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At least 613 records · Page 34

Protein Crystal Growth Under Forced Solution Flow: Experimental Setup and General Response of Lysozyme

We have experimentally studied the effects of solution flow on the growth kinetics of the protein lysozyme. To this end, we have expanded our interferometry setup by a novel crystallization cell and solution recirculation system. This combination permits monitoring of interface morphology and kinetics with a depth resolution of 200 A at bulk flow rates of up to 2000 micron/s. Particular attention was paid to the prevention of protein denaturation that is often associated with the pumping of protein solutions. We found that at bulk flow rates it less than 250 microns/s the average growth rate and step velocity, R(sub avg) and upsilon(sub avg) increase with increasing it. This can be quantitatively understood in terms of the enhanced, convective solute supply to the interface. With high-purity solutions, it u greater than 250 microns/s lead to growth deceleration, and, at low supersaturations sigma, to growth cessation. When solutions containing approx. 1% of other protein impurities were used, growth deceleration occurred at any u greater than 0 and cessation in the low sigma experiments was reached at about half the it causing cessation with pure solution. The flow-induced changes in R(sub avg) and upsilon(sub avg) including growth cessation, were reversible and reproducible, independent of the direction of the u-changes and solution purity. Hence, we attribute the deceleration to the convection-enhanced supply of impurities to the interface, which at higher flow rates overpowers the effects of enhanced interfacial solute concentration. Most importantly, we found that convective transport leads to a significant reduction in kinetics fluctuations, in agreement with our earlier expectations for the lysozyme system. This supports our hypothesis that these long-term fluctuations represent an intrinsic response feature of the coupled bulk transport-interfacial kinetics system in the mixed growth control regime.

Vekilov, P. G.↗

Modelling and Estimation of Dynamic Ocean Topography Within Global Geopotential Solutions

In this poster, we will present a report on the ongoing investigation "Improved Gravitational and Dynamic Height Models Through the use of Oceanographic Data." we have used a two year mean (1993-1994) of the Dynamic ocean Topography (DOT) field implied by the Semtner and Chervin POCM_4B model, and developed normal equations in surface spherical harmonics to degree and order 30. These normal equations, were combined with normal equations derived from TOPEX and ERS-1 altimeter data over the same time period. Combination solutions (based on satellite tracking data, altimeter data, surface gravity data and OCM data) were were developed Test solutions were obtained estimating the DOT field to 2Ox2O and 3ox3O. These solutions were tested with independent DOT values computed over 38 WOCE hydrographic sections, which contained a total of 3072 stations and represented 216000 km of travelled lines. The weighted standard deviation of the differences between the DOT obtained from the hydrographic data and and the field estimated from the joint combination solutions was computed for each of the test models, the weighted standard deviation for the baseline combination solution excluding the POCM4_B data was 9.7 cm for a DOT solution to 30x30, where introducing the POCM4_B data into the combination model reduced the standard deviation to 9.2 cm, indicating the the introduction of oceanographic information benefits the solution for the dynamic ocean topography. We will discuss the weighting schemes applied and the method of solution. Another aspect of our investigation involves testing alternate parametric representations of the dynamic height field. We looked at the alternative representations in terms of the Proudman functions (PF), and compared these to the use of spherical harmonics (SH) to represent the dynamic ocean topography, using once again the 1993 and 1994 output of the POCM4_B OCM as the reference model. A significant advantage of PF's over SH's is that the former require no "fill-in" values over areas where the DOT is undefined. We show that the PF and SH results using equal number of parameters agree quite well in overall content. In addition, PFs appear better suited for representation of high frequency signals close to the signal boundary. The development of the PF solutions for the DOT will be described and the statistics of the comparisons will be presented.

