Crystals

The high cost of Pt-based electrode materials limits the commercialization of fuel cells and their subsequent application in renewable energy production. It is thus necessary to develop economical, high-performance electrodes alongside biofuels to reduce the pollution associated with the production of energy. Tin dioxide–copper foil (SnO₂–Cu) electrode materials are herein developed using an electrodeposition process. Cyclic voltammetry, chronoamperometry, and potentiodynamic polarization methods are used to electrochemically characterize the electrode materials, with the results revealing that their excellent catalytic properties result in them delivering a high current. The surface morphologies of the developed electrodes are examined using scanning electron microscopy, with the results showing that upon an increase in the deposition time, a finer deposit of SnO₂ is formed on the surface of the Cu foil. Consequently, electrochemical oxidation using an enhanced surface area of the material leads to it exhibiting a high current and excellent corrosion resistance. Powder X-ray diffraction was used to confirm the successful depositing of SnO₂ on the surface of Cu. The fuel cell fabricated using the SnO₂–Cu electrode is promising for use in clean energy generation, as it can be prepared at low cost compared to conventionally used electrodes. Full article

Biodegradable alloys in Mg have the advantages of traditional metallic materials and those of biodegradable polymers with superior strength, lower density and ideal rigidity for fixing bone fractures. The biocompatibility and biodegradability of the five concentrations of Mg-0.5Ca-xZr alloys used were assessed using clinical and laboratory examinations that followed over time: tissue reaction, histological and imaging (RX, CT and SEM) evolution at 1, 2, 4 and 8 weeks after implant. The main purpose of this study was to investigate in vivo the long-term effect of Mg-0.5Ca-xZr alloys in rats. The results confirmed that Mg-0.5Ca-xZr alloys are biocompatible and biodegradable and are recommended to be used as possible materials for new orthopedics devices. Full article

Gradient structures containing nanograins in the surface layer have been introduced into Inconel 718 (IN718) nickel-based alloy using the surface mechanical grinding treatment technique. The thermal stability of the gradient IN718 alloy was investigated. Annealing studies reveal that nanograins with a grain size smaller than 40 nm exhibited significantly better thermal stability than those with larger grain size. Transmission electron microscopy analyses reveal that the enhanced thermal stability was attributed to the formation of grain boundaries with low energy configurations. This study provides new insight on strategies to improve the thermal stability of nanocrystalline metals. Full article

Sulvanites have the parent formula Cu₃MCh₄. The metal M belongs to group 5 and Ch is a chalcogen. The tantalum sulvanites Cu₃TaS₄ and Cu₃TaSe₄ are predicted to have wide band gaps and p-type conductivity and show promise in optoelectronic applications. Their potential as p-type transparent conductors or efficient photocatalysts for visible-light water splitting is a valuable incentive to explore these materials in their nanoscale form, toward bottom-up processing opportunities. Reported herein are the first syntheses of nanosized Cu₃TaS₄ and Cu₃TaSe₄ sulvanites, which preserve the parent cubic crystal structure but show that morphology at the nanoscale is dependent of the reaction conditions. The two solution-based methods for synthesizing the tantalum S and Se sulvanites result in Cu₃TaS₄ or Cu₃TaSe₄ nanocrystals (NCs) with prismatic morphology, or, in the case of Cu₃TaSe₄, could lead to core-shell spherical nanostructures. The Cu₃TaS₄ NCs and Cu₃TaSe₄ NCs have good absorption in the UV-Vis region, while the Cu₃TaSe₄ core-shell NCs possess broad absorption bands not only in the UV-Vis but also in the near-infrared region. Photoluminescence measurements of Cu₃TaS₄ and Cu₃TaSe₄ reveal optical bandgaps of 2.54 and 2.32 eV, respectively, consistent with the values measured in bulk. Additionally, the current–voltage (I-V) curve of Cu₃TaS₄ NCs proves its electrical conductivity. Full article

