposition is attributed to the dependence of the peritectic temperature Tp of MgO-doped Nd1+xBa2-xCu3Oy solid solution (MgO-doped Nd-123ss, where ss indicates solid solution) compounds on both oxygen partial pressure during the melt process and the level of solid solution (x). The peritectic decomposition temperature of MgO-doped Nd-123ss, with x ranging from 0 to 0.5 under p(O2) = 1.00 atm, was observed to remain constant at 1120 °C. Tp was observed to decrease linearly as a function of solid solution level, on the other hand, under oxygen partial pressures of both p(O2) = 0.21 and 0.01 atm. Based on these results, MgO-doped NdBCO seed crystals should be grown under reduced oxygen partial pressure in order to obtain a stable MgO-doped NdBCO seed crystal suitable for cold-seeding processes of large-grain (RE)BCO bulk superconductors (where RE is a rare earth element).

A solid solution series of atacamite type Ni{sub 2x}Mg{sub 2−2x}Cl(OH){sub 3}

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

Bette, Sebastian; Dinnebier, Robert E.; Röder, Christian

2015-08-15

For the first time a complete solid solution series Ni{sub 2x}Mg{sub 2−2x}Cl(OH){sub 3} of an atacamite type alkaline main group metal chloride, Mg{sub 2}Cl(OH){sub 3}, and a transition group metal chloride, Ni{sub 2}Cl(OH){sub 3}, was prepared and characterized by chemical and thermal analysis as well as by Raman and IR spectroscopy, and high resolution laboratory X-ray powder diffraction. All members of the solid solution series crystallize in space group Pnam (62). The main building units of these crystal structures are distorted, edge-linked Ni/MgO{sub 4}Cl{sub 2} and Ni/MgO{sub 5}Cl octahedra. The distribution of Ni{sup 2+}- and Mg{sup 2+}-ions among these twomore » metal-sites within the solid solution series is discussed in detail. The crystallization of the solid solution phases occurs via an intermediate solid solution series, (Ni/Mg)Cl{sub 2x}(OH){sub 2−2x}, with variable Cl: OH ratio up to the 1:3 ratio according to the formula Ni{sub 2x}Mg{sub 2−2x} Cl(OH){sub 3}. For one isolated intermediate solid solution member, Ni{sub 0.70}Mg{sub 0.30}Cl{sub 0.58}(OH){sub 1.42}, the formation and crystal structure is presented as well. - Graphical abstract: For the first time a complete solid solution series, Ni{sub 2x}Mg{sub 2−2x} Cl(OH){sub 3}, was synthesized and characterized. Structure solution by revealed that Ni{sup 2+} prefers to occupy the Jahn–Teller-like distorted hole, out of two available cation sites. Substitution of Ni{sup 2+} by Mg{sup 2+} in atacamite type Ni{sub 2}Cl(OH){sub 3} results in systematic band shifts in Raman and IR spectra as well as in systematic changes in thermal properties. The α-polymorphs M{sub 2}Cl(OH){sub 3} with M=Mg{sup 2+}, Ni{sup 2+} and other divalent transition metal ions, as described in literature, were identified as separate compounds. - Highlights: • First synthesis of solid solution series between main and transition metal chloride. • Ni{sup 2+} prefers to occupy Jahn–Teller-like distorted octahedral holes. • Substitution of Ni{sup 2+} by Mg{sup 2+} results in systematic Raman and IR band shifts. • α-Polymorphs M{sub 2}Cl(OH){sub 3} with M=Mg{sup 2+}, Ni{sup 2+}, … as described in literature do not exist.« less

SOLIDS PRECIPITATION EVENT IN MCU CAUSAL ANALYSIS AND RECOMMENDATIONS FROM SOLIDS RECOVERY TEAM

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

Garrison, A.; Aponte, C.

A process upset occurred in the Modular Caustic-Side Solvent Extraction Unit (MCU) facility on April 6th, 2014. During recovery efforts, a significant amount of solids were found in the Salt Solution Feed Tank (SSFT), Salt Solution Receipt Tanks (SSRTs), two extraction contactors, and scrub contactors. The solids were identified by Savannah River National Laboratory (SRNL) as primarily sodium oxalate and sodium alumina silicate (NAS) with the presence of some aluminum hydroxide. NAS solids have been present in the SSFT since simulant runs during cold chemical startup of MCU in 2007, and have not hindered operations since that time. During themore » process upset in April 2014, the oxalate solids partially blocked the aqueous outlet of the extraction contactors, causing salt solution to exit through the contactor organic outlet to the scrub contactors with the organic phase. This salt solution overwhelmed the scrub contactors and passed with the organic phase to the strip section of MCU. The partially reversed flow of salt solution resulted in a Strip Effluent (SE) stream that was high in Isopar™ L, pH and sodium. The primary cause of the excessive solids accumulation in the SSRTs and SSFT at MCU is attributed to an increase in the frequency of oxalic acid cleaning of the 512-S primary filter. Agitation in the SSRTs at MCU in response to cold weather likely provided the primary mechanism to transfer the solids to the contactors. Sources of the sodium oxalate solids are attributed to the oxalic acid cleaning solution used to clean the primary filter at the Actinide Removal Process (ARP) filtration at 512-S, as well as precipitation from the salt batch feed, which is at or near oxalate saturation. The Solids Recovery Team was formed to determine the cause of the solids formation and develop recommendations to prevent or mitigate this event in the future. A total of 53 recommendations were generated. These recommendations were organized into 4 focus areas: • Improve understanding of oxalate equilibrium and kinetics in salt solutions • Reduction/elimination of oxalic acid cleaning in 512-S • Flowsheet optimization • Improving diagnostic capability The recommendations implemented prior to resumption of MCU operations provide a risk mitigation or detection function through additional sampling and observation. The longer term recommendations provide a framework to increase the basic process knowledge of both oxalate chemistry and filtration behavior and then facilitate decisions that improve the salt flowsheet as a system.« less

Dendrite Suppression by Synergistic Combination of Solid Polymer Electrolyte Crosslinked with Natural Terpenes and Lithium-Powder Anode for Lithium-Metal Batteries.

PubMed

Shim, Jimin; Lee, Jae Won; Bae, Ki Yoon; Kim, Hee Joong; Yoon, Woo Young; Lee, Jong-Chan

2017-05-22

Lithium-metal anode has fundamental problems concerning formation and growth of lithium dendrites, which prevents practical applications of next generation of high-capacity lithium-metal batteries. The synergistic combination of solid polymer electrolyte (SPE) crosslinked with naturally occurring terpenes and lithium-powder anode is promising solution to resolve the dendrite issues by substituting conventional liquid electrolyte/separator and lithium-foil anode system. A series of SPEs based on polysiloxane crosslinked with natural terpenes are prepared by facile thiol-ene click reaction under mild condition and the structural effect of terpene crosslinkers on electrochemical properties is studied. Lithium powder with large surface area is prepared by droplet emulsion technique (DET) and used as anode material. The effect of the physical state of electrolyte (solid/liquid) and morphology of lithium-metal anode (powder/foil) on dendrite growth behavior is systematically studied. The synergistic combination of SPE and lithium-powder anode suggests an effective solution to suppress the dendrite growth owing to the formation of a stable solid-electrolyte interface (SEI) layer and delocalized current density. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Finite element analysis of the effect of a non-planar solid-liquid interface on the lateral solute segregation during unidirectional solidification

NASA Technical Reports Server (NTRS)

Carlson, F. M.; Chin, L.-Y.; Fripp, A. L.; Crouch, R. K.

1982-01-01

The effect of solid-liquid interface shape on lateral solute segregation during steady-state unidirectional solidification of a binary mixture is calculated under the assumption of no convection in the liquid. A finite element technique is employed to compute the concentration field in the liquid and the lateral segregation in the solid with a curved boundary between the liquid and solid phases. The computational model is constructed assuming knowledge of the solid-liquid interface shape; no attempt is made to relate this shape to the thermal field. The influence of interface curvature on the lateral compositional variation is investigated over a range of system parameters including diffusivity, growth speed, distribution coefficient, and geometric factors of the system. In the limiting case of a slightly nonplanar interface, numerical results from the finite element technique are in good agreement with the analytical solutions of Coriell and Sekerka obtained by using linear theory. For the general case of highly non-planar interface shapes, the linear theory fails and the concentration field in the liquid as well as the lateral solute segregation in the solid can be calculated by using the finite element method.

Band-gap tailoring and visible-light-driven photocatalytic performance of porous (GaN)1-x(ZnO)x solid solution.

PubMed

Wu, Aimin; Li, Jing; Liu, Baodan; Yang, Wenjin; Jiang, Yanan; Liu, Lusheng; Zhang, Xinglai; Xiong, Changmin; Jiang, Xin

2017-02-21

(GaN) 1-x (ZnO) x solid solution has attracted extensive attention due to its feasible band-gap tunability and excellent photocatalytic performance in overall water splitting. However, its potential application in the photodegradation of organic pollutants and environmental processing has rarely been reported. In this study, we developed a rapid synthesis process to fabricate porous (GaN) 1-x (ZnO) x solid solution with a tunable band gap in the range of 2.38-2.76 eV for phenol photodegradation. Under visible-light irradiation, (GaN) 0.75 (ZnO) 0.25 solid solution achieved the highest photocatalytic performance compared to other (GaN) 1-x (ZnO) x solid solutions with x = 0.45, 0.65 and 0.85 due to its higher redox capability and lower lattice deformation. Slight Ag decoration with a content of 1 wt% on the surface of the (GaN) 0.75 (ZnO) 0.25 solid solution leads to a significant enhancement in phenol degradation, with a reaction rate eight times faster than that of pristine (GaN) 0.75 (ZnO) 0.25 . Interestingly, phenol in aqueous solution (10 mg L -1 ) can also be completely degraded within 60 min, even under the direct exposure of sunlight irradiation. The photocurrent response indicates that the enhanced photocatalytic activity of (GaN) 0.75 (ZnO) 0.25 /Ag is directly induced by the improved transfer efficiency of the photogenerated electrons at the interface. The excellent phenol degradation performance of (GaN) 1-x (ZnO) x /Ag further broadens their promising photocatalytic utilization in environmental processing, besides in overall water splitting for hydrogen production.

Experimental investigation of halogen-bond hard-soft acid-base complementarity.

PubMed

Riel, Asia Marie S; Jessop, Morly J; Decato, Daniel A; Massena, Casey J; Nascimento, Vinicius R; Berryman, Orion B

2017-04-01

The halogen bond (XB) is a topical noncovalent interaction of rapidly increasing importance. The XB employs a `soft' donor atom in comparison to the `hard' proton of the hydrogen bond (HB). This difference has led to the hypothesis that XBs can form more favorable interactions with `soft' bases than HBs. While computational studies have supported this suggestion, solution and solid-state data are lacking. Here, XB soft-soft complementarity is investigated with a bidentate receptor that shows similar associations with neutral carbonyls and heavy chalcogen analogs. The solution speciation and XB soft-soft complementarity is supported by four crystal structures containing neutral and anionic soft Lewis bases.

Fabrication of Heterogeneous-Phase Solid-Solution Promoting Band Structure and Charge Separation for Enhancing Photocatalytic CO2 Reduction: A Case of ZnXCa1-XIn2S4.

PubMed

Zeng, Chao; Huang, Hongwei; Zhang, Tierui; Dong, Fan; Zhang, Yihe; Hu, Yingmo

2017-08-23

Photocatalytic CO 2 reduction into solar fuels illustrates huge charm for simultaneously settling energy and environmental issues. The photoreduction ability of a semiconductor is closely correlated to its conduction band (CB) position. A homogeneous-phase solid-solution with the same crystal system always has a monotonously changed CB position, and the high CB level has to be sacrificed to achieve a benign photoabsorption. Herein, we report the fabrication of heterogeneous-phase solid-solution Zn X Ca 1-X In 2 S 4 between trigonal ZnIn 2 S 4 and cubic CaIn 2 S 4 . The Zn X Ca 1-X In 2 S 4 solid solutions with orderly tuned photoresponsive range from 540 to 640 nm present a more negative CB level and highly enhanced charge-separation efficiency. Profiting from these merits, all of these Zn X Ca 1-X In 2 S 4 solid solutions exhibit remarkably strengthened photocatalytic CO 2 reduction performance under visible light (λ > 420 nm) irradiation. Zn 0.4 Ca 0.6 In 2 S 4 , bearing the most negative CB position and highest charge-separation efficiency, casts the optimal photocatalytic CH 4 and CO evolution rates, which reach 16.7 and 6.8 times higher than that of ZnIn 2 S 4 and 7.2 and 3.9 times higher than that of CaIn 2 S 4 , respectively. To verify the crucial role of the heterogeneous-phase solid solution in promoting the band structure and photocatalytic performance, another heterogeneous-phase solid-solution Zn X Cd 1-X In 2 S 4 has been synthesized. It also displays an upshifted CB level and promoted charge separation. This work may provide a new perspective into the development of an efficient visible-light driven photocatalyst for CO 2 reduction and other photoreduction reactions.

Novel Nanostructured Solid Materials for Modulating Oral Drug Delivery from Solid-State Lipid-Based Drug Delivery Systems.

PubMed

Dening, Tahnee J; Rao, Shasha; Thomas, Nicky; Prestidge, Clive A

2016-01-01

Lipid-based drug delivery systems (LBDDS) have gained significant attention in recent times, owing to their ability to overcome the challenges limiting the oral delivery of poorly water-soluble drugs. Despite the successful commercialization of several LBDDS products over the years, a large discrepancy exists between the number of poorly water-soluble drugs displaying suboptimal in vivo performances and the application of LBDDS to mitigate their various delivery challenges. Conventional LBDDS, including lipid solutions and suspensions, emulsions, and self-emulsifying formulations, suffer from various drawbacks limiting their widespread use and commercialization. Accordingly, solid-state LBDDS, fabricated by adsorbing LBDDS onto a chemically inert solid carrier material, have attracted substantial interest as a viable means of stabilizing LBDDS whilst eliminating some of the various limitations. This review describes the impact of solid carrier choice on LBDDS performance and highlights the importance of appropriate solid carrier material selection when designing hybrid solid-state LBDDS. Specifically, emphasis is placed on discussing the ability of the specific solid carrier to modulate drug release, control lipase action and lipid digestion, and enhance biopharmaceutical performance above the original liquid-state LBDDS. To encourage the interested reader to consider their solid carrier choice on a higher level, various novel materials with the potential for future use as solid carriers for LBDDS are described. This review is highly significant in guiding future research directions in the solid-state LBDDS field and fostering the translation of these delivery systems to the pharmaceutical marketplace.

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

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

Solid solutions of HfB 2-ZrB 2 mixtures were prepared by high-energy ball milling of diboride and additive powders followed by spark plasma sintering (SPS). A mixture of stoichiometric 1:1 HfB 2-ZrB 2 borides was the base composition to which Hf, Zr, Ta, LaB 6 or Gd 2O 3 was added. Hf, Zr and Ta were added in order to bring the boron-to-metal ratio down to 1.86, rendering the boride as MeB 1.86. In the case of LaB 6 and Gd 2O 3, 1.8 mol% was added. Electroanalytical behavior of hydrogen evolution reactions was evaluated in 1 M H 2SO 4more » and 1 M NaOH solutions. The LaB 6 additive material showed Tafel slopes of 125 and 90 mV/decade in acidic and alkaline solutions respectively. The Hf and Zr rich samples showed Tafel slopes of about 120 mV/decade in both electrolytes. The over potentials of hydrogen evolution reactions (at 10 mA/cm 2) in the alkaline solution were about 100 mV lower than those in acidic solution. The metal-rich diborides and addition of LaB 6 showed better hydrogen evolution reaction (HER) activities than the base 1:1 HfB 2-ZrB 2 stoichiometric diboride solid solution. Furthermore, the higher activity of metal-rich borides could be attributed to the increased electron population at the d-orbitals of the metal shown by band structure modeling calculations using the Density Functional Theory approach.« less

Tautomeric and ionisation forms of dopamine and tyramine in the solid state

NASA Astrophysics Data System (ADS)

Cruickshank, Laura; Kennedy, Alan R.; Shankland, Norman

2013-11-01

Crystallisation of the phenylethylamine neurotransmitter dopamine from basic aqueous solution yielded the 3-phenoxide Zwitterionic tautomer, despite this being a minority form in the solution state. In the crystal structure, dopamine has a dimeric [OCCOH]2 hydrogen bonded catechol motif that expands through Nsbnd H⋯O interactions to give a 2-dimensional sheet of classical hydrogen bonds. These sheets are further interconnected by Nsbnd H⋯π interactions. The structurally related base tyramine crystallises under similar conditions as a hemihydrate with all four possible species of tyramine present (cationic, anionic, Zwitterionic and neutral) in the crystal structure. Single crystal X-ray diffraction studies at 121 and 293 K showed dynamic hydrogen atom disorder for the phenol/phenoxide group, suggesting that the tyramine speciation observed arises from a solid-state process.

Solvent effect on the vibrational spectra of Carvedilol.

PubMed

Billes, Ferenc; Pataki, Hajnalka; Unsalan, Ozan; Mikosch, Hans; Vajna, Balázs; Marosi, György

2012-09-01

Carvedilol (CRV) is an important medicament for heart arrhythmia. The aim of this work was the interpretation of its vibrational spectra with consideration on the solvent effect. Infrared and Raman spectra were recorded in solid state as well in solution. The experimental spectra were evaluated using DFT quantum chemical calculations computing the optimized structure, atomic net charges, vibrational frequencies and force constants. The same calculations were done for the molecule in DMSO and aqueous solutions applying the PCM method. The calculated force constants were scaled to the experimentally observed solid state frequencies. The characters of the vibrational modes were determined by their potential energy distributions. Solvent effects on the molecular properties were interpreted. Based on these results vibrational spectra were simulated. Copyright © 2012 Elsevier B.V. All rights reserved.

Isotope Labeling for Solution and Solid-State NMR Spectroscopy of Membrane Proteins

PubMed Central

Verardi, Raffaello; Traaseth, Nathaniel J.; Masterson, Larry R.; Vostrikov, Vitaly V.; Veglia, Gianluigi

2013-01-01

In this chapter, we summarize the isotopic labeling strategies used to obtain high-quality solution and solid-state NMR spectra of biological samples, with emphasis on integral membrane proteins (IMPs). While solution NMR is used to study IMPs under fast tumbling conditions, such as in the presence of detergent micelles or isotropic bicelles, solid-state NMR is used to study the structure and orientation of IMPs in lipid vesicles and bilayers. In spite of the tremendous progress in biomolecular NMR spectroscopy, the homogeneity and overall quality of the sample is still a substantial obstacle to overcome. Isotopic labeling is a major avenue to simplify overlapped spectra by either diluting the NMR active nuclei or allowing the resonances to be separated in multiple dimensions. In the following we will discuss isotopic labeling approaches that have been successfully used in the study of IMPs by solution and solid-state NMR spectroscopy. PMID:23076578

Efficacy of pectin solution for preventing gastro-esophageal reflux events in patients with percutaneous endoscopic gastrostomy.

PubMed

Adachi, Kyoichi; Furuta, Kenji; Aimi, Masahito; Fukazawa, Kousuke; Shimura, Shino; Ohara, Shunji; Nakata, Shuji; Inoue, Yukiko; Ryuko, Kanji; Ishine, Junichi; Katoh, Kyoko; Hirata, Toshiaki; Ohhata, Shuzo; Katoh, Setsushi; Moriyama, Mika; Sumikawa, Masuko; Sanpei, Mari; Kinoshita, Yoshikazu

2012-05-01

The aim of this study was to determine the efficacy of pectin solution, which increases the viscosity of liquid nutrient, for prevention of gastro-esophageal reflux in comparison with half-solid nutrient. The subjects were 10 elderly patients undergoing percutaneous endoscopic gastrostomy feeding. Twenty-four-hour esophageal multichannel intraluminal impedance and pH testing was performed during intake of half-solid nutrient and a combination of pectin solution and liquid nutrient. During 4 h after delivery, there was no significant difference in the total number of gastro-esophageal reflux events between the feeding of the half-solid nutrient and the combination of pectin solution and liquid nutrient (5.7 ± 1.2 vs 5.3 ± 1.0/4 h). Acidic reflux after delivery of the half-solid nutrient was significantly more frequent than that after delivery of the combination of pectin solution and liquid nutrient (80.7% vs 60.4%, p = 0.018). The incidence of gastro-esophageal reflux reaching the upper portion of the esophagus tended to be higher during delivery of the half-solid nutrient than during delivery of the combination of pectin solution and liquid nutrient (47.4% vs 34.0%, p = 0.153). In conclusion, the usage of pectin solution combined with liquid nutrient is effective for preventing acidic gastro-esophageal reflux and gastro-esophageal reflux reaching the upper portion of the esophagus.

Investigation of Phase Mixing in Amorphous Solid Dispersions of AMG 517 in HPMC-AS Using DSC, Solid-State NMR, and Solution Calorimetry.

PubMed

Calahan, Julie L; Azali, Stephanie C; Munson, Eric J; Nagapudi, Karthik

2015-11-02

Intimate phase mixing between the drug and the polymer is considered a prerequisite to achieve good physical stability for amorphous solid dispersions. In this article, spray dried amorphous dispersions (ASDs) of AMG 517 and HPMC-as were studied by differential scanning calorimetry (DSC), solid-state NMR (SSNMR), and solution calorimetry. DSC analysis showed a weakly asymmetric (ΔTg ≈ 13.5) system with a single glass transition for blends of different compositions indicating phase mixing. The Tg-composition data was modeled using the BKCV equation to accommodate the observed negative deviation from ideality. Proton spin-lattice relaxation times in the laboratory and rotating frames ((1)H T1 and T1ρ), as measured by SSNMR, were consistent with the observation that the components of the dispersion were in intimate contact over a 10-20 nm length scale. Based on the heat of mixing calculated from solution calorimetry and the entropy of mixing calculated from the Flory-Huggins theory, the free energy of mixing was calculated. The free energy of mixing was found to be positive for all ASDs, indicating that the drug and polymer are thermodynamically predisposed to phase separation at 25 °C. This suggests that miscibility measured by DSC and SSNMR is achieved kinetically as the result of intimate mixing between drug and polymer during the spray drying process. This kinetic phase mixing is responsible for the physical stability of the ASD.

A Three-State System Based on Branched DNA Hybrids.

PubMed

He, Shiliang; Richert, Clemens

2018-03-26

There is a need for materials that respond to chemical or physical stimuli through a change in their structure. While a transition between water-soluble form and solid is not uncommon for DNA-based structures, systems that transition between three different states at room temperature and ambient pressure are rare. Here we report the preparation of branched DNA hybrids with eight oligodeoxycytidylate arms via solution-phase, H-phosphonate-based synthesis. Some hybrids assemble into hydrogels upon lowering the pH, acting as efficient gelators at pH 4-6, but can also transition into a more condensed solid state form upon exposure to divalent cations. Together with the homogeneous solutions that the i-motif-forming compounds give at neutral pH, three-state systems result. Each state has its own color, if chromophores are included in the system. The assembly and gelation properties can be tuned by choosing the chain length of the arms. Their responsive properties make the dC-rich DNA hybrids candidates for smart material applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of solute additions on the steady-state creep behavior of dispersion-strengthened aluminum.

NASA Technical Reports Server (NTRS)

Reynolds, G. H.; Lenel, F. V.; Ansell, G. S.

1971-01-01

The effect of solute additions on the steady-state creep behavior of coarse-grained dispersion-strengthened aluminum alloys was studied. Recrystallized dispersion-strengthened solid solutions were found to have stress and temperature sensitivities quite unlike those observed in single-phase solid solutions having the same composition and grain size. The addition of magnesium or copper to the matrix of a recrystallized dispersion-strengthened aluminum causes a decrease in the steady-state creep rate which is much smaller than that caused by similar amounts of solute in single-phase solid solutions. All alloys exhibited essentially a 4.0 power stress exponent in agreement with the model of Ansell and Weertman. The activation energy for steady-state creep in dispersion-strengthened Al-Mg alloys, as well as the stress dependence, was in agreement with the physical model of dislocation climb over the dispersed particles.

A high performance flexible all solid state supercapacitor based on the MnO2 sphere coated macro/mesoporous Ni/C electrode and ionic conducting electrolyte

NASA Astrophysics Data System (ADS)

Zhi, Jian; Reiser, Oliver; Wang, Youfu; Hu, Aiguo

2016-06-01

A high contact resistance between the active materials and the current collector, a low ionic conductivity of the gel electrolyte, and an impenetrable electrode structure are the three major barriers which greatly limit the capacitance of MnO2 in solid state supercapacitors. As a potential solution to these problems, in this work we report a novel electrode for solid state supercapacitors, based on a ternary system composed of hierarchical MnO2 spheres as the active material, macroporous Ni foam as gel penetrable skeletons and an ordered mesoporous carbon (OMC) membrane as the charge-transport accelerating layer. By employing butyl-3-methylimidazolium chloride (BMIMCl) modified gels as the ionic conducting electrolyte, the utilization efficiency of MnO2 on the specific capacitance was enhanced up to 88% of the theoretical value, delivering a volumetric capacitance of 81 F cm-3, which is the highest value among MnO2 based solid state supercapacitors. Moreover, such a flexible device exhibits exceptional volumetric energy and power density (6.6 Wh L-1 and 549 W L-1, based on the whole device volume) combined with a small capacity loss of 8.5% after 6000 cycles under twisting. These encouraging findings unambiguously overcome the energy bottleneck of MnO2 in solid state supercapacitors, and open up a new application of macro/mesoporous materials in flexible devices.A high contact resistance between the active materials and the current collector, a low ionic conductivity of the gel electrolyte, and an impenetrable electrode structure are the three major barriers which greatly limit the capacitance of MnO2 in solid state supercapacitors. As a potential solution to these problems, in this work we report a novel electrode for solid state supercapacitors, based on a ternary system composed of hierarchical MnO2 spheres as the active material, macroporous Ni foam as gel penetrable skeletons and an ordered mesoporous carbon (OMC) membrane as the charge-transport accelerating layer. By employing butyl-3-methylimidazolium chloride (BMIMCl) modified gels as the ionic conducting electrolyte, the utilization efficiency of MnO2 on the specific capacitance was enhanced up to 88% of the theoretical value, delivering a volumetric capacitance of 81 F cm-3, which is the highest value among MnO2 based solid state supercapacitors. Moreover, such a flexible device exhibits exceptional volumetric energy and power density (6.6 Wh L-1 and 549 W L-1, based on the whole device volume) combined with a small capacity loss of 8.5% after 6000 cycles under twisting. These encouraging findings unambiguously overcome the energy bottleneck of MnO2 in solid state supercapacitors, and open up a new application of macro/mesoporous materials in flexible devices. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr02215d

Effective spring stiffness for a periodic array of interacting coplanar penny-shaped cracks at an interface between two dissimilar isotropic materials

PubMed Central

Lekesiz, Huseyin; Katsube, Noriko; Rokhlin, Stanislav I.; Seghi, Robert R.

2013-01-01

An effective spring stiffness approximation is proposed for a hexagonal array of coplanar penny shaped cracks located at the interface between two dissimilar solids. The approximation is based on the factorization of the solution on the material dissimilarity factor, the crack interaction factor and the effective spring stiffness solution for non-interacting cracks in a homogeneous material. Such factorization is exact and was validated for 2D collinear cracks between two dissimilar solids. The crack interaction factor is obtained using a recently developed model for stress intensity factors for an array of coplanar penny shaped cracks in a homogeneous material; also the material dissimilarity function recently obtained for non-interacting penny shaped crack at the interface between two dissimilar materials is employed. The obtained solution is useful for an assessment by ultrasonic measurements of the interface stiffness in bonded structures for monitoring the interfacial microdamage growth due to mechanical loading and environmental factors. PMID:27175036

Assessment of Recovery of Milk Protein Allergens from Processed Food for Mass Spectrometry Quantification.

PubMed

Groves, Kate; Cryar, Adam; Walker, Michael; Quaglia, Milena

2018-01-01

Assessing the recovery of food allergens from solid processed matrixes is one of the most difficult steps that needs to be overcome to enable the accurate quantification of protein allergens by immunoassay and MS. A feasibility study is described herein applying International System of Units (SI)-traceably quantified milk protein solutions to assess recovery by an improved extraction method. Untargeted MS analysis suggests that this novel extraction method can be further developed to provide high recoveries for a broad range of food allergens. A solution of α-casein was traceably quantified to the SI for the content of α-S1 casein. Cookie dough was prepared by spiking a known amount of the SI-traceable quantified solution into a mixture of flour, sugar, and soya spread, followed by baking. A novel method for the extraction of protein food allergens from solid matrixes based on proteolytic digestion was developed, and its performance was compared with the performance of methods reported in the literature.

Development of a model to predict the adsorption of lead from solution on a natural streambed sediment

USGS Publications Warehouse

Brown, David Wayne; Hem, John David

1984-01-01

Adsorption of solutes by solid mineral surfaces commonly influences the dissolved ionic composition of natural waters. A model based on electrical double-layer theory has been developed which appears to be capable of characterizing the surface chemical behavior of a natural fine-grained sediment containing mostly quartz and feldspar. This variable surface charge-variable surface potential (VSC-VSP) model differs from others in being capable of evaluating more closely the effect of total metal ion activity on the pH-dependent change in electrical potential at the solid surface. The model was tested using 10-4 molar solutions of lead and a silt-size fraction of sediment from the bed of Colma Creek, a small stream in urban northern San Mateo County, California. The average deviation of measured percent adsorption and values calculated from the model was 6.6 adsorption percent from pH 2.0 to pH 7.0.

Effective spring stiffness for a periodic array of interacting coplanar penny-shaped cracks at an interface between two dissimilar isotropic materials.

PubMed

Lekesiz, Huseyin; Katsube, Noriko; Rokhlin, Stanislav I; Seghi, Robert R

2013-08-15

An effective spring stiffness approximation is proposed for a hexagonal array of coplanar penny shaped cracks located at the interface between two dissimilar solids. The approximation is based on the factorization of the solution on the material dissimilarity factor, the crack interaction factor and the effective spring stiffness solution for non-interacting cracks in a homogeneous material. Such factorization is exact and was validated for 2D collinear cracks between two dissimilar solids. The crack interaction factor is obtained using a recently developed model for stress intensity factors for an array of coplanar penny shaped cracks in a homogeneous material; also the material dissimilarity function recently obtained for non-interacting penny shaped crack at the interface between two dissimilar materials is employed. The obtained solution is useful for an assessment by ultrasonic measurements of the interface stiffness in bonded structures for monitoring the interfacial microdamage growth due to mechanical loading and environmental factors.

Interdiffusion and reaction between U and Zr

NASA Astrophysics Data System (ADS)

Park, Y.; Newell, R.; Mehta, A.; Keiser, D. D.; Sohn, Y. H.

2018-04-01

The microstructural development and diffusion kinetics were examined for the binary U vs. Zr system using solid-to-solid diffusion couples, U vs. Zr, annealed at 580 °C for 960 h, 650 °C for 480 h, 680 °C for 240 h, and 710 °C for 96 h. Scanning and transmission electron microscopies with X-ray energy dispersive spectroscopy were employed for detailed microstructural and compositional analyses. Interdiffusion and reaction in U vs. Zr diffusion couples primarily produced: δ-UZr2 solid solution (hP3) and α‧-U at 580 °C; and (γU,βZr) solid solution (cI2) and α‧-U at 650°, 680° and 710 °C. The α‧-phase was confirmed as a reduced variant of the α-U orthorhombic structure with lattice parameters, a × b × c = 2.65 × 5.40 × 4.75 (Å) with a negligible solubility for Zr at room temperature. Concentration profiles were examined to determine interdiffusion coefficients, integrated interdiffusion coefficients, and intrinsic diffusion coefficients using Boltzmann-Matano, Wagner, and Heumann analyses, respectively. Composition-dependence of interdiffusion coefficients were documented for α-U, δ-UZr2 (at 580 °C) and (γU,βZr) solid solution (at 650°, 680° and 710 °C). U was determined to intrinsically diffuse faster than Zr, approximately by an order of magnitude, in the δ-UZr2 at 580 °C, and (γU,βZr) phases at 650°, 680° and 710 °C. Based on Darken's approach, thermodynamic data available in literature were coupled to estimate the tracer diffusion coefficients and atomic mobilities of U and Zr.

