Phase Structure Research Articles

Incorporation of Pd Single-Atom Sites in Perovskite with an Excellent Selectivity toward Photocatalytic Semihydrogenation of Alkynes.

Semihydrogenation is a crucial industrial process. Noble metals such as Pd have been extensively studied in semihydrogenation reactions, owing to their unique catalytic activity toward hydrogen activation. However, the overhydrogenation of alkenes to alkanes often happens due to the rather strong adsorption of alkenes on Pd active phases. Herein, we demonstrate that the incorporation of Pd active phases as single-atom sites in perovskite lattices such as SrTiO3 can greatly alternate the electronic structure and coordination environment of Pd active phases to facilitate the desorption of alkenes rather than further hydrogenation. Furthermore, the incorporated Pd sites can be well stabilized without sintering by a strong host-guest interaction with SrTiO3 during the activation of H species in hydrogenation reactions. As a result, the Pd incorporated SrTiO3 (Pd-SrTiO3) exhibits an excellent time-independent selectivity (>99.9 %) and robust durability for the photocatalytic semihydrogenation of phenylacetylene to styrene. This strategy based on incorporation of active phases in perovskite lattices will have broad implications in the development of high-performance photocatalysts for selective hydrogenation reactions.

Titanium Dioxide and Photocatalysis: A Detailed Overview of the Synthesis, Applications, Challenges, Advances and Prospects for Sustainable Development

The term “photocatalysis” has recently gained high popularity, and various products using photocatalytic functions have been commercialized. Of all the materials that may be used as photocatalysts, titanium dioxide (TiO2) is virtually the only one that is now and most likely will remain appropriate for industrial application. Water and air purification systems, sterilization, hydrogen evolution, self-cleaning surfaces, and photoelectrochemical conversion are just a few of the products and applications in the environmental and energy domains that make extensive use of TiO2 photocatalysis. This is due to the fact that TiO2 has the lowest cost, most stability, and most effective photoactivity. Furthermore, history attests to its safety for both people and the environment because it has been used as a white pigment since antiquity. This review discusses some important aspects and issues concerning different synthesis methods and their influence on the structure and properties of TiO2, as well as the concept of photocatalysis based on it as a promising biocompatible functional material that has been widely used in recent years. The advantages of TiO2 applications in various fields of science and technology are discussed, including environmental protection, photocatalysis including self-cleaning surfaces, water and air purification systems, hydrogen liberation, photovoltaic energy, cancer diagnosis and therapy, coatings and dental products, etc. Information on the structure and properties of TiO2 phases is presented, as well as modern methods of synthesizing functional materials based on it. A detailed review of the basic principles of TiO2 photocatalysis is then given, with a brief introduction to the modern concept of TiO2 photocatalysis. Recent advances in the fundamental understanding of TiO2 photocatalysis at the atomic-molecular level are highlighted, and advances in TiO2 photocatalysis from the perspective of design and engineering of new materials are discussed. The challenges and prospects of TiO2 photocatalysis are briefly discussed.

Imaging magnetic transition of magnetite to megabar pressures using quantum sensors in diamond anvil cell

High-pressure diamond anvil cells have been widely used to create novel states of matter. Nevertheless, the lack of universal in-situ magnetic measurement techniques at megabar pressures makes it difficult to understand the underlying physics of materials’ behavior at extreme conditions, such as high-temperature superconductivity of hydrides and the formation or destruction of the local magnetic moments in magnetic systems. Here, we break through the limitations of pressure on quantum sensors by modulating the uniaxial stress along the nitrogen-vacancy axis and develop the in-situ magnetic detection technique at megabar pressures with high sensitivity (~1μT/Hz\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\sim 1{{{\\rm{\\mu }}}}{{{\\rm{T}}}}/\\sqrt{{{{\\rm{Hz}}}}}$$\\end{document}) and sub-microscale spatial resolution. By directly imaging the magnetic field and the evolution of magnetic domains, we observe the macroscopic magnetic transition of Fe3O4 in the megabar pressure range from ferrimagnetic (α-Fe3O4) to weak ferromagnetic (β-Fe3O4) and finally to paramagnetic (γ-Fe3O4). The scenarios for magnetic changes in Fe3O4 characterized here shed light on the direct magnetic microstructure observation in bulk materials at high pressure and contribute to understanding magnetism evolution in the presence of numerous complex factors such as spin crossover, altered magnetic interactions and structural phase transitions.