Lemoine, Frank G.↗

Advanced in Visualization of 3D Time-Dependent CFD Solutions

Numerical simulations of complex 3D time-dependent (unsteady) flows are becoming increasingly feasible because of the progress in computing systems. Unfortunately, many existing flow visualization systems were developed for time-independent (steady) solutions and do not adequately depict solutions from unsteady flow simulations. Furthermore, most systems only handle one time step of the solutions individually and do not consider the time-dependent nature of the solutions. For example, instantaneous streamlines are computed by tracking the particles using one time step of the solution. However, for streaklines and timelines, particles need to be tracked through all time steps. Streaklines can reveal quite different information about the flow than those revealed by instantaneous streamlines. Comparisons of instantaneous streamlines with dynamic streaklines are shown. For a complex 3D flow simulation, it is common to generate a grid system with several millions of grid points and to have tens of thousands of time steps. The disk requirement for storing the flow data can easily be tens of gigabytes. Visualizing solutions of this magnitude is a challenging problem with today's computer hardware technology. Even interactive visualization of one time step of the flow data can be a problem for some existing flow visualization systems because of the size of the grid. Current approaches for visualizing complex 3D time-dependent CFD solutions are described. The flow visualization system developed at NASA Ames Research Center to compute time-dependent particle traces from unsteady CFD solutions is described. The system computes particle traces (streaklines) by integrating through the time steps. This system has been used by several NASA scientists to visualize their CFD time-dependent solutions. The flow visualization capabilities of this system are described, and visualization results are shown.

Lane, David A.↗

Lunar Dust and Lunar Simulant Activation, Monitoring, Solution and Cellular Toxicity Properties

During the Apollo missions, many undesirable situations were encountered that must be mitigated prior to returning humans to the moon. Lunar dust (that part of the lunar regolith less than 20 m in diameter) was found to produce several problems with astronaut s suits and helmets, mechanical seals and equipment, and could have conceivably produced harmful physiological effects for the astronauts. For instance, the abrasive nature of the dust was found to cause malfunctions of various joints and seals of the spacecraft and suits. Additionally, though efforts were made to exclude lunar dust from the cabin of the lunar module, a significant amount of material nonetheless found its way inside. With the loss of gravity correlated with ascent of the lunar module from the lunar surface to rendezvous with the command module, much of the major portions of the contaminating soil and dust began to float, irritating the astronaut s eyes and being inhaled into their lungs. Our goal has been to understand some of the properties of lunar dust that could lead to possible hazards for humans. Due to the lack of an atmosphere, there is nothing to protect the lunar soil from ultraviolet radiation, solar wind, and meteorite impacts. These processes could all serve to activate the soil, or produce reactive surface species. In order to understand the possible toxic effects of the reactive dust, it is necessary to reactivate the dust, as samples returned during the Apollo missions were exposed to the atmosphere of the Earth. We have used grinding and UV exposure to mimic some of the processes occurring on the Moon. The level of activation has been monitored using two methods: fluorescence spectroscopy and electron paramagnetic resonance spectroscopy (EPR). These techniques allow the monitoring of hydroxyl radical production in solution. We have found that grinding of lunar dust produces 2-3 times the concentration of hydroxyl radicals as lunar simulant and 10 times that of quartz. Exposure of the lunar dust to UV radiation under vacuum was also found to lead to hydroxyl radical production. After grinding, we have also monitored loss of reactivity of the dusts by exposing them to conditions of known humidity and temperature. From these tests, it was found that the reactivity half-life of lunar simulant is approximately 3 hours, while that of quartz is approximately 2 hours. Placing lunar dust in solution could lead to effects on mechanical and physiological systems, as well as other biological systems. For instance, while it is known that lunar dust is highly abrasive and caused a variety of problems with suits and equipment during Apollo, it is unknown as to how these properties might be affected in the presence of water or other liquids. It is possible that the dust may release minerals (e.g., metallic nanophase Fe) into solution that could speed corrosion or rust. Also, as lunar dust produces hydroxyl radicals (and possibly other reactive oxygen species) in solution, these radicals could also lead to the breakdown of suit or habitat materials. In the body (i.e., in lung solution), the effects could be two-fold. First, if the lunar dust dissolves, it may release an excess of elements (such as zero-valence metallic Fe) that are necessary for bodily functions but only in certain concentration ranges. For lunar dust, the presence of nanophase iron being released into the body is a concern. Secondly, the hydroxyl radicals or other reactive oxygen species produced by the dust in solution could conceivably interact with cells, leading to various problems. We have studied the dissolution of both ground and unground lunar simulant in buffer solutions of different pH. The concentration of a number of species was determined using mass spectrometry. These studies showed that lowering the pH of the solution causes a dramatic increase in the amount of each element released into solution and that grinding also produces higher concentrations. Finally, we have perfmed initial tests aimed at understanding the effects of lunar simulant on cellular systems. Alveolar epithelial cells were cultured and exposed to different concentrations of dust suspended in cell culture media. After predetermined amounts of time, the media was removed and the concentrations of important inflammatory cytokines (IL6, IL8, and TNF-alpha ) were measured. The results of these tests are being used to develop the correct protocols for tests to be performed using lunar dust samples.

