Editor’s Choice Articles

Single-layer graphene decorated with monodisperse copper nanoparticles can support the size and mass-dependent catalysis of the selective electrochemical reduction of CO${}_2$ to ethylene (C${}_2$H${}_4$). In this study, various active adsorption sites of nanostructured Cu-decorated graphene have been calculated by using density functional theory to provide insight into its catalytic activity toward carbon dioxide electroreduction. Based on the results of our calculations, an enhanced adsorption of the CO${}_2$ molecule and CH${}_2$ counterpart placed atop of Cu-decorated graphene compared to adsorption at pristine Cu metal surfaces was predicted. This approach explains experimental observations for carbon-based catalysts that were found to be promising for the two-electron reduction reaction of CO${}_2$ to CO and, further, to ethylene. Active adsorption sites that lead to a better catalytic activity of Cu-decorated graphene, with respect to general copper catalysts, were identified. The atomic configuration of the most selective CO${}_2$ toward the reduction reaction nanostructured catalyst is suggested. Full article

The microstructures of Mg-1Sn-2.5Y (wt%) alloys solidified under high pressures were investigated. In addition, a mathematical model was established to analyze the effects of solidification pressure and cooling rate on the average grain size. The results show that the alloy was solidified under high pressure and temperature gradient using the cooling rate difference in the high pressure chamber, resulting in the formation of the outer equiaxed zone, the columnar zone, and the equiaxed zone in the sample. With an increase in the solidification pressure, the columnar-to-equiaxed transition was inhibited in Mg-1Sn-2.5Y alloy. In the outer fine equiaxed zone and the columnar zone, the solubility of Sn in the Mg matrix increased with an increase in solidification pressure. The average secondary dendrite arm spacing decreased from 14–17 μm under 1 GPa to 9–11 μm under 1.5 GPa. Increases in pressure and cooling rate resulted in a reduction in average grain size. Full article

The growing interest in energy storage has led to the urgent need for the development of high-performance cathode electrodes. The commercialized materials MOF-235 and TiO₂-P25 exhibit characteristics that may be suitable as electrodes but there are inherent challenges that have yet to be addressed in the literature. In this study, a high-pressure hydrothermal synthesized MOF-235 and sol-gel-made TiO₂-P25 were tested for battery performance. The results indicate that MOF-235 does not possess the desired performance due to uncontrollable agglomeration. On the other hand, TiO₂-P25 showed good cycling life, and the performance can be further optimized by doping and minimizing the particle size. Additionally, SEM and TEM were applied for surface characterization, providing evidence that mesoporous TiO₂-25 inhibits photo-generated carrier recombination. The mesoporous energy storage mechanism of those two materials is also discussed. This research will provide technical support for the industrialization of those two mesoporous materials. Full article

The nanostructuring of the (100) PbS single crystal surface was studied under varying argon plasma treatment conditions. The initial PbS single crystals were grown by high-pressure vertical zone melting, cut into wafer samples, and polished. Subsequently, the PbS single crystals were treated with inductively coupled argon plasma under varying treatment parameters such as ion energy and sputtering time. Plasma treatment with ions at a minimum energy of 25 eV resulted in the formation of nanotips with heights of 30–50 nm. When the ion energy was increased to 75–200 eV, two types of structures formed on the surface: high submicron cones and arrays of nanostructures with various shapes. In particular, the 120 s plasma treatment formed specific cruciform nanostructures with lateral orthogonal elements oriented in four <100> directions. In contrast, plasma treatment with an ion energy of 75 eV for 180 s led to the formation of submicron quasi-spherical lead structures with diameters of 250–600 nm. The nanostructuring mechanisms included a surface micromasking mechanism with lead formation and the vapor–liquid–solid mechanism, with liquid lead droplets acting as self-forming micromasks and growth catalysts depending on the plasma treatment conditions (sputtering time and rate). Full article

The crystallographic orientation relationship between α and β phases during the non-equilibrium heat treatment of a Cu-37 wt. % Zn alloy was investigated. With this aim, Cu-37 wt. % Zn alloy plates with a thickness of 2 mm were heated at 810 °C for 1 h and then were quenched in water. The microstructure and texture of heat-treated samples were analyzed using optical microscopy and electron backscattered diffraction. By this non-equilibrium heat treatment, β phase was formed on both the grain boundaries and grain interiors. In addition, the Σ3 twin boundaries acted as preferred areas for α→β transformation. The orientation imaging microscopy results revealed a Kurdjumov–Sachs (K–S) orientation relationship between α and β phases. Furthermore, the details of microstructural evolution and texture analysis were discussed. Full article

Cryocrystallography is a widely used method for determining the crystal structure of macromolecules. This technique uses a cryoenvironment, which significantly reduces the radiation damage to the crystals and has the advantage of requiring only one crystal for structural determination. In standard cryocrystallography, a single crystal is used for collecting diffraction data, which include single-crystal diffraction patterns. However, the X-ray data recorded often may contain diffraction patterns from several crystals. The indexing of multicrystal diffraction patterns in cryocrystallography requires more precise data processing techniques and is therefore time consuming. Here, an approach for processing multicrystal diffraction data using a serial crystallography program is introduced that allows for the integration of multicrystal diffraction patterns from a single image. Multicrystal diffraction data were collected from lysozyme crystals and processed using the serial crystallography program CrystFEL. From 360 images containing multicrystal diffraction patterns, 1138 and 691 crystal lattices could be obtained using the XGANDALF and MOSFLM indexing algorithms, respectively. Using this indexed multi-lattice information, the crystal structure of the lysozyme could be determined successfully at a resolution of 1.9 Å. Therefore, the proposed approach, which is based on serial crystallography, is suitable for processing multicrystal diffraction data in cryocrystallography. Full article

Polycrystalline nickel-based superalloys tend to have large grains within component areas where high loads are dominant during operation. Due to these large grains, caused by the manufacturing and cooling process, the orientation of each grain becomes highly important, since it influences the elastic and plastic behaviour of the material. With the usage of the open source codes NEPER and FEPX, polycrystalline models of Inconel 738 LC were generated and their elastic and crystal plasticity behaviour simulated in dependence of different orientation distributions under uniaxial loading. Orientation distributions close to the [100] direction showed the lowest Young’s moduli as well as the highest elastic strains before yielding, as expected. Orientations close to the [$\overline{5}$89] direction, showed the lowest elastic strains and therefore first plastic deformation under strain loading due to the highest shear stress in the slip systems caused by the interaction of Young’s modulus and the Schmid factor. Full article

