Search Results (433)

Functionally graded aluminum matrix composites are of interest for applications requiring region-dependent mechanical and tribological performance. In this study, the micro-structure, hardness, and abrasive wear properties of functionally graded Al/ZrB₂ compo-site materials produced by an in situ centrifugal casting method were investigated. The ZrB₂ reinforcement phase was synthesized in situ within the molten aluminum matrix, and functional grading was achieved through the action of centrifugal force during solidification. Samples taken from cylindrical castings were characterized using optical microscopy, scanning electron microscopy (SEM), X-Ray diffraction (XRD), density measurements, Brinell hardness testing, and abrasive wear experiments. Phase analyses con-firmed the successful in situ formation of ZrB₂ and verified that the phase distribution in-creased toward the direction of centrifugal force. Hardness increased with reinforcement content, rising from approximately 28 HB in the matrix-rich region to 68 HB and 72 HB in regions reinforced with 12% and 15% ZrB₂, respectively. Abrasive wear behavior was evaluated using the pin-on-disk method, and a Taguchi L (3⁵) orthogonal array was employed for experimental design. Statistical analyses showed that the composite region was the most influential parameter affecting wear performance, followed by abrasive particle size and applied load, while sliding distance and sliding speed were not statistically significant. These findings demonstrate that in situ centrifugal casting is an effective approach for producing functionally graded Al/ZrB₂ composites with improved hardness and wear resistance. Full article

Laboratory-scale cryogenic X-ray microtomography was employed for the first time to investigate the early structural evolution of polyurethane (PU) foams. This method enables ex situ studying the internal morphology of the frozen reactive mixture at various times before cell impingement. In this work, the precision of the method was evaluated by studying the early bubble formation and growth under different blowing agents and catalyst contents. It was detected that tripling the catalyst weight content doubled cell nucleation density, from 8.9 × 10⁵ to 1.8 × 10⁶ cells cm⁻³. Yet, doubling the water content has lesser impact on nucleation but leads to fast speeds of cell growth and, in turn, lower relative density at equal reaction times. Overall, it is demonstrated that laboratory cryogenic microtomography can be used to democratise the 3D investigation of the internal structure of foams which was until now only possible in synchrotron facilities. In addition, this method can help elucidate the mechanisms of nucleation and degeneration via directly measuring the density of bubbles and distance between them in the reactive mixture. Finally, this methodology could be extended to recent laboratory nanotomography systems utilizing X-ray tubes with nanometric spot sizes, thereby enabling the confident identification of nucleation events. Full article

Designing and constructing heterojunctions has emerged as a pivotal strategy for improving the photocatalytic efficiency of semiconductors. In this study, we report the controlled synthesis of an Au/Zn₃In₂S₆ Schottky junction through a combination of hydrothermal and in situ photodeposition methods. The structural, morphological, and photoelectrochemical properties of the catalyst were meticulously characterized using a suite of techniques including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), photoelectrochemical (PEC) measurements, and electron spin resonance (ESR) spectroscopy. The optimized 3% Au/Zn₃In₂S₆ composite exhibited a remarkable enhancement in both photocatalytic activity and stability, achieving a 90.4% removal of bisphenol A (BPA) under UV–visible light irradiation within 100 min. The corresponding first-order reaction rate constant was approximately 1.366 h⁻¹, nearly 4.37 times greater than that of the pristine Zn₃In₂S₆. This substantial improvement can be attributed to several key factors, including increased BPA adsorption, enhanced light absorption, and the efficient charge separation facilitated by the Au/Zn₃In₂S₆ heterojunction. Photogenerated holes, superoxide radicals, and hydroxyl radicals were identified as the primary reactive species responsible for the BPA degradation. This work highlights the potential of metal-modified semiconductors for advanced photocatalytic applications, offering insights into the design of highly efficient materials for environmental remediation. Full article

Cesium lead chloride (CsPbCl₃) is a stable, wide-bandgap perovskite with significant potential for ultraviolet (UV) photodetection and blue light-emitting diodes (LEDs). However, the dynamical mechanisms of ferroelastic domain walls associated with the dielectric relaxations in a single-crystal have rarely been reported. In this work, we observed reversible phase transitions from cubic to tetragonal, and further to orthorhombic symmetry, accompanied by the formation and evolution of strip-like ferroelastic domain walls, using in situ X-ray diffraction (XRD), differential scanning calorimetry (DSC), polarized optical microscopy (POM), and dielectric measurements. Notably, the dielectric studies revealed low temperature (~170–180 K) frequency-dependent loss peaks that we attribute to the pinning of polarized domain walls by chloride vacancies. We also found that the formation or disappearance of ferroelastic domain walls near the octahedral tilting transition temperatures leads to pronounced anomalies in the dielectric permittivity. These findings clarify the intrinsic phase behavior of CsPbCl₃ single crystals and underscore the significant contribution of ferroelastic domain walls to its dielectric response, providing insights for optimizing its optoelectronic performance. Full article

