Search Results (81)

In coastal saline soil regions, foundation instability frequently arises due to salt heave, dissolution-induced weakening and corrosion-driven degradation. To enhance the engineering performance of fine-grained saline soil, this study evaluates the effectiveness of Enzyme-Induced Carbonate Precipitation (EICP) treatment under varying salinity levels and curing solution concentrations. Mechanical properties, hydraulic behavior and water stability were examined through unconfined compressive strength (UCS), disintegration and permeability tests, complemented by microstructural analyses using XRD and SEM. The results indicate that EICP notably improves mechanical strength, water stability and reduced permeability. The UCS of treated specimens increased by 37–152% relative to untreated soil, and disintegration time was prolonged by 214–563%. The permeability coefficient was reduced by 45.8–95.7%, demonstrating effective suppression of seepage channels. The optimal stabilization performance was achieved at 0.02% salinity and curing concentrations of 1.0–1.3×. Excessive salinity distorted vaterite crystal morphology and weakened cementation. XRD and SEM analyses revealed that vaterite dominated the calcium carbonate polymorphs, while ionic complexity influenced crystal structure, ACC conversion and pore-filling performance. These findings confirm the feasibility of applying EICP for improving fine-grained coastal saline soils and provide practical engineering guidance for coastal subgrades, reclamation foundations and port infrastructures. Full article

Transition metal (TM)-doped zinc oxide (ZnO) and zirconium dioxide (ZrO₂) nanocrystals exhibit complex correlations between crystal structure, defect chemistry, vibrational properties, and magnetic behavior that are strongly governed by synthesis route and dopant incorporation mechanisms. This review critically summarizes recent progress on Fe-, Mn-, and Co-doped ZnO and ZrO₂ nanocrystals synthesized by wet chemical, hydrothermal, and microwave-assisted hydrothermal methods, with emphasis on synthesis-driven phase evolution and apparent solubility limits. ZnO and ZrO₂ are treated as complementary host lattices: ZnO is a semiconducting, piezoelectric oxide with narrow solubility limits for most 3d dopants, while ZrO₂ is a dielectric, polymorphic oxide in which transition metal doping may stabilize tetragonal or cubic phases. Structural and microstructural studies using X-ray diffraction, electron microscopy, Raman spectroscopy, and Mössbauer spectroscopy demonstrate that at low dopant concentrations, TM ions may be partially incorporated into the host lattice, giving rise to diluted or defect-mediated magnetic behavior. When solubility limits are exceeded, nanoscopic secondary oxide phases emerge, leading to superparamagnetic, ferrimagnetic, or spin-glass-like responses. Magnetic measurements, including DC magnetization and AC susceptibility, reveal a continuous evolution from paramagnetism in lightly doped samples to dynamic magnetic states characteristic of nanoscale magnetic entities. Vibrational spectroscopy highlights phonon confinement, surface optical phonons, and disorder-activated modes that sensitively reflect nanocrystal size, lattice strain, and defect populations, and often correlate with magnetic dynamics. Rather than classifying these materials as diluted magnetic semiconductors, this review adopts a synthesis-driven and correlation-based framework that links dopant incorporation, local structural disorder, vibrational fingerprints, and magnetic response. By emphasizing multi-technique characterization strategies required to distinguish intrinsic from extrinsic magnetic contributions, this review provides practical guidelines for interpreting magnetism in TM-doped oxide nanocrystals and outlines implications for applications in photocatalysis, sensing, biomedicine, and electromagnetic interference (EMI) shielding. Full article

Background/Objectives: Emulsion-based semisolid formulations are important delivery systems for many applications, including pharmaceuticals, cosmetics and food. The manufacturing process for such formulations typically involves a series of heating, cooling, mixing and emulsification steps. Stabilizing agents are usually included in such formulations, as emulsions are intrinsically unstable and are prone to various destabilization mechanisms. Precise control of each processing parameter and the selection of an appropriate stabilizing agent are essential for delivering products with long-term stability and the desired properties. In this study, the effects of emulsification temperature and the selection of the stabilizing agent on key product attributes were investigated to enable improved design and optimization of both the formulation and manufacturing process. Methods: Model emulsion systems containing propylene glycol (PG) as the dispersed phase and mineral oil as the continuous phase were prepared at different emulsification temperatures to cover both pre-crystallization and post-crystallization regimes. Three stabilizing agents, namely mono-and-diglyceride (MDG), neat monoglyceride (MG) and neat diglyceride (DG), were studied. Their crystallization behavior was first examined to determine crystallization temperatures and crystal morphologies. The resulting emulsion samples were then characterized in terms of their microstructure, physical stability and rheological properties. Results: The emulsions prepared under post-crystallization conditions exhibited better physical stability, higher rheological parameters (crossover stress and viscosity) and a more rigid microstructure compared to those formed under pre-crystallization conditions, regardless of the stabilizer used. Rheological properties were found to corelate well with physical stability. In the pre-crystallization regime, poor stability could partially be mitigated by lowering the emulsification temperature. MG was generally more effective than DG in stabilizing the emulsions and led to higher rheological properties, despite both crystallizing into the same polymorph within the system. This difference in performance was attributed to variations in the crystal morphology and spatial distribution within the emulsion. Notably, the MG-stabilized emulsions also displayed a self-hardening effect during storage. Conclusions: The selection of the appropriate stabilizing agents and processing conditions tailored to the specific system is critical for the successful manufacture of emulsion-based semisolid products with an optimized performance. Full article

