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At least 595 records · Page 33
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

First principles prediction of the Al-Li phase diagram including configurational and vibrational entropic contributions

The whole Al-Li phase diagram is predicted from first principles calculations and statistical mechanics including the effect of configurational and vibrational entropy. The formation enthalpy of different configurations at different temperatures was accurately predicted by means of cluster expansions that were fitted from first principles calculations. The vibrational entropic contribution of each configuration was determined from the bond length vs. bond stiffness relationships for each type of bond and the Gibbs free energy of the different phases was obtained as a function of temperature from Monte Carlo simulations. The predicted phase diagram was in excellent agreement with the currently accepted experimental one in terms of the stable (AlLi, Al 2 Li 3 , AlLi 2 , Al 4 Li 9 ) and metastable (Al 3 Li) phases, of the phase boundaries between them and of the maximum stability temperature of line compounds. In addition, it provided accurate information about the gap between Al 3 Li and AlLi solvus lines. Finally, the influence of the vibrational entropy on the correct prediction of the phase diagram is discussed. Overall, the methodology shows that accurate phase diagrams of alloys of technological interest can be predicted from first principles calculations.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Polymorphic structure evolution and large piezoelectric response of lead-free (Ba,Ca)(Zr,Ti)O{sub 3} ceramics

The polymorphic structure evolution of (Ba,Ca)(Zr,Ti)O{sub 3} piezoelectric ceramics was investigated by analysis of the in situ X-ray diffraction and dielectric spectra. The results indicated that a confined orthorhombic (O) phase region induced by the approach of the rhombohedral (R) and tetragonal (T) phases existed in an extremely narrow temperature range of (Ba{sub 0.85}Ca{sub 0.15})(Zr{sub 0.1}Ti{sub 0.9})O{sub 3} composition. The electric properties near the O–T phase boundaries of (Ba{sub 0.95}Ca{sub 0.05})(Zr{sub 0.05}Ti{sub 0.95})O{sub 3} and (Ba{sub 0.85}Ca{sub 0.15})(Zr{sub 0.1}Ti{sub 0.9})O{sub 3} were compared. The results suggested that the confined O phase region is an important factor that contributes to the extremely large piezoelectric response.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Communication: Spin-boson model with diagonal and off-diagonal coupling to two independent baths: Ground-state phase transition in the deep sub-Ohmic regime

We investigate a spin-boson model with two boson baths that are coupled to two perpendicular components of the spin by employing the density matrix renormalization group method with an optimized boson basis. It is revealed that in the deep sub-Ohmic regime there exists a novel second-order phase transition between two types of doubly degenerate states, which is reduced to one of the usual types for nonzero tunneling. In addition, it is found that expectation values of the spin components display jumps at the phase boundary in the absence of bias and tunneling.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Theoretical study on phase coexistence in ferroelectric solid solutions near the tricritical point

Phase coexistence in ferroelectric solid solutions near the tricritical point has been theoretically analyzed by using the Landau-Devonshire theory. Results revealed that different phases having similar potential wells could coexist in a narrow composition range near the tricritical point in the classical Pb(Zr{sub 1−x}Ti{sub x})O{sub 3} system. The potential barrier between potential wells increases with the decrease of temperature. Coexisting phases or different domains of the same phase can produce adaptive strains to maintain atomic coherency at the interfaces or domain walls. Such compatibility strains have influence on the energy potential as well as the stability of relative phases, leading to the appearance of energetically unfavorable monoclinic phases. Those competing and coexisting phases also construct an easy phase transition path with small energy barrier in between, so that very small stimuli can produce large response in compositions near the morphotropic phase boundary, especially near the tricritical point.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Phase transitions, domain structure, and pseudosymmetry in La- and Ti-doped BiFeO{sub 3}