Structural phase transition from rhombohedral to monoclinic phase and physical properties of (1-x) Bi0.85La0.15FeO3 – (x) Ca0.5Sr0.5TiO3 ceramics prepared by the solid-state route

In the present work, a series of solid solutions were synthesized using the solid-state reaction method for x = 0.0, 0.05, 0.10, and 0.15 in system (1-x)Bi0.85La0.15FeO₃-(x)Ca0.5Sr0.5TiO3 or ((1-x)BLFO-(x)CSTO) ceramics. Structural, optical, dielectric, and ferroelectric properties were studied in detail to investigate the impact of CSTO doping in BFO. Rietveld analysis of X-ray diffraction data of all samples revealed the formation of a single-phase solid solution with a distorted rhombohedral perovskite structure for x = 0.00 and 0.05, characterized by R3c symmetry, a mix of rhombohedral (R3c) and monoclinic (Cc) phases for x = 0.10 (R3c 31 % and Cc 69 %), whereas for x = 0.15 a single-phase solid solution with Cc symmetry was found. UV–visible analysis demonstrated that the optical band gap was increased from 2.11 eV for x = 0.0 to 2.21 eV for x = 0.15 in the visible range, and can be used in photovoltaics applications. The room temperature dielectric properties were measured, and a crucial role of CSTO was revealed in modifying the dielectric properties of BLFO ceramics; the dielectric constant and dielectric loss at 10 kHz change from εr = 82 and tanδ = 0.88 for x = 0.0 to εr = 116 and tanδ = 1.08 for x = 0.15. The leakage current density decreases while increasing the CSTO % from x = 0.0 to 0.15 due to the suppression of oxygen and Bi vacancies, a fact that is further reflected in the ferroelectric properties of CSTO-doped BFO ceramics. Room temperature ferroelectric properties improved with CSTO doping, and Pr was found to be 0.24 μC/cm2, 0.28 μC/cm2, and 0.84 μC/cm2 for x = 0.05, 0.10, and 0.15, respectively.

The Effect of Fe Content on the Shape Memory Effect of Ni-Mn-Ga-Fe Shape Memory Alloy Microwires after Ordering Heat Treatment

The shape memory capabilities of Heusler alloy microwires with two different contents of Fe element instead of Ga element following step-by-step ordering heat treatment were explored based on the stoichiometric ratio of Ni2MnGa. The melt-drawing technique was used to create the polycrystalline microwires, and the two microwires had Fe atomic contents of 4.7 at.% and 5.5 at.%, respectively. The field emission scanning electron microscope was used to analyze the microwire’s surface condition as well as the microscopic tensile fracture morphology. Using an X-ray diffractometer, the microwires’ crystal structure was identified for phase analysis. Differential scanning calorimetry was used to examine the microwires’ behavior during martensitic transformation. Using a dynamic mechanical stretcher, the elongation and recovery rate of microwires’ one- and two-way shape memory behavior were examined. The findings demonstrated that the microwire phase structure, martensitic transformation behavior, and shape memory capabilities all displayed good properties after the heat treatment was ordered.

Development of Interpenetrating Phase Structure AZ91/Al2O3 Composites with High Stiffness, Superior Strength and Low Thermal Expansion Coefficient

Development of Interpenetrating Phase Structure AZ91/Al2O3 Composites with High Stiffness, Superior Strength and Low Thermal Expansion Coefficient

Mechanical and Tribological Properties of Laminated (NbTaMoW)Nx Films.

