Intermediate Metastable Phase Research Articles

Orientation-dependent deformation mechanisms of alpha-uranium single crystals under shock compression

Large-scale non-equilibrium molecular dynamics (NEMD) simulations were employed to investigate the dynamic deformations of alpha-uranium (α-U) single crystals subjected to varying shock strengths along low-index crystallographic orientations. The pronounced anisotropy of α-U gives rise to a complex microstructural evolution under shock loading. In-depth microstructural analysis of post-shock specimens reveals the identification of multiple dynamic deformation mechanisms. Notably, when the shock loading direction aligns with the a-axis, dynamic deformation of the α-U single crystals is primarily dominated by lattice instability, which attributes to a crystalline-to-amorphous transition serving as the dominant shear stress relaxation pathway. On the other hand, shock loading along the b-axis results in an abundance of deformation twins, with twinning planes identified as (130) and (13¯0). During the twinning event, the α-U matrix undergoes a transition to a metastable intermediate phase, subsequently decomposing into a composite structure comprising α-U twins and matrix. This unconventional twinning mechanism significantly deviates from classical theories. Furthermore, upon loading along the c-axis, twinning and a phase transition from α-U to body-centered tetragonal phase (bct-U) occur in α-U single crystal samples. Given that the pressure threshold of this phase transition predicted by ab initio calculations is as high as ∼270 GPa, the phase transition from α-U to bct-U might be implausible. An alternative interatomic potential of uranium with the higher pressure threshold was employed to reinvestigate the shock response of α-U single crystals along the c-axis. The phase transition of α-U to bct-U disappears, and twinning dominates the plastic deformation, with the twinning orientation conforming to the {112} twinning. The strong anisotropy of the α-U lattice triggers a wealth of orientation-dependent dynamic deformation mechanisms. The activation of the twinning system is evidently associated with the loading direction, constituting the potential cause for the discovery of multiple twinning variants during the deformation in polycrystalline uranium.

Layer-by-layer phase transformation in Ti3O5 revealed by machine-learning molecular dynamics simulations

Reconstructive phase transitions involving breaking and reconstruction of primary chemical bonds are ubiquitous and important for many technological applications. In contrast to displacive phase transitions, the dynamics of reconstructive phase transitions are usually slow due to the large energy barrier. Nevertheless, the reconstructive phase transformation from β- to λ-Ti3O5 exhibits an ultrafast and reversible behavior. Despite extensive studies, the underlying microscopic mechanism remains unclear. Here, we discover a kinetically favorable in-plane nucleated layer-by-layer transformation mechanism through metadynamics and large-scale molecular dynamics simulations. This is enabled by developing an efficient machine learning potential with near first-principles accuracy through an on-the-fly active learning method and an advanced sampling technique. Our results reveal that the β−λ phase transformation initiates with the formation of two-dimensional nuclei in the ab-plane and then proceeds layer-by-layer through a multistep barrier-lowering kinetic process via intermediate metastable phases. Our work not only provides important insight into the ultrafast and reversible nature of the β−λ transition, but also presents useful strategies and methods for tackling other complex structural phase transitions.

Is La3Ni2O6.5 a Bulk Superconducting Nickelate?

Superconducting states onsetting at moderately high temperatures have been observed in epitaxially stabilized RENiO2-based thin films. However, recently, it has also been reported that superconductivity at high temperatures is observed in bulk La3Ni2O7-δ at high pressure, opening further possibilities for study. Here we report the reduction profile of La3Ni2O7 in a stream of 5% H2/Ar gas and the isolation of the metastable intermediate phase La3Ni2O6.45, which is based on Ni2+. Although this reduced phase does not superconduct at ambient or high pressures, it offers insights into the Ni-327 system and encourages future study of nickelates as a function of oxygen content.