Jeevarajan, A.S.↗

A General Closed-Form Solution for the Lunar Reconnaissance Orbiter (LRO) Antenna Pointing System

The National Aeronautics and Space Administration s (NASA) Lunar Reconnaissance Orbiter (LRO) launched on June 18, 2009 from the Cape Canaveral Air Force Station aboard an Atlas V launch vehicle into a direct insertion trajectory to the Moon LRO, designed, built, and operated by the NASA Goddard Space Flight Center in Greenbelt, MD, is gathering crucial data on the lunar environment that will help astronauts prepare for long-duration lunar expeditions. During the mission s nominal life of one year its six instruments and one technology demonstrator will find safe landing site, locate potential resources, characterize the radiation environment and test new technology. To date, LRO has been operating well within the bounds of its requirements and has been collecting excellent science data images taken from the LRO Camera Narrow Angle Camera (LROC NAC) of the Apollo landing sites have appeared on cable news networks. A significant amount of information on LRO s science instruments is provided at the LRO mission webpage. LRO s Attitude Control System (ACS), in addition to controlling the orientation of the spacecraft is also responsible for pointing the High Gain Antenna (HGA). A dual-axis (or double-gimbaled) antenna, deployed on a meter-long boom, is required to point at a selected Earth ground station. Due to signal loss over the distance from the Moon to Earth, pointing precision for the antenna system is very tight. Since the HGA has to be deployed in spaceflight, its exact geometry relative to the spacecraft body is uncertain. In addition, thermal distortions and mechanical errors/tolerances must be characterized and removed to realize the greatest gain from the antenna system. These reasons necessitate the need for an in-flight calibration. Once in orbit around the moon, a series of attitude maneuvers was conducted to provide data needed to determine optimal parameters to load onboard, which would account for the environmental and mechanical errors at any antenna orientation. The nominal geometry for the HGA involves an outer gimbal axis that is exactly perpendicular to the inner gimbal axis, and a target direction that is exactly perpendicular to the outer gimbal axis. For this nominal geometry, closed-form solutions of the desired gimbal angles are simple to get for a desired target direction specified in the spacecraft body fame. If the gimbal axes and the antenna boresight are slightly misaligned, the nominal closed-form solution is not sufficiently accurate for computing the gimbal angles needed to point at a target. In this situation, either a general closed-form solution has to be developed for a mechanism with general geometries, or a correction scheme has to be applied to the nominal closed-form solutions. The latter has been adopted for Solar Dynamics Observatory (SDO) as can be seen in Reference 1, and the former has been used for LRO. The advantage of the general closed-form solution is the use of a small number of parameters for the correction of nominal solutions, especially in the regions near singularities. Singularities here refer to cases when the nominal closed-form solutions have two or more solutions. Algorithm complexity, however, is the disadvantage of the general closed-form solution.

Shah, Neerav↗

On the Solution of the Continuity Equation for Precipitating Electrons in Solar Flares

Electrons accelerated in solar flares are injected into the surrounding plasma, where they are subjected to the influence of collisional (Coulomb) energy losses. Their evolution is modeled by a partial differential equation describing continuity of electron number. In a recent paper, Dobranskis & Zharkova claim to have found an "updated exact analytical solution" to this continuity equation. Their solution contains an additional term that drives an exponential decrease in electron density with depth, leading them to assert that the well-known solution derived by Brown, Syrovatskii & Shmeleva, and many others is invalid. We show that the solution of Dobranskis & Zharkova results from a fundamental error in the application of the method of characteristics and is hence incorrect. Further, their comparison of the "new" analytical solution with numerical solutions of the Fokker-Planck equation fails to lend support to their result.We conclude that Dobranskis & Zharkova's solution of the universally accepted and well-established continuity equation is incorrect, and that their criticism of the correct solution is unfounded. We also demonstrate the formal equivalence of the approaches of Syrovatskii & Shmeleva and Brown, with particular reference to the evolution of the electron flux and number density (both differential in energy) in a collisional thick target. We strongly urge use of these long-established, correct solutions in future works.

