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Results for “solid state reaction”

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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Thin-Film Paradigm to Probe Interfacial Diffusion during Solid-State Metathesis Reactions

We highlight a paradigm for studying complex reaction mechanisms that guide the synthesis of materials. Thin films of FeCl 2 and Na 2 S 2 were deposited to study the metathesis reaction to form FeS 2 and NaCl. In situ X-ray reflectivity was used to monitor the interface between materials, which revealed a slow, impeded reaction at high temperatures as compared to previous studies using powder samples. AC impedance and X-ray photoelectron spectroscopy provided insight into distribution of elements and conductivity of the phases present during the reaction, and phase-field modeling was used to elucidate the diffusion of ions throughout the thin-film bilayers. Here, the use of thin-film bilayers provides a simplified system to study solid-state metathesis reactions and highlights the complexity of diffusion at solid-state interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Phase-field modeling of solid-state metathesis reactions with the charge neutrality constraint

In this work, we present a phase-field model that captures the evolution of ionic concentrations and phase fractions during solid-state metathesis (SSM) reactions where diffusion limits the rate of transformation. The evolution of the mole fraction of each ion is obtained via governing equations that describe the reduction of a free energy, which includes an energy landscape with local minima located at compositions corresponding to stable products. We utilized two Lagrange multipliers to impose constraints of electroneutrality as well as on the sum of mole fractions, which were then eliminated to derive set of two partial differential equations that describe the dynamics of the mole fraction evolution. From these governing equations, the expressions for effective mobilities for the cations and the anions were obtained. We first study the effect of mobilities of ions on the reaction kinetics, using a simple model considering the ions with an identical absolute value of charge numbers. The simulation results show that the overall characteristic mobility, defined as the sum of the two effective ionic mobilities, provides an excellent measure of the rate at which reaction progresses and that the ratio of the effective mobilities of the anions and the cations signifies the manner by which the reaction progresses. We then generalize the model to consider ions with different charge numbers and tuned the mobility of ions based on their diffusion coefficients reported in the literature and experimental data from a thin-film experiment for the synthesis of FeS 2 to demonstrate the capability of the model to predict the phase evolution during SSM reactions. In particular, the simulation predicts nonplanar phase evolution, which is recently observed in thin-film reactions for the synthesis of FeS 2 via transmission electron microscopy. The approach can serve as a basis for models for phase transformations in other multiphase ionic mixtures, such as in all-solid-state batteries and in ionic liquids.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Selective formation of metastable polymorphs in solid-state synthesis

Metastable polymorphs often result from the interplay between thermodynamics and kinetics. Despite advances in predictive synthesis for solution-based techniques, there remains a lack of methods to design solid-state reactions targeting metastable materials. Here, we introduce a theoretical framework to predict and control polymorph selectivity in solid-state reactions. This framework presents reaction energy as a rarely used handle for polymorph selection, which influences the role of surface energy in promoting the nucleation of metastable phases. Through in situ characterization and density functional theory calculations on two distinct synthesis pathways targeting LiTiOPO 4 , we demonstrate how precursor selection and its effect on reaction energy can effectively be used to control which polymorph is obtained from solid-state synthesis. A general approach is outlined to quantify the conditions under which metastable polymorphs are experimentally accessible. With comparison to historical data, this approach suggests that using appropriate precursors could enable targeted materials synthesis across diverse chemistries through selective polymorph nucleation.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Computationally Predicted High-Throughput Free-Energy Phase Diagrams for the Discovery of Solid-State Hydrogen Storage Reactions