Spinel-based hydroxyapatite composite (SHC) has been synthesized utilizing bovine bones as the source of the hydroxyapatite (HAp) and beverage cans as the aluminum (Al) source. The bovine bones were defatted and calcined in the air atmosphere to transform them into hydroxyapatite. The beverage cans were cut and milled to obtain fine Al powder and then sieved to obtain three different particle mesh size fractions: +100#, −140# + 170#, and −170#, or Al particle size of >150, 90–150, and <90 µm, respectively. The SHC was synthesized using the self-propagating intermediate-temperature synthesis (SIS) method at 900 °C for 2 h with (HAp:Al:Mg) ratio of (87:10:3 wt.%) and various compaction pressure of 100, 171, and 200 MPa. It was found that the mechanical properties of the SHC are influenced by the Al particle size and the compaction pressure. Smaller particle size produces the tendency of increasing the hardness and reducing the porosity of the composite. Meanwhile, increasing compaction pressure produces a reduction of the SHC porosity. The increase in the hardness is also observed by increasing the compaction pressure except for the smallest Al particle size (<90 µm), where the hardness instead becomes smaller. Full article

Solitons in liquid crystals have received increasing attention due to their importance in fundamental physical science and potential applications in various fields. The study of solitons in liquid crystals has been carried out for over five decades with various kinds of solitons being reported. Recently, a number of new types of solitons have been observed, among which, many of them exhibit intriguing dynamic behaviors. In this paper, we briefly review the recent progresses on experimental investigations of solitons in liquid crystals. Full article

The reprecipitation and evolution of γ’ precipitates during various cooling approaches from supersolvus temperature are studied experimentally and via phase field simulation in nickel-based single crystal superalloys. The focus of this paper is to explore the influence of cooling methods on the evolution of the morphology and the distribution of γ’ precipitates. It is demonstrated that small and uniform spherical shape γ’ particles formed with air cooling method. When the average cooling rate decreases, the particle number decreases while the average matrix and precipitate channel widths increase. The shape of γ’ precipitates which changed from spherical to cubic and irregular characteristics due to the elastic interaction and elements diffusion are observed with the decrease of the average cooling rate. The phase field simulation results are in good agreement with the experimental results in this paper. The research is a benefit for the study of the rejuvenation heat treatment in re-service nickel-based superalloys. Full article

Nitrogen-containing 0Cr19Ni10 (304 NG) austenitic stainless steel plays a significant role in Generation IV reactor pressure vessels. The structure and properties of 304 NG are heavily influenced by the grain boundaries (GBs), especially the initial mechanical response and dislocation evolutions. Hence, in this paper, we carried out molecular dynamics (MD) simulations to investigate the effects of the GB angles on the initial deformation of 304 models under nanoindentation. It is found that the GB angle has great effects on the mechanical properties of 304 NG. With the GB angles changing from 90° to 150°, the values of Young’s modulus and maximum shear stress first decrease and then increase due to decreasing of the interaction among the GBs and the grain interiors (GIs) and the smoother shape of GBs. The hardening region slope decreases rapidly result from the GB angles changing the grain size on the both sides, which fully fits the Hall–Petch relationship. After the dislocations reaching the GBs along the slip system, the dislocation piles-up on the GBs at first, and then GBs serve as a source of dislocation and emit dislocation to free surface with the depth of nanoindentation increasing. This work provides a better understanding on the angle effects of GBs in materials. Full article

The present work highlights a new general method devoted to computations of the clamped linear electro-optical coefficients from the measured fundamental vibrational frequencies and the nonlinear dielectric susceptibility constants. The calculations are based on the formula analog to that of the Lyddane–Sachs–Teller relation, which is systematically used for the calculations of the clamped linear electro-optical coefficient of oxide ferroelectric crystals such as LiNbO₃, LiTaO₃, BaTiO₃, PbTiO₃, and KNbO₃. The computed electro-optical coefficients are in good agreement with those obtained from direct measurements and the first-principles calculations or other semi-empirical models. In addition, the famous $r51$ or $r42$ coefficients of the tetragonal BaTiO₃, PbTiO₃, and KNbO₃ crystals are finally calculated with high accuracy and discussed in connection with the soft mode behavior. Full article

Numerous investigations on the development of the relaxor-PbTiO₃ ferroelectric crystals have been carried out since their extraordinary properties were revealed. Recent developments on these crystals have offered further advances in electromechanical applications. In this review, recent developments on relaxor-PbTiO₃ crystals and their practical applications are reviewed. The single crystal growth methods are first discussed. Two different strategies, poling and doping, for piezoelectric improvement are surveyed in the following section. After this, the anisotropic features of the single crystals are discussed. Application perspectives arising from the property improvements for electromechanical devices are finally reviewed. Full article

Protein and DNA co-crystals are most commonly prepared to reveal structural and functional details of DNA-binding proteins when subjected to X-ray diffraction. However, biomolecular crystals are notoriously unstable in solution conditions other than their native growth solution. To achieve greater application utility beyond structural biology, biomolecular crystals should be made robust against harsh conditions. To overcome this challenge, we optimized chemical DNA ligation within a co-crystal. Co-crystals from two distinct DNA-binding proteins underwent DNA ligation with the carbodiimide crosslinking agent 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) under various optimization conditions: 5′ vs. 3′ terminal phosphate, EDC concentration, EDC incubation time, and repeated EDC dose. This crosslinking and DNA ligation route did not destroy crystal diffraction. In fact, the ligation of DNA across the DNA–DNA junctions was clearly revealed via X-ray diffraction structure determination. Furthermore, crystal macrostructure was fortified. Neither the loss of counterions in pure water, nor incubation in blood serum, nor incubation at low pH (2.0 or 4.5) led to apparent crystal degradation. These findings motivate the use of crosslinked biomolecular co-crystals for purposes beyond structural biology, including biomedical applications. Full article