Laminated (NbTaMoW)Nx films were prepared via co-sputtering. The sputtering variables were a substrate holder rotation speed of 2 and 10 rpm and a nitrogen flow ratio (fN2 = N2/(Ar + N2)) of 0.1, 0.2, and 0.4. The (NbTaMoW)Nx films fabricated at 30 rpm displayed columnar structures. The phase structures of the laminated (NbTaMoW)Nx films varied from multiple body-centered cubic phases to a nanocrystalline and a face-centered cubic phase as the fN2 increased from 0.1 to 0.2 and 0.4. The mechanical and tribological properties of the laminated (NbTaMoW)Nx films were evaluated. The laminated (NbTaMoW)Nx films deposited at an fN2 of 0.4 had hardnesses of 25.2 and 26.1 GPa when prepared at 2 and 10 rpm, respectively, lower than the value of 29.9 GPa for the columnar (NbTaMoW)Nx film prepared at an fN2 of 0.4 and 30 rpm. In contrast, the wear resistances of the laminated (NbTaMoW)Nx films were superior to those of the columnar (NbTaMoW)Nx films.

Application of Soft Magnetic Composite in XEV Motor Core Manufacturing: Process Effects and Performance Analysis

This study explores the application of AncorLam HR (Höganäs, Sweden), a soft magnetic composite material, in the stator core of an axial flux permanent magnet drive motor. Building on previous research that provided mechanical and thermal properties of the material, the focus is on analyzing how the manufacturing process affects the motor core’s shape. A bulk prototype was created based on case 3, which demonstrated the least deviation in density and internal stress. The prototypes were produced under the conditions of SPM 7 and 90 °C, and a heat treatment in a nitrogen atmosphere for 1 h, resulting in an average density error of 0.54%, confirming process effectiveness. A microstructural analysis using scanning electron microscopy (SEM) on Sample 2, with the highest density, confirmed consistency between simulation and prototype trends. Electron backscatter diffraction (EBSD) and X-ray diffraction (XRD) analyses revealed that the internal phase structure remained unchanged. Energy-dispersive spectroscopy (EDS) and transmission electron microscopy (TEM) identified the elimination of phosphorus (P) during molding, affecting the insulating layer, a critical factor for SMC materials. In motor simulations and actual measurements, the average torque was recorded as 37.7 N·m and 34.7 N·m at 1500 rpm and 27.7 N·m and 25.1 N·m at 2000 rpm, respectively. The torque comparison observed in the actual measurements compared to the simulation results indicates that the output loss increases in the actual measurements due to the deterioration of the insulation performance judged based on the microstructure evaluation. This study confirms the viability of using AncorLam HR in motor cores for electric vehicles and provides key data for improving the performance.

Pressure-induced anomaly of transport properties and structural transition in layered ferromagnetic metal TlCo2S2

In this work, the structural and transport properties of ferromagnetic metal TlCo2S2 with ThCr2Si2-type crystal structure are systematically studied using high-pressure synchrotron x-ray powder diffraction, electrical transport measurements and first-principles calculations. All the resistances of TlCo2S2 between 1.4 GPa and 5.2 GPa exhibit an upturn at TS and an obvious hysteresis is observed below TS when measured in the cooling and heating processes. As the pressure increases, TS gradually increases and the resistances display a metallic behavior without any anomaly in the whole temperature region above 5.2 GPa, indicating that a possible structural phase transition occurs at TS and is beyond the room temperature above 5.2 GPa. High-pressure x-ray diffraction measurements combined with crystal structure prediction indicate that at room temperature TlCo2S2 undergoes a structural phase transition from a tetragonal phase (I4/mmm) to an orthorhombic structure (Bmab) at Pc ≈6.8 GPa, which is consistent with the results of the resistances under high pressure. Our results indicate that a first-order structural phase transition of TlCo2S2 is induced by high pressure and then results in the anomaly of the electrical transport properties.