The design of multinary solid-state material systems that undergo reversible phase changes via changes in temperature and pressure provides a potential means of safely storing hydrogen. However, fully mapping the stabilities of known or newly targeted compounds relative to competing phases at reaction conditions has previously required many stringent experiments or computationally demanding calculations of each compound’s change in Gibbs energy with respect to temperature, G(T). Here, we have extended the approach of constructing chemical potential phase diagrams based on ΔG f (T) to enable the analysis of phase stability at non-zero temperatures. We first performed density functional theory calculations to compute the formation enthalpies of binary, ternary, and quaternary compounds within several compositional spaces of current interest for solid-state hydrogen storage. Temperature effects on solid compound stability were then accounted for using our recently introduced machine learned descriptor for the temperature-dependent contribution G δ (T) to the Gibbs energy G(T). From these Gibbs energies, we evaluated each compound’s stability relative to competing compounds over a wide range of conditions and show using chemical potential and composition phase diagrams that the predicted stable phases and H2 release reactions are consistent with experimental observations. This demonstrates that our approach rapidly computes the thermochemistry of hydrogen release reactions for compounds at sufficiently high accuracy relative to experiment to provide a powerful framework for analyzing hydrogen storage materials. This framework based on G(T) enables the accelerated discovery of active materials for a variety of technologies that rely on solid-state reactions involving these materials.

08 HYDROGEN↗
DOE OSTI2021

LaNi x Fe 1– x O 3–δ as a Robust Redox Catalyst for CO 2 Splitting and Methane Partial Oxidation

The current study reports LaNi 0.5 Fe 0.5 O 3–δ as a robust redox catalyst for CO 2 splitting and methane partial oxidation at relatively low temperatures (~700 °C) in the context of a hybrid redox process. Specifically, perovskite-structured LaNi x Fe 1–x O 3–δ (LNFs) with nine different compositions (x = 0.05–0.5) were prepared and investigated. Among the samples evaluated, LaNi 0.4 Fe 0.6 O 3–δ and LaNi 0.5 Fe 0.5 O 3–δ showed superior redox performance, with ~90% CO 2 and methane conversions and >90% syngas selectivity. The standalone LNFs also demonstrated performance comparable to that of LNF promoted by mixed conductive Ce 0.85 Gd 0.1 Cu 0.05 O 2–δ (CGCO). Long-term testing of LaNi 0.5 Fe 0.5 O 3–δ indicated that the redox catalyst gradually loses its activity over repeated redox cycles, amounting to approximately 0.02% activity loss each cycle, averaged over 500 cycles. This gradual deactivation was found to be reversible by deep oxidation with air. Further characterizations indicated that the loss of activity resulted from a slow accumulation of iron carbide (Fe 3 C and Fe 5 C 2 ) phases, which cannot be effectively removed during the CO 2 splitting step. Reoxidation with air removed the carbide phases, increased the availability of Fe for the redox reactions via solid-state reactions with La 2 O 3 , and decreased the average crystallite size of La 2 O 3 . As a result, reactivating the redox catalyst periodically, e.g., once every 40 cycles, was shown to be highly effective, as confirmed by operating the redox catalyst over 900 cumulative cycles while maintaining satisfactory redox performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Synthesis and Post-Processing of Chemically Homogeneous Nanothreads from 2,5-Furandicarboxylic Acid

Compared with conventional, solution-phase approaches, solid-state reaction methods can provide unique access to novel synthetic targets. Nanothreads—one-dimensional diamondoid polymers formed through the compression of small molecules—represent a new class of materials produced via solid-state reactions, however, the formation of chemically homogeneous products with targeted functionalization represents a persistent challenge. Through careful consideration of molecular precursor stacking geometry and functionalization, we report here the scalable synthesis of chemically homogeneous, functionalized nanothreads through the solid-state polymerization of 2,5-furandicarboxylic acid. The resulting product possesses high-density, pendant carboxyl functionalization along both sides of the backbone, enabling new opportunities for the post-synthetic processing and chemical modification of nanothread materials applicable to a broad range of potential applications.

