Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “phase pure”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Discovery and Characterization of a Metastable Cubic Interstitial Nickel–Carbon System with an Expanded Lattice

Metastable, i.e., kinetically favored but thermodynamically not stable, interstitial solid solutions of carbon in iron are well-understood. Carbon can occupy the interstitial atoms of the host metal, altering its properties. Alloying of the host metal results in the stabilization of the FeC x phases, widening its application. Pure nickel finds niche applications, mainly focusing on catalysis, while nickel alloys are widely applied, e.g., in gas turbines, reactors, and seawater piping. Nickel carbide (Ni 3 C) is the well-known stable Ni–C system displaying a rhombohedral (R3̅c) crystal structure. Some reports describe an elusive cubic Ni–C system, observed during certain catalytic reactions occurring on nickel and formed by the occupation of the interstitials of the metal with carbon: to date, the stabilization and characterization of this phase have not been accomplished. Hereby, we report on the synthesis of a cubic metastable NiC x phase using chemical vapor deposition of methane on supported nickel nanoparticles. The structure was predicted by DFT/ReaxFF, synthesized and monitored with in situ time-resolved synchrotron XRD, and experimentally confirmed by Rietveld refinement and (S)TEM-EELS under ambient conditions. The results show an Fm3̅m phase with a lattice parameter of a = 3.749 ± 0.037 Å at room temperature, with the highest ever reported atomic percentage of carbon occupying the octahedral interstices of 23.1%, resulting in a NiC 0.3 phase. The degree of occupation of the interstitial voids by carbon can be controlled, enabling the tuning of the host metal’s d-spacing and composition, highlighting the applicability of this synthesis route for catalytic nanoparticle preparation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Experiments on the Capillary Condensation/Evaporation Hysteresis of Pure Fluids and Binary Mixtures in Cylindrical Nanopores

Here, a new experimental method, i.e., isochoric cooling/heating cycle measurement using differential scanning calorimeter (DSC), is applied to investigate the hysteretic phenomenon of pure components and mixtures confined in two different types of cylindrical nanopores (SBA-15 and KIT-6). The capillary condensation/evaporation hysteresis end point (T he ) for a specific system is determined by performing a series of measurements with different densities by increasing initial temperature and pressure. We confirm that for a pure component, T he is lower when confined in smaller nanopores, whereas T he for CH 4 /CO 2 and CH 4 /C 2 H 6 mixtures at the specific composition investigated are higher than that of pure CO 2 and C 2 H 6 , respectively, when confined in the same nanopores. To the best of our knowledge, this is the first time that T he of fluid mixture is experimentally studied, which further demonstrates that binary mixtures behave similarly to pure fluids when confined in nanoporous media. At low temperatures where hysteresis is observed, the shape as well as the duration of the exothermic peak (due to capillary condensation) and endothermic peak (due to capillary evaporation) indicate that capillary condensation, rather than capillary evaporation, takes place at/near a thermodynamic equilibrium. Within the accuracy of the measurements, we find that the total heat of capillary condensation is identical to that of capillary evaporation for all systems examined, regardless of the presence of hysteresis. By comparing the heat per unit volume among different systems, we also find that the heat per unit volume of the phase transition of confined pure fluid is lower than that of bulk, which further demonstrates that the molar density of confined pure liquid is less than that of bulk pure liquid at saturation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Phase Diagram of Active Brownian Spheres: Crystallization and the Metastability of Motility-Induced Phase Separation

Motility-induced phase separation (MIPS), the phenomenon in which purely repulsive active particles undergo a liquid-gas phase separation, is among the simplest and most widely studied examples of a nonequilibrium phase transition. Here, we show that states of MIPS coexistence are in fact only metastable for three-dimensional active Brownian particles over a very broad range of conditions, decaying at long times through an ordering transition we call active crystallization. At an activity just above the MIPS critical point, the liquid-gas binodal is superseded by the crystal-fluid coexistence curve, with solid, liquid, and gas all coexisting at the triple point where the two curves intersect. Nucleating an active crystal from a disordered fluid, however, requires a rare fluctuation that exhibits the nearly close-packed density of the solid phase. The corresponding barrier to crystallization is surmountable on a feasible timescale only at high activity, and only at fluid densities near maximal packing. The glassiness expected for such dense liquids at equilibrium is strongly mitigated by active forces, so that the lifetime of liquid-gas coexistence declines steadily with increasing activity, manifesting in simulations as a facile spontaneous crystallization at incredibly high activity.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Systematic study on the phase transition of confined fluid mixture up to the critical region