Preferential diffusion in concentrated solid solution alloys: NiFe, NiCo and NiCoCr

DOE PAGES

Zhao, Shijun; Osetsky, Yuri; Zhang, Yanwen

2017-02-13

In single-phase concentrated solid-solution alloys (CSAs), including high entropy alloys (HEAs), remarkable mechanical properties are exhibited, as well as extraordinary corrosion and radiation resistance compared to pure metals and dilute alloys. But, the mechanisms responsible for these properties are unknown in many cases. In this work, we employ ab initio molecular dynamics based on density functional theory to study the diffusion of interstitial atoms in Ni and Ni-based face-centered cubic CSAs including NiFe, NiCo and NiCoCr. We model the defect trajectories over >100 ps and estimate tracer diffusion coefficients, correlation factors and activation energies. Furthermore, we found that the diffusionmore » mass transport in CSAs is not only slower than that in pure components, i.e. sluggish diffusion, but also chemically non-homogeneous. The results obtained here can be used in understanding and predicting the atomic segregation and phase separation in CSAs under irradiation conditions.« less

A microstructure-based yield stress and work-hardening model for textured 6xxx aluminium alloys

NASA Astrophysics Data System (ADS)

Khadyko, M.; Myhr, O. R.; Dumoulin, S.; Hopperstad, O. S.

2016-04-01

The plastic properties of an aluminium alloy are defined by its microstructure. The most important factors are the presence of alloying elements in the form of solid solution and precipitates of various sizes, and the crystallographic texture. A nanoscale model that predicts the work-hardening curves of 6xxx aluminium alloys was proposed by Myhr et al. The model predicts the solid solution concentration and the particle size distributions of different types of metastable precipitates from the chemical composition and thermal history of the alloy. The yield stress and the work hardening of the alloy are then determined from dislocation mechanics. The model was largely used for non-textured materials in previous studies. In this work, a crystal plasticity-based approach is proposed for the work hardening part of the nanoscale model, which allows including the influence of the crystallographic texture. The model is evaluated by comparison with experimental data from uniaxial tensile tests on two textured 6xxx alloys in five temper conditions.

Electrodeposition mechanism and characterization of Ni-Cu alloy coatings from a eutectic-based ionic liquid

NASA Astrophysics Data System (ADS)

Wang, Shaohua; Guo, Xingwu; Yang, Haiyan; Dai, JiChun; Zhu, Rongyu; Gong, Jia; Peng, Liming; Ding, Wenjiang

2014-01-01

The electrodeposition mechanism, microstructures and corrosion resistances of Ni-Cu alloy coatings on Cu substrate were investigated in a choline chloride-urea (1:2 molar ratio) eutectic-based ionic liquid (1:2 ChCl-urea IL) containing nickel and copper chlorides. Cyclic voltammetry showed that the onset reduction potentials for Cu (∼-0.32 V) and for Ni (∼-0.47 V) were close to each other, indicating that Ni-Cu co-deposition could be easily achieved in the absence of complexing agent which was indispensable in aqueous plating electrolyte. Chronoamperometric investigations revealed that Ni-Cu deposits followed the three-dimensional instantaneous nucleation/growth mechanism, thus producing a solid solution. The compositions, microstructures and corrosion resistances of Ni-Cu alloy coatings were significantly dependent on the deposition current densities. Ni-Cu alloy coatings were α-Ni(Cu) solid solutions, and the coating containing ∼17.6 at.% Cu exhibited the best corrosion resistance because of its dense and crack-free structure.

Zirconia ceramics for excess weapons plutonium waste

NASA Astrophysics Data System (ADS)

Gong, W. L.; Lutze, W.; Ewing, R. C.

2000-01-01

We synthesized a zirconia (ZrO 2)-based single-phase ceramic containing simulated excess weapons plutonium waste. ZrO 2 has large solubility for other metallic oxides. More than 20 binary systems A xO y-ZrO 2 have been reported in the literature, including PuO 2, rare-earth oxides, and oxides of metals contained in weapons plutonium wastes. We show that significant amounts of gadolinium (neutron absorber) and yttrium (additional stabilizer of the cubic modification) can be dissolved in ZrO 2, together with plutonium (simulated by Ce 4+, U 4+ or Th 4+) and impurities (e.g., Ca, Mg, Fe, Si). Sol-gel and powder methods were applied to make homogeneous, single-phase zirconia solid solutions. Pu waste impurities were completely dissolved in the solid solutions. In contrast to other phases, e.g., zirconolite and pyrochlore, zirconia is extremely radiation resistant and does not undergo amorphization. Baddeleyite (ZrO 2) is suggested as the natural analogue to study long-term radiation resistance and chemical durability of zirconia-based waste forms.

Fluidized bed gasification of extracted coal

DOEpatents

Aquino, D.C.; DaPrato, P.L.; Gouker, T.R.; Knoer, P.

1984-07-06

Coal or similar carbonaceous solids are extracted by contacting the solids in an extraction zone with an aqueous solution having a pH above 12.0 at a temperature between 65/sup 0/C and 110/sup 0/C for a period of time sufficient to remove bitumens from the coal into said aqueous solution, and the extracted solids are then gasified at an elevated pressure and temperature in a fluidized bed gasification zone (60) wherein the density of the fluidized bed is maintained at a value above 160 kg/m/sup 3/. In a preferred embodiment of the invention, water is removed from the aqueous solution in order to redeposit the extracted bitumens onto the solids prior to the gasification step. 2 figs., 1 tab.

A study of advanced magnesium-based hydride and development of a metal hydride thermal battery system

NASA Astrophysics Data System (ADS)

Zhou, Chengshang

Metal hydrides are a group of important materials known as energy carriers for renewable energy and thermal energy storage. A concept of thermal battery based on advanced metal hydrides is studied for heating and cooling of cabins in electric vehicles. The system utilizes a pair of thermodynamically matched metal hydrides as energy storage media. The hot hydride that is identified and developed is catalyzed MgH2 due to its high energy density and enhanced kinetics. TiV0.62Mn1.5, TiMn2, and LaNi5 alloys are selected as the matching cold hydride. A systematic experimental survey is carried out in this study to compare a wide range of additives including transitions metals, transition metal oxides, hydrides, intermetallic compounds, and carbon materials, with respect to their effects on dehydrogenation properties of MgH2. The results show that additives such as Ti and V-based metals, hydride, and certain intermetallic compounds have strong catalytic effects. Solid solution alloys of magnesium are exploited as a way to destabilize magnesium hydride thermodynamically. Various elements are alloyed with magnesium to form solid solutions, including indium and aluminum. Thermodynamic properties of the reactions between the magnesium solid solution alloys and hydrogen are investigated, showing that all the solid solution alloys that are investigated in this work have higher equilibrium hydrogen pressures than that of pure magnesium. Cyclic stability of catalyzed MgH2 is characterized and analyzed using a PCT Sievert-type apparatus. Three systems, including MgH2-TiH 2, MgH2-TiMn2, and MgH2-VTiCr, are examined. The hydrogenating and dehydrogenating kinetics at 300°C are stable after 100 cycles. However, the low temperature (25°C to 150°C) hydrogenation kinetics suffer a severe degradation during hydrogen cycling. Further experiments confirm that the low temperature kinetic degradation can be mainly related the extended hydrogenation-dehydrogenation reactions. Proof-of-concept prototypes are built and tested, demonstrating the potential of the system as HVAC for transportation vehicles. The performance of the concept-demonstration-unit show both high heating/cooling power and high energy densities. An extended cycling test shows degradation on the performance of the system. To solve this problem, a metal hydride hydrogen compressor is proposed for aiding the recharge process of the system.

Phase-field modeling of diffusional phase behaviors of solid surfaces: A case study of phase-separating Li XFePO 4 electrode particles

DOE PAGES

Heo, Tae Wook; Chen, Long-Qing; Wood, Brandon C.

2015-04-08

In this paper, we present a comprehensive phase-field model for simulating diffusion-mediated kinetic phase behaviors near the surface of a solid particle. The model incorporates elastic inhomogeneity and anisotropy, diffusion mobility anisotropy, interfacial energy anisotropy, and Cahn–Hilliard diffusion kinetics. The free energy density function is formulated based on the regular solution model taking into account the possible solute-surface interaction near the surface. The coherency strain energy is computed using the Fourier-spectral iterative-perturbation method due to the strong elastic inhomogeneity with a zero surface traction boundary condition. Employing a phase-separating Li XFePO 4 electrode particle for Li-ion batteries as a modelmore » system, we perform parametric three-dimensional computer simulations. The model permits the observation of surface phase behaviors that are different from the bulk counterpart. For instance, it reproduces the theoretically well-established surface modes of spinodal decomposition of an unstable solid solution: the surface mode of coherent spinodal decomposition and the surface-directed spinodal decomposition mode. We systematically investigate the influences of major factors on the kinetic surface phase behaviors during the diffusional process. Finally, our simulation study provides insights for tailoring the internal phase microstructure of a particle by controlling the surface phase morphology.« less

Synthesis of Pyridine– and Pyrazine–BF 3 Complexes and Their Characterization in Solution and Solid State

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

Chénard, Etienne; Sutrisno, Andre; Zhu, Lingyang

2016-03-31

Following the discovery of the redox-active 1,4- bis-BF 3-quinoxaline complex, we undertook a structure- activity study with the objective to understand the active nature of the quinoxaline complex. Through systematic synthesis and characterization, we have compared complexes prepared from pyridine and pyrazine derivatives, as heterocyclic core analogues. This paper reports the structural requirements that give rise to the electrochemical features of the 1,4-bis-BF 3-quinoxaline adduct. Using solution and solidstate NMR spectroscopy, the role of aromatic ring fusion and nitrogen incorporation in bonding and electronics was elucidated. We establish the boron atom location and its interaction with its environment from 1Dmore » and 2D solution NMR, X-ray diffraction analysis, and 11B solid-state NMR experiments. Crystallographic analysis of single crystals helped to correlate the boron geometry with 11B quadrupolar coupling constant (CQ) and asymmetry parameter (ηQ), extracted from 11B solid-state NMR spectra. Additionally, computations based on density functional theory were performed to predict electrochemical behavior of the BF 3-heteroaromatic complexes. We then experimentally measured electrochemical potential using cyclic voltammetry and found that the redox potentials and CQ values are similarly affected by electronic changes in the complexes.« less

Local structural relaxation around Co2+ along the hardystonite-Co-åkermanite melilite solid solution

NASA Astrophysics Data System (ADS)

Ardit, Matteo; Cruciani, Giuseppe; Dondi, Michele

2012-10-01

Six pure compounds belonging to the hardystonite (Ca2ZnSi2O7)-Co-åkermanite (Ca2CoSi2O7) solid solution were investigated by the combined application of X-ray powder diffraction and electronic absorption spectroscopy. Structural refinements of the XRPD data revealed a negative excess volume of mixing due to the single isovalent substitution of Co for Zn in the tetrahedral site. In agreement with the diffraction data, deconvolution of the optical spectra showed a progressive decreasing of the crystal field strength parameter 10 Dq moving toward the Co-åkermanite end-member, meaning that the local cobalt-oxygen bond distance, < {{Co}}{-}{{O}}rangle^{{local}} , increased along the join with the amount of cobalt. The calculated structural relaxation coefficient around the fourfold coordinated Co2+ in the Ca2(Zn1- x Co x )Si2O7 join was ɛ = 0.69, very far from the one predicted by the Vegard's law ( ɛ = 0) and at variance with ɛ = 0.47 previously found for tetrahedrally coordinated Co2+ in gahnite-Co-aluminate spinel solid solution. This difference is consistent with the largest constraints existing on the spinel structure, based on cubic closest packing, compared to the more flexible layered melilite structure.

Scattering of focused ultrasonic beams by cavities in a solid half-space.

PubMed

Rahni, Ehsan Kabiri; Hajzargarbashi, Talieh; Kundu, Tribikram

2012-08-01

The ultrasonic field generated by a point focused acoustic lens placed in a fluid medium adjacent to a solid half-space, containing one or more spherical cavities, is modeled. The semi-analytical distributed point source method (DPSM) is followed for the modeling. This technique properly takes into account the interaction effect between the cavities placed in the focused ultrasonic field, fluid-solid interface and the lens surface. The approximate analytical solution that is available in the literature for the single cavity geometry is very restrictive and cannot handle multiple cavity problems. Finite element solutions for such problems are also prohibitively time consuming at high frequencies. Solution of this problem is necessary to predict when two cavities placed in close proximity inside a solid can be distinguished by an acoustic lens placed outside the solid medium and when such distinction is not possible.

Exact periodic cross-kink wave solutions for the new (2+1)-dimensional KdV equation in fluid flows and plasma physics.

PubMed

Liu, Jian-Guo; Du, Jian-Qiang; Zeng, Zhi-Fang; Ai, Guo-Ping

2016-10-01

The Korteweg-de Vries (KdV)-type models have been shown to describe many important physical situations such as fluid flows, plasma physics, and solid state physics. In this paper, a new (2 + 1)-dimensional KdV equation is discussed. Based on the Hirota's bilinear form and a generalized three-wave approach, we obtain new exact solutions for the new (2 + 1)-dimensional KdV equation. With the help of symbolic computation, the properties for some new solutions are presented with some figures.

Garnet: featured mineral group at the 1993 Tucson Show

USGS Publications Warehouse

Modreski, P.J.

1993-01-01

The garnets are a common but complex group of minerals. They are perhaps the mineral kingdom's best example of solid solution: a relationship in which minerals have chemical compositions that are intermediate between two or more ideal end-member species. In garnet, we deal with a complex group of solid-solution series between as many as 14 end-member minerals. The varying intergradations of solid solution between these different end-members help to explain the garnet group's variety of color, environment of occurrence, gem use, and variation in such physical properties as specific gravity, refractive index, and hardness. -from Author

[Experimental investigation of the straw pre-treatment to enhance its high solid anaerobic digestion].

PubMed

Jiang, Jian-Guo; Zhao, Zhen-Zhen; Du, Xue-Juan; Sui, Ji-Chao; Wu, Shi-Yao

2007-04-01

The straw contains a high content of lignin, which cannot be well utilized by anaerobic bacteria in high solid anaerobic digestion process. This paper presents the experimental investigation of the straw pre-treatment, which aims to destroy the complex structure of the lignin to enhance its high solid anaerobic digestion. The straw is pre-treated in different solutions including NaOH, ammonia, H2SO4, and carbamide. The pre-treating effects are expressed by COD concentration dissolved in the solutions and the 14-day biogas generation in the enhanced aerogenic experiment. Different affecting factors, such as the concentration of the chemical solution, the species of the straw, the pre-treatment reaction time, the reaction temperature and the size of the straw, are investigated. The results show that NaOH solution is the most effective pre-treatment chemical among the four different solutions. The experimental results still indicate that the accumulative biogas production can be 1 500 mL (10 g straw) in 14 days after pre-treatment in 4 mg/L NaOH solution and the dissolved COD in the solution reaches 39 000 mg/L after 24 hours. In addition, the experiment shows that the lignin content in the straw is reduced from 28% to 19% after pre-treatment in 1.5% (in weight) NaOH solution, and it can improve the straw treatment efficiency using high solid anaerobic digestion process.

Quinary wurtzite Zn-Ga-Ge-N-O solid solutions and their photocatalytic properties under visible light irradiation

PubMed Central

Xie, Yinghao; Wu, Fangfang; Sun, Xiaoqin; Chen, Hongmei; Lv, Meilin; Ni, Shuang; Liu, Gang; Xu, Xiaoxiang

2016-01-01

Wurtzite solid solutions between GaN and ZnO highlight an intriguing paradigm for water splitting into hydrogen and oxygen using solar energy. However, large composition discrepancy often occurs inside the compound owing to the volatile nature of Zn, thereby prescribing rigorous terms on synthetic conditions. Here we demonstrate the merits of constituting quinary Zn-Ga-Ge-N-O solid solutions by introducing Ge into the wurtzite framework. The presence of Ge not only mitigates the vaporization of Zn but also strongly promotes particle crystallization. Synthetic details for these quinary compounds were systematically explored and their photocatalytic properties were thoroughly investigated. Proper starting molar ratios of Zn/Ga/Ge are of primary importance for single phase formation, high particle crystallinity and good photocatalytic performance. Efficient photocatalytic hydrogen and oxygen production from water were achieved for these quinary solid solutions which is strongly correlated with Ge content in the structure. Apparent quantum efficiency for optimized sample approaches 1.01% for hydrogen production and 1.14% for oxygen production. Theoretical calculation reveals the critical role of Zn for the band gap reduction in these solid solutions and their superior photocatalytic acitivity can be understood by the preservation of Zn in the structure as well as a good crystallinity after introducing Ge. PMID:26755070

Quinary wurtzite Zn-Ga-Ge-N-O solid solutions and their photocatalytic properties under visible light irradiation.

PubMed

Xie, Yinghao; Wu, Fangfang; Sun, Xiaoqin; Chen, Hongmei; Lv, Meilin; Ni, Shuang; Liu, Gang; Xu, Xiaoxiang

2016-01-12

Wurtzite solid solutions between GaN and ZnO highlight an intriguing paradigm for water splitting into hydrogen and oxygen using solar energy. However, large composition discrepancy often occurs inside the compound owing to the volatile nature of Zn, thereby prescribing rigorous terms on synthetic conditions. Here we demonstrate the merits of constituting quinary Zn-Ga-Ge-N-O solid solutions by introducing Ge into the wurtzite framework. The presence of Ge not only mitigates the vaporization of Zn but also strongly promotes particle crystallization. Synthetic details for these quinary compounds were systematically explored and their photocatalytic properties were thoroughly investigated. Proper starting molar ratios of Zn/Ga/Ge are of primary importance for single phase formation, high particle crystallinity and good photocatalytic performance. Efficient photocatalytic hydrogen and oxygen production from water were achieved for these quinary solid solutions which is strongly correlated with Ge content in the structure. Apparent quantum efficiency for optimized sample approaches 1.01% for hydrogen production and 1.14% for oxygen production. Theoretical calculation reveals the critical role of Zn for the band gap reduction in these solid solutions and their superior photocatalytic acitivity can be understood by the preservation of Zn in the structure as well as a good crystallinity after introducing Ge.

Contribution of Lattice Distortion to Solid Solution Strengthening in a Series of Refractory High Entropy Alloys

NASA Astrophysics Data System (ADS)

Chen, H.; Kauffmann, A.; Laube, S.; Choi, I.-C.; Schwaiger, R.; Huang, Y.; Lichtenberg, K.; Müller, F.; Gorr, B.; Christ, H.-J.; Heilmaier, M.

2018-03-01

We present an experimental approach for revealing the impact of lattice distortion on solid solution strengthening in a series of body-centered-cubic (bcc) Al-containing, refractory high entropy alloys (HEAs) from the Nb-Mo-Cr-Ti-Al system. By systematically varying the Nb and Cr content, a wide range of atomic size difference as a common measure for the lattice distortion was obtained. Single-phase, bcc solid solutions were achieved by arc melting and homogenization as well as verified by means of scanning electron microscopy and X-ray diffraction. The atomic radii of the alloying elements for determination of atomic size difference were recalculated on the basis of the mean atomic radii in and the chemical compositions of the solid solutions. Microhardness (μH) at room temperature correlates well with the deduced atomic size difference. Nevertheless, the mechanisms of microscopic slip lead to pronounced temperature dependence of mechanical strength. In order to account for this particular feature, we present a combined approach, using μH, nanoindentation, and compression tests. The athermal proportion to the yield stress of the investigated equimolar alloys is revealed. These parameters support the universality of this aforementioned correlation. Hence, the pertinence of lattice distortion for solid solution strengthening in bcc HEAs is proven.

Quinary wurtzite Zn-Ga-Ge-N-O solid solutions and their photocatalytic properties under visible light irradiation

NASA Astrophysics Data System (ADS)

Xie, Yinghao; Wu, Fangfang; Sun, Xiaoqin; Chen, Hongmei; Lv, Meilin; Ni, Shuang; Liu, Gang; Xu, Xiaoxiang

2016-01-01

Wurtzite solid solutions between GaN and ZnO highlight an intriguing paradigm for water splitting into hydrogen and oxygen using solar energy. However, large composition discrepancy often occurs inside the compound owing to the volatile nature of Zn, thereby prescribing rigorous terms on synthetic conditions. Here we demonstrate the merits of constituting quinary Zn-Ga-Ge-N-O solid solutions by introducing Ge into the wurtzite framework. The presence of Ge not only mitigates the vaporization of Zn but also strongly promotes particle crystallization. Synthetic details for these quinary compounds were systematically explored and their photocatalytic properties were thoroughly investigated. Proper starting molar ratios of Zn/Ga/Ge are of primary importance for single phase formation, high particle crystallinity and good photocatalytic performance. Efficient photocatalytic hydrogen and oxygen production from water were achieved for these quinary solid solutions which is strongly correlated with Ge content in the structure. Apparent quantum efficiency for optimized sample approaches 1.01% for hydrogen production and 1.14% for oxygen production. Theoretical calculation reveals the critical role of Zn for the band gap reduction in these solid solutions and their superior photocatalytic acitivity can be understood by the preservation of Zn in the structure as well as a good crystallinity after introducing Ge.

Zinc-aluminum oxide solid solution nanosheets obtained by pyrolysis of layered double hydroxide as the photoanodes for dye-sensitized solar cells.

PubMed

Xu, Zhiyuan; Shi, Jingjing; Haroone, Muhammad Sohail; Chen, Wenpeng; Zheng, Shufang; Lu, Jun

2018-04-01

Due to the superiority of metal-doped ZnO compared to TiO 2 , the Zn-M (M = Al 3+ , Ga 3+ , Cr 3+ , Ti 4+ , Ce 4+ ) mixed metal oxide solid solutions have been extensively studied for photocatalytic and photovoltaic applications. In this work, a systematic research has proceeded for the preparation of a zinc-aluminum oxide semiconductor as a photoanode for the dye-sensitized solar cells (DSSCs) by a simple pyrolysis route with the Zn-Al layered double hydroxide (LDH) as a precursor. The Zn-Al oxide solid solution has been applied for DSSCs as an electron acceptor, which is used to study the influence of different Al content and sintering temperature on the device efficiency. Finally, the Zn-Al oxide solid solution with calcination temperature 600 °C and Al 27 at.% content exhibits the best performance. The photoelectric efficiency improved 100 times when the Al 3+ content decreased from 44 to 27 at.%. The Zn x Al y O solid solution show a reasonable efficiency as photoanode materials in DSSCs, with the best preliminary performance reported so far, and shows its potential application for the photovoltaic devices. Copyright © 2018 Elsevier Inc. All rights reserved.

Superhard Rhenium/Tungsten Diboride Solid Solutions.

PubMed

Lech, Andrew T; Turner, Christopher L; Lei, Jialin; Mohammadi, Reza; Tolbert, Sarah H; Kaner, Richard B

2016-11-02

Rhenium diboride (ReB 2 ), containing corrugated layers of covalently bonded boron, is a superhard metallic compound with a microhardness reaching as high as 40.5 GPa (under an applied load of 0.49 N). Tungsten diboride (WB 2 ), which takes a structural hybrid between that of ReB 2 and AlB 2 , where half of the boron layers are planar (as in AlB 2 ) and half are corrugated (as in ReB 2 ), has been shown not to be superhard. Here, we demonstrate that the ReB 2 -type structure can be maintained for solid solutions of tungsten in ReB 2 with tungsten content up to a surprisingly large limit of nearly 50 atom %. The lattice parameters for the solid solutions linearly increase along both the a- and c-axes with increasing tungsten content, as evaluated by powder X-ray and neutron diffraction. From micro- and nanoindentation hardness testing, all of the compositions within the range of 0-48 atom % W are superhard, and the bulk modulus of the 48 atom % solid solution is nearly identical to that of pure ReB 2 . These results further indicate that ReB 2 -structured compounds are superhard, as has been predicted from first-principles calculations, and may warrant further studies into additional solid solutions or ternary compounds taking this structure type.

Mechanical properties and the electronic structure of transition of metal alloys

NASA Technical Reports Server (NTRS)

Arsenault, R. J.; Drew, H. D.

1977-01-01

This interdiscipline research program was undertaken in an effort to investigate the relationship between the mechanical strength of Mo based alloys with their electronic structure. Electronic properties of these alloys were examined through optical studies, and the classical solid solution strengthening mechanisms were considered, based on size and molecular differences to determine if these mechanisms could explain the hardness data.

Preparation of resveratrol-loaded nanoporous silica materials with different structures

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

Popova, Margarita, E-mail: mpopova@orgchem.bas.bg; Szegedi, Agnes; Mavrodinova, Vesselina

2014-11-15

Solid, nanoporous silica-based spherical mesoporous MCM-41 and KIL-2 with interparticle mesoporosity as well as nanosized zeolite BEA materials differing in morphology and pore size distribution, were used as carriers for the preparation of resveratrol-loaded delivery systems. Two preparation methods have been applied: (i) loading by mixing of resveratrol and mesoporous carrier in solid state and (ii) deposition in ethanol solution. The parent and the resveratrol loaded carriers were characterized by XRD, TEM, N2 physisorption, thermal analysis, and FT-IR spectroscopy. The influence of the support structure on the adsorption capacity and the release kinetics of this poorly soluble compound were investigated.more » Our results indicated that the chosen nanoporous silica supports are suitable for stabilization of trans-resveratrol and reveal controlled release and ability to protect the supported compound against degradation regardless of loading method. The solid-state dry mixing appears very effective for preparation of drug formulations composed of poorly soluble compound. - Graphical abstract: trans-Resveratrol was stabilized in the pores of BEA zeolite, MCM-41and KIL2 mesoporous silicas. - Highlights: • BEA, KIL-2 and MCM-41 materials were used as carriers for resveratrol loading. • Resveratrol encapsulation in ethanol solution and solid state procedure were applied. • The solid-state preparation appears very effective for stabilization of trans-resveratrol.« less

Approximate analysis of the formation of a buoyant solid sphere in a supercooled melt

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

Solomon, A.D.; Wilson, D.G.; Alexiades, V.

1986-03-01

A mathematical model is presented for the idealized formation and development of a buoyant sphere solidifying in an infinite pool of supercooled liquid. The solid and liquid are of the same pure material and the solid is less dense than the liquid. Initially the liquid is at a uniform temperature that is below its equilibrium freezing temperature, T/sub cr/, but above the so called hypercooled temperature, T/sub cr/ - H/c/sub L/. Here H and c/sub L/ are the latent heat of solidification and the specific heat of the liquid, respectively. An approximate solution is derived based on the Megerlin approximationmore » method. 11 refs.« less

Solid-state emissive triarylborane-based BODIPY dyes: photophysical properties and fluorescent sensing for fluoride and cyanide ions.

PubMed

Fu, Guang-Liang; Pan, Hong; Zhao, Yi-Hong; Zhao, Cui-Hua

2011-12-07

We disclose two novel BODIPY dyes, which contain the bulky substituent, [(4-dimesitylboryl)phenyl]ethynyl at 2- and 2,6-positions. The steric bulkiness of the boryl group is effective to suppress the intermolecular interaction in the solid state and thus these two compounds display intense fluorescence not only in solution but also in the solid state. In addition, the BODIPY dyes display sensitive fluorescence responses to fluoride and cyanide anions through the complexation with the boron center of the boryl group and the subsequent decomposition of the BODIPY core, illustrating their potential uses for the fluorescence sensing of fluoride and cyanide ions.

Comparison of the solid-phase fragment condensation and phase-change approaches in the synthesis of salmon I calcitonin.

PubMed

Gatos, D; Tzavara, C

2001-02-01

Salmon I calcitonin was synthesized using both phase-change and conventional solid-phase fragment condensation (SPFC) approaches, utilizing the Rink amide linker (Fmoc-amido-2,4-dimethoxybenzyl-4-phenoxyacetic acid) combined with 2-chlorotrityl resin and the Fmoc/tBu(Trt)-based protection scheme. Phase-change synthesis, performed by the selective detachment of the fully protected C-terminal 22-mer peptide-linker from the resin and subsequent condensation in solution with the N-terminal 1-10 fragment, gave a product of slightly less purity (85 vs. 92%) than the corresponding synthesis on the solid-phase. In both cases salmon I calcitonin was easily obtained in high purity.

Method of making supercritical fluid molecular spray films, powder and fibers

DOEpatents

Smith, Richard D.

1988-01-01

Solid films are deposited, or fine powders formed, by dissolving a solid material into a supercritical fluid solution at an elevated pressure and then rapidly expanding the solution through a heated nozzle having a short orifice into a region of relatively low pressure. This produces a molecular spray which is directed against a substrate to deposit a solid thin film thereon, or discharged into a collection chamber to collect a fine powder. In another embodiment, the temperature of the solution and nozzle is elevated above the melting point of the solute, which is preferably a polymer, and the solution is maintained at a pressure such that, during expansion, the solute precipitates out of solution within the nozzle in a liquid state. Alternatively, a secondary solvent mutually soluble with the solute and primary solvent and having a higher critical temperature than that of primary solvent is used in a low concentration (<20%) to maintain the solute in a transient liquid state. The solute is discharged in the form of long, thin fibers. The fibers are collected at sufficient distance from the orifice to allow them to solidify in the low pressure/temperature region.

Using solid 13C NMR coupled with solution 31P NMR spectroscopy to investigate molecular species and lability of organic carbon and phosphorus from aquatic plants in Tai Lake, China

USDA-ARS?s Scientific Manuscript database

Aquatic plants are involved in the storage and release capacity for organic matter and nutrients. In this study, solid 13C and solution 31P nuclear magnetic resonance (NMR) spectroscopy were used to characterize the biomass samples of six aquatic plants. Solid 13C NMR spectroscopy revealed the domin...

Synergistic Strategy to Enhance the Thermoelectric Properties of CoSbS1-xSex Compounds via Solid Solution.

PubMed

Yao, Wei; Yang, Dingfeng; Yan, Yanci; Peng, Kunling; Zhan, Heng; Liu, Anping; Lu, Xu; Wang, Guoyu; Zhou, Xiaoyuan

2017-03-29

High thermal conductivity of CoSbS-based limited its own prospect application in thermoelectric energy conversion. Solid solution is an effective approach to optimize the performance of thermoelectric materials with high lattice thermal conductivity because of the enhanced phonons scattering from disorder atoms. In this paper, we have synthesized and measured the thermoelectric properties of solid solution CoSbS 1-x Se x (x = 0, 0.05, 0.10, 0.15, 0.20, 0.30) series samples. The collaborative optimization (enhancing the power factors and reducing the thermal conductivities) to add zT values were realized via substitution of S atoms with the isoelectronic Se atoms in the matrix. Meanwhile, the lowest room temperature lattice thermal conductivity in CoSbS-based materials is obtained (4.72 W m -1 K -1 ) at present. Benefiting from the results of synergistic strategy, a zT of 0.35 was achieved at 923 K for sample CoSbS 0.85 Se 0.15 , a 59% improvement as compared with that of the pristine CoSbS. Band calculation demonstrated that CoSbS 0.85 Se 0.15 present a similar band dispersion with CoSbS. The mechanism of point defect scattering for reducing the lattice thermal conductivity at room temperature, was also analyzed by the Callaway model. The contributions to decrease the room temperature lattice thermal conductivity from the mass and the strain fluctuation in the crystal are comparable. These results can also be extended to other high-efficiency thermoelectric materials with stiff bond and smaller Gruneisen parameters.

Simulation of radial solute segregation in vertical Bridgman growth of pyridine-doped benzene, a surrogate for binary organic nonlinear optical materials

NASA Astrophysics Data System (ADS)

Lee, Hanjie; Pearlstein, Arne J.