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

Understanding the Electronic Behavior of f-Element Intermetallics

Due to their partially filled f-orbitals, lanthanide and actinide intermetallic materials exhibit intriguing electronic, structural, and magnetic properties. These materials provide a unique platform to explore exotic magnetic and quantum phenomena that arise from their strongly correlated f-electrons, offering insights into f-electron behavior. Incorporating light elements such as boron and carbon can significantly impact the electronic, chemical, and physical properties of these materials, with varying influence between lanthanides and actinides due to the more localized f-electrons in lanthanides. In this work, lanthanide-based intermetallic single crystals containing light atoms were synthesized using the molten metal flux growth method. In this method, one or more low-melting metals such as aluminum, gallium, tin, and bismuth are used in excess as the reaction medium. This solution-state approach allows for lower reaction temperatures compared to solid-state reactions and enables the isolation of kinetic products rather than thermodynamically stable compounds. The synthesized crystals were analyzed using an extensive array of analytical and computational characterization techniques, including single crystal X-ray diffraction, scanning electron microscopy, energy-dispersive spectroscopy, magnetization measurements, and density functional theory calculations. These analyses provided detailed insights into the structural and magnetic properties of the synthesized materials.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗
DOE OSTI2021

Role of Pairwise Reactions on the Synthesis of Li 0.3 La 0.57 TiO 3 and the Resulting Structure–Property Correlations

The performance of single-ion conductors is highly sensitive to the material’s defect chemistry. Tuning these defects is limited for solid-state reactions as they occur at particle–particle interfaces, which provide a complex evolving energy landscape for atomic rearrangement and product formation. In this report, we investigate the (1) order of addition and (2) lithium precursor decomposition temperature and their effect on the synthesis and grain boundary conductivity of the perovskite lithium lanthanum titanium oxide (LLTO). We use an intimately mixed sol–gel, a solid-state reaction of Li precursor + La 2 O 3 + TiO 2 , and Li precursor + amorphous La 0.57 TiO x as different chemical routes to change the way in which the elements are brought together. The results show that the perovskite can accommodate a wide range of Li deficiencies (upward of 50%) while maintaining the tetragonal LLTO structure, indicating that X-ray diffraction (XRD) is insufficient to fully characterize the chemical nature of the product (i.e., Li-deficient LLTO may behave differently than stoichiometric LLTO). Variations in the relative intensities of different reflections in XRD suggest variations in the La ordering within the crystal structure between synthesis methods. Furthermore, the choice of the precursor and the order of addition of the reactants lower the time required to form a pure phase. Density functional theory calculations of the formation energy of possible reaction intermediates support the hypothesis that a greater thermodynamic driving force to form LLTO leads to a greater LLTO yield. Here, the retention of lithium is correlated with the thermal decomposition temperature of the Li precursor and the starting material mixing strategy. Taking the results together suggests that cations that share a site with Li should be mixed early to avoid ordering. Such cation ordering inhibits Li motion, leading to higher Li ion resistance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

High-throughput investigation of crystal-to-glass transformation of Ti–Ni–Cu ternary alloy

A high-throughput investigation of metallic glass formation via solid-state reaction was reported in this paper. Combinatorial multilayered thin-film chips covering the entire Ti-Ni-Cu ternary system were prepared using ion beam sputtering technique. Microbeam synchrotron X-ray diffraction (XRD) and X-ray fluorescence (XRF) measurements were conducted, with 1,325 data points collected from each chip, to map out the composition and the phase constitution before and after annealing at 373 K for 110 hours. The composition dependence of the crystal-to-glass transition by solid-state reaction was surveyed using this approach. The resulting composition-phase map is consistent with previously reported results. Time-of-flight secondary ion mass spectroscopy (ToF-SIMS) was performed on the representative compositions to determine the inter-diffusion between layers, the result shows that the diffusion of Ti is the key factor for the crystal-to-glass transition. In addition, both layer thickness and layer sequence play important roles as well. This work demonstrates that combinatorial chip technique is an efficient way for systematic and rapid study of crystal-to-glass transition for multi-component alloy systems.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Reversible Phase Transitions Enable Cyclic Isothermal CO 2 Capture in Redox‐Activated Perovskite‐Structured Sorbents

