Crystal Transition Research Articles

Stress relief and crystal face transition process contribute to the stability of zinc anodes

Zn electrodes are suffering the dendrite growth owing to the enrichment of local space charge, distinct exposed face and residual stress. In this work, we investigated the crystal face properties and stress state of Zn foil through static energy calculations, dynamic crystal growth analysis and finite element simulation of stress states. Then thermal driven is deployed to modify the exposure face and residual stress of Zn foil, aiming for a dendrite-free electrode. The calculation of surface energies and simulation of crystal growth models for different crystal faces indicate that the (001) face can maintain stability during deposition. Inspired by this mechanism, the (101) exposed commercial Zn foil is modified by thermal processing. Firstly, the exposure level of the (001) face increases, though only the peak corresponding to the (002) crystal face is observed, due to the extinction effect of the densely packed plane (001) face. Further, the surface morphology becomes smooth and the stress is released with the progresses time. These stress relief and crystal face transition process strengthen the uniformity of ion distribution, and increase the interface stability during the crystal growth, which reduce the defect sites in the deposition. As a result, the Zn electrode exhibits tiny voltage hysteresis and outstanding cycle stability, which reveals improved electrochemical performance. Additionally, Li and Na can also be improved in exposed crystal faces and release strain energy through similar methods to enhance cycling stability.

Revaling the mechanism of microscopic kinking phenomena in Hf6Ta2O17 superstructures

As a promising candidate for a new-generation thermal barrier coating material, Hf6Ta2O17 is characterized by its unique long-period superstructures and excellent mechanical properties. In this study, the unique "kinking" phenomenon of the atomic arrangement in Hf6Ta2O17 crystals is directly visualized via high-resolution transmission electron microscopy for the first time. The evolution of the microstructure, and particularly the micro-mechanism of the "kinking" phenomenon, have been further explored by first-principles calculations. The study suggests that this phenomenon is primarily triggered by the rotation of the polyhedral structure, resulting from the partial elongation or shortening of the Ta-O bond length. These structural alterations are believed to directly influence the macroscopic mechanical properties and can improve the tensile properties of the Hf6Ta2O17 crystals. The findings of this study provide an important microscopic perspective for understanding the strain-induced crystal structure transformation. The quantitative analysis of the strengths of Ta-O and Hf-O bonds in different coordination polyhedra reveals the electronic structure changes behind the crystal structure transition, thus providing a new theoretical basis for an in-depth understanding of the behavior of crystals under the external stress.

Unlocking the potential of cation vacancy-enriched ZnMn1.75O4 cathode for advanced aqueous aluminum-ion batteries

Manganese oxides are widely utilized in aqueous aluminum-ion batteries (AIBs) due to their high voltage and diverse crystal structures. However, the Jahn-Teller effect induced by Mn-O6 units results in irreversible structural damage. Here, we synthesized ZnMn1.75O4 (ZMO) cathodes loaded onto a carbon framework with manganese vacancies (VMn) for AIBs through ion substitution, manganese extraction, and carbonization on Mn-MIL. VMn stabilizes the ZMO structure by damping Mn-O bond vibrations and fosters Mn-O-C bonds between oxide particles and the carbon framework, effectively suppressing irreversible Mn2+ dissolution. Vacancy-modified cathodes provide more ion insertion sites, promoting ion diffusion. Ex-situ characterization revealed dominant H+ and Al3+ insertion behavior during different voltage regimes. Upon initial discharge, ion insertion into vacant lattice sites causes lattice distortions in adjacent unit cells, prompting ZMO to undergo a crystal structure transition and partial zinc deintercalation, resulting in a more stable cathode structure. Therefore, Al/ZMO batteries exhibit enhanced electrochemical performance.