Study on the silicide phase control and room temperature mechanical properties of Nb-Si-Ti based alloys via B and Mg-microalloying

The Nb-16Si-20Ti-4Cr-1.5Al-4Hf-4Zr-1Ta-xB (x=0, 2, 4)-yMg (y=0, 0.2, 0.4) alloys were prepared by non-consumable arc melting. The effects of B and Mg addition on the microstructure and room temperature fracture toughness have been investigated. The results reveal that when the content of B element reached 4 at.%, the intermediate metastable phase Nb3Si was precipitated in Nb-Si based alloys. The cooperation of B and Mg synergistically enhances the room temperature fracture toughness of Nb-Si based alloy. B and Mg element causes the eutectic point of Nb-Si based alloy to shift to the right. The 2B-0.4Mg alloy shows the best fracture toughness, and its KQ value is 14.41 MPa·m 1/2, which increased by 34% compared to the matrix alloy. Crack deflection and secondary cracking increase the room-temperature fracture toughness of Nb-Si-based alloys.

Exploring the Influence of Malachite Forming on Oxide-Derived Copper Electrodes on C2+ Product Selectivity

Electrocatalytic activity and C2 product selectivity of two distinguished oxide-derived Cu in electrochemical carbon dioxide reduction reaction (CO2RR) were investigated. Cu oxide layers electrodeposited at different deposition rates exhibited different morphologies, the electrode with a more compact structure was found selective to C2 products with two times higher faradaic efficiencies (40%). Both Cu+ and Cu2+ species have been identified on the surface of oxide-derived Cu electrodes by X-ray photoelectron spectroscopy (XPS). Also, oxide-derived electrodes were investigated by X-ray diffraction (XRD). Results confirmed the presence of Cu oxide phases for primary electrodes, which were then fully reduced to the metallic Cu after CO2RR. Moreover, SEM investigations helped us distinguish the morphology of the two electrodes and monitor morphological differences before and after CO2RR. To shed light on the adsorbed species, intermediate (metastable) phases, and reaction mechanisms during CO2RR, electrochemical surface-enhanced Raman spectroscopy (SERS) was utilized. This method helped us vividly observe the formation of a metastable phase (malachite) on the electrode surface, which showed lower FEs for C2 products. Moreover, the analysis of SERS indicated a strong tie between the presence of the malachite phase and strongly adsorbed CO on electrode surfaces, preventing dimerization and further reduction. This malachite phase terminating the surface can hinder the charge transport and interfere with further reductions in C2 products. Figure 1

Thermodynamic and Kinetic Studies of Dolomite Formation: A Review

The “dolomite problem”, which has confused scientists for nearly two centuries, is an important fundamental geological problem. The mineralogical characteristics of carbonate minerals show that the dolomite structure consists of an ordered arrangement of alternating layers of Ca2+ and Mg2+ cations interspersed with CO32− anion layers normal to the c-axis. The dolomite structure violates the c glide plane in the calcite structure, which means that dolomite has R3¯ space group symmetry. The ordered dolomite has superlattice XRD reflections [e.g., (101), (015) and (021)], which distinguish it from calcite and high-Mg calcite. The calculation of thermodynamic parameters shows that modern seawater has a thermodynamic tendency of dolomite precipitation and the dolomitization reaction can be carried out in standard state. However, the latest thermodynamic study shows that modern seawater is not conducive to dolomitization, and that seawater is favorable for dolomitization in only a few regions, such as Abu Dhabi, the Mediterranean and the hypersaline lagoons in Brazil. The kinetic factors of dolomite formation mainly consist of the hydration of Mg2+, the presence of sulfate and the activity of carbonate. Current studies have shown that the presence of microorganisms, exopolymeric substances (EPS), organic molecules, carboxyl and hydroxyl functional groups associated with microorganisms and organic molecules, clay minerals with negative charges and dissolved silica facilitate magnesium ions to overcome hydration and thus promote Mg2+ incorporation into growing Ca-Mg carbonates. Similarly, the metabolic activity of microorganisms is conducive to the increase in alkalinity. However, the inhibitory effect of sulfate on dolomite formation seems to be overestimated, and sulfate may even be a catalyst for dolomite formation. Combining the carbonate crystallization mechanism with thermodynamic and kinetic factors suggests that the early stage of dolomite precipitation or the dolomitization reaction may be controlled by kinetics and dominated by unstable intermediate phases, while metastable intermediate phases later transform to ordered dolomite via an Ostwald’s step rule.