2000-09-01

We present steady axisymmetric computations of solute distributions and radial segregation for vertical Bridgman growth of pyridine-doped benzene, a binary aromatic system with anisotropic solid-phase thermal conductivity, that serves as a model of solute transport in crystal growth of organic nonlinear optical materials. The radial variation of solid-phase mass fraction ( Cs) of pyridine, which is rejected at the growing interface, depends strongly on growth conditions. High growth velocities tend to increase Cs near the centerline, the ampoule wall, or both, and low growth velocities give more nearly uniform radial distributions. The maximum ampoule-wall temperature gradient also affects radial segregation, with convex-to-the-liquid interfaces at small temperature gradients being associated with radially monotonic Cs distributions, and ridged interfaces at higher gradients being associated with nonmonotonic distributions having maxima at the centerline and ampoule wall. Nonuniformity is strongly determined by both interface shape and the nature of the flow near the interface. Solute is transported down to the interface by a large toroidal vortex, and swept radially inward to the centerline by a second, flattened toroidal cell. When the interface is depressed at its junction with the ampoule wall, rejected solute accumulates in the overlying liquid, where convection is relatively weak, resulting in local solute enrichment of the solid. Computations at normal and zero gravity show that for two very similar interface shapes, a maximum in the radial solid-phase solute distribution at the ampoule wall is associated with the interface shape, while the maximum on the centerline is associated with sweeping of solute to the centerline by a vortical flow on the interface. We also show that radial solute segregation depends significantly on whether account is taken of the anisotropy of the solid-phase thermal conductivity. Finally, the computations provide guidance as to the minimum ampoule length required to produce an axially uniform solute distribution over at least part of the length of a boule.

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

Islam, Md. Shafiqul, E-mail: shafique@eng.ukm.my; Hannan, M.A., E-mail: hannan@eng.ukm.my; Basri, Hassan

Highlights: • Solid waste bin level detection using Dynamic Time Warping (DTW). • Gabor wavelet filter is used to extract the solid waste image features. • Multi-Layer Perceptron classifier network is used for bin image classification. • The classification performance evaluated by ROC curve analysis. - Abstract: The increasing requirement for Solid Waste Management (SWM) has become a significant challenge for municipal authorities. A number of integrated systems and methods have introduced to overcome this challenge. Many researchers have aimed to develop an ideal SWM system, including approaches involving software-based routing, Geographic Information Systems (GIS), Radio-frequency Identification (RFID), or sensormore » intelligent bins. Image processing solutions for the Solid Waste (SW) collection have also been developed; however, during capturing the bin image, it is challenging to position the camera for getting a bin area centralized image. As yet, there is no ideal system which can correctly estimate the amount of SW. This paper briefly discusses an efficient image processing solution to overcome these problems. Dynamic Time Warping (DTW) was used for detecting and cropping the bin area and Gabor wavelet (GW) was introduced for feature extraction of the waste bin image. Image features were used to train the classifier. A Multi-Layer Perceptron (MLP) classifier was used to classify the waste bin level and estimate the amount of waste inside the bin. The area under the Receiver Operating Characteristic (ROC) curves was used to statistically evaluate classifier performance. The results of this developed system are comparable to previous image processing based system. The system demonstration using DTW with GW for feature extraction and an MLP classifier led to promising results with respect to the accuracy of waste level estimation (98.50%). The application can be used to optimize the routing of waste collection based on the estimated bin level.« less

Enhanced photovoltaic performance and stability with a new type of hollow 3D perovskite {en}FASnI 3

DOE PAGES

Ke, Weijun; Stoumpos, Constantinos C.; Zhu, Menghua; ...

2017-08-30

Perovskite solar cells have revolutionized the fabrication of solution-processable solar cells. The presence of lead in the devices makes this technology less attractive, and alternative metals in perovskites are being researched as suitable alternatives. We demonstrate a new type of tin-based perovskite absorber that incorporates both ethylenediammonium (en) and formamidinium (FA), forming new materials of the type {en}FASnI 3. The three-dimensional ASnI 3 structure is stable only with methylammonium, FA, and Cs cations, and the bandgap can be tuned with solid solutions, such as ASnI 3-xBr x. We show that en can serve as a new A cation capable ofmore » achieving marked increases in the bandgap without the need for solid solutions. The en introduces a new bandgap tuning mechanism that arises from massive Schottky style defects. In addition, incorporation of the en cation in the structure markedly increases the air stability and improves the photoelectric properties of the tin-based perovskite absorbers. Our best-performing {en}FASnI 3 solar cell has the highest efficiency of 7.14%, which is achieved for a lead-free perovskite cell, and retains 96% of its initial efficiency after aging over 1000 hours with encapsulation. Our results introduce a new approach for improving the performance and stability of tin-based, lead-free perovskite solar cells.« less

Enhanced photovoltaic performance and stability with a new type of hollow 3D perovskite {en}FASnI 3

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

Ke, Weijun; Stoumpos, Constantinos C.; Zhu, Menghua

Perovskite solar cells have revolutionized the fabrication of solution-processable solar cells. The presence of lead in the devices makes this technology less attractive, and alternative metals in perovskites are being researched as suitable alternatives. We demonstrate a new type of tin-based perovskite absorber that incorporates both ethylenediammonium (en) and formamidinium (FA), forming new materials of the type {en}FASnI 3. The three-dimensional ASnI 3 structure is stable only with methylammonium, FA, and Cs cations, and the bandgap can be tuned with solid solutions, such as ASnI 3-xBr x. We show that en can serve as a new A cation capable ofmore » achieving marked increases in the bandgap without the need for solid solutions. The en introduces a new bandgap tuning mechanism that arises from massive Schottky style defects. In addition, incorporation of the en cation in the structure markedly increases the air stability and improves the photoelectric properties of the tin-based perovskite absorbers. Our best-performing {en}FASnI 3 solar cell has the highest efficiency of 7.14%, which is achieved for a lead-free perovskite cell, and retains 96% of its initial efficiency after aging over 1000 hours with encapsulation. Our results introduce a new approach for improving the performance and stability of tin-based, lead-free perovskite solar cells.« less

Enhanced photovoltaic performance and stability with a new type of hollow 3D perovskite {en}FASnI3

PubMed Central

Ke, Weijun; Stoumpos, Constantinos C.; Zhu, Menghua; Mao, Lingling; Spanopoulos, Ioannis; Liu, Jian; Kontsevoi, Oleg Y.; Chen, Michelle; Sarma, Debajit; Zhang, Yongbo; Wasielewski, Michael R.; Kanatzidis, Mercouri G.

2017-01-01

Perovskite solar cells have revolutionized the fabrication of solution-processable solar cells. The presence of lead in the devices makes this technology less attractive, and alternative metals in perovskites are being researched as suitable alternatives. We demonstrate a new type of tin-based perovskite absorber that incorporates both ethylenediammonium (en) and formamidinium (FA), forming new materials of the type {en}FASnI3. The three-dimensional ASnI3 structure is stable only with methylammonium, FA, and Cs cations, and the bandgap can be tuned with solid solutions, such as ASnI3−xBrx. We show that en can serve as a new A cation capable of achieving marked increases in the bandgap without the need for solid solutions. The en introduces a new bandgap tuning mechanism that arises from massive Schottky style defects. In addition, incorporation of the en cation in the structure markedly increases the air stability and improves the photoelectric properties of the tin-based perovskite absorbers. Our best-performing {en}FASnI3 solar cell has the highest efficiency of 7.14%, which is achieved for a lead-free perovskite cell, and retains 96% of its initial efficiency after aging over 1000 hours with encapsulation. Our results introduce a new approach for improving the performance and stability of tin-based, lead-free perovskite solar cells. PMID:28875173

Spectroscopic studies of the intramolecular hydrogen bonding in o-hydroxy Schiff bases, derived from diaminomaleonitrile, and their deprotonation reaction products

NASA Astrophysics Data System (ADS)

Szady-Chełmieniecka, Anna; Kołodziej, Beata; Morawiak, Maja; Kamieński, Bohdan; Schilf, Wojciech

2018-01-01

The structural study of five Schiff bases derived from diaminomaleonitrile (DAMN) and 2-hydroxy carbonyl compounds was performed using 1H, 13C and 15N NMR methods in solution and in the solid state as well. ATR-FTIR and X-Ray spectroscopies were used for confirmation of the results obtained by NMR method. The imine obtained from DAMN and benzaldehyde was synthesized as a model compound which lacks intramolecular hydrogen bond. Deprotonation of all synthesized compounds was done by treating with tetramethylguanidine (TMG). NMR data revealed that salicylidene Schiff bases in DMSO solution exist as OH forms without intramolecular hydrogen bonds and independent on the substituents in aromatic ring. In the case of 2-hydroxy naphthyl derivative, the OH proton is engaged into weak intramolecular hydrogen bond. Two of imines (salDAMN and 5-BrsalDAMN) exist in DMSO solution as equilibrium mixtures of two isomers (A and B). The structures of equilibrium mixture in the solid state have been studied by NMR, ATR-FTIR and X-Ray methods. The deprotonation of three studied compounds (salDAMN, 5-BrsalDAMN, and 5-CH3salDAMN) proceeded in two different ways: deprotonation of oxygen atom (X form) or of nitrogen atom of free primary amine group of DAMN moiety (Y form). For 5-NO2salDAMN and naphDAMN only one form (X) was observed.

Free energies of formation of WC and WzC and the thermodynamic properties of carbon in solid tungsten

NASA Technical Reports Server (NTRS)

Gupta, D. K.; Seigle, L. L.

1974-01-01

The activity of carbon in the two-phase regions - W + WC and W + W2C was obtained from the carbon content of iron rods equilibrated with mixtures of metal plus carbide powders. From this activity data the standard free energies of formation of WC and W2C were calculated. The temperature of the invariant reaction W2C = W + WC was fixed at 1570 + or - 5K. Using available solubility data for C in solid W, the partial molar free energy of C in the dilute solid solution was also calculated. The heat of solution of C in W, and the excess entropy for the interstitial solid solution, were computed, assuming that the carbon atoms reside in the octahedral interstices of bcc W.

Optical and Piezoelectric Study of KNN Solid Solutions Co-Doped with La-Mn and Eu-Fe.

PubMed

Peña-Jiménez, Jesús-Alejandro; González, Federico; López-Juárez, Rigoberto; Hernández-Alcántara, José-Manuel; Camarillo, Enrique; Murrieta-Sánchez, Héctor; Pardo, Lorena; Villafuerte-Castrejón, María-Elena

2016-09-28

The solid-state method was used to synthesize single phase potassium-sodium niobate (KNN) co-doped with the La 3+ -Mn 4+ and Eu 3+ -Fe 3+ ion pairs. Structural determination of all studied solid solutions was accomplished by XRD and Rietveld refinement method. Electron paramagnetic resonance (EPR) studies were performed to determine the oxidation state of paramagnetic centers. Optical spectroscopy measurements, excitation, emission and decay lifetime were carried out for each solid solution. The present study reveals that doping KNN with La 3+ -Mn 4+ and Eu 3+ -Fe 3+ at concentrations of 0.5 mol % and 1 mol %, respectively, improves the ferroelectric and piezoelectric behavior and induce the generation of optical properties in the material for potential applications.

Optical and Piezoelectric Study of KNN Solid Solutions Co-Doped with La-Mn and Eu-Fe

PubMed Central

Peña-Jiménez, Jesús-Alejandro; González, Federico; López-Juárez, Rigoberto; Hernández-Alcántara, José-Manuel; Camarillo, Enrique; Murrieta-Sánchez, Héctor; Pardo, Lorena; Villafuerte-Castrejón, María-Elena

2016-01-01

The solid-state method was used to synthesize single phase potassium-sodium niobate (KNN) co-doped with the La3+–Mn4+ and Eu3+–Fe3+ ion pairs. Structural determination of all studied solid solutions was accomplished by XRD and Rietveld refinement method. Electron paramagnetic resonance (EPR) studies were performed to determine the oxidation state of paramagnetic centers. Optical spectroscopy measurements, excitation, emission and decay lifetime were carried out for each solid solution. The present study reveals that doping KNN with La3+–Mn4+ and Eu3+–Fe3+ at concentrations of 0.5 mol % and 1 mol %, respectively, improves the ferroelectric and piezoelectric behavior and induce the generation of optical properties in the material for potential applications. PMID:28773925

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

Chezhina, N.V., E-mail: chezhina@nc2490.spb.edu; Korolev, D.A.; Zhuk, N.A.

On the basis of the results of magnetic susceptibility and ESR studies of the Bi{sub 3}Nb{sub 1−x}Fe{sub x}O{sub 7−δ} solid solutions iron atoms in the solid solutions of cubic modification of bismuth niobate were found to exist as Fe(III) monomers and exchange bound Fe(III)-O-Fe(III) dimers with antiferro- and ferromagnetic type of superexchange. The exchange parameters and the distribution of monomers and dimers in the solid solutions were calculated as a function of paramagnetic atom content. - Graphical abstract: The study of the Bi{sub 3}Nb{sub 1−x}Fe{sub x}O{sub 7−δ} solid solutions showed that the introduction of iron atoms into the structure ofmore » Bi{sub 3}NbO{sub 7} stabilizes the cubic structure of bismuth niobate making the phase transition tetragonal ↔ cubic structure irreversible. In the Bi{sub 3}Nb{sub 1−x}Fe{sub x}O{sub 7−δ} solid solutions we observe the formation of dimers with antiferro- and ferromagnetic exchange. Such clusters are partially retained even at the infinite dilution of the solid solution, which testifies for their rigidity. A sufficiently high parameter of ferromagnetic exchange in a dimer (+53 cm{sup −1}) seems to result from iron atoms being located in the vicinity of oxygen vacancy. - Highlights: • The reversible transition cubic – tetragonal modifications in Bi{sub 3}NbO{sub 7} becomes irreversible. • Only cubic modification of Bi{sub 3}Nb{sub 1-x}Fe{sub x}O{sub 7-δ} is stable due to clusters of Fe atoms. • These clusters are sufficiently strong and retained even at the infinite dilution. • The calculations of magnetic susceptibility give the distribution of the clusters and single atoms.« less

Stabilization of lead in an alkali-activated municipal solid waste incineration fly ash-Pyrophyllite-based system.

PubMed

Shiota, Kenji; Nakamura, Takafumi; Takaoka, Masaki; Aminuddin, Siti Fatimah; Oshita, Kazuyuki; Fujimori, Takashi

2017-10-01

This work focuses on the stabilization and speciation of lead (Pb) in a composite solid produced from an alkali-activated municipal solid waste incineration fly ash (MSWIFA)-pyophyllite-based system. The solid product was synthesized after mixtures of raw materials (dehydrated pyrophyllite, MSWIFA, 14 mol/L aqueous sodium hydroxide, and sodium silicate solution) were cured at 105 °C for 24 h. The product could reduce the leaching of Pb and the Pb concentration in the leachate was 7.0 × 10 -3 using the Japanese leaching test and 9.7 × 10 -4  mg/L using toxicity characteristics leaching procedure method, which satisfied the respective test criteria and successfully stabilized Pb in this system. The solid product had a compressive strength of 2 MPa and consisted mainly of crystalline phases. Scanning electron microscopy with X-ray analysis and X-ray absorption fine structure suggested that Pb was present along with Al, Si, and O, and that the atomic environment around the Pb was similar to that of PbSiO 3 . These results suggest that the alkali-activated MSWIFA-pyrophyllite-based system could be used to stabilize Pb in MSWIFA. Copyright © 2017 Elsevier Ltd. All rights reserved.

Determining the Release of Radionuclides from Tank 18F Waste Residual Solids: FY2016 Report

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

King, William D.; Hobbs, David T.

Pore water leaching studies were conducted on actual Savannah River Site (SRS) Tank 18F residual waste solids to support Liquid Waste tank closure efforts. A test methodology was developed during previous simulant testing to produce slurries of tank residual solids and grout-representative solids in grout pore water solutions (based on SRS groundwater compositions) with pH and E h values expected during the aging of the closed waste tank. The target conditions are provided below where the initial pore water has a reducing potential and a relatively high pH (Reducing Region II). The pore water is expected to become increasingly oxidizingmore » with time (Oxidizing Region II) and during the latter stages of aging (Oxidizing Region III) the pH is expected to decrease. For the reducing case, tests were conducted with both unwashed and washed Tank 18F residual solids. For the oxidizing cases (Oxidizing Regions II and III), all samples were washed with simulated grout pore water solutions prior to testing, since it is expected that these conditions will occur after considerable pore water solution has passed through the system. For the reducing case, separate tests were conducted with representative ground grout solids and with calcium carbonate reagent, which is the grout phase believed to be controlling the pH. Ferrous sulfide (FeS) solids were also added to the reducing samples to lower the slurry E h value. Calcium carbonate solids were used as the grout-representative solid phase for each of the oxidizing cases. Air purge-gas with and without CO 2 removed was transferred through the oxidizing test samples and nitrogen purge-gas was transferred through the reducing test samples during leach testing. The target pH values were achieved to within 0.5 pH units for all samples. Leaching studies were conducted over an E h range of approximately 0.7 V. However, the highest and lowest E h values achieved of ~+0.5 V and ~-0.2 V were significantly less positive and less negative, respectively, than the target values. Achievement of more positive and more negative E h values is believed to require the addition of non-representative oxidants and reductants, respectively.« less

Using colloidal silica as isolator, diverter and blocking agent for subsurface geological applications

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

Bourcier, William L.; Roberts, Sarah K.; Roberts, Jeffery J.

A system for blocking fast flow paths in geological formations includes preparing a solution of colloidal silica having a nonviscous phase and a solid gel phase. The solution of colloidal silica is injected into the geological formations while the solution of colloidal silica is in the nonviscous phase. The solution of colloidal silica is directed into the fast flow paths and reaches the solid gel phase in the fast flow paths thereby blocking flow of fluid in the fast paths.

Containerless synthesis of amorphous and nanophase organic materials

DOEpatents

Benmore, Chris J.; Weber, Johann R.

2016-05-03

The invention provides a method for producing a mixture of amorphous compounds, the method comprising supplying a solution containing the compounds; and allowing at least a portion of the solvent of the solution to evaporate while preventing the solute of the solution from contacting a nucleation point. Also provided is a method for transforming solids to amorphous material, the method comprising heating the solids in an environment to form a melt, wherein the environment contains no nucleation points; and cooling the melt in the environment.

Electrochemical luminescence determination of hyperin using a sol-gel@graphene luminescent composite film modified electrode for solid phase microextraction

NASA Astrophysics Data System (ADS)

Zou, Xiaojun; Shang, Fang; Wang, Sui

2017-02-01

In this paper, a novel electrochemiluminescence (ECL) sensor of sol-gel@graphene luminescent composite film modified electrode for hyperin determination was prepared using graphene (G) as solid-phase microextraction (SPME) material, based on selective preconcentration of target onto an electrode and followed by luminol ECL detection. Hyperin was firstly extracted from aqueous solution through the modified GCE. Hydrogel, electrogenerated chemiluminescence reagents, pH of working solution, extraction time and temperature and scan rate were discussed. Under the optimum conditions, the change of ECL intensity was in proportion to the concentration of hyperin in the range of 0.02-0.24 μg/mL with a detection limit of 0.01 μg/mL. This method showed good performance in stability, reproducibility and precision for the determination of hyperin.

An iterative Riemann solver for systems of hyperbolic conservation law s, with application to hyperelastic solid mechanics

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

Miller, Gregory H.

2003-08-06

In this paper we present a general iterative method for the solution of the Riemann problem for hyperbolic systems of PDEs. The method is based on the multiple shooting method for free boundary value problems. We demonstrate the method by solving one-dimensional Riemann problems for hyperelastic solid mechanics. Even for conditions representative of routine laboratory conditions and military ballistics, dramatic differences are seen between the exact and approximate Riemann solution. The greatest discrepancy arises from misallocation of energy between compressional and thermal modes by the approximate solver, resulting in nonphysical entropy and temperature estimates. Several pathological conditions arise in commonmore » practice, and modifications to the method to handle these are discussed. These include points where genuine nonlinearity is lost, degeneracies, and eigenvector deficiencies that occur upon melting.« less

Alternative solution model for the ternary carbonate system CaCO3 - MgCO3 - FeCO3 - I. A ternary Bragg-Williams ordering model

USGS Publications Warehouse

McSwiggen, P.L.

1993-01-01

The minerals of the ternary carbonate system CaCO3 - MgCO3 - FeCO3 represent a complex series of solid solutions and ordering states. An understanding of those complexities requires a solution model that can both duplicate the subsolidus phase relationships and generate correct values for the activities. Such a solution model must account for the changes in the total energy of the system resulting from a change in the ordering state of the individual constituents. Various ordering models have been applied to binary carbonate systems, but no attempts have previously been made to model the ordering in the ternary system. This study derives a new set of equations that allow for the equilibrium degree of order to be calculated for a system involving three cations mixing on two sites, as in the case of the ternary carbonates. The method is based on the Bragg-Williams approach. From the degree of order, the mole fractions of the three cations in each of the two sites can be determined. Once the site occupancies have been established, a Margules-type mixing model can be used to determine the free energy of mixing in the solid solution and therefore the activities of the various components. ?? 1993 Springer-Verlag.

Unexpected Solubility Enhancement of Drug Bases in the Presence of a Dimethylaminoethyl Methacrylate Copolymer.

PubMed

Saal, Wiebke; Ross, Alfred; Wyttenbach, Nicole; Alsenz, Jochem; Kuentz, Martin

2018-01-02

The methacrylate copolymer Eudragit EPO (EPO) has previously shown to greatly enhance solubilization of acidic drugs via ionic interactions and by multiple hydrophobic contacts with polymeric side chains. The latter type of interaction could also play a role for solubilization of other compounds than acids. The aim of this study was therefore to investigate the solubility of six poorly soluble bases in presence and absence of EPO by quantitative ultrapressure liquid chromatography with concomitant X-ray powder diffraction analysis of the solid state. For a better mechanistic understanding, spectra and diffusion data were obtained by 1 H nuclear magnetic resonance (NMR) spectroscopy. Unexpected high solubility enhancement (up to 360-fold) was evidenced in the presence of EPO despite the fact that bases and polymer were both carrying positive charges. This exceptional and unexpected solubilization was not due to a change in the crystalline solid state. NMR spectra and measured diffusion coefficients indicated both strong drug-polymer interactions in the bulk solution, and diffusion data suggested conformational changes of the polymer in solution. Such conformational changes may have increased the accessibility and extent of hydrophobic contacts thereby leading to increased overall molecular interactions. These initially surprising solubilization results demonstrate that excipient selection should not be based solely on simple considerations of, for example, opposite charges of drug and excipient, but it requires a more refined molecular view. Different solution NMR techniques are especially promising tools to gain such mechanistic insights.

The use of carrier RNA to enhance DNA extraction from microfluidic-based silica monoliths.

PubMed

Shaw, Kirsty J; Thain, Lauren; Docker, Peter T; Dyer, Charlotte E; Greenman, John; Greenway, Gillian M; Haswell, Stephen J

2009-10-12

DNA extraction was carried out on silica-based monoliths within a microfluidic device. Solid-phase DNA extraction methodology was applied in which the DNA binds to silica in the presence of a chaotropic salt, such as guanidine hydrochloride, and is eluted in a low ionic strength solution, such as water. The addition of poly-A carrier RNA to the chaotropic salt solution resulted in a marked increase in the effective amount of DNA that could be recovered (25ng) compared to the absence of RNA (5ng) using the silica-based monolith. These findings confirm that techniques utilising nucleic acid carrier molecules can enhance DNA extraction methodologies in microfluidic applications.

Solid state phase change materials for thermal energy storage in passive solar heated buildings

NASA Astrophysics Data System (ADS)

Benson, D. K.; Christensen, C.

1983-11-01

A set of solid state phase change materials was evaluated for possible use in passive solar thermal energy storage systems. The most promising materials are organic solid solutions of pentaerythritol, pentaglycerine and neopentyl glycol. Solid solution mixtures of these compounds can be tailored so that they exhibit solid-to-solid phase transformations at any desired temperature within the range from less than 25 deg to 188 deg. Thermophysical properties such as thermal conductivity, density and volumetric expansion were measured. Computer simulations were used to predict the performance of various Trombe wall designs incorporating solid state phase change materials. Optimum performance was found to be sensitive to the choice of phase change temperatures and to the thermal conductivity of the phase change material. A molecular mechanism of the solid state phase transition is proposed and supported by infrared spectroscopic evidence.

Atomistic simulation of mineral-melt trace-element partitioning

NASA Astrophysics Data System (ADS)

Allan, Neil L.; Du, Zhimei; Lavrentiev, Mikhail Yu.; Blundy, Jon D.; Purton, John A.; van Westrenen, Wim

2003-09-01

We discuss recent advances in computational approaches to trace-element incorporation in minerals and melts. It is crucial to take explicit account of the local structural environment of each ion in the solid and the change in this environment following the introduction of a foreign atom or atoms. Particular attention is paid to models using relaxation (strain) energies and solution energies, and the use of these different models for isovalent and heterovalent substitution in diopside and forsterite. Solution energies are also evaluated for pyrope and grossular garnets, and pyrope-grossular solid solutions. Unfavourable interactions between dodecahedral sites containing ions of the same size and connected by an intervening tetrahedron lead to larger solubilities of trace elements in the garnet solid solution than in either end member compound and to the failure of Goldschmidt's first rule. Our final two examples are the partitioning behaviour of noble gases, which behave as 'ions of zero charge' and the direct calculation of high-temperature partition coefficients between CaO solid and melt via Monte Carlo simulations.

Hydrothermal synthesis of pollucite, analcime and their solid solutions and analysis of their properties

NASA Astrophysics Data System (ADS)

Jing, Zhenzi; Cai, Kunchuan; Li, Yan; Fan, Junjie; Zhang, Yi; Miao, Jiajun; Chen, Yuqian; Jin, Fangming

2017-05-01

Pollucite, as a perfect long-term potential host for radioactive Cs immobilization, barely exists in pure form naturally but in an isomorphism form between pollucite and analcime due to coexistence of Cs and Na. Pollucite could be hydrothermally synthesized with Cs-polluted soil or clay minerals which contain Cs and Na, and it is necessary to study the properties of the synthesis if Cs and Na contained. Pure pollucite, analcime and their solid solutions were hydrothermally synthesized with chemicals, and it was found that the most formed pollucite analcime solid solutions with Cs/(Cs + Na) ratios of 2/6-5/6 had very similar properties in mineral composition, morphology and size, structural water (Cs cations) and coordination environment to pollucite. This also suggests that even coexistence of Cs and Na in nature, pollucite favors to form due to site preference for Cs over Na, which leads to the property and the structure of the most solid solutions similar to that of pollucite.

Optimisation of dynamic nuclear polarisation of [1-13C] pyruvate by addition of gadolinium-based contrast agents

NASA Astrophysics Data System (ADS)

Friesen-Waldner, Lanette; Chen, Albert; Mander, Will; Scholl, Timothy J.; McKenzie, Charles A.

2012-10-01

Dynamic nuclear polarisation (DNP) of carbon-13 (13C) enriched endogenous compounds provides a novel means for magnetic resonance imaging and spectroscopy of biological processes. Adding small amounts of gadolinium-based contrast agents (GBCAs) to the 13C-enriched substrate matrix increases the amount of hyperpolarisation that can be achieved, but also may decrease the longitudinal relaxation time (T1) of the 13C nucleus in solution. This study examined the effects of five different GBCA at concentrations of 0.5, 1, 2, and 3 mM on [1-13C]-enriched pyruvic acid. It was found that contrast agents with an open chain structure (Gadobenate dimeglumine, Gadopentetate dimeglumine, Gadodiamide) caused the largest enhancement (up to 82%) in solid state polarisation relative to solutions without GBCA. In the liquid state, T1 of pyruvate decreased by as much as 62% and polarisation was much lower (70%) relative to solutions without GBCA added. Conversely, for GBCA with macrocyclic structures (Gadoterate meglumine, Gadoteridol), the solid state polarisation enhancement was only slightly less than the open chain GBCA, but enhanced polarisation was retained much better in the liquid state with minimal decrease in T1 (25% at the highest GBCA concentrations). Near maximum polarisation in the solid state was obtained at a GBCA concentration of 2 mM, with a higher concentration of 3 mM producing minimal improvement. These results indicate that the macrocyclic contrast agents provide the best combination of high solid state and liquid state polarisations with minimal loss of T1 in experiments with hyperpolarised 13C-enriched pyruvate. This suggests that macrocyclic contrast agents should be the GBCA of choice for maximising signal in experiments with hyperpolarised 13C-enriched pyruvate, particularly for in vivo measurements where shortened substrate T1 is especially problematic.

Acyl guanidine inhibitors of β-secretase (BACE-1): optimization of a micromolar hit to a nanomolar lead via iterative solid- and solution-phase library synthesis.

PubMed

Gerritz, Samuel W; Zhai, Weixu; Shi, Shuhao; Zhu, Shirong; Toyn, Jeremy H; Meredith, Jere E; Iben, Lawrence G; Burton, Catherine R; Albright, Charles F; Good, Andrew C; Tebben, Andrew J; Muckelbauer, Jodi K; Camac, Daniel M; Metzler, William; Cook, Lynda S; Padmanabha, Ramesh; Lentz, Kimberley A; Sofia, Michael J; Poss, Michael A; Macor, John E; Thompson, Lorin A

2012-11-08

This report describes the discovery and optimization of a BACE-1 inhibitor series containing an unusual acyl guanidine chemotype that was originally synthesized as part of a 6041-membered solid-phase library. The synthesis of multiple follow-up solid- and solution-phase libraries facilitated the optimization of the original micromolar hit into a single-digit nanomolar BACE-1 inhibitor in both radioligand binding and cell-based functional assay formats. The X-ray structure of representative inhibitors bound to BACE-1 revealed a number of key ligand:protein interactions, including a hydrogen bond between the side chain amide of flap residue Gln73 and the acyl guanidine carbonyl group, and a cation-π interaction between Arg235 and the isothiazole 4-methoxyphenyl substituent. Following subcutaneous administration in rats, an acyl guanidine inhibitor with single-digit nanomolar activity in cells afforded good plasma exposures and a dose-dependent reduction in plasma Aβ levels, but poor brain exposure was observed (likely due to Pgp-mediated efflux), and significant reductions in brain Aβ levels were not obtained.

Metal-Rich Transition Metal Diborides as Electrocatalysts for Hydrogen Evolution Reactions in a Wide Range of pH

DOE PAGES

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

2016-09-23

Solid solutions of HfB 2-ZrB 2 mixtures were prepared by high-energy ball milling of diboride and additive powders followed by spark plasma sintering (SPS). A mixture of stoichiometric 1:1 HfB 2-ZrB 2 borides was the base composition to which Hf, Zr, Ta, LaB 6 or Gd 2O 3 was added. Hf, Zr and Ta were added in order to bring the boron-to-metal ratio down to 1.86, rendering the boride as MeB 1.86. In the case of LaB 6 and Gd 2O 3, 1.8 mol% was added. Electroanalytical behavior of hydrogen evolution reactions was evaluated in 1 M H 2SO 4more » and 1 M NaOH solutions. The LaB 6 additive material showed Tafel slopes of 125 and 90 mV/decade in acidic and alkaline solutions respectively. The Hf and Zr rich samples showed Tafel slopes of about 120 mV/decade in both electrolytes. The over potentials of hydrogen evolution reactions (at 10 mA/cm 2) in the alkaline solution were about 100 mV lower than those in acidic solution. The metal-rich diborides and addition of LaB 6 showed better hydrogen evolution reaction (HER) activities than the base 1:1 HfB 2-ZrB 2 stoichiometric diboride solid solution. Furthermore, the higher activity of metal-rich borides could be attributed to the increased electron population at the d-orbitals of the metal shown by band structure modeling calculations using the Density Functional Theory approach.« less

Towards wall functions for the prediction of solute segregation in plane front directional solidification

NASA Astrophysics Data System (ADS)

Chatelain, M.; Rhouzlane, S.; Botton, V.; Albaric, M.; Henry, D.; Millet, S.; Pelletier, D.; Garandet, J. P.