The phase transitions and domain structure of the promising PbO-free solid solution series, (0.95-x)BiFeO{sub 3}-xLaFeO{sub 3}-0.05La{sub 2/3}TiO{sub 3}, were investigated. X ray diffraction (XRD) revealed a transition from a ferroelectric R3c to a PbZrO{sub 3}-like (Pbam) antiferroelectric (AFE) structure at x = 0.15 followed by a transition to a paraelectric (PE, Pnma) phase at x > 0.30. The ferroelastic/ferroelectric twin domain width decreased to 10–20 nm with increasing x as the AFE phase boundary was approached but coherent antiphase tilted domains were an order of magnitude greater. This domain structure suggested the local symmetry (20 nm) is lower than the average structure (R3c, a{sup −}a{sup −}a{sup −}) of the tilted regions. The PE phase (x = 0.35) exhibited a dominant a{sup −}a{sup −}c{sup +} tilt system with Pnma symmetry but diffuse reflections at ∼1/4(ooe) positions suggest that short range antipolar order is residual in the PE phase. The complex domain structure and phase assemblage of this system challenge the conventional interpretation of phase transitions based on macroscopic symmetry. Instead, it supports the notion that frustration driven by chemical distributions at the nanometric level influences the local or pseudo-symmetry as well as the domain structure, with XRD giving only the average macroscopic structure.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2026

Mott vs Kondo: Influence of various density functional based methods on the Ce isostructural phase transition mechanism

The cerium iso-structural phase transition (γ–α) is dominated by f-electron localization changes that results in a magnetic ordering change and a volume collapse. Generally, these physics are difficult to capture with ab initio and first principles methods. However, previous works have shown various methods to be successful in predicting at least some of the physics of the γ to α phase transition. Therefore, here, we perform a broad survey of density functional based methods across three levels of theory and types of functions [GGA (generalized gradient approximation), MetaGGA, and hybrid functionals] and compare the results, focusing on hydrostatic compression across the phase boundary at zero kelvin. For the methods that best reproduce experimental results, we directly probe the predicted mechanisms and frame the results in the Mott/Kondo debate, assessing how the underlying methods and assumptions of different functionals can assess the physical drivers in the phase transition, providing insight into the governing processes of this unique phase transition.

36 MATERIALS SCIENCE↗
NASA NTRS1982

Studies on aqueous two phase polymer systems useful for partitioning of biological materials

The two phase systems that result when aqueous solutions of dextran and poly(ethylene glycol) (PEG) are mixed above a critical concentration of a few percent provide a useful medium for the separation of biological cell subpopulations via partition between the top, PEG-rich phase and the liquid-liquid phase boundary. Interfacial tensions of such systems have been measured by the rotating drop technique and found to range between 0.1-100 micro-N/m. The tension was found to depend on the length of the tie line describing the system on a phase diagram, via a power law relationship which differed depending on the concentration of Na phosphate buffer present. The electrokinetic properties of drops of one phase suspended in the other were studied for a variety of systems. It was found that the droplet electrophoretic mobility increased monotonically with phosphate concentration and drop diameter but exhibited the opposite sign from that anticipated from phosphate partition measurements. It was possible to take advantage of these electrokinetic properties and dramatically enhance the speed of phase separation through application of relatively small electric fields.

Brooks, D. E.↗
DOE OSTI2013

Magnetotransport properties of quasi-one-dimensionally channeled vertically aligned heteroepitaxial nanomazes

A unique quasi-one-dimensionally channeled nanomaze structure has been self-assembled in the (La{sub 0.7}Sr{sub 0.3}MnO{sub 3}){sub 1−x}:(ZnO){sub x} vertically aligned nanocomposites (VANs). Significantly enhanced magnetotransport properties have been achieved by tuning the ZnO composition x. The heteroepitaxial VAN thin films, free of large angle grain boundaries, exhibit a maximum low-field magnetoresistance (LFMR) of 75% (20 K and 1 T). The enhanced LFMR close to the percolation threshold is attributed to the spin-polarized tunneling through the ferromagnetic/insulating/ferromagnetic vertical sandwiches in the nanomazes. This study suggests that the phase boundary in the nanomaze structure is an alternative approach to produce decoupled ferromagnetic domains and thus to achieve enhanced magnetoresistance.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2016