Phase transformations in WC-Cr3C2-Ni thermal spray coatings under low, medium and high thermal input: Part 2 – DSC analysis and heat-treated coating characterisation

Conventionally, bulk WC and Cr3C2-based carbide compositions have been used independently of each other. However, recent investigations have begun to explore combining these carbides together within the same composite/hard metal coating system. This work explored the diversity of phases produced in the coatings from a 42 wt% WC-42 wt% Cr3C2–16 wt% Ni powder sprayed under “low”, “medium” and “high” thermal input conditions using high velocity oxygen-fuel (HVOF), an argon‑helium (ArHe) plasma and an argon‑hydrogen (ArH2) plasma respectively. The thermally driven solid-state transformations in the coatings were investigated as a function of carbide dissolution/decomposition, using differential scanning calorimetry (DSC). All coatings exhibited a well defined exothermic peak attributed to the transformation of the metastable supersaturated Ni-alloy and WC1-X phases in the as-sprayed coatings, into the equilibrium Ni alloy and a mix of the intermediate metastable carbide phases β-W2C and Cr3C2-Y. At higher temperatures the metastable compounds transformed to the equilibrium phases of ε-W2C and Cr3C2. A defining feature of the XRD analysis was the significant shift in lattice positions of all phases, indicating substitutional alloying. The mechanisms of phase formation are discussed.

Kinetic effects inducing metastable intermediate phase in PbK2LiNb5O15 single crystal

The kinetic effects accompanying an unusual ferroelectric-paraelectric phase transition is analyzed in the PbK2LiNb5O15 single crystal. The ferroelectric-paraelectric phase transition takes place at Curie temperature (TC) of 639 K, being strongly influenced by the heating/cooling rate (υ). The phase transition occurs through metastable intermediate phases spanning a 40 K interval. These kinetic effects and relaxation phenomena are highlighted around the phase transition region. The dielectric measurements, which have been performed at 500 kHz considering different temperature rates, on heating and cooling, have shown not only the variation of TC as a function of υ, but also, the widening of the dielectric thermal hysteresis as a function of υ.

Stability and Metastability of Li3YCl6 and Li3HoCl6

Abstract Metastable solid electrolytes exhibit superior conductivity compared to stable ones, making them a subject of considerable interest. However, synthesis of the metastable phase is affected by multiple thermodynamic and kinetic parameters, leading to ambiguity in the organization of stability and metastability. In this study, we organized remnant and intermediate metastability based on temperature. The intermediate metastable phase, which is less stable than the temperature-independent stable phase, typically transforms into the stable phase(s) at high temperatures. In contrast, the remnant metastable phase is formed by first obtaining most stable phase at specific temperatures and then “trapping” it by rapidly changing the temperature. By investigating Li+ conducting chlorides, Li3MCl6 (M = Y and Ho), we demonstrated that heating starting materials to approximately 600 K produced low-temperature Li3MCl6 phase with one formula unit while further heating resulted in high-temperature Li3MCl6 phase with three formula units. Annealing quenched Li3MCl6 at 573 K resulted in a phase transition from the high-temperature to low-temperature phase, indicating that the high-temperature phase was remnant metastable at low temperatures.

Influence of the Precursor Structure on the Formation of Tungsten Oxide Polymorphs.

Understanding material nucleation processes is crucial for the development of synthesis pathways for tailormade materials. However, we currently have little knowledge of the influence of the precursor solution structure on the formation pathway of materials. We here use in situ total scattering to show how the precursor solution structure influences which crystal structure is formed during the hydrothermal synthesis of tungsten oxides. We investigate the synthesis of tungsten oxide from the two polyoxometalate salts, ammonium metatungstate, and ammonium paratungstate. In both cases, a hexagonal ammonium tungsten bronze (NH4)0.25WO3 is formed as the final product. If the precursor solution contains metatungstate clusters, this phase forms directly in the hydrothermal synthesis. However, if the paratungstate B cluster is present at the time of crystallization, a metastable intermediate phase in the form of a pyrochlore-type tungsten oxide, WO3·0.5H2O, initially forms. The pyrochlore structure then undergoes a phase transformation into the tungsten bronze phase. Our studies thus experimentally show that the precursor cluster structure present at the moment of crystallization directly influences the formed crystalline phase and suggests that the precursor structure just prior to crystallization can be used as a tool for targeting specific crystalline phases of interest.