2017-10-01

The present paper focuses on solute segregation occurring in directional solidification processes with sharp solid/liquid interface, like silicon crystal growth. A major difficulty for the simulation of such processes is their inherently multi-scale nature: the impurity segregation problem is controlled at the solute boundary layer scale (micrometers) while the thermal problem is ruled at the crucible scale (meters). The thickness of the solute boundary layer is controlled by the convection regime and requires a specific refinement of the mesh of numerical models. In order to improve numerical simulations, wall functions describing solute boundary layers for convecto-diffusive regimes are derived from a scaling analysis. The aim of these wall functions is to obtain segregation profiles from purely thermo-hydrodynamic simulations, which do not require solute boundary layer refinement at the solid/liquid interface. Regarding industrial applications, various stirring techniques can be used to enhance segregation, leading to fully turbulent flows in the melt. In this context, the scaling analysis is further improved by taking into account the turbulent solute transport. The solute boundary layers predicted by the analytical model are compared to those obtained by transient segregation simulations in a canonical 2D lid driven cavity configuration for validation purposes. Convective regimes ranging from laminar to fully turbulent are considered. Growth rate and molecular diffusivity influences are also investigated. Then, a procedure to predict concentration fields in the solid phase from a hydrodynamic simulation of the solidification process is proposed. This procedure is based on the analytical wall functions and on solute mass conservation. It only uses wall shear-stress profiles at the solidification front as input data. The 2D analytical concentration fields are directly compared to the results of the complete simulation of segregation in the lid driven cavity configuration. Finally, an additional output from the analytical model is also presented. We put in light the correlation between different species convecto-diffusive behaviour; we use it to propose an estimation method for the segregation parameters of various chemical species knowing segregation parameters of one specific species.

Both solubility and chemical stability of curcumin are enhanced by solid dispersion in cellulose derivative matrices.

PubMed

Li, Bin; Konecke, Stephanie; Wegiel, Lindsay A; Taylor, Lynne S; Edgar, Kevin J

2013-10-15

Amorphous solid dispersions (ASD) of curcumin (Cur) in cellulose derivative matrices, hydroxypropylmethylcellulose acetate succinate (HPMCAS), carboxymethylcellulose acetate butyrate (CMCAB), and cellulose acetate adipate propionate (CAAdP) were prepared in order to investigate the structure-property relationship and identify polymer properties necessary to effectively increase Cur aqueous solution concentration. XRD results indicated that all investigated solid dispersions were amorphous, even at a 9:1 Cur:polymer ratio. Both stability against crystallization and Cur solution concentration from these ASDs were significantly higher than those from physical mixtures and crystalline Cur. Remarkably, curcumin was also stabilized against chemical degradation in solution. Chemical stabilization was polymer-dependent, with stabilization in CAAdP>CMCAB>HPMCAS>PVP, while matrices enhanced solution concentration as PVP>HPMCAS>CMCAB≈CAAdP. HPMCAS/Cur dispersions have useful combinations of pH-triggered release profile, chemical stabilization, and strong enhancement of Cur solution concentration. Copyright © 2013 Elsevier Ltd. All rights reserved.

Energetics of a uranothorite (Th 1–xU xSiO 4) solid solution

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

Guo, Xiaofeng; Szenknect, Stephanie; Mesbah, Adel

High-temperature oxide melt solution calorimetric measurements were completed to determine the enthalpies of formation of the uranothorite, (USiO 4) x–(ThSiO 4) 1–x, solid solution. Phase-pure samples with x values of 0, 0.11, 0.21, 0.35, 0.71, and 0.84 were prepared, purified, and characterized by powder X-ray diffraction, electron probe microanalysis, thermogravimetric analysis and differential scanning calorimetry coupled with in situ mass spectrometry, and high-temperature oxide melt solution calorimetry. This work confirms the energetic metastability of coffinite, USiO 4, and U-rich intermediate silicate phases with respect to a mixture of binary oxides. Furthermore, variations in unit cell parameters and negative excess volumesmore » of mixing, coupled with strongly exothermic enthalpies of mixing in the solid solution, suggest short-range cation ordering that can stabilize intermediate compositions, especially near x = 0.5.« less

Energetics of a uranothorite (Th 1–xU xSiO 4) solid solution

DOE PAGES

Guo, Xiaofeng; Szenknect, Stephanie; Mesbah, Adel; ...

2016-10-11

High-temperature oxide melt solution calorimetric measurements were completed to determine the enthalpies of formation of the uranothorite, (USiO 4) x–(ThSiO 4) 1–x, solid solution. Phase-pure samples with x values of 0, 0.11, 0.21, 0.35, 0.71, and 0.84 were prepared, purified, and characterized by powder X-ray diffraction, electron probe microanalysis, thermogravimetric analysis and differential scanning calorimetry coupled with in situ mass spectrometry, and high-temperature oxide melt solution calorimetry. This work confirms the energetic metastability of coffinite, USiO 4, and U-rich intermediate silicate phases with respect to a mixture of binary oxides. Furthermore, variations in unit cell parameters and negative excess volumesmore » of mixing, coupled with strongly exothermic enthalpies of mixing in the solid solution, suggest short-range cation ordering that can stabilize intermediate compositions, especially near x = 0.5.« less

Fast synthesis of topographic mask effects based on rigorous solutions

NASA Astrophysics Data System (ADS)

Yan, Qiliang; Deng, Zhijie; Shiely, James

2007-10-01

Topographic mask effects can no longer be ignored at technology nodes of 45 nm, 32 nm and beyond. As feature sizes become comparable to the mask topographic dimensions and the exposure wavelength, the popular thin mask model breaks down, because the mask transmission no longer follows the layout. A reliable mask transmission function has to be derived from Maxwell equations. Unfortunately, rigorous solutions of Maxwell equations are only manageable for limited field sizes, but impractical for full-chip optical proximity corrections (OPC) due to the prohibitive runtime. Approximation algorithms are in demand to achieve a balance between acceptable computation time and tolerable errors. In this paper, a fast algorithm is proposed and demonstrated to model topographic mask effects for OPC applications. The ProGen Topographic Mask (POTOMAC) model synthesizes the mask transmission functions out of small-sized Maxwell solutions from a finite-difference-in-time-domain (FDTD) engine, an industry leading rigorous simulator of topographic mask effect from SOLID-E. The integral framework presents a seamless solution to the end user. Preliminary results indicate the overhead introduced by POTOMAC is contained within the same order of magnitude in comparison to the thin mask approach.

Prediction of Ablation Rates from Solid Surfaces Exposed to High Temperature Gas Flow

NASA Technical Reports Server (NTRS)

Akyuzlu, Kazim M.; Coote, David

2013-01-01

A mathematical model and a solution algorithm is developed to study the physics of high temperature heat transfer and material ablation and identify the problems associated with the flow of hydrogen gas at very high temperatures and velocities through pipes and various components of Nuclear Thermal Rocket (NTR) motors. Ablation and melting can be experienced when the inner solid surface of the cooling channels and the diverging-converging nozzle of a Nuclear Thermal Rocket (NTR) motor is exposed to hydrogen gas flow at temperatures around 2500 degrees Kelvin and pressures around 3.4 MPa. In the experiments conducted on typical NTR motors developed in 1960s, degradation of the cooling channel material (cracking in the nuclear fuel element cladding) and in some instances melting of the core was observed. This paper presents the results of a preliminary study based on two types of physics based mathematical models that were developed to simulate the thermal-hydrodynamic conditions that lead to ablation of the solid surface of a stainless steel pipe exposed to high temperature hydrogen gas near sonic velocities. One of the proposed models is one-dimensional and assumes the gas flow to be unsteady, compressible and viscous. An in-house computer code was developed to solve the conservations equations of this model using a second-order accurate finite-difference technique. The second model assumes the flow to be three-dimensional, unsteady, compressible and viscous. A commercial CFD code (Fluent) was used to solve the later model equations. Both models assume the thermodynamic and transport properties of the hydrogen gas to be temperature dependent. In the solution algorithm developed for this study, the unsteady temperature of the pipe is determined from the heat equation for the solid. The solid-gas interface temperature is determined from an energy balance at the interface which includes heat transfer from or to the interface by conduction, convection, radiation, and ablation. Two different ablation models are proposed to determine the heat loss from the solid surface due to the ablation of the solid material. Both of them are physics based. Various numerical simulations were carried out using both models to predict the temperature distribution in the solid and in the gas flow, and then predict the ablation rates at a typical NTR motor hydrogen gas temperature and pressure. Solid mass loss rate per foot of a pipe was also calculated from these predictions. The results are presented for fully developed turbulent flow conditions in a sample SS pipe with a 6 inch diameter.

Nanostructured lipid carriers: effect of solid phase fraction and distribution on the release of encapsulated materials.

PubMed

Dan, Nily

2014-11-25

Emulsions, solid lipid nanoparticles (SLN), and nanostructured lipid carriers (NLC) containing a mix of liquid and solid domains are of interest as encapsulation vehicles for hydrophobic compounds. Studies of the release rate from these particles yield contradictory results: Some find that increasing the fraction of solid phase increases the rate of release and others the opposite. In this paper we study the release of encapsulated materials from lipid-based nanoparticles using Monte Carlo simulations. We find that, quite surprisingly, the release rate is largely insensitive to the size of solid domains or the fraction of solid phase. However, the distribution of the domains significantly affects the rate of release: Solid domains located at the interface with the surrounding solution inhibit transport, while nanoparticles where the solid domains are concentrated in the center enhance it. The latter can lead to release rates in NLCs that are faster than in the equivalent emulsions. We conclude that controlling the release rate from NLCs requires the ability to determine the location and distribution of the solid phase, which may be achieved through choice of the surfactants stabilizing the particles, incorporation of nucleation sites, and/or the cooling rates and temperatures.

Microstructural and microchemical studies of phase stability in V-O solid solution

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

Ghosh, Chanchal, E-mail: chanchal@igcar.gov.in

2017-02-15

Over the last couple of decades vanadium and V-based alloys have received significant attention as a potential structural material for fusion power applications because of their favourable mechanical properties under irradiation and at elevated temperatures. They are also considered as the advanced options of storage materials for hydrogen and its isotopes. However, the higher affinity of V for O, C and N poses critical challenges in its engineering applications since they lead to degradation of mechanical properties. They can further interact with the matrix to produce metallic oxy-carbo-nitride precipitates. To a certain limit, these precipitates are beneficial and can bemore » exploited to enhance the mechanical behaviour of the alloy through suitable microstructural design. However, this requires a prior knowledge of the interaction between the alloy and the impurity solutes. In the present work vanadium specific experiments have been designed and carried out to bring out the V-interstitial solute interaction by charging oxygen in the near surface region of vanadium. Microstructural and microchemical behaviour of the V-O solid solution has been studied through HRTEM (high resolution transmission electron microscopy) and HAADF (high angle annular dark field) coupled with EELS. Quantitative electron microscopy has been carried out to study structural modification of the alloy in atomic level caused by O charging. - Highlights: •Controlled experiments were carried out in pulsed laser ablation set-up to promote V-O interaction. • As a consequence of O dissolution, V transformed into a bct structure which is otherwise a bcc structure. •In V-O solid solution, dissolved O in the V matrix introduces significant amount of lattice strain. • Present work can be extended for introducing interstitial O in other pure transition metals and their alloys.« less

Recent advances in ruthenium complex-based light-driven water oxidation catalysts.

PubMed

Xue, Long-Xin; Meng, Ting-Ting; Yang, Wei; Wang, Ke-Zhi

2015-11-01

The light driven splitting of water is one of the most attractive approaches for direct conversion of solar energy into chemical energy in the future. Ruthenium complexes as the water oxidation catalysts (WOCs) and light sensitizers have attracted increasing attention, and have made a great progress. This mini-review highlights recent progress on ruthenium complex-based photochemical and photoelectrochemical water oxidation catalysts. The recent representative examples of these ruthenium complexes that are in homogeneous solution or immobilized on solid electrodes, are surveyed. In particular, special attention has been paid on the supramolecular dyads with photosensitizer and WOC being covalently hold together, and grafted onto the solid electrode. Copyright © 2015 Elsevier B.V. All rights reserved.

A facile synthesis of Zn(x)Cd(1-x)S/CNTs nanocomposite photocatalyst for H2 production.

PubMed

Wang, Lei; Yao, Zhongping; Jia, Fangzhou; Chen, Bin; Jiang, Zhaohua

2013-07-21

The sulfide solid solution has become a promising and important visible-light-responsive photocatalyst for hydrogen production nowadays. Zn(x)Cd(1-x)S/CNT nanocomposites were synthesized to improve the dispersion, adjust the energy band gap, and enhance the separation of the photogenerated electrons and holes. The as-prepared photocatalysts were characterized by scanning electron-microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV-visible diffuse reflectance spectra (UV-visible), respectively. And the effects of CNTs on structure, composition and optical absorption property of the sulfide solid solutions were investigated along with their inherent relationships. For Zn0.83Cd0.17S/CNTs, sulfide solid solution is assembled along the CNTs orderly, with a diameter of 100 nm or so. XPS analysis shows that there is bonding effect between the solid solutions and the CNTs due to the strong adsorption of Zn(2+) and Cd(2+) on the surface of CNTs. There are two obvious absorption edges for Zn0.83Cd0.17S/CNTs, corresponding to two kinds of sulfide solid solutions with different molar ratios of Zn/Cd. The hybridization of solid solutions with CNTs makes the absorption spectrum red shift. The photocatalytic property was evaluated by splitting Na2S + Na2SO3 solution into H2, and the highest rate of H2 evolution of 6.03 mmol h(-1) g(-1) was achieved over Zn0.83Cd0.17S/CNTs. The high activity of photocatalytic H2 production is attributed to the following factors: (1) the optimum band gap and a moderate position of the conduction band (which needs to match the irradiation spectrum of the Xe lamp best), (2) the efficient separation of photogenerated electrons and holes by hybridization, and (3) the improvement of the dispersion of nanocomposites by assembling along the CNTs as well.

A duality theorem-based algorithm for inexact quadratic programming problems: Application to waste management under uncertainty

NASA Astrophysics Data System (ADS)

Kong, X. M.; Huang, G. H.; Fan, Y. R.; Li, Y. P.

2016-04-01

In this study, a duality theorem-based algorithm (DTA) for inexact quadratic programming (IQP) is developed for municipal solid waste (MSW) management under uncertainty. It improves upon the existing numerical solution method for IQP problems. The comparison between DTA and derivative algorithm (DAM) shows that the DTA method provides better solutions than DAM with lower computational complexity. It is not necessary to identify the uncertain relationship between the objective function and decision variables, which is required for the solution process of DAM. The developed method is applied to a case study of MSW management and planning. The results indicate that reasonable solutions have been generated for supporting long-term MSW management and planning. They could provide more information as well as enable managers to make better decisions to identify desired MSW management policies in association with minimized cost under uncertainty.

Synthesis, structural and semiconducting properties of Ba(Cu1/3 Sb2/3)O3-PbTiO3 solid solutions

NASA Astrophysics Data System (ADS)

Singh, Chandra Bhal; Kumar, Dinesh; Prashant, Verma, Narendra Kumar; Singh, Akhilesh Kumar

2018-05-01

We report the synthesis and properties of a new solid solution 0.05Ba(Cu1/3Sb2/3)O3-0.95PbTiO3 (BCS-PT) which shows the semiconducting properties. In this study, we have designed new perovskite-type (ABO3) solid solution of BCS-PT that have tunable optical band gap. BCS-PT compounds were prepared by conventional solid-state reaction method and their structural, micro-structural and optical properties were analyzed. The calcination temperature for BCS-PT solid solutions has been optimized to obtain a phase pure system. The Reitveld analysis of X-ray data show that all samples crystallize in tetragonal crystal structure with space group P4mm. X-ray investigation revealed that increase in calcination temperature led to increase of lattice parameter `a' while `c' parameter value lowered. The band gap of PbTiO3 is reduced from 3.2 eV to 2.8 eV with BCS doping and with increasing calcination temperature it further reduces to 2.56 eV. The reduced band gap indicated that the compounds are semiconducting and can be used for photovoltaic device applications.

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.

High temperature resistant cermet and ceramic compositions

NASA Technical Reports Server (NTRS)

Phillips, W. M. (Inventor)

1978-01-01

Cermet compositions having high temperature oxidation resistance, high hardness and high abrasion and wear resistance, and particularly adapted for production of high temperature resistant cermet insulator bodies are presented. The compositions are comprised of a sintered body of particles of a high temperature resistant metal or metal alloy, preferably molybdenum or tungsten particles, dispersed in and bonded to a solid solution formed of aluminum oxide and silicon nitride, and particularly a ternary solid solution formed of a mixture of aluminum oxide, silicon nitride and aluminum nitride. Also disclosed are novel ceramic compositions comprising a sintered solid solution of aluminum oxide, silicon nitride and aluminum nitride.

Chemically and compositionally modified solid solution disordered multiphase nickel hydroxide positive electrode for alkaline rechargeable electrochemical cells

DOEpatents

Ovshinsky, Stanford R.; Corrigan, Dennis; Venkatesan, Srini; Young, Rosa; Fierro, Christian; Fetcenko, Michael A.

1994-01-01

A high capacity, long cycle life positive electrode for use in an alkaline rechargeable electrochemical cell comprising: a solid solution nickel hydroxide material having a multiphase structure that comprises at least one polycrystalline .gamma.-phase including a polycrystalline .gamma.-phase unit cell comprising spacedly disposed plates with at least one chemical modifier incorporated around the plates, the plates having a range of stable intersheet distances corresponding to a 2.sup.+ oxidation state and a 3.5.sup.+, or greater, oxidation state; and at least one compositional modifier incorporated into the solid solution nickel hydroxide material to promote the multiphase structure.

Crystal doping aided by rapid expansion of supercritical solutions.

PubMed

Vemavarapu, Chandra; Mollan, Matthew J; Needham, Thomas E

2002-01-01

The purpose of this study was to test the utility of rapid expansion of supercritical solution (RESS) based cocrystallizations in inducing polymorph conversion and crystal disruption of chlorpropamide (CPD). CPD crystals were recrystallized by the RESS process utilizing supercritical carbon dioxide as the solvent. The supercritical region investigated for solute extraction ranged from 45 to 100 degrees C and 2000 to 8000 psi. While pure solute recrystallization formed stage I of these studies, stage II involved recrystallization of CPD in the presence of urea (model impurity). The composition, morphology, and crystallinity of the particles thus produced were characterized utilizing techniques such as microscopy, thermal analysis, x-ray powder diffractometry, and high-performance liquid chromatography. Also, comparative evaluation between RESS and evaporative crystallization from liquid solvents was performed. RESS recrystallizations of commercially available CPD (form A) resulted in polymorph conversion to metastable forms C and V, depending on the temperature and pressure of the recrystallizing solvent. Cocrystallization studies revealed the formation of eutectic mixtures and solid solutions of CPD + urea. Formation of the solid solutions resulted in the crystal disruption of CPD and subsequent amorphous conversion at urea levels higher than 40% wt/wt. Consistent with these results were the reductions in melting point (up to 9 degrees C) and in the DeltaH(f) values of CPD (up to 50%). Scanning electron microscopy revealed a particle size reduction of up to an order of magnitude upon RESS processing. Unlike RESS, recrystallizations from liquid organic solvents lacked the ability to affect polymorphic conversions. Also, the incorporation of urea into the lattice of CPD was found to be inadequate. In providing the ability to control both the particle and crystal morphologies of active pharmaceutical ingredients, RESS proved potentially advantageous to crystal engineering. Rapid crystallization kinetics were found vital in making RESS-based doping superior to conventional solvent-based cocrystallizations.

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

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

Spark plasma sintered transition metal diborides such as HfB 2, ZrB 2 and their solid solutions were investigated as electrode materials for electrochemical hydrogen evolutions reactions (HER) in 1 M H 2SO 4 and 1 M NaOH electrolytes. HfB 2 and ZrB 2 formed complete solid solutions when mixed in 1:1, 1:4, and 4:1 ratios and they were stable in both electrolytes. The HER kinetics of the diborides were slower in the basic solution than in the acidic solutions. The Tafel slopes in 1 M H 2SO 4 were in the range of 0.15 - 0.18 V/decade except for puremore » HfB 2 which showed a Tafel slope of 0.38 V/decade. In 1 M NaOH the Tafel slopes were in the range of 0.12 - 0.27 V/decade. The composition of Hf xZr 1-xB 2 solid solutions with x = 0.2 - 0.8, influenced the exchange current densities, overpotentials and Tafel slopes of the HER. As a result, the EIS data were fitted with a porous film equivalent circuit model in order to better understand the HER behavior. In addition, modeling calculations, using density functional theory approach, were carried out to estimate the density of states and band structure of the boride solid solutions.« less

Electrical resistivity of the UAs 1- xSex solid solutions

NASA Astrophysics Data System (ADS)

Breandon, C.; Bartholin, H.; Tchapoutian, R.; Therond, P. G.; Schoenes, J.; Vogt, O.

1987-01-01

The electrical resistivity ϱ of UAs 1- xSex solid solutions has been measured between 13 K and room temperature. The magnetic phase diagram has been deduced. Effects of uniaxial stress on ϱ allow to understand some results and to reveal anisotropy of ϱ.

A new solid-phase extraction disk based on a sheet of single-walled carbon nanotubes.

PubMed

Niu, Hong Yun; Cai, Ya Qi; Shi, Ya Li; Wei, Fu Sheng; Liu, Jie Min; Jiang, Gui Bin

2008-11-01

A new kind of solid-phase extraction disk based on a sheet of single-walled carbon nanotubes (SWCNTs) is developed in this study. The properties of such disks are tested, and different disks showed satisfactory reproducibility. One liter of aqueous solution can pass through the disk within 10-100 min while still allowing good recoveries. Two disks (DD-disk) can be stacked to enrich phthalate esters, bisphenol A (BPA), 4-n-nonylphenol (4-NP), 4-tert-octylphenol (4-OP) and chlorophenols from various volumes of solution. The results show that SWCNT disks have high extraction ability for all analytes. The SWCNT disk can extract polar chlorophenols more efficiently than a C(18) disk from water solution. Unlike the activated carbon disk, analytes adsorbed by the new disks can be eluted completely with 8-15 mL of methanol or acetonitrile. Finally, the DD-disk system is used to pretreat 1000-mL real-world water samples spiked with BPA, 4-OP and 4-NP. Detection limits of 7, 25, and 38 ng L(-1) for BPA, 4-OP, and 4-NP, respectively, were achieved under optimized conditions. The advantages of this new disk include its strong adsorption ability, its high flow rate and its easy preparation.

A simple and rapid in situ preconcentration method for the determination of phosphate in environmental waters by use of solid-phase extraction, and its applications to brackish lake waters.

PubMed

Okumura, M; Tong, L; Fujinaga, K; Seike, Y

2001-05-01

A simple and rapid in situ preconcentration method for the determination of phosphate in environmental waters has been developed for field analysis. This method is based on solid-phase extraction on a zirconium-loaded Sep-Pack Accell CM cartridge (Zr-SP) and is applicable to studies in which sampling is performed by use of a graduated syringe to prevent contamination and to ensure easy operation at sampling sites. The Zr-SP cartridge was prepared by passing 0.1 mol L(-1) zirconium solution through a Sep-Pak Accell CM cartridge, packed with cation exchange sorbent based on a silica matrix. The adsorption of phosphate and its desorption depend only on the pH of the solution. A water sample containing phosphate was adjusted to pH 2 and passed through the Zr-SP cartridge to collect it. The retained phosphate was quantitatively eluted with 0.5 mol L(-1) sodium hydroxide solution. The phosphate retained in the Zr-SP cartridge was stable for at least one month. The established preconcentration method was successfully applied to brackish lake waters to investigate seasonal changes in the distribution and behavior of phosphate in a brackish lake.

Calorimetric determination of energetics of solid solutions of UO 2+ x with CaO and Y 2O 3

NASA Astrophysics Data System (ADS)

Mazeina, Lena; Navrotsky, Alexandra; Greenblatt, Martha

2008-02-01

Quantitative study of thermodynamic properties of solid solutions of UO 2+ x with divalent and trivalent oxides is important for predicting the behavior of oxide fuel. Although early literature work measured vapor pressure in some of these solid solutions, direct calorimetric measurements of enthalpies of formation have been hampered by the refractory nature of such oxides. First measurements of the enthalpies of formation in the systems UO 2+ x-CaO and UO 2+ x-YO 1.5, obtained by high-temperature oxide melt solution calorimetry, are reported. Both systems show significantly negative (exothermic) heats of formation from binary oxides (UO 2, plus O 2 and CaO or YO 1.5, as well as from UO 2 plus UO 3 and CaO or YO 1.5), consistent with reported free energy measurements in the urania-yttria system. The energetic contributions of oxygen content (oxidation of U 4+) and of charge balanced ionic substitution as well as defect clustering are discussed. Behavior of urania-yttria is compared to that of corresponding systems in which the tetravalent ion is Ce, Zr, or Hf. The substantial additional stability in the solid solutions compared to pure UO 2+ x may retard, in both thermodynamic and kinetic sense, the oxidation and leaching of spent fuel to form aqueous U 6+ and solid uranyl phases.

FIDDLE: A Computer Code for Finite Difference Development of Linear Elasticity in Generalized Curvilinear Coordinates

NASA Technical Reports Server (NTRS)

Kaul, Upender K.

2005-01-01

A three-dimensional numerical solver based on finite-difference solution of three-dimensional elastodynamic equations in generalized curvilinear coordinates has been developed and used to generate data such as radial and tangential stresses over various gear component geometries under rotation. The geometries considered are an annulus, a thin annular disk, and a thin solid disk. The solution is based on first principles and does not involve lumped parameter or distributed parameter systems approach. The elastodynamic equations in the velocity-stress formulation that are considered here have been used in the solution of problems of geophysics where non-rotating Cartesian grids are considered. For arbitrary geometries, these equations along with the appropriate boundary conditions have been cast in generalized curvilinear coordinates in the present study.

The influence of mixing water on the thermophysical properties of nanofluids based on solar salt and silica nanoparticles

NASA Astrophysics Data System (ADS)

Muñoz-Sánchez, B.; Nieto-Maestre, J.; Iparraguirre-Torres, I.; Sánchez-García, J. A.; Julia, J. E.; García-Romero, A.

2016-05-01

The use of nanofluids (NFs) based on Solar Salt (SS) and nanoparticles (NPs), either as Thermal Energy Storage (TES) material or as Heat Transfer Fluid (HTF), is attracting great interest in recent years. Many authors [1,3] have reported important improvements on the thermophysical properties (specific heat capacity cp,thermal conductivity k) of NFs based on SS and ceramic NPs. These improvements would lead to important savings and better performance of TES facilities on new Concentrated Solar Power (CSP) plants due to lower quantities of material required and smaller storage tanks. To achieve these advantageous features in the final NFs, it is essential to avoid NP agglomeration during their preparation. Different synthesis procedures have been reported: mixing of solid NPs within a SS solution by means of ultrasounds [1-3], direct mixing of solid NPs and molten salt [4]. In this work, NFs based on SS and 1% by wt. of silica NPs were synthetized from a SS-water solution and a commercial water-silica NF called Ludox HS 30% (Sigma-Aldrich). The influence of the mixing water volume (MW) on the cp of NFs was evaluated. With this aim, the cp of these samples was measured by Differential Scanning Calorimetry (DSC) both in the solid and the liquid state. In addition, the distribution of sizes was measured during the whole preparation process by Dynamic Light Scattering (DLS). Further information about sizes and uniformity of the final NFs was obtained from Scanning Electron Microscopy (SEM) images. X-ray Diffraction (XRD) patterns of the SS and final NF were performed.

Lattice crossover and phase transitions in NdAlO{sub 3}-GdAlO{sub 3} system

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

Vasylechko, L., E-mail: crystal-lov@polynet.lviv.ua; Shmanko, H.; Ohon, N.

2013-02-15

Phase and structural behaviour in the (1-x)NdAlO{sub 3}-xGdAlO{sub 3} system in a whole concentration range has been studied by means of in situ high-resolution X-ray synchrotron powder diffraction technique and differential thermal analysis. Two kinds of solid solutions Nd{sub 1-x}Gd{sub x}AlO{sub 3} have been found at room temperature: one with rhombohedral (x<0.15) and one with orthorhombic (x{>=}0.20) symmetry. A morphotropic phase transition occurs at x Almost-Equal-To 0.15, where the co-existence of both phases was observed. Peculiarity of the orthorhombic solid solution is the lattice parameter crossover at the compositions with x=0.33, 0.49 and 0.62. First-order structural transition Pbnm{r_reversible}R3{sup Macron }cmore » has been detected both from in situ powder diffraction and thermal analysis data. Continuous phase transformation R3{sup Macron }c{r_reversible}Pm3{sup Macron }m above 2140 K has been predicted for Nd-rich sample Nd{sub 0.85}Gd{sub 0.15}AlO{sub 3} from the extrapolation of high-temperature behaviour of the lattice parameter ratio of the rhombohedral phase. Based on the experimental data, the phase diagram of the pseudo-binary system NdAlO{sub 3}-GdAlO{sub 3} has been constructed. - Graphical abstract: Concentration dependencies of normalized lattice parameters of Nd{sub 1-x}Gd{sub x}AlO{sub 3} perovskite solid solutions. Highlights: Black-Right-Pointing-Pointer Two kinds of solid solutions Nd{sub 1-x}Gd{sub x}AlO{sub 3} were found in the NdAlO{sub 3}-GdAlO{sub 3} system. Black-Right-Pointing-Pointer Morphotropic transition between both perovskite phases occurs at x Almost-Equal-To 0.15. Black-Right-Pointing-Pointer Lattice parameter crossover was found in orthorhombic solid solution. Black-Right-Pointing-Pointer Temperature driven first-order phase transition Pbnm{r_reversible}R3{sup Macron }c was found in Nd{sub 1-x}Gd{sub x}AlO{sub 3}. Black-Right-Pointing-Pointer Phase diagram of the pseudo-binary system NdAlO{sub 3}-GdAlO{sub 3} has been constructed.« less

Numerical study of the influence of solid polarization on electrophoresis at finite Debye thickness.

PubMed

Bhattacharyya, Somnath; De, Simanta

2015-09-01

The influence of solid polarization on the electrophoresis of a uniformly charged dielectric particle for finite values of the particle-to-fluid dielectric permittivity ratio is analyzed quantitatively without imposing the thin Debye length or weak-field assumption. Present analysis is based on the computation of the coupled Poisson-Nernst-Planck and Stokes equations in the fluid domain along with the Laplace equation within the solid. The electrophoretic velocity is determined through the balance of forces acting on the particle. The solid polarization of the charged particle produces a reduction on its electrophoretic velocity compared to a nonpolarizable particle of the same surface charge density. In accordance with the existing thin-layer analysis, our computed results for thin Debye layer shows that the solid polarization is important only when the applied electric field is strong. When the Debye length is in the order of the particle size, the electrophoretic velocity decreases with the rise of the particle permittivity and attains a saturation limit at large values of the permittivity. Our computed solution for electrophoretic velocity is in agreement with the existing asymptotic analyses based on a thin Debye layer for limiting cases.

Mixing Acid Salts and Layered Double Hydroxides in Nanoscale under Solid Condition

PubMed Central

Nakayama, Hirokazu; Hayashi, Aki

2014-01-01

The immobilization of potassium sorbate, potassium aspartate and sorbic acid in layered double hydroxide under solid condition was examined. By simply mixing two solids, immobilization of sorbate and aspartate in the interlayer space of nitrate-type layered double hydroxide, so called intercalation reaction, was achieved, and the uptakes, that is, the amount of immobilized salts and the interlayer distances of intercalation compounds were almost the same as those obtained in aqueous solution. However, no intercalation was achieved for sorbic acid. Although intercalation of sorbate and aspartate into chloride-type layered double hydroxide was possible, the uptakes for these intercalation compounds were lower than those obtained using nitrate-type layered double hydroxide. The intercalation under solid condition could be achieved to the same extent as for ion-exchange reaction in aqueous solution, and the reactivity was similar to that observed in aqueous solution. This method will enable the encapsulation of acidic drug in layered double hydroxide as nano level simply by mixing both solids. PMID:25080007

Mixing Acid Salts and Layered Double Hydroxides in Nanoscale under Solid Condition.

