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We report on high-pressure torsion (HPT) processing of Si and related semiconducting materials, and discuss their phase transformations and electrical, thermal, and optical properties. In-situ synchrotron x-ray diffraction revealed that the metastable bc8-structure Si-III and r8-structure Si-XII in the HPT-processed Si samples gradually disappeared and hexagonal-diamond Si-IV appeared during annealing up to 473 K. The formation of Si-III/XII in the samples processed at a nominal pressure of 6 GPa indicated the strain-induced phase transformation from diamond-cubic Si-I to a high-pressure tetragonal Si-II phase during HPT processing, and a following phase transformation from Si-II to Si-III/XII upon decompression. The resistivity decreased with increasing the number of anvil rotations due to the formation of semimetallic Si-III. The thermal conductivity of Si was reduced to -3 Wm-1K-1 after HPT processing. A weak and broad photoluminescence peak associated with Si-I nanograins appeared in the visible light region after annealing. Metastable bc8-Si0.5Ge0.5 with a semimetallic property was formed by HPT processing of a traveling-liquidus-zone-grown Si0.5Ge0.5 crystal. These results indicate that the application of HPT processing to Si and related semiconductors paves the way to novel devices utilizing nanograins and metastable phases. [ABSTRACT FROM AUTHOR]

Abstract This study investigates the microstructural characteristics and mechanical properties of a laser welded AZ80 magnesium alloy. The welding process led to the formation of coarse-grained fusion zone (FZ), where a secondary phase formed continuous network. Mg17Al12 precipitation and coarsening of grain boundaries occurred in the heat affected zone. The welded joint exhibited excellent mechanical properties with a yield strength of 202 MPa and a joint efficiency of 92%. The microstructure analysis via EPMA and EBSD in conjunction with synchrotron X-ray diffraction analysis reveals that precipitates and increased dislocation density in the fusion zone are primary strengthening mechanisms for the laser welded AZ80 Mg alloy.

On the rising demand for eco‐friendly refractories, reducing the use of likely toxic magnesia‐chromium aggregates remains a challenge. Previous studies by some of the authors have proposed Cr‐free alternative compositions, although the morphology of the spinel precipitates has varied across the different suggested systems. The mechanisms involved in the formation of these distinct morphologies were unclear and, therefore, are the focus of this work. In all compositions, SEM/electron backscatter diffraction revealed cube–cube orientation relationships between matrix and precipitates, indicating that their formation is influenced by the lattice parameter misfit (δ), which was measured using synchrotron X‐ray diffraction. It could be concluded that coarser and spherical precipitates form to minimize their surface‐to‐volume ratio in compositions with high absolute δ‐values. Conversely, low‐misfit systems enable the spinel to form a 3D‐network. The potential use of this knowledge to tailor the microstructure of novel compositions was demonstrated by a small Nb2O5 addition into one of the proposed compositions. [ABSTRACT FROM AUTHOR]

The present study introduces a processing strategy for synchrotron scanning 3D X‐ray diffraction (s3DXRD) data, aimed at addressing the challenges posed by large, highly deformed, polyphase materials such as crystalline rocks. Leveraging symmetric Bragg reflections known as Friedel pairs, our method enables diffraction events to be precisely located within the sample volume. This method allows for fitting the phase, crystal structure and unit‐cell parameters at the intra‐grain scale on a voxel grid. The processing workflow incorporates several new modules, designed to (i) efficiently match Friedel pairs in large s3DXRD datasets containing up to 108 diffraction peaks; (ii) assign phases to each pixel or voxel, resolving potential ambiguities arising from overlap in scattering angles between different crystallographic phases; and (iii) fit the crystal orientation and unit cell locally on a point‐by‐point basis. We demonstrate the effectiveness of our technique on fractured granite samples, highlighting the ability of the method to characterize complex geological materials and show their internal structure and mineral composition. Additionally, we include the characterization of a metal gasket made of a commercial aluminium alloy, which surrounded the granite sample during experiments. The results show the effectiveness of the technique in recovering information about the internal texture and residual strain of materials that have undergone high levels of plastic deformation. [ABSTRACT FROM AUTHOR]

