Phase Stability Research Articles

Predicting metastable oxide-to-hydroxide phase transformations by bulk and interface thermodynamics: application to the phase stability of aluminium oxides and hydroxides in water

Fundamental understanding of the phase stability of oxides in aqueous environments is of eminent importance for a broad range of disciplines, such as corrosion, tribology, catalysis, medical implants, biosensing and environmental sciences. Most oxide-to-hydroxide phase transformation sequences proceed by consecutive formation of different metastable hydroxide phases towards the most stable bulk hydroxide phase, in accord with Ostwald's Rule of Stages and thus in contradiction with bulk thermodynamics. In this work, a novel unified thermodynamic model is presented for predicting such metastable oxide-to-hydroxide phase transformation sequences by accounting for the energy barrier(s) associated with the creation of new interface(s) between the competing parent and product phase(s). To this end, semi-empirical expressions for the estimation of the interface energies between metals, oxides and/or hydroxides were derived based on the macroscopic atom approach. Application of the model to the phase stability of aluminium in water (at neutral pH) for 298 ≤ T ≤ 500 K predicts a solid-state phase transformation sequence from Al → am-Al2O3 → (pseudo)boehmite, in accord with experimental observations. Subsequent competing formation of the trihydroxide phases bayerite and gibbsite by a dissolution-precipitation on the (pseudo)boehmite surface is equally favoured and critically depends on the hydrolysis of dissolved Al3+ species in solution, as governed by e.g. pH, temperature and the presence of foreign ions in solution.

The influence of the elemental valence on the thermophysical properties of high entropy (La0.2Sm0.2Eu0.2Yb0.2Y0.2)2(Ce0.5Zr0.5)2O7 coatings for thermal barrier application

Commercial yttria-stabilized zirconia (YSZ) thermal barrier coatings (TBCs) are no longer sufficient for the stringent demands in the high operating temperature and excellent thermophysical properties of the high-performance gas turbines and aviation engines. High entropy ceramics, distinguished by their superior thermophysical properties, have risen as a potential substitute for TBCs. However, the realm of atmospheric plasma spraying (APS) in the creation of these advanced TBCs remains relatively unexplored. In this work, three distinct high-entropy (La0.2Sm0.2Eu0.2Yb0.2Y0.2)2(Ce0.5Zr0.5)2O7 coatings were developed through the meticulous alteration of spraying power. The effects of spraying power on the microstructure, valence states of constituent elements and thermophysical properties of the coatings were deeply investigated. The results indicated that all the as-sprayed coatings exhibit a defect fluorite structure. Spraying power does have a significant impact on the thermophysical properties of the coatings. With the decrease in spraying power, the thermal conductivity of the coatings shows a progressive reduction, whereas the coefficient of thermal expansion (CTE) exhibits a gradual increase. This trend is closely related to valence states of constituent elements in the coatings. The resulting coating exhibits a low thermal conductivity of 0.54 W⋅m-1⋅K-1, a high CTE of 11.22×10-6·K-1 and a superior phase stability at elevated temperatures.

The structural, elastic, optoelectronic properties and hydrogen storage capability of lead-free hydrides XZrH3 (X: Mg/Ca/Sr/Ba) for hydrogen storage application: A DFT study

Perovskite hydrides are promising materials for hydrogen capacity application to achieve the US DOE on-board criteria. We have investigated novel perovskite hydrides XZrH3 (X: Mg/Ca/Sr/Ba) for H2 storage and transportation applications. In this study we investigates the physical properties of XZrH3 light materials for solid-state hydrogen storage application by incorporating the DFT framework with the CASTEP code. We have theoretically examined the structural, mechanical, electronic, optical, and hydrogen storage properties of these materials. The selected compounds were fully relaxed and optimized in the cubic phase space group Pm-3 m. Structural phase stability was confirmed through thermodynamic, and mechanical analyses. Mechanical properties, evaluated based on Poisson’s ratio, the Puagh’s ratio, and Cauchy pressure, indicate the ductile behavior with a preference for ionic bonding. The electronic structure analysis reveals the metallic behavior of these materials. Optical calculations were also performed to provide additional insights into the physical properties of H2 compounds. The gravimetric hydrogen storage capacities were calculated as 2.55, 2.25, 1.66, and 1.31 wt% for MgZrH3, CaZrH3, SrZrH3, And BaZrH3 hydrides respectively. The identified properties of XZrH3 suggest that these materials could significantly enhance hydrogen storage systems, with potential integration into existing energy technologies, offering a pathway toward more efficient and sustainable hydrogen-based solutions.