A persistent mineralization process in alveolar bone throughout the postnatal growth stage in rats

ObjectiveAlveolar bone quality is essential for the maxillofacial integrity and function, and depends on alveolar bone mineralization. This study aims to investigate the in vivo changes in alveolar bone mineralization, from the perspective of mineral deposition and crystal transition in postnatal rats. DesignNine postnatal time points of Wistar rats, ranging from day 1 to 56, were set to obtain the maxillary alveolar bone samples. Each time point consisted of ninety rats, with 45 females and 45 males. Macromorphology of alveolar bone was reconducted by Micro-Computed Tomography and the mineral content was quantified via Thermogravimetric analysis, Scanning Electron Microscope, High-Resolution Transmission Electron Microscopy and vibrational spectroscopy. Furthermore, the crystallinity and composition were characterized by vibrational spectroscopy, X-ray Diffraction, X-ray Photoelectron Spectroscopy and Selected Area Electron Diffraction. ResultsThe progressive increase of mineral deposition was accompanied by substantial growth in alveolar bone mass and volume in postnatal rats. Whereas the mineral percentage initially decreased and then increased, reaching a nadir on postnatal day 14 (P14) when tooth eruption was first observed. Besides, localized mineralization was initiated by the formation of amorphous precursors and then converted into mineral crystals, while there was no statistically significant change in the average crystallinity of the bone during growth. ConclusionMineralization of alveolar bone is ongoing throughout the early growth in postnatal rats. Mineral deposition increases with age, whereas the crystallinity remains stable within a certain range. Besides, the mineral percentage reaches its lowest point on P14, which may be attributed to tooth eruption.

Size Reduction to Enhance Crystal-to-Liquid Phase Transition Induced by E-to-Z Photoisomerization Based on Molecular Crystals of Phenylbutadiene Ester.

Harnessing the photoinduced phase transitions in organic crystals, especially the changes in shape and structure across various dimensions, offers a fascinating avenue for exact spatiotemporal control, which is crucial for developing future smart devices. In our study, we report a new photoactive molecular crystal made from (E)-2-(3-phenyl-allylidene)malonate ((E)-PADM). When exposed to ultraviolet (UV) light at 365 nm, this compound experiences an E-to-Z photoisomerization in liquid solution and a crystal-to-liquid phase transition in solid crystals. Remarkably, nanoscopic crystalline rods boost their melting rate and degree compared to bulk crystals, indicating that miniaturization enhances the photoinduced melting effect. Our results demonstrate a simple approach to rapidly drive molecular crystals into liquids via photochemical reactions and phase transitions.

Excellent electrocaloric performance achieved by the high-entropy strategy

Electrocaloric effect (ECE) materials have garnered significant interest for their potential in creating more portable, compact cooling solutions and reducing greenhouse gas emissions. Enhancing both the temperature change ΔT and the temperature span Tspan of ECE materials remains a formidable challenge. The diverse and flexible local polarization in the high-entropy ferroelectric materials hold promise for addressing this issue. A series of high-entropy ferroelectric ceramics with composition (1-x)PbTiO3-xPb(Mg0.2Zn0.2Nb0.2Ta0.2W0.2)O3 has been synthesized using a solid-state reaction. As x increases, the crystal structure transitions towards a cubic phase, and the freezing temperature Tf decreases from 92 to 47 °C. There is a notable reduction in the coercive field, and the polarization reaches the maximum value of 32.07 μC/cm2 at x = 0.75. Utilizing the direct method, the samples with x = 0.725 and x = 0.75 achieve an optimal ΔT of 0.35 K and Tspan of 123 K at an electric field of 20 kV/cm, respectively. The ΔT and Tspan of the sample with x = 0.75 observed by the indirect method surpass 1 K and 100 K, respectively, at an electric field of 55 kV/cm. This study highlights the potential of employing a high-entropy approach to achieve superior ECE performance, paving the way for the development of advanced cooling technologies.

Synthesis, structure, spectral and luminescence studies of novel guanidinium aryl(oxy)(sulfanyl)(sulfonyl)acetates

