Crystalline Phase Research Articles

Phosphate's second life: Upcycling phosphogypsum and clay by-product through acid geopolymer technology

The present study explores the repurposing of large amounts of phosphoric acid by-products, specifically phosphogypsum (PG), by evaluating its effectiveness as a precursor in acid-activated geopolymer technology. Geopolymers were elaborated using PG and calcined clays, activated with phosphoric acid. The research focused on evaluating the mechanical properties and microstructure of these geopolymers after a 28-day curing period. X-ray diffraction (XRD) analysis revealed the formation of new crystalline phases, including brushite, newberite, and berlinite. Fourier-transform infrared (FTIR) spectroscopy confirmed the presence of P-O and Si-O-Al bonds, indicative of successful geopolymerization. Scanning electron microscopy (SEM) imaging demonstrated a dense, cohesive microstructure in optimized samples. Based on the response surface methodology, the study identified optimal conditions for maximum compressive strength: 28.83% PG content, 14.39mol/L phosphoric acid concentration, and a curing temperature of 72.45°C. This optimized formulation produced a dense, cohesive microstructure with a notable compressive strength of 21.46MPa. The leaching test confirmed that no harmful substances were released from the geopolymer samples. These results suggest that PG can be effectively recycled through geopolymer technology for use in the construction industry.

In-silico Studies, Synthesis, and Antacid Activities of Magnesium (II) Complexes.

Nowadays, acidity is a severe problem worldwide caused by excessive gastric acid secretion by the stomach and proximal intestine. Antacids are drugs capable of buffering stomach acid. Therefore, in our research work, we have reported the in-silico studies, synthesis, characterization, and evaluation of antacid activities of magnesium (II) complexes via the acid-base neutralization process. In this research, some magnesium complexes were synthesized and their antacid behavior was compared with marketed products. Also, in-silico studies were performed on H+/K+ ATPase (Proton pump). All synthesized compounds were characterized by various spectroscopic techniques like UV-Vis, FT-IR, XRD, and DSC techniques. Spectroscopic analysis results showed that the semicarbazone ligand shows keto-enol isomerism and forms a coordinated stable complex with magnesium ions in the crystalline phase. The FT-IR results confirmed the presence of Mg-O stretching, N-H bending, and C=N stretching vibrations in Mg (II) complexes. The antacid activities of Mg (II) complexes were excellent as compared to the semicarbazone ligand and comparable with that of marketed antacid drugs like ENO, and Pantop-D. Insilco studies also confirmed that semicarbazone ligand and its Mg (II) complexes were both found to be fitted into the active sites of molecular targets, and Mg (II) complexes showed better binding affinities towards macromolecular as compared to semicarbazone ligand.

Highly active and stable mixed-phase In2O3-supported Ni catalyst for CO2 hydrogenation to methanol

Ni/In2O3 catalysts perform well for CO2 hydrogenation to methanol. However, there is still room for improvement in terms of methanol selectivity. In this study, Ni/In2O3 catalysts with distinct crystalline phases of indium oxide, namely cubic In2O3 (c-In2O3) and a mixed phase of cubic and hexagonal In2O3 (h + c-In2O3), were synthesized. The results showed that the Ni/h + c-In2O3 catalyst demonstrated the greatest catalytic performance, with a methanol selectivity of 96.7 % and a space time yield of methanol of 15.79 mmol·g−1·h−1 at 2 MPa, 300°C, and 24.0 L·g−1·h−1. Based on the characterization results, we concluded that the improvement of the methanol synthesis performance on the Ni/h + c-In2O3 catalyst was mainly due to improved hydrogen dissociation ability and the increased surface oxygen vacancies. The energy barrier (Ea) of the rate-limiting steps for the CH3OH and CO productions was calculated. The decreased Ea(CH3OH) and increased Ea(CO) indicate the favorable improvement of catalytic activity and selectivity for CH3OH production by Ni/In2O3, especially for Ni/h-In2O3(104).