PubMed

Nakayama, Hirokazu; Hayashi, Aki

2014-07-30

The immobilization of potassium sorbate, potassium aspartate and sorbic acid in layered double hydroxide under solid condition was examined. By simply mixing two solids, immobilization of sorbate and aspartate in the interlayer space of nitrate-type layered double hydroxide, so called intercalation reaction, was achieved, and the uptakes, that is, the amount of immobilized salts and the interlayer distances of intercalation compounds were almost the same as those obtained in aqueous solution. However, no intercalation was achieved for sorbic acid. Although intercalation of sorbate and aspartate into chloride-type layered double hydroxide was possible, the uptakes for these intercalation compounds were lower than those obtained using nitrate-type layered double hydroxide. The intercalation under solid condition could be achieved to the same extent as for ion-exchange reaction in aqueous solution, and the reactivity was similar to that observed in aqueous solution. This method will enable the encapsulation of acidic drug in layered double hydroxide as nano level simply by mixing both solids.

Enhanced photoelectric performance in self-powered UV detectors based on ZnO nanowires with plasmonic Au nanoparticles scattered electrolyte

NASA Astrophysics Data System (ADS)

Zeng, Yiyu; Ye, Zhizhen; Lu, Bin; Dai, Wei; Pan, Xinhua

2016-04-01

Vertically aligned ZnO nanowires (NWs) were grown on a fluorine-doped tin-oxide-coated glass substrate by a hydrothermal method. Au nanoparticles were well dispersed in the mixed solution of ethanol and deionized water. A simple self-powered ultraviolet detector based on solid-liquid heterojunction was fabricated, utilizing ZnO NWs as active photoanode and such prepared mixed solution as electrolyte. The introduction of Au nanoparticles results in considerable improvements in the responsivity and sensitivity of the device compared with the one using deionized water as electrolyte, which is attributed to the enhanced light harvesting by Au nanoparticles.

Solid phase monofunctionalization of gold nanoparticles using ionic exchange resin as polymer support.

PubMed

Zou, Jianhua; Dai, Qiu; Wang, Jinhai; Liu, Xiong; Huo, Qun

2007-07-01

A solid phase modification method using anionic exchange resin as polymer support was developed for the synthesis of monofunctional gold nanoparticles. Based on a "catch and release" mechanism to control the number of functional groups attached to the nanoparticle surface, bifunctional thiol ligands with a carboxylic acid end group were first immobilized at a controlled density on anionic exchange resin through electrostatic interactions. Gold nanoparticles were then immobilized to the anionic exchange resin by a one-to-one place exchange reaction between resin-bound thiol ligands and butanethiol-protected gold nanoparticles in solution. After cleaving off from the resin under mild conditions, gold nanoparticles with a single carboxyl group attached to the surface were obtained as the major product. Experimental conditions such as the solvents used for ligand loading and solid phase place exchange reaction, and the loading density of the ligands, were found to play a critical role towards the successful synthesis of monofunctional nanoparticles. Overall, the noncovalent bond-based ligand immobilization technique reported here greatly simplified the process of solid phase monofunctionalization of nanoparticles compared to a previously reported covalent bond-based ligand immobilization technique.

Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State

DOE PAGES

Pace, Natalie A.; Zhang, Weimin; Arias, Dylan H.; ...

2017-11-30

The conjugated polymer poly(benzothiophene dioxide) (PBTDO1) has recently been shown to exhibit efficient intramolecular singlet fission in solution. We investigate the role of intermolecular interactions in triplet separation dynamics after singlet fission. We use transient absorption spectroscopy to determine the singlet fission rate and triplet yield in two polymers differing only by side-chain motif in both solution and the solid state. Whereas solid-state films show singlet fission rates identical to those measured in solution, the average lifetime of the triplet population increases dramatically and is strongly dependent on side-chain identity. These results show that it may be necessary to carefullymore » engineer the solid-state microstructure of these 'singlet fission polymers' to produce the long-lived triplets needed to realize efficient photovoltaic devices.« less

Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State

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

Pace, Natalie A.; Zhang, Weimin; Arias, Dylan H.

The conjugated polymer poly(benzothiophene dioxide) (PBTDO1) has recently been shown to exhibit efficient intramolecular singlet fission in solution. We investigate the role of intermolecular interactions in triplet separation dynamics after singlet fission. We use transient absorption spectroscopy to determine the singlet fission rate and triplet yield in two polymers differing only by side-chain motif in both solution and the solid state. Whereas solid-state films show singlet fission rates identical to those measured in solution, the average lifetime of the triplet population increases dramatically and is strongly dependent on side-chain identity. These results show that it may be necessary to carefullymore » engineer the solid-state microstructure of these 'singlet fission polymers' to produce the long-lived triplets needed to realize efficient photovoltaic devices.« less

Degradation of Highly Alloyed Metal Halide Perovskite Precursor Inks: Mechanism and Storage Solutions

DOE PAGES

Dou, Benjia; Wheeler, Lance M.; Christians, Jeffrey A.; ...

2018-03-14

Whereas the promise of metal halide perovskite (MHP) photovoltaics (PV) is that they can combine high efficiency with solution-processability, the chemistry occurring in precursor inks is largely unexplored. Herein, we investigate the degradation of MHP solutions based on the most widely used solvents, dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). For the MHP inks studied, which contain formamidinium (FA+), methylammonium (MA+), cesium (Cs+), lead (Pb2+), bromide (Br-), and iodide (I-), dramatic compositional changes are observed following storage of the inks in nitrogen in the dark. We show that hydrolysis of DMF in the precursor solution forms dimethylammonium formate, which subsequently incorporatesmore » into the MHP film to compromise the ability of Cs+ and MA+ to stabilize FA+-based MHP. The changes in solution chemistry lead to a modification of the perovskite film stoichiometry, band gap, and structure. The solid precursor salts are stable when ball-milled into a powder, allowing for the storage of large quantities of stoichiometric precursor materials.« less

Degradation of Highly Alloyed Metal Halide Perovskite Precursor Inks: Mechanism and Storage Solutions

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

Dou, Benjia; Wheeler, Lance M.; Christians, Jeffrey A.

Whereas the promise of metal halide perovskite (MHP) photovoltaics (PV) is that they can combine high efficiency with solution-processability, the chemistry occurring in precursor inks is largely unexplored. Herein, we investigate the degradation of MHP solutions based on the most widely used solvents, dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). For the MHP inks studied, which contain formamidinium (FA+), methylammonium (MA+), cesium (Cs+), lead (Pb2+), bromide (Br-), and iodide (I-), dramatic compositional changes are observed following storage of the inks in nitrogen in the dark. We show that hydrolysis of DMF in the precursor solution forms dimethylammonium formate, which subsequently incorporatesmore » into the MHP film to compromise the ability of Cs+ and MA+ to stabilize FA+-based MHP. The changes in solution chemistry lead to a modification of the perovskite film stoichiometry, band gap, and structure. The solid precursor salts are stable when ball-milled into a powder, allowing for the storage of large quantities of stoichiometric precursor materials.« less

The mechanical problems on additive manufacturing of viscoelastic solids with integral conditions on a surface increasing in the growth process

NASA Astrophysics Data System (ADS)

Parshin, D. A.; Manzhirov, A. V.

2018-04-01

Quasistatic mechanical problems on additive manufacturing aging viscoelastic solids are investigated. The processes of piecewise-continuous accretion of such solids are considered. The consideration is carried out in the framework of linear mechanics of growing solids. A theorem about commutativity of the integration over an arbitrary surface increasing in the solid growing process and the time-derived integral operator of viscoelasticity with a limit depending on the solid point is proved. This theorem provides an efficient way to construct on the basis of Saint-Venant principle solutions of nonclassical boundary-value problems for describing the mechanical behaviour of additively formed solids with integral satisfaction of boundary conditions on the surfaces expanding due to the additional material influx to the formed solid. The constructed solutions will retrace the evolution of the stress-strain state of the solids under consideration during and after the processes of their additive formation. An example of applying the proved theorem is given.

Characterization, dissolution and solubility of the hydroxypyromorphite-hydroxyapatite solid solution [(PbxCa1-x)5(PO4)3OH] at 25 °C and pH 2-9.

PubMed

Zhu, Yinian; Huang, Bin; Zhu, Zongqiang; Liu, Huili; Huang, Yanhua; Zhao, Xin; Liang, Meina

2016-01-01

The interaction between Ca-HAP and Pb(2+) solution can result in the formation of a hydroxyapatite-hydroxypyromorphite solid solution [(PbxCa1-x)5(PO4)3(OH)], which can greatly affect the transport and distribution of toxic Pb in water, rock and soil. Therefore, it's necessary to know the physicochemical properties of (PbxCa1-x)5(PO4)3(OH), predominantly its thermodynamic solubility and stability in aqueous solution. Nevertheless, no experiment on the dissolution and related thermodynamic data has been reported. Dissolution of the hydroxypyromorphite-hydroxyapatite solid solution [(PbxCa1-x)5(PO4)3(OH)] in aqueous solution at 25 °C was experimentally studied. The aqueous concentrations were greatly affected by the Pb/(Pb + Ca) molar ratios (XPb) of the solids. For the solids with high XPb [(Pb0.89Ca0.11)5(PO4)3OH], the aqueous Pb(2+) concentrations increased rapidly with time and reached a peak value after 240-720 h dissolution, and then decreased gradually and reached a stable state after 5040 h dissolution. For the solids with low XPb (0.00-0.80), the aqueous Pb(2+) concentrations increased quickly with time and reached a peak value after 1-12 h dissolution, and then decreased gradually and attained a stable state after 720-2160 h dissolution. The dissolution process of the solids with high XPb (0.89-1.00) was different from that of the solids with low XPb (0.00-0.80). The average K sp values were estimated to be 10(-80.77±0.20) (10(-80.57)-10(-80.96)) for hydroxypyromorphite [Pb5(PO4)3OH] and 10(-58.38±0.07) (10(-58.31)-10(-58.46)) for calcium hydroxyapatite [Ca5(PO4)3OH]. The Gibbs free energies of formation (ΔG f (o) ) were determined to be -3796.71 and -6314.63 kJ/mol, respectively. The solubility decreased with the increasing Pb/(Pb + Ca) molar ratios (XPb) of (PbxCa1‒x)5(PO4)3(OH). For the dissolution at 25 °C with an initial pH of 2.00, the experimental data plotted on the Lippmann diagram showed that the solid solution (PbxCa1-x)5(PO4)3(OH) dissolved stoichiometrically at the early stage of dissolution and moved gradually up to the Lippmann solutus curve and the saturation curve for Pb5(PO4)3OH, and then the data points moved along the Lippmann solutus curve from right to left. The Pb-rich (PbxCa1-x)5(PO4)3(OH) was in equilibrium with the Ca-rich aqueous solution. Graphical abstractLippmann diagrams for dissolution of the hydroxypyromorphite-hydroxyapatite solid solution [(PbxCa1-x)5(PO4)3OH] at 25 ˚C and an initial pH of 2.00.

Stabilization of cesium in alkali-activated municipal solid waste incineration fly ash and a pyrophyllite-based system.

PubMed

Shiota, Kenji; Nakamura, Takafumi; Takaoka, Masaki; Aminuddin, Siti Fatimah; Oshita, Kazuyuki; Fujimori, Takashi

2017-11-01

Environmentally sound treatments are required to dispose of municipal solid waste incineration fly ash (MSWIFA) contaminated with radioactive cesium (Cs) from the Fukushima Daiichi nuclear power plant accident in Japan. This study focuses on the stabilization of Cs using an alkali-activated MSWIFA and pyophyllite-based system. Three composite solid products were synthesized after mixtures of raw materials (dehydrated pyrophyllite, MSWIFA, 14 mol/L aqueous sodium hydroxide, and sodium silicate solution) were cured at 105 °C for 24 h. Three types of MSWIFAs were prepared as raw fly ash, raw fly ash with 0.1% CsCl, and raw fly ash with 40% CsCl to understand the stabilization mechanism of Cs. Cs stabilization in two solid products was successful, with less than 6.9% leaching observed from two types tests, and was partly successful for the solid product with the highest concentration of Cs. X-ray diffraction showed that all of the solid products produced several crystalline phases, and that pollucite was formed in the highest Cs concentration product. The X-ray absorption fine structure and scanning electron microscopy with X-ray analysis suggested that most Cs species formed pollucite in the two solid products from MSWIFA with added CsCl. This system provides a technique for the direct stabilization of Cs in MSWIFA. Copyright © 2017 Elsevier Ltd. All rights reserved.

Kinetic precipitation of solution-phase polyoxomolybdate followed by transmission electron microscopy: a window to solution-phase nanostructure.

PubMed

Zhu, Yan; Cammers-Goodwin, Arthur; Zhao, Bin; Dozier, Alan; Dickey, Elizabeth C

2004-05-17

This study aimed to elucidate the structural nature of the polydisperse, nanoscopic components in the solution and the solid states of partially reduced polyoxomolybdate derived from the [Mo132] keplerate, [(Mo)Mo5]12-[Mo2 acetate]30. Designer tripodal hexamine-tris-crown ethers and nanoscopic molybdate coprecipitated from aqueous solution. These microcrystalline solids distributed particle radii between 2-30 nm as assayed by transmission electron microscopy (TEM). The solid materials and their particle size distributions were snap shots of the solution phase. The mother liquor of the preparation of the [Mo132] keplerate after three days revealed large species (r=20-30 nm) in the coprecipitate, whereas [Mo132] keplerate redissolved in water revealed small species (3-7 nm) in the coprecipitate. Nanoparticles of coprecipitate were more stable than solids derived solely from partially reduced molybdate. The TEM features of all material analyzed lacked facets on the nanometer length scale; however, the structures diffracted electrons and appeared to be defect-free as evidenced by Moiré patterns in the TEM images. Moiré patterns and size-invariant optical densities of the features in the micrographs suggested that the molybdate nanoparticles were vesicular.

Solute redistribution in dendritic solidification with diffusion in the solid

NASA Technical Reports Server (NTRS)

Ganesan, S.; Poirier, D. R.

1989-01-01

An investigation of solute redistribution during dendritic solidification with diffusion in the solid has been performed using numerical techniques. The extent of diffusion is characterized by the instantaneous and average diffusion parameters. These parameters are functions of the diffusion Fourier number, the partition ratio and the fraction solid. Numerical results are presented as an approximate model, which is used to predict the average diffusion parameter and calculate the composition of the interdendritic liquid during solidification.

Assessing the Selectivity of Extractant Solutions for Recovering Labile Arsenic Associated with Iron (Hydr)oxides and Sulfides in Sediments

EPA Science Inventory

Sequential extractions can provide analytical constraints on the identification of mineral phases that control arsenic speciation in sediments. Model solids were used in this study to evaluate different solutions designed to extract arsenic from relatively labile solid phases. ...

Thermodynamics of aragonite-strontianite solid solutions: Results from stoichiometric solubility at 25 and 76°C

USGS Publications Warehouse

Plummer, Niel; Busenberg, E.

1987-01-01

Neither equilibrium nor stoichiometric saturation is observed at 76°C during laboratory recrystallization of strontianite-aragonite solid solutions even after apparent 100 percent conversion to a narrow secondary composition and demonstration of a nearly constant composition system for periods of 300 hours.

A fluorescent chemosensor for Zn(II). Exciplex formation in solution and the solid state.

PubMed

Bencini, Andrea; Berni, Emanuela; Bianchi, Antonio; Fornasari, Patrizia; Giorgi, Claudia; Lima, Joao C; Lodeiro, Carlos; Melo, Maria J; de Melo, J Seixas; Parola, Antonio Jorge; Pina, Fernando; Pina, Joao; Valtancoli, Barbara

2004-07-21

The macrocyclic phenanthrolinophane 2,9-[2,5,8-triaza-5-(N-anthracene-9-methylamino)ethyl]-[9]-1,10-phenanthrolinophane (L) bearing a pendant arm containing a coordinating amine and an anthracene group forms stable complexes with Zn(II), Cd(II) and Hg(II) in solution. Stability constants of these complexes were determined in 0.10 mol dm(-3) NMe(4)Cl H(2)O-MeCN (1:1, v/v) solution at 298.1 +/- 0.1 K by means of potentiometric (pH metric) titration. The fluorescence emission properties of these complexes were studied in this solvent. For the Zn(II) complex, steady-state and time-resolved fluorescence studies were performed in ethanol solution and in the solid state. In solution, intramolecular pi-stacking interaction between phenanthroline and anthracene in the ground state and exciplex emission in the excited state were observed. From the temperature dependence of the photostationary ratio (I(Exc)/I(M)), the activation energy for the exciplex formation (E(a)) and the binding energy of the exciplex (-DeltaH) were determined. The crystal structure of the [ZnLBr](ClO(4)).H(2)O compound was resolved, showing that in the solid state both intra- and inter-molecular pi-stacking interactions are present. Such interactions were also evidenced by UV-vis absorption and emission spectra in the solid state. The absorption spectrum of a thin film of the solid complex is red-shifted compared with the solution spectra, whereas its emission spectrum reveals the unique featureless exciplex band, blue shifted compared with the solution. In conjunction with X-ray data the solid-state data was interpreted as being due to a new exciplex where no pi-stacking (full overlap of the pi-electron cloud of the two chromophores - anthracene and phenanthroline) is observed. L is a fluorescent chemosensor able to signal Zn(II) in presence of Cd(II) and Hg(II), since the last two metal ions do not give rise either to the formation of pi-stacking complexes or to exciplex emission in solution.

Magnetic graphene oxide modified with choline chloride-based deep eutectic solvent for the solid-phase extraction of protein.

PubMed

Huang, Yanhua; Wang, Yuzhi; Pan, Qi; Wang, Ying; Ding, Xueqin; Xu, Kaijia; Li, Na; Wen, Qian

2015-06-02

Four kinds of green deep eutectic solvents (DESs) based on choline chloride (ChCl) have been synthesized and coated on the surface of magnetic graphene oxide (Fe3O4@GO) to form Fe3O4@GO-DES for the magnetic solid-phase extraction of protein. X-ray diffraction (XRD), vibrating sample magnetometer (VSM), Fourier transform infrared spectrometry (FTIR), field emission scanning electron microscopy (FESEM) and thermal gravimetric analysis (TGA) were employed to characterize Fe3O4@GO-DES, and the results indicated the successful preparation of Fe3O4@GO-DES. The UV-vis spectrophotometer was used to measure the concentration of protein after extraction. Single factor experiments proved that the extraction amount was influenced by the types of DESs, solution temperature, solution ionic strength, extraction time, protein concentration and the amount of Fe3O4@GO-DES. Comparison of Fe3O4@GO and Fe3O4@GO-DES was carried out by extracting bovine serum albumin, ovalbumin, bovine hemoglobin and lysozyme. The experimental results showed that the proposed Fe3O4@GO-DES performs better than Fe3O4@GO in the extraction of acidic protein. Desorption of protein was carried out by eluting the solid extractant with 0.005 mol L(-1) Na2HPO4 contained 1 mol L(-1) NaCl. The obtained elution efficiency was about 90.9%. Attributed to the convenient magnetic separation, the solid extractant could be easily recycled. Copyright © 2015 Elsevier B.V. All rights reserved.

Manipulation of oligonucleotides immobilized on solid supports - DNA computations on surfaces

NASA Astrophysics Data System (ADS)

Liu, Qinghua

The manipulation of DNA oligonucleotides immobilized on various solid supports has been studied intensively, especially in the area of surface hybridization. Recently, surface-based biotechnology has been applied to the area of molecular computing. These surface-based methods have advantages with regard to ease of handling, facile purification, and less interference when compared to solution methodologies. This dissertation describes the investigation of molecular approaches to DNA computing. The feasibility of encoding a bit (0 or 1) of information for DNA-based computations at the single nucleotide level was studied, particularly with regard to the efficiency and specificity of hybridization discrimination. Both gold and glass surfaces, with addressed arrays of 32 oligonucleotides, were employed with similar hybridization results. Although single-base discrimination may be achieved in the system, it is at the cost of a severe decrease in the efficiency of hybridization to perfectly matched sequences. This compromises the utility of single nucleotide encoding for DNA computing applications in the absence of some additional mechanism for increasing specificity. Several methods are suggested including a multiple-base encoding strategy. The multiple-base encoding strategy was employed to develop a prototype DNA computer. The approach was demonstrated by solving a small example of the Satisfiability (SAT) problem, an NP-complete problem in Boolean logic. 16 distinct DNA oligonucleotides, encoding all candidate solutions to the 4-variable-4-clause-3-SAT problem, were immobilized on a gold surface in the non-addressed format. Four cycles of MARK (hybridization), DESTROY (enzymatic destruction) and UNMARK (denaturation) were performed, which identified and eliminated members of the set which were not solutions to the problem. Determination of the answer was accomplished in the READOUT (sequence identification) operation by PCR amplification of the remaining molecules and hybridization to an addressed array. Four answers were determined and the S/N ratio between correct and incorrect solutions ranged from 10 to 777, making discrimination between correct and incorrect solutions to the problem straightforward. Additionally, studies of enzymatic manipulations of DNA molecules on surfaces suggested the use of E. coli Exonuclease I (Exo I) and perhaps EarI in the DESTROY operation.

Laser-induced fluorescence spectrometer based on tunable color center laser for low-impurity-solution diagnostic and analysis

NASA Astrophysics Data System (ADS)

Basiev, Tasoltan T.; Fedorov, Vladimir V.; Karasik, Alexander Y.; Lin'kov, S. I.; Orlovskii, Yurii V.; Osiko, Vyacheslav V.; Panov, Vitaly A.; Prokhorov, Alexander M.; Vorob'ev, Ivan N.; Zverev, Peter G.

1996-11-01

Solid state (SS) tunable LiF:F2 color center laser with second and fourth harmonic generation for visible and ultra violet spectral ranges was developed for the laser induced fluorescence spectroscopy (LIFS). The construction and properties of excitation, registration and flame atomization systems for water solution diagnostic are discussed. The testing experiment with low iron concentrated water sample exhibits ultrahigh sensitivity which was estimated to be 0.05 ppb in our set-up. The SS LIFS spectrometer developed is usable to measure more than 42 metal elements in solution on the ppm, ppb level for various medical and biological applications.

Method Using Water-Based Solvent to Prepare Li7La3Zr2O12 Solid Electrolytes.

PubMed

Huang, Xiao; Lu, Yang; Jin, Jun; Gu, Sui; Xiu, Tongping; Song, Zhen; Badding, Michael E; Wen, Zhaoyin

2018-05-09

Li-garnet Li 7 La 3 Zr 2 O 12 (LLZO) is a promising candidate of solid electrolytes for high-safety solid-state Li + ion batteries. However, because of its high reactivity to water, the preparation of LLZO powders and ceramics is not easy for large-scale amounts. Herein, a method applying water-based solvent is proposed to demonstrate a possible solution. Ta-doped LLZO, that is, Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO), and its LLZTO/MgO composite ceramics are made by attrition milling, followed by a spray-drying process using water-based slurries. The impacts of parameters of the method on the structure and properties of green and sintered pellets are studied. A relative density of ∼95%, a Li-ion conductivity of ∼3.5 × 10 -4 S/cm, and uniform grain size LLZTO/MgO garnet composite ceramics are obtained with an attrition-milled LLZTO/MgO slurry that contains 40 wt % solids and 2 wt % polyvinyl alcohol binder. Li-sulfur batteries based on these ceramics are fabricated and work under 25 °C for 20 cycles with a Coulombic efficiency of 100%. This research demonstrates a promising mass production method for the preparation of Li-garnet ceramics.

Chemical oxidative and solid state synthesis of low molecular weight polymers for organic field effect transistors

NASA Astrophysics Data System (ADS)

Mahale, Rajashree Y.; Dharmapurikar, Satej S.; Chini, Mrinmoy Kumar

2018-03-01

Solution processability of the precursor molecules is a major issue owing to their limited solubility for the synthesis of conjugated polymers. Therefore, we favour the solvent free solid state chemical oxidative polymerization route for the synthesis of diketopyrrolopyrrole (DPP) based donor-acceptor (D-A) type conjugated polymers. D-A type polymer Poly(S-OD-EDOT) which contains DPP coupled with EDOT donor units is synthesized via solid state polymerization method. The polymer is employed as an active layer for organic field-effect transistors to measure charge transport properties. The Polymer shows good hole mobility 3.1 × 10-2 cm2 V-1 s-1, with a on/off ratio of 1.1 × 103.

High-Solids Polyimide Precursor Solutions

NASA Technical Reports Server (NTRS)

Chuang, Chun-Hua (Inventor)

2004-01-01

The invention is a highly concentrated stable solution of polymide precursors (monometers) having a solids content ranging from about 80 to 98 percent by weight in lower aliphatic alcohols i.e. methyl and/or ethylalcohol. the concentrated polyimide precursos solution comparisons effective amounts of at least one aromatic diamine, at least one aromatic dianhydride, and a monofunctional endcap including monoamines, monoanhydrides and lower alkyl esters of said monoanhydrides. These concentrated polyimide precursor solutions are particularly useful for the preparation of fibrous prepregs and composites for use in structural materials for military and civil applications.

PROCESS OF MAKING A NEUTRONIC REACTOR FUEL ELEMENT COMPOSITION

DOEpatents

Alter, H.W.; Davidson, J.K.; Miller, R.S.; Mewherter, J.L.

1959-01-13

A process is presented for making a ceramic-like material suitable for use as a nuclear fuel. The material consists of a solid solution of plutonium dioxide in uranium dioxide and is produced from a uranyl nitrate -plutonium nitrate solution containing uraniunm and plutonium in the desired ratio. The uranium and plutonium are first precipitated from the solution by addition of NH/ sub 4/OH and the dried precipitate is then calcined at 600 C in a hydrogen atmosphere to yield the desired solid solution of PuO/sub 2/ in UO/sub 2/.

Interfacial Microstructure and Its Influence on Resistivity of Thin Layers Copper Cladding Steel Wires

NASA Astrophysics Data System (ADS)

Li, Hongjuan; Ding, Zhimin; Zhao, Ruirong

2018-04-01

The interfacial microstructure and resistivity of cold-drawn and annealed thin layers copper cladding steel (CCS) wires have been systematically investigated by the methods of scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and resistivity testing. The results showed that the Cu and Fe atoms near interface diffused into each other matrixes. The Fe atoms diffused into Cu matrixes and formed a solid solution. The mechanism of solid solution is of substitution type. When the quantity of Fe atoms exceeds the maximum solubility, the supersaturated solid solution would form Fe clusters and decompose into base Cu and α-Fe precipitated phases under certain conditions. A few of α-Fe precipitates was observed in the copper near Cu/Fe interfaces of cold-drawn CCS wires, with 1-5 nm in size. A number of α-Fe precipitates of 1-20 nm in size can be detected in copper near Cu/Fe interfaces of CCS wires annealed at 850°C. When annealing temperature was less than 750°C, the resistivity of CCS wires annealed was lower than that of cold-drawn CCS wires. However, when annealing temperature was above 750°C, the resistivity of CCS wires was greater than that of cold-drawn CCS wires and increased with rising the annealing temperature. The relationship between nanoscale α-Fe precipitation and resistivity of CCS wires has been well discussed.

Thermodynamics of concentrated solid solution alloys

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

Gao, Michael C.; Zhang, C.; Gao, P.

This study reviews the three main approaches for predicting the formation of concentrated solid solution alloys (CSSA) and for modeling their thermodynamic properties, in particular, utilizing the methodologies of empirical thermo-physical parameters, CALPHAD method, and first-principles calculations combined with hybrid Monte Carlo/Molecular Dynamics (MC/MD) simulations. In order to speed up CSSA development, a variety of empirical parameters based on Hume-Rothery rules have been developed. Herein, these parameters have been systematically and critically evaluated for their efficiency in predicting solid solution formation. The phase stability of representative CSSA systems is then illustrated from the perspectives of phase diagrams and nucleation drivingmore » force plots of the σ phase using CALPHAD method. The temperature-dependent total entropies of the FCC, BCC, HCP, and σ phases in equimolar compositions of various systems are presented next, followed by the thermodynamic properties of mixing of the BCC phase in Al-containing and Ti-containing refractory metal systems. First-principles calculations on model FCC, BCC and HCP CSSA reveal the presence of both positive and negative vibrational entropies of mixing, while the calculated electronic entropies of mixing are negligible. Temperature dependent configurational entropy is determined from the atomic structures obtained from MC/MD simulations. Current status and challenges in using these methodologies as they pertain to thermodynamic property analysis and CSSA design are discussed.« less

Thermodynamics of concentrated solid solution alloys

DOE PAGES

Gao, Michael C.; Zhang, C.; Gao, P.; ...

2017-10-12

This study reviews the three main approaches for predicting the formation of concentrated solid solution alloys (CSSA) and for modeling their thermodynamic properties, in particular, utilizing the methodologies of empirical thermo-physical parameters, CALPHAD method, and first-principles calculations combined with hybrid Monte Carlo/Molecular Dynamics (MC/MD) simulations. In order to speed up CSSA development, a variety of empirical parameters based on Hume-Rothery rules have been developed. Herein, these parameters have been systematically and critically evaluated for their efficiency in predicting solid solution formation. The phase stability of representative CSSA systems is then illustrated from the perspectives of phase diagrams and nucleation drivingmore » force plots of the σ phase using CALPHAD method. The temperature-dependent total entropies of the FCC, BCC, HCP, and σ phases in equimolar compositions of various systems are presented next, followed by the thermodynamic properties of mixing of the BCC phase in Al-containing and Ti-containing refractory metal systems. First-principles calculations on model FCC, BCC and HCP CSSA reveal the presence of both positive and negative vibrational entropies of mixing, while the calculated electronic entropies of mixing are negligible. Temperature dependent configurational entropy is determined from the atomic structures obtained from MC/MD simulations. Current status and challenges in using these methodologies as they pertain to thermodynamic property analysis and CSSA design are discussed.« less

In situ characterization of uranium and americium oxide solid solution formation for CRMP process: first combination of in situ XRD and XANES measurements.

PubMed

Caisso, Marie; Picart, Sébastien; Belin, Renaud C; Lebreton, Florent; Martin, Philippe M; Dardenne, Kathy; Rothe, Jörg; Neuville, Daniel R; Delahaye, Thibaud; Ayral, André

2015-04-14

Transmutation of americium in heterogeneous mode through the use of U1-xAmxO2±δ ceramic pellets, also known as Americium Bearing Blankets (AmBB), has become a major research axis. Nevertheless, in order to consider future large-scale deployment, the processes involved in AmBB fabrication have to minimize fine particle dissemination, due to the presence of americium, which considerably increases the risk of contamination. New synthesis routes avoiding the use of pulverulent precursors are thus currently under development, such as the Calcined Resin Microsphere Pelletization (CRMP) process. It is based on the use of weak-acid resin (WAR) microspheres as precursors, loaded with actinide cations. After two specific calcinations under controlled atmospheres, resin microspheres are converted into oxide microspheres composed of a monophasic U1-xAmxO2±δ phase. Understanding the different mechanisms during thermal conversion, that lead to the release of organic matter and the formation of a solid solution, appear essential. By combining in situ techniques such as XRD and XAS, it has become possible to identify the key temperatures for oxide formation, and the corresponding oxidation states taken by uranium and americium during mineralization. This paper thus presents the first results on the mineralization of (U,Am) loaded resin microspheres into a solid solution, through in situ XAS analysis correlated with HT-XRD.