Amorphous Solid Forms of Ranolazine and Tryptophan and Their Relaxation to Metastable Polymorphs.

Different methods were explored for the amorphization of ranolazine, a sparingly soluble anti-anginal drug, such as mechanochemistry, quench-cooling, and solvent evaporation from solutions. Amorphous phases, with Tg values lower than room temperature, were obtained by cryo-milling and quench-cooling. New forms of ranolazine, named II and III, were identified from the relaxation of the ranolazine amorphous phase produced by cryo-milling, which takes place within several hours after grinding. At room temperature, these metastable polymorphs relax to the lower energy polymorph I, whose crystal structure was solved in this work for the first time. A binary co-amorphous mixture of ranolazine and tryptophan was produced, with three important advantages: higher glass transition temperature, increased kinetic stability preventing relaxation of the amorphous to crystalline phases for at least two months, and improved aqueous solubility. Concomitantly, the thermal behavior of amorphous tryptophan obtained by cryo-milling was studied by DSC. Depending on experimental conditions, it was possible to observe relaxation directly to the lower energy form or by an intermediate metastable crystalline phase and the serendipitous production of the neutral form of this amino acid in the pure solid phase.

Spotting Interface Structuring during Na‐Insertion into the NaSICON Na3V2(PO4)3 by EQCM and Operando Fiber Optic Infrared Spectroscopy

AbstractReliable operation of Na‐ion batteries requires a mastering of the interfacial processes governing intercalation kinetics. Ion desolvation, amongst others, is a crucial phenomenon as far as power applications are envisioned. Studying the intricacies of interfacial processes faces experimental challenges. Here the complementary use of electrochemical quartz crystal microbalance (EQCM) and operando infrared fiber evanescent wave spectroscopy (IR‐FEWS) combined with molecular dynamics (MD) simulations is reported to investigate the electrode/electrolyte interface of polyanionic Na‐insertion compounds Na3V2(PO4)3 (NVP) and Na3V2(PO4)2F3 (NVPF). Through screening of various electrolytes that differ in their solvation energy and viscosity, the existence of an unusual mass uptake/depletion signal is demonstrated at the NVP interfaces only, indicative of a dissimilarity in migration kinetics of solvent molecules between NVP and NVPF interfaces as supported by IR‐FEWS. This finding is rationalized by positing that sodium depletion is caused by the unusually rapid ion diffusion within NVP mediated by an intermediate metastable phase, which leads to opposite Na+ concentration and free solvent molecule gradients at the interface that causes the unusual and anomalous feature observed on EQCM frequency profiles. This feature does not appear with NVPF showing lower ionic diffusion. Altogether, this fundamental study provides valuable fundamental insights into the interface structuring of insertion compounds depending upon their Na+ mobility.

Polymorphism of VO2 thin film: M1, T, and M2 single phase synthesis using pulsed laser deposition

Vanadium dioxide (VO2) can undergo a reversible insulator-to-metal transition (IMT) along with a structural phase transition from monoclinic M1 to rutile tetragonal R at about 68ºC, thereby making a range of optic and electronic applications possible. The structural phase transition from monoclinic M1 to rutile tetragonal R can occur via two other intermediate metastable phases of triclinic T and monoclinic M2. Due to their narrow thermodynamic stability, selective phase deposition of VO2 thin films is a major challenge. In the present study, apart from synthesizing the VO2 thin film with M1 phase, we also selectively elaborated the T and M2 phases using pulsed laser deposition (PLD) by simply controlling the repetition rate of the laser. Analysis of the structural, morphological, nanomechanical, thermochromic, and optical properties of each of these polymorphs demonstrated strong dependence of these properties on the VO2 phases, and hence on the laser repetition rate. The ability to stabilize different polymorphs of VO2 thin films paves the way for novel structures that are promising for new device functionalities.