The possibilities of LiNbO₃-Tm³⁺ crystals for optical cooling based on anti-Stokes luminescence in the wavelength range of 1818–2200 nm are investigated. The concentration dependences of the final temperature of the crystal have been determined under continuous (CW) excitation at wavelengths of 1822–1977 nm with a pump intensity $F_p=5\times {10}^{21}{\mathrm{cm}}^{-2}{\mathrm{s}}^{-1}$. It was shown that significant cooling with ?T = 22 K, 19 K, and 16.4 K can be achieved, respectively, with excitation at wavelengths 1977, 1967, and 1948 nm. Full article

Serial Synchrotron Crystallography (SSX) is rapidly emerging as a promising technique for collecting data for time-resolved structural studies or for performing room temperature micro-crystallography measurements using micro-focused beamlines. SSX is often performed using high frame rate detectors in combination with continuous sample scanning or high-viscosity or liquid jet injectors. When performed using ultra-bright X-ray Free Electron Laser (XFEL) sources serial crystallography typically involves a process known as ’diffract-and-destroy’ where each crystal is measured just once before it is destroyed by the intense XFEL pulse. In SSX, however, particularly when using high-viscosity injectors (HVIs) such as Lipidico, the crystal can be intercepted multiple times by the X-ray beam prior to exiting the interaction region. This has a number of important consequences for SSX including whether these multiple-hits can be incorporated into the data analysis or whether they need to be excluded due to the potential impact of radiation damage. Here, we investigate the occurrence and characteristics of multiple hits on single crystals using SSX with lipidico. SSX data are collected from crystals as they tumble within a high viscous stream of silicone grease flowing through a micro-focused X-ray beam. We confirmed that, using the Eiger 16M, we are able to collect up to 42 frames of data from the same single crystal prior to it leaving the X-ray interaction region. The frequency and occurrence of multiple hits may be controlled by varying the sample flow rate and X-ray beam size. Calculations of the absorbed dose confirm that these crystals are likely to undergo radiation damage but that nonetheless incorporating multiple hits into damage-free data should lead to a significant reduction in the number of crystals required for structural analysis when compared to just looking at a single diffraction pattern from each crystal. Full article

We synthesized and studied the polymeric compound {[Cu₂(µ₄-EDTA)(Him)₂] 2H₂O}_n (1). The single-crystal structure is reported along with an in depth characterization of its thermal stability (TGA), spectral properties (FT-IR, Vis-UV and RSE), and magnetic behavior. The crystal consists of infinite 2D-networks built by centrosymmetric dinuclear motifs, constructed by means of a bridging anti,syn-carboxylate group from each asymmetric unit. Each layer guides Him ligands toward their external faces. They are connected by intermolecular (Him)N-H···O(carboxylate) bonds and antiparallel π–π stacking between symmetry related pairs of Him ligands, and then pillared in a 3D-network with parallel channels, where disordered water molecules are guested. About half of the labile water is lost from these channels over a wide temperature range (r.t. to 210 °C) before the other one, most strongly retained by the cooperating action of (water)O1-H(1A)···O(carboxylate) and (water) O1-H(1B)···π(Him) interactions. The latter is lost when organic ligands start to burn. ESR spectra and magnetic measurements indicated that symmetry related Cu(II) centers connected by the bridging carboxylate groups behave magnetically not equivalently, enabling an exchange interaction larger than their individual Zeeman energies. Full article

Extensive use of fossil fuels can lead to energy depletion and serious environmental pollution. Therefore, it is necessary to solve these problems by developing clean energy. Graphene materials own the advantages of high electrocatalytic activity, high conductivity, excellent mechanical strength, strong flexibility, large specific surface area and light weight, thus giving the potential to store electric charge, ions or hydrogen. Graphene-based nanocomposites have become new research hotspots in the field of energy storage and conversion, such as in fuel cells, lithium-ion batteries, solar cells and thermoelectric conversion. Graphene as a catalyst carrier of hydrogen fuel cells has been further modified to obtain higher and more uniform metal dispersion, hence improving the electrocatalyst activity. Moreover, it can complement the network of electroactive materials to buffer the change of electrode volume and prevent the breakage and aggregation of electrode materials, and graphene oxide is also used as a cheap and sustainable proton exchange membrane. In lithium-ion batteries, substituting heteroatoms for carbon atoms in graphene composite electrodes can produce defects on the graphitized surface which have a good reversible specific capacity and increased energy and power densities. In solar cells, the performance of the interface and junction is enhanced by using a few layers of graphene-based composites and more electron-hole pairs are collected; therefore, the conversion efficiency is increased. Graphene has a high Seebeck coefficient, and therefore, it is a potential thermoelectric material. In this paper, we review the latest progress in the synthesis, characterization, evaluation and properties of graphene-based composites and their practical applications in fuel cells, lithium-ion batteries, solar cells and thermoelectric conversion. Full article

