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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Molecular dynamics study of salt–solution interface: Solubility and surface charge of salt in water

The NaCl salt–solution interface often serves as an example of an uncharged surface. However, recent laser-Doppler electrophoresis has shown some evidence that the NaCl crystal is positively charged in its saturated solution. Using molecular dynamics (MD) simulations, we have investigated the NaCl salt–solution interface system, and calculated the solubility of the salt using the direct method and free energy calculations, which are kinetic and thermodynamic approaches, respectively. The direct method calculation uses a salt–solution combined system. When the system is equilibrated, the concentration in the solution area is the solubility. In the free energy calculation, we separately calculate the chemical potential of NaCl in two systems, the solid and the solution, using thermodynamic integration with MD simulations. When the chemical potential of NaCl in the solution phase is equal to the chemical potential of the solid phase, the concentration of the solution system is the solubility. The advantage of using two different methods is that the computational methods can be mutually verified. We found that a relatively good estimate of the solubility of the system can be obtained through comparison of the two methods. Furthermore, we found using microsecond time-scale MD simulations that the positively charged NaCl surface was induced by a combination of a sodium-rich surface and the orientation of the interfacial water molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

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

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 two 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.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Homoleptic An(IV) Dimethyl Sulfoxide Complexes of Th–Pu Enable Insight into Solution Speciation and Redox

A family of 8- and 9- coordinate homoleptic dimethyl sulfoxide An(IV) complexes is used to evaluate the solvation properties of tetravalent actinide ions in dimethyl sulfoxide (DMSO) vs aqueous media. These compounds are prepared from aqueous mixtures of DMSO and yield crystalline solids, whose solid-state electronic absorption spectra are compared to solution phase spectra, providing insight into the solution speciation. The thermodynamics of the equilibria between the 8- and 9-coordinate compounds were determined experimentally and computationally, showing a trend that correlates with ionic radius. Cyclic voltammetry data for the +IV/+III couples of Np and Pu in the DMSO electrolyte indicate that the +IV ions are significantly stabilized compared to aqueous media due to the more donating nature of DMSO compared to water. As a result, computational studies of these systems indicate that further reactivity may take place upon reduction to the +III oxidation state.

Actinides↗
DOE OSTI2014

Critical point analysis of phase envelope diagram

Phase diagram or phase envelope is a relation between temperature and pressure that shows the condition of equilibria between the different phases of chemical compounds, mixture of compounds, and solutions. Phase diagram is an important issue in chemical thermodynamics and hydrocarbon reservoir. It is very useful for process simulation, hydrocarbon reactor design, and petroleum engineering studies. It is constructed from the bubble line, dew line, and critical point. Bubble line and dew line are composed of bubble points and dew points, respectively. Bubble point is the first point at which the gas is formed when a liquid is heated. Meanwhile, dew point is the first point where the liquid is formed when the gas is cooled. Critical point is the point where all of the properties of gases and liquids are equal, such as temperature, pressure, amount of substance, and others. Critical point is very useful in fuel processing and dissolution of certain chemicals. Here in this paper, we will show the critical point analytically. Then, it will be compared with numerical calculations of Peng-Robinson equation by using Newton-Raphson method. As case studies, several hydrocarbon mixtures are simulated using by Matlab.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Phase Stability and Optoelectronic Properties of the Bixbyite Phase in the Gallium–Indium–Tin–Oxide System

X‐ray diffraction techniques were used to determine the phase boundaries of the In 2 O 3 solid solution phase in the Ga 2 O 3 – In 2 O 3 – SnO 2 ternary system. The effects of Ga and Sn content on the unit cell dimensions of the bixbyite phase were calculated by a linear regression fit, the results of which indicate the two substitutive cations have opposite and independent effects on the lattice parameter. These results suggest that the cations do not strongly interact with each other in the crystal. Measurements of optoelectronic properties were also taken on single‐phase bulk specimens within the solid solution to establish their dependence on composition. As anticipated, Sn doping yields corresponding increases in conductivity, reduction in the absolute value of Seebeck coefficient, and increase in optical band gap. In contrast, these properties are not significantly affected by varying Ga content, confirming that Ga behaves as an isovalent dopant at the low doping levels involved.

