Change In Crystal Structure Research Articles

Preparation and property of (NaZn)3+-substituted Sc2Mo3O12 ceramics with negative thermal expansion

To modulate the negative thermal expansion (NTE) performances of Sc2Mo3O12 ceramics, (NaZn)3+-substituted Sc2Mo3O12 ceramics were prepared via solid-state reactions. The crystal phase, morphology, and NTE properties of the NaxZnxSc2−x(MoO4)3 (0 ≤ x ≤ 1) samples were investigated. XRD results reveal that NaxZnxSc2−x(MoO4)3 samples undergo a change in crystal structure from orthorhombic to hexagonal phase due to (NaZn)3+ doping. (NaZn)3+ introduction also promotes grain growth and increases the density of the NaxZnxSc2−x(MoO4)3 ceramics. With the increase in (NaZn)3+ substitution, NaxZnxSc2−x(MoO4)3 ceramics exhibit stronger NTE, and the thermal expansion coefficients (CTEs) improve from −4.74 × 10−6 to −8.77 × 10−6 °C−1 in 30–650 °C. High-temperature XRD results reveal that the hexagonal NaxZnxSc2−x(MoO4)3 samples exhibit anisotropic NTE. With the increase in (NaZn)3+ substitution, the linear CTEs of the a and b axes decreased from −13.17 × 10−6 to −15.93 × 10−6 °C−1, while one of the c axes decreased from 18.38 × 10−6 to 12.27 × 10−6 °C−1. Consequently, hexagonal NaxZnxSc2−x(MoO4)3 samples present stronger NTE as the content x rises.

Charge transfer behavior of triboelectric polymers and triboelectric sensors operated under ultrahigh pressure

AbstractThe energy generation performance of triboelectric materials under ultrahigh pressure remains to be investigated. Here, the variations in molecular structure and built‐in electric field of triboelectric polymers under ultrahigh pressure have been thoroughly studied. The attenuation of built‐in electric field and the escaping of triboelectric charges under ultrahigh pressure are observed in different triboelectric polymers, whereas the existence of deep traps allows the built‐in electric field to be recoverable with the release of pressure. Moreover, the macromolecular conformational changes, including twisting molecular chains and crystal structure changes, can also induce the redistribution of deep traps, leading to a sudden increase in built‐in electric field under specific pressure. Finally, a triboelectric sensor for ultrahigh pressure condition is fabricated with excellent cycle repeatability and a total thickness of 2 mm, which has a sensitivity of 0.07 V MPa−1 within a linear region of 1–100 MPa. This study offers in‐depth insight into the physical understanding of charge behavior both on interface and in bulk of triboelectric materials, whereas the proposed ultrahigh pressure sensors can promote various potential applications of triboelectric sensor in extreme environments.

Polymerization of Potassium Azide in Liquid Nitrogen Using Nanosecond-Pulsed Spark Plasma

In this manuscript, we report on the synthesis of a polynitrogen material from a potassium azide precursor using nanosecond-pulsed spark discharge plasma in liquid nitrogen. The polynitrogen material was characterized using Raman and Fourier transform infrared (FTIR) spectroscopy and identified as K2N6, with planar N6 rings and K- ions that have P6/mmm symmetry. An analysis of the mechanism behind such a transformation shows the importance of direct plasma–chemical effects in polymerization, while the crystal structure changes are believed to be due to plasma-emitted radiation in the ultraviolet range.

CRYSTAL STRUCTURE CHANGE OF CELLULOSE DUE TO GASEOUS AMMONIA TREATMENT

Dissolving pulp was treated with ammonia gas at 20 °C at different pressure levels. The modified pulp was analysed with regard to the change in crystal structure from cellulose I to III. X-ray diffraction and Raman spectroscopy were used as analytical methods. It was found that the transformation of cellulose from cellulose I to III takes place above a defined pressure level, which could be recorded continuously as a function of pressure. Below the characteristic pressure level, the cellulose is still present as cellulose I after treatment. This pressure level is lowered by the presence of water. The ammonia gas is therefore able to swell the crystalline areas of the cellulose starting from a defined process intensity, causing the cellulose to recrystallize in a different structure. Finally, the cellulose III obtained was partially converted back into cellulose I by water boiling.

