Crystal Transition Research Articles

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.

Effects of Cu on the high-entropy alloys of CuxCoCrFeNi: Experiment and molecular dynamics simulations

The effects of Cu on the structure and properties of CuxCoCrFeNi were investigated experimentally and compared with the results of molecular dynamics simulations. Experimental results revealed that the alloy's crystal structure transitions from a single FCC to a biphasic FCC as Cu content increases. Mechanical testing indicated that increasing Cu content initially boosts, then reduces the alloy's yield and tensile strength, while elongation consistently increases, demonstrating enhanced plasticity. Additionally, nanoindentation tests further substantiated the notable impact of Cu content on alloy hardness. The nanoindentation simulation results show that the dislocation density increases and then decreases with the increase of Cu content, which explains the change of alloy properties with the increase of Cu content from a microscopic point of view. These findings offer valuable insights for designing and optimizing high-entropy alloys.

New insights into the growth characteristics and crystal morphology of α-hemihydrate gypsum induced by organic acid crystallization agents during PG conversion

The stockpiling of phosphogypsum (PG) poses a substantial risk of environmental pollution.To reduce the stockpile of PG and enhance its value, this research utilized phosphogypsum to produce α-hemihydrate gypsum (a-HH).The study elucidates the crystallization process of α-HH, which involves Ca2+ helical growth and coordinated filling by SO42- and H2O. Succinic acid, malic acid, L-aspartic acid are used as agents to transform PG into α-HH. α-HH is developed using a modified vapor pressure method. XRD, XPS, FT-IR, SEM, zeta potential, intensity testing, and molecular dynamics simulations are some methods used to study its crystal growth characteristics, morphological structure, and mechanical strength. These analyses aim to explore the impact and mechanism of succinic acid, malic acid, L-aspartic acid on the properties of α-HH. The results indicate that α-HH assumes a monoclinic crystal form, appearing as needles. Upon the addition of succinic acid, malic acid, and L-aspartic acid, the aspect ratio of α-HH crystals decreases, and the crystal morphology transitions from a rod-like needle structure to a short and stout structure.Notably, Malic acid demonstrates the most effective results.The study further demonstrates that the flexural and compressive strengths of all α-HH specimens surpass 4.5 MPa and 30 MPa, respectively, meeting the requirements for high-strength gypsum, specifically α30.Simultaneously, this study reveals that succinic acid, malic acid, L-aspartic acid form cyclic chelates with Ca2+ on the prominent surface of α-HH through oxygen atoms in the carbon base of the molecules, thereby altering the crystalline morphology of α-HH. The regulation of α-HH crystalline morphology depends primarily on the spacing and electron-donating ability between carbon-based oxygen atoms in the molecules of succinic acid, malic acid, L-aspartic acid. Introducing conjugated electron-donating groups into the adjacent positions of organic acids can more effectively enhance their ability to regulate the crystalline morphology of α-HH. This study further demonstrates that the regulation ability is directly proportional to the polarity of the organic acid molecules.

Evidence for electron-hole crystals in a Mott insulator.

The coexistence of correlated electron and hole crystals enables the realization of quantum excitonic states, capable of hosting counterflow superfluidity and topological orders with long-range quantum entanglement. Here we report evidence for imbalanced electron-hole crystals in a doped Mott insulator, namely, α-RuCl3, through gate-tunable non-invasive van der Waals doping from graphene. Real-space imaging via scanning tunnelling microscopy reveals two distinct charge orderings at the lower and upper Hubbard band energies, whose origin is attributed to the correlation-driven honeycomb hole crystal composed of hole-rich Ru sites and rotational-symmetry-breaking paired electron crystal composed of electron-rich Ru-Ru bonds, respectively. Moreover, a gate-induced transition of electron-hole crystals is directly visualized, further corroborating their nature as correlation-driven charge crystals. The realization and atom-resolved visualization of imbalanced electron-hole crystals in a doped Mott insulator opens new doors in the search for correlated bosonic states within strongly correlated materials.

Influence of a transverse magnetic field on wakefield oscillations around a charged dust grain in complex plasma

In the presence of ion streaming, the potential around dust particles immersed in plasma becomes anisotropic. In this scenario, the repulsive Debye–Hückel potential is superimposed with an attractive wake potential. This work presents an analytical study of the complex behavior of such a wake potential in the presence of a magnetic field (oriented transversely to the ion flow) and ion-neutral collisions using linear response formalism, both in subsonic and supersonic regimes. The amplitude and periodicity of this potential are found to be controlled by the interplay among ion streaming velocity, ion cyclotron frequency, and ion-neutral collision frequency. Due to the tunable nature of this potential, it is possible to control the crystal formation, phase transitions, and transport properties of dusty plasma by adjusting the external magnetic field. The study also reveals that the wake potential almost disappears in a collision-dominant regime.