The mechanical properties of high-entropy alloys are superior to those of traditional alloys. However, the key problem of finding a strengthening mechanism is still challenging. In this work, the molecular dynamics method is used to calculate the tensile properties of face-centered cubic Al_0.1CoCrFeNi high-entropy alloys containing Σ3 grain boundaries and without grain boundary. The atomic model was established by the melting rapid cooling method, then stretched by the static drawing method. The common neighbor analysis and dislocation extraction algorithm are used to analyze the crystal evolution mechanism of Σ3 grain boundaries to improve the material properties of high-entropy alloys during the tensile test. The results show that compared with the mechanical properties Al_0.1CoCrFeNi high-entropy alloys without grain boundary, the yield strength and Young’s modulus of a high-entropy alloy containing Σ3 grain boundary are obviously larger than that of high-entropy alloys without grain boundary. Dislocation type includes mainly 1/6<112> Shockley partial dislocations, a small account of 1/6<110> Stair-rod, 1/2<110>perfect dislocation, and 1/3<111> Hirth dislocations. The mechanical properties of high-entropy alloys are improved by dislocation entanglement and accumulation near the grain boundary. Full article

A gene encoding LgEstI was cloned from a bacterial fish pathogen, Lactococcus garvieae. Sequence and bioinformatic analysis revealed that LgEstI is close to the acetyl esterase family and had maximum similarity to a hydrolase (UniProt: Q5UQ83) from Acanthamoeba polyphaga mimivirus (APMV). Here, we present the results of LgEstI overexpression and purification, and its preliminary X-ray crystallographic analysis. The wild-type LgEstI protein was overexpressed in Escherichia coli, and its enzymatic activity was tested using p-nitrophenyl of varying lengths. LgEstI protein exhibited higher esterase activity toward p-nitrophenyl acetate. To better understand the mechanism underlying LgEstI activity and subject it to protein engineering, we determined the high-resolution crystal structure of LgEstI. First, the wild-type LgEstI protein was crystallized in 0.1 M Tris-HCl buffer (pH 7.1), 0.2 M calcium acetate hydrate, and 19% (w/v) PEG 3000, and the native X-ray diffraction dataset was collected up to 2.0 Å resolution. The crystal structure was successfully determined using a molecular replacement method, and structure refinement and model building are underway. The upcoming complete structural information of LgEstI may elucidate the substrate-binding mechanism and provide novel strategies for subjecting LgEstI to protein engineering. Full article

The physics of quantum many-body systems have been studied using bulk correlated materials, and recently, moiré superlattices formed by atomic bilayers have appeared as a novel platform in which the carrier concentration and the band structures are highly tunable. In this brief review, we introduce an intermediate platform between those systems, namely, a band-filling- and bandwidth-tunable electric double-layer transistor based on a real organic Mott insulator κ-(BEDT-TTF)₂Cu[N(CN)₂]Cl. In the proximity of the bandwidth-control Mott transition at half filling, both electron and hole doping induced superconductivity (with almost identical transition temperatures) in the same sample. The normal state under electric double-layer doping exhibited non-Fermi liquid behaviors as in many correlated materials. The doping levels for the superconductivity and the non-Fermi liquid behaviors were highly doping-asymmetric. Model calculations based on the anisotropic triangular lattice explained many phenomena and the doping asymmetry, implying the importance of the noninteracting band structure (particularly the flat part of the band). Full article

A UV Nonlinear optical (NLO) crystal is one of the key devices in all-solid-state laser technology, and borate halides show outstanding potential due to their abundant structural diversity and short UV cut-off edges. In this article, the sizable UV NLO crystal of K₃B₆O₁₀Br (KBOB) has been grown with lead-containing and lead-free fluxes systems using the high-temperature top-seeded solution growth (TSSG) method. Energy Dispersive X-ray Spectroscopy (EDS) and transmittance spectra illustrate the influence of Pb²⁺ ions on the transmittance properties and laser-induced damage threshold (LDT). The thermal property, namely, thermal expansion, thermal conductivity, and thermal diffusivity curves, were characterized. Moreover, a small variation of thermal refractive indexes was analyzed to illustrate the advantage of KBOB in the application for temperature-fluctuated specific regions. Full article

Charge-transfer salts based on bis(ethylenedioxy)tetrathiafulvalene (BEDO-TTF or BO for short) provide a stable two-dimensional (2D) metallic state, while the electrical resistance often shows an upturn at low temperatures below ~10 K. Such 2D weak carrier localization was first recognized for BO salts in the Langmuir–Blodgett films fabricated with fatty acids; however, it has not been characterized in charge-transfer solid crystals. In this paper, we discuss the carrier localization of two crystalline BO charge-transfer salts with or without magnetic ions at low temperatures through the analysis of the weak negative magnetoresistance. The phase coherence lengths deduced with temperature dependence are largely dominated by the electron–electron scattering mechanism. These results indicate that the resistivity upturn at low temperatures is caused by the 2D weak localization. Disorders causing elastic scattering within the metallic domains, such as those of terminal ethylene groups, should be suppressed to prevent the localization. Full article

Liquid crystal (LC) micro-droplet arrays are elegant systems that have a range of applications, such as chemical and biological sensing, due to a sensitivity to changes in surface properties and strong optical activity. In this work, we utilize self-assembled monolayers (SAMs) to chemically micro-pattern surfaces with preferred regions for LC occupation. Exploiting discontinuous dewetting, dragging a drop of fluid over the patterned surfaces demonstrates a novel, high-yield method of confining LC in chemically defined regions. The broad applicability of this method is demonstrated by varying the size and LC phase of the droplets. Although the optical textures of the droplets are dictated by topological constraints, the additional SAM interface is shown to lock in inhomogeneous alignment. The surface effects are highly dependent on size, where larger droplets exhibit asymmetric director configurations in nematic droplets and highly knotted structures in cholesteric droplets. Full article