Systematic experimental study on the phase transition of confined fluids up to the critical region has been performed, in which many new insights have been obtained. For confined pure fluids, compared to the bulk phase, the critical point shifts to lower pressure and temperature, but the relative shift of critical pressure is much larger than that of critical temperature. The behavior of the shift, i.e., the shift as a function of pore size, is dependent on the pore type. For confined fluid mixtures, compared to the bulk phase, the critical point also shifts to lower pressure and temperature, and the relative shift of critical pressure is also much larger than that of critical temperature. Confined fluid mixture behaves similarly to confined pure fluid, i.e., it exhibits hysteresis at lower temperature range and does not exhibit phase coexistence or phase envelope. An equation of state for confined pure fluids, based on the Generalized van der Waals partition function, has also been developed and demonstrated to accurately predict the capillary condensation of simple molecules in MCM-41. The parameters of the equation of state are derived from experimental critical point.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Understanding the Role of Cesium on Chemical Complexity in Methylammonium-Free Metal Halide Perovskites

Mixed cesium- and formamidinium-based metal halide perovskites (MHPs) are emerging as ideal photovoltaic materials due to their promising performance and improved stability. While theoretical predictions suggest that a larger composition ratio of Cs (≈30%) aids the formation of a pure photoactive α-phase, high photovoltaic performances can only be realized in MHPs with moderate Cs ratios. In fact, elemental mixing in a solution can result in chemical complexities with non-equilibrium phases, causing chemical inhomogeneities localized in the MHPs that are not traceable with global device-level measurements. Thus, the chemical origin of the complexities and understanding of their effect on stability and functionality remain elusive. Herein, through spatially resolved analyses, the fate of local chemical structures, particularly the evolution pathway of non-equilibrium phases and the resulting local inhomogeneities in MHPs is comprehensively explored. It is illustrated that Cs-rich MHPs have substantial local inhomogeneities at the initial crystallization step, which do not fully convert to the α-phase and thereby compromise the optoelectronic performance of the materials. These fundamental observations allow the authors to draw a complete chemical landscape of MHPs including nanoscale chemical mechanisms, providing indispensable insights into the realization of a functional materials platform.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

NOx sequestration by calcium aluminate cementitious materials

This study quantifies NO{sub x} uptake efficiency and explores NO{sub x} binding mechanisms in calcium aluminate cementitious (CAC) materials. Comparison between unmodified and TiO{sub 2}-modified CAC separates intrinsic NO{sub x} binding mechanisms from those related to photocatalysis. Attributed to surface-related heterogeneous reactions, the NO{sub x} binding occurs in unmodified CAC at nitrite-to-nitrate ratio of 1: 1.3 and can be increased with surface area. The photocatalytic reactions in TiO{sub 2}-modified CAC increase NO{sub x} uptake, and ~50% of converted NO{sub x} resists releasing back into the environment via dissolution. Compared to previously studied ordinary portland cement (OPC) materials, CAC increases NO{sub x} uptake capacity and demonstrates a more permanent NO{sub x} binding, potentially mitigating concerns related to the release of previously bound N-species in OPC. Examination of the interaction between NO{sub x} and a synthetic pure aluminum-bearing phase shows that the permanent NO{sub x} uptake in CAC could be largely attributed to the chemical binding of converted NO{sub x} within aluminum-bearing phases.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Deducing subnanometer cluster size and shape distributions of heterogeneous supported catalysts

Abstract Infrared (IR) spectra of adsorbate vibrational modes are sensitive to adsorbate/metal interactions, accurate, and easily obtainable in-situ or operando. While they are the gold standards for characterizing single-crystals and large nanoparticles, analogous spectra for highly dispersed heterogeneous catalysts consisting of single-atoms and ultra-small clusters are lacking. Here, we combine data-based approaches with physics-driven surrogate models to generate synthetic IR spectra from first-principles. We bypass the vast combinatorial space of clusters by determining viable, low-energy structures using machine-learned Hamiltonians, genetic algorithm optimization, and grand canonical Monte Carlo calculations. We obtain first-principles vibrations on this tractable ensemble and generate single-cluster primary spectra analogous to pure component gas-phase IR spectra. With such spectra as standards, we predict cluster size distributions from computational and experimental data, demonstrated in the case of CO adsorption on Pd/CeO 2 (111) catalysts, and quantify uncertainty using Bayesian Inference. We discuss extensions for characterizing complex materials towards closing the materials gap.