Study on the effect of temperature on the microstructure and mechanical properties of as-cast CoCr2Ni3.5VAl1.5Ti high-entropy alloy

This study investigates the microstructure and mechanical properties of a CoCr2Ni3.5VAl1.5Ti high entropy alloy (HEA) annealed at 500 °C, 700 °C, 900 °C and 1100 °C for 6 h. The alloy was prepared using a vacuum induction melting furnace and annealed at the specified temperatures for 6 h. It was then characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electron backscatter diffraction (EBSD). The results indicate that with increasing annealing temperature, the alloy's phase structure transitions gradually from multiphase (fcc, bcc, hcp) to predominantly fcc phase, with relatively stable elemental distributions. Annealing at 500 °C–900 °C mainly strengthens the alloy through precipitates and dislocation strengthening, whereas at 1100 °C, strengthening occurs through grain boundary strengthening and precipitate growth, enhancing the material's strength and ductility. The alloy exhibits optimal comprehensive performance after annealing at 1100 °C. This study provides important insights for optimizing the heat treatment process of HEAs.

An Investigation of Oxides of Tantalum Produced by Pulsed Laser Ablation and Continuous Wave Laser Heating.

Recent progress has seen multiple Ta2O5 polymorphs generated by different synthesis techniques. However, discrepancies arise when these polymorphs are produced in widely varying thermodynamic conditions and characterized using different techniques. This work aimed to characterize and compare Ta2O5 particles formed at high and low temperatures using nanosecond pulsed laser ablation (PLA) and continuous wave (CW) laser heating of a local area of tantalum in either air or an 18O2 atmosphere. Scanning electron microscopy (SEM) and Raman spectroscopy of the micrometer-sized particles generated by PLA were consistent with either a localized amorphous Ta2O5 phase or a similar, but not identical, crystalline β-Ta2O5 phase. The Raman spectrum of the material formed at the point of CW laser impingement was in good agreement with the previously established ceramic "H-Ta2O5" phase. TEM and electron diffraction analysis of these particles indicated the phase structure matched an oxygen-vacated superstructure of monoclinic H-Ta2O5. Further from the point of laser impingement, CW heating produced particles with a Raman spectrum that matched β-Ta2O5. We confirmed that the high-temperature ceramic phase characterized in previous work by Raman spectroscopy was the same monoclinic phase characterized in different work by TEM and could be produced by direct laser heating of metal in air.

Contour Detection Algorithm for α Phase Structure of TB6 Titanium Alloy fused with Multi-Scale Fretting Features

Aiming at the problems of inaccuracy in detecting the α phase contour of TB6 titanium alloy. By combining computer vision technology with human vision mechanisms, the spatial characteristics of the α phase can be simulated to obtain the contour accurately. Therefore, an algorithm for α phase contour detection of TB6 titanium alloy fused with multi-scale fretting features is proposed. Firstly, through the response of the classical receptive field model based on fretting and the suppression of new non-classical receptive field model based on fretting, the information maps of the α phase contour of the TB6 titanium alloy at different scales are obtained; then the information map of the smallest scale contour is used as a benchmark, the neighborhood is constructed to judge the deviation of other scale contour information, and the corresponding weight value is calculated; finally, Gaussian function is used to weight and fuse the deviation information, and the contour detection result of TB6 titanium alloy α phase is obtained. In the Visual Studio 2013 environment, 484 metallographic images with different temperatures, strain rates, and magnifications were tested. The results show that the performance evaluation F value of the proposed algorithm is 0.915, which can effectively improve the accuracy of α phase contour detection of TB6 titanium alloy.

Ultrahigh Energy-Storage in Dual-Phase Relaxor Ferroelectric Ceramics.

High-performance dielectric energy-storage ceramics are beneficial for electrostatic capacitors used in various electronic systems. However, the trade-off between reversible polarizability and breakdown strength poses a significant challenge in simultaneously achieving high energy density and efficiency. Here a strategy is presented to address this issue by constructing a dual-phase structure through in situ phase separation. (Bi0.5Na0.5)TiO3-BaTiO3-based relaxor ferroelectric ceramics are developed, creating a grain-separated dual perovskite phase structure using a facile solid-state reaction method. These ceramics feature two interactive relaxor phases with diversified nanoscale polar structures and heterogeneous grain boundaries, synergistically contributing to high polarization with low hysteresis, substantially increased resistivity, and suppressed electrostrain. Remarkably, a record-high energy density of 23.6Jcm-3 with a high efficiency of 92% under 99kVmm-1 is achieved in the bulk ceramic capacitor. This strategy holds promise for enhancing overall energy-storage performance and related functionalities in ferroelectrics.