This study examines the interfacial and structural evolution of titanium disulfide (TiS₂) during Ca²⁺ intercalation/deintercalation in concentrated aqueous CaCl₂. Electrochemical measurements were combined with ex situ X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy to characterize the solvation structure, potential window, and reversibility in concentrated CaCl₂ electrolytes. Increasing the CaCl₂ concentration from 1.0 to 8.0 M was accompanied by reduced gas evolution and an expanded practical operating window. Stepwise analysis identified the potential range −1.00 to 0.10 V (vs. the saturated calomel electrode) as a practical window that minimized TiO₂/S₈ formation while preserving reversible Ca²⁺ intercalation. Ex situ XRD showed reversible (001) shifts, consistent with interlayer expansion and contraction, and peak broadening was indicative of partial amorphization and defects. XPS revealed CaS and polysulfides (S_z²⁻, 2 ≤ z ≤ 8) to be the prevalent surface species with limited Ca(OH)₂ and CaSO₄; within the detection limits, no chlorine-containing reduction products were observed after charging. The electrochemical and spectroscopic results indicate that intercalation is accompanied by partial sulfur-centered reduction and defect signatures, with associated changes in the interfacial charge-transfer characteristics and reversibility. These findings link the potential, interfacial chemistry, and lattice response, and suggest design considerations for stable aqueous multivalent-ion storage. Full article

A method for synthesizing an in situ composite based on the A201 aluminum–copper alloy is proposed, utilizing a Self-propagating High-temperature Synthesis (SHS) reaction via the SHSB (Self-propagating High-temperature Synthesis in Bath) process. In this study, a novel synthesis approach is presented, involving a liquid titanium–solid carbon reaction to form titanium carbide (TiC) particles within the A201 alloy, in contrast to the typical solid–solid (Ti–C) reaction. The outcome of this process is the formation of TiC particles, which are primarily located along grain boundaries and contribute to grain refinement, particularly of the (α)Al phase. A focused study of the in situ TiC-reinforced composite was conducted using XRF, optical microscopy (OM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Vickers microhardness measurements. The present study has a basic research character and focuses on the description of a novel synthesis method for the production of titanium carbides. This reaction proceeds as a solid–liquid type reaction between carbon and titanium. Phase and transmission analyses confirmed the formation of titanium carbides. Furthermore, based on the A201 alloy, the potential for alloy modification was demonstrated, which may inhibit the growth of primary α-aluminum phase grains and thus reduce the susceptibility to hot cracking. Full article

A common method to examine the reliability of thin films and small volumes of irradiated materials being used in aerospace, energy, and protective coating applications is biaxial straining. With such tests, the fracture and deformation mechanisms occurring under multi-axial stress states can be investigated, which can strongly differ from the simpler uniaxial one. However, devices that can apply a precise and synchronously applied biaxial strain tend to be too large for foils or thin films and do not allow for additional observation methods to be applied to examine film fracture or deformation during the test. A prototype device that can apply synchronous equi-biaxial and semi-biaxial strains and can be combined with multiple in situ methods is introduced. The device is light and compact in design, which allows it to be mounted on optical light microscopes, atomic force microscopes, inside scanning electron microscopes, and even on X-ray beamlines for reflection or transmission measurements. Additionally, digital image correlation was utilized in two geometries to measure strains on a local or global level. The possible errors associated with the device and experiments on polyimide foils and a 100 nm tungsten film on polyimide are presented. Full article

Addressing the significant pressure for carbon emission reduction in the cement industry, the development of novel cement materials capable of achieving “in situ carbon sequestration” has become an important research focus. This study introduces nesquehonite (MgCO₃·3H₂O, NQ) as a functional admixture into the Portland cement system, systematically investigating its effects on the cement hydration process, the evolution of hydration products, and its carbon sequestration efficiency. Through designed penetration resistance tests and hydration tests with a high water-to-solid ratio, this research utilized X-ray diffraction analysis to determine the phase composition and content of hydration products at different ages. This was combined with scanning electron microscopy to observe microstructural evolution and Nano Measure software 1.2.5 for ettringite crystal size measurement, analyzing the impact of NQ on the early hydration process of P.I cement. The results indicate that the incorporation of NQ significantly alters the early hydration of P.I cement. The Mg²⁺ and CO₃²⁻ ions released upon its dissolution interact with Ca²⁺ and OH⁻ in the pore solution, effectively promoting the early precipitation of carbon sequestration products such as calcium carbonate and minor magnesium-containing carbonates. The addition of 10% NQ hindered the crystallization of Ca(OH)₂ before 6 h but promoted its formation after 24 h. Mechanical property tests revealed that a sample with an optimal 3% NQ dosage not only increased the paste’s penetration resistance but also enhanced the compressive strength of the 1-day hardened sample by 8.37% compared to the plain sample, without a decrease and even a slight increase at 28 days. This enhancement is closely related to the microstructural strengthening effect induced by the carbonation products. This study confirms the feasibility of using NQ to steer the cement hydration pathway towards a low-carbon direction, revealing its dual functionality in regulating hydration and sequestering carbon within cement-based materials. The findings provide a new theoretical basis and technical pathway for developing high-performance, low-carbon cement. Full article