A new spirooxindole hybrid engrafted imidazo[2,1-b]thiazole core structure was designed and achieved via [3+2] cycloaddition reaction approach. One multi-component reaction between the ethylene derivative based imidazo[2,1-b]thiazole scaffold with 6-Cl-isatin and the secondary amine under heat conditions afforded the desired compound in a stereoselective manner. The relative absolute configuration was assigned based on single-crystal X-ray diffraction analysis. Hirshfeld calculations for 4 revealed the importance of the H…H (36.8%), H…C (22.9%), Cl…H (10.4%) and S…H (6.6%), as well as the O…H (4.7%), N…H (5.3%), Cl…C (1.6%), Cl…O (1.0%) and N…O (0.5%) contacts in the crystal stability. DFT calculations showed excellent straight-line correlations (R² = 0.9776–0.9962) between the calculated and experimental geometric parameters. The compound has polar nature (3.1664 Debye). TD-DFT and GIAO calculations were used to assign and correlate the experimental UV-Vis and NMR spectra, respectively. Full article

We present analytical calculations of the energies and eigenfunctions of all normal modes of excitation of charge $+1$ two-dimensional splay (bend) disclinations confined to an annular region with inner radius $R_1$ and outer radius $R_2$ and with perpendicular (tangential) boundary conditions on the region’s inner and outer perimeters. Defects such as these appear in islands in smectic-C films and can in principle be created in bolaamphiphilic nematic films. Under perpendicular boundary conditions on the two surfaces and when the ratio $\beta =K_s/K_b$ of the splay to bend 2D Frank constants is less than one, the splay configuration is stable for all values $\mu =R_2/R_1$. When $\beta >1$, the splay configuration is stable only for $\mu$ less than a critical value ${\mu }_c\left(\beta \right)$, becoming unstable to a “spiral” mixed splay-bend configuration for $\mu >{\mu }_c$. The same behavior occurs in trapped bend defects with tangential boundary conditions but with $K_s$ and $K_b$ interchanged. By calculating free energies, we verify that the transition from a splay or bend configuration to a mixed one is continuous. We discuss the differences between our calculations that yield expressions for experimentally observable excitation energies and other calculations that produce the same critical points and spiral configurations as ours but not the same excitation energies. We also calculate measurable correlation functions and associated decay times of angular fluctuations. Full article

In this work, we studied the phase composition, local structure and mechanical characteristics of ZrO₂ crystals partially stabilized with Y₂O₃ and co-doped with Nd₂O₃, CeO₂, Er₂O₃, Tb₂O₃ and Yb₂O₃. Crystals were grown by directional melt crystallization in a cold container. The phase composition and structure of crystals were studied by X-ray diffractometry and transmission electron microscopy. The study of the features of the incorporation of rare-earth cations with different ionic radii into the transformable (t) and nontransformable (t’) tetragonal phases was carried out by the method of selective laser spectroscopy and time-resolved spectroscopy. Mechanical characteristics such as microhardness and fracture toughness were studied by the indentation method. It is shown that the phase composition and structure of crystals at the same total concentration of doping oxides depends on the degree of substitution of Y³⁺ cations by rare-earth cations. Rare earth ions of the beginning of the lanthanide series predominantly occupy positions in the nontransformable tetragonal phase of crystals based on zirconium dioxide. Ions of the end of a series of lanthanides do not show selectivity when entering the transformable (t) phase and nontransformable (t’) phase. The study of the mechanical characteristics of the crystals showed that the values of fracture toughness increase with an increase in the ionic radius of the rare earth element of the co-doped oxide, while the values of the microhardness of the crystals slightly decrease. Full article

Three functionalized chalcones containing combinations of nitro functional groups have been synthesized via Claisen-Schmidt condensation between 2-nitroacetophenone and nitrobenzaldehyde, and the crystal structures obtained ((E)-1,3-bis(2-nitrophenyl)prop-2-en-1-one, 1a, (E)-1-(2-nitrophenyl)-3-(3-nitrophenyl)prop-2-en-1-one, 1b and (E)-1-(2-nitrophenyl)-3-(4-nitrophenyl)prop-2-en-1-one, 1c), C₁₅H₁₀N₂O_5, are reported. Compounds 1a and 1c crystallized in the triclinic centrosymmetric space group P$\overline{1}$, whereas compound 1b crystallized in the orthorhombic space group Pbca. The X-ray analysis reveals that structures 1a and 1b exhibits s-trans conformation, whereas structure 1c exists in s-cis conformation, concerning the olefinic double bonds. In addition, the results show that the position of the nitro substituent attached to the aromatic B-ring has a direct effect on the molecular coplanarity of these compounds. The Hirshfeld surface analysis suggests that the non-covalent π-π stacking interactions are the most important contributors for the crystal packing of 1a and 1b. In 1c, the crystal packing is mainly stabilized by weak intermolecular C―H···O interactions due to the planar nature of the molecule. Full article

A terahertz metasurface that is imbedded into a dye-doped liquid crystal (DDLC) cell is fabricated in this work. After the metasurface-imbedded DDLC cell is irradiated with a linearly polarized pump beam, the irradiated cell is measured with a terahertz spectrometer. The irradiation of the pump beam causes the adsorption of the dye on one of the substrates of the cell, scattering incident terahertz waves and decreasing the transmittances of the terahertz metasurface at all the frequencies of its resonance spectrum. In addition, these transmittances decrease with an increase in the irradiation times of the pump beam. The adsorbed dye molecules are erased from the substrate after the cell is heated by a hot plate. The cell has similar spectra before the irradiation of the pump beam and after the heating of the hot plate. The aforementioned results reveal that the metasurface-imbedded DDLC cell is an optically tunable and thermally erasable terahertz intensity modulator. Therefore, this cell has the potential in developing intensity attenuators for terahertz imaging, frequency isolators for terahertz telecommunication, and spatial light modulators for terahertz information encryption and decryption. Full article

Acoustic tunneling is an essential property for phononic crystals in a Dirac-cone state. By analyzing the linear dispersion relations for the accidental degeneracy of Bloch eigenstates, the influence of geometric parameters on opening the Dirac-cone state and the directional band gaps’ widths are investigated. For two-dimensional hexachiral phononic crystals, for example, the four-fold accidental degenerate Dirac point emerges at the center of the irreducible Brillouin zone (IBZ). The Dirac cone properties and the band structure inversion problem are discussed. Finally, to verify acoustic transmission properties near the double-Dirac-cone frequency region, the numerical calculation of the finite-width phononic crystal structure is carried out, and the acoustic transmission tunneling effect is proved. The results enrich and expand the manipulating method in the topological insulator problem for hexachiral phononic crystals. Full article