Pioneering computational insights into the structural, magnetic, and thermoelectric properties of A3XN (A=Co, Fe; X=Cu, Zn) anti-perovskites for advanced material applications

This study pioneers the utilization of computer-controlled simulations to elucidate the structural, elastic, electronic, and thermoelectric properties of A3XN anti-perovskites (A = Co, Fe; X = Cu, Zn). Starting with the development of a detailed structural model, structural optimization calculations identify the stable Pm-3m cubic phase, aligning with experimental findings. Also, these optimizations indicate the ferromagnetic phase stability of A3XN anti-perovskites, further supported by positive Curie-Weiss constants of 60 K, 80 K, and 100 K for Co₃CuN, Co₃ZnN, and Fe₃CuN, respectively. The spin-dependent electronic properties, including band structure and density of states, are explored using multiple exchange-correlation (XC) functionals—GGA, GGA + U, and GGA + mBJ. The results uphold the metallic nature of the materials, accompanied by significant spin magnetic moments. Specifically, the calculated values of magnetic moments for Co3CuN, Co3ZnN, and Fe3CuN are 5.08 μB, 3.70 μB, and 7.61 μB, respectively. Furthermore, we compute the Curie temperatures for each compound, 942.48 K for Co3CuN, 692.7 K for Co3ZnN, and 1400.41 K for Fe3CuN, which are substantially elevated, indicating robust ferromagnetic behavior that persists well above ambient conditions. Mechanical properties, including stability, deformation behavior, and ductility, are validated through elastic calculations, with various mechanical anisotropy factors examined. From an application perspective, the thermoelectric characteristics of Co3CuN, Co3ZnN, and Fe3CuN are meticulously evaluated, focusing on parameters like the Seebeck coefficient, electrical conductivity, thermal conductivity, power factor and figure of merit (zT). The analysis highlights promising power factor values of 3.0×1011(W/cm.K2), 4.0×1011(W/cm.K2), and 6.0×1011(W/cm.K2) for Co3CuN, Co3ZnN, and Fe3CuN, respectively, suggesting potential for enhanced efficiency in thermopower generation, particularly in waste heat recovery applications. Furthermore, the study provides a comprehensive analysis of the ground-state optical properties of A3XN, including the dielectric constant, photoconductivity, reflectivity, refractive index, absorption coefficient, and extinction coefficient. The reflectivity spectra demonstrate high reflectivity of 45 % across visible and ultravioletregions, suggesting suitability for applications in coatings designed to mitigate solar heating effects.

Realizing near-full density monophasic tetragonal 1.5-mol% yttria-stabilized zirconia ceramics via current-ramp flash sintering

This study demonstrates the successful fabrication of near-full density monophasic tetragonal 1.5-mol% yttria-stabilized zirconia (1.5YSZ) ceramics using current-ramp flash (CRF) sintering technique. The process involved regulating Joule heating in the samples by fine-tuning the input power through an alternating current field (nominal current density: 50 mA·mm−2) within a 3-minute timeframe at a furnace temperature of 1100°C. This approach effectively enhanced grain size uniformity, which is crucial for preventing sample cracking associated with spontaneous tetragonal-to-monoclinic (T→M) phase transformation, thereby promoting densification with average relative densities exceeding 99%. The highest average fracture toughness of the 1.5YSZ samples was measured at 9.2 MPa·m0.5 using the standardized single-edge pre-cracked beam method. This toughness is approximately double that of commonly used 3YSZ samples produced by CRF sintering, all of which exhibited comparable average grain sizes and relative densities. Additionally, the 1.5YSZ samples demonstrated nearly identical resistance to low-temperature degradation (LTD) compared to the 3YSZ samples after accelerated hydrothermal aging at 140°C for 15 hours, roughly equivalent to 60 years at 37°C. The reduced yttria concentration in 1.5YSZ facilitates T→M phase transformation at lower stress thresholds, enhancing toughness through increased crack shielding from a larger volume fraction of transformed grains. Furthermore, the uniform yttria distribution in 1.5YSZ, revealed by scanning transmission electron microscopy, compensates for the reduced tetragonal phase stability and contributes to improved LTD resistance. Notably, these exceptional properties were achieved at a furnace temperature 300°C lower and with a sintering duration several hours shorter than those of conventionally-sintered counterparts.