Optimized magnetic properties of a Terfenol-D alloy in an extended temperature range using a high magnetic field

Tb–Dy–Fe alloys are among the most suitable magnetostrictive materials for high-power transducers. Optimizing magnetic properties in an extended temperature range could ensure the stable operation of transducers. In this work, a high magnetic field is applied to the directional solidification of Tb–Dy–Fe alloys. We study the microstructure, crystallographic orientation, magnetic susceptibility, crystal structure, and magnetic domain of samples. When the content and alignment of the magnetic phase along with crystallographic orientation remain basically invariant, the magnetic susceptibility of samples increases with the magnetic flux density of the high magnetic field throughout the temperature range from 273 K to Curie temperature (T C). At 4 T, the maximum magnetic susceptibility is increased by ∼ 40% compared with the sample without a high magnetic field applied, and the advantage is maintained in the range ∼ 300 K. Analysis shows that the enhancement of magnetic susceptibility is not due to the change in crystal structure, as commonly believed, but to the highly ordered alignment of magnetic domains. This research provides a new method for improving the temperature properties of magnetic materials using a high magnetic field.

Study on the interaction between Mg2C monolayer and VA group trihydrides under strain engineering

The influence of biaxial strain ranging from −5–15 % on the physical properties of Mg2C monolayer was systematically investigated. The study revealed that Mg2C undergoes a phase transition from metallic to semimetallic to semiconducting under varying degrees of strain. This characteristic allows Mg2C to exhibit diverse physical property changes under strain control. Additionally, the adsorption behavior of several toxic group VA trihydride gas molecules (NH3, PH3, AsH3, SbH3) on Mg2C was examined. The results indicate that within a strain range of −5–10 %, Mg2C shows the most significant adsorption effect on NH3, with adsorption energies ranging from −0.9 eV to −5 eV. Strain significantly impacts the physical properties of the adsorption system. All four systems exhibit a semiconductor phase transition within the strain range of 2–3 %. Between 10 % and 12 % strain, the adsorption energy of the four systems increases rapidly. Strains exceeding 12 % induce structural changes in the original crystal structure. This discovery not only supports the application of Mg2C as a gas sensor material but also provides new empirical references for regulating two-dimensional material properties through strain engineering.

Repair Engineering of Crystal Structure in van der Waals Materials by Probe Electron Beam.

The advancement of electronic technology has led to increasing research on performance and stability. Continuous electrical pulse stimulation can cause crystal structure changes, affecting performance and accelerating aging. Controlled repair of these defects is crucial. In this study, we investigated crystal structure changes in van der Waals (vdW) InSe crystals under continuous electric pulses by using electron beam lithography (EBL) and spherical aberration corrected transmission electron microscopy (Cs-TEM). Results show that electrical pulses induce amorphous regions in the InSe lattice, increasing the device resistance. We used Cs-STEM probe scanning for precise repair, abbreviated SPRT, to optimize device performance. SPRT is related to electric fields induced by the electron beam and can be applied to other 2D materials like α-In2Se3 and CrSe2, offering a potential approach to extend device lifespan.

Thermokinetics and reactive mechanism of lead azide (LA) in atmosphere/temperature mixed environment

To establish the influence of atmospheric and temperature factors on the stability of LA, a combined environmental stress testing device was designed to simulate reaction characteristics. Morphological characterization methods of SEM and FTIR were carried out to explore the changes of crystal structure, as the pyrolysis behavior of LA under the combined environmental stress was investigated by DSC with two isoconversional kinetic methods and thermal safety software (TSS). The research indicates that CO2 and H2O react with LA to generate basic lead carbonate in the air atmosphere, together with the stimulation of thermal stress, the synergistic effect formed microvoids to erode the crystal structure of LA. The microvoid effect reduced the apparent activation energy (Ea) from 156.47 to 29.52 kJ/mol as the order of degradation of thermal stability of LA was Air > N2 > CO2, which demonstrated that CO2 and N2 atmosphere have a particular protective effect for LA storage, transportation, and application. The pyrolysis reaction mechanism model of LA under the combined environment factors testing was the same as the original LA through the calculation of TSS, thereby the findings could contribute to a better understanding of available boundary conditions for LA.