Dolgonos, Alex↗
DOE OSTI2014

Phase diagram of the CulnSe{sub 2}-CuGaSe{sub 2} pseudobinary system studied by combined ab initio density functional theory and thermodynamic calculation

The phase diagram of the CuInSe{sub 2}-CuGaSe{sub 2} pseudobinary system was determined using a combination of special quasirandom structure approach, ab initio density functional theory calculations, and thermodynamic modelling. It is shown that the CuIn{sub 1−x}Ga{sub x}Se{sub 2} solution phase has a tendency to phase separation at low temperature. The calculated consolute temperature is 485 K. It is found that both the binodal and spinodal curves are significantly asymmetric and on both curves there are a local maximum and a local minimum, which have not been reported in the previous studies. Our phase diagram can well explain the finding that the inhomogeneity of CuIn{sub 0.25}Ga{sub 0.75}Se{sub 2} is higher than that of CuIn{sub 0.75}Ga{sub 0.25}Se{sub 2} at the same temperature, while the previous phase diagrams cannot. Hence, our phase diagram should be more reliable and applicable.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2017

Stable colloids in molten inorganic salts

A colloidal solution is a homogeneous dispersion of particles or droplets of one phase (solute) in a second, typically liquid, phase (solvent). Colloids are ubiquitous in biological, chemical and technological processes1, 2, homogenizing highly dissimilar constituents. To stabilize a colloidal system against coalescence and aggregation, the surface of each solute particle is engineered to impose repulsive forces strong enough to overpower van der Waals attraction and keep the particles separated from each other2. Electrostatic stabilization3, 4 of charged solutes works well in solvents with high dielectric constants, such as water (dielectric constant of 80). In contrast, colloidal stabilization in solvents with low polarity, such as hexane (dielectric constant of about 2), can be achieved by decorating the surface of each particle of the solute with molecules (surfactants) containing flexible, brush-like chains2, 5. Here we report a class of colloidal systems in which solute particles (including metals, semiconductors and magnetic materials) form stable colloids in various molten inorganic salts. The stability of such colloids cannot be explained by traditional electrostatic and steric mechanisms. Screening of many solute–solvent combinations shows that colloidal stability can be traced to the strength of chemical bonding at the solute–solvent interface. Theoretical analysis and molecular dynamics modelling suggest that a layer of surface-bound solvent ions produces long-ranged charge-density oscillations in the molten salt around solute particles, preventing their aggregation. Colloids composed of inorganic particles in inorganic melts offer opportunities for introducing colloidal techniques to solid-state science and engineering applications.

Zhang, Hao↗
DOE OSTI2017

Mechanical properties examined by nanoindentation for selected phases relevant to the development of monolithic uranium-molybdenum metallic fuels

Nanomechanical properties, specifically the reduced modulus and hardness of several intermetallic and solid solution phases are reported here to assist the development of the U-10 wt% Mo (U-10Mo) monolithic fuel system for research and test reactors. Findings from this study and reported values of mechanical properties provide data critical for understanding and predicting the structural behavior of the fuel system during fabrication and irradiation. The phases examined are products of interdiffusion and reaction between (1) the AA6061 cladding and the Zr diffusion barrier, namely (Al,Si) 3 Zr and Al 3 Zr, (2) the U-10Mo fuel and the Zr diffusion barrier, namely UZr 2 , Mo 2 Zr, and a-U, and (3) the U (or U-10Mo) and Mo, namely a mixture gradient of α- and γ-phases. The UC inclusions observed within the fuel alloy were also examined. Only phases present in thick or continuous microstructure on cross-sectioned fuel plates and diffusion couples were investigated for reduced modulus and hardness. Concentration-dependence of room-temperature reduced modulus in U solid solution with 0–10 wt% Mo was semi-quantitatively modeled based on mixture of α- and γ-phases and solid solutioning within the γ-phase.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2019

Impact of Blend Proportion on the Miscibility and Thermal Characteristics of Synthetic Plastic-Derived Polypentapeptide with Commercially Available Polyvinyl Alcohol

Plastic-based polypeptides are versatile entities formed to conceive a broad range of scaffold biomaterials. They possess distinct, repetitive, hydrophobic sequences that confer conservation, reversibility, temperature-dependent self-association and dissociation properties. The repeating sequence of plastic-based peptides, poly(AVGVP) have been synthesized by the solution phase method and characterized by {sup 13}C and {sup 1}H-NMR spectroscopy. The intermolecular interactions between poly(AVGVP) and polyvinyl alcohol (PVA) was explored in solution and solid phase by diverse analytical methods. The interaction parameters, namely; α, β, µ and ∆[η]{sub m} obtained from the dilute solution viscometric approach, unveiled that the two polymers were miscible up to 40% of the polypeptide in the blends. Besides, Fourier transform infrared (FTIR) spectroscopy authenticated the formation of strong intermolecular hydrogen bonds connecting blend networks. Further, other analytical techniques such as DSC, SEM and XRD probes advocated the miscibility results. Thermogravimetric investigation of the blends confirmed the proportionate decrease of the thermal stability with the increase of polypentapeptide, attributable to the intermolecular amalgamation between the polypeptide and PVA. The blends and plain poly(AVGVP) degraded completely at about 700 °C, whereas the virgin PVA was about only 60% at this temperature. Graphic Abstract: .