Spectroscopy of Single AlInAs Quantum Dots

NASA Astrophysics Data System (ADS)

Derebezov, I. A.; Gaisler, A. V.; Gaisler, V. A.; Dmitriev, D. V.; Toropov, A. I.; Kozhukhov, A. S.; Shcheglov, D. V.; Latyshev, A. V.; Aseev, A. L.

2018-03-01

A system of quantum dots based on Al x In1- x As/Al y Ga1- y As solid solutions is investigated. The use of Al x In1- x As wide-gap solid solutions as the basis of quantum dots substantially extends the spectral emission range to the short-wavelength region, including the wavelength region near 770 nm, which is of interest for the development of aerospace systems of quantum cryptography. The optical characteristics of Al x In1- x As single quantum dots grown by the Stranski-Krastanov mechanism were studied by cryogenic microphotoluminescence. The statistics of the emission of single quantum dot excitons was studied using a Hanbury Brown-Twiss interferometer. The pair photon correlation function indicates the sub-Poissonian nature of the emission statistics, which directly confirms the possibility of developing single-photon emitters based on Al x In1- x As quantum dots. The fine structure of quantum dot exciton states was investigated at wavelengths near 770 nm. The splitting of the exciton states is found to be similar to the natural width of exciton lines, which is of great interest for the development of entangled photon pair emitters based on Al x In1- x As quantum dots.

A combined calorimetric and computational study of the energetics of rare earth substituted UO 2 systems

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

Zhang, Lei; Solomon, Jonathan M.; Asta, Mark

2015-09-01

The energetics of rare earth substituted UO2 solid solutions (U1-xLnxO2-0.5x+y, where Ln = La, Y, and Nd) are investigated employing a combination of calorimetric measurements and density functional theory based computations. Calculated and measured formation enthalpies agree within 10 kJ/mol for stoichiometric oxygen/metal compositions. To better understand the factors governing the stability and defect binding in rare earth substituted urania solid solutions, systematic trends in the energetics are investigated based on the present results and previous computational and experimental thermochemical studies of rare earth substituted fluorite oxides (A1-xLnxO2-0.5x, where A = Hf, Zr, Ce, and Th). A consistent trend towardsmore » increased energetic stability with larger size mismatch between the smaller host tetravalent cation and the larger rare earth trivalent cation is found for both actinide and non-actinide fluorite oxide systems where aliovalent substitution of Ln cations is compensated by oxygen vacancies. However, the large exothermic oxidation enthalpy in the UO2 based systems favors oxygen rich compositions where charge compensation occurs through the formation of uranium cations with higher oxidation states.« less

Emergency deployable core catcher

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

Rosewell, M.P.

An emergency melt down core catcher apparatus for a nuclear reactor having a retrofitable eutectic solute holding vessel connected to a core containment vessel with particle transferring fluid and particles or granules of solid eutectic solute materials contained therein and transferable by automatically operated valve means to transport and position the solid eutectic solute material in a position below the core to catch and react with any partial or complete melt down of the fuel core.

Eco-friendly luminescent solar concentrators with low reabsorption losses and resistance to concentration quenching based on aqueous-solution-processed thiolate-gold nanoclusters

NASA Astrophysics Data System (ADS)

Huang, H. Y.; Cai, K. B.; Chang, L. Y.; Chen, P. W.; Lin, T. N.; Lin, C. A. J.; Shen, J. L.; Talite, M. J.; Chou, W. C.; Yuan, C. T.

2017-09-01

Heavy-metal-containing quantum dots (QDs) with engineered electronic states have been served as luminophores in luminescent solar concentrators (LSCs) with impressive optical efficiency. Unfortunately, those QDs involve toxic elements and need to be synthesized in a hazardous solvent. Recently, biocompatible, eco-friendly gold nanoclusters (AuNCs), which can be directly synthesized in an aqueous solution, have gained much attention for promising applications in ‘green photonics’. Here, we explored the solid-state photophysical properties of aqueous-solution-processed, glutathione-stabilized gold nanoclusters (GSH-AuNCs) with a ligand-to-metal charge-transfer (LMCT) state for developing ‘green’ LSCs. We found that such GSH-AuNCs exhibit a large Stokes shift with almost no spectral overlap between the optical absorption and PL emission due to the LMCT states, thus, suppressing reabsorption losses. Compared with GSH-AuNCs in solution, the photoluminescence quantum yields (PL-QYs) of the LSCs can be enhanced, accompanied with a lengthened PL lifetime owing to the suppression of non-radiative recombination rates. In addition, the LSCs do not suffer from severe concentration-induced PL quenching, which is a common weakness for conventional luminophores. As a result, a common trade-off between light-harvesting efficiency and solid-state PL-QYs can be bypassed due to nearly-zero spectral overlap integral between the optical absorption and PL emission. We expect that GSH-AuNCs hold great promise for serving as luminophores for ‘green’ LSCs by further enhancing solid-state PL-QYs.

Eco-friendly luminescent solar concentrators with low reabsorption losses and resistance to concentration quenching based on aqueous-solution-processed thiolate-gold nanoclusters.

PubMed

Huang, H Y; Cai, K B; Chang, L Y; Chen, P W; Lin, T N; Lin, C A J; Shen, J L; Talite, M J; Chou, W C; Yuan, C T

2017-09-15

Heavy-metal-containing quantum dots (QDs) with engineered electronic states have been served as luminophores in luminescent solar concentrators (LSCs) with impressive optical efficiency. Unfortunately, those QDs involve toxic elements and need to be synthesized in a hazardous solvent. Recently, biocompatible, eco-friendly gold nanoclusters (AuNCs), which can be directly synthesized in an aqueous solution, have gained much attention for promising applications in 'green photonics'. Here, we explored the solid-state photophysical properties of aqueous-solution-processed, glutathione-stabilized gold nanoclusters (GSH-AuNCs) with a ligand-to-metal charge-transfer (LMCT) state for developing 'green' LSCs. We found that such GSH-AuNCs exhibit a large Stokes shift with almost no spectral overlap between the optical absorption and PL emission due to the LMCT states, thus, suppressing reabsorption losses. Compared with GSH-AuNCs in solution, the photoluminescence quantum yields (PL-QYs) of the LSCs can be enhanced, accompanied with a lengthened PL lifetime owing to the suppression of non-radiative recombination rates. In addition, the LSCs do not suffer from severe concentration-induced PL quenching, which is a common weakness for conventional luminophores. As a result, a common trade-off between light-harvesting efficiency and solid-state PL-QYs can be bypassed due to nearly-zero spectral overlap integral between the optical absorption and PL emission. We expect that GSH-AuNCs hold great promise for serving as luminophores for 'green' LSCs by further enhancing solid-state PL-QYs.

Performance of a biogas upgrading process based on alkali absorption with regeneration using air pollution control residues.

PubMed

Baciocchi, Renato; Carnevale, Ennio; Costa, Giulia; Gavasci, Renato; Lombardi, Lidia; Olivieri, Tommaso; Zanchi, Laura; Zingaretti, Daniela

2013-12-01

This work analyzes the performance of an innovative biogas upgrading method, Alkali absorption with Regeneration (AwR) that employs industrial residues and allows to permanently store the separated CO2. This process consists in a first stage in which CO2 is removed from the biogas by means of chemical absorption with KOH or NaOH solutions followed by a second stage in which the spent absorption solution is contacted with waste incineration Air Pollution Control (APC) residues. The latter reaction leads to the regeneration of the alkali reagent in the solution and to the precipitation of calcium carbonate and hence allows to reuse the regenerated solution in the absorption process and to permanently store the separated CO2 in solid form. In addition, the final solid product is characterized by an improved environmental behavior compared to the untreated residues. In this paper the results obtained by AwR tests carried out in purposely designed demonstrative units installed in a landfill site are presented and discussed with the aim of verifying the feasibility of this process at pilot-scale and of identifying the conditions that allow to achieve all of the goals targeted by the proposed treatment. Specifically, the CO2 removal efficiency achieved in the absorption stage, the yield of alkali regeneration and CO2 uptake resulting for the regeneration stage, as well as the leaching behavior of the solid product are analyzed as a function of the type and concentration of the alkali reagent employed for the absorption reaction. Copyright © 2013 Elsevier Ltd. All rights reserved.

Single molecule magnet behavior of a pentanuclear Mn-based metallacrown complex: solid state and solution magnetic studies.

PubMed

Zaleski, Curtis M; Tricard, Simon; Depperman, Ezra C; Wernsdorfer, Wolfgang; Mallah, Talal; Kirk, Martin L; Pecoraro, Vincent L

2011-11-21

The magnetic behavior of the pentanuclear complex of formula Mn(II)(O(2)CCH(3))(2)[12-MC(Mn(III)(N)shi)-4](DMF)(6), 1, was investigated using magnetization and magnetic susceptibility measurements both in the solid state and in solution. Complex 1 has a nearly planar structure, made of a central Mn(II) ion surrounded by four peripheral Mn(III) ions. Solid state variable-field dc magnetic susceptibility experiments demonstrate that 1 possesses a low value for the total spin in the ground state; fitting appropriate expressions to the data results in antiferromangetic coupling both between the peripheral Mn(III) ions (J = -6.3 cm(-1)) and between the central Mn(II) ion and the Mn(III) ones (J' = -4.2 cm(-1)). In order to obtain a reasonable fit, a relatively large single ion magnetic anisotropy (D) value of 1 cm(-1) was necessary for the central Mn(II) ion. The single crystal magnetization measurements using a microsquid array display a very slight opening of the hysteresis loop but only at a very low temperature (0.04 K), which is in line with the ac susceptibility data where a slow relaxation of the magnetization occurs just around 2 K. In frozen solution, complex 1 displays a frequency dependent ac magnetic susceptibility signal with an energy barrier to magnetization reorientation (E) and relaxation time at an infinite temperature (τ(o)) of 14.7 cm(-1) and 1.4 × 10(-7) s, respectively, demonstrating the single molecule magnetic behavior in solution.

NiF2/NaF:CaF2/Ca Solid-State High-Temperature Battery Cells

NASA Technical Reports Server (NTRS)

West, William; Whitacre, Jay; DelCastillo, Linda

2009-01-01

Experiments and theoretical study have demonstrated the promise of all-solid-state, high-temperature electrochemical battery cells based on NiF2 as the active cathode material, CaF2 doped with NaF as the electrolyte material, and Ca as the active anode material. These and other all-solid-state cells have been investigated in a continuing effort to develop batteries for instruments that must operate in environments much hotter than can be withstood by ordinary commercially available batteries. Batteries of this type are needed for exploration of Venus (where the mean surface temperature is about 450 C), and could be used on Earth for such applications as measuring physical and chemical conditions in geothermal wells and oil wells. All-solid-state high-temperature power cells are sought as alternatives to other high-temperature power cells based, variously, on molten anodes and cathodes or molten eutectic salt electrolytes. Among the all-solid-state predecessors of the present NiF2/NaF:CaF2/Ca cells are those described in "Solid-State High-Temperature Power Cells" (NPO-44396), NASA Tech Briefs, Vol. 32, No. 5 (May 2008), page 40. In those cells, the active cathode material is FeS2, the electrolyte material is a crystalline solid solution of equimolar amounts of Li3PO4 and LiSiO4, and the active anode material is Li contained within an alloy that remains solid in the intended high operational temperature range.

Flexible poly(ethylene carbonate)/garnet composite solid electrolyte reinforced by poly(vinylidene fluoride-hexafluoropropylene) for lithium metal batteries

NASA Astrophysics Data System (ADS)

He, Zijian; Chen, Long; Zhang, Bochen; Liu, Yongchang; Fan, Li-Zhen

2018-07-01

Solid-state electrolytes with high ionic conductivities, great flexibility, and easy processability are needed for high-performance solid-state rechargeable lithium batteries. In this work, we synthesize nanosized cubic Li6.25Al0.25La3Zr2O12 (LLZO) by solution combustion method and develop a flexible garnet-based composite solid electrolyte composed of LLZO, poly(ethylene carbonate) (PEC), poly(vinylidene fluoride-hexafluoropropylene) (P(VdF-HFP) and lithium bis(fluorosulfonyl)imide (LiFSI)). In the flexible composite solid electrolytes, LLZO nanoparticles, as ceramic matrix, have a positive effect on ionic conductivities and lithium ion transference number (tLi+). PEC, as a fast ion-conducting polymer, possesses high tLi+ inherently. P(VdF-HFP), as a binder, can strengthen mechanical properties. Consequently, the as-prepared composite solid electrolyte demonstrates high tLi+ (0.82) and superb thermal stability (remaining LLZO matrix after burning). All-solid-state LiFePO4|Li cells assembled with the flexible composite solid electrolyte deliver a high initial discharge specific capacity of 121.4 mAh g-1 and good cycling stability at 55 °C.

Investigation of Plutonium and Uranium Precipitation Behavior with Gadolinium as a Neutron Poison

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

Visser, A.E.

2003-10-17

The caustic precipitation of plutonium (Pu)-containing solutions has been investigated to determine whether the presence of 3:1 uranium (U):Pu in solutions stored in the H-Canyon Facility at the U.S. Department of Energy's (DOE) Savannah River Site (SRS) would adversely impact the use of gadolinium nitrate (Gd(NO3)3) as a neutron poison. In the past, this disposition strategy has been successfully used to discard solutions containing approximately 100 kg of Pu to the SRS high level waste (HLW) system. In the current experiments, gadolinium (as Gd(NO3)3) was added to samples of a 3:1 U:Pu solution, a surrogate 3 g/L U solution, andmore » a surrogate 3 g/L U with 1 g/L Pu solution. A series of experiments was then performed to observe and characterize the precipitate at selected pH values. Solids formed at pH 4.5 and were found to contain at least 50 percent of the U and 94 percent of the Pu, but only 6 percent of the Gd. As the pH of the solution increased (e.g., pH greater than 14 with 1.2 or 3.6 M sodium hydroxide (NaOH) excess), the precipitate contained greater than 99 percent of the Pu, U, and Gd. After the pH greater than 14 systems were undisturbed for one week, no significant changes were found in the composition of the solid or supernate for each sample. The solids were characterized by X-ray diffraction (XRD) which found sodium diuranate (Na2U2O7) and gadolinium hydroxide (Gd(OH)3) at pH 14. Thermal gravimetric analysis (TGA) indicated sufficient water molecules were present in the solids to thermalize the neutrons, a requirement for the use of Gd as a neutron poison. Scanning electron microscopy (SEM) was also performed and the accompanying back-scattering electron analysis (BSE) found Pu, U, and Gd compounds in all pH greater than 14 precipitate samples. The rheological properties of the slurries at pH greater than 14 were also investigated by performing precipitate settling rate studies and measuring the viscosity and density of the materials. Based on the results of these experiments, poisoning the Pu-U solutions with Gd and subsequent neutralization is a viable process for discarding the Pu to the SRS HLW system.« less

Various nanoparticle morphologies and surface properties of waterborne polyurethane controlled by water

PubMed Central

Zhou, Xing; Fang, Changqing; Lei, Wanqing; Du, Jie; Huang, Tingyi; Li, Yan; Cheng, Youliang

2016-01-01

Water plays important roles in organic reactions such as polyurethane synthesis, and the aqueous solution environment affects polymer morphology and other properties. This paper focuses on the morphology and surface properties of waterborne polyurethane resulting from the organic reaction in water involving different forms (solid and liquid), temperatures and aqueous solutions. We provide evidence from TEM observations that the appearance of polyurethane nanoparticles in aqueous solutions presents diverse forms, including imperfect spheres, perfect spheres, perfect and homogenous spheres and tubes. Based on the results on FTIR, GPC, AFM and XRD experiments, we suggest that the shape of the nanoparticles may be decided by the crimp degree (i.e., the degree of polyurethane chains intertangling in the water environment) and order degree, which are determined by the molecular weight (Mn) and hydrogen bonds. Meanwhile, solid water and high-temperature water can both reduce hard segments that gather on the polyurethane film surface to reduce hydrophilic groups and produce a soft surface. Our findings show that water may play key roles in aqueous polymer formation and bring order to molecular chains. PMID:27687001

Self-assembling semiconducting polymers--rods and gels from electronic materials.

PubMed

Clark, Andrew P-Z; Shi, Chenjun; Ng, Benny C; Wilking, James N; Ayzner, Alexander L; Stieg, Adam Z; Schwartz, Benjamin J; Mason, Thomas G; Rubin, Yves; Tolbert, Sarah H

2013-02-26

In an effort to favor the formation of straight polymer chains without crystalline grain boundaries, we have synthesized an amphiphilic conjugated polyelectrolyte, poly(fluorene-alt-thiophene) (PFT), which self-assembles in aqueous solutions to form cylindrical micelles. In contrast to many diblock copolymer assemblies, the semiconducting backbone runs parallel, not perpendicular, to the long axis of the cylindrical micelle. Solution-phase micelle formation is observed by X-ray and visible light scattering. The micelles can be cast as thin films, and the cylindrical morphology is preserved in the solid state. The effects of self-assembly are also observed through spectral shifts in optical absorption and photoluminescence. Solutions of higher-molecular-weight PFT micelles form gel networks at sufficiently high aqueous concentrations. Rheological characterization of the PFT gels reveals solid-like behavior and strain hardening below the yield point, properties similar to those found in entangled gels formed from surfactant-based micelles. Finally, electrical measurements on diode test structures indicate that, despite a complete lack of crystallinity in these self-assembled polymers, they effectively conduct electricity.

Automatic Assignment of Methyl-NMR Spectra of Supramolecular Machines Using Graph Theory.

PubMed

Pritišanac, Iva; Degiacomi, Matteo T; Alderson, T Reid; Carneiro, Marta G; Ab, Eiso; Siegal, Gregg; Baldwin, Andrew J

2017-07-19

Methyl groups are powerful probes for the analysis of structure, dynamics and function of supramolecular assemblies, using both solution- and solid-state NMR. Widespread application of the methodology has been limited due to the challenges associated with assigning spectral resonances to specific locations within a biomolecule. Here, we present Methyl Assignment by Graph Matching (MAGMA), for the automatic assignment of methyl resonances. A graph matching protocol examines all possibilities for each resonance in order to determine an exact assignment that includes a complete description of any ambiguity. MAGMA gives 100% accuracy in confident assignments when tested against both synthetic data, and 9 cross-validated examples using both solution- and solid-state NMR data. We show that this remarkable accuracy enables a user to distinguish between alternative protein structures. In a drug discovery application on HSP90, we show the method can rapidly and efficiently distinguish between possible ligand binding modes. By providing an exact and robust solution to methyl resonance assignment, MAGMA can facilitate significantly accelerated studies of supramolecular machines using methyl-based NMR spectroscopy.

EXAFS characterisation of metal bonding in highly luminescent, UV stable, water-soluble and biocompatible lanthanide complexes

NASA Astrophysics Data System (ADS)

Kalyakina, A.; Utochnikova, V.; Trigub, A.; Zubavichus, Y.; Kuzmina, N.; Bräse, S.

2016-05-01

The combination of X-ray diffraction with EXAFS was employed to assess the coordination environment of lanthanide complexes in solutions. This method is based on the assumption that the local structure of lanthanide complexes in solution combines elements of the crystal structure of the complex in the solid state (single- or polycrystalline) and the elements of the local structure of a lanthanide salt, completely dissociated in the solvent (usually chlorides). The success of this approach is demonstrated with the lanthanide (III) 2,3,4,5,6-pentafluorobenzoate complexes, where the local structure in aqueous and methanol solutions were estimated. Moreover, the dissociation degree of the complexes in aqueous and methanol solutions was evaluated.

Rapid and solvent-free solid-state synthesis and characterization of Zn3V2O8 nanostructures and their phenol red aqueous solution photodegradation

NASA Astrophysics Data System (ADS)

Mazloom, Fatemeh; Masjedi-Arani, Maryam; Salavati-Niasari, Masoud

2017-08-01

Zinc vanadate (Zn3V2O8) nanostructures have been successfully synthesized via simple, rapid and solvent-free solid-state method by using different complex precursors of Zn and NH4VO3 as novel starting materials. Effects of various zinc (II) Schiff base complex precursors and calcination temperatures were investigated to reach optimum condition. It was found that particle size and optical property of the as-prepared products could be greatly influenced via these parameters. The products were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectra, energy dispersive X-ray microanalysis (EDX), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Photoluminescence and ultraviolet-visible (UV-Vis) spectroscopy. The photocatalytic activity of zinc vanadate nano and bulk structures were compared by degradation of phenol red aqueous solution.

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

Stacking fault energies of face-centered cubic concentrated solid solution alloys

DOE PAGES

Zhao, Shijun; Stocks, G. Malcolm; Zhang, Yanwen

2017-06-22

We report the stacking fault energy (SFE) for a series of face-centered cubic (fcc) equiatomic concentrated solid solution alloys (CSAs) derived as subsystems from the NiCoFeCrMn and NiCoFeCrPd high entropy alloys based on ab initio calculations. At low temperatures, these CSAs display very low even negative SFEs, indicating that hexagonal close-pack ( hcp) is more energy favorable than fcc structure. The temperature dependence of SFE for some CSAs is studied. With increasing temperature, a hcp-to- fcc transition is revealed for those CSAs with negative SFEs, which can be attributed to the role of intrinsic vibrational entropy. The analysis of themore » vibrational modes suggests that the vibrational entropy arises from the high frequency states in the hcp structure that originate from local vibrational mode. Furthermore, our results underscore the importance of vibrational entropy in determining the temperature dependence of SFE for CSAs.« less

Atomistic simulation of the influence of Cr on the mobility of the edge dislocation in Fe(Cr) alloys

NASA Astrophysics Data System (ADS)

Hafez Haghighat, S. M.; Terentyev, D.; Schäublin, R.

2011-10-01

In this work Fe-Cr compounds, as model alloys for the ferritic base steels that are considered as main candidates for the structural materials of the future fusion reactors, are studied using molecular dynamics simulations. The Cr or so-called α' precipitates, which are obstacles to dislocations, affect mechanical properties, leading to hardening and loss of ductility. The flow stress to move an edge dislocation in a Cr solid solution in pure Fe is studied as a function of Cr content. The strength of a nanometric Cr precipitate as obstacle to an edge dislocation in pure Fe is investigated as a function of its Cr content. Results show that with increasing Cr content the precipitate obstacle strength increases, with a strong sensitivity to the local atomic order. Temperature induces a monotonic decrease of the flow stress of the Cr solid solution and of the Cr precipitate obstacle strength.

Stacking fault energies of face-centered cubic concentrated solid solution alloys

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

Zhao, Shijun; Stocks, G. Malcolm; Zhang, Yanwen

We report the stacking fault energy (SFE) for a series of face-centered cubic (fcc) equiatomic concentrated solid solution alloys (CSAs) derived as subsystems from the NiCoFeCrMn and NiCoFeCrPd high entropy alloys based on ab initio calculations. At low temperatures, these CSAs display very low even negative SFEs, indicating that hexagonal close-pack ( hcp) is more energy favorable than fcc structure. The temperature dependence of SFE for some CSAs is studied. With increasing temperature, a hcp-to- fcc transition is revealed for those CSAs with negative SFEs, which can be attributed to the role of intrinsic vibrational entropy. The analysis of themore » vibrational modes suggests that the vibrational entropy arises from the high frequency states in the hcp structure that originate from local vibrational mode. Furthermore, our results underscore the importance of vibrational entropy in determining the temperature dependence of SFE for CSAs.« less

High-Temperature Thermoelectric Properties of (1 - x) SrTiO3 - ( x) La1/3NbO3 Ceramic Solid Solution

NASA Astrophysics Data System (ADS)

Srivastava, Deepanshu; Azough, F.; Molinari, M.; Parker, S. C.; Freer, R.

2015-06-01

Ceramics based on SrTiO3 are of growing interest as thermoelectric materials because of their high-temperature stability and non-toxicity. Substitution of La and Nb into the perovskite structure provides opportunities to control both the microstructure and properties. Ceramic solid solutions of (1 - x) SrTiO3 - ( x) La1/3NbO3 were prepared by the mixed oxide route, using compositional steps of x = 0.1. Pressed pellets were sintered at temperatures of 1573 K to 1723 K in air. Addition of aliovalent ions (La3+, Nb5+) on the A/B sites (Sr2+, Ti4+) led to A-Site cation deficiency in the stoichiometric compositions and other defect structures which increased carrier concentration. A maximum ZT of 0.004 was obtained for the x = 0.2 stoichiometric sample, although much higher ZT values are possible by sample reduction.

Characterization of pH-fractionated humic acids with respect to their dissociation behaviour.

PubMed

Klučáková, Martina

2016-04-01

Humic acids were divided into several fractions using buffer solutions as extraction agents with different pH values. Two methods of fractionation were used. The first one was subsequent dissolution of bulk humic acids in buffers adjusted to different pH. The second one was sequential dissolution in buffers with increasing pH values. Experimental data were compared with hypothesis of partial solubility of humic acids in aqueous solutions. Behaviour of humic fractions obtained by sequential dissolution, original bulk sample and residual fractions obtained by subsequent dissolution at pH 10 and 12 agrees with the hypothesis. Results demonstrated that regardless the common mechanism, solubility and dissociation degree of various humic fractions may be very different and can be estimated using parameters of the model based on the proposed mechanism. Presented results suggest that dissolving of solid humic acids in water environment is more complex than conventional solubility behaviour of sparingly soluble solids.

Superior lithium adsorption and required magnetic separation behavior of iron-doped lithium ion-sieves

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

Wang, Shulei; Zheng, Shili; Wang, Zheming

The recent research on adsorption-based lithium recovery from lithium-containing solutions has been centred on adsorption capacity and separation of lithium ion-sieves powder from solutions. Herein, an effective iron-doped lithium titanium oxide (Fe-doped Li 2TiO 3) was synthesized by Fe-doping via solid state reactions followed by acid treatment to form iron-doped lithium ion-sieves (Fe/Ti-x(H)). The resulting solid powder displays both superior adsorption capacity of lithium and high separation efficiency of the adsorbent from the solutions. SEM imaging and BET surface area measurement results showed that at Fe doping levels x ≤ 0.15, Fe-doping led to grain shrinkage as compared to Limore » 2TiO 3 and at the same time the BET surface area increased. The Fe/Ti-0.15(H) exhibited saturated magnetization values of 13.76 emu g -1, allowing effective separation of the material from solid suspensions through the use of a magnet. Consecutive magnetic separation results suggested that the Fe/Ti-0.15(H) powders could be applied at large-scale and continuously removed from LiOH solutions with separation efficiency of 96% or better. Lithium adsorption studies indicated that the equilibrium adsorption capacity of Fe/Ti-0.15(H) in LiOH solutions (1.8 g L -1 Li, pH 12) reached 53.3 mg g -1 within 24 h, which was higher than that of pristine Li 2TiO 3 (50.5 mg g-1) without Fe doping. Competitive adsorption and regeneration results indicated that the Fe/Ti-0.15(H) possessed a high selectivity for Li with facile regeneration. Therefore, it could be expected that the iron-doped lithium ion-sieves have practical applicability potential for large scale lithium extraction and recovery from lithium-bearing solutions.« less

Superior lithium adsorption and required magnetic separation behavior of iron-doped lithium ion-sieves

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

Wang, Shulei; Zheng, Shili; Wang, Zheming

The recent research on adsorption-based lithium recovery from lithium-containing solutions has been centred on adsorption capacity and separation of lithium ion-sieves powder from solutions. Herein, an effective iron-doped lithium titanium oxide (Fe-doped Li2TiO3) was synthesized by Fe-doping via solid state reactions followed by acid treatment to form iron-doped lithium ion-sieves (Fe/Ti-x(H)). The resulting solid powder displays both superior adsorption capacity of lithium and high separation efficiency of the adsorbent from the solutions. SEM imaging and BET surface area measurement results showed that at Fe doping levels x0.15, Fe-doping led to grain shrinkage as compared to Li2TiO3 and at the samemore » time the BET surface area increased. The Fe/Ti-0.15(H) exhibited saturated magnetization values of 13.76 emu g-1, allowing effective separation of the material from solid suspensions through the use of a magnet. Consecutive magnetic separation results suggested that the Fe/Ti-0.15(H) powders could be applied at large-scale and continuously removed from LiOH solutions with separation efficiency of 96% or better. Lithium adsorption studies indicated that the equilibrium adsorption capacity of Fe/Ti-0.15(H) in LiOH 2 solutions (1.8 g L-1 Li, pH 12) reached 53.3 mg g-1 within 24 h, which was higher than that of pristine Li2TiO3 (50.5 mg g-1) without Fe doping. Competitive adsorption and regeneration results indicated that the Fe/Ti-0.15(H) possessed a high selectivity for Li with facile regeneration. Therefore, it could be expected that the iron-doped lithium ion-sieves have practical applicability potential for large scale lithium extraction and recovery from lithium-bearing solutions.« less

Superior lithium adsorption and required magnetic separation behavior of iron-doped lithium ion-sieves

DOE PAGES

Wang, Shulei; Zheng, Shili; Wang, Zheming; ...

2018-09-09

The recent research on adsorption-based lithium recovery from lithium-containing solutions has been centred on adsorption capacity and separation of lithium ion-sieves powder from solutions. Herein, an effective iron-doped lithium titanium oxide (Fe-doped Li 2TiO 3) was synthesized by Fe-doping via solid state reactions followed by acid treatment to form iron-doped lithium ion-sieves (Fe/Ti-x(H)). The resulting solid powder displays both superior adsorption capacity of lithium and high separation efficiency of the adsorbent from the solutions. SEM imaging and BET surface area measurement results showed that at Fe doping levels x ≤ 0.15, Fe-doping led to grain shrinkage as compared to Limore » 2TiO 3 and at the same time the BET surface area increased. The Fe/Ti-0.15(H) exhibited saturated magnetization values of 13.76 emu g -1, allowing effective separation of the material from solid suspensions through the use of a magnet. Consecutive magnetic separation results suggested that the Fe/Ti-0.15(H) powders could be applied at large-scale and continuously removed from LiOH solutions with separation efficiency of 96% or better. Lithium adsorption studies indicated that the equilibrium adsorption capacity of Fe/Ti-0.15(H) in LiOH solutions (1.8 g L -1 Li, pH 12) reached 53.3 mg g -1 within 24 h, which was higher than that of pristine Li 2TiO 3 (50.5 mg g-1) without Fe doping. Competitive adsorption and regeneration results indicated that the Fe/Ti-0.15(H) possessed a high selectivity for Li with facile regeneration. Therefore, it could be expected that the iron-doped lithium ion-sieves have practical applicability potential for large scale lithium extraction and recovery from lithium-bearing solutions.« less

MBSSAS: A code for the computation of margules parameters and equilibrium relations in binary solid-solution aqueous-solution systems

USGS Publications Warehouse

Glynn, P.D.

1991-01-01

The computer code MBSSAS uses two-parameter Margules-type excess-free-energy of mixing equations to calculate thermodynamic equilibrium, pure-phase saturation, and stoichiometric saturation states in binary solid-solution aqueous-solution (SSAS) systems. Lippmann phase diagrams, Roozeboom diagrams, and distribution-coefficient diagrams can be constructed from the output data files, and also can be displayed by MBSSAS (on IBM-PC compatible computers). MBSSAS also will calculate accessory information, such as the location of miscibility gaps, spinodal gaps, critical-mixing points, alyotropic extrema, Henry's law solid-phase activity coefficients, and limiting distribution coefficients. Alternatively, MBSSAS can use such information (instead of the Margules, Guggenheim, or Thompson and Waldbaum excess-free-energy parameters) to calculate the appropriate excess-free-energy of mixing equation for any given SSAS system. ?? 1991.

High temperature resistant cermet and ceramic compositions. [for thermal resistant insulators and refractory coatings

NASA Technical Reports Server (NTRS)

Phillips, W. M. (Inventor)

1978-01-01

High temperature oxidation resistance, high hardness and high abrasion and wear resistance are properties of cermet compositions particularly to provide high temperature resistant refractory coatings on metal substrates, for use as electrical insulation seals for thermionic converters. The compositions comprise a sintered body of particles of a high temperature resistant metal or metal alloy, preferably molybdenum or tungsten particles, dispersed in and bonded to a solid solution formed of aluminum oxide and silicon nitride, and particularly a ternary solid solution formed of a mixture of aluminum oxide, silicon nitride and aluminum nitride. Ceramic compositions comprising a sintered solid solution of aluminum oxide, silicon nitride and aluminum nitride are also described.