Improving Photocatalytic Efficiency with Titanium Dioxide Quantum Dots

Titanium dioxide quantum dots (TiO2-QDs), synthesized using a microwave-assisted method, represent a significant advancement in photocatalysis, particularly in the treatment of environmental pollutants. This study focuses on TiO2-QDs synthesized at 200°C for a duration of 5 minutes, using titanium butoxide as a precursor. Characterization through TEM, XRD, PL, and UV-Vis-DRS analyses revealed uniform quantum dots with an average size of 5.28 nm, a bandgap energy of 3.22 eV, and a crystalline anatase phase, indicative of high photocatalytic activity. Notably, these TiO2-QDs demonstrated exceptional performance in degrading methylene blue (MB) in water, achieving a remarkable treatment efficiency of 97.6% in 120 min, significantly outperforming both conventional titanium dioxide nanoparticles and commercial titanium dioxide materials. The reaction conditions were evaluated based on factors such as catalyst dose, initial MB concentration, and pH. The results indicate that optimal degradation efficiency of MB was achieved at a pH of 7, with a catalyst dose of 0.15 g/L and at a low MB concentration. The efficiency slightly decreased to 94.5% after five reuse cycles, emphasizing its significant reusability and stability. Copyright © 2024 by Authors, Published by BCREC Publishing Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Protection of 316L Steel Against LBE Corrosion by a CaO-MgO-Al2O3-SiO2 Glass–Ceramic Coating

A CaO-MgO-Al2O3-SiO2 glass–ceramic coating was prepared by the slurry method and subsequent sintering to improve the corrosion resistance of 316L steel in liquid lead–bismuth eutectic alloy at high temperatures. The glass–ceramic coating, sintered at 884 °C, was dense and demonstrated strong adhesion to the substrate. It was composed of the crystalline phases diopside (CaMgSi2O6) and anorthite (CaAl2Si2O8) and had an average Vickers hardness of 595 HV, which was over three times that of 316L steel. After corrosion in an oxygen-saturated, static lead–bismuth eutectic alloy at 500 °C for 1000 h, the uncoated 316L experienced significant mass gain (0.04 g) due to severe oxidative corrosion, resulting in the formation of Fe3O4 and Pb2O on its surface. In contrast, the glass–ceramic-coated specimens showed a very small mass gain (0.0012 g) after corrosion. The coating maintained good thermal stability; its crystalline phase composition remained largely unchanged after the corrosion test. The glass–ceramic coating still exhibited dense microstructure and tightly adhered to the substrate after corrosion. There was no evident penetration of lead–bismuth into the coating, and no dissolution of the coating’s elements into the lead–bismuth alloy was detected. These observations confirm that the glass–ceramic coating possessed superior corrosion resistance in liquid lead–bismuth eutectic environments.

Degradation of Concrete Cement Stone Under the Influence of Aspergillus niger Fungi

The concepts of physical and chemical transformations occurring in cement concrete under conditions of microbiological deterioration can be used to control the processes of the destruction of cement concretes in order to ensure the required durability and to predict the service life of products. The study of changes in the structural and phase composition of cement stone made of Portland cement grade CEM I 42.5N in the process of fungal deterioration for 6 months when moistened, as well as a sample of a concrete wall exposed to fungal microorganisms for 20 years, was carried out. Diffractograms of the studied cement stone samples contain a large number of pronounced narrow peaks and indicate a highly crystalline structure of phases with the presence of an X-ray amorphous phase of calcium hydrosilicates and tobermorite gel in the cement stone. Changes in the structure of cement stone under the influence of fungi are confirmed by the data of a derivatographic analysis. A decrease in the content of calcium hydrosilicates and ettringite, as well as other crystalline phases in cement stone, leads to a decrease in compressive strength by about 15% over 6 months of fungal degradation. Similar changes after 20 years of exposure to microorganisms suggest deterioration in the strength characteristics of concrete.