A series of promising luminescent materials, nonlinear optical crystals, and physiologically active compounds – aryl(oxy)(sulfanyl)(sulfonyl)acetates of guanidine (A) of unknown type was synthesized. Various functional groups present in (A) were identified using FTIR spectroscopy. 1H and 13C NMR spectral studies further confirm the molecular structure (A). Crystals of guanidinium 4-chlorophenyl(sulfanyl)acetate (1) and guanidinium 4-chlorophenyl(sulfonyl)acetate (2) were successfully grown. They belong to the same lowest symmetry category, but to different crystal systems: monoclinic (1) and orthorhombic (2).It has been established that intrinsic optical absorption begins at a wavelength of ∼ 290 nm for crystalline compound (1) and ∼ 335 nm for crystal (2). The intrinsic luminescence spectrum of crystal (1) includes two bands with maxima at 300 and 515 nm. In the intrinsic luminescence spectrum of crystal (2), only one band is observed with a maximum at 350 nm. Such luminescence in both crystals is excited in the intrinsic absorption bands, as well as by X-ray radiation. In addition, in the near ultraviolet and throughout the visible region, where optical absorption is not detected (it is very weak), low-inertia (less than 10 ns) rather intense luminescence of uncontrolled impurity-defect centers is excited.The spectral bands of optical absorption, photo- and X-ray luminescence discovered in experiments were systematized using a diagram of energy levels and quantum transitions in crystals and defect centers of the compounds under study.

Investigation on itraconazole solubility in aqueous solutions based on models, solvent effect, thermodynamic analysis and quantum chemical calculations

The mole-fraction solubility of itraconazole in four aqueous blends of ethanol/isopropanol/DMSO/methanol within the temperature range of 283.15 to 323.15 K was experimentally obtained using the isothermal shake-flask method. Under the identical temperature and ethanol/isopropanol/DMSO/methanol composition, itraconazole solubility in DMSO+water is much higher than that in ethanol/isopropanol/methanol + water. At the same temperature, the solubility increases monotonically with organic solvent concentration. X-ray power diffraction analysis demonstrated that over the course of the investigations, there was no crystal transition or solvate formation. The modified van’t Hoff-Jouyban-Acree and Jouyban-Acree models adequately related the solubility to solvent composition and temperature, with relative average deviations (RADs) not exceeding 7.65 %. Furthermore, the extended Hildebrand solubility approach was utilized to quantitatively characterize the solubility behavior at 298.15 K for the mixtures of ethanol/isopropanol/DMSO/methanol plus water. In both instances, the RADs were maintained below 4.12 %. The solubility parameter and dipolarity-polarizability of solutions have a major impact on the solubility fluctuation, as indicated by the analysis of the linear solvation energy relationship. The preferential solvation of itraconazole at 298.15 K was examined using the efficient approach of inverse Kirkwood-Buff integrals. The preferred solvation parameters showed positive values in blends within rich and moderate ethanol/isopropanol/DMSO/methanol composition regions. This suggests that the organic solvents preferentially solvated itraconazole. When itraconazole dissolved in the blends, thermodynamic analysis of the entropy-enthalpy compensation and dissolution parameters revealed both an endothermic and an enthalpy-driven mechanism. Furthermore, the microscopic electrostatic characteristics of basicity and acidity were effectively demonstrated by means of the electrostatic potential of molecular surface. The −C=O and −N=groups of the itraconazole molecule, which link the five-membered ring, are the primary targets of the electrophilic attack. An independent gradient model based on Hirshfeld partition analysis was used to demonstrate the weak interactions between itraconazole and solvents.

Stabilization and high thermoelectric performance of high-entropy-type cubic AgBi(S, Se, Te)2

As thermoelectric generators can convert waste heat into electricity, they play an important role in energy harvesting. The metal chalcogenide AgBiSe2 is one of the high-performance thermoelectric materials with low lattice thermal conductivity (κlat), but it exhibits temperature-dependent crystal structural transitions from hexagonal to rhombohedral, and finally a cubic phase as the temperature rises. The high figure-of-merit ZT is obtained only for the high-temperature cubic phase. In this study, we utilized the high-entropy-alloy (HEA) concept for AgBiSe2 to stabilize the cubic phase throughout the entire temperature range with enhanced thermoelectric performance. We synthesized high-entropy-type AgBiSe2−2xSxTex bulk polycrystals and realized the stabilization of the cubic phase from room temperature to 800 K for x ≥ 0.6. The ultra-low κlat of 0.30 Wm−1K−1 and the high peak ZT ∼ 0.9 at around 750 K were realized for cubic AgBiSe2−2xSxTex without carrier tuning. In addition, the average ZT value of x = 0.6 and 0.7 for the temperature range of 360–750 K increased to 0.38 and 0.40, respectively, which are comparable to the highest previously reported values.