Influence of Dy in solid solution on the degradation behavior of binary Mg-Dy alloys in cell culture medium.

PubMed

Yang, Lei; Ma, Liangong; Huang, Yuanding; Feyerabend, Frank; Blawert, Carsten; Höche, Daniel; Willumeit-Römer, Regine; Zhang, Erlin; Kainer, Karl Ulrich; Hort, Norbert

2017-06-01

Rare earth element Dy is one of the promising alloying elements for magnesium alloy as biodegradable implants. To understand the effect of Dy in solid solution on the degradation of Mg-Dy alloys in simulated physiological conditions, the present work studied the microstructure and degradation behavior of Mg-Dy alloys in cell culture medium. It is found the corrosion resistance enhances with the increase of Dy content in solid solution in Mg. This can be attributed to the formation of a relatively more corrosion resistant Dy-enriched film which decreases the anodic dissolution of Mg. Copyright © 2017 Elsevier B.V. All rights reserved.

Chemistry [Sahuarita High School Career Curriculum Project].

ERIC Educational Resources Information Center

Lane, Robert

This course entitled "Chemistry" is one of a series of instructional guides prepared by teachers for the Sahuarita High School (Arizona) Career Curriculum Project. It consists of three packages, the first dealing with solids, liquids and solutions, the second with acids, bases and anions, and the third with cation analysis. These packages are…

Multidimensional Analysis of Copper Ore Flotation in Terms of Applied Hydrophobizing Agents

NASA Astrophysics Data System (ADS)

Pięta, Paulina; Niedoba, Tomasz; Surowiak, Agnieszka

2018-03-01

Flotation is a method of enrichment used to distribute particles, which differ in their surface properties. Hydrophobic solids intrinsically create contact at the solid-liquid-gas interface. However, not all minerals, including copper minerals, can be characterized by this crucial ability. In that case it is necessary to use the collector reagents which guarantees a high efficiency of the enrichment process. The main aim of the paper was to examine the impact of selected collector types and dosages on the results of Polish sandstone copper ore flotation and to find optimal parameter values for products that meet quality and quantity requirements. The laboratory tests were carried out with an application of two types of collectors (Hostaflot, sodium ethyl xanthate aqueous solution) in dosages 100 and 150 g/Mg. Data analysis was based on the use of the taxonomy methods in order to select optimal conditions of collector dosage and type. Based on the indexes, it was found that the best enrichment effects were obtained with a sodium ethyl xanthate aqueous solution 150 g/Mg.

Formation of (FexMn(2-x))O3 solid solution and high sulfur capacity properties of Mn-based/M41 sorbents for hot coal gas desulfurization.

PubMed

Zhang, Y; Liu, B S; Zhang, F M; Zhang, Z F

2013-03-15

Several MCM-41 materials were synthesized at different conditions by hydrothermal procedure using cheap and easily available industrial water glass as silica source. Fe doped manganese-based oxide/MCM-41 sorbents were prepared by a sol-gel method. The effects of loadings of metal oxide, Fe/Mn molar ratios over MCM-41 and reaction temperature on the performance of sorbent for hot coal gas desulfurization were investigated. Various techniques such as BET, XRD, XPS, LRS and HRTEM were used to characterize the sorbents. The result indicated Fe(3+) ions could occupy a position of Mn(3+) in cubic lattice of Mn2O3 and the (FexMn2-x)O3 solid solution is mainly active phase of sorbent. Moreover, the result of nine successive sulfurization-regeneration cycles of sorbent showed high sulfur adsorption capacity and endurable stability of FeMn4Ox/MCM-41 for H2S removal. Copyright © 2013 Elsevier B.V. All rights reserved.

Lanthanide Contraction as a Design Factor for High-Performance Half-Heusler Thermoelectric Materials.

PubMed

Liu, Yintu; Fu, Chenguang; Xia, Kaiyang; Yu, Junjie; Zhao, Xinbing; Pan, Hongge; Felser, Claudia; Zhu, Tiejun

2018-06-25

Forming solid solutions, as an effective strategy to improve thermoelectric performance, has a dilemma that alloy scattering will reduce both the thermal conductivity and carrier mobility. Here, an intuitive way is proposed to decouple the opposite effects, that is, using lanthanide contraction as a design factor to select alloying atoms with large mass fluctuation but small radius difference from the host atoms. Typical half-Heusler alloys, n-type (Zr,Hf)NiSn and p-type (Nb,Ta)FeSb solid solutions, are taken as paradigms to attest the validity of this design strategy, which exhibit greatly suppressed lattice thermal conductivity and maintained carrier mobility. Furthermore, by considering lanthanide contraction, n-type (Zr,Hf)CoSb-based alloys with high zT of ≈1.0 are developed. These results highlight the significance of lanthanide contraction as a design factor in enhancing the thermoelectric performance and reveal the practical potential of (Zr,Hf)CoSb-based half-Heusler compounds due to the matched n-type and p-type thermoelectric performance. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Defect energetics of concentrated solid-solution alloys from ab initio calculations: Ni 0.5Co 0.5, Ni 0.5Fe 0.5, Ni 0.8Fe 0.2 and Ni 0.8Cr 0.2

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

Zhao, Shijun; Stocks, George Malcolm; Zhang, Yanwen

2016-08-03

It has been shown that concentrated solid solution alloys possess unusual electronic, magnetic, transport, mechanical and radiation-resistant properties that are directly related to underlying chemical complexity. Because every atom experiences a different local atomic environment, the formation and migration energies of vacancies and interstitials in these alloys exhibit a distribution, rather than a single value as in a pure metal or dilute alloy. In this study, using ab initio calculations based on density functional theory and special quasirandom structure, we have characterized the distribution of defect formation energy and migration barrier in four Ni-based solid-solution alloys: Ni 0.5Co 0.5, Nimore » 0.5Fe 0.5, Ni 0.8Fe 0.2 and Ni 0.8Cr 0.2. As defect formation energies in finite-size models depend sensitively on the elemental chemical potential, we have developed a computationally efficient method for determining it which takes into account the global composition and the local short-range order. In addition we have compared the results of our ab initio calculations to those obtained from available embedded atom method (EAM) potentials. Our results indicate that the defect formation and migration energies are closely related to the specific atomic size in the structure, which further determines the elemental diffusion properties. In conclusion, different EAM potentials yield different features of defect energetics in concentrated alloys, pointing to the need for additional potential development efforts in order to allow spatial and temporal scale-up of defect and simulations, beyond those accessible to ab initio methods.« less

Defect energetics of concentrated solid-solution alloys from ab initio calculations: Ni0.5Co0.5, Ni0.5Fe0.5, Ni0.8Fe0.2 and Ni0.8Cr0.2.

PubMed

Zhao, Shijun; Stocks, G Malcolm; Zhang, Yanwen

2016-09-14

It has been shown that concentrated solid solution alloys possess unusual electronic, magnetic, transport, mechanical and radiation-resistant properties that are directly related to underlying chemical complexity. Because every atom experiences a different local atomic environment, the formation and migration energies of vacancies and interstitials in these alloys exhibit a distribution, rather than a single value as in a pure metal or dilute alloy. Using ab initio calculations based on density functional theory and special quasirandom structures, we have characterized the distribution of defect formation energy and migration barrier in four Ni-based solid-solution alloys: Ni0.5Co0.5, Ni0.5Fe0.5, Ni0.8Fe0.2, and Ni0.8Cr0.2. As defect formation energies in finite-size models depend sensitively on the elemental chemical potential, we have developed a computationally efficient method for determining it which takes into account the global composition and the local short-range order. In addition we have compared the results of our ab initio calculations to those obtained from available embedded atom method (EAM) potentials. Our results indicate that the defect formation and migration energies are closely related to the specific atoms in the structure, which further determines the elemental diffusion properties. Different EAM potentials yield different features of defect energetics in concentrated alloys, pointing to the need for additional potential development efforts in order to allow spatial and temporal scale-up of defect and simulations, beyond those accessible to ab initio methods.

Carbon deposition thresholds on nickel-based solid oxide fuel cell anodes I. Fuel utilization

NASA Astrophysics Data System (ADS)

Kuhn, J.; Kesler, O.

2015-03-01

In the first of a two part publication, the effect of fuel utilization (Uf) on carbon deposition rates in solid oxide fuel cell nickel-based anodes was studied. Representative 5-component CH4 reformate compositions (CH4, H2, CO, H2O, & CO2) were selected graphically by plotting the solutions to a system of mass-balance constraint equations. The centroid of the solution space was chosen to represent a typical anode gas mixture for each nominal Uf value. Selected 5-component and 3-component gas mixtures were then delivered to anode-supported cells for 10 h, followed by determination of the resulting deposited carbon mass. The empirical carbon deposition thresholds were affected by atomic carbon (C), hydrogen (H), and oxygen (O) fractions of the delivered gas mixtures and temperature. It was also found that CH4-rich gas mixtures caused irreversible damage, whereas atomically equivalent CO-rich compositions did not. The coking threshold predicted by thermodynamic equilibrium calculations employing graphite for the solid carbon phase agreed well with empirical thresholds at 700 °C (Uf ≈ 32%); however, at 600 °C, poor agreement was observed with the empirical threshold of ∼36%. Finally, cell operating temperatures correlated well with the difference in enthalpy between the supplied anode gas mixtures and their resulting thermodynamic equilibrium gas mixtures.

Microstructure investigation on micropore formation in microporous silica materials prepared via a catalytic sol-gel process by small angle X-ray scattering.

PubMed

Shimizu, Wataru; Hokka, Junsuke; Sato, Takaaki; Usami, Hisanao; Murakami, Yasushi

2011-08-04

The so-called sol-gel technique has been shown to be a template-free, efficient way to create functional porous silica materials having uniform micropores. This appears to be closely linked with a postulation that the formation of weakly branched polymer-like aggregates in a precursor solution is a key to the uniform micropore generation. However, how such a polymer-like structure can precisely be controlled, and further, how the generated low-fractal dimension solution structure is imprinted on the solid silica materials still remain elusive. Here we present fabrication of microporous silica from tetramethyl orthosilicate (TMOS) using a recently developed catalytic sol-gel process based on a nonionic hydroxyacetone (HA) catalyst. Small angle X-ray scattering (SAXS), nitrogen adsorption porosimetry, and transmission electron microscope (TEM) allowed us to observe the whole structural evolution, ranging from polymer-like aggregates in the precursor solution to agglomeration with heat treatment and microporous morphology of silica powders after drying and hydrolysis. Using the HA catalyst with short chain monohydric alcohols (methanol or ethanol) in the precursor solution, polymer-like aggregates having microscopic correlation length (or mesh-size) < 2 nm and low fractal dimensions ∼2, which is identical to that of an ideal coil polymer, can selectively be synthesized, yielding the uniform micropores with diameters <2 nm in the solid materials. In contrast, the absence of HA or substitution of 1-propanol led to considerably different scattering behavior reflecting the particle-like aggregate formation in the precursor solution, which resulted in the formation of mesopores (diameter >2 nm) in the solid product due to apertures between the particle-like aggregates. The data demonstrate that the extremely fine porous silica architecture comes essentially from a gaussian polymer-like nature of the silica aggregates in the precursor having the microscopic mesh-size and their successful imprint on the solid product. The result offers a general but significantly efficient route to creating precisely designed fine porous silica materials under mild condition that serve as low refractive index and efficient thermal insulation materials in their practical applications.

Temperature Dependence of the Mechanical Properties of Equiatomic Solid Solution Alloys with FCC Crystal Structures

DOE PAGES

Wu, Zhenggang; Bei, Hongbin; Pharr, George M.; ...

2014-10-03

We found that compared to decades-old theories of strengthening in dilute solid solutions, the mechanical behavior of concentrated solid solutions is relatively poorly understood. A special subset of these materials includes alloys in which the constituent elements are present in equal atomic proportions, including the high-entropy alloys of recent interest. A unique characteristic of equiatomic alloys is the absence of “solvent” and “solute” atoms, resulting in a breakdown of the textbook picture of dislocations moving through a solvent lattice and encountering discrete solute obstacles. Likewise, to clarify the mechanical behavior of this interesting new class of materials, we investigate heremore » a family of equiatomic binary, ternary and quaternary alloys based on the elements Fe, Ni, Co, Cr and Mn that were previously shown to be single-phase face-centered cubic (fcc) solid solutions. The alloys were arc-melted, drop-cast, homogenized, cold-rolled and recrystallized to produce equiaxed microstructures with comparable grain sizes. Tensile tests were performed at an engineering strain rate of 10 -3 s -1 at temperatures in the range 77–673 K. Unalloyed fcc Ni was processed similarly and tested for comparison. The flow stresses depend to varying degrees on temperature, with some (e.g. NiCoCr, NiCoCrMn and FeNiCoCr) exhibiting yield and ultimate strengths that increase strongly with decreasing temperature, while others (e.g. NiCo and Ni) exhibit very weak temperature dependencies. Moreover, to better understand this behavior, the temperature dependencies of the yield strength and strain hardening were analyzed separately. Lattice friction appears to be the predominant component of the temperature-dependent yield stress, possibly because the Peierls barrier height decreases with increasing temperature due to a thermally induced increase of dislocation width. In the early stages of plastic flow (5–13% strain, depending on material), the temperature dependence of strain hardening is due mainly to the temperature dependence of the shear modulus. In all the equiatomic alloys, ductility and strength increase with decreasing temperature down to 77 K. Keywords« less

GEANT4 simulations of a novel 3He-free thermalization neutron detector

NASA Astrophysics Data System (ADS)

Mazzone, A.; Finocchiaro, P.; Lo Meo, S.; Colonna, N.

2018-05-01

A novel concept for 3He-free thermalization detector is here investigated by means of GEANT4 simulations. The detector is based on strips of solid-state detectors with 6Li deposit for neutron conversion. Various geometrical configurations have been investigated in order to find the optimal solution, in terms of value and energy dependence of the efficiency for neutron energies up to 10 MeV. The expected performance of the new detector are compared with those of an optimized thermalization detector based on standard 3He tubes. Although an 3He-based detector is superior in terms of performance and simplicity, the proposed solution may become more appealing in terms of costs in case of shortage of 3He supply.

Exact finite elements for conduction and convection

NASA Technical Reports Server (NTRS)

Thornton, E. A.; Dechaumphai, P.; Tamma, K. K.

1981-01-01

An approach for developing exact one dimensional conduction-convection finite elements is presented. Exact interpolation functions are derived based on solutions to the governing differential equations by employing a nodeless parameter. Exact interpolation functions are presented for combined heat transfer in several solids of different shapes, and for combined heat transfer in a flow passage. Numerical results demonstrate that exact one dimensional elements offer advantages over elements based on approximate interpolation functions.

Confirming the 3D Solution Structure of a Short Double-Stranded DNA Sequence Using NMR Spectroscopy

ERIC Educational Resources Information Center

Ruhayel, Rasha A.; Berners-Price, Susan J.

2010-01-01

2D [superscript 1]H NOESY NMR spectroscopy is routinely used to give information on the closeness of hydrogen atoms through space. This work is based on a 2D [superscript 1]H NOESY NMR spectrum of a 12 base-pair DNA duplex. This 6-h laboratory workshop aims to provide advanced-level chemistry students with a basic, yet solid, understanding of how…

Why the developing world is the perfect market place for solid state lighting

NASA Astrophysics Data System (ADS)

Schultz, Christoph; Platonova, Inna; Doluweera, Ganesh; Irvine-Halliday, Dave

2008-08-01

Much has been written about the daily challenge for survival faced by countless millions of developing world families and the overdeveloped world has offered a number of solutions by which those at the base of the economic pyramid (BOP) can help themselves. Light Up The World (LUTW), the global leader in bringing Renewable Energy (RE) based Solid State Lighting (SSL) to the developing world, offers yet another solution, and one that comes with a very high probability of success. In this paper we discuss: the critical role played by micro credit (banking for the poor); a typical example of a developing world community and their lighting needs and expenditures; how SSL can contribute positively to all eight of the Millennium Development Goals; the micro and macroeconomics of SSL at the BOP, its numerous societal benefits and its potential perverse outcomes; and thought there will always be a role for the donation based model, it is only through the market model that safe, healthy and affordable SSL will reach the majority of the BOP, such are the staggering numbers involved. LUTW's fundamental goal, through the facilitation of RE based SSL, is to improve the quality of life of those, who through no fault of their own, find themselves trapped in a cycle of poverty.

Dynamic nuclear polarization methods in solids and solutions to explore membrane proteins and membrane systems.

PubMed

Cheng, Chi-Yuan; Han, Songi

2013-01-01

Membrane proteins regulate vital cellular processes, including signaling, ion transport, and vesicular trafficking. Obtaining experimental access to their structures, conformational fluctuations, orientations, locations, and hydration in membrane environments, as well as the lipid membrane properties, is critical to understanding their functions. Dynamic nuclear polarization (DNP) of frozen solids can dramatically boost the sensitivity of current solid-state nuclear magnetic resonance tools to enhance access to membrane protein structures in native membrane environments. Overhauser DNP in the solution state can map out the local and site-specific hydration dynamics landscape of membrane proteins and lipid membranes, critically complementing the structural and dynamics information obtained by electron paramagnetic resonance spectroscopy. Here, we provide an overview of how DNP methods in solids and solutions can significantly increase our understanding of membrane protein structures, dynamics, functions, and hydration in complex biological membrane environments.

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.

Cooking with Fire: The Mutagenicity- and PAH-Emission Factors of Solid-Fuel Cookstoves

EPA Science Inventory

Emissions from solid fuels used for cooking cause ~4 million premature deaths per year. Advanced solid-fuel cookstoves are a potential solution, but they should be assessed by appropriate performance indicators, including biological effects. We evaluated two categories of solid...

Nickel Nanocatalyst Ex-Solution from Ceria-Nickel Oxide Solid Solution for Low Temperature CO Oxidation.

PubMed

Singhania, Amit; Gupta, Shipra Mital

2018-07-01

In this work, in situ growth of Ni nanocatalysts to attach onto the ceria (CeO2) surface through direct Ni ex-solution from the NiO-CeO2 solid solution in a reducing atmosphere at high temperatures with an aim to improve the catalytic activity, and stability for low temperature carbon monoxide (CO) oxidation reaction have been reported. The NiO-CeO2 solid solutions were prepared by solution combustion method, and the results of XRD and RAMAN showed that doping of Ni increases the oxygen vacancies due to charge compensation. Ni is clearly visible in XRD and TEM of Ni ex-solved sample (R-UCe5Ni10) after reduction of NiO-CeO2 (UCe5Ni10) sample by 5% H2/Ar reduction at 1000 °C. TEM analysis revealed a size of 9.2 nm of Ni nanoparticle that is ex-solved on the surface CeO2. This ex-solved sample showed very high catalytic activity (T50 ~ 110 °C), and stability (100 h) for CO oxidation reaction as compared to prepared solid solution samples. This is due to the highly active metallic nano-phase which is ex-solved on the surface of CeO2 and strongly adherent to the support. The apparent activation energy Ni ex-solved sample is found out to be 48.4 kJ mol-1. Thus, the above Ni ex-solved sample shows a practical applicability for the CO reaction.

Hydration mechanisms of two polymorphs of synthetic ye'elimite

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

Cuesta, A.; Álvarez-Pinazo, G.; Sanfélix, S.G.

2014-09-15

Ye'elimite is the main phase in calcium sulfoaluminate cements and also a key phase in sulfobelite cements. However, its hydration mechanism is not well understood. Here we reported new data on the hydration behavior of ye'elimite using synchrotron and laboratory powder diffraction coupled to the Rietveld methodology. Both internal and external standard methodologies have been used to determine the overall amorphous contents. We have addressed the standard variables: water-to-ye'elimite ratio and additional sulfate sources of different solubilities. Moreover, we report a deep study of the role of the polymorphism of pure ye'elimites. The hydration behavior of orthorhombic stoichiometric and pseudo-cubicmore » solid-solution ye'elimites is discussed. In the absence of additional sulfate sources, stoichiometric-ye'elimite reacts slower than solid-solution-ye'elimite, and AFm-type phases are the main hydrated crystalline phases, as expected. Moreover, solid-solution-ye'elimite produces higher amounts of ettringite than stoichiometric-ye'elimite. However, in the presence of additional sulfates, stoichiometric-ye'elimite reacts faster than solid-solution-ye'elimite.« less

Solid Solution Photocatalyst with Spontaneous Polarization Exhibiting Low Recombination Toward Efficient CO2 Photoreduction.

PubMed

Zhou, Peng; Wang, Xin; Yan, Shicheng; Zou, Zhigang

2016-08-23

Decreasing the recombination of photogenerated carriers is a major challenge for efficiently converting solar energy into chemical energy by photocatalysis. Here, we have demonstrated that growth of a polar GaN:ZnO solid solution single crystal along its polarization axis is beneficial to efficient separation of photogenerated carriers, owing to the periodic potential barriers and wells generated from the periodically positive and negative atom arrangements in crystal structure. Local charge imbalance caused by replacing Ga(3+) with Zn(2+) leads to a polarization vector in the {0 0 0 1} planes of GaN:ZnO solid solution, thus forming a 1 D electron transport path along [2 1‾  1‾  0] in the {0 0 0 1} planes of GaN:ZnO solid solution to decrease recombination. Shorting the hole-transport distance by synthesizing porous nanoplates can further decrease recombination under the polarization field and improve the performance of polar photocatalyst in photoreduction of CO2 into CH4 . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Crystal-chemistry insight into the photocatalytic activity of BiOCl x Br1- x nanoplate solid solutions

NASA Astrophysics Data System (ADS)

Xu, Huan-Yan; Han, Xu; Tan, Qu; Wu, Ke-Jia; Qi, Shu-Yan

2017-06-01

In this study, a facile alcoholysis method was developed to synthesize BiOCl x Br1- x nanoplates at room temperature and atmospheric pressure. In this route, strong acid or alkaline environment was absolutely avoided to realize the high exposure of {001} crystal facets. The regular changes in XRD peaks and cell parameters as a function of the Br content strongly declared that the obtained BiOCl x Br1- x products belonged to a group of solid solutions. The 2D nanosheets with in-plane wrinkles were clearly observed in TEM images. Interestingly, as the Br content increased, band gaps of BiOCl x Br1- x solid solutions gradually decreased. The photocatalytic degradation of RhB under simulated sunlight irradiation indicated that BiOCl0.5Br0.5 had the best photocatalytic activity. From the viewpoint of crystal chemistry, the photocatalytic activity of BiOCl x Br1- x solid solutions was closely related with the exposure amount of {001} facets, interlayer spacing of (001) plane and energy-level position of valence band.

Mechanochemical synthesis and physico-chemical investigations of new materials for gas sensors

NASA Astrophysics Data System (ADS)

Shubenkova, E. G.

2018-01-01

Solid solutions of the InSb-ZnTe semiconductor system containing up to 20 mol.% of ZnTe were synthesized for the first time. The role of mechanochemical treatment in the process of obtaining solid solutions of this system is shown. Solid solutions in the InSb-ZnTe system have been identified by Raman spectroscopy, and the optical properties of its components have been studied. On the basis of an analysis of the anti-stokes spectral radiation distribution the solid solutions formation was identified both on the dependence of the spectral distribution maximum’s shift on the composition of the InSb1-x-ZnTex system, and by estimating the radiation intensity of the initial binary semiconductors at frequencies corresponding to the LO- and TO- vibrations of the binary compounds crystal lattice. The values of the band gap for InSb, (InSb)0.95(ZnTe)0.05 and (InSb)0.9(ZnTe)0.1 were calculated, their values were 0.22 eV, 0.30 eV and 0.38 eV, respectively.

Structural modifications of polymethacrylates: impact on thermal behavior and release characteristics of glassy solid solutions.

PubMed

Claeys, Bart; De Coen, Ruben; De Geest, Bruno G; de la Rosa, Victor R; Hoogenboom, Richard; Carleer, Robert; Adriaensens, Peter; Remon, Jean Paul; Vervaet, Chris

2013-11-01

Polymethacrylates such as Eudragit® polymers are well established as drug delivery matrix. Here, we synthesize several Eudragit E PO (n-butyl-, dimethylaminoethyl-, methyl-methacrylate-terpolymer) analogues via free radical polymerization. These polymers are processed via hot melt extrusion, followed by injection molding and evaluated as carriers to produce immediate release solid solution tablets. Three chemical modifications increased the glass transition temperature of the polymer: (a) substitution of n-butyl by t-butyl groups, (b) reduction of the dimethylaminoethyl methacrylate (DMAEMA) content, and (c) incorporation of a bulky isobornyl repeating unit. These structural modifications revealed the possibility to increase the mechanical stability of the tablets via altering the polymer Tg without influencing the drug release characteristics and glassy solid solution forming properties. The presence of DMAEMA units proved to be crucial with respect to API/polymer interaction (essential in creating glassy solid solutions) and drug release characteristics. Moreover, these chemical modifications accentuate the need for a more rational design of (methacrylate) polymer matrix excipients for drug formulation via hot melt extrusion and injection molding. Copyright © 2013 Elsevier B.V. All rights reserved.

Influence of anionic substitution on the electrolyte electroreflectance study of band edge transitions in single crystal Cu2ZnSn(SxSe1-x)4 solid solutions

NASA Astrophysics Data System (ADS)

Levcenco, S.; Dumcenco, D.; Wang, Y. P.; Huang, Y. S.; Ho, C. H.; Arushanov, E.; Tezlevan, V.; Tiong, K. K.

2012-06-01

Single crystals of Cu2ZnSn(SxSe1-x)4 (CZTSSe) solid solutions were grown by chemical vapor transport technique using iodine trichloride as a transport agent. As confirmed by X-ray investigations, the as-grown CZTSSe solid solutions are single phase and crystallized in kesterite structure. The lattice parameters of CZTSSe were determined and the S contents of the obtained crystals were estimated by Vegard's law. The composition dependent band gaps of CZTSSe solid solutions were studied by electrolyte electroreflectance (EER) measurements at room temperature. From a detailed lineshape fit of the EER spectra, the band gaps of CZTSSe were determined accurately and were found to decrease almost linearly with the increase of Se content, which agreed well with the recent theoretical first-principle calculations by S. Chen, A. Walsh, J.H. Yang, X.G. Gong, L. Sun, P. X. Yang, J.H. Chu, S.H. Wei, Phys. Rev. B 83 (2011) 125201 (5pp).

A high performance flexible all solid state supercapacitor based on the MnO2 sphere coated macro/mesoporous Ni/C electrode and ionic conducting electrolyte.

PubMed

Zhi, Jian; Reiser, Oliver; Wang, Youfu; Hu, Aiguo

2016-06-09

A high contact resistance between the active materials and the current collector, a low ionic conductivity of the gel electrolyte, and an impenetrable electrode structure are the three major barriers which greatly limit the capacitance of MnO2 in solid state supercapacitors. As a potential solution to these problems, in this work we report a novel electrode for solid state supercapacitors, based on a ternary system composed of hierarchical MnO2 spheres as the active material, macroporous Ni foam as gel penetrable skeletons and an ordered mesoporous carbon (OMC) membrane as the charge-transport accelerating layer. By employing butyl-3-methylimidazolium chloride (BMIMCl) modified gels as the ionic conducting electrolyte, the utilization efficiency of MnO2 on the specific capacitance was enhanced up to 88% of the theoretical value, delivering a volumetric capacitance of 81 F cm(-3), which is the highest value among MnO2 based solid state supercapacitors. Moreover, such a flexible device exhibits exceptional volumetric energy and power density (6.6 Wh L(-1) and 549 W L(-1), based on the whole device volume) combined with a small capacity loss of 8.5% after 6000 cycles under twisting. These encouraging findings unambiguously overcome the energy bottleneck of MnO2 in solid state supercapacitors, and open up a new application of macro/mesoporous materials in flexible devices.

[Formulation and special investigations of innovative intraoral solid dosage forms.

PubMed

Kristo, K; kATONA, B; Piukovics, P; Olah, I; Sipos, B; Sipos, S E; Sovany, T; Hodi, K; Ifi Regdon, G

During our work, we summarized the types of solid dosage forms which were in the focus of attention in the last years because of their innovative pharmaceutical technology solution and simple use. The biopharmaceutics of solid dosage forms for intraoral use and the advantages of the use of these dosages forms were presented in general. However, these dosage forms cannot always be prepared with conventional pharmaceutical processes, therefore the special pharmaceutical solutions which can be applied for their preparation were presented. In addition to testing the European Pharmacopoeia dosage forms, the special tests which can be applied for the characterization of innovative solid dosage forms were highlighted.

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.

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.

Possibility of adjusting the photoluminescence spectrum of Ca scheelites to the emission spectrum of incandescent lamps: [ nCaWO4-(1- n)CaMoO4]: Eu3+ solid solutions

NASA Astrophysics Data System (ADS)

Bakovets, V. V.; Zolotova, E. S.; Antonova, O. V.; Korol'kov, I. V.; Yushina, I. V.

2016-12-01

The specific features of the photoluminescence of [ nCaWO4-(1- n)CaMoO4]:Eu3+ solid solutions with the scheelite structure are examined using X-ray phase analysis and photoluminescence, Raman scattering, and diffuse reflectance spectroscopy. The studied features are associated with a change in the long- and short-range orders of the crystal lattice upon variations in the composition of solutions in the range n = 0-1.0 (with a pitch of 0.2) at a concentration of red photoluminescence activator Eu3+ of 2 mol %. The mechanism of the modification of photoluminescence of solid solutions upon variations in their composition has been discussed. Anomalies in the variations in parameters of the crystal lattice, its short-range order, and luminescence spectra have been observed in the transition from pure compounds CaMoO4:Eu3+ and CaWO4:Eu3+ to solutions; the concentration of Eu3+ ions in the centrosymmetric localization increases (decreases) in the transition from the molybdate (tungstate). It has been demonstrated that the spectral radiant emittance of solid solution [0.4CaWO4-0.6CaMoO4]:Eu3+ (2 mol %) is the closest to that of an incandescent lamp.

Synthesis and photocatalytic degradation study of methylene blue dye under visible light irradiation by Fe1-xBixVO4 solid solutions (0 ≤ x ≤ 1.0)

NASA Astrophysics Data System (ADS)

Bera, Ganesh; Reddy, V. R.; Mal, Priyanath; Das, Pradip; Turpu, G. R.

2018-05-01

The novel hetero-structures Fe1-xBixVO4 solid solutions (0 ≤ x ≤ 1.0) with the two dissimilar end member of FeVO4 - BiVO4, were successfully synthesized by the standard solid state reaction method. The structural and chemical properties of as prepared photo-catalyst samples were characterized by X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FT-IR) and UV-visible absorption spectroscopy techniques. It is confirmed from the results of XRD, Raman and FT-IR that FeVO4 and BiVO4 are in triclinic (space group P-1 (2)) and monoclinic (space group I2/b (15)) phases respectively. The Bi incorporation into Fe site of FeVO4 emerges as hetero-structures of both the end members of the solid solutions. In addition, the photocatalytic activity in the degradation of methylene blue (MB) dye under visible light irradiation was carried out through UV-visible spectroscopy measurement of photo-catalysts FeVO4, BiVO4 and mixed phases of both photo-catalyst. The results indicate that under visible light irradiation the photocatalytic activity of mixed phases were very effective and higher than the both single phases of the solid solutions. The composition x= 0.25 exhibits an excellent photocatalytic property for the degradation of MB solution under visible light irradiation rather than other.

Enhancement of dissolution rate through eutectic mixture and solid solution of posaconazole and benznidazole.