CuxS films as photoelectrodes for visible-light water splitting

Copper sulfides are appealing semiconductors for optoelectronics applications requiring visible-light activity, such as solar water splitting, due to their relatively low band gaps and earth-abundance. This study investigates the effect of deposition conditions, including substrate temperature and background gas pressure, on the characteristics and photoelectrochemical performance of copper sulfide (CuxS) films grown by pulsed laser deposition (PLD) on Si (100) substrates. The results reveal that varying the deposition parameters influences the crystalline phases, morphology, and optoelectronic properties of the films. For deposition at room temperature, the films exhibited covellite CuS phase, while elevated deposition temperatures (250 °C and 500 °C) led to the formation of Cu1.8S and Cu2S phases, resulting in narrowing of the band gap, with the increased temperature also enhancing the film crystallinity and surface roughness. As a result of the changes in film morphology and crystal structure, photocurrent density magnitudes increased with higher deposition temperatures, reaching 0.747 mA/cm2 at −0.8 V for films deposited at 500 °C under vacuum, at least an order of magnitude higher than reported in comparable previous studies of the photoelectrochemical performance of CuxS. Background gas pressure only slightly affected the photocurrent density, with changes in photoactivity also correlating with changes in film roughness and band gap. The results demonstrate the good visible-light activity and behavior of CuxS as a stand-alone photoelectrode material, with tunability based on the fabrication conditions, suggesting their potential use in photoelectrochemical and other solar energy conversion applications.

Fire-resistant and mechanically-robust phosphorus-doped MoS2/epoxy composite as barrier of the thermal runaway propagation of lithium-ion batteries

Thermal runaway propagation (TRP) is an utmost safety issue in battery modules owing to its derivative accidents of fire or explosion. This study develops a novel flame-retardant epoxy resin (EP) board to prevent the battery TRP. The phosphorus doped MoS2 nanowires (PR-MoS2) is designed and incorporated into EP matrix to acquire EP/3.0 PR-MoS2 composite. The composite shows 159.4 % increase in char yield, 56.7 % decrease in peak heat release rate, 56.6 % reduction in peak CO production rate. By using EP/PR-MoS2-3 (EP/3.0 PR-MoS2 composite with thickness of 3 mm) between 103450-pouch cells, TRP can be effectively stopped. Meanwhile, the temperature of surviving battery remains below 100 °C. Of note, the minimum changes in internal crystal structure, chemical composition and electrochemical characteristics are discerned for the surviving battery. This research will offer inspirations for the design of TRP suppression materials, guaranteeing the safety the battery.

Study on Electrochemical Characteristics of Crystal Structure Changes Effects of Silicon Anode Materials for Lithium Ion Batteries