Hardness is an essential property in the design of refractory high entropy alloys (RHEAs). This study shows how a neural network (NN) model can be used to predict the hardness of a RHEA, for the first time. We predicted the hardness of several alloys, including the novel C_0.1Cr₃Mo_11.9Nb₂₀Re₁₅Ta₃₀W₂₀ using the NN model. The hardness predicted from the NN model was consistent with the available experimental results. The NN model prediction of C_0.1Cr₃Mo_11.9Nb₂₀Re₁₅Ta₃₀W₂₀ was verified by experimentally synthesizing and investigating its microstructure properties and hardness. This model provides an alternative route to determine the Vickers hardness of RHEAs. Full article

The initial stages of debonding at hard-particle interfaces during rupture is relevant to the fracture of most structural alloys, yet details of the mechanistic process for rupture at the atomic scale are poorly understood. In this study, we employ molecular dynamics simulation of a spherical Al₂Cu θ precipitate in an aluminum matrix to examine the earliest stages of void formation and nanocrack growth at the particle-matrix interface, at temperatures ranging from 200–400 K and stresses ranging from 5.7–7.2 GPa. The simulations revealed a three-stage process involving (1) stochastic instantaneous or delayed nucleation of excess free volume at the particle-matrix interface involving only tens of atoms, followed by (2) steady time-dependent crack growth in the absence of dislocation activity, followed by (3) dramatically accelerated crack growth facilitated by crack-tip dislocation emission. While not all three stages were present for all stresses and temperatures, the second stage, termed lattice-trapped delamination, was consistently the rate-limiting process. This lattice-trapped delamination process was determined to be a thermally activated brittle fracture mode with an unambiguous Arrhenius activation energy of 1.37 eV and an activation area of 1.17 Ų. The role of lattice-trapped delamination in the early stages of particle delamination is not only relevant at the high strain-rates and stresses associated with shock spallation, but Arrhenius extrapolation suggests that the mechanism also operates during quasi-static rupture at micrometer-scale particles. Full article

Molecular dynamics (MD) simulations provide a physics-based approach to understanding protein structure and dynamics. Here, we used this intriguing tool to validate the experimental structural model of Hyp-1, a pathogenesis-related class 10 (PR-10) protein from the medicinal herb Hypericum perforatum, with potential application in various pharmaceutical therapies. A nanosecond MD simulation using the all-atom optimized potentials for liquid simulations (OPLS–AA) force field was performed to reveal that experimental atomic displacement parameters (ADPs) underestimate their values calculated from the simulation. The average structure factors obtained from the simulation confirmed to some extent the relatively high compliance of experimental and simulated Hyp-1 models. We found, however, many outliers between the experimental and simulated side-chain conformations within the Hyp-1 model, which prompted us to propose more reasonable energetically preferred rotameric forms. Therefore, we confirmed that MD simulation may be applicable for the verification of refined, experimental models and the explanation of their structural intricacies. Full article

The bridge between classical continuum plasticity and crystal plasticity is becoming narrower with continuously improved computational power and with engineers’ desire to obtain more information and better accuracy from their simulations, incorporating at the same time more effects about the microstructure of the material. This paper presents a short overview of the main current techniques employed in crystal plasticity formulations for finite element analysis, as to serve as a point of departure for researchers willing to incorporate microstructure effects in elastoplastic simulations. We include both classical and novel crystal plasticity formulations, as well as the different approaches to model dislocations in crystals. Full article

The Frank-Read model, as a way of generating dislocations in metals and alloys, is widely accepted. In the early 1960s, Li proposed an alternate mechanism. Namely, grain boundary sources for dislocations, with the aim of providing a different model for the Hall-Petch relation without the need of dislocation pile-ups at grain boundaries, or Frank-Read sources inside the grain. This article provides a review of his model, and supporting evidence for grain boundaries or interfacial sources of dislocations, including direct observations using transmission electron microscopy. The Li model has acquired new interest with the recent development of nanomaterial and multilayers. It is now known that nanocrystalline metals/alloys show a behavior different from conventional polycrystalline materials. The role of grain boundary sources in nanomaterials is reviewed briefly. Full article