PubMed

Figueirêdo, Camila Bezerra Melo; Nadvorny, Daniela; de Medeiros Vieira, Amanda Carla Quintas; Soares Sobrinho, José Lamartine; Rolim Neto, Pedro José; Lee, Ping I; de La Roca Soares, Monica Felts

2017-06-15

Benznidazole (BNZ), the only commercialized antichagasic drug, and the antifungal compound posaconazole (PCZ) have shown synergistic action in the therapy of Chagas disease, however both active pharmaceutical ingredients (APIs) exhibit low aqueous solubility potentially limiting their bioavailability and therapeutic efficacy. In this paper, we report for the first time the formation of a eutectic mixture as well as an amorphous solid solution of PCZ and BNZ (at the same characteristic ratio of 80:20wt%), which provided enhanced solubility and dissolution rate for both APIs. This eutectic system was characterized by DSC and the melting points obtained were used for the construction of a phase diagram. The preservation of the characteristic PXRD patterns and the IR spectra of the parent APIs, and the visualization of a characteristic eutectic lamellar crystalline microstructure using Confocal Raman Microscopy confirm this system as a true eutectic mixture. The PXRD result also confirms the amorphous nature of the prepared solid solution. Theoretical chemical analyses indicate the predominance of π-stacking interactions in the amorphous solid solution, whereas an electrostatic interaction between the APIs is responsible for maintaining the alternating lamellar crystalline microstructure in the eutectic mixture. Both the eutectic mixture and the amorphous solid solution happen to have a characteristic PCZ to BNZ ratio similar to that of their pharmacological doses for treating Chagas disease, thus providing a unique therapeutic combination dose with enhanced apparent solubility and dissolution rate. Copyright © 2017 Elsevier B.V. All rights reserved.

(Nbx, Zr1-x)4AlC3 MAX Phase Solid Solutions: Processing, Mechanical Properties, and Density Functional Theory Calculations.

PubMed

Lapauw, Thomas; Tytko, Darius; Vanmeensel, Kim; Huang, Shuigen; Choi, Pyuck-Pa; Raabe, Dierk; Caspi, El'ad N; Ozeri, Offir; To Baben, Moritz; Schneider, Jochen M; Lambrinou, Konstantina; Vleugels, Jozef

2016-06-06

The solubility of zirconium (Zr) in the Nb4AlC3 host lattice was investigated by combining the experimental synthesis of (Nbx, Zr1-x)4AlC3 solid solutions with density functional theory calculations. High-purity solid solutions were prepared by reactive hot pressing of NbH0.89, ZrH2, Al, and C starting powder mixtures. The crystal structure of the produced solid solutions was determined using X-ray and neutron diffraction. The limited Zr solubility (maximum of 18.5% of the Nb content in the host lattice) in Nb4AlC3 observed experimentally is consistent with the calculated minimum in the energy of mixing. The lattice parameters and microstructure were evaluated over the entire solubility range, while the chemical composition of (Nb0.85, Zr0.15)4AlC3 was mapped using atom probe tomography. The hardness, Young's modulus, and fracture toughness at room temperature as well as the high-temperature flexural strength and E-modulus of (Nb0.85, Zr0.15)4AlC3 were investigated and compared to those of pure Nb4AlC3. Quite remarkably, an appreciable increase in fracture toughness was observed from 6.6 ± 0.1 MPa/m(1/2) for pure Nb4AlC3 to 10.1 ± 0.3 MPa/m(1/2) for the (Nb0.85, Zr0.15)4AlC3 solid solution.

Spectroscopic studies of the intramolecular hydrogen bonding in o-hydroxy Schiff bases, derived from diaminomaleonitrile, and their deprotonation reaction products.

PubMed

Szady-Chełmieniecka, Anna; Kołodziej, Beata; Morawiak, Maja; Kamieński, Bohdan; Schilf, Wojciech

2018-01-15

The structural study of five Schiff bases derived from diaminomaleonitrile (DAMN) and 2-hydroxy carbonyl compounds was performed using 1 H, 13 C and 15 N NMR methods in solution and in the solid state as well. ATR-FTIR and X-Ray spectroscopies were used for confirmation of the results obtained by NMR method. The imine obtained from DAMN and benzaldehyde was synthesized as a model compound which lacks intramolecular hydrogen bond. Deprotonation of all synthesized compounds was done by treating with tetramethylguanidine (TMG). NMR data revealed that salicylidene Schiff bases in DMSO solution exist as OH forms without intramolecular hydrogen bonds and independent on the substituents in aromatic ring. In the case of 2-hydroxy naphthyl derivative, the OH proton is engaged into weak intramolecular hydrogen bond. Two of imines (salDAMN and 5-BrsalDAMN) exist in DMSO solution as equilibrium mixtures of two isomers (A and B). The structures of equilibrium mixture in the solid state have been studied by NMR, ATR-FTIR and X-Ray methods. The deprotonation of three studied compounds (salDAMN, 5-BrsalDAMN, and 5-CH 3 salDAMN) proceeded in two different ways: deprotonation of oxygen atom (X form) or of nitrogen atom of free primary amine group of DAMN moiety (Y form). For 5-NO 2 salDAMN and naphDAMN only one form (X) was observed. Copyright © 2017 Elsevier B.V. All rights reserved.

A framework for qualitative reasoning about solid objects

NASA Technical Reports Server (NTRS)

Davis, E.

1987-01-01

Predicting the behavior of a qualitatively described system of solid objects requires a combination of geometrical, temporal, and physical reasoning. Methods based upon formulating and solving differential equations are not adequate for robust prediction, since the behavior of a system over extended time may be much simpler than its behavior over local time. A first-order logic, in which one can state simple physical problems and derive their solution deductively, without recourse to solving the differential equations, is discussed. This logic is substantially more expressive and powerful than any previous AI representational system in this domain.

Analytical close-form solutions to the elastic fields of solids with dislocations and surface stress

NASA Astrophysics Data System (ADS)

Ye, Wei; Paliwal, Bhasker; Ougazzaden, Abdallah; Cherkaoui, Mohammed

2013-07-01

The concept of eigenstrain is adopted to derive a general analytical framework to solve the elastic field for 3D anisotropic solids with general defects by considering the surface stress. The formulation shows the elastic constants and geometrical features of the surface play an important role in determining the elastic fields of the solid. As an application, the analytical close-form solutions to the stress fields of an infinite isotropic circular nanowire are obtained. The stress fields are compared with the classical solutions and those of complex variable method. The stress fields from this work demonstrate the impact from the surface stress when the size of the nanowire shrinks but becomes negligible in macroscopic scale. Compared with the power series solutions of complex variable method, the analytical solutions in this work provide a better platform and they are more flexible in various applications. More importantly, the proposed analytical framework profoundly improves the studies of general 3D anisotropic materials with surface effects.

Room-temperature ferromagnetic transitions and the temperature dependence of magnetic behaviors in FeCoNiCr-based high-entropy alloys

NASA Astrophysics Data System (ADS)

Na, Suok-Min; Yoo, Jin-Hyeong; Lambert, Paul K.; Jones, Nicholas J.

2018-05-01

High-entropy alloys (HEAs) containing multiple principle alloying elements exhibit unique properties so they are currently receiving great attention for developing innovative alloy designs. In FeCoNi-based HEAs, magnetic behaviors strongly depend on the addition of alloying elements, usually accompanied by structural changes. In this work, the effect of non-magnetic components on the ferromagnetic transition and magnetic behaviors in equiatomic FeCoNiCrX (X=Al, Ga, Mn and Sn) HEAs was investigated. Alloy ingots of nominal compositions of HEAs were prepared by arc melting and the button ingots were cut into discs for magnetic measurements as functions of magnetic field and temperature. The HEAs of FeCoNiCrMn and FeCoNiCrSn show typical paramagnetic behaviors, composed of solid solution FCC matrix, while the additions of Ga and Al in FeCoNiCr exhibit ferromagnetic behaviors, along with the coexistence of FCC and BCC phases due to spinodal decomposition. The partial phase transition in both HEAs with the additions of Ga and Al would enhance ferromagnetic properties due to the addition of the BCC phase. The saturation magnetization for the base alloy FeCoNiCr is 0.5 emu/g at the applied field of 20 kOe (TC = 104 K). For the HEAs of FeCoNiCrGa and FeCoNiCrAl, the saturation magnetization significantly increased to 38 emu/g (TC = 703 K) and 25 emu/g (TC = 277 K), respectively. To evaluate the possibility of solid solution FCC and BCC phases in FeCoNiCr-type HEAs, we introduced a parameter of valence electron concentration (VEC). The proposed rule for solid solution formation by the VEC was matched with FeCoNiCr-type HEAs.

Machine learning assisted first-principles calculation of multicomponent solid solutions: estimation of interface energy in Ni-based superalloys

NASA Astrophysics Data System (ADS)

Chandran, Mahesh; Lee, S. C.; Shim, Jae-Hyeok

2018-02-01

A disordered configuration of atoms in a multicomponent solid solution presents a computational challenge for first-principles calculations using density functional theory (DFT). The challenge is in identifying the few probable (low energy) configurations from a large configurational space before DFT calculation can be performed. The search for these probable configurations is possible if the configurational energy E({\\boldsymbol{σ }}) can be calculated accurately and rapidly (with a negligibly small computational cost). In this paper, we demonstrate such a possibility by constructing a machine learning (ML) model for E({\\boldsymbol{σ }}) trained with DFT-calculated energies. The feature vector for the ML model is formed by concatenating histograms of pair and triplet (only equilateral triangle) correlation functions, {g}(2)(r) and {g}(3)(r,r,r), respectively. These functions are a quantitative ‘fingerprint’ of the spatial arrangement of atoms, familiar in the field of amorphous materials and liquids. The ML model is used to generate an accurate distribution P(E({\\boldsymbol{σ }})) by rapidly spanning a large number of configurations. The P(E) contains full configurational information of the solid solution and can be selectively sampled to choose a few configurations for targeted DFT calculations. This new framework is employed to estimate (100) interface energy ({σ }{{IE}}) between γ and γ \\prime at 700 °C in Alloy 617, a Ni-based superalloy, with composition reduced to five components. The estimated {σ }{{IE}} ≈ 25.95 mJ m-2 is in good agreement with the value inferred by the precipitation model fit to experimental data. The proposed new ML-based ab initio framework can be applied to calculate the parameters and properties of alloys with any number of components, thus widening the reach of first-principles calculation to realistic compositions of industrially relevant materials and alloys.

Effect of Minor Alloying Elements on Localized Corrosion Behavior of Aluminum-Copper-Magnesium based Solid Solution Alloys

NASA Astrophysics Data System (ADS)

Aburada, Tomohiro

2011-12-01

The effects and mechanistic roles of a minor alloying element, Ni, on the localized corrosion behavior were explored by studying (Al75Cu 17Mg8)97Ni3 and Al70Cu 18Mg12 amorphous alloys. To explore the minor alloying element limited to the outer surface layers, the corrosion behavior of Al70Cu 18Mg12 amorphous alloy in solutions with and without Ni 2+ was also studied. Both Ni alloying and Ni2+ in solution improved the localized corrosion resistance of the alloys by ennobling the pitting and repassivation potentials. Pit growth by the selective dissolution of Al and Mg was also suppressed by Ni alloying. Remaining Cu and Ni reorganized into a Cu-rich polycrystalline nanoporous structure with continuous ligaments in pits. The minor Ni alloying and Ni2+ in solution suppressed the coarsening of the ligaments in the dealloyed nanoporous structure. The presence of relatively immobile Ni atoms at the surface suppressed the surface diffusion of Cu, which reduced the coarsening of the nanoporous structure, resulting in the formation of 10 to 30 nm wide Cu ligaments. Two mechanistic roles of minor alloying elements in the improvement of the pitting corrosion resistance of the solid solution alloys are elucidated. The first role is the suppression of active dissolution by altering the atomic structure. Ni in solid solution formed stronger bonds with Al, and reduces the probability of weaker Al-Al bonds. The second role is to hinder dissolution by producing a greater negative shift of the true interfacial potential at the dissolution front under the dealloyed layer due to the greater Ohmic resistance through the finer porous structure. These effects contributed to the elevation of pitting potentials by ennobling the applied potential required to produce enough dissolution for the stabilization of pits. Scientifically, this thesis advances the state of understanding of alloy dissolution, particularly the role of minor alloying elements on preferential oxidation at the atomic, nanometer, and micrometer scales. Technological implementations of the findings of the research are also discussed, including a new route to synthesize nanoporous materials with tunable porosity and new corrosion mitigation strategies for commercial Al-based alloys containing the detrimental Al2CuMg phase.

Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4}: Novel keesterite type solid solutions

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

Lopez-Vergara, F., E-mail: fer_martina@u.uchile.cl; Galdamez, A., E-mail: agaldamez@uchile.cl; Manriquez, V.

2013-02-15

A new family of Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4} chalcogenides has been synthesized by conventional solid-state reactions at 850 Degree-Sign C. The reactions products were characterized by powder X-ray diffraction (XRD), energy-dispersive X-ray analysis (SEM-EDS), Raman spectroscopy and magnetic susceptibility. The crystal structures of two members of the solid solution series Cu{sub 2}Mn{sub 0.4}Co{sub 0.6}SnS{sub 4} and Cu{sub 2}Mn{sub 0.2}Co{sub 0.8}SnS{sub 4} have been determined by single-crystal X-ray diffraction. Both phases crystallize in the tetragonal keesterite-type structure (space group I4{sup Macron }). The distortions of the tetrahedral volume of Cu{sub 2}Mn{sub 0.4}Co{sub 0.6}SnS{sub 4} and Cu{sub 2}Mn{sub 0.2}Co{sub 0.8}SnS{sub 4}more » were calculated and compared with the corresponding differences in the Cu{sub 2}MnSnS{sub 4} (stannite-type) end-member. The compounds show nearly the same Raman spectral features. Temperature-dependent magnetization measurements (ZFC/FC) and high-temperature susceptibility indicate that these solid solutions are antiferromagnetic. - Graphical abstract: View along [100] of the Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4} structure showing tetrahedral units and magnetic measurement ZFC-FC at 500 Oe. The insert shows the 1/{chi}-versus-temperature plot fitted by a Curie-Weiss law. Highlights: Black-Right-Pointing-Pointer Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4} solid solutions belong to the family of compounds adamantine. Black-Right-Pointing-Pointer Resolved single crystals of the solid solutions have space group I4{sup Macron }. Black-Right-Pointing-Pointer The distortion of the tetrahedral volume of Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4} were calculated. Black-Right-Pointing-Pointer These solid solutions are antiferromagnetic.« less

An interactive modeling program for the generation of planar polygons for boundary type solids representations of wire frame models

NASA Technical Reports Server (NTRS)

Ozsoy, T.; Ochs, J. B.

1984-01-01

The development of a general link between three dimensional wire frame models and rigid solid models is discussed. An interactive computer graphics program was developed to serve as a front end to an algorithm (COSMIC Program No. ARC-11446) which offers a general solution to the hidden line problem where the input data is either line segments of n-sided planar polygons of the most general type with internal boundaries. The program provides a general interface to CAD/CAM data bases and is implemented for models created on the Unigraphics VAX 11/780-based CAD/CAM systems with the display software written for DEC's VS11 color graphics devices.

Investigating the Co-Adsorption Behavior of Nucleic-Acid Base (Thymine and Cytosine) and Melamine at Liquid/Solid Interface

NASA Astrophysics Data System (ADS)

Zhao, Huiling; Li, Yinli; Chen, Dong; Liu, Bo

2016-12-01

The co-adsorption behavior of nucleic-acid base (thymine; cytosine) and melamine was investigated by scanning tunneling microscopy (STM) technique at liquid/solid (1-octanol/graphite) interface. STM characterization results indicate that phase separation happened after dropping the mixed solution of thymine-melamine onto highly oriented pyrolytic graphite (HOPG) surface, while the hetero-component cluster-like structure was observed when cytosine-melamine binary assembly system is used. From the viewpoints of non-covalent interactions calculated by using density functional theory (DFT) method, the formation mechanisms of these assembled structures were explored in detail. This work will supply a methodology to design the supramolecular assembled structures and the hetero-component materials composed by biological and chemical compound.

Structural studies of TiC{sub 1−x}O{sub x} solid solution by Rietveld refinement and first-principles calculations

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

Jiang, Bo, E-mail: youqin5912@yahoo.com.cn; Hou, Na; Huang, Shanyan

2013-08-15

The lattice parameters, structural stability and electronic structure of titanium oxycarbides (TiC{sub 1−x}O{sub x}, 0≤x≤1) solid solution were investigated by Rietveld refinement and first-principles calculations. Series of TiC{sub 1−x}O{sub x} were precisely synthesized by sintering process under the vacuum. Rietveld refinement results of XRD patterns show the properties of continuous solid solution in TiC{sub 1−x}O{sub x} over the whole composition range. The lattice parameters vary from 0.4324 nm to 0.4194 nm decreasing with increasing oxygen concentration. Results of first-principles calculations reveal that the disorder C/O structure is stable than the order C/O structure. Further investigations of the vacancy in Ti{submore » 1−Va}(C{sub 1−x}O{sub x}){sub 1−Va} solid solution present that the structure of vacancy segregated in TiO-part is more stable than the disorder C/O structure, which can be ascribed to the Ti–Ti bond across O-vacancy and the charge redistributed around Ti-vacancy via the analysis of the electron density difference plots and PDOS. - Graphical abstract: XRD of series of titanium oxycarbides (TiC{sub 1−x}O{sub x}, 0≤x≤1) solid solution prepared by adjusting the proportion of TiO in the starting material. Highlights: • Titanium oxycarbides were obtained by sintering TiO and TiC under carefully controlled conditions. • Rietveld refinement results show continuous solid solution with FCC structure in TiC{sub 1−x}O{sub x}. • The disorder C/O structure is stable than the order C/O structure. • Introduction of vacancy segregated in TiO-part is more stable than disorder C/O structure. • Ti–Ti bond across O-vacancy and the charge redistributed around Ti-vacancy enhance structural stability.« less

Solid-phase electrochemical reduction of graphene oxide films in alkaline solution

NASA Astrophysics Data System (ADS)

Basirun, Wan J.; Sookhakian, Mehran; Baradaran, Saeid; Mahmoudian, Mohammad R.; Ebadi, Mehdi

2013-09-01

Graphene oxide (GO) film was evaporated onto graphite and used as an electrode to produce electrochemically reduced graphene oxide (ERGO) films by electrochemical reduction in 6 M KOH solution through voltammetric cycling. Fourier transformed infrared and Raman spectroscopy confirmed the presence of ERGO. Electrochemical impedance spectroscopy characterization of ERGO and GO films in ferrocyanide/ferricyanide redox couple with 0.1 M KCl supporting electrolyte gave results that are in accordance with previous reports. Based on the EIS results, ERGO shows higher capacitance and lower charge transfer resistance compared to GO.

Thermoelectric Devices Cool, Power Electronics

NASA Technical Reports Server (NTRS)

2009-01-01

Nextreme Thermal Solutions Inc., based in Research Triangle Park, North Carolina, licensed thermoelectric technology from NASA s Jet Propulsion Laboratory. This has allowed the company to develop cutting edge, thin-film thermoelectric coolers that effective remove heat generated by increasingly powerful and tightly packed microchip components. These solid-state coolers are ideal solutions for applications like microprocessors, laser diodes, LEDs, and even potentially for cooling the human body. Nextreme s NASA technology has also enabled the invention of thermoelectric generators capable of powering technologies like medical implants and wireless sensor networks.

Creation of Novel Solid-Solution Alloy Nanoparticles on the Basis of Density-of-States Engineering by Interelement Fusion.

PubMed

Kobayashi, Hirokazu; Kusada, Kohei; Kitagawa, Hiroshi

2015-06-16

Currently 118 known elements are represented in the periodic table. Of these 118 elements, only about 80 elements are stable, nonradioactive, and widely available for our society. From the viewpoint of the "elements strategy", we need to make full use of the 80 elements to bring out their latent ability and create innovative materials. Furthermore, there is a strong demand that the use of rare or toxic elements be reduced or replaced while their important properties are retained. Advanced science and technology could create higher-performance materials even while replacing or reducing minor or harmful elements through the combination of more abundant elements. The properties of elements are correlated directly with their electronic states. In a solid, the magnitude of the density of states (DOS) at the Fermi level affects the physical and chemical properties. In the present age, more attention has been paid to improving the properties of materials by means of alloying elements. In particular, the solid-solution-type alloy is advantageous because the properties can be continuously controlled by tuning the compositions and/or combinations of the constituent elements. However, the majority of bulk alloys are of the phase-separated type under ambient conditions, where constituent elements are immiscible with each other. To overcome the challenge of the bulk-phase metallurgical aspects, we have focused on the nanosize effect and developed methods involving "nonequilibrium synthesis" or "a process of hydrogen absorption/desorption". We propose a new concept of "density-of-states engineering" for the design of materials having the most desirable and suitable properties by means of "interelement fusion". In this Account, we describe novel solid-solution alloys of Pd-Pt, Ag-Rh, and Pd-Ru systems in which the constituent elements are immiscible in the bulk state. The homogeneous solid-solution alloys of Pd and Pt were created from Pd core/Pt shell nanoparticles using a hydrogen absorption/desorption process as a trigger. Several atom percent replacements of Pd with Pt atoms resulted in a significantly enhanced hydrogen absorption capacity compared with Pd nanoparticles. AgxRh1-x and PdxRu1-x solid-solution alloy nanoparticles were also developed by nonequilibrium synthesis based on a polyol method. The AgxRh1-x nanoparticles demonstrated hydrogen storage properties, although pure metal nanoparticles of each constituent element do not adsorb hydrogen. AgxRh1-x is therefore considered to possess a similar electronic structure to Pd as a synthetic pseudo-palladium. The PdxRu1-x nanoparticles showed enhanced catalytic activity for CO oxidation, with the highest catalytic activity found using the equimolar Pd0.5Ru0.5 nanoparticles. The catalytic activity of the Pd0.5Ru0.5 nanoparticles exceeds that of the widely used and best-performing Ru catalysts for CO oxidation and is also higher than that of neighboring Rh on the periodic table. Our present work provides a guiding principle for the design of a suitable DOS shape according to the intended physical and/or chemical properties and a method for the development of novel solid-solution alloys.

Quick, easy, cheap, effective, rugged, and safe sample preparation approach for pesticide residue analysis using traditional detectors in chromatography: A review.

PubMed

Rahman, Md Musfiqur; Abd El-Aty, A M; Kim, Sung-Woo; Shin, Sung Chul; Shin, Ho-Chul; Shim, Jae-Han

2017-01-01

In pesticide residue analysis, relatively low-sensitivity traditional detectors, such as UV, diode array, electron-capture, flame photometric, and nitrogen-phosphorus detectors, have been used following classical sample preparation (liquid-liquid extraction and open glass column cleanup); however, the extraction method is laborious, time-consuming, and requires large volumes of toxic organic solvents. A quick, easy, cheap, effective, rugged, and safe method was introduced in 2003 and coupled with selective and sensitive mass detectors to overcome the aforementioned drawbacks. Compared to traditional detectors, mass spectrometers are still far more expensive and not available in most modestly equipped laboratories, owing to maintenance and cost-related issues. Even available, traditional detectors are still being used for analysis of residues in agricultural commodities. It is widely known that the quick, easy, cheap, effective, rugged, and safe method is incompatible with conventional detectors owing to matrix complexity and low sensitivity. Therefore, modifications using column/cartridge-based solid-phase extraction instead of dispersive solid-phase extraction for cleanup have been applied in most cases to compensate and enable the adaptation of the extraction method to conventional detectors. In gas chromatography, the matrix enhancement effect of some analytes has been observed, which lowers the limit of detection and, therefore, enables gas chromatography to be compatible with the quick, easy, cheap, effective, rugged, and safe extraction method. For liquid chromatography with a UV detector, a combination of column/cartridge-based solid-phase extraction and dispersive solid-phase extraction was found to reduce the matrix interference and increase the sensitivity. A suitable double-layer column/cartridge-based solid-phase extraction might be the perfect solution, instead of a time-consuming combination of column/cartridge-based solid-phase extraction and dispersive solid-phase extraction. Therefore, replacing dispersive solid-phase extraction with column/cartridge-based solid-phase extraction in the cleanup step can make the quick, easy, cheap, effective, rugged, and safe extraction method compatible with traditional detectors for more sensitive, effective, and green analysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimizing Blue Persistent Luminescence in (Sr 1-δ Ba δ ) 2 MgSi 2 O 7: Eu 2+ ,Dy 3+ via Solid Solution for Use in Point-of-Care Diagnostics

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

Finley, Erin; Cobb, Angelica; Duke, Anna

Inorganic persistent luminescent phosphors are an excellent class of optical reporters for enabling sensitive point-of-care diagnostics, particularly with smartphone-based biosensing devices in testing formats such as the lateral flow assay (LFA). Here, the development of persistent phosphors for this application is focused on the solid solution (Sr 1-δBa δ) 2MgSi 2O 7:Eu 2+,Dy 3+ (δ = 0, 0.125, 0.25, 0.375), which is prepared using a high-temperature solid-state reaction as confirmed by synchrotron X-ray powder diffraction. The substitution of barium for strontium enables control over the Eu 2+ 5d-orbital crystal field splitting (CFS) as a tool for tuning the emission wavelengthmore » while maintaining luminescence lifetimes >9 min across the composition range. Thermoluminescence measurements of the solid solution provide evidence that trap states contribute to the persistent lifetimes with the trap depths also remaining constant as a function of composition. Time-gated luminescence images of these compounds are captured on a smartphone arranged in a layout to mimic a point-of-care test and demonstrate the viability of using these materials as optical reporters. Moreover, comparing the blue-emitting (Sr 0.625Ba 0.375) 2MgSi 2O 7:Eu 2+,Dy 3+ and the green-emitting SrAl 2O 4:Eu 2+,Dy 3+ in a single LFA-type format shows these two compounds can be detected and resolved simultaneously, thereby permitting the development of a multiplexed LFA.« less

Normal and anomalous nuclear spin-lattice relaxation at high temperatures in Sc-H(D), Y-H, and Lu-H solid solutions

NASA Astrophysics Data System (ADS)

Barnes, R. G.; Han, J.-W.; Torgeson, D. R.; Baker, D. B.; Conradi, M. S.; Norberg, R. E.

1995-02-01

We report the results of measurements of the proton (1H) spin-lattice relaxation rate R1 at high temperatures (to ~1400 K) in the hcp (α) solid-solution phases of the Sc-H, Y-H, and Lu-H systems, and of R1(45Sc) in Sc-H and Sc-D solid solutions. The latter measurements show unambiguous evidence of an anomalous increase at ~1000 K, whereas R1(1H) shows no such increase at any temperature. This behavior of R1(1H) contrasts with that in the bcc V-H, etc., solid solutions where anomalous relaxation occurs below ~1000 K, and in all investigated metal dihydride phases, MH2-x. The anomalous R1(1H) behavior in α-VHx, α-NbHx, etc., may be understood in terms of fast spin relaxation in the H2 gas in equilibrium with the solid, mediated by fast gas-solid exchange of hydrogen. However, in the present systems, α-ScHx, α-YHx, etc., the H2 gas pressure in equilibrium with the hcp systems is extremely low, resulting in negligible H2 concentration in the gas phase, and consequently a negligible contribution to R1(1H). In contrast, some of the present measurements indicate that the R1(45Sc) anomaly does result from the hydrogen content of the metal, but the mechanism remains unexplained.

Phase Behaviour and Miscibility Studies of Collagen/Silk Fibroin Macromolecular System in Dilute Solutions and Solid State.

PubMed

Ghaeli, Ima; de Moraes, Mariana A; Beppu, Marisa M; Lewandowska, Katarzyna; Sionkowska, Alina; Ferreira-da-Silva, Frederico; Ferraz, Maria P; Monteiro, Fernando J

2017-08-18

Miscibility is an important issue in biopolymer blends for analysis of the behavior of polymer pairs through the detection of phase separation and improvement of the mechanical and physical properties of the blend. This study presents the formulation of a stable and one-phase mixture of collagen and regenerated silk fibroin (RSF), with the highest miscibility ratio between these two macromolecules, through inducing electrostatic interactions, using salt ions. For this aim, a ternary phase diagram was experimentally built for the mixtures, based on observations of phase behavior of blend solutions with various ratios. The miscibility behavior of the blend solutions in the miscible zones of the phase diagram was confirmed quantitatively by viscosimetric measurements. Assessing the effects of biopolymer mixing ratio and salt ions, before and after dialysis of blend solutions, revealed the importance of ion-specific interactions in the formation of coacervate-based materials containing collagen and RSF blends that can be used in pharmaceutical, drug delivery, and biomedical applications. Moreover, the conformational change of silk fibroin from random coil to beta sheet, in solution and in the final solid films, was detected by circular dichroism (CD) and Fourier transform infrared spectroscopy (FTIR), respectively. Scanning electron microscopy (SEM) exhibited alterations of surface morphology for the biocomposite films with different ratios. Surface contact angle measurement illustrated different hydrophobic properties for the blended film surfaces. Differential scanning calorimetry (DSC) showed that the formation of the beta sheet structure of silk fibroin enhances the thermal stability of the final blend films. Therefore, the novel method presented in this study resulted in the formation of biocomposite films whose physico-chemical properties can be tuned by silk fibroin conformational changes by applying different component mixing ratios.

Room-temperature synthesis of Zn(0.80)Cd(0.20)S solid solution with a high visible-light photocatalytic activity for hydrogen evolution.

PubMed

Wang, Dong-Hong; Wang, Lei; Xu, An-Wu

2012-03-21

Visible light photocatalytic H(2) production from water splitting is of great significance for its potential applications in converting solar energy into chemical energy. In this study, a series of Zn(1-x)Cd(x)S solid solutions with a nanoporous structure were successfully synthesized via a facile template-free method at room temperature. The obtained solid solutions were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), ultraviolet-visible (UV-vis) diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDS) and N(2) adsorption-desorption analysis. The solid solutions show efficient photocatalytic activity for H(2) evolution from aqueous solutions containing sacrificial reagents S(2-) and SO(3)(2-) under visible-light irradiation without a Pt cocatalyst, and loading of the Pt cocatalyst further improves the visible-light photocatalytic activity. The optimal photocatalyst with x = 0.20 prepared at pH = 7.3 displays the highest activity for H(2) evolution. The bare and 0.25 wt% Pt loaded Zn(0.80)Cd(0.20)S nanoparticles exhibit a high H(2) evolution rate of 193 μmol h(-1) and 458 μmol h(-1) under visible-light irradiation (λ ≥ 420 nm), respectively. In addition, the bare and 0.25 wt% Pt loaded Zn(0.80)Cd(0.20)S catalysts show a high H(2) evolution rate of 252 and 640 μmol h(-1) under simulated solar light irradiation, respectively. Moreover, the Zn(0.80)Cd(0.20)S catalyst displays a high photocatalytic stability for H(2) evolution under long-term light irradiation. The incorporation of Cd in the solid solution leads to the visible light absorption, and the high content of Zn in the solid solution results in a relatively negative conduction band, a modulated band gap and a rather wide valence bandwidth, which are responsible for the excellent photocatalytic performance of H(2) production and for the high photostability. This journal is © The Royal Society of Chemistry 2012

Convergent solid-phase and solution approaches in the synthesis of the cysteine-rich Mdm2 RING finger domain.

PubMed

Vasileiou, Zoe; Barlos, Kostas; Gatos, Dimitrios

2009-12-01

The RING finger domain of the Mdm2, located at the C-terminus of the protein, is necessary for regulation of p53, a tumor suppressor protein. The 48-residues long Mdm2 peptide is an important target for studying its interaction with small anticancer drug candidates. For the chemical synthesis of the Mdm2 RING finger domain, the fragment condensation on solid-phase and the fragment condensation in solution were studied. The latter method was performed using either protected or free peptides at the C-terminus as the amino component. Best results were achieved using solution condensation where the N-component was applied with the C-terminal carboxyl group left unprotected. The developed method is well suited for large-scale synthesis of Mdm2 RING finger domain, combining the advantages of both solid-phase and solution synthesis. (c) 2009 European Peptide Society and John Wiley & Sons, Ltd.