Graphite is widely used as a representative anode material in commercialized lithium-ion secondary batteries. However, with a theoretical capacity of 370 mAh/g, it is difficult to manufacture high-capacity/high-density lithium-ion secondary batteries. Therefore, research is actively underway to find high-capacity substances to replace graphite. Silicon anode materials are currently attracting attention as next-generation high-capacity cathode materials. Silicon forms Li4.4Si when fully charged through an alloying/dealloying process with lithium during the reaction. Graphite is intercalation/deintercalation in reaction with lithium and LiC6 is formed when fully charged. That's why silicon has a theoretical capacity of 3800 mAh/g, about 10 times that of graphite.However, silicon is a high-capacity electrode material that overcomes the theoretical capacity limit of graphite, and has the disadvantage of experiencing volume expansion of about 400% during repeated charge/discharge cycles. Problems such as material cracks due to volume expansion can affect the safety of the battery. Various studies are being conducted to solve silicon-related challenges to effectively utilize silicon materials. Previous studies have explored the use of binders or additives to mitigate volume expansion. In addition, various types of silicon materials such as Si alloy and SiOx are being developed to suppress volume expansion through matrix formation. Nevertheless, despite the development of silicon materials, structural changes in the charging and discharging process of silicon remain unclear.This study aims to analyze the structural changes that occur during the charging and discharging process of silicon. The experiment evaluates the electrochemical characteristics of crystalline silicon and amorphous silicon and compares the behavior and structural changes during charging/discharging. The volumetric expansion measurements are performed with electrochemical characterization, and ex-situ X-ray diffraction (XRD) and transmission electron microscope (TEM) analyses are performed for comparison with crystal structural changes.

Unveiling Reaction Mechanisms of Non-Aqueous Zn-Ion Batteries – Zn/LiFePO4 System

Zinc-ion batteries (ZIBs) are among the most promising energy storage technologies because of their low cost, safety, and environmental friendliness. In this work, we focus on investigating the electrochemical reaction mechanisms of ZIBs with Lithium iron phosphate (LiFePO4) as an active material in the positive electrode, Zn(OTf)2+LiCl dissolving Tetraethylene glycol dimethyl ether (TEGDME) as the electrolyte, as well as metallic Zinc as the negative electrode. After testing the ZIB cells by galvanostatic cycling, the cells with TEGDME exhibit the best electrochemical performance in terms of long-term stability. The initial specific discharge capacity is 118.3 mAh g-1 and the capacity retention is 91.4% after 100 cycles at a current density of 10 mA g-1. We propose the reaction mechanisms during the charge-discharge processes involve extraction/insertion processes of Li+ into/out of the olivine structure of LiFePO4 as evidenced by X-ray near-edge spectroscopy (XANES). According to X-ray diffraction (XRD) analysis of the discharged and charged LiFePO4 electrodes, the crystal structure changes from LiFePO4 to FePO4 when charging and back into LiFePO4 again when discharging. Besides, XRD and scanning electron microscopy (SEM) confirm that the cycled Zn electrode is hardly present with passivation and/or corrosion. Therefore, this new combination of Zn/LiFePO4 and TEGDME has a potential for ZIB applications.

Evaluation of gamma rays shielding properties of bismuth tungstate with different morphologies

To develop lead-free gamma-ray shielding material, bismuth tungstate (Bi2WO6) nanocrystals were synthesized under different conditions of precursor solution by hydrothermal method and composite material based on polyurethane and bismuth tungstate nanocrystals were prepared and evaluated using gamma ray sources in this study. The effects of crystal structure and morphology on the gamma ray shielding properties of bismuth tungstate were specially investigated. Results indicated that pH value of precursors solution had significant effect on the synthesis of bismuth tungstate: orthorhombic Bi2WO6 were obtained under acidic or neutral conditions while tetragonal Bi0.875W0.125O1.6875 were obtained under strongly alkaline condition. With the increase of pH value, the morphology of bismuth tungstate changed from flower-like microspheres to persimmon-like microstructures, and then to randomly stacked nanosheets. Bismuth tungstate nanocrystals were added to polyurethane to prepare flexible gamma-ray shielding material and the gamma ray shielding properties were also tested with energy of 59.5 keV, 81.0 keV and 121.8 keV. For orthorhombic persimmon-like bismuth tungstate (Bi2WO6) which were produced under weak acidic or neutral condition (pH = 2, 5, 7), it was found that the linear attenuation coefficient of gamma ray grew by about 8 % when pH changing from 2 to 7 for all energy tested. While for tetragonal bismuth tungstate (Bi0.875W0.125O1.6875), weakly alkaline condition (pH = 9) induced significant decrease (9 %@59.5 keV, 17 %@81.0 keV and 11 %121.8 keV) of linear attenuation coefficient compared with neutral condition, which could be explained by the dramatic crystal structure change of bismuth tungstate. More alkaline synthesizing condition would make finer granularity of bismuth tungstate and the linear attenuation coefficient increased when pH change from 9 to 12. In addition, obvious differences of mechanical properties were also observed between the composites prepared using different crystalline bismuth tungstates. The results of this study provide a reference for the development of new flexible radiation shielding materials with non-toxicity, light weight and high efficiency.