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

Observation of a mixed close-packed structure in superionic water

The study of superionic (SI) water has been a highly active research area since its theoretical prediction. Despite significant experimental and computational efforts, its melting curve and the stability of different oxygen lattices remain debated, impacting our understanding of SI ice’s peculiar transport properties. Experimental results at lower pressures show disagreement, whereas data at higher pressures are scarce due to the extreme challenges of such experiments. In this work, we present ultrafast X-ray diffraction results of water compressed by multiple shocks to pressures up to ~ 180 GPa. At pressures exceeding 150 GPa and temperatures around 2500 K, our diffraction patterns challenge the pure FCC-SI phase model, providing experimental evidence of the mixed close-packed superionic phase predicted by advanced ab initio calculations. At lower pressures, we observe simultaneous signatures of BCC and FCC structures within a pressure-temperature range consistent with some static-compression experiments, helping to resolve contradictory results in literature. These insights offer new constraints on the stability domains of SI phases and reveal detailed structural features, such as stacking faults. Our results advance the structural understanding of high-pressure SI ice to a level approaching that of ice I polymorphs, with potential implications for water-rich interiors of giant planets.

Andriambariarijaona, Leon [Centre National de la R↗
DOE OSTI2024

Advanced thermal/environmental barrier coatings of high-entropy rare earth disilicates tuned by strong anharmonicity of Eu 2 Si 2 O 7

Advancing thermal/environmental barrier coating (TEBC) materials with integrated thermal-mechanical functions is paramount for safeguarding SiC-based ceramic matrix composites (CMCs) in high-efficiency gas turbines. Herein, we employ a synergistic approach, combining density functional theory (DFT) methods and combinatorial chemistry techniques, to design high-performance and low-cost RE 2 Si 2 O 7 (RE = rare earth elements) TEBC materials tailored for enhanced compatibility with SiC-based CMCs. Expanding on phase stability of alloying pure RE 2 Si 2 O 7 , the investigation extends to the mechanical and thermal properties of solid solution systems, including Er 1/2 Y 3/4 Yb 3/4 Si 2 O 7 , Gd 1/4 Er 1/4 Y 3/4 Yb 3/4 Si 2 O 7 , and Eu 1/4 Er 1/4 Y 3/4 Yb 3/4 Si 2 O 7 . The solid solution systems exhibit a major reduction in lattice thermal conductivity relative to their pure counterparts, achieving ultralow values of 0.25 to 0.39 W m −1 K −1 at 1500 K. Furthermore, the coefficients of thermal expansion (CTE) of these solid solutions are precisely tuned within the desired range for SiC (4.4 to 5.5 × 10 −6 K −1 ), while maintaining good mechanical properties. Here, in particular, the addition of Eu 2 Si 2 O 7 demonstrates to be an important variable to the tuning of CTE and lattice thermal conductivity by leveraging its strong anharmonicity, presenting a pioneering avenue for fine-tuning material properties. In summary, this research not only identifies promising TEBC materials with superior thermal properties, but also introduces a valuable computational material design methodology for the rapid discovery of complex materials for harsh environments.

36 MATERIALS SCIENCE↗
DOE OSTI2025

SOLEDGE3X full vessel plasma boundary simulations of ITER non-active phase plasmas

The onset of detachment in the ITER machine is analyzed in this work through the help of 2D-axisymmetric boundary plasma simulations with the SOLEDGE3X-EIRENE code, which features a numerical domain for the plasma solver extending up to the first wall. The plasma boundary is computed in scenarios from the first non-active phase of ITER, in pure H and at 20 MW. This set of simulations is used in two aspects: first, to study the plasma detachment in the divertor, and second, the plasma conditions, fluxes, and beryllium erosion at the first wall. Here, the code results are also compared to those obtained with the well-established SOLPS-ITER code, which includes a plasma numerical domain only covering the main SOL. Results show an increase in the SOL width λ q with increasing density, and a detailed analysis is carried out, for the first time, on each of the different plasma-neutral interactions in the code’s physics model in EIRENE. The gross beryllium erosion rates of first wall panels are estimated from 2D simulations, with the aim of assessing their sensitivity to two parameters: the divertor density regime, and the presence of density shoulders in the far-SOL formed by enhanced perpendicular transport at this location. The erosion contributions from neutrals and ions are considered in each case, and the charge-exchange atoms fluxes and energy distributions are provided, highlighting the two atom populations (cold and charge-exchange).