Polar charge density wave in a superconductor with crystallographic chirality

Symmetry plays an important role in determining the physical properties in condensed matter physics, as the symmetry operations of any physical property must include the symmetry operations of the point group of the crystal. As a consequence, crystallographic polarity and chirality are expected to have an impact on the Cooper pairing in a superconductor. While superconductivity with crystallographic polarity and chirality have both been found in a few crystalline phases separately; however, their coexistence and material realizations have not been studied. Here, by utilizing transport, Raman scattering, and transmission electron microscopy, we unveil a unique realization of superconductivity in single-crystalline Mo3Al2C (superconducting Tc=8 K) with a polar charge-density-wave phase and well-defined crystallographic chirality. We show that the intriguing charge density wave order leads to a noncentrosymmetric-nonpolar to polar transition below T*=155K via breaking both the translational and rotational symmetries. Superconductivity emerges in this polar and chiral crystal structure below Tc=8 K. Our results establish that Mo3Al2C is a superconductor with crystallographic polarity and chirality simultaneously, and motivate future studies of unconventional superconductivity in this category.

Microemulsion Templating Synthesis of Hierarchical Porous Ag‐Doped SiO2‐TiO2 Composites for Efficient Degradation of Noxious Methylene Blue Dye: Effect of Calcination Environment

AbstractWe report herein a dual function mesoporous structure of titanium oxide based porous carbon with large surface‐to‐volume ratios for efficient degradation of noxious methylene blue dye (MB) from an aqueous environment. The mesoporous photocatalysts is fabricated via direct template synthesis of highly ordered silica‐titania monolith doped with Ag0/Ag2O starting from a quaternary microemulsion liquid crystalline phase. The produced monoliths are subjected in‐situ to doping by growing silver, in the cubic cavities, and on the silica/titania structure's domain. This study investigated the efficiency of novel composite materials, consisting of silver‐doped silica‐titania (SiO2/TiO2), which is synthesized using the microemulsion templating approach. The photocatalytic performance of the synthesized composite in the photodegradation of MB has been studied. The procedure of photodegradation was employed to achieve decolorization of the cationic MB dye using visible light. The catalyst effectively achieved the decolorization of the dyed solution through the processes of adsorption and photodegradation. The composite consisting of SiO2, TiO2, and Ag2O at a ratio of 1 : 1:0.5, which underwent calcination in an air environment (AgOST), exhibited a removal efficiency of 99 % compared to its calcined state under argon (AgSTC).

High-Temperature Steam Oxidation and Surface Microstructure Evolution of Fe13Cr6Al(1–4)Mo0.15Y Alloys

The current study investigated the microstructure evolution and anti-corrosion behavior of low Y doping alloys of Fe13Cr6Al(1–4)Mo0.15Y subjected to high-temperature steam (800 °C to 1300 °C). The results indicate that steam oxidation induces the growth of high-quality oxidation film that is thermodynamically driven, with rapid increases in the thickness from 800 °C to 1300 °C without film convolution and spallation. The film convolution and spallation were successfully suppressed through on-site formation of the high-temperature stable ternary crystalline phase (Y2Mo3O12) and decreasing of the thickness of α-Al2O3 oxidation film during the fabrication and oxidation scenario. The on-site steam oxidation rate has been significantly suppressed, with lower weight gain and less oxidizing film convolution than monolithic FeCrAlMo alloy, through the addition of a low concentration of Y.

Phase Evolution, Mechanical, and Electrical Properties of Lightweight Ceramic Prepared Using Scoria at Low Temperature

This study aimed to produce lightweight, eco-friendly ceramic materials with superior properties using natural raw materials and low processing temperatures. Five ceramic samples were fabricated using red clay and varying contents of volcanic scoria (10%, 20%, 30%, 40%, and 50%) through sintering at 950 °C for 4 h. The crystalline phases, electrical properties, porosity, and mechanical strength of all the ceramic specimens were comprehensively evaluated. It was determined that the chemical composition of the raw materials and the resulting phases significantly influenced these various attributes. The XRD analysis revealed that the ceramic samples primarily consisted of the crystalline phases gehlenite, low quartz, and anorthite, along with the minor wollastonite and hematite phases. As the scoria content was increased, the MgO and Fe2O3 concentrations also increased, leading to a reduction in dielectric constant, dielectric loss, and electric conductivity. Moreover, the porosity of samples decreases from S10 to S50 due to the increase in the percentage of scoria and this reduction in porosity led to increased bending strength. The findings of this study suggest that volcanic scoria can serve as a viable eco-friendly raw material to produce lightweight ceramics with excellent electrical and mechanical properties, presenting cost-effective and energy-efficient solutions for various applications.