Differential Phase Analysis for Volcanic Tremor Detection and Source Location

AbstractWe present observations showing that during episodes of volcanic tremors, the phase of inter‐station cross‐correlations becomes stable. We propose a new quantity, the phase coherence, to identify the differential phase stability in recordings obtained from a single pair of stations, which is extrapolated to the seismic network. Then, we present a new approach based on the estimation of differential travel times through the differential phase measurements, to locate the sources of tremors occurring at the end of 2015 at the Klyuchevskoy Volcanic Group in Kamchatka, Russia. We present evidence supporting the existence of two types of activity happening simultaneously during the tremor episode: the main tremor source, originating from a region located between 7 and 9 km depth under the main volcanoes, and the widespread occurrence of weak low‐frequency earthquakes occurring at random locations. We show how the phase coherence and the differential phases can be used to provide information on the stability of the tremor source position and to estimate its location.

Sb-anchoring single-crystal engineering enables ultra-high-Ni layered oxides with high-voltage tolerance and long-cycle stability

Ni-rich layered oxides are promising cathodes for Li-ion batteries, but the inherent structural defects result in severe surface/bulk degradation during long cycling, especially at high cutoff voltage. Herein we propose a Sb-anchoring single-crystalline engineering to enhance the microstructural and electrochemical stability of ultra-high-Ni layered oxides, where the surface-enriched Sb doping inhibits Li-Ni mixing, suppressing the undesired layered to mixed/rock-salt phase transformation; the bulk-doped Sb rivets into Ni sites, reinforcing the bulk phase stability; the single-crystal endows enhanced crack resistance and reduced surface area, preventing surface parasitic reactions and the subsequent proliferation of cathode electrolyte interfaces. In-situ XRD reveals an essential correlation between cycle stability and phase reversibility, whereas Sb doping into both surface and bulk structures showcases a continuous anchoring effect, largely enhancing the phase transformation reversibility. DFT calculations prove a high oxidation tolerance, as Ni2+ diffusion barrier is higher than the pure cathode. A representative Li(Ni0.9Co0.05Mn0.05)0.99Sb0.01O2 cathode exhibits a high-voltage up to 4.6V, and a Li(Ni0.9Co0.05Mn0.05)0.99Sb0.01O2//graphite full-cell demonstrates an ultra-high capacity retention of 93.4% after 1000 cycles at 1C in 3.0−4.2V. This simple and efficient cathode engineering will promote the promising application of Ni-rich layered oxides in high-energy Li-ion batteries.

Phase stability of convergence zone propagation at mid-frequency.

Mid-frequency transmissions (1.5 to 7.5 kHz) from a towed source to a drifting array one convergence zone away demonstrate smoothly varying phase. Calculations of the strength and diffraction parameters Φ and Λ for a representative background environment predict partially saturated propagation. For a single convergence zone path, the evolving phase rate due to the changing internal wave field corresponds to a narrowband coherent integration time, defined by the length of a discrete Fourier transform that likely captures the signal, from ∼370 s at 10 kHz to ∼1370 s at 1 kHz in the absence of source motion. Simulated propagation with a split-step parabolic equation solver through a sound speed field with thermocline fine structure and a Garrett-Munk internal wave displacement field provides a full wave picture that is consistent with the statistical predictions. Experimental data from the Philippine Sea demonstrates signal phase that is highly correlated with source tow body vertical excursions, measured by a pressure sensor, that couple into horizontal motion. The received signal can be integrated for up to 128 s at 5.5 kHz, with the upper limit thought to be due to non-uniform source motion rather than ocean dynamics.