Sun: flares↗

Intermediate accelerated solutions as generic late-time attractors in a modified Jordan-Brans-Dicke theory

In this paper we investigate the evolution of a Jordan-Brans-Dicke scalar field, Φ, with a power-law potential in the presence of a second scalar field, φ, with an exponential potential, in both the Jordan and the Einstein frames. We present the relation of our model with the induced gravity model with power-law potential and the integrability of this kind of models is discussed when the quintessence field φ is massless, and has a small velocity. The fact that for some fine-tuned values of the parameters we may get some integrable cosmological models, makes our choice of potentials very interesting. We prove that in Jordan-Brans-Dicke theory, the de Sitter solution is not a natural attractor. Instead, we show that the attractor in the Jordan frame corresponds to an ''intermediate accelerated'' solution of the form a(t) ≅ e{sup α{sub 1} t{sup p{sup {sub 1}}}}, as t → ∞ where α{sub 1} > 0 and 0 < p{sub 1} < 1, for a wide range of parameters. Furthermore, when we work in the Einstein frame we get that the attractor is also an ''intermediate accelerated'' solution of the form a(t) ≅ e{sup α{sub 2} tp{sub 2}} as t → ∞ where α{sub 2} > 0 and 0<p{sub 2}<1, for the same conditions on the parameter space as in the Jordan frame. In the special case of a quadratic potential in the Jordan frame, or for a constant potential in the Einstein's frame, the above intermediate solutions are of saddle type. These results were proved using the center manifold theorem, which is not based on linear approximation. Finally, we present a specific elaboration of our extension of the induced gravity model in the Jordan frame, which corresponds to a particular choice of a linear potential of Φ. The dynamical system is then reduced to a two dimensional one, and the late-time attractor is linked with the exact solution found for the induced gravity model. In this example the ''intermediate accelerated'' solution does not exist, and the attractor solution has an asymptotic de Sitter-like evolution law for the scale factor. Apart from some fine-tuned examples such as the linear, and quadratic potential U(Φ) in the Jordan frame, it is true that ''intermediate accelerated'' solutions are generic late-time attractors in a modified Jordan-Brans-Dicke theory.

79 ASTRONOMY AND ASTROPHYSICS↗

Crystallization of Trehalose in Frozen Solutions and its Phase Behavior during Drying

To study the crystallization of trehalose in frozen solutions and to understand the phase transitions during the entire freeze-drying cycle. Aqueous trehalose solution was cooled to -40 C in a custom-designed sample holder. The frozen solution was warmed to -18 C and annealed, and then dried in the sample chamber of the diffractometer. XRD patterns were continuously collected during cooling, annealing and drying. After cooling, hexagonal ice was the only crystalline phase observed. However, upon annealing, crystallization of trehalose dihydrate was evident. Seeding the frozen solution accelerated the solute crystallization. Thus, phase separation of the lyoprotectant was observed in frozen solutions. During drying, dehydration of trehalose dihydrate yielded a substantially amorphous anhydrous trehalose. Crystallization of trehalose, as trehalose dihydrate, was observed in frozen solutions. The dehydration of the crystalline trehalose dihydrate to substantially amorphous anhydrate occurred during drying. Therefore, analyzing the final lyophile will not reveal crystallization of the lyoprotectant during freeze-drying. The lyoprotectant crystallization can only become evident by continuous monitoring of the system during the entire freeze-drying cycle. In light of the phase separation of trehalose in frozen solutions, its ability to serve as a lyoprotectant warrants further investigation.

99 GENERAL AND MISCELLANEOUS↗

Numerical similarity solution for a variable coefficient K(m, n) equation

A technique for finding numerical similarity solutions to an initial boundary value problem (IBVP) for generalized K(m, n) equations is described. The equation under consideration is nonlinear and has variable coefficients. The original problem is transformed with the aid of Lie symmetries to an initial value problem (IVP) for a nonlinear third-order ordinary differential equation. The existence and uniqueness of the solution are examined, and the problem is consequently solved with the aid of a finite-difference scheme for various values of the governing parameters. In lieu of an exact symbolic solution, the scheme is validated by comparing the numerical solutions with the approximate analytic solutions obtained with the aid of the method of successive approximations in their region of validity. The accuracy, efficiency, and consistency of the scheme are demonstrated. Numerical solutions to the original initial boundary value problem are constructed for selected parameter values with the aid of the transforms. The qualitative behavior of the solutions as a function of the governing parameters is analyzed, and it is found that the examined IBVPs for generalized K(m, n) equations with variable coefficients that are functions of time, do not admit solitary wave or compacton solutions.