Sorption‐enhanced steam reforming and gasification using CO 2 sorbents enable the production of H 2 ‐rich syngas from carbonaceous feedstocks but are limited by significant temperature swings and sintering‐induced activity loss. Perovskite‐structured oxides are presented herein as sintering‐resistant, redox‐activated isothermal CO 2 sorbents capable of overcoming these challenges by releasing lattice oxygen to partially oxidize the carbonaceous feedstock while capturing CO 2 , shifting equilibrium toward H 2 production. Building on this, the structural and thermodynamic impact of Fe doping on the CO 2 sorption properties of SrMn 1‐ x Fe x O 3‐ δ is investigated for sorption‐enhanced reforming. Experimental results demonstrate that these sorbents enable isothermal production of high‐quality, H 2 ‐enriched syngas from carbonaceous feedstocks. Laboratory and synchrotron‐based powder X‐ray diffraction analyses, coupled with density functional theory calculations, reveal the structural dynamics and energy landscape of the SrMn 1‐ x Fe x O 3‐ δ perovskite system under reaction conditions, elucidating the solid‐state reaction pathway and the effect of Fe doping on the extent of carbonation.

CO2 capture↗
DOE OSTI2025

Synthesizing intermetallic thermoelectric materials using metal flux growth method

With zero energy poverty by 2050 goals, exploring innovative energy technologies is essential. Thermoelectric materials (TEMs) have the potential to harness waste heat and convert it to electricity (e.g., for spacecraft power, sensors, and cryogenic cooling). Two limitations of thermoelectric compounds are their low efficiency and limited pool of materials. Optimizing the efficiency of TEMs is challenging due to the interdependent relationship between electrical and thermal conductivity. A deeper understanding of electronic properties and lattice thermal conductivity is necessary to “understand, predict and ultimately control” the thermoelectric properties of TEMs. Understanding the influence of light-atom-doping and intrinsic defects on the electronic properties of the f-element containing TEMs are important questions that need to be answered to design and synthesize TEMs with optimal parameters. The purpose of this work is to understand how doping f-element based TEMs with light elements, such as carbon and boron, would impact the crystal structure, bond lengths, band gaps, and thermoelectric characteristics. High-quality f¬-element containing intermetallic single crystals are grown in metal flux media. In molten metal flux growth method, one or more low-melting metals such as aluminum, gallium, tin, and bismuth are used in excess as the reaction medium. As these are solution-state reactions, we can use lower temperatures than solid-state reactions and isolate the kinetic products instead of the thermodynamically stable compound. Then these are characterized using X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, magnetization, electrical and thermal conductivities, and thermoelectric power.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗
DOE OSTI2021

Observing and Modeling the Sequential Pairwise Reactions that Drive Solid‐State Ceramic Synthesis

Abstract Solid‐state synthesis from powder precursors is the primary processing route to advanced multicomponent ceramic materials. Designing reaction conditions and precursors for ceramic synthesis can be a laborious, trial‐and‐error process, as heterogeneous mixtures of precursors often evolve through a complicated series of reaction intermediates. Here, ab initio thermodynamics is used to model which pair of precursors has the most reactive interface, enabling the understanding and anticipation of which non‐equilibrium intermediates form in the early stages of a solid‐state reaction. In situ X‐ray diffraction and in situ electron microscopy are then used to observe how these initial intermediates influence phase evolution in the synthesis of the classic high‐temperature superconductor YBa 2 Cu 3 O 6+ x (YBCO). The model developed herein rationalizes how the replacement of the traditional BaCO 3 precursor with BaO 2 redirects phase evolution through a low‐temperature eutectic melt, facilitating the formation of YBCO in 30 min instead of 12+ h. Precursor selection plays an important role in tuning the thermodynamics of interfacial reactions and emerges as an important design parameter in planning kinetically favorable synthesis pathways to complex ceramic materials.

36 MATERIALS SCIENCE↗