Thermal masses and trapped-ion quantum spin models: a self-consistent approach to Yukawa-type interactions in the λϕ4 model

The quantum simulation of magnetism in trapped-ion systems makes use of the crystal vibrations to mediate pairwise interactions between spins, which are encoded in the internal electronic states of the ions, and measured in experiments that probe the real-time dynamics. These interactions can be accounted for by a long-wavelength relativistic theory, where the phonons are described by a coarse-grained Klein-Gordon field ϕ(x) locally coupled to the spins that acts as a carrier, leading to an analogue of pion-mediated Yukawa interactions. In the vicinity of a structural transition of the ion crystal, one must go beyond the Klein-Gordon fields, and include additional λϕ4 terms responsible for phonon-phonon scattering. This leads to quantum effects that can be expressed by Feynman loop integrals that modify the range of the Yukawa-type spin interactions; an effect that could be used to probe the underlying fixed point of this quantum field theory (QFT). Unfortunately, the rigidity of the trapped-ion crystal makes it challenging to observe genuine quantum effects, such as the flow of the critical point with the quartic coupling λ. We hereby show that thermal effects, which can be controlled by laser cooling, can unveil this flow through the appearance of thermal masses in interacting QFTs. We perform self-consistent calculations that resum certain Feynman diagrams and, additionally, go beyond mean-field theory to predict how measurements on the trapped-ion spin system can probe key properties of the λϕ4 QFT.

Frustration of H-Bonding and Frustrated Packings in a Hexamorphic Crystal System with Reversible Crystal-Crystal Transitions.

The study of transitions between polymorphic phases is a less investigated chapter of the widely studied book of polymorphism. In this paper, we discuss the phase behavior of a new compound that has been rationally designed to show frustration of H-bonds for the strong amide N-H donor, which cannot be involved in H-bonding nor in van der Waals interactions. The compound (ImB) is a showcase of almost all possible cases of transitions between polymorphs [monotropic/enantiotropic, fast/slow, diffusive/displacive, and single-crystal-to-single-crystal (SCSC)] and of relation between polymorphs with different Z'. Six crystal phases (I, II, III, IV, V, and VI) were identified for it with five crystal-crystal transitions. Two transitions are reversible/SCSC/fast. Of the three monotropic transitions, all non-SCSC, one is slow, and the others are fast. Of the two enantiotropic SCSC transitions, one does not exhibit undercooling, while the other shows strong undercooling. Phase III, with Z' = 6, is stable at room temperature between phase II (Z' = 1), stable at high temperature, and phase IV (Z' = 2), stable at low temperature. All six polymorphs are based on the same O-H···O═C H-bonding synthon, which produces infinite chains in five polymorphs and ring tetramers in one. The sequence of reversible SCSC transitions IV ⇆ III ⇆ II involves a remarkable ping pong of the symmetry rules by which H-bonded chains are built. Based on all of this, a possible roadmap for prediction of SCSC transitions in crystals is shortly outlined.

Ion-Exchanging Lead-Free Perovskite with Tunable Emission Wavelengths for Chemical and Fluorescent Double-Modal Anticounterfeiting Application.

Novel and covert fluorescence is quite desirable for fluorescent anticounterfeiting application. Here, Cs2InCl5·H2O/Sb and Cs2NaInCl6/Sb with high photoluminescence quantum yields (PLQYs) of 99.61 and 99.9%, respectively, were achieved. Considering the excellent optical performances together with the high similarity of the two crystal structures, we tried to realize the crystal structure transition from Cs2InCl5·H2O/Sb to Cs2NaInCl6/Sb by an ion-exchange method. It was well done by just adding the NaCl precursor with different concentrations in the Cs2InCl5·H2O/Sb product. Interestingly, a gradual color change from yellow to orange, warm white, white, cool white, and blue was achieved in the process of crystal structure transition. The energy-transfer dynamic models of Cs2InCl5·H2O/Sb, the white product, and Cs2NaInCl6/Sb were identified. The chemical reaction and UV fluorescence properties made it possible for application in chemical and fluorescent double-modal anticounterfeiting and highly decreased the possibility of being cracked and copied. Especially, when salt for daily cooking was used to replace NaCl, a similar phenomenon happened as that of the 99.9% NaCl precursor, which made it easy to be applicated. The combination of chemical and optical verifications provides two levels of security and unbreakable encryption. The results demonstrate that the transition from Cs2InCl5·H2O/Sb to Cs2NaInCl6/Sb is highly promising in fluorescent anticounterfeiting application.