97 MATHEMATICS AND COMPUTING↗

Analytical solution for two-phase flow in a wellbore using the drift-flux model

This paper presents analytical solutions for steady-state, compressible two-phase flow through a wellbore under isothermal conditions using the drift flux conceptual model. Although only applicable to highly idealized systems, the analytical solutions are useful for verifying numerical simulation capabilities that can handle much more complicated systems, and can be used in their own right for gaining insight about two-phase flow processes in wells. The analytical solutions are obtained by solving the mixture momentum equation of steady-state, two-phase flow with an assumption that the two phases are immiscible. These analytical solutions describe the steady-state behavior of two-phase flow in the wellbore, including profiles of phase saturation, phase velocities, and pressure gradients, as affected by the total mass flow rate, phase mass fraction, and drift velocity (i.e., the slip between two phases). Close matching between the analytical solutions and numerical solutions for a hypothetical CO{sub 2} leakage problem as well as to field data from a CO{sub 2} production well indicates that the analytical solution is capable of capturing the major features of steady-state two-phase flow through an open wellbore, and that the related assumptions and simplifications are justified for many actual systems. In addition, we demonstrate the utility of the analytical solution to evaluate how the bottomhole pressure in a well in which CO{sub 2} is leaking upward responds to the mass flow rate of CO{sub 2}-water mixture.

42 ENGINEERING↗

Static and spherically symmetric solutions in a scenario with quadratic curvature contribution

In this work we investigate analytic static and spherically symmetric solutions of a generalized theory of gravity in the Einstein–Cartan formalism. The main goal consists in analysing the behaviour of the solutions under the influence of a quadratic curvature term in the presence of cosmological constant and no torsion. In the first incursion we found an exact de Sitter-like solution. This solution is obtained by imposing vanishing torsion in the field equations. On the other hand, by imposing vanishing torsion directly in the action, we are able to find a perturbative solution around the Schwarzschild–de Sitter usual solution. We briefly discuss classical singularities for each solution and the event and cosmological horizons. A primer discussion on the thermodynamics of the geometrical solutions is also addressed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Aqueous geochemistry at gigapascal pressures: NMR spectroscopy of fluoroborate solutions

Aqueous geochemistry could be extended considerably if nuclear-magnetic resonance (NMR) methods could be adapted to study solutions at elevated temperatures and pressures. We therefore designed an NMR probe that can be used to study aqueous solutions at gigapascal pressures. Fluoride solutions were chosen for study because 19 F couples to other nuclei in the solutions ( 31 P and 11 B) in ways that make peak assignments unequivocal. Correspondingly, NMR spectra of 19 F- and 11 B were collected on aqueous HBF 4 -NH 4 PF 6 solutions to pressures up to 2.0 GPa. At pressure, peaks in the 19 F spectra were clear and assignable to the BF 4 – (aq), F – (aq) and BF 3 OH – (aq) ions, and these aqueous complexes varied in signal intensity with pressure and time, for each solution. Peaks in the 11 B spectra at pressure could be assigned to the BF 4 – (aq) and BF 3 OH – (aq) species. Additionally, there is a single peak that is assignable to H 3 BO 3 o (aq) and B(OH) 4 – (aq) in rapid-exchange equilibria. These peaks broaden and move with pressure in ways that suggest reversible interconversion of borate and fluoroborate species. The PF 6 – ion was found to provide a suitable 19 F shift and intensity standard for high-pressure spectra because it was chemically inert. Here, the positions and intensities of the doublet peak also remains constant as a function of pressure and pH. Addition of electrolytes considerably distorts the phase diagram of water such that the stability region of the aqueous solution expands to well beyond the 0.8 GPa freezing pressure of pure water; some fluoroborate solutions remain liquid until almost 2.0 GPa.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nonrelativistic grey S n -transport radiative-shock solutions

We present semi-analytic radiative-shock solutions in which grey Sn-transport is used to model the radiation, and we include both constant cross sections and cross sections that depend on temperature and density. These new solutions solve for a variable Eddington factor (VEF) across the shock domain, which allows for interesting physics not seen before in radiative-shock solutions. Comparisons are made with the grey nonequilibrium-diffusion radiative-shock solutions of Lowrie and Edwards [1], which assumed that the Eddington factor is constant across the shock domain. It is our experience that the local Mach number is monotonic when producing nonequilibrium-diffusion solutions, but that this monotonicity may disappear while integrating the precursor region to produce Sn-transport solutions. For temperature- and density-dependent cross sections we show evidence of a spike in the VEF in the far upstream portion of the radiative-shock precursor. We show evidence of an adaptation zone in the precursor region, adjacent to the embedded hydrodynamic shock, as conjectured by Drake [2, 3], and also confirm his expectation that the precursor temperatures adjacent to the Zel’dovich spike take values that are greater than the downstream post-shock equilibrium temperature. We also show evidence that the radiation energy density can be nonmonotonic under the Zel’dovich spike, which is indicative of anti-diffusive radiation flow as predicted by McClarren and Drake [4]. We compare the angle dependence of the radiation flow for the Sn-transport and nonequilibriumdiffusion radiation solutions, and show that there are considerable differences in the radiation flow between these models across the shock structure. Lastly, we analyze the radiation flow to understand the cause of the adaptation zone, as well as the structure of the Sn-transport radiation-intensity solutions across the shock structure.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Effects of Ag and Zr solutes on dislocation emission from Σ11(332)[110] symmetric tilt grain boundaries in Cu: Bigger is not always better