Mechanical properties of CoCrFeNi-X (X = Ti,Sn) high entropy alloy and tribological properties in simulated seawater environment

Five multimajor element CoCrFeNi-X(X = Ti,Sn) high entropy alloys (HEA) were prepared by vacuum hot press sintering. The phase composition, mechanical properties and tribological properties of CoCrFeNi-X(X = Ti,Sn) alloys in simulated seawater were investigated. The phase structure of CoCrFeNiTi high-entropy alloy is solid solution FCC phase, R phase, σ phase, and Laves phase. But after addition Sn elements, the phase structure become the FCC phase and Ni-Sn solid solution phase. CoCrFeNiTi alloy has lower density (7.17 g/cm3) and higher hardness (750 HV) than that of CoCrFeNiSn. The compressive yield strength of CoCrFeNiTi HEA is better than CoCrFeNiSn HEA. The CoCrFeNiSn high-entropy alloys showed lower wear rates. The main reason is that SnO2 is generated on the wear scar surface, which has good wetting and corrosion inhibition effects, so CoCrFeNiSn HEA shows better wear resistance in simulated seawater. The main wear mechanism of the CoCrFeNiSn HEA is abrasive wear, oxidative wear, exfoliation wear and corrosive wear.

Simulation of the Evolution of Phase Composition and Austenite Grain Size upon Multi-Pass Hot Deformationof Low-Alloy Steels

The paper presents a model for predicting the structural characteristics and phase composition of low-alloy steels upon hot rolling in the multi-pass deformation mode. The model considers recovery, dynamic, primary, dynamic and static recrystallization of grains, and the normal grain growth, as well as nucleation (including accelerated nucleation during deformation), growth or dissolution, and coarsening of carbonitride particles. The comparison between the calculated results and the experimental data available in the publications shows a satisfactory agreement.

Structural and Electronic Phase Transitions in Three Stable Tin-Sulfur Metallic Chalcogenides under High Pressure.

As a representative homologous series, tin-bearing metallic chalcogenides (SnxSy) have sparked considerable attention because of their stoichiometric compositions and structural diversities. In this work, three stable compounds, SnS, Sn2S3, and SnS2, were screened from SnxSy and a comprehensive investigation on their structural and electrical transport properties was performed up to 60.1 GPa using a diamond anvil cell (DAC) under different hydrostatic environments. Upon nonhydrostatic compression, SnS underwent the Pnma-to-Cmcm transition accompanied by metallization at 7.6 GPa, followed by the Cmcm-to-Pm3̅m transformation at 17.8 GPa. For SnS2, the pressure-induced metallization and isostructural phase transition (IPT) occurred successively at 31.2 and 46.6 GPa, respectively. As an intermediate composition, Sn2S3 first experienced an IPT at 10.8 GPa, and then, the Pnma-to-Cmcm transition concomitantly with metallization occurred at 16.9 GPa, analogous to the high-pressure structural transformation routes of SnS and SnS2. The 0.6-5.4 GPa pressure hysteresis was detectable for the phase transitions of SnxSy under quasi-hydrostatic and hydrostatic conditions owing to the influence of deviatoric stress. In comprehensive consideration of our high-pressure Raman scattering and electrical conductivity results, the systematic construction of a pressure-phase state diagram on SnxSy not only unveils its composition-structure-property relation but also advances the in-depth exploration for other IVA-VIA metallic chalcogenides.