The luminescence of materials in condensed phases is affected by not only their molecular structures but also their aggregated structures. In this study, we designed new liquid-crystalline luminescent materials based on biphenylacetylene with a bulky trimethylsilyl terminal group and a flexible alkoxy chain. The luminescence properties of the prepared materials were evaluated, with a particular focus on the effects of phase transitions, which cause changes in the aggregated structures. The length of the flexible chain had no effect on the luminescence in solution. However, in crystals, the luminescence spectral shape depended on the chain length because varying the chain length altered the crystal structure. Interestingly, negative thermal quenching of the luminescence from these materials was observed in condensed phases, with the isotropic phase obtained at high temperatures exhibiting a considerable increase in luminescence intensity. This thermal enhancement of the luminescence suggests that the less- or nonemissive aggregates formed in crystals are dissociated in the isotropic phase. These findings can contribute toward the development of new material design concepts for useful luminescent materials at high temperatures. Full article

Temperature-dependent crystal structure alterations in the brownmillerite-type material Ba₂In₂O₅ play a fundamental role in its applications: (i) photocatalytic CO₂ conversion; (ii) oxygen transport membranes; and (iii) proton conduction. This is connected to a reversible uptake of up an equimolar amount of water. In this study, in situ X-ray and neutron diffraction were combined with Raman spectroscopy and solid-state nuclear magnetic resonance experiments to unravel the effects of Cr doping and water content on the crystal structure transitions of Ba₂In₂O₅(H₂O)_x over a wide temperature range (10 K ≤ T ≤ 1573 K, x < 1). A mixture of isolated and correlated protons was identified, leading to a highly dynamic situation for the protons. Hence, localisation of the protons by diffraction techniques was not possible. Cr doping led to an overall higher degree of disorder and stabilisation of the tetragonal polymorph, even at 10 K. In contrast, a further disordering at high temperatures, leading to a cubic polymorph, was found at 1123 K. Cr doping in Ba₂In₂O₅ resulted in severe structural changes and provides a powerful way to adjust its physical properties to the respective application. Full article

This study focused on the crystal and electronic structures of a newly discovered phase in the Al-Cr-Sc system. The latter two species do not mix in a binary alloy, but can be alloyed with aluminium in the vicinity of the Al_2−xCr_xSc composition, where 0.3 < x < 0.5. After preparation of the pure constituents via arc melting, high-temperature annealing at 990 °C for 240 h was required to achieve full mixing of the elements. A detailed characterisation of the crystal structure, alloy microstructure and stability was obtained using single-crystal X-ray diffraction (SCXRD) and powder X-ray diffraction (PXRD), in addition to transmission electron microscopy (TEM), especially in high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) mode, scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDXS) and differential scanning calorimetry (DSC) measurements. The crystal structure was refined to a hexagonal unit cell of the MgZn₂ type, space group no. 194, P6₃/mmc, which belongs to the Laves phases family. Special attention was paid to the occupancy of the crystallographic sites that were filled by both Cr and Al atoms. First-principles calculations based on the density functional theory (DFT) were performed to investigate the electronic structure of this ternary phase. The total density of states (DOS) exhibited a pronounced sp character, where a shallow pseudo-gap was visible 0.5 eV below the Fermi energy that brought a small but definite contribution to the thermodynamic stability of the compound. Full article

Simultaneous occurrence of Dirac-like cones at the center of the Brillouin zone (Γ) at two different energy states is termed Dual-Dirac-like cones (DDC) in this article. The occurrence of DDC is a rare phenomenon. Thus, the generation of multiple Dirac-like cones at the center of the Brillouin zone is usually non-manipulative and poses a challenge to achieve through traditional accidental degeneracy. However, if predictively created, DDC will have multiple engineering applications with acoustics and vibration. Thus, the possibilities of creating DDC have been identified herein using a simple square periodic array of tunable square phononic crystals (PnCs) in air media. It was found that antisymmetric deaf bands may play critical roles in tracking the DDC. Hence, pivoting on the deaf bands at two different energy states, an optimized tuning parameter was found to achieve Dirac-like cones at two distinct frequency states, simultaneously. Orthogonal wave transport identified as key Dirac phenomena was achieved at two frequencies, herein. It was identified that beyond the Dirac-like cone, the Dirac phenomena remain dominant when a doubly degenerated state created by a top band with positive curvature and a near-flat deaf band are lifted from a bottom band with negative curvature. Utilizing a mechanism of rotating the PnCs near a fixed deaf band, frequencies are tracked to form the DDC, and orthogonal wave transport is demonstrated. Exploiting the dispersion behavior, unique acoustic phenomena, such as ballistic wave transmission, pseudo diffusion and acoustic cloaking are also demonstrated at the Dirac frequencies using numerical simulation. The proposed tunable acoustic PnCs will have important applications in acoustic and ultrasonic imaging, waveguiding and even acoustic computing. Full article

This study demonstrates controllable random lasing emissions in a dye-doped nematic liquid crystal (DDNLC)-infiltrated microcapillary. The emission wavelength of the micro tube laser can be adjusted by changing the focusing position of the pumped pulses on the center or the periphery of the liquid crystal region of the microcapillary. In addition, with doping azo-dyes in the DDNLC of the micro tube laser, optical controllability of the lasing intensity and wavelength can be further achieved. The controllable micro tube laser may find highly widespread photonic applications in multicolor emitting sources, and vibration and UV sensors. Full article

An as-grown domain structure in nominally pure and Mn-doped calcium orthovanadate (CVO) crystals was studied by several methods of domain imaging: optical microscopy, piezoelectric force microscopy, and Cherenkov-type second harmonic generation. The combination of imaging methods provided an opportunity for comprehensive study of the domain structure on the polar surface and in the bulk of the samples. It was shown that, in nominally pure CVO crystals, an irregular 3D maze of rounded domains, with charged walls, essentially tilted from the polar direction, was present. It was proposed that the domain structure was formed just below the phase transition temperature and persisted during subsequent cooling. Such behavior is due to effective bulk screening of the depolarization field and a low value of the pyroelectric field which appears during cooling. The revealed formation of triangular domains and flat fragments of domain walls in Mn-doped CVO was attributed to polarization reversal under the action of the polar component of the pyroelectric field, above the threshold value for domain switching. This fact represents the first observation of the domain switching in CVO crystals. Full article