36 MATERIALS SCIENCE↗
DOE OSTI2018

Accelerated reactions in field desorption mass spectrometry

Field desorption mass spectrometry under ambient conditions is used to study solution-phase organic reactions in micro-volumes. Reagent solution is transferred onto the microdendrites of the field emitter, and reaction products are examined online by mass spectrometry. Three reactions, hydrazone formation by phenyl hydrazine and indoline-2,3-dione, the Katritzky reaction between a pyrylium salt and anisidine, and the Hantzsch synthesis of 1,4-dihydropyridine, were investigated, and reaction acceleration was observed to different extents. The increase in rate relative to the corresponding bulk reactions is attributed to solvent evaporation (simple concentration effect) and to the increase of surface-to-volume ratio (enhanced interfacial reactions). A distinguishing feature of this method of reaction acceleration, relative to that based on nano electrospray ionization, is the observation of radical cations and the formation of radical cation products. The research also breaks new ground in using field emitters at atmospheric pressure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Isolating solvent–solute hydrogen bonding interactions via 2D IR solvation shell spectroscopy

The solvation shell around a solute is a fundamental feature of liquid-phase solutions, determining the behavior and properties of both the solute and the overall solution. Direct experimental measurements of the solvation shell properties are challenging due to the strong signals generated from the bulk solvent, which overwhelm the small contribution of the solvation shell. Here, we use ultrafast two dimensional infrared (2D IR) spectroscopy and intermolecular cross-peaks to isolate the IR absorption spectrum of methanol molecules in the solvation shell surrounding the solute N-methylacetamide. We demonstrate that the intermolecular coupling between the solvent and solute vibrations is indirectly mediated by a low-frequency hydrogen-bonding mode, suggesting an important mechanism for anharmonic coupling induced by hydrogen bonds. From the relative frequency shifts and cross-peak anisotropy, we find that methanol molecules surrounding N-methylacetamide form stronger and distinctly oriented hydrogen bonds than those in the bulk solvent. Here, we also compare these results with the solvent spectra of the solute N,N-dimethylacetamide to investigate how solute structural changes alter the solvation shell and the contribution of N–H hydrogen bond donation. Our results are supported by molecular dynamics simulations, which provide detailed insights into the hydrogen-bonding distributions. Through these results, we demonstrate 2D solvation shell spectroscopy to be a valuable method for investigating solvation structures and dynamics without interference from the bulk solvent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Innovative Phase Change Thermal Energy Storage Solution for Baseload Power Phase 1 Final Report

The primary purpose of this project is to develop and validate an innovative, scalable phase change salt thermal energy storage (TES) system that can interface with Infinia’s family of free-piston Stirling engines (FPSE). This TES technology is also appropriate for Rankine and Brayton power converters. Solar TES systems based on latent heat of fusion rather than molten salt temperature differences, have mTany advantages that include up to an order of magnitude higher energy storage density, much higher temperature operation, and elimination of pumped loops for most of Infinia’s design options. DOE has funded four different concepts for solar phase change TES, including one other Infinia awarded project using heat pipes to transfer heat to and from the salt. The unique innovation in this project is an integrated TES/pool boiler heat transfer system that is the simplest approach identified to date and arguably has the best potential for minimizing the levelized cost of energy (LCOE). The Phase 1 objectives are to design, build and test a 1-hour TES proof-of-concept lab demonstrator integrated with an Infinia 3 kW Stirling engine, and to conduct a preliminary design of a 12-hour TES on-sun prototype.

14 SOLAR ENERGY↗
DOE OSTI2019

Anion Distribution, Structural Distortion, and Symmetry-Driven Optical Band Gap Bowing in Mixed Halide Cs2SnX6 Vacancy Ordered Double Perovskites

Mixed anion compounds in the Fm$\bar{3}$m vacancy ordered perovskite structure were synthesized and characterized experimentally and computationally with a focus on compounds where A = Cs + . Pure anion Cs 2 SnX 6 compounds were formed with X = Cl, Br, and I using a room temperature solution phase method. Mixed anion compounds were formed as solid solutions of Cs 2 SnCl 6 and Cs 2 SnBr 6 and a second series from Cs 2 SnBr 6 and Cs 2 SnI 6 . Single phase structures formed across the entirety of both composition series with no evidence of long-range anion ordering observed by diffraction. A distortion of the cubic A 2 BX 6 structure was identified in which the spacing of the BX 6 octahedra changes to accommodate the A site cation without reduction of overall symmetry. Optical band gap values varied with anion composition between 4.89 eV in Cs 2 SnCl 6 to 1.35 eV in Cs 2 SnI 6 but proved highly nonlinear with changes in composition. In mixed halide compounds, it was found that lower energy optical transitions appeared that were not present in the pure halide compounds, and this was attributed to lowering of the local symmetry within the tin halide octahedra. The electronic structure was characterized by photoemission spectroscopy, and Raman spectroscopy revealed vibrational modes in the mixed halide compounds that could be assigned to particular mixed halide octahedra. This analysis was used to determine the distribution of octahedra types in mixed anion compounds, which was found to be consistent with a near-random distribution of halide anions throughout the structure, although some deviations from random halide distribution were noted in mixed iodide–bromide compounds, where the larger iodide anions preferentially adopted trans configurations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Crystalline, liquid crystalline, and isotropic phases of sodium deoxycholate in water