This study reports the discovery, contextualization, and archaeometric analysis of a unique metal pilgrim flask recovered from the sacred well of Santa Cristina (Paulilatino, Sardinia, Italy), a major sanctuary complex of the Nuragic period. Misidentified for several decades following its 20th-century excavation, the object has now been reinterpreted as a nearly intact, full-scale pilgrim flask manufactured from pewter—a material previously unrecorded in Sardinian protohistoric contexts. Typological comparison with related artefacts from the Levant, Cyprus, and Etruria reveals close formal and morphological affinities with Sardinian ceramic flasks and, in particular, with miniature bronze flasks documented in Nuragic and Villanovan assemblages. The morphological congruence suggests that the Santa Cristina vessel may have functioned as a prototype or symbolic referent for these miniature exemplars. The associated presence of eastern Mediterranean-style figurines and other imported materials further underscores the sanctuary’s involvement in elite ritual practices and participation in long-distance exchange networks. From a technological perspective, selected areas of the vessel were investigated using non-destructive Energy-Dispersive X-Ray Fluorescence (EDXRF) analysis, supported by Monte Carlo simulation of the in situ measurements, and External Reflectance Fourier-Transform Infrared (ER-FTIR) spectroscopy. The combined results indicate a pewter alloy characterized by elevated tin and lead contents, confirming the object’s exceptional technological status within the Sardinian protohistoric metallurgical repertoire. Full article

Geological Carbon Sequestration (GCS) plays a crucial role in addressing climate change, particularly in oil and gas development. Understanding the reaction of supercritical CO₂ under in situ conditions and its effects on minerals is essential for advancing GCS technology. This study investigates the reaction mechanisms of feldspar (potassium and sodium feldspar) and clay minerals (chlorite, illite, montmorillonite, kaolinite) in CO₂ environments. The impacts on mineral crystal structures, morphologies, and elemental compositions were analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and ion concentration measurements (ICP-OES and ICP-MS). The results show that feldspar minerals exhibit lower reaction rates, with sodium feldspar dissolving faster than potassium feldspar, due to the higher solubility of sodium ions in acidic conditions. Chlorite showed significant crystal structure damage after 30 days, while montmorillonite underwent both dissolution and precipitation, influenced by interlayer cation dissociation. Kaolinite exhibited minimal reaction, primarily showing localized dissolution. Additionally, the formation of siderite (FeCO₃) was observed as Fe²⁺ substituted for Ca²⁺ in CaCO₃, highlighting the role of iron-bearing carbonates in CO₂ interactions. The study provides insights into the factors influencing mineral reactivity, including mineral structure, ion exchange capacity, and solubility, and suggests that chlorite, montmorillonite, and illite are more reactive under reservoir conditions, while kaolinite shows higher resistance to CO₂-induced reactions. These findings offer valuable data for optimizing GCS technologies and predicting long-term sequestration outcomes. Full article

Objective: The aim of this work is to improve the understanding of the mechanisms underlying the polymorphic transformations of pharmaceutical materials during milling. Elucidating these mechanisms is essential for controlling the polymorphism of active pharmaceutical ingredients and thereby improving their performance. Method: The structural evolution of various pharmaceutical compounds (sulfamerazine, glycine, mannitol, and famotidine) upon milling was followed using ex situ laboratory X-ray diffraction and in situ synchrotron measurements, complemented by DSC analyses. Results: For each compound, the kinetics of the polymorphic transformation was found to be sigmoidal and the presence of an intermediate amorphous phase during the transition from the initial to the final polymorphic form was also identified. Conclusions: The kinetic data obtained for sulfamerazine and glycine, together with the detection of an amorphous intermediate during the transformations of mannitol and famotidine, support the conclusion that milling-induced polymorphic transformations in pharmaceutical materials generally proceed via an amorphization–recrystallization mechanism. Full article