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

PANDA as midrapidity detector for a future HESR Collider at FAIR

Exciting new scientific opportunities are presented for the PANDA detector at the High Energy Storage Ring in the redefined $$\overline{\text {p}} \text {p}(A)$$ p ¯ p ( A ) collider mode, HESR-C, at the Facility for Antiproton and Ion Research (FAIR) in Europe. The high luminosity, $$L \sim 10^{31}$$ L ~ 10 31 cm $$^{-2}$$ - 2 s $$^{-1}$$ - 1 , and a wide range of intermediate and high energies, $$\sqrt{s_{\text {NN}}}$$ s NN up to 30 GeV for $$\overline{\text {p}} \text {p}(A)$$ p ¯ p ( A ) collisions will allow to explore a wide range of exciting topics in QCD, including the study of the production of excited open charm and bottom states, nuclear bound states containing heavy (anti)quarks, the interplay of hard and soft physics in the dilepton production, probing short-range correlations in nuclei, and the exploration of the early, complete $$\overline{\text {p}}$$ p ¯ -p- annihilation phase, where an initially pure Yang–Mills gluon plasma is formed.

Physics↗
NASA NTRS1998

Advanced far infrared blocked impurity band detectors based on germanium liquid phase epitaxy

This research has shown that epilayers with residual impurity concentrations of 5 x 10(sup 13) cm(exp -3) can be grown by producing the purest Pb available in the world. These epilayers have extremely low minority acceptor concentrations, which is ideal for fabrication of IR absorbing layers. The Pb LPE growth of Ge also has the advantageous property of gettering Cu from the epilayer and the substrate. Epilayers have been grown with intentional Sb doping for IR absorption on lightly doped substrates. This research has proven that properly working Ge BIB detectors can be fabricated from the liquid phase as long as pure enough solvents are available. The detectors have responded at reach minimum wavenumbers. Optimization of the Sb doping concentration should further decrease the photoionization energy of these detectors. Ge BIB detectors have been fabricated that respond to 60 cm(exp -1) with low responsivity. Through reduction of the minority residual impurities, detector performance has reached responsivities of 1 A/W. These detectors have exhibited quantum efficiency and NEP values that rival conventional photoconductors and are expected to provide a much more sensitive tool for new scientific discoveries in a number of fields, including solid state studies, astronomy, and cosmology.

Olsen, C. S.↗
NASA NTRS2011

Gravito-Inertial Force Resolution in Perception of Synchronized Tilt and Translation

Natural movements in the sagittal plane involve pitch tilt relative to gravity combined with translation motion. The Gravito-Inertial Force (GIF) resolution hypothesis states that the resultant force on the body is perceptually resolved into tilt and translation consistently with the laws of physics. The purpose of this study was to test this hypothesis for human perception during combined tilt and translation motion. EXPERIMENTAL METHODS: Twelve subjects provided verbal reports during 0.3 Hz motion in the dark with 4 types of tilt and/or translation motion: 1) pitch tilt about an interaural axis at +/-10deg or +/-20deg, 2) fore-aft translation with acceleration equivalent to +/-10deg or +/-20deg, 3) combined "in phase" tilt and translation motion resulting in acceleration equivalent to +/-20deg, and 4) "out of phase" tilt and translation motion that maintained the resultant gravito-inertial force aligned with the longitudinal body axis. The amplitude of perceived pitch tilt and translation at the head were obtained during separate trials. MODELING METHODS: Three-dimensional mathematical modeling was performed to test the GIF-resolution hypothesis using a dynamical model. The model encoded GIF-resolution using the standard vector equation, and used an internal model of motion parameters, including gravity. Differential equations conveyed time-varying predictions. The six motion profiles were tested, resulting in predicted perceived amplitude of tilt and translation for each. RESULTS: The modeling results exhibited the same pattern as the experimental results. Most importantly, both modeling and experimental results showed greater perceived tilt during the "in phase" profile than the "out of phase" profile, and greater perceived tilt during combined "in phase" motion than during pure tilt of the same amplitude. However, the model did not predict as much perceived translation as reported by subjects during pure tilt. CONCLUSION: Human perception is consistent with the GIF-resolution hypothesis even when the gravito-inertial force vector remains aligned with the body during periodic motion. Perception is also consistent with GIF-resolution in the opposite condition, when the gravito-inertial force vector angle is enhanced by synchronized tilt and translation.