From Rate Measurements to Mechanistic Data for Condensed Matter Reactions: A Case Study Using the Crystallization of [Zn(OH 2 ) 6 ][ZnCl 4 ]

The kinetics of crystallization of the R = 3 hydrate of zinc chloride, [Zn(OH 2 ) 6 ][ZnCl 4 ], is measured by time-resolved synchrotron x-ray diffraction, time-resolved neutron diffraction, and by differential scanning calorimetry. It is shown that analysis of the rate data using the classic Kolmogorov, Johnson, Mehl, Avrami (KJMA) kinetic model affords radically different rate constants for equivalent reaction conditions. Reintroducing the amount of sample measured by each method into the kinetic model, using our recently developed modified-KJMA model (M-KJMA), it is shown that each of these diverse rate measurement techniques can give the intrinsic, material specific rate constant, the velocity of the phase boundary, v pb . These data are then compared to the velocity of the crystallization front directly measured optically. The time-resolved diffraction methods uniquely monitor the loss of the liquid reactant and formation of the crystalline product demonstrating that the crystallization of this hydrate phase proceeds through no intermediate phases. The temperature dependent v pb data are then well fit to transition zone theory to extract activation parameters. These demonstrate that the rate-limiting component to this crystallization reaction is the ordering of the waters (or protons) of hydration into restricted positions of the crystalline lattice resulting in large negative entropy of activation.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Determination of density of states, conduction mechanisms and dielectric properties of nickel disulfide nanoparticles

Temperature and frequency dependent ac electrical measurements were used to explore density of states, conduction mechanisms and dielectric properties of nickel disulfide (NiS{sub 2}) nanoparticles. The NiS{sub 2} nanoparticles were prepared by conventional one step solid state reaction method at 250 °C. X-ray diffraction (XRD) confirmed cubic phase of prepared nanoparticles. Scanning electron microscope (SEM) images revealed presence of irregular shaped nanoparticles as small as 50 nm. The ac electrical measurements were carried out from 300 K to 413 K. Two depressed semicircular arcs from 20 Hz to 2 MHz showed presence of bulk and grain boundary phases in NiS{sub 2} nanoparticles at all temperatures. Small polaron hopping conduction from 300 K to 393 K and correlated barrier hopping conduction mechanism at temperatures higher than 393 K was observed. High value of density of states (of the order of 10{sup 24} eV{sup −1}cm{sup −3}) was calculated from ac conductivity. At low frequencies high values (of the order of 10{sup 4}-10{sup 7}) of real part of dielectric constant (ε′) were observed at different temperatures. These observations suggest that NiS{sub 2} nanoparticles may find applications in electronic devices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2013

Higher-order compositional modeling of three-phase flow in 3D fractured porous media based on cross-flow equilibrium

Numerical simulation of multiphase compositional flow in fractured porous media, when all the species can transfer between the phases, is a real challenge. Despite the broad applications in hydrocarbon reservoir engineering and hydrology, a compositional numerical simulator for three-phase flow in fractured media has not appeared in the literature, to the best of our knowledge. In this work, we present a three-phase fully compositional simulator for fractured media, based on higher-order finite element methods. To achieve computational efficiency, we invoke the cross-flow equilibrium (CFE) concept between discrete fractures and a small neighborhood in the matrix blocks. We adopt the mixed hybrid finite element (MHFE) method to approximate convective Darcy fluxes and the pressure equation. This approach is the most natural choice for flow in fractured media. The mass balance equations are discretized by the discontinuous Galerkin (DG) method, which is perhaps the most efficient approach to capture physical discontinuities in phase properties at the matrix-fracture interfaces and at phase boundaries. In this work, we account for gravity and Fickian diffusion. The modeling of capillary effects is discussed in a separate paper. We present the mathematical framework, using the implicit-pressure-explicit-composition (IMPEC) scheme, which facilitates rigorous thermodynamic stability analyses and the computation of phase behavior effects to account for transfer of species between the phases. A deceptively simple CFL condition is implemented to improve numerical stability and accuracy. We provide six numerical examples at both small and larger scales and in two and three dimensions, to demonstrate powerful features of the formulation.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2015