Catalytic Conversion of Levulinic Acid over Sn-BTC and Sn-H3-5-SIP Heterogeneous Acid Catalysts

This work presents the synthesis and characterization of materials that contain Sn metal clusters formed by ligands of trimesic acid (Sn-BTC) or 5-sulfobenzene-1,3-dicarboxylic acid (Sn-H3-5-SIP). These catalysts were used to convert levulinic acid with ethanol to produce ethyl levulinate under mild reaction conditions. The characterization results confirmed that Sn is mainly present in the cassiterite crystalline phase with a tetragonal rutile structure in octahedral and tetrahedral coordination in the materials. The assembly of trimesic acid (a hard base) with metal species (Sn) results in the formation of acid and thermally stable metal–organic frameworks. The use of 5-sulfobenzene-1,3-dicarboxylic acid instead of trimesic acid in the synthesis incorporates sulfonic groups in the material, enhancing the total acidity of the Sn-H3-5-SIP catalyst compared to the Sn-BTC material. The Sn-H3-5-SIP catalyst exhibited the highest catalytic activity when converting levulinic acid with ethanol, resulting in a turnover frequency (TOF) of 0.0495 s−1, which is a 50% increase compared to the TOF of the Sn-BTC catalyst (0.0329 s−1). This result can be attributed to its higher concentration of acid sites (2.23 ± 0.05 mmol H+/gcat) and specific area (139 m2/g). Thus, materials containing tin metal clusters and sulfonic groups are promising materials that could be used as catalysts for synthesizing ethyl levulinate under mild reaction conditions.

Relaxation processes in the oriented polyvinylidene fluoride films with various crystalline phase composition

Relaxation processes in the oriented polyvinylidene fluoride films with various crystalline phase composition

Regulating oxygen vacancies to optimize the electronic structure and catalytic activity of tungsten oxides for hydrogen evolution reaction

The undesirable intrinsic activity of tungsten oxides derived from poor conductivity and adverse hydrogen absorption energy is insufficient for their practical application. Herein, the tungsten oxides with adjustable oxygen vacancies were synthesized by a facile pyrolysis of ammonium paratungstate hydrate in controllable atmospheres. The structural characterizations confirmed that oxygen vacancies and crystalline phases in tungsten oxides depend on the pyrolysis atmosphere. The electrochemical test indicated a strong dependence between catalytic activity and oxygen vacancies in tungsten oxides. Combining experimental results and density functional theory calculations verified that introducing oxygen vacancies into tungsten oxides effectively modulates the surface electronic structure. The enhanced electronic conductivity by reducing band gap accelerates the electron transfer from catalysts into the reactive species. The optimized hydrogen adsorption energy by electron migration from O into W promotes the activation of reactive species at W sites and the desorption from O sites, thereby accelerating the reaction kinetics.

Simulation of dissolution of cerium trifluoride in a mixture of LIF–NaF–KF

The study of phase diagrams of multicomponent molten mixtures is traditionally carried out either by experimental measurements or thermodynamic calculations based on known experimental data. Atomistic modeling occupies a significantly smaller share in the methodology, and the capabilities of this approach have been poorly studied. In this work, we simulated the dissolution of cerium trifluoride in the ternary eutectic of lithium, sodium, and potassium fluorides using the molecular dynamics method. A time- and ensemble-scale simulation of the coexisting crystalline phase and melt at several temperatures was carried out. The influence of ensemble size was studied. The rate of dissolution was studied depending on temperature. The asymptote of the dependence agrees well with the experimental liquidus temperature for a given composition. A conclusion is given about the possibility of using molecular dynamics to determine the complete solubility of a melt component.