Wood, Scott J.↗
NASA NTRS2012

Supercritical CO2 Cleaning System for Planetary Protection and Contamination Control Applications

Current spacecraft-compatible cleaning protocols involve a vapor degreaser, liquid sonication, and alcohol wiping. These methods are not very effective in removing live and dead microbes from spacecraft piece parts of slightly complicated geometry, such as tubing and loosely fitted nuts and bolts. Contamination control practices are traditionally focused on cleaning and monitoring of particulate and oily residual. Vapor degreaser and outgassing bakeout have not been proven to be effective in removing some less volatile, hydrophilic biomolecules of significant relevance to life detection. A precision cleaning technology was developed using supercritical CO2 (SCC). SCC is used as both solvent and carrier for removing organic and particulate contaminants. Supercritical fluid, like SCC, is characterized by physical and thermal properties that are between those of the pure liquid and gas phases. The fluid density is a function of the temperature and pressure. Its solvating power can be adjusted by changing the pressure or temperature, or adding a secondary solvent such as alcohol or water. Unlike a regular organic solvent, SCC has higher diffusivities, lower viscosity, and lower surface tension. It readily penetrates porous and fibrous solids and can reach hard-to-reach surfaces of the parts with complex geometry. Importantly, the CO2 solvent does not leave any residue. The results using this new cleaning device demonstrated that both supercritical CO2 with 5% water as a co-solvent can achieve cleanliness levels of 0.01 mg/cm2 or less for contaminants of a wide range of hydrophobicities. Experiments under the same conditions using compressed Martian air mix, which consists of 95% CO2, produced similar cleaning effectiveness on the hydrophobic compounds. The main components of the SCC cleaning system are a high-pressure cleaning vessel, a boil-off vessel located downstream from the cleaning vessel, a syringe-type high-pressure pump, a heat exchanger, and a back pressure regulator (BPR). After soaking the parts to be cleaned in the clean vessel for a period, the CO2 with contaminants is flushed out of the cleaning vessel using fresh CO2 in a first-in-first-out (FIFO) method. The contaminants are either precipitating out in the boil-off container or being trapped in a filter subsystem. The parts to be cleaned are secured in a basket inside and can be rotated up to 1,400 rpm by a magnetic drive. The fluid flows within the vessel generate tangential forces on the parts surfaces, enhancing the cleaning effectiveness and shortening the soaking time. During the FIFO flushing, the pump subsystem pushes fresh CO2 into the cleaning vessel at a constant flow rate between 0.01 and 200 mL/min, while the BPR regulates the pressure in the cleaning vessel to within 0.1 bar by controlling the needle position in an outlet valve. The fresh CO2 gas flows through the heat exchanger at a given temperature before entering the cleaning vessel. A platinum resistance thermometer (PRT) reads the cleaning vessel interior temperature that can be controlled to within 0.1 K. As a result, cleaning vessel temperature remains constant during the FIFO flushing. There is no change in solvent power during FIFO flushing since both temperature and pressure inside the cleaning vessel remain unchanged, thus minimizing contaminants left behind. During decompression, both temperature and pressure are strictly controlled to prevent bubbles from generating in the cleaning vessel that could stir up the contaminants that sank to the bottom by gravity.

Lin, Ying↗
NASA NTRS2014

The Investigation of Magnesium Perchlorate/Iron Phase-mineral Mixtures as a Possible Source of Oxygen and Chlorine Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument onboard the Curiosity rover detect-ed O2 and HCl gas releases from the Rocknest (RN) eolian bedform and the John Klein (JK) and Cumber-land (CB) drill hole materials in Gale Crater (Fig. 1) [1,2]. Chlorinated hydrocarbons have also been detect-ed by the SAM quadrupole mass spectrometer (QMS) and gas chromatography/mass spectrometer (GCMS) [1,2,3,4]. These detections along with the detection of perchlorate (ClO4(-)) by the Mars Phoenix Lander's Wet Chemistry Laboratory (WCL) [5] suggesting perchlo-rate is a possible candidate for evolved O2 and chlorine species. Laboratory thermal analysis of individual per-chlorates has yet to provide an unequivocal tempera-ture match to the SAM O2 and HCl release data [1,2]. Catalytic reactions of Fe phases in the Gale Crater ma-terial with perchlorates can potentially reduce the de-composition temperatures of these otherwise pure per-chlorate/chlorate phases [e.g., 6,7]. Iron mineralogy found in the Rocknest materials when mixed with Ca-perchlorate was found to cause O2 release temperatures to be closer match to the SAM O2 release data and enhance HCl gas releases. Exact matches to the SAM data has unfortnunately not been achieved with Ca-perchlorate-Fe-phase mixtures [8]. The effects of Fe-phases on magnesium perchlorate thermal decomposi-tion release of O2 and HCl have not been evaluated and may provide improved matches to the SAM O2 and HCl release data. This work will evaluate the thermal decomposition of magnesium perchlorate mixed with fayalite/magnetite phase and a Mauna Kea palagonite (HWMK 919). The objectives are to 1) summarize O2 and HCl releases from the Gale Crater materials, and 2) evaluate the O2 and HCl releases from the Mg-perchlorate + Fe phase mixtures to determine if Mg-perchlorate mixed with Fe-phases can explain the Gale Crater O2 and HCl releases.