Atomic structure and electronic band structure are fundamental properties for understanding the mechanism of superconductivity. Motivated by the discovery of pressure-induced high-temperature superconductivity at 80 K in the bilayer Rud-dlesden-Popper nickelate La3Ni2O7, the atomic structure and electronic band structure of the trilayer nickelate La4Ni3O10 under pressure up to 44.3 GPa are investigated. A structural transition from the monoclinic P21/a space group to the tetragonal I4/mmm around 12.6–13.4 GPa is identified, accompanied by a drop of resistance below 7 K. Density functional theory calculations suggest that the bonding state of Ni 3 d z 2 orbital rises and crosses the Fermi level at high pressures, which may give rise to possible superconductivity observed in resistance under pressure in La4Ni3O10. The trilayer nickelate La4Ni3O10 shows some similarities with the bilayer La3Ni2O7 and has unique properties, providing a new platform to investigate the underlying mechanism of superconductivity in nickelates. [ABSTRACT FROM AUTHOR]

The advancement of heterogeneous catalysts incorporating metal clusters in the nanometric size range has garnered significant attention due to their extraordinary catalytic activity and selectivity. The detailed characterization and understanding of the atomic structure of these metal clusters within catalysts is crucial for elucidating the underlying reaction mechanisms. In the present study, a distinctive three-atom PdNi cluster, characterized by two Pd atoms at terminal positions and a central Ni atom, was synthesized over mordenite zeolite. The presence of atomic PdNi clusters within the eight-membered ring side pocket area was confirmed by multiple advanced analytical techniques, including magic-angle spinning nuclear magnetic resonance spectroscopy, synchrotron X-ray powder diffraction, extended X-ray absorption fine structure spectroscopy, and high-angle annular dark-field scanning transmission electron microscopy. The catalytic activity of the confined active species was examined by the carbene-mediated reactions of ethyl-2-diazoacetate to ethyl-2-methoxyacetate as a model reaction. Compared to the Pd-mordenite and Ni-mordenite, the PdNi-mordenite catalyst incorporates a PdNi cluster, which demonstrates a superior performance, achieving 100% conversion and high selectivity under the same reaction conditions. Our study elucidates the potential of constructing bimetallic clusters in zeolites, providing valuable insights for developing new heterogeneous catalysts applicable to a wide range of catalytic processes. [ABSTRACT FROM AUTHOR]

Mn2(C2H6N6)4(NO3)4·2H2O (Mn) as one of the energetic coordination complexes was chosen for high‐pressure research. In this work, Mn was analyzed by in situ Raman scattering, infrared absorption, and synchrotron angle‐dispersive X‐ray diffraction (ADXRD) technologies up to ~20 GPa at room temperature. The vibrational modes of Mn at ambient pressure were comprehensively resolved based on the experimental results. Detailed spectral analyses revealed that Mn underwent three pressure‐induced phase transitions at 0.5, 2.5, and 5.7 GPa, respectively. ADXRD experiments confirmed the existence of these three phase transitions in Raman and infrared spectra analyses. Based on the analysis of the vibrational spectra and the changes of lattice parameters under pressure, it can be considered that the deformation of the 3‐hydrazino‐4‐amino‐1, 2, 4‐triazole (HATr) ligand led to the first phase transition, and the distortion of the triazole ring induced the second phase transition, and the rearrangement of the hydrogen bonds resulted in the third phase transition. In addition, it can be inferred from Raman spectra and ADXRD data that Mn may have experienced the abnormal expansion during the first phase transition. This work may lay the foundation for further investigating the structure and properties of energetic coordination complexes under pressure. [ABSTRACT FROM AUTHOR]

Compressibility and pressure-induced structural evolution of kokchetavite, the hexagonal polymorph of KAlSi3O8, has been studied up to 11.8 GPa using synchrotron single-crystal X-ray diffraction. Two phase transitions were observed at pressures of ~0.3 and 10.4 GPa. Kokchetavite-I (as-synthesized, P6/mcc) transforms into kokchetavite-II with the P 6 c2 space group. Kokchetavite-II → kokchetavite-III phase transition at ~10.4 GPa is accompanied by a change of symmetry to probably orthorhombic. After pressure release, kokchetavite reverts to the initial single-crystal state with P6/mcc space group. A second-order Birch-Murnaghan equation of state was calculated for phase kokchetavite-II with coefficients V0 = 1486(3) Å3, K0 = 59(2) GPa. [ABSTRACT FROM AUTHOR]