It is known that a propagating wave at a certain spatial point can be decomposed into plane waves propagating at different angles. In this work, by designing a gradient index phononic crystal lens (GRIN PCL) with transverse-continuous leaf-like unit cells, we theoretically and experimentally show that the spatial-domain propagating waves in finite periodic structures can be linked to their time-domain vibration behaviors. The full-field instantaneous focusing behaviors of Lamb waves in the proposed leaf-like GRIN PCL give an example of the wave-vibration linkage in finite periodic structures while allowing a certain complexity. The conclusion in this paper can help one skip iterative time-consuming finite element analysis (e.g., time-stepping solutions) to avoid possible numerical instabilities occurred in calculating transient wave field on practical finite metamaterials or phononic crystals having unit cells with complicated configurations. Full article

In this work, pure and silver (Ag)-loaded TiO₂ nanocrystals (NCs) with various concentrations of Ag were prepared by soft chemical route and the effect of Ag nanoparticles (NPs) on the functional properties of TiO₂ was studied. X-ray diffraction (XRD) and Raman studies confirmed that the synthesized product had single-phase nature and high crystalline quality. The crystallite size was decreased from 18.3 nm to 13.9 nm with the increasing in concentration of Ag in TiO₂ NCs. FESEM micrographs showed that the pure and AgNPs-loaded TiO₂ have spherical morphology and uniform size distribution with the size ranging from 20 to 10 nm. Raman spectroscopy performed on pure and AgNPs-loaded TiO₂ confirms the presence of anatase phase and AgNPs. Optical properties show the characteristics peaks of TiO₂ and the shifting of the peaks position was observed by changing the concentration of Ag. The tuning of bandgap was found to be observed with the increase in Ag, which could be ascribed to the synergistic effect between silver and TiO₂ NCs. Density functional theory calculations are carried out for different Ag series of doped TiO₂ lattices to simulate the structural and electronic properties. The analysis of the electronic structures show that Ag loading induces new localized gap states around the Fermi level. Moreover, the introduction of dopant states in the gap region owing to Ag doping can be convenient to shift the absorption edge of pristine TiO₂ through visible light. Full article

The effective mechanical properties of a polycrystal depend directly on the single-crystal properties of each grain and its crystallographic orientation with respect to the load axis. While the micromechanical approach has been used quite extensively to study the influence of grain shape and crystallographic texture on the resulting mechanical behavior of a polycrystal, the influence of the crystal plasticity parameters, which describe the constitutive behavior of the single crystal, requires to be investigated systemically because, typically, these parameters are fitted to describe a given material behavior. In the current research, this gap is filled by systemically studying the effect of changes in crystal plasticity parameters on the effective mechanical properties of polycrystals. The numerical model employed here consists of a representative volume element of 100 grains, and the material properties are described by using a non-local crystal plasticity model. A proper homogenization technique was used to homogenize the micromechanical results to an effective macroscopic material response. The equivalent stress versus equivalent plastic strain curve was obtained numerically by introducing the Voce-type hardening law, mimicking the material behavior in uniaxial tensile tests. The four parameters of the Voce-type hardening law were fitted to the macroscopic stress-strain curves, and the correlation between the crystal plasticity parameters and the Voce parameters has been studied, which is an efficient way to study the influence of microscopic material descriptions on the macroscopic behavior of polycrystals. Full article

Modularity is an important construction principle of many inorganic crystal structures that has been used for the analysis of structural relations, classification, structure description and structure prediction. The principle of maximal simplicity for modular inorganic crystal structures can be formulated as follows: in a modular series of inorganic crystal structures, the most common and abundant in nature and experiments are those arrangements that possess maximal simplicity and minimal structural information. The latter can be quantitatively estimated using information-based structural complexity parameters. The principle is applied for the modular series based upon 0D (lovozerite family), 1D (biopyriboles) and 2D (spinelloids and kurchatovite family) modules. This principle is empirical and is valid for those cases only, where there are no factors that may lead to the destabilization of simplest structural arrangements. The physical basis of the principle is in the relations between structural complexity and configurational entropy sensu stricto (which should be distinguished from the entropy of mixing). It can also be seen as an analogy of the principle of least action in physics. Full article

The single most important structural material, and the major Portland cement binding phase in application globally, is calcium silicate hydrate (C-S-H). The concentration has increasingly changed due to its atomic level comprehension because of the chemistry and complex structures of internal C-S-H cohesion in cement crystals at different lengths. This perspective aimed at describing on calcium-silicate-hydrates (C-S-H) structures with differing contents of Ca/Si ratio based on the report entitled “Quantum mechanical metric for internal cohesion in cement crystals” published by C. C. Dharmawardhana, A. Misra and Wai-Yim Ching. Crystal structural and bond behaviors in synthesized C-S-H were also discussed. The investigator studied large subset electronic structures and bonding of the common C-S-H minerals. From each bonding type, the results and findings show a wide variety of contributions, particularly hydrogen bonding, that allow critical analyses of spectroscopic measurement and constructions of practical C-S-H models. The investigator found that the perfect overall measurement for examining crystal cohesions of the complex substances is the total bond density (TBOD), which needs to be substituted for traditional metrics such as calcium to silicon ratios. In comparison to Tobermorite and Jennite, hardly known orthorhombic phased Suolunites were revealed to have greater cohesion and total order distribution density than those of the hydrated Portland cement backbone. The findings of the perspective showed that utilizing quantum mechanical metrics, the total bond orders and total bond order distributions are the most vital criteria for assessing the crystalline cohesions in C-S-H crystals. These metrics encompass effects of both interatomic interactions and geometric elements. Thus, the total bond order distribution and bond order offer comprehensive and in-depth measures for the overall behaviors of these diverse groups of substances. The total bond order distributions must clearly be substituted for the conventional and longstanding Ca/Si ratios applied in categorizing the cement substances. The inconspicuous Suolunite crystals were found to have the greatest total bond order distributions and the perfect bonding characteristics, compositions, and structures for cement hydrates. Full article