Magnetic field induced isotropic ferrofluid to ferronematic phase transition in thermotropic liquid crystal

Experiments on liquid crystals doped with ferromagnetic nanoparticles predicted the isotropic ferrofluid to ferronematic phase transition. The magnetic field induced isotropic ferrofluid to ferronematic phase transition in thermotropic liquid crystal has been studied theoretically. Theoretical model is based on Flory–Huggins theory of isotropic mixing and Landau-de Gennes theory. The impact of ferromagnetic nanoparticles and magnetic field on the isotropic ferrofluid to ferronematic phase transition and transition temperature has been discussed. Theoretical results predict the magnetic field induced critical point of the isotropic ferrofluid to ferronematic phase transition. The temperature and volume fraction of ferromagnetic nanoparticles dependence of the magnetic birefringence and Cotton-Mouton constant are calculated.

A new order parameter model for the improper ferroelastic phase transitions in KMnF3 single crystal.

This paper proposes a new order parameter model which satisfactorily explains complicated symmetry changes, the temperature-pressure (T-P) phase diagram and elastic anomalies observed experimentally with the improper ferroelastic phase transitions in multiferroic KMnF3 single crystal. First, it is shown that the order parameter model is transformed according to the four-dimensional reducible representation of the wavevector star channel group. Second, based on the order parameter model and the singularity theory, the sixth-order structurally stable Landau potential model is constructed. Finally, the theoretical T-P phase diagram is plotted and the elastic anomalies possible for each of the phase transitions are discussed.

Drosophila immune cells transport oxygen through PPO2 protein phase transition

Insect respiration has long been thought to be solely dependent on an elaborate tracheal system without assistance from the circulatory system or immune cells1,2. Here we describe that Drosophila crystal cells—myeloid-like immune cells called haemocytes—control respiration by oxygenating Prophenoloxidase 2 (PPO2) proteins. Crystal cells direct the movement of haemocytes between the trachea of the larval body wall and the circulation to collect oxygen. Aided by copper and a neutral pH, oxygen is trapped in the crystalline structures of PPO2 in crystal cells. Conversely, PPO2 crystals can be dissolved when carbonic anhydrase lowers the intracellular pH and then reassembled into crystals in cellulo by adhering to the trachea. Physiologically, larvae lacking crystal cells or PPO2, or those expressing a copper-binding mutant of PPO2, display hypoxic responses under normoxic conditions and are susceptible to hypoxia. These hypoxic phenotypes can be rescued by hyperoxia, expression of arthropod haemocyanin or prevention of larval burrowing activity to expose their respiratory organs. Thus, we propose that insect immune cells collaborate with the tracheal system to reserve and transport oxygen through the phase transition of PPO2 crystals, facilitating internal oxygen homeostasis in a process that is comparable to vertebrate respiration.

Photo-triggered Phase Transition of Crystals and Photoactuation.

Photo-triggered phase transition is a new type of phase transition in which a photochromic crystal with a thermal phase transition transforms into an identical high-temperature phase in a temperature region lower than the thermal phase transition temperature upon light irradiation. Here, we report a second crystal that exhibits a photo-triggered phase transition, thereby demonstrating that the photo-triggered phase transition is a general phenomenon that occurs in crystals. When the chiral salicylidenephenylethylamine crystal was irradiated with ultraviolet (UV) light, the photo-triggered phase transition occurred in the temperature range -30 to -10 °C. The photo-triggered phase transition is induced by local stress due to trans-keto molecules produced by photoisomerization near the irradiated surface. Crystal cantilevers exhibited stepwise bending by the combination of the photo-triggered phase transition and photoisomerization. Alternate irradiation with UV and visible light achieved locomotion of single crystals driven by repeated stepwise bending. Finally, a detailed comparison of photo-triggered and non-photo-triggered phase transition crystals revealed that a sufficient molecular conformation change in affordable crystal voids, smooth photoisomerization, and most likely a chiral molecular arrangement are required for inducing the photo-triggered phase transition.