MCrAlY (M = Ni and/or Co) metallic coatings are essential for the protection of hot-end components against thermal and corrosion damage. Increasing the Al content is considered a feasible solution to improve the high-temperature performance of MCrAlY coatings. In this paper, the effects of high Al contents (12–20 wt.%) on the phase constituents and cast microstructures in MCrAlY alloys were studied by high-energy X-ray diffraction and electron microscopy techniques combined with phase equilibria calculations. High Al content improved the stability of β, σ, and α phases. Meanwhile, an evolution of the cast microstructure morphology from a dendrite structure to an equiaxed grain structure was observed. The thermal properties were analyzed, which were closely related to the phase constituents and solid-to-solid phase transitions at evaluated temperatures. This work is instructive for developing high-Al-content MCrAlY coatings for next-generation thermal barrier applications. [ABSTRACT FROM AUTHOR]

High-entropy alloys (HEAs) possess outstanding features such as corrosion resistance, irradiation resistance, and good mechanical properties. A few HEAs have found applications in the fields of aerospace and defense. Extensive studies on the deformation mechanisms of HEAs can guide microstructure control and toughness design, which is vital for understanding and studying state-of-the-art structural materials. Synchrotron X-ray and neutron diffraction are necessary techniques for materials science research, especially for in situ coupling of physical/chemical fields and for resolving macro/microcrystallographic information on materials. Recently, several researchers have applied synchrotron X-ray and neutron diffraction methods to study the deformation mechanisms, phase transformations, stress behaviors, and in situ processes of HEAs, such as variable-temperature, high-pressure, and hydrogenation processes. In this review, the principles and development of synchrotron X-ray and neutron diffraction are presented, and their applications in the deformation mechanisms of HEAs are discussed. The factors that influence the deformation mechanisms of HEAs are also outlined. This review focuses on the microstructures and micromechanical behaviors during tension/compression or creep/fatigue deformation and the application of synchrotron X-ray and neutron diffraction methods to the characterization of dislocations, stacking faults, twins, phases, and intergrain/interphase stress changes. Perspectives on future developments of synchrotron X-ray and neutron diffraction and on research directions on the deformation mechanisms of novel metals are discussed. [ABSTRACT FROM AUTHOR]

The research regarding high entropy alloys (HEAs) has proved them to be suitable for engineering applications. Nevertheless, assessing their processability is key for industrial deployment. Of special relevance in terms of processing techniques arised welding. In this work, Gas Tungsten Arc Welding (GTAW) was chosen as a processing method to attest for the suitability of the equiatomic CoCrFeMnNi HEA for one of the most common real-world mechanical solicitations, tensile loading. We delve into an in-situ synchrotron X-ray diffraction analysis of the mechanical behavior of a high-performing GTAW CoCrFeMnNi HEA joint. Local analysis of the microstructure evolution, considering the base material, heat affected zone and fusion zone, was performed by tracking changes in the diffracted intensity and lattice strain. Orientation-dependent evolution is highlighted by considering partial azimuthal integration detailing texture impact across the joint. Evidence of strain concentration at specific locations is correlated with the microstructure and overall macroscopic mechanical behavior. [ABSTRACT FROM AUTHOR]

The endohedral lithium fulleride, Li+@C60•−, is a potential precursor for new families of molecular superconducting and electronic materials beyond those accessible to date from C60 itself. Solid Li@C60 comprises (Li@C60)2 dimers, isostructural and isoelectronic with the (C59N)2 units found in solid azafullerene. Here, we investigate the structural and vibrational properties of Li@C60 samples synthesized by electrolytic reduction routes. The resulting materials are of high quality, with crystallinity far superior to that of their antecedents isolated by chemical reduction. They permit facile, unambiguous identification of both the reduced state of the fulleride units and the interball C-C bonds responsible for dimerization. However, severe orientational disorder conceals any crystal symmetry lowering due to the presence of dimers. Diffraction reveals the adoption of a hexagonal crystal structure (space group P63/mmc) at both low temperatures and high pressures, typically associated with close-packing of spherical monomer units. Such a situation is reminiscent of the structural behavior of the high-pressure Phase I of solid dihydrogen, H2. [ABSTRACT FROM AUTHOR]