Solute additions are commonly used to stabilize nanocrystalline materials against grain growth, and can simultaneously enhance the strength of the material by impeding dislocation emission from the grain boundaries. In this study we demonstrate using molecular dynamics (MD) simulations that the effect of solutes on dislocation nucleation depends on the distribution of solutes at the grain boundary, and can vary dramatically depending on the solute type. Solutes with a smaller positive size mismatch to the host can be more effective in suppressing dislocation emission from grain boundaries than others that have larger mismatch. In particular, although Ag solutes have a smaller misfit with Cu than Zr solutes, the effect of Ag on the dislocation nucleation from grain boundaries in Cu can be larger than the corresponding effect of Zr. Furthermore, these findings are relevant to the search for optimal solute additions, which can strengthen a nanocrytalline material by suppressing the nucleation of dislocation slip from grain boundaries, while stabilizing it against grain growth.

36 MATERIALS SCIENCE↗

A new soil mixing layer model for simulating conservative solute loss from initially saturated soil to surface runoff

Surface water pollution due to solute loss from soil to surface runoff is a serious threat to the environment, and it is of great significance to predict the solute loss. While soil mixing layer theory has been widely used to predict the solute loss, it has been observed that the conventional soil mixing layer models with constant mixing layer depth underestimate solute concentration in surface runoff, and thus underestimate the solute loss after surface runoff starts. This study introduced a new soil mixing layer model with a new concept that the mixing layer depth increases downward with time after surface runoff occurs. This new concept was implemented by adding a mixing front between the soil mixing layer and its underlying soil layer, which is conceptually similar to the wetting front of soil infiltration given by the Green-Ampt equation. This is equivalent to treating the soil mixing layer as a deforming control volume. A mechanistic explanation for the new model was presented. This study also developed a closed form solution of the new model. The new model was evaluated by simulating five laboratory experiments conducted by two groups of researchers. The first two experiments have ponding water, and consider different drainage and runoff conditions at both early and late runoff times. The other three experiments do not have ponding water, and consider different infiltration conditions at the bottom of soil boxes. Simulation results of the five experiments show that the new model resolves the underestimation problem of conventional soil mixing layer models. The new model is subject to a total of six limits such as that the new model only considers conservative solute. Three limits are related to the assumptions used to derive the closed form solution, and they may be alleviated in a future research as briefly discussed at the end of the paper.

54 ENVIRONMENTAL SCIENCES↗

Solid state synthesis, crystal growth and optical properties of urea and p-chloronitrobenzene solid solution

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 and 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.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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

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, 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.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

On Thermodynamic and Kinetic Mechanisms for Stabilizing Surface Solid Solutions

Many processes for energy storage rely on transformations between phases with strong separation tendencies. In these systems, performance limitations can arise from undesirable chemical and mechanical factors associated with the phase separation behavior. Solid solutions represent a desirable alternative, provided the conditions for their formation are known. In the present work, we invoke linear stability theory and diffuse-interface mesoscopic simulations to demonstrate that solid solutions can be stabilized near surface layers of phase-separating systems. Two factors are found to drive surface solid-solution formation: surface relaxation of solution self-strain energy and anisotropy of diffusion mobility. Using a strongly phase-separating LiXFePO4 particle as a model system, we show that the relaxation of the solution self-strain energy competes against the relaxation of the coherency strain energy to stabilize surface solid solutions. Our theoretical understanding also suggests that highly anisotropic diffusion mobility can provide an alternative kinetic route to achieve the same aim, with stabilizing behavior strongly dependent on the specific alignment of the surface orientation. Our findings provide fundamental guidance for manipulating solid-solution behavior in nanoscale structures, in which surface effects become especially significant. Beyond energy storage materials, our findings have important implications for understanding solid-solution formation in other phase-separating systems from metal alloys to ceramics.

25 ENERGY STORAGE↗