The microstructure evolution of AA2060 Al alloy containing Li during two-stage homogenization treatment was investigated by optical microscopy (OM), scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS), differential scanning calorimeter (DSC), transmission electron microscopy (TEM), mechanical properties and Vickers micro-hardness test methods. The results demonstrate that severe precipitation of θ(Al₂Cu) and S(Al₂CuMg) phase existed in the as-cast alloy, especially in the center position. Cu elements were concentrated at grain boundary and gradually decreased from the boundary to the interior. Numerous eutectic phases of θ(Al₂Cu) and S (Al₂CuMg) containing Zn and Ag elements were segregated at grain boundaries. The overheating temperature of the as-cast alloy is 497 °C. After two-stage homogenization treatment, the θ(Al₂Cu) and S (Al₂CuMg) in the surface, middle and center positions were completely dissolved into the matrix, thus achieved uniform homogenization effect. Moreover, water cooling could prevent the precipitation after homogenization, which provided good performance of the studied alloy. The optimum two-stage homogenization treatment of AA2060 alloy was 460 °C/4 h + 490 °C/2 4 h. The homogenization kinetic analysis was discussed as well. Full article

Organic-inorganic hybrid perovskite materials have attracted tremendous attention as a key material in various optoelectronic devices. Distinctive optoelectronic properties, such as a tunable energy band position, long carrier diffusion lengths, and high charge carrier mobility, have allowed rapid progress in various perovskite-based optoelectronic devices (solar cells, photodetectors, light emitting diodes (LEDs), and lasers). Interestingly, the developments of each field are based on different characteristics of perovskite materials which are suitable for their own applications. In this review, we provide the fundamental properties of perovskite materials and categorize the usages in various optoelectronic applications. In addition, the prerequisite factors for those applications are suggested to understand the recent progress of perovskite-based optoelectronic devices and the challenges that need to be solved for commercialization. Full article

The Laser Floating Zone (LFZ) technique, also known as Laser-Heated Pedestal Growth (LHPG), has been developed throughout the last several decades as a simple, fast, and crucible-free method for growing high-crystalline-quality materials, particularly when compared to the more conventional Verneuil, Bridgman–Stockbarger, and Czochralski methods. Multiple worldwide efforts have, over the years, enabled the growth of highly oriented polycrystalline and single-crystal high-melting materials. This work attempted to critically review the most representative advancements in LFZ apparatus and experimental parameters that enable the growth of high-quality polycrystalline materials and single crystals, along with the most commonly produced materials and their relevant physical properties. Emphasis will be given to materials for photonics and optics, as well as for electrical applications, particularly superconducting and thermoelectric materials, and to the growth of metastable phases. Concomitantly, an analysis was carried out on how LFZ may contribute to further understanding equilibrium vs. non-equilibrium phase selectivity, as well as its potential to achieve or contribute to future developments in the growth of crystals for emerging applications. Full article

Measurement of recovery and recrystallization kinetics of tungsten at high temperature is a key issue for many applications, such as plasma facing units in the framework of thermonuclear fusion. These kinetics are mostly derived from Vickers hardness and EBSD measurements, which can lead to some inaccuracies due to the competition between recovery and recrystallization mechanisms. A complementary/alternative approach based on statistical grid nanoindentation is proposed in this paper. The basic idea is to assume that the fraction recrystallized can be deduced using the hardness probability density function measured on a fully recrystallized sample. The hardness probability density function of the set of non-recrystallized grains can then be analyzed. The methodology was applied to rolled tungsten samples annealed at high temperature. It was clearly observed that recovery and recrystallization overlapped in terms of softening fraction in the investigated time–temperature range. Activation energy of the static recovery mechanism is in the correct order of magnitude compared to bulk self-diffusion in tungsten. High-throughput nanoindentation analysis appears as a promising way to investigate recrystallization/recovery mechanisms in metals. Full article