This paper describes the main results from an experimental investigation into the thermal stability of a cold-rolled Al–Y alloy. Tensile tests performed on specimens of the alloy and pure Al in annealed states reveal superior anti-softening properties of the former specimens relative to the latter counterparts. Origins of such thermal stability and underlying recovery and recrystallization kinetics are studied using electron microscopy and high energy X-ray diffraction (HEXRD) techniques. Microscopic observations reveal that recovery and recrystallization begin in the specimens of pure Al at a much lower temperature than in the specimens of Al–Y alloy. Onset of the recovery process in the Al–Y alloy is observed to begin with dislocation rearrangements in the β-Al3Y phases. The onset is followed by more substantial reduction in dislocation density, shrinkage of the β-Al3Y phases, and coarsening of the α-Al grains. The alloy contains stacking faults, which interestingly remain stable during the annealing treatments contributing to the thermal stability. The observed mechanisms are further confirmed by tracking the evolution of peaks under the in-situ synchrotron X-ray diffraction with heating. Onset of recovery was observed at 280 °C in both α-Al and β-Al3Y phases, while substantial shrinkage and spheroidization of β-Al3Y phases and decrease in dislocation density were detected at 400 °C causing loss of the alloy strength. Thermodynamic calculation showed that solubility of Y rapidly increases in α-Al at temperatures above 400 °C explaining the spheroidization and shrinkage of the β-Al3Y phases by diffusion of Y into the Al matrix.

A natural intermediate member of the scapolite solid solution {Me47; chemical formula: (Na1.86Ca1.86K0.23Fe0.01)(Al4.36Si7.64)O24[Cl0.48(CO3)0.48(SO4)0.01]}, with the unusual I4/m space group, has been studied at various temperatures and combined high-T and high-P by means of in situ single-crystal and powder X-ray diffraction, using both conventional and synchrotron X-ray sources. In addition, single-crystal neutron diffraction data were collected at ambient-T and 685 °C. A fit of the experimental V-T data with a thermal equation of state yielded a thermal expansion coeficient at ambient conditions: αV25°C = 1/V0·(∂V/∂T)P,25°C = 1.74(3)·10–5 K–1. A comparative analysis of the elastic behavior of scapolite based on this study and previous high-T XRD data suggests that a thorough re-investigation of the diferent members of the marialite-meionite solid solution is needed to fully understand the role of crystal chemistry on the thermal behavior of these complex nonbinary solid solutions. The experimental data obtained within the full temperature range of analysis at ambient pressure confirm that the investigated sample always preserves the I4/m space group, and possible implications on the metastability of I4/m intermediate scapolite are discussed. Neutron difraction data show that no significant Si and Al rearrangement among the T sites occurs between 25 and 685 °C. The combined high-T and high-P data show that at 650 °C and between 10.30(5) and 10.71(5) GPa a phase transition toward a triclinic polymorph occurs, with a positive Clapeyron slope (i.e., dP/dT > 0). A comprehensive description of the atomic-scale structure deformation mechanisms induced by temperature and/or pressure, including those leading to structural instability, is provided based on single-crystal structure refinements. [ABSTRACT FROM AUTHOR]

In situ techniques are essential to understanding the behavior of electrocatalysts under operating conditions. When employed, in situ synchrotron grazing-incidence X-ray diffraction (GI-XRD) can provide time-resolved structural information of materials formed at the electrode surface. In situ cells, however, often require epoxy resins to secure electrodes, do not enable electrolyte flow, or exhibit limited chemical compatibility, hindering the study of non-aqueous electrochemical systems. Here, a versatile electrochemical cell for air-free in situ synchrotron GI-XRD during non-aqueous Li-mediated electrochemical N2 reduction (Li-N2R) has been designed. This cell not only fulfills the stringent material requirements necessary to study this system but is also readily extendable to other electrochemical systems. Under conditions relevant to non-aqueous Li-N2R, the formation of Li metal, LiOH and Li2O as well as a peak consistent with the α-phase of Li3N was observed, thus demonstrating the functionality of this cell toward developing a mechanistic understanding of complicated electrochemical systems.