Multi-objective optimisation and verification of creep-resistant Ni-base superalloy for electron-beam powder-bed-fusion

This paper reports the use of integrated computational alloy design, coupled with a rapid printability screening method, to downselect from a total of 70000 datasets in design space to five candidates in the first step, and then from five to one in the second step. The new Ni-base superalloy with compositions of Ni-5.03Al-2.69Co-5.63Cr-0.04Hf-1.91Mo-2.36Re-3.32Ta-0.57Ti-8.46W-0.05C-0.019B exhibits an optimal balance of density (8.82 g/cm2), printability (freezing range of 107 °C), thermal stability (γ′-volume fraction of 50.7% at 980 °C and low Md‾ value) and creep (rupture time of 612 h at 980 °C/120 MPa). The micro-hardness varies mildly from 417.2 ± 18.5 to 434.7 ± 14.6 HV, suggesting good phase stability. This is substantiated by microstructure observations, which revealed the absence of a topologically close-packed phase. Machine-learning tools of the artificial neural network (ANN), random forest, and support vector regression, respectively, were used to predict creep rupture time. The ANN algorithm achieves the highest accuracy in predicting creep life. By recognising the “black box” nature of the ANN, interpretability analysis was conducted using the local interpretable model-agnostic method. The analysis supports that the ANN model truly learned meaningful functional relationships, and thus is judged as reliable. Feature correlation evaluation outcome emphasises the importance of incorporating microstructure-related input features.

Navigating Challenges and Promises for Next‐Generation CsPbIBr2 Perovskite Solar Cells: A Review

AbstractGiven the increasing demand for electricity due to modernization and population growth, there is an urgent need to develop renewable energy conversion technologies such as photovoltaics. Among these technologies, CsPbIBr2, an all‐inorganic lead halide‐based perovskite, has shown promise due to its thermal stability, phase stability, and ease of fabrication. However, challenges remain, particularly in addressing device hysteresis and stability. Novel materials and optimized device designs could help overcome these challenges. This comprehensive review discusses strategies such as interface engineering, film quality improvement, compositional engineering, defect passivation, band alignments, and metal ion doping to enhance the performance of CsPbIBr2‐based perovskite films and, in turn, their potential for photovoltaic applications.

The effect of trace vanadium addition on mechanical properties, microstructure and austenite phase characteristics in a 3.9% Al-Delta TRIP steel

This study aimed to examine the effect of adding 0.12 wt% vanadium on the properties of delta TRIP steel through microstructural and mechanical investigations. The delta ferrite phase was observed in all annealing temperatures and samples. Carrying out bainitic transformation at 350 °C for 6, 10, and 15 min resulted in the stability of the austenite phase and the formation of ferritic bainite phase after heat treatment. The presence of vanadium led to the formation of MC precipitate phases and reduced the remaining austenite percentage from 14% to 6% by weight in the heat-treated sample. The low percentage of austenite in vanadium-containing steel has weakened the TRIP effect in strengthening. On the other hand, the presence of MC precipitates has compensated for the reduction in strength from the TRIP strengthening process through precipitation hardening and reducing the grain size of the delta ferrite phase. The resulting properties (UTS: 866 MPa and El: 41.3%) have led to the creation of a formability index of 35 GPa% in vanadium-containing steel, which is better than the mechanical properties (UTS: 857 MPa and El: 37.4%) and the formability index of vanadium-free steel (32 GPa%). These factors make this steel a suitable option for automotive industry applications. Based on these features make this steel a suitable candidate for automotive industries. Microstructural investigations revealed that the addition of vanadium reduces the grain size of the delta ferrite phase. Typically, the austenite phase forms around the ferritic bainite phase and delta ferrite grain boundaries. During tensile testing, it transforms into martensite through the TRIP process.

Molecular-Level Understanding of Phase Stability in Phase-Change Nanoemulsions for Thermal Energy Storage by NMR Spectroscopy.