An optically activated, enhancement mode heterostructure field effect transistor is proposed and analytically studied. A particular feature of this device is its gate region, which is made of a photovoltaic GaN/AlN-based superlattice detector for a wavelength of 1.55 µm. Since the inter-subband transition in this superlattice does normally not interact with TE-polarized (or vertically incoming) radiation, a metallic second-order diffraction grating on the transistor gate results in a re-orientation of the light into the horizontal direction—thus providing the desired TM-polarization. Upon illumination of this gate, efficient inter-subband absorption lifts electrons from the ground to the first excited quantized state. Due to partial screening of the strong internal polarization fields between GaN quantum wells and AlN barriers, this slightly diagonal transition generates an optical rectification voltage. Added to a constant electrical bias, this optically produced gate voltage leads to a noticeable increase of the transistor’s source-drain current. The magnitude of the bias voltage is chosen to result in maximal transconductance. Since such a phototransistor based on high-bandgap material is a device involving only fast majority carriers, very low dark and leakage currents are expected. The most important advantage of such a device, however, is the expected switching speed and, hence, its predicted use as an optical logic gate for photonic computing. In the absence of a p-n-junction and thus of both a carrier-induced space charge region, and the parasitic capacitances resulting thereof, operation frequencies of appropriately designed, sufficiently small phototransistors reaching 100 GHz are envisaged. Full article

A molecular field theory of the cholesteric ordering in nematic nanocomposites doped with chiral nanoparticles was developed taking into consideration chiral dispersion interaction between rod-like nanoparticles. It was shown that the inverse pitch of the cholesteric helical structure is proportional to the anisotropy of the effective polarizability and the anisotropy of the effective gyration tensor of a nanoparticle in the nematic host. The theory enables one to predict the helical sense inversion induced by a change of the low-frequency dielectric susceptibility of the nematic host phase. The components of the high-frequency effective polarizability and the effective optical activity of a gold rod-like nanoparticle in a particular nematic solvent were calculated numerically. Full article

A covalent serine protease inhibitor—Na-p-Tosyl-Lysyl Chloromethylketone (TCK) is a modified lysine residue tosylated at the N-terminus and chloromethylated at the C-terminus, one molecule of which is capable of forming two covalent bonds with both Ser and His catalytic residues, was co-crystallized with modified oligopeptidase B (OpB) from Serratia proteomaculans (PSPmod). The kinetics study, which preceded crystallization, shows that the stoichiometry of TCK-dependent inhibition of PSPmod was 1:2 (protein:inhibitor). The crystal structure of the PSPmod-TCK complex, solved at a resolution of 2.3 Å, confirmed a new type of inhibitor binding. Two TCK molecules were bound to one enzyme molecule: one with the catalytic Ser, the other with the catalytic His. Due to this mode of binding, the intermediate state of PSPmod and the disturbed conformation of the catalytic triad were preserved in the PSPmod-TCK complex. Nevertheless, the analysis of the amino acid surroundings of the inhibitor molecule bound to the catalytic Ser and its comparison with that of antipain-bound OpB from Trypanosoma brucei provided an insight in the structure of the PSPmod substrate-binding pocket. Supposedly, the new type of binding is typical for the interaction of chloromethylketone derivatives with two-domain OpBs. In the open conformational state that these enzymes are assumed in solution, the disordered configuration of the catalytic triad prevents simultaneous interaction of one inhibitor molecule with two catalytic residues. Full article

Structural defects and compositional uniformity remain the major problems affecting the performance of (Cd, Zn)Te (CZT) based detector devices. Understanding the mechanism of growth and defect formation is therefore fundamental to improving the crystal quality. In this frame, space experiments for the growth of CZT by the Travelling Heater Method (THM) under microgravity are scheduled. A detailed ground-based program was performed to determine experimental parameters and three CZT crystals were grown by the THM. The structural defects, compositional homogeneity and resistivity of these ground-based crystals were investigated. A ZnTe content variation was observed at the growth interface and a high degree of stress associated with extensive dislocation networks was induced, which propagated into the grown crystal region according to the birefringence and X-ray White Beam Topography (XWBT) results. By adjusting the growth parameters, the ZnTe variations and the resulting stress were efficiently reduced. In addition, it was revealed that large inclusions and grain boundaries can generate a high degree of stress, leading to the formation of dislocation slip bands and subgrain boundaries. The dominant defects, including grain boundaries, dislocation networks and cracks in the interior of crystals, led to the resistivity variation in the crystals. The bulk resistivity of the as-grown crystals ranged from 10⁹ Ωcm to 10¹⁰ Ωcm. Full article

We propose a new method to determine the absolute structure of chiral crystals, which is based on the chiral asymmetry of multiple scattering diffraction. It manifests as a difference in the azimuthal dependence of the forbidden Bragg reflection intensity measured with left and right circularly polarized X-ray beams. Contrary to the existing ones, the suggested method does not use X-ray anomalous dispersion. The difference between the Renninger scans with circularly polarized X-rays has been experimentally demonstrated for the 001 reflection intensities in the right- and left-handed quartz single crystals. A Jmulti-based code on model-independent three-wave-diffraction approach has been developed for quantitative description of our experimental results. The proposed method can be applied to various structures including opaque, organic and monoatomic crystals, even with only light elements. To determine the type of isomer, the Renninger plot of a single forbidden reflection is sufficient. Full article

In this paper, kinematic relations and constitutive laws in crystal plasticity are analyzed in the context of geometric nonlinearity description and fulfillment of thermodynamic requirements in the case of elastic deformation. We consider the most popular relations: in finite form, written in terms of the unloaded configuration, and in rate form, written in terms of the current configuration. The presence of a corotational derivative in the relations formulated in terms of the current configuration testifies to the fact that the model is based on the decomposition of motion into the deformation motion and the rigid motion of a moving coordinate system, and precisely the stress rate with respect to this coordinate system is associated with the strain rate. We also examine the relations of the mesolevel model with an explicit separation of a moving coordinate system and the elastic distortion of crystallites relative to it in the deformation gradient. These relations are compared with the above formulations, which makes it possible to determine how close they are. The results of the performed analytical calculations show the equivalence or similarity (in the sense of the response determined under the same influences) of the formulation and are supported by the results of numerical calculation. It is shown that the formulation based on the decomposition of motion with an explicit separation of the moving coordinate system motion provides a theoretical framework for the transition to a similar formulation in rate form written in terms of the current configuration. The formulation of this kind is preferable for the numerical solution of boundary value problems (in a case when the current configuration and, consequently, contact boundaries, are not known a priori) used to model the technological treatment processes. Full article