Sodium deoxycholate (NaDC) is an important example of bile salts, representing systems with complex phase behavior involving both crystalline and mesophase structures. In this study, properties of NaDC-water mixtures were evaluated as a function of composition and temperature via X-ray diffraction with synchrotron (sXRD) and laboratory radiation sources, water sorption, polarized light, hot-stage microscopy, and freezing-point osmometry. Several phases were detected depending on the composition and temperature, including isotropic solution phase, liquid crystalline (LC) phase, crystalline hydrate, and ice. The LC phase was identified as hexagonal structure by sXRD, with up to 14 high-order reflections detected. The crystalline phase was found to be nonstoichiometric hydrate, based on XRD and water sorption data. The phase diagram of NaDC-water system has been refined based on both results of this study and other reports in literature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Helium irradiated cavity formation and defect energetics in Ni-based binary single-phase concentrated solid solution alloys

In this study, binary single-phase concentrated solid solution alloys (SPCSAs), including Ni 80 Co 20 , Ni 80 Fe 20 , Ni 80 Cr 20 , Ni 80 Pd 20 , and Ni 80 Mn 20 (in atomic percentage), were irradiated with 200 keV He + ions at 500 °C. He cavity size and density distribution were systematically investigated using transmission electron microscope. Here we show that alloying elements have a clear impact on He cavity formation. Cavity size is the smallest in Ni 80 Mn 20 but the largest in Ni 80 Co 20 . Alloying elements could also substantially affect cavity density profile. In-depth examination of cavities at peak damage region (~500 nm) and at low damage region (~300 nm) demonstrates that cavity size is depth (damage) dependent. Competition between consumption and production of vacancies and He atoms could lead to varied cavity size. Density functional theory (DFT) calculations were performed to obtain the formation and migration energies of interstitials and vacancies. Combined experimental and simulation results show that smaller energy gap between interstitial and vacancy migration energies may lead to smaller cavity size and narrower size distribution observed in Ni 80 Mn 20 , comparing with Ni 80 Co 20 . Finally, the results of this study call attention to alloying effects of specific element on cavity formation and defect energetics in SPCSAs, and could provide fundamental understanding to predict radiation effects in more complexed SPCSAs, such as high entropy alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2015

The physical chemistry of Criegee intermediates in the gas phase

Here, carbonyl oxides, also known as Criegee intermediates, are key intermediates in both gas phase ozonolysis of unsaturated hydrocarbons in the troposphere and solution phase organic synthesis via ozonolysis. Although the study of Criegee intermediates in both arenas has a long history, direct studies in the gas phase have only recently become possible through new methods of generating stabilised Criegee intermediates in sufficient quantities. This advance has catalysed a large number of new experimental and theoretical investigations of Criegee intermediate chemistry. In this article we review the physical chemistry of Criegee intermediates, focusing on their molecular structure, spectroscopy, unimolecular and bimolecular reactions. These recent results have overturned conclusions from some previous studies, while confirming others, and have clarified areas of investigation that will be critical targets for future studies. In addition to expanding our fundamental understanding of Criegee intermediates, the rapidly expanding knowledge base will support increasingly predictive models of their impacts on society.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Quantum cluster equilibrium model of N-methylformamide–water binary mixtures

The established quantum cluster equilibrium (QCE) approach is refined and applied to N-methylformamide (NMF) and its aqueous solution. The QCE method is split into two iterative cycles: one which converges to the liquid phase solution of the QCE equations and another which yields the gas phase. By comparing Gibbs energies, the thermodynamically stable phase at a given temperature and pressure is then chosen. The new methodology avoids metastable solutions and allows a different treatment of the mean-field interactions within the gas and liquid phases. These changes are of crucial importance for the treatment of binary mixtures. For the first time in a QCE study, the cis-trans-isomerism of a species (NMF) is explicitly considered. Cluster geometries and frequencies are calculated using density functional theory (DFT) and complementary coupled cluster single point energies are used to benchmark the DFT results. Independent of the selected quantum-chemical method, a large set of clusters is required for an accurate thermodynamic description of the binary mixture. The liquid phase of neat NMF is found to be dominated by the cyclic trans-NMF pentamer, which can be interpreted as a linear trimer that is stabilized by explicit solvation of two further NMF molecules. This cluster reflects the known hydrogen bond network preferences of neat NMF.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