A 1D micromechanics-based constitutive model for the thermoviscoelastic behavior of crosslinked semicrystalline shape memory polymers: Numerical simulation and experimental validation

Abstract The paper develops a 1D thermoviscoelastic constitutive model for the crystallization- and melting-induced one-way and two-way shape memory effects, as well as isothermal yielding behaviors, of crosslinked semi-crystalline polymers. A micromolecular chain model is proposed to characterize the transition between the amorphous and crystalline phases. Structural equations including a modified Eying model that combine phase transition and viscoelasticity equations are employed to predict the shape memory effects. An extensive experimental campaign has been carried out on poly (ethylene-co-vinyl acetate) (EVA) based semi-crystalline elastomers to characterize the thermoviscoelastic temperature-stress-strain relations of the material under different loading and rate conditions. Some results guide the determination of the model parameters, while the rest validate the model capabilities. Comparisons with the experimental results show that the model can well reproduce the stress-strain-temperature responses, providing valuable insights for application development.

Crystal Evolution of Amorphous Poly(lactic acid) During Simultaneous Multi‐step Tensile Deformation and Annealing

ABSTRACTThe cold‐crystallization and crystal evolution of amorphous poly(lactic acid) (PLA) are analyzed during multistep tensile deformation and annealing at 70°C using in situ synchrotron wide‐angle X‐ray scattering (WAXS) measurements. The 2D‐WAXS diffraction pattern reveals that the PLA crystalline structure forms perpendicular to the draw direction. The annealing process lets to a rearrangement of the crystalline structure, while the stretching causes crystal contraction. Both WAXS and FTIR analyses confirm that the crystals developed through stretching and annealing are in the α′‐form. The crystallinity of PLA increases with higher deformation strains and longer annealing times. The orientation degree of both crystalline and amorphous phases of PLA, as indicated by the Hermans orientation factor and dichroic ratio of 956 cm−1 band (evaluated by WAXS and polarized FTIR analysis, respectively) also increase. The enhanced cold‐crystallization ability of PLA is attributed to the synergistic effect of tensile deformation and annealing, rather than either technique alone. The unusual crystallization phenomenon observed during multistep tensile deformation coupled with annealing provides valuable insights into the crystallization and crystal evolution of PLA.

Epitaxial Orientation-Controlled High Crystallinity and Ferroelectric Properties in Hf0.5Zr0.5O2 Films.

Hafnium-based binary oxides are essential for fabricating nanoscale high-density ferroelectric memory devices. However, effective strategies to control and improve their thin-film single crystallinity and metastable ferroelectricity remain elusive, hindering potential applications. Here, using NdGaO3 (NGO) substrates with four crystalline orientations, we report a systematic study of the structural characterizations and ferroelectric properties of epitaxial Hf0.5Zr0.5O2 (HZO) films, demonstrating orientation-controlled high crystallinity and enhanced ferroelectric properties. HZO films grown on NGO(001) and NGO(110) substrates exhibit relatively low crystallinity and a significant presence of the monoclinic phase. In contrast, HZO films grown on NGO(100) and NGO(010) possess high single crystallinity and a dominant ferroelectric phase. These differences are attributed to the surface symmetry of the NGO substrate, which favors the formation of 4- or 2-fold domain configurations. Moreover, the optimized HZO films exhibit a large polarization (2Pr) of ∼50 μC/cm2, enhanced fatigue behavior up to 1011 cycles, improved retention of 2Pr ∼ 40 μC/cm2 after 10 years, and characteristic polarization switching speeds in the submicrosecond range. Our results highlight the importance of modulating the single crystallinity and ferroelectric phase fraction of HfO2-based films to enhance ferroelectric properties, further revealing the potential of epitaxial symmetry engineering.