Atom probe tomography study of internal interfaces in Cu{sub 2}ZnSnSe{sub 4} thin-films

We report on atom probe tomography studies of the composition at internal interfaces in Cu{sub 2}ZnSnSe{sub 4} thin-films. For Cu{sub 2}ZnSnSe{sub 4} precursors, which are deposited at 320 °C under Zn-rich conditions, grain boundaries are found to be enriched with Cu irrespective of whether Cu-poor or Cu-rich growth conditions are chosen. Cu{sub 2}ZnSnSe{sub 4} grains are found to be Cu-poor and excess Cu atoms are found to be accumulated at grain boundaries. In addition, nanometer-sized ZnSe grains are detected at or near grain boundaries. The compositions at grain boundaries show different trends after annealing at 500 °C. Grain boundaries in the annealed absorber films, which are free of impurities, are Cu-, Sn-, and Se-depleted and Zn-enriched. This is attributed to dissolution of ZnSe at the Cu-enriched grain boundaries during annealing. Furthermore, some of the grain boundaries of the absorbers are enriched with Na and K atoms, stemming from the soda-lime glass substrate. Such grain boundaries show no or only small changes in composition of the matrix elements. Na and K impurities are also partly segregated at some of the Cu{sub 2}ZnSnSe{sub 4}/ZnSe interfaces in the absorber, whereas for the precursors, only Na was detected at such phase boundaries possibly due to a higher diffusivity of Na compared to K. Possible effects of the detected compositional fluctuations on cell performance are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Quantifying intermediate-frequency heterogeneities of SOFC electrodes using X-ray computed tomography

The electrodes in solid oxide fuel cells (SOFCs) consist of three phases interconnected in three dimensions. The volume needed to describe quantitatively such microstructures depends on several lengths scales, which are functions of materials properties and fabrication methods. This work focuses on quantifying the volume needed to represent “intermediate frequency” heterogeneities in electrodes of a commercial SOFC using X-ray computed tomography (CT) over two different length scales. Electrode volumes of 150 x 150 x 9 μm 3 were extracted from a synchrotron-based micro-CT data set, with 13 μm 3 voxels. 13.6 x 19.8 x 19.4 μm 3 of the cathode and 26.3 x 24.8 x 15.7 μm 3 of the anode were extracted from laboratory nano-CT data sets, both with 65 3 nm 3 voxels. After comparing the variation across sub-regions for the greyscale values from the micro-CT, and for the phase fractions and triple phase boundary densities from the nano-CT, it was found that the sub-region length scales needed to yield statistically similar average values were an order of magnitude larger than those expected to capture the “high frequency” heterogeneity related to the discrete nature of the three phases in electrodes. In conclusion, the challenge of quantifying such electrodes using available experimental methods is discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Phase transition dynamics in one-dimensional halide perovskite crystals

Triiodide perovskites CsPbI 3 , CsSnI 3 , and FAPbI 3 (where FA is formamidinium) are highly promising materials for a range of optoelectronic applications in energy conversion. However, they are thermodynamically unstable at room temperature, preferring to form low-temperature (low-T) non-perovskite phases with one-dimensional anisotropic crystal structures. While such thermodynamic behavior represents a major obstacle toward realizing high-performance devices based on their high-temperature (high-T) perovskite phases, the underlying phase transition dynamics are still not well understood. In this work, we use in situ optical micro-spectroscopy to quantitatively study the transition from the low-T to high-T phases in individual CsSnI 3 and FAPbI 3 nanowires. We reveal a large blueshift in the photoluminescence (PL) peak (~38 meV) at the low-T/high-T two-phase interface of partially transitioned FAPbI 3 wire, which may result from the lattice distortion at the phase boundary. Compared to the experimentally derived activation energy of CsSnI 3 (~1.93 eV), the activation energy of FAPbI 3 is relatively small (~0.84 eV), indicating a lower kinetic energy barrier when transitioning from a face-sharing octahedral configuration to a corner-sharing one. Further, the phase propagation rate in CsSnI 3 is observed to be relatively high, which may be attributed to a high concentration of Sn vacancies. Our results could not only facilitate a deeper understanding of phase transition dynamics in halide perovskites with anisotropic crystal structures, but also enable controllable manipulation of optoelectronic properties via local phase engineering.