In this work, a combination of in-situ high synchrotron X-ray diffraction and electron backscattered diffraction were used to systematically investigate the activation and evolution of the deformation mechanisms in an as-cast Fe42Mn28Co10Cr15Si5 metastable high entropy alloy deformed until fracture at room temperature. This work unveils the critical role of the dual-phase γ-f.c.c. / ε-h.c.p. microstructure on the deformation response of the alloy. The different deformation modes, i.e., slip, transformation induced plasticity (TRIP) and transformation induced twinning (TWIP), were seen to initiate at different loading stresses and then to overlap. Quantitative microstructural characterization, which included the evolution of the phase fraction, stress partitioning, dislocation density, c/a ratio and lattice strain for different planes, was performed to elucidate the role of each phase on the macroscopic mechanical response of the metastable high entropy alloy. Furthermore, the magnitude of the different strengthening contributions has been quantified for the first time.

Lipid crystallization under moderate hydrostatic pressure treatments (200 MPa, 20 °C, 1–24 h) was studied in palm kernel stearin (PS 100%) and its blends with sunflower oil (PS 80, 90 % w/w). Hyperbarically-crystallized samples exhibited significantly higher firmness, elastic modulus and critical stress values as compared to those of the samples crystallized at atmospheric pressure.These data indicate that moderate hydrostatic pressure favored the formation of a higher amount of small palm kernel stearin crystals as compared to those formed at atmospheric pressure. Pressurization did not affect fat polymorphism, but was able to enhance nucleation instead of crystal growth.This work clearly demonstrated the efficacy of moderate hydrostatic pressure in steering lipid crystallization, opening interesting possible applications of high-pressure processing technology in the fat manufacturing sector.

Lithium (Li) metal serving as an anode has the potential to double or triple stored energies in rechargeable Li batteries. However, they typically have short cycling lifetimes due to parasitic reactions between the Li metal and electrolyte. It is critically required to develop early fault-detection methods for different failure mechanisms and quick lifetime-prediction methods to ensure rapid development. Prior efforts to determine the dominant failure mechanisms have typically required destructive cell disassembly. In this study, non-destructive diagnostic method based on rest voltages and coulombic efficiency are used to easily distinguish the different failure mechanisms-from loss of Li inventory, electrolyte depletion, and increased cell impedance-which are deeply understood and well validated by experiments and modeling. Using this new diagnostic method, the maximum lifetime of a Li metal cell can be quickly predicted from tests of corresponding anode-free cells, which is important for the screenings of electrolytes, anode stabilization, optimization of operating conditions, and rational battery design.

Detonation spraying is commonly used to form protective and functional coatings. The influence of the temperature and velocity of spraying particles on the quality of the coatings is frequently analyzed by the study of single splats. However, to date, there has been limited research on the interaction and structure formation at the splat/substrate interface during detonation spraying. In this paper, copper splats and coatings were formed on steel substrates using three different spraying modes: 'cold', 'normal', and 'hot'. The features of the particle/substrate interaction were studied experimentally and by numerical simulation using the smoothed particle hydrodynamics (SPH) method. The simulation revealed the deformation and temperature history of the particles and substrate during impact. The structure of the splats and coatings was characterized using scanning electron microscopy (SEM) and synchrotron X-ray diffraction (SXRD). The microstructure of the coatings sprayed in the 'normal' and 'hot' modes consists of columnar crystals, indicating complete melting of the particles. The coating obtained in the 'cold' mode consists of a mixture of molten, partially molten, and unmolten particles. SXRD analysis revealed an increase in dislocation density in the sprayed coatings compared to the initial powder. The sprayed material mainly contains screw dislocations, while the initial powder predominantly contains edge dislocations. The approach used, combining materials characterization techniques and numerical simulation, has great potential for analyzing the coating formation process and can be applied to the optimization of thermal spraying parameters of various materials. The results of this study may be of interest to other researchers working in the field of thermal spraying of copper-based alloys. [ABSTRACT FROM AUTHOR]