Structural investigation of the liquid crystalline phases of three homologues from the nOS5 series (n = 9, 10, 11) by X-ray diffraction

ABSTRACT Polarizing optical microscopy and differential scanning calorimetry are used to determine the phase sequence of three liquid crystalline 4-pentylphenyl-4’-n-alkyloxythiobenzoates with n = 9, 10, 11. The X-ray diffraction method is applied for structural characterisation of the liquid crystalline phases. The smectic layer spacing, tilt angle, average distance between the long axes of molecules and correlation length of the short-range order are determined as a function of temperature. For the crystal-like smectic phases with the hexagonal or herring-bone packing, the unit cell parameters are obtained. The presence of the tilted hexagonal phase for n = 10, 11 and tilted herring-bone phase for n = 9, 10 is indicated, although the direction of the tilt cannot be determined.

Effects of Incorporating TiO2 Aggregates on the Growth, Anticorrosion, and Antibacterial Properties of Electrodeposited Multifunctional Coatings Based on Sn-Ni Materials

Multifunctional coatings based on Sn-Ni materials with and without titanium oxide nanoparticles (TiO2NPs) incorporation were prepared using the electrochemical deposition technique at 70 °C. TiO2NPs were dispersed in the electrolyte bath, and their influence on the surface texture, crystalline phase, and properties was investigated. Various techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive X-ray microanalysis (EDX) were used to characterize the prepared coatings. The formation mechanism of the deposited coatings has been demonstrated to be consistent with the electrochemical behavior of instantaneous growth, and the three-dimensional growth is controlled by diffusion phenomena. The anticorrosion effectiveness of the coatings was assessed using potentiodynamic polarization curves and electrochemical impedance spectroscopy in an artificial sweat medium, while the bactericidal activity of the composite coatings (the ability to induce cell death) was evaluated in accordance with the ISO 27447:2019 test. The influence of TiO2NPs at a low concentration of 1 g/L on the composition, structure, and properties of the deposited coatings was demonstrated. Particular attention was paid to the relationship between the anticorrosive and bactericidal properties of the coatings and their structure composition and wetting properties. The synergistic effect of chemical composition and surface-wetting properties has been demonstrated to enhance the anticorrosive and bactericidal properties of the prepared coatings.

Optimization and Investigation of Hemoglobin‐Loaded ZIF‐90 Metal–Organic Framework Nanoparticles as Artificial Oxygen Carriers

AbstractBlood transfusions are vital, yet limited shelf‐life and storage conditions of red blood cells (RBCs) hinder their use in emergencies. Hemoglobin‐based oxygen carriers (HBOCs) aim to address these challenges, but previous versions faced clinical setbacks due to safety concerns related to hemoglobin (Hb) extravasation. ZIF‐90, a novel metal–organic framework variant where imidazole‐2‐carboxaldehyde (2‐ICA) is bridged to Zn2+ ions, is explored. Optimizing Zn2+:2‐ICA ratios and Hb concentrations, Hb‐loaded ZIF‐90 nanoparticles (NPs) are synthesized in one‐step and under mild synthesis conditions. These NPs achieve a 25.1% yield, 7.0 mg mL−1 Hb concentration, 70.3% encapsulation efficiency (EE), and 96.4% drug loading. They exhibit a left‐shifted oxygen dissociation curve with p50 of ≈8 mmHg, indicating enhanced oxygen release at lower partial oxygen pressures as compared to native RBCs. This feature makes Hb‐loaded ZIF‐90 NPs suitable for certain medical applications including ischemia‐reperfusion injury management. Furthermore, the impact of two prominent capping agents: polyvinylpyrrolidone and polyethylene glycol (PEG) is assessed. PEG improves 2‐ICA incorporation and stabilizes the ZIF‐90 crystalline phase, albeit with reduced yield, Hb content, and EE. The findings underscore the potential of Hb‐loaded ZIF‐90 NPs as next‐generation HBOCs, offering enhanced uniformity, high Hb content, and efficient oxygen binding and release properties for medical applications.