Co1-xS/N, S-codoped carbon loaded porous carbon cloth as flexible electrode for high performance supercapacitors

The capacitive performances of flexible electrodes highly depend on their architectures and redox activity. In this work, Co1-xS/N, S-codoped carbon (NSC) loaded porous carbon cloth (p-CC) was prepared through an etching procedure and a followed repeated-sulfurization process. Since the porous CC could accommodate more Co1-xS nanoparticles and the phase structure of Co1-xS was well controlled by the repeated-sulfurization process, the obtained p-CC/Co1-xS/NSC electrode with optimized composition and architecture exhibits high areal capacitances of 1263.8 mF cm−2 at 1 mA cm−2 and 858.6 mF cm−2 at 50 mA cm−2. The deposited NSC on Co1-xS could effectively prevent their slipping and agglomeration, and thus make the electrode exhibit high capacitance retention of 99.7 % after 20,000 charge–discharge tests. The all-solid-state symmetric supercapacitor assembled by the formed electrodes and ionic liquid/gel electrolyte shows a maximum energy density of 1.34 mWh cm−3 at the power density of 9.55 mW cm−3. These results present a new strategy for the construction of cobalt-sulfide/carbon based flexible electrode with high capacitive performances.

Room temperature phase transition and luminescence behavior of a novel metal‐free ionic crystal [C7H16NO][ClO4

Metal‐free ionic crystals have attracted tremendous attention for their environmental friendliness, biocompatibility, easy fabrication and structural variability. Herein, a metal‐free ionic crystal [C7H16NO][ClO4] ([C7H16NO] = 1‐methyl‐4‐piperidinemethanol) with a dielectric transition at room temperature was designed and constructed. Differential scanning calorimetry (DSC) proved that there exists a reversible phase transition near room temperature at 304 K, accompanied with switchable dielectric behaviors between the low and high dielectric states. The single crystal structure show that the mechanism of such structural phase transition mainly results from the dynamic motion of perchlorate anions. The compound is further shown to exhibit remarkable luminescent properties, characterized by a prolonged lifetime of 18.6 ns. This work offers valuable insights into the construction of room temperature phase‐transition ionic crystals involved with dielectric switching and blue luminescence properties.

Crystallite Size Effects on Electrical Properties of Nickel Chromite (NiCr2O4) Spinel Ceramics: A Study of Structural, Magnetic, and Dielectric Transitions

The effect of sintering temperature on the structural, magnetic, and dielectric properties of NiCr2O4 ceramics was investigated. A powder X-ray analysis indicates that the prepared nanocrystallites effectively inhibit the cooperative Jahn–Teller distortion, thereby stabilizing the high-temperature cubic phase structure with space group Fd-3m. Multiple transitions are confirmed by temperature-dependent magnetization M(T) data. Moreover, the magnetization value decreases and the Curie temperature increases with a decrease in the crystallite size. The low-temperature-dependent real permittivity (ε′-T) for a NiCr2O4 crystallite size of 78 nm exhibits a broad maximum at 40 K that is independent of frequency. This establishes a correlation between electric ordering and the underlying magnetic structure. The temperature dependency of the dielectric constant at fixed frequencies for both NiCr2O4 crystallite sizes rises with temperature for a certain range of frequencies. A significant improvement is evident: the dielectric constant (ε’) at room temperature reaches approximately 5738 for the sample with 28 nm crystallites, while the 78 nm crystallite sample shows a noticeable drop to ε’~174. The frequency-dependent conductivity curves for both types of NiCr2O4 nanocrystallites have different conductivity values. The lower-crystallite-size sample demonstrates higher conductivity values than the 78 nm crystallite size one. This observation is attributed to the decrease in crystallite size, which increases the number of grain boundaries and, consequently, scatters a higher number of charge carriers.

Crystal structure of the incommensurate modulated high-pressure phase of the potassium guaninate monohydrate.

The crystal structure of the incommensurate modulated phase of potassium guaninate monohydrate has been solved on the basis of high-pressure single-crystal X-ray diffraction data. The modulated structure was described as a `mosaic' sequence of three different local configurations of two neighbouring guaninate rings. In contrast to known examples of incommensurate modulated organic compounds, the modulation functions of all atoms are discontinuous. This is the first example of the experimental detection of an incommensurate modulated crystal structure that can be modelled using the special `soliton mode' modulation function proposed by Aramburu et al. [(1995), J. Phys. Condens. Matter, 7, 6187-6196].