The unit-cell parameters and volumes of geikielite (MgTiO3) and ilmenite (FeTiO3) were investigated at high temperatures up to 700 K and ambient pressure, using in-situ angle-dispersive synchrotron X-ray diffraction. No phase transition was detected over the experimental temperature range. Using (Berman in J Petrol 29:445–522, 1988. 10.1093/petrology/29.2.445) equations to fit the temperature-volume data, the volumetric thermal expansion coefficients at ambient conditions (αV0) of MgTiO3 and FeTiO3 were obtained as follows: 2.55 (6) × 10–5 K−1 and 2.82 (10) × 10–5 K−1, respectively. We infer that the larger effective ionic radius of Fe2+(VI) (0.78 Å) than that of Mg2+(VI) (0.72 Å) renders FeTiO3 has a larger volumetric thermal expansivity than MgTiO3. Simultaneously, the refined axial thermal expansion coefficients under ambient conditions are αa0 = 0.74 (3) × 10–5 K−1 and αc0 = 1.08 (5) × 10–5 K−1 for the a-axis and c-axis of MgTiO3, respectively, and αa0 = 0.95 (5) × 10–5 K−1 and αc0 = 0.92 (12) × 10–5 K−1 for the a-axis and c-axis of FeTiO3, respectively. The axial thermal expansivity of MgTiO3 is anisotropic, but that of FeTiO3 is nearly isotropic. We infer that the main reason for the different axial thermal expansivity between MgTiO3 and FeTiO3 is that the thermal expansion mode of the Mg-O bond in MgTiO3 is different from that of the Fe–O bonds in FeTiO3. [ABSTRACT FROM AUTHOR]

Magnetic properties in perovskite titanates ATiO3‐δ (A = Ca, Sr, Ba) were investigated before and after arc melting. Crystal structure analysis was conducted by powder synchrotron X‐ray diffraction with Rietveld refinements. Quantitative chemical element analysis was carried out by X‐ray photoelectron spectroscopy. Magnetic measurements were conducted by vibrating sample magnetometer and X‐ray magnetic circular dichroism (XMCD). The magnetic properties are found to be affected by impurities of 3d elements such as Fe, Co, and Ni. Depending on the composition and crystal structure, the occupation of the magnetic ions in perovskite titanates is selectively varied, which is interpreted to be the origin of the different magnetic behaviors in arc‐melted perovskite titanates ATiO3‐δ (A = Ca, Sr, Ba). In addition, both formation of oxygen vacancies and the reduction of Ti4+ to Ti3+ during arc‐melting also play a role as proven by XMCD. Nevertheless, preferential site occupation of magnetic impurities is dominant in the magnetic properties of arc‐melted perovskite ATiO3‐δ (A = Ca, Sr, Ba). [ABSTRACT FROM AUTHOR]

We report the P-V-T equation of state measurements of B4C to 50 GPa and approximately 2500 K in laser-heated diamond anvil cells. We obtain an ambient temperature, third-order Birch–Murnaghan fit to the P-V data that yields a bulk modulus K0 of 221(2) GPa and derivative, (dK/dP)0 of 3.3(1). These were used in fits with both a Mie–Grüneisen–Debye model and a temperature-dependent, Birch–Murnaghan equation of state that includes thermal pressure estimated by thermal expansion (α) and a temperature-dependent bulk modulus (dK0/dT). The ambient pressure thermal expansion coefficient (α0 + α1T), Grüneisen γ(V) = γ0(V/V0)q and volume-dependent Debye temperature, were used as input parameters for these fits and found to be sufficient to describe the data in the whole P-T range of this study. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 1)'. [ABSTRACT FROM AUTHOR]