Phase change materials (PCMs) are latent heat storage materials that can store or release thermal energy while undergoing thermodynamic phase transitions. Organic PCMs can be emulsified in water in the presence of surfactants to enhance thermal conductivity and enable applications as heat transfer fluids. However, PCM nanoemulsions often become unstable during thermal cycling. To better understand the molecular origins of phase stability in PCM nanoemulsions, we designed a model PCM nanoemulsion system and studied how the molecular-level environments and dynamics of the surfactants and oil phase changed upon thermal cycling using liquid-state nuclear magnetic resonance (NMR) spectroscopy. The model system used octadecane as the oil phase, stearic acid as the surfactant, and aqueous NaOH as the continuous phase. The liquid fraction of octadecane within the nanoemulsions was quantified noninvasively during thermal cycling by liquid-state 1H single-pulse NMR measurements, revealing the extent of octadecane supercooling as a function of temperature. The mean droplet size of the PCM nanoemulsions, measured by dynamic light scattering (DLS), was correlated with the liquid content of octadecane to explain phase instability in the solid-liquid coexistence region. Quantitative 13C single-pulse NMR experiments established that the carbonyl surfactant head groups were present in multiple distinct environments during thermal cycling. After repeated thermal cycling, the 13C signal intensity of the carbonyl surfactant head groups decreased, indicating that the surfactant head groups lost molecular mobility. The results explain, in part, the origin of phase instability of PCM nanoemulsions upon thermal cycling.

Insights into the Theranostic Activity of Nonoxido VIV: Lysosome-Targeted Anticancer Metallodrugs.

Developing new anticancer agents can be useful, with the ability to diagnose and treat cancer worldwide. Previously, we focused on examining the effects of nonoxidovanadium(IV) complexes on insulin mimetic and cytotoxicity activity. In this study, in addition to the cytotoxic activity, we evaluated their bioimaging properties. This study investigates the synthesis of four stable nonoxido VIV complexes [VIV(L1-4)2] (1-4) using aroylhydrazone ligands (H2L1-4) and their full characterization in solid state and the solution phase stability using various physicochemical techniques. The biomolecular (DNA/HSA) interaction of the complexes was evaluated by using conventional methods. The in vitro cytotoxicity of 1-4 was studied against A549 and LN-229 cancer cell lines and found that drug 2 displayed the highest activity among the four. Since 1-4 are fluorescently active, live cell imaging was used to evaluate their cellular localization activity. Complexes specifically target the lysosome and damage lysosome integrity by producing an excessive amount (9.7-fold) of reactive oxygen species (ROS) compared to the control, which may cause cell apoptosis. Overall, this study indicates that 2 has the greatest potential for the development of multifunctional theranostic agents that combine imaging capabilities and anticancer properties of nonoxidovanadium(IV)-based metallodrugs.

Controlled Vapor-Liquid-Solid Growth of Long and Remarkably Thin Pb1-xSnxTe Nanowires with Strain-Tunable Ferroelectric Phase Transition.

The Pb1-xSnxTe family of compounds possess a wide range of intriguing and useful physical properties, including topologically protected surface states, robust ferroelectricity, remarkable thermoelectric properties, and potential topological superconductivity. Compared to bulk crystals, one-dimensional (1D) nanowires (NWs) offer a unique platform to enhance the functional properties and enable new capabilities, e.g., to realize 1D Majorana zero modes for quantum computations. However, it has been challenging to achieve controlled synthesis of ultrathin Pb1-xSnxTe (0 ≤ x ≤ 1) nanowires in the truly 1D region. In this work, we report on a Au-catalyzed vapor-liquid-solid (VLS) growth of remarkably thin (20-30 nm) and sufficiently long (several to tens of micrometers) Pb1-xSnxTe nanowires of high single-crystalline quality in a controlled fashion. This controlled growth was achieved by enhancing the incorporation of Te into the Au catalyst particle to facilitate the precipitation of the Sn/Pb species and suppress the enlargement of the particle, which we identified as a major challenge for the growth of ultrathin nanowires. Our growth strategy can be easily extended to other compound and alloy nanowires, where the constituent elements have different incorporation rates into the catalyst particle. Furthermore, the growth of thin Pb1-xSnxTe nanowires enabled strain-dependent electrical transport measurements, which shows an enhancement of electrical resistance and ferroelectric transition temperature induced by uniaxial tensile strain along the nanowire axial direction, consistent with density functional theory calculations of the structural phase stability.