In large-scale radiological events, there is a need to triage affected individuals based on their biological absorbed dose. Biodosimetry measures biological responses in relation to the received dose. Radiation-responsive protein biomarkers in peripheral blood lymphocytes, especially intracellular proteins, have been validated for biodosimetry with immunochemical-based measurement methods. However, these antibody-based assays can suffer from stability and batch-to-batch variations. Aptamers are single-stranded oligonucleotide alternatives to antibodies that are stable and much smaller in size, making them ideal probes for intracellular targets. However, few aptamers have been developed against intracellular targets, and these efforts are especially hampered due to the time-consuming nature of the conventional aptamer selection method. An efficient method for isolating aptamers against intracellular radiation-responsive proteins is not available yet. Herein, we used a microfluidic aptamer isolation method to develop an aptamer against the intracellular radiation biomarker BAX in blood lymphocytes. The isolated aptamer has a dissociation constant of 6.95 nM against human BAX protein and a bright detail similarity score of 1.9 when colocalizing with anti-BAX aptamer intracellularly. The in situ labeling of the intracellular BAX protein also shows the aptamer can be used to differentiate 2.5 Gy or 3 Gy of radiation in ex vivo human and in vivo mouse peripheral blood samples exposed to X-rays. In conclusion, this proof-of-concept study indicates that the microfluidic-enabled aptamer isolation method could be used for the development of a panel of targeted intracellular proteins for radiation biodosimetry applications. Full article

Thin liquid film corrosion is a critical failure mechanism for the atmospheric environment and industrial infrastructure. This review systematically examines relevant methods and recent advances in characterizing and simulating this phenomenon. Various measurement methods for liquid film thickness, composition, and conductivity are investigated, with particular focus on the advantages of non-contact optical technology and X-ray fluorescence (XRF) in in situ monitoring and analysis. For corrosion simulation, the finite element method (FEM), cellular automaton (CA), and molecular dynamics (MD) are widely used. Their combination has synergistic potential in revealing essential corrosion mechanisms and establishing prediction models across scales. Full article

The coordination chemistry of a hydrazinylpyrazine-derived Schiff base ligand (L1), formed in situ from salicylaldehyde and 2-hydrazinopyrazine, with Fe(III) salts has been systematically investigated under varied synthetic conditions. Six discrete Fe(III) complexes (1a–1e and 2) were isolated and structurally characterised via single-crystal X-ray diffraction, revealing diverse coordination geometries ranging from five-coordinate pseudo-trigonal bipyramidal to six-coordinate pseudo-octahedral environments. The supramolecular architectures are governed by a rich interplay of non-covalent interactions, including hydrogen bonding, halogen bonding, and π–π stacking, which significantly influence the crystallisation pathways and final solid-state structures. Continuous shape measure (CShM) analysis highlights substantial geometric distortion in the bis-tridentate complexes, attributed to the steric and electronic constraints imposed by the ligand. Powder X-ray diffraction and infrared spectroscopy confirm the presence of multiple phases in bulk samples, underscoring the kinetic competition between crystallisation and coordination. The results demonstrate that supramolecular stabilisation of monoligated species can kinetically inhibit bis-ligation, with ligand excess and solvent polarity serving as key parameters to direct complex speciation. These findings provide insight into the delicate balance between coordination geometry, ligand strain, and supramolecular assembly in Fe(III) Schiff base complexes. Full article

Aluminum nitride (AlN), a III-V wide-bandgap semiconductor, has attracted significant attention for high-temperature and high-power applications. However, achieving p-type doping in AlN remains challenging. In this study, p-type AlN thin films were fabricated via magnetron sputtering using Mg-Al alloy targets with varying Mg concentrations (0.01 at.%, 0.02 at.%, and 0.5 at.%), followed by ex situ high-temperature annealing to facilitate Mg diffusion and electrical activation. The structural, morphological, and electrical properties of the films were systematically characterized using X-ray diffraction (XRD), white light interferometry (WLI), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and Hall effect measurements. The results demonstrate that at a Mg doping concentration of 0.02 at.%, the films exhibit optimal crystallinity, uniform Mg distribution, and a favorable balance between carrier concentration and mobility, resulting in effective p-type conductivity. Increasing Mg doping leads to higher surface roughness and the formation of columnar and conical grain structures. While high Mg doping (0.5 at.%) significantly increases carrier concentration and decreases resistivity, it also reduces mobility due to enhanced impurity and carrier–carrier scattering, negatively impacting hole transport. XPS and EDS analyses confirm Mg incorporation and the formation of Mg-N and Al-Mg bonds. Overall, this study indicates that controlled Mg doping combined with high-temperature annealing can achieve p-type AlN films to a certain extent, though mobility and carrier activation remain limited, providing guidance for the development of high-performance AlN-based bipolar devices. Full article