Pazufloxacin is a fluoroquinolone antibiotic synthesized by Toyama Chemical Co., Ltd. (Tokyo, Japan) in the 1990s. Up until now, the X-ray crystal structure of its mesylate salt had not been determined. The dissolution and recrystallization of pazufloxacin mesylate from different solvents afforded the salts pazufloxacinium mesylate (1), pazufloxacinium mesylate dihydrate (2), pazufloxacinium mesylate hydrate (3) and pazufloxacinium mesylate bis(peroxosolvate) (4), which were all crystallographically characterized. Molecular and crystal structures of these compounds, as well as their thermal behavior, were studied. For all compounds, single-crystal X-ray diffraction confirmed that a proton migrates from methanesulfonic acid to the amino group of pazufloxacin to form a salt. Dehydration of two hydrates occurs as a two-step single-crystal-to-powder process, leading to the formation of two metastable polymorphs of the anhydrous salt. In the solid state, the peroxosolvate compound is stable under ambient conditions for several months, thus making this drug–drug solid suitable for topical application. Full article

Polymorphism critically influences the solid-state properties of organic molecules, affecting stability, solubility, and functionality. We investigated the polymorphic behavior of enantiomerically pure (+)-(6aS,11aS)-medicarpin through combined experimental and computational analyses. Single-crystal X-ray diffraction revealed two distinct chiral polymorphs: the previously reported monoclinic P2₁ form and a newly identified orthorhombic P2₁2₁2₁ form with a fully chiral packing arrangement. The discovery of this previously unreported polymorph underscores the subtle yet decisive effects of solvent and conformational flexibility in directing crystallization. Detailed structural analysis reveals that, whereas the P2₁ form is only stabilized by a single dominant electrostatic interaction, the P2₁2₁2₁ form features a more complex network comprising C-H···π contacts, bifurcated C-H···O hydrogen bonds, and aromatic edge-to-face interactions. Further investigation of a functionalized p-nitrobenzoate derivative corroborates the critical influence of molecular substituents and crystallization conditions on packing motifs. Lattice energy DFT calculations confirm that each polymorph is stabilized by distinct electrostatic and dispersive interaction patterns, illustrating the complex energetic landscape of polymorph selection. Altogether, this work provides a framework for understanding and anticipating which polymorph is likely to form under specific solvent and crystallization conditions, offering insights for future strategies in materials design and guiding the pursuit of patentable crystalline forms in pharmaceutical applications. Full article

Polypropylene (PP), with its good physical, thermal, and mechanical properties and excellent processing capabilities, has become one of the most used synthetic polymers. It is known that the overall properties of semicrystalline polymers, including PP, are governed by morphology, which is influenced by the crystallization behavior of the polymer under specific conditions. The most important industrial PP remains the isotactic one, and it has been studied extensively for its polymorphic characteristics and crystallization behavior for over half a century. Due to its regular chain structure, isotactic polypropylene (iPP) belongs to the group of polymers with a high tendency for crystallization. The rapid quenching of molten iPP fails to produce a completely amorphous polymer but leads to an intermediate crystalline order. On the other hand, slow cooling yields a material with high crystalline content. The processing conditions that occur in practice and industry are between these two extremes and, in some cases, are even very close. Therefore, the study of limits in processability and the impact of extreme preparation conditions on morphology, structure, thermal, and mechanical properties fills a gap in the current understanding of how the processing conditions of iPP can be used to design the desired properties for specific applications and is in the focus of this research. The first set of samples (Q samples) was obtained by rapid quenching, while the second was prepared by very slow cooling from the melt to room temperature (SC samples). Testing of samples was performed by optical microscopy (OM), scanning electron microscopy (SEM), wide-angle X-ray diffraction (WAXD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), dynamic dielectric spectroscopy (DDS), and mechanical measurements. Characterization revealed that slowly cooled samples exhibited a significantly higher degree of crystallinity and larger crystallites (χ ≥ 55% and L₍₁₁₀₎ ≈ 20 nm), compared to quenched samples (χ < 30%, L₍₁₁₀₎ ≤ 3 nm). Mechanical testing showed a drastic contrast: quenched samples exhibited elongation at break > 500%, while slowly cooled samples broke below 15%, reflecting their brittle behavior. For the first time, DDS is applied to investigate molecular mobility differences between processing-dependent structural forms, specifically the mesomorphic (smectic) and α-monoclinic forms. In slowly cooled samples, α relaxation exhibited both enhanced intensity and an upward temperature shift, indicating stronger structural constraints due to a much higher crystalline phase content and significantly larger crystallite size, respectively. These findings provide novel insights into the structure–property–processing relationship, which is crucial for industrial applications. Full article