Sutter, B.↗
DOE OSTI2026

From molecular to macroscopic: predicting liquid–liquid phase equilibria and small-angle scattering of mixtures of organic liquids from atomistic simulation using Kirkwood–Buff theory

Macroscopic phase equilibria between solutions define the functionality of many biological and industrial processes, yet they are challenging to predict due to the inherent complexity of liquids containing large molecules. This work introduces an approach for the purely predictive calculation of such phase equilibria in temperature-composition space from molecular dynamics (MD) simulations at one temperature in the single-phase region. We use an approach developed previously to obtain the entropic and enthalpic contributions to the free energy of mixing from the atomic-scale information given by MD simulations via Kirkwood–Buff theory. This allows us to accurately estimate the free energy of mixing as a function of temperature, and thus obtain liquid–liquid phase equilibria, including liquid–liquid critical points, associated binodal and spinodal lines, and composition fluctuations across a region of temperature and composition. Results for binary malonamide–alkane systems are validated by comparison to a direct experimental probe of the fluctuations: the small angle X-ray scattering intensity near zero wavenumber. The MDKB → Phase method demonstrated here provides a significant improvement in predicting liquid–liquid equilibria and free energy as a function of temperature for our systems of interest compared to conventional thermodynamic models. The accurate performance of this purely predictive approach lies in its preservation of atomistic details when determining thermodynamic properties. Furthermore, its inherent extensibility to multi-component systems will likely make the MDKB → Phase approach a valuable general tool for connecting molecular interactions to macroscopic phase equilibria and for the computational screening of materials for targeted thermodynamic behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Phase transformation and growth mechanism of RF sputtered ferroelectric lead scandium tantalate (PbSc 0.5 Ta 0.5 O 3 ) films

Lead scandium tantalate (PbSc 0.5 Ta 0.5 O 3 , PST), an order/disorder ferroelectric, is a potential candidate for electrocaloric cooling and pyroelectric infrared (IR) detector. In this work, we report the phase transformation kinetics from two series of samples containing pure amorphous and mixture of amorphous and pyrochlore to desired perovskite phase using postdeposition rapid thermal processing (RTP) as well as growth mechanism of RF sputtered PST thin films using excess lead target on platinized silicon (Pt/Ti/SiO 2 /Si) substrates. We find that small changes in the temperature ramp have a large effect on the degree of perovskite conversion (ferroelectric phase), orientation (crystallographic texture), and long-range order parameter (< S 111 >). Through isothermal annealing, we obtained optimal perovskite phase at ≥700°C temperature. The phase transformation is characterized by spontaneous formation of center-type in-plane radial rosette-like structures revealed by scanning electron microscopy. The PST perovskite crystallites were found to coexist with pyrochlore in RTP annealed films. The volume fractions for perovskite and pyrochlore phase were obtained from the analysis of “rosettes” and respective X-ray diffraction intensities which helped to determine various parameters associated with phase kinetics (n, k, and activation energy, Ea) and accompanying growth. The effective activation energies of perovskite transition and growth were found to be 332 ± 11 kJ/mol (345 ± 11 kJ/mol) and 114 ± 10 kJ/mol (122 ± 10 kJ/mol), respectively, for pure amorphous only (and mixed amorphous and pyrochlore) phase following nucleation-growth controlled Avrami's equation. A linear growth rate (n~1) for the perovskite phase indicates predominant interface-controlled process and diffusion-limited phenomena thus inhibiting rosette size owing to reactant depletion and soft impingement at the grain boundary. However, the growth behavior is isotropic in two-dimension parallel to the plane of the substrates for both sample series. Furthermore, lead loss was severe for in-situ growth and RTP combined with conventional furnace annealing than those of RTP only films, which were closer to stoichiometric albeit with excess lead and marginal oxygen vacancies (V o ).

36 MATERIALS SCIENCE↗