36 MATERIALS SCIENCE↗
DOE OSTI2016

In-situ transmission electron microscopy imaging of formation and evolution of Li{sub x}WO{sub 3} during lithiation of WO{sub 3} nanowires

The phase transition from monoclinic WO{sub 3} to cubic Li{sub x}WO{sub 3} during lithiation of WO{sub 3} is one of the key features for tungsten oxide as the most used electrochromic material. Conventionally, the lithium intercalation of WO{sub 3} has been studied by building generic layered electrochromic device combining with structural characterization and electrochemistry measurement at macro scale. In-situ transmission electron microscopy (in-situ TEM) has been proposed as a method for revealing the detailed mechanism of structural, physical, and chemical properties. Here, we use in-situ TEM method to investigate the formation and evolution of Li{sub x}WO{sub 3} in real-time during the electrochemical lithiation of WO{sub 3} nanowires. The dynamic lithiation process is recorded by TEM imaging, diffraction, and electron energy loss spectroscopy. The WO{sub 3}-Li{sub x}WO{sub 3} phase boundary of reaction front has been observed at high resolution. The timeliness of crystallinity of Li{sub x}WO{sub 3} and the intercalation channels for Li ions are also identified. Moreover, the co-existence of both polycrystalline Li-poor area and amorphous Li-rich phases of Li{sub x}WO{sub 3} was found. Our results provide an insight into the basic lithiation process of WO{sub 3}, which is significantly important for understanding the electrochromic mechanism of tungsten oxide.

36 MATERIALS SCIENCE↗
NASA NTRS2001

Calculation of Phase Equilibria in the Y2O3-Yb2O3-ZrO2 System

Rare earth oxide stabilized zirconias find a wide range of applications. An understanding of phase equilibria is essential to all applications. In this study, the available phase boundary data and thermodynamic data is collected and assessed. Calphad-type databases are developed to completely describe the Y2O3-ZrO2, Yb2O3-ZrO2, and Y2O3-Yb2O3 systems. The oxide units are treated as components and regular and subregular solution models are used. The resultant calculated phase diagrams show good agreement with the experimental data. Then the binaries are combined to form the database for the Y2O3-Yb2O3-ZrO2 psuedo-ternary.

Jacobson, Nathan S.↗
DOE OSTI2013

Effects of high energy Au-ion irradiation on the microstructure of diamond films

The effects of 2.245 GeV Au-ion irradiation and subsequent annealing processes on the evolution of microstructure of diamond films with microcrystalline (MCD) or ultra-nanocrystalline (UNCD) granular structure were investigated, using near edge x-ray absorption fine structure and electron energy loss spectroscopy in transmission electron microscopy. For MCD films, the Au-ion irradiation disintegrated some of the diamond grains, resulting in the formation of nano-sized carbon clusters embedded in a matrix of amorphous carbon (a-C). The annealing process recrystallized the diamond grains and converted the a-C into nano-sized graphite particulates and, at the same time, induced the formation of nano-sized i-carbon clusters, the bcc structured carbon with a{sub 0} = 0.432 nm. In contrast, for UNCD films, the Au-ion irradiation transformed the grain boundary phase into nano-sized graphite, but insignificantly altered the crystallinity of the grains of the UNCD films. The annealing process recrystallized the materials. In some of the regions, the residual a-C phases were transformed into nano-sized graphites, whereas in other regions i-carbon nanoclusters were formed. The difference in irradiation-induced microstructural transformation behavior between the MCD and the UNCD films is ascribed to the different granular structures of the two types of films.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