Synthesis and characterization of TiO2/ZnO/SiO2 nanocomposite using pyrrolidinium-based ionic liquids via sol–gel-hydrothermal method for photocatalytic removal of Pb (II) ions

This study aims to synthesize TiO2 with precise particle morphology, a large surface area, a stable anatase phase at high temperatures, and enhanced catalytic activity in the visible light spectrum. TiO2 was combined with ZnO and SiO2 to form a TiO2/ZnO/SiO2 composite (TZS). A TiO2/ZnO/SiO2 composite (TZS) was synthesized via sol–gel-hydrothermal method at 180 °C for 24 h employing a water-pyrrolidinium-based ionic liquid mixture. XRD analysis confirmed anatase, zincite, and amorphous silica phases post-calcination at 450 °C. Compared to water alone, TZS synthesized with the water-ILs media exhibited higher surface area and narrower band gap energy. TG-DTA analysis confirmed anatase phase stability up to 1000 °C. SEM and TEM images showed TZS particles synthesized using water as spherical, while the water-ILs mixture produced nanocoral, nanorod, and nanocubic morphologies. In photocatalysis, TZS synthesized with water-ILs removed Pb(II) ions by 99.98 %, surpassing water-synthesized TZS at 95.49 % indicating superior photocatalytic of TZS synthesized with water-ILs.

Probing the thermodynamics of charged Gauss Bonnet AdS black holes with the Lyapunov exponent

In this paper, we investigate the thermodynamic properties of the charged AdS Gauss–Bonnet black holes and their associations with the Lyapunov exponent. The chaotic features of the black holes and the isobaric heat capacity characterized by the Lyapunov exponent are studied to reveal the thermodynamic stability of the black hole phases. By considering both the timelike and null geodesics, we find that the relationship between the Lyapunov exponent and the Hawking temperature can accurately represent the features of the Small/Large phase transition and even the triple point. We also reveal the properties of the difference in the Lyapunov exponent as an order parameter. It is demonstrated that there is a negative correlation between the Lyapunov exponent and the size of the black hole shadow, which can be used to bridge the thermodynamic properties and the shadow of black holes.

First Principles Study of the Phase Stability, the Li Ionic Diffusion, and the Conductivity of the Li10GexMo1−xP2S12 of Superionic Conductors

Using first-principles density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations, we performed this study on the phase stability, the intrinsic redox stability, and the Li+ conductivity of Li10GexMo1−xP2S12 (x = 0~1) superionic conductors. Molybdenum (Mo) is expected to replace expensive germanium (Ge) to lower tmaterial costs, reduce sensitivity to ambient water and oxygen, and achieve acceptable Li+ conductivity. The ab initio first principle molecular dynamics simulations show that room-temperature Li+ conductivity is 1.12 mS·cm−1 for the Li10Ge0.75Mo0.25P2S12 compound, which is comparable to the theoretical value of 6.81 mS·cm−1 and the experimental measured one of 12 mS·cm−1 of the Li10GeP2S12 (LGPS) structure. For Li10GexMo1−xP2S12 (x = 0, 0.25, 0.5 and 1) compounds, the density of states and the projection fractional wave state density were calculated. It was found that when Ge atoms were partially replaced by Mo atoms, the band gap remained unchanged at 2.5 eV, but deep level defects appeared in Mo-substituted compounds. Fortunately, this deep level defect is difficult to ionize at room temperature, so it has no effect on the electronic conductivity of Mo substitute compounds, making Mo substitution a suitable solution for electrolyte materials. The projection fractional wave state density calculation shows that the covalent bond between Mo and S is stronger than that between Ge and S, which reduces the sensitivity of Mo-substituted compounds to water and oxygen contents in the air. In addition, the partial state density coincidence curve between Li and S elements disappears in the 25% Mo-substituted compound with energies of 4–5 eV, indicating that the Li2S by-product is decreased.