The stomatopod Odontodactylus scyllarus uses weaponized club-like appendages to attack its prey. These clubs are made of apatite, chitin, amorphous calcium carbonate, and amorphous calcium phosphate organized in a highly hierarchical structure with multiple regions and layers. We follow the development of the biomineralized club as a function of time using clubs harvested at specific times since molting. The clubs are investigated using a broad suite of techniques to unravel the biomineralization history of the clubs. Nano focus synchrotron x-ray diffraction and x-ray fluorescence experiments reveal that the club structure is more organized with more sub-regions than previously thought. The recently discovered impact surface has crystallites in a different size and orientation than those in the impact region. The crystal unit cell parameters vary to a large degree across individual samples, which indicates a spatial variation in the degree of chemical substitution. Energy dispersive spectroscopy and Raman spectroscopy show that this variation cannot be explained by carbonation and fluoridation of the lattice alone. X-ray fluorescence and mass spectroscopy show that the impact surface is coated with a thin membrane rich in bromine that forms at very initial stages of club formation. Proteomic studies show that a fraction of the club mineralization protein-1 has brominated tyrosine suggesting that bromination of club proteins at the club surface is an integral component of the club design. Taken together, the data unravel the spatio-temporal changes in biomineral structure during club formation. Mantis shrimp hunt using club-like appendages that contain apatite, chitin, amorphous calcium carbonate, and amorphous calcium phosphate ordered in a highly hierarchical structure. To understand the formation process of the club we analyze clubs harvested at specific times since molting thereby constructing a club formation map. By combining several methods ranging from position resolved synchrotron X-ray diffraction to proteomics, we reveal that clubs form from an organic membrane with brominated protein and that crystalline apatite phases are present from the very onset of club formation and grow in relative importance over time. This reveals a complex biomineralization process leading to these fascinating biomineralized tools. [Display omitted] [ABSTRACT FROM AUTHOR]

A mathematical description of crystal structure is proposed consisting of two parts: the underlying translational periodicity and the distinct atomic positions up to the symmetry operations in the unit cell, consistent with the International Tables for Crystallography. By the Cauchy-Born hypothesis, such a description can be integrated with the theory of continuum mechanics to calculate a derived crystal structure produced by solid-solid phase transformation. In addition, the expressions for the orientation relationship between the parent lattice and the derived lattice are generalized. The derived structure rationalizes the lattice parameters and the general equivalent atomic positions that assist the indexing process of X-ray diffraction analysis for low-symmetry martensitic materials undergoing phase transformation. The analysis is demonstrated in a CuAlMn shape memory alloy. From its austenite phase (L21 face-centered cubic structure), it is identified that the derived martensitic structure has orthorhombic symmetry Pmmn with the derived lattice parameters ad = 4.36491, bd = 5.40865 and cd = 4.2402 Å, by which the complicated X-ray Laue diffraction pattern can be well indexed, and the orientation relationship can be verified.

In this work, the formation of carbide with the concertation of carbon at 0.1 at.% in refractory high-entropy alloy (RHEA) Mo15Nb20Re15Ta30W20 was studied under both ambient and high-pressure high-temperature conditions. The x-ray diffraction of dilute carbon (C)-doped RHEA under ambient pressure showed that the phases and lattice constant of RHEA were not influenced by the addition of 0.1 at.% C. In contrast, C-doped RHEA showed unexpected phase formation and transformation under combined high-pressure and high-temperature conditions by resistively employing the heated diamond anvil cell (DAC) technique. The new FCC_L12 phase appeared at 6 GPa and 809 °C and preserved the ambient temperature and pressure. High-pressure and high-temperature promoted the formation of carbides Ta3C and Nb3C, which are stable and may further improve the mechanical performance of the dilute C-doped alloy Mo15Nb20Re15Ta30W20.

The combination of poorly-soluble drugs with small molecule co-formers to generate amorphous solid dispersions (ASDs) has great potential to improve dissolution rate and kinetic solubility, and thus increase the bioavailability of these active ingredients. However, such ASDs are known to be unstable and to crystallise upon storage or heating. In this work, we explore the crystallisation of flufenamic acid (FFA) from ASDs prepared with trehalose. FFA-trehalose mixtures were prepared at a range of w/w composition ratios, heated to melting and crash cooled to form ASDs. They were then subject to a further heat/cool cycle, which was monitored by simultaneous differential scanning calorimetry – X-ray diffraction to observe the phase changes occurring. These varied with the composition of the blend. Upon short-term storage, formulations with low trehalose contents (FFA:trehalose 5:1 w/w) recrystallised into form I FFA, while higher trehalose contents crystallised to FFA form IV. When heated, all FFA trehalose combinations ultimately recrystallised into form I before melting. Upon a second cooling cycle, systems with low trehalose content (FFA:trehalose 5:1 w/w) recrystallised into form IV, while higher trehalose contents led to FFA form I. It is thus clear that even with a single excipient it is possible to control the crystallisation pathway through judicious choice of the formulation parameters.