Structure and solidification of the (Fe0.75B0.15Si0.1)100-xTax (x=0–2) melts: Experiment and machine learning

Fe–B–Si system is a matrix for synthesis of new functional materials with exceptional magnetic and mechanical properties. Progress in this area is associated with the search for optimal doping conditions. This theoretical and experimental study is aimed to address the influence of Ta alloying on the structure of undercooled (Fe0.75B0.15Si0.1)100-xTax (x = 0–2) melts, their undercoolability and the processes of structure formation during solidification. Small concentration of Ta complicates standard ab initio and machine learning investigations. We developed a technique for fast and stable training of machine learning interatomic potential (MLIP) in this case and uncovered the structure of undercooled (Fe0.75B0.15Si0.1)100-xTax (х = 0–2) melts. Molecular dynamic simulations with MLIP showed that at Ta concentration of 1 at.% there is a sharp change in the chemical short-range ordering in the melt associated with a change in the interaction of Ta atoms. This effect leads to a restructuring of the cluster formation in the system. At the same time, our experimental investigation shows that melts with a Ta content of 1 at.% have the greatest tendency to undercoolability. Alloying with Ta promotes the formation of primary crystals of Fe2B, and at a concentration of more than 1.5 at.% Ta, also of FeTaB. Herewith, near 1 at.% Ta, the crystallization of the melt proceeds nontrivially: with the formation of two intermediate metastable phases Fe3B and Fe2Ta Laves phase. Also, the highest tendency to amorphization under conditions of quick quenching is exhibited by a melt with a Ta concentration of 1 at.%. The results not only provide understanding of optimal alloying of Fe–B–Si materials but also promote a machine learning method for numerical design of metallic alloys with a small dopant concentration.

Temperature-Dependent Phase Evolution in FePt-Based Nanocomposite Multiple-Phased Magnetic Alloys

A quaternary Fe-Pt-Nb-B alloy has been fabricated by the melt spinning method with the purpose of the formation of crystallographically coherent multiple magnetic phases, emerging from the same metastable precursor, as well as to investigate the phase interactions and the influence of their coupling on magnetic performances. For this purpose, extended structural and magnetic investigations were undertaken by making use of X-ray diffraction, transmission electron microscopy, and 57Fe Mössbauer spectroscopy, as well as magnetic measurements using SQUID magnetometry. It was documented that intermediate metastable phases formed during primary crystallization, in intermediate stages of annealing, and a growth-dominated mode was encountered for the secondary crystallization stage upon annealing at 700 °C and 800 °C where fcc Fe3Pt and fct Fe2B polycrystalline were formed. The Mössbauer investigations have documented rigorously the hyperfine parameters of each of the observed phases. The fcc A1 FePt phase was shown to exhibit a peculiar ferromagnetic transition, and this transition has been proven to occur gradually between 300 K and 77 K. The magnetic measurements allowed us to identify the annealing at 700 °C as optimal for obtaining good magnetic features. Coercive field dependence shows similarities to the random anisotropy model for samples annealed at 500 °C to 700 °C which are nanocrystalline. These results show good perspectives for use in applications where different magnetic states are required at different operating temperatures.

Nanostructured ZnSb films composited with Bi2Te3 topological insulators exhibit strongly unusual p–n conduction conversion upon crystallization

The crystallization of a local p-type ZnSb material can be deterministically tuned by doping with the n-type topological insulator Bi 2 Te 3 . Upon annealing, pure ZnSb shows a transition across three states, namely, high resistance, intermediate resistance, and low resistance. The metastable intermediate ZnSb phase has p-type conduction. Here, we find that the metastable ZnSb phase of the pure ZnSb film is significantly suppressed by Bi 2 Te 3 doping, and the underlying conduction is changed into n-type conduction because Bi 2 Te 3 doping induces a change in crystallization and simultaneously changes the type of crystalline phases. Nanoprecipitate formation and crystallization transition are the driving forces of the composition-dependent p–n conduction conversion. The X-ray diffraction, X-ray photoelectron and Raman spectroscopy results of the crystalline thin films suggest that the local bonding arrangement around Sb atoms changes. The Bi–Sb topological insulators are thus mainly responsible for the p–n transition and ultralow resistance shift shown by ZnSb–Bi 2 Te 3 alloys.