Effects of voltage stress conditions on degradation of iridium-based catalysts occurring during high-frequency operation of PEM water electrolysis

Proton exchange membrane water electrolysis (PEMWE) is needed to store renewable energy in the form of hydrogen. To improve the performance of PEMWE, elucidating the degradation mechanism of iridium (Ir)-based catalysts used for oxygen evolution reaction (OER) that is a rate-determining step is important. To date, it is known that one important reason for that is undesirable change in crystal structure of Ir. To further evaluate its degradation mechanism, in this study, effects of operating voltage conditions on crystal structure of Ir are investigated because the voltage conditions can accelerate changes in crystal structure of Ir. Especially how Ir was changed into an unfavorable metallic form was analyzed. PEMWE single cells under conditions of (i) a constant voltage of 1.9 V, (ii) a voltage cycle of 1.7–1.9 V, then a constant voltage of 1.9 V, and (iii) an applied voltage cycle with open circuit voltage (OCV). In the OCV condition, the crystalline structure of Ir was irreversibly transformed into a metallic form. This transformation induced lower OER activity than other crystalline states of Ir, followed by lower performance of PEMWE single cells. These findings help to establish baseline protocols for the stable operation of PEMWEs using Ir-based catalysts.

Solid Solutions of Plastic/Ferroelectric Crystals: Toward Tailor-Made Functional Materials.

Plastic crystals that show ferroelectricity are highly promising materials for a wide range of applications. Their inherent remarkable malleability and highly symmetric cubic structures in the plastic crystal phase ensure that their ferroelectricity and related properties are retained in their bulk polycrystals. To develop functional materials based on such plastic/ferroelectric crystals, methods to tune their properties for specific applications are required. Here, we report the preparation of solid solutions of plastic/ferroelectric ionic crystals by mixing crystals with a common anion but different cations, or crystals with a common cation but different anions, which allows a continuous modification of the Curie temperature of the ferroelectric system over a range of 100 K. This adjustment of the Curie temperature allows the flexible tuning of the pyroelectric properties of the solid solutions, including a significant enhancement of room-temperature performance. The solid solutions also exhibit morphotropic phase boundaries in the composition-temperature phase diagrams, which shows an abrupt change in crystal structures with a variation of composition. This study showcases a simple and versatile property-tuning method that can be expected to pave the way for major progress in the development of materials based on plastic/ferroelectric crystals, which will eventually advance to the stage of pursuing tailor-made functional materials with desired properties.

Improving electrochemical properties by Na+ doping for Co-Free Li-Rich Mn-based layered oxide

The capacity of Co-free Li-rich Mn-based layered oxide decreases rapidly due to the irreversible lattice oxygen lose and the crystal structure change. The sodium modified cathode materials are synthesized via the sol–gel method and the electrochemical properties are investigated. Specifically, the first discharge capacity of Li1.18Na0.02Mn0.54Ni0.26O2 is 150.5 mAh·g−1 at 2C, demonstrating a capacity preservation rate of 94.1 % after 100 cycles. And the diffusion coefficient of Li1.18Na0.02Mn0.54Ni0.26O2 is 1.2152 × 10-15, which is better than 1.3798 × 10-16 of the undoped material. This work demonstrates that appropriate Na+ doping can stabilize the crystal structure, increase the lithium layer spacing and reduce the irrevocable escape of lattice oxygen within material.