Two methods for the determination of geometrically necessary dislocation (GND) densities are implemented in a lower-order strain-gradient crystal plasticity finite element model. The equations are implemented in user material (UMAT) subroutines. Method I has a direct and unique solution for the density of GNDs, while Method II has unlimited solutions, where an optimization technique is used to determine GND densities. The performance of each method for capturing the formation of slip bands based on the calculated GND maps is critically analyzed. First, the model parameters are identified using single crystal simulations. This is followed by importing the as-measured microstructure for a deformed α-zirconium specimen into the finite element solver to compare the numerical results obtained from the models to those measured experimentally using the high angular resolution electron backscatter diffraction technique. It is shown that both methods are capable of modeling the formation of slip bands that are parallel to those observed experimentally. Formation of such bands is observed in both GND maps and plastic shear strain maps without pre-determining the slip band domain. Further, there is a negligible difference between the calculated grain-scale stresses and elastic lattice rotations from the two methods, where the modeling results are close to the measured ones. However, the magnitudes and distributions of calculated GND densities from the two methods are very different. Full article

Four new gadolinium(III) metal-organic frameworks containing 2,2′-bipyridyl (bpy) or 1,10-phenanthroline (phen) chelate ligands and trans-1,4-cyclohexanedicarboxylate (chdc²⁻) were synthesized. Their crystal structures were determined by single-crystal X-ray diffraction analysis. All four coordination frameworks are based on the binuclear carboxylate building units. In the compounds [Gd₂(bpy)₂(chdc)₃]·H₂O (1) and [Gd₂(phen)₂(chdc)₃]·0.5DMF (2), the six-connected {Ln₂(L)₂(OOCR)₆} blocks form a 3D network with the primitive cubic (pcu) topology. In the compounds [Gd₂(NO₃)₂(phen)₂(chdc)₂]·2DMF (3) and [Gd₂Cl₂(phen)₂(chdc)₂]·0.3DMF·2.2dioxane (4), the four-connected {Ln₂(L)₂(X)₂OOCR)₄} units (where X = NO₃⁻ for 3 or Cl⁻ for 4) form a 2D square-grid (sql) network. The solid-state luminescent properties were investigated for the synthesized frameworks. Bpy-containing compound 1 shows no luminescence, possibly due to the paramagnetic quenching by Gd³⁺ cation. In contrast, the phenathroline-containing MOFs 2–4 possess yellow emission under visible excitation (λ_ex = 460 nm) with the tuning of the characteristic wavelength by the coordination environment of the metal center. Full article

In this work, we investigated the porosity distribution and separation property of the porous crystal layer formed via the polythermal process. The proposed porosity distribution model, considering both the cooling profile and the crystal settling effect, provided simulative results that met the MRI analysis experimental results with suitable agreement. Significant porosity variation from the top to the bottom of the crystal layer ($\varphi$ from 0.75 to 0.55 under rapid cooling profile) was detected. Meanwhile, the vertical supersaturation degree gradient induced by the fluid fluctuation could impact nucleation and crystal growth kinetic along with crystal particle settling. The resulting crystal layer possessed various impurity inclusion conditions. Under a moderate cooling profile (0.4 K·min⁻¹), the volume fraction of closed pores against overall pores decreased from 0.75 to 0.36. The proposed model and experimental analysis approach were demonstrated to be helpful for porosity distribution simulation and impure inclusion analysis of layer crystallization. Full article

The review provides a summary of the current methods of tracing photoexcitation processes and structural dynamics in the solid state, putting major emphasis on the X-ray diffraction techniques (time-resolved Laue diffraction on synchrotron sources and time-resolved serial femtosecond crystallography on X-ray free-electron lasers). The recent developments and nowadays experimental possibilities in the field are discussed along with the data processing and analysis approaches, and illustrated with some striking literature examples of the respective successful studies. Selected complementary methods, such as ultrafast electron diffraction or time-resolved X-ray absorption spectroscopy, are briefly presented. Full article

The study of diamond surfaces is traditionally undertaken in geology and materials science. As a sample material, two natural diamond crystals of type Ia were selected, and their luminescence and nitrogen state was characterized. In order to etch the surface catalytic hydrogenation was performed using Fe particles as an etchant. Micromorphology of the surface was investigated by scanning electron and laser confocal microscopy. It was demonstrated that etching occurred perpendicular to the crystal surface, with no signs of tangential etching. The average depth of caverns did not exceed 20–25 μm with a maximal depth of 40 μm. It is concluded that catalytic hydrogenation of natural type Ia diamonds is effective to produce a porous surface that can be used in composites or as a substrate material. Additionally, the comparison of results with porous microsculptures observed on natural impact diamond crystals from the Popigai astrobleme revealed a strong resemblance. Full article

The performance of a prototype opaque-type colored silicon-based solar cell integrated with liquid crystalline cholesteric layers is investigated. These devices were developed using only organic components and wet processes, without complicated vacuum processes. The evaluated performances of the prototype solar cells were inferior to those of the other types of previously reported colored solar cells because of the inherent limitations of the cholesteric layers, such as the limited reflectance (~50%), narrow color gamut, and viewing angle-dependent color changes. We propose effective strategies for improving the performance of colored solar cell modules integrated with cholesteric layers. Full article

Liquid Crystal Thermography is a widely used experimental technique in the gas turbine heat transfer community. In turbine heat transfer, determination of the convective heat transfer coefficient (h) and adiabatic film cooling effectiveness (η) is imperative in order to design hot gas path components that can meet the modern-day engine performance and emission goals. LCT provides valuable information on the local surface temperature, which is used in different experimental methods to arrive at the local h and η. The detailed nature of h and η through LCT sets it apart from conventional thermocouple-based measurements and provides valuable insights into cooling designers for concept development and its further iterations. This article presents a comprehensive review of the state-of-the-art experimental methods employing LCT, where a critical analysis is presented for each, as well as some recent investigations (2016–present) where LCT was used. The goal of this article is to familiarize researchers with the evolving nature of LCT given the advancements in instrumentation and computing capabilities, and its relevance in turbine heat transfer problems in current times. Full article