Controlling the TE-TM splitting of topological photonic interface states by precise incident angle adjustment

Topological phases in photonic systems have garnered significant attention, often relying on precise structural design for generating non-trivial topological phases. However, this dependency on fixed structures limits their adaptability. This study systematically explores incident angle-induced topological phase transitions in a one-dimensional photonic crystal (PC). Both TE and TM polarized modes undergo topological phase transitions at the same critical transition angles. Additionally, the TM-polarized mode undergoes a unique topological phase transition at the Brewster angle. When these two kinds of transition angles coincide, even if the band structure of the TM-polarized mode undergoes an open-close-reopen process, the topological properties of the corresponding bandgap remain unchanged. Based on theoretical analysis, we design the composite PCs comprising two interfaced PCs having common bandgaps but different topological properties. By tuning the incident angle, we theoretically and experimentally achieve TE-TM splitting of topological interface states in the visible region, which may have potential applications in optical communications, optical switching, photonic integrated circuits, and so on.

Laser additive manufacturing of a CoCr-based medium-entropy alloy: Impressive stacking fault-induced nanotwinning strengthening through rapid solidification

The directed energy deposition (DED) technique was used to deposit a CoCrNiWC medium entropy alloy (MEA) through a robotic-assisted laser additive manufacturing (LAM) machine. The microstructural features, including solidification grains, structural defects, and phase transformations, along with uniaxial tensile behavior in different orientations, were comprehensively studied. Furthermore, a quantitative assessment was carried out to evaluate the contribution of strengthening mechanisms through apprising stacking fault constant of 11362 MPa nm for the developed MEA, enrolling the impact of FCC to HCP crystal structure transition for the cobalt matrix after rapid cooling LAM solidification in the solid-state board. In addition, the presence of numerous ordinary screw dislocations interacting with each other, stacking faults (SFs), nanotwins, and refined grains led to their hindering as the critical factor for strengthening. The SF intersections resulted in the formation of effective Lomer-Cottrell (LC) locks and nanotwins, which were barriers to slip and attributed to dislocation interactions. Accordingly, the rapid cooling solidification of the LAM process contributed to impressive mechanical properties of deposited CoCr-based MEA with remarkable yield and tensile strengths of ∼895 and 1410 MPa, confirming the direct contributions of statistically stored dislocations upon impact SF and nanotwining strengthening.

Optimizing crystal transitions in low-temperature, low-concentration NaOH solutions to prepare cellulose I and II composite materials

Optimizing crystal transitions in low-temperature, low-concentration NaOH solutions to prepare cellulose I and II composite materials

Exploring Colloidal Phase Transitions of Imogolite Nanotubes by Evaporation Induced Self‐Assembly in Levitation

AbstractEvaporation‐induced self‐assembly (EISA) is a versatile method for generating organized superstructures from colloidal particles, offering diverse design possibilities through the manipulation of colloid size, shape, substrate nature, and environmental conditions. While some work highlighted the potential of EISA to investigate phase transitions of inorganic liquid crystals, the influence of sample environment to determine their phase diagrams is often overlooked. In this work, the self‐assembly of lyotropic liquid crystals is compared by EISA on substrates, and by acoustic levitation (absence of substrate). The focus is on imogolite nanotubes, a model colloidal system of 1D charged objects, due to their tunable morphology and rich liquid‐crystalline phase behavior. It demonstrates the feasibility to obtain phase transitions in levitating droplets and on soft hydrophobic substrates, whereas self‐assembly is limited on rigid hydrophilic supports. Moreover, the aspect ratio of the nanotubes proves to be a pivotal factor, influencing both transitions and the resulting materials shape and surface. Besides material shaping, acoustic levitation emerges as a promising method for studying phase transitions by EISA, toward the rapid establishment of phase diagrams from diluted to highly concentrated states using a limited volume of sample.