Effect of A-site excess on the shape memory effect of sodium bismuth titanate ceramics

The impact of A-site excess on the shape memory effect of Na0.5Bi0.5TiO3 ceramics was investigated. We found that the recoverable plastic-like strain was increased by more than 10 % by A-site excess. The enhancement is attributed to the change in crystal structure from a rhombohedral phase to a monoclinic one, which further changes the phase transition behavior between the ferroelectric and nonpolar phases. Suppression of grain size and the generation of defects after the addition of excess Bi and Na were proposed for the appearance of monoclinic phase. This investigation proposes a viable approach to modulate the shape memory effect of Na0.5Bi0.5TiO3-based ceramics through the manipulation of the crystal structure and the associated phase transition processes, ultimately influencing the shape memory characteristics.

Effect of crystal orientation on surface/subsurface damage characteristics of nano-cutting Ni-based single crystal superalloy

In ultra-precision machining, material anisotropy has an essential impact on surface generation and subsurface damage. In this work, the molecular dynamics method is applied to create the diamond nano-cutting models of Ni-based single crystal (NBSX) superalloy workpieces with different crystal orientations, and the surface/subsurface damage characteristics, crystal structure changes, cutting force, and atomic temperature and stress are discussed. The results show significant differences in surface/subsurface quality, crystal structure transformation, cutting force, atomic temperature and stress distributions and dislocation density obtained from nano-cutting workpieces along different crystal orientations. In four groups of workpieces, the surface/subsurface quality is used as an evaluation index, which shows that the [110](001) crystal orientation has the best cutting effect, and the [111](1‾ 10) crystal orientation is the worst cutting direction. This work reveals the damage generation mechanism of the machined surface/subsurface of NBSX superalloy on an atomic scale, which provides technical support for improving machining quality and optimizing machining parameters.

Study on fluorine vacancy defects in yttrium fluoride coating materials

Abstract Rare-earth fluoride coating materials have attracted wide attention as a substitute for ThF4 low-refractive index materials. However, the coating materials and coated films fail to achieve the desired results due to vacancy defects caused by their fluorine-loss decomposition characteristics. To explore the rare earth fluoride coating materials’ fluorine loss influence law, the melt crystallization method is used to simulate the yttrium fluoride (YF3) pre-melting process through the electronic paramagnetic resonance (EPR) obtained at different temperatures under the fluorine vacancy defects change rule. According to the number of unpaired spintrons, the number of spintrons in each vacancy is calculated. The results show that the fluorine vacancy defects increase with the increase of temperature, the formation of YF3 fluorine vacancy defects does not affect the change of crystal structure, and the addition of the additive ammonium hydrogen fluoride (NH4HF2) can reduce the oxygen content of YF3 and effectively inhibit the formation of fluorine vacancy. The effect is gradually obvious with the amount of additives added.

Valuation of the significant hypoglycemic activity of black currant anthocyanin extract by both starch structure transformation and glycosidase activity inhibition

The objective of this study was to investigate the impact of anthocyanin-rich black currant extract (BCE) on the structural properties of starch and the inhibition of glycosidases, gathering data and research evidence to support the use of low glycemic index (GI) foods. The BCE induced a change in the starch crystal structure from A-type to V-type, resulting in a drop in digestibility from 81.41 % to 65.57 %. Furthermore, the inhibitory effects of BCE on glycosidases activity (α-glucosidase: IC50 = 0.13 ± 0.05 mg/mL and α-amylase: IC50 = 2.67 ± 0.16 mg/mL) by inducing a change in spatial conformation were confirmed through in vitro analysis. The presence of a 5′-OH group facilitated the interaction between anthocyanins and receptors of amylose, α-amylase, and α-glucosidase. The glycosyl moiety enhanced the affinity for amylose yet lowered the inhibitory effect on α-amylase. The in vivo analysis demonstrated that BCE resulted in a reduction of 3.96 mM·h in blood glucose levels (Area Under Curve). The significant hypoglycemic activity, particularly the decrease in postprandial blood glucose levels, highlights the potential of utilizing BCE in functional foods for preventing diabetes.