First-principles calculations of phase stability, electronic structure, mechanical properties and thermal conductivities of TMH2 (TM=V, Nb, Ta) metal hydrides

TMH2 (TM = V, Nb, Ta) metal hydrides can be used as potential hydrogen storage materials. However, there have been no available data on the mechanical and thermodynamic properties of these hydrides, especially TaH2. Herein, based on first-principles calculations, the phase stability, electronic structure, mechanical properties and thermal conductivities of TMH2 (TM = V, Nb, Ta) hydrides are investigated. The results show that VH2, NbH2, and TaH2 are thermodynamically and dynamically stable. The calculated electronic structures show that these three hydrides possess electron orbital hybridization among atoms and strong chemical bonding. The chemical bonds in TMH2 are mainly ionic and partially covalent. According to the calculated Poisson's ratios, Pugh’s ratio and Cauchy pressures, VH2, NbH2, and TaH2 are ductile. Moreover, these three hydrides have elastic anisotropy and good damage tolerance. Finally, the predicted thermodynamic properties indicate that TMH2 can be used as potential thermal insulating materials.

The connection between the accumulation of structural defects caused by proton irradiation and the destruction of the near-surface layer of Li4SiO4 – Li2TiO3 ceramics

The key problem of using lithium-containing ceramics as materials of breeders for the propagation of tritium in thermonuclear reactors is phase stability, as well as the preservation of strength and thermophysical parameters of ceramics during their operation, which is accompanied by the accumulation of fission products in the near-surface layers, alongside mechanical influences from the outside. Moreover, in contrast to other types of ceramics, the presence of lithium in the composition of the samples under study leads to limitations in the use of classical analysis methods (scanning electron microscopy, energy dispersive analysis or optical spectroscopy) of structural changes caused by the accumulation of radiation damage, which requires the use of more complex methods for the assessment of the defect concentration in the structure, as well as establishing their relationship with the deterioration of strength and thermophysical parameters, playing a key role in determining the stability mechanisms and further exploitation of ceramics for tritium production. In this regard, the aim of the study is to determine the kinetics of changes in the near-surface layer of two-phase Li4SiO4 – Li2TiO3 ceramics associated with the accumulation of structural distortions caused by irradiation, as well as their relationship with strain embrittlement and disorder. During the studies, it was found that the accumulation of implanted hydrogen in the near-surface layer under high-dose irradiation initiates deformation distortion processes, the intensity of which depends on the ratio of components in the ceramics, according to which the optimal compositions of two-phase ceramics are ratios of components from 0.3 to 0.6. Determination of the type of defects in the composition of the damaged layer, as well as their concentration, was carried out using the electron spin resonance (ESP) method. During the studies, it was found that at low irradiation fluences, the dominant role in the accumulation of structural defects is played by vacancy defects associated with E′-centers, the formation of which is associated with structural distortions, while as the fluence grows, the structure is dominated by deformation disordering caused by the accumulation of Ti3+ defects and HC2 centers (SiO43-), the concentrations of which have a clear dependence on the phase composition of the ceramics.

Ab-initio investigation of structural, electronic, thermoelectric and optical properties of Full-Heusler X2MnB (X = Ti, Zr) for energy harvesting applications

In this manuscript comprehensive first-principles calculations have been presented for Full-Heusler X2MnB (X = Ti, Zr) compounds. This work includes detailed observations of the structural stability, origin of the transport phenomenon, optical properties, and electronic response. Structural parameters support the previous findings by confirming structural stability in the non-magnetic phase. Ti2MnB (Zr2MnB) valence band maxima and conduction band minima have bandgaps of 0.217 (0.301) eV and 0.181 (0.209) eV for PBE-GGA (mBJ) approximations which lie between L-L symmetry points. Due to the comparative measurements of the two states, the DOS results show that the Ti1/Zr1, Ti2/Zr2 Mn eg, and t2g states mainly contribute to the valence band region for Ti2MnB and Zr2MnB alloys, confirming their ionic nature. The computation of the overall electronic parameters’ reveals semiconducting nature. Thermoelectric properties have been calculated as a function of temperature in the 100–1200 K range. The positive values of Seebeck coefficients specify p-type character of X2MnB While at 300 K, Zr2MnB and Ti2MnB showed the highest Seebeck coefficients, measuring roughly values of 268 (µK/V) and 243 (µK/V), respectively. These values suggest that the material exhibits high thermoelectric performance. Though high optical absorption coefficient and low reflectivity in the visible and ultra violet regions, confirms use of these materials in solar cell applications. These findings suggest that material holds great potential for use in thermoelectrical applications which can support in upcoming experimental considerations.