Protein Crystallization from a Preordered Metastable Intermediate Phase Followed by Real-Time Small-Angle Neutron Scattering

We present a systematic study using real-time small-angle neutron scattering (SANS) and optical microscopy to follow the protein crystallization process in the presence of a metastable intermediate...

Phase decomposition in nanocrystalline Cr0.8Cu0.2 thin films

Metastable Cr0.8Cu0.2 alloy thin films with nominal thickness of 360 nm have been deposited on Si(100) substrate by co-evaporation of Cu and Cr using molecular beam epitaxy (MBE). Phase evolution, microstructure, stress development, and crystallographic texture in Cr0.8Cu0.2 thin films have been investigated by X-ray diffraction (XRD), atom probe tomography (APT) and transmission electron microscopy (TEM) combined with energy dispersive X-ray spectroscopy (EDS) during annealing of the films in the temperature range 200–450 °C. X-ray diffraction of the as-deposited thin film shows single phase bcc crystal structure of the film whereas APT observation of fine precipitates in the film matrix due to inherent compositional fluctuation indicates onset of phase separation via spinodal decomposition regime. XRD (in-situ) and APT investigation of 300 °C annealed film reveals that the early stage of phase separation involves localized formation of metastable intermediate bcc precipitate phase having 60 at% Cr and 40 at% Cu approximately (~Cr0.6Cu0.4). For longer duration of annealing at temperature ≥350 °C, such metastable bcc precipitates act as heterogeneous nucleation sites for the onset of precipitation of Cu rich fcc Cu(Cr) phase which indicates a change of phase separation mechanism from ‘spinodal decomposition’ to ‘nucleation and growth’. Annealing of the film at temperature ≥400 °C for longer duration leads to the formation of a two phase structure with Cu rich fcc precipitate phase in a Cr rich bcc matrix. Observed phase decomposition is accompanied by significant changes in the microstructure, residual stress and crystallographic texture in the Cr rich bcc film matrix which leads to the minimization of both surface and strain energies and thereby a reduction of total Gibbs free energy of the thin film. Thermodynamic model calculation has been presented in order to understand the nucleation pathway of Cu rich stable fcc Cu(Cr) precipitates via non-classical nucleation of metastable intermediate bcc Cr0.6Cu0.4 phase.

Vacancy-Enabled O3 Phase Stabilization for Manganese-Rich Layered Sodium Cathodes.

Manganese-rich layered oxide materials hold great potential as low-cost and high-capacity cathodes for Na-ion batteries. However, they usually form a P2 phase and suffer from fast capacity fade. In this work, an O3 phase sodium cathode has been developed out of a Li and Mn-rich layered material by leveraging the creation of transition metal (TM) and oxygen vacancies and the electrochemical exchange of Na and Li. The Mn-rich layered cathode material remains primarily O3 phase during sodiation/desodiation and can have a full sodiation capacity of ca. 220 mAh g-1 . It delivers ca. 160 mAh g-1 specific capacity between 2-3.8 V with >86 % retention over 250 cycles. The TM and oxygen vacancies pre-formed in the sodiated material enables a reversible migration of TMs from the TM layer to the tetrahedral sites in the Na layer upon de-sodiation and sodiation. The migration creates metastable states, leading to increased kinetic barrier that prohibits a complete O3-P3 phase transition.

In Situ Monitoring of a Quasi Solid-State Diffusion-Driven Cocrystallization in the Diphenylamine–Benzophenone System

Diphenylamine reacts with benzophenone in the solid state through the formation of a eutectic liquid intermediate, from which the final product, in the form of a hydrogen-bonded cocrystal, is finally formed. By a simple experiment, the phase diagram of the benzophenone/diphenylamine system is effectively divided into two parts, which enabled monitoring of the overall process from the side of each reactant separately. Accompanied by isothermal and nonisothermal spectroscopic monitoring of the system, this provides additional details of the mechanistic pathway of the process of cocrystal formation through a metastable liquid intermediate phase.