The pressure dependence of structural behavior in the orthorhombic (Pccn, PI) and monoclinic (P2₁/c, PII) polymorphs of the compound [Fe(PM-BiA)₂(NCS)₂], where PM–BiA = (N–(2′–pyridylmethylene)–4-amino–bi–pheynyl), is studied with synchrotron single-crystal X-ray diffraction and vibrational spectroscopy. Both polymorphs are stable up to ∼1.5 GPa, with a spin state transition occurring only in polymorph PII under hydrostatic conditions as documented by single-crystal synchrotron diffraction. The diffraction data also provide evidence of the formation of superstructures for both PI, with a doubled c axis, and PII, with a doubled b axis, on applying pressures above 2 GPa. The LS and HS states seem to coexist at high-pressures for both polymorphs studied with synchrotron infrared spectroscopy at quasi-hydrostatic conditions. Such results indicate that the occurrence of spin-crossover transformations in [Fe(PM-BiA)₂(NCS)₂] might strongly depend on the stress in the sample. Full article

Non-isothermal differential scanning calorimetry (DSC) and Raman microscopy were used to study the crystallization behavior of the 20–50 μm amorphous nifedipine (NIF) powder. In particular, the study was focused on the diffusionless glass-crystal (GC) growth mode occurring below the glass transition temperature (T_g). The exothermic signal associated with the GC growth was indeed directly and reproducibly recorded at heating rates q⁺ ≤ 0.5 °C·min⁻¹. During the GC growth, the α_p polymorphic phase was exclusively formed, as confirmed via Raman microscopy. In addition to the freshly prepared NIF samples, the crystallization of the powders annealed for 7 h at 20 °C was also monitored—approx. 50–60% crystallinity was achieved. For the annealed NIF powders, the confocal Raman microscopy verified a proportional absence of the crystalline phase on the sample surface (indicating its dominant formation along the internal micro-cracks, which is characteristic of the GC growth). All DSC data were modeled in terms of the solid-state kinetic equation paired with the autocatalytic model; the kinetic complexity was described via reaction mechanism based on the overlap of 3–4 independent processes. The kinetic trends associated with decreasing q⁺ were identified, confirming the temperature-dependent kinetic behavior, and used to calculate a theoretical kinetic prediction conformable to the experimentally performed 7 h annealing at 20 °C. The theoretical model slightly underestimated the true extent of the GC growth, predicting the crystallinity to be 35–40% after 7 h (such accuracy is still extremely good in comparison with the standard kinetic approaches nowadays). Further research in the field of kinetic analysis should thus focus on the methodological ways of increasing the accuracy of considerably extrapolated kinetic predictions. Full article

This study prepared palm stearin/linseed oil-based margarines (PST/LO-BMs) and palm stearin/linseed oil oleogel-based margarines (PST/LO-OBM) by incorporating varying proportions (20–60% oil phase) of linseed oil (LO) and LO-based oleogel, respectively. By comparing PST/LO-OBMs and PST/LO-BMs, it was found that the introduction of phytosterol–γ-oryzanol (PO) complexes and glycerol monostearate (GMS) to PST/LO-OBM induced three distinct crystalline morphologies: needle-like crystals, spherical crystals, and cluster-type crystals. These crystal assemblies synergistically constructed a robust three-dimensional network, effectively entrapping both aqueous droplets and liquid oil fractions while substantially reinforcing the structural integrity of PST/LO-OBM. Notably, the incorporated gelators modified the crystallization behavior, where GMS likely served as a nucleating site promoting triglyceride crystallization. This structural modulation yielded favorable β’-form crystal polymorphism, which is critically associated with enhanced textural properties. Comparative analysis with commercial margarine revealed that the PST45/LO40-OBM formulation exhibited comparable rheological performance, crystalline type, and thermal properties, while demonstrating superior nutritional characteristics, containing elevated levels of α-linolenic acid (23.54%), phytosterol (1410 mg/100 g), and γ-oryzanol (2110 mg/100 g). These findings provide fundamental insights for margarine alternatives with nutritional attributes. Full article

Triiodide salts are of interest for a variety of applications, including but not limited to electrochemical and photochemical devices, as antimicrobials and disinfectants, in supramolecular chemistry and crystal engineering, and in ionic liquids and deep eutectic solvents. Our work has focused on the design of salt–solvate cocrystals and deep eutectic solvents in which the triiodide anion interacts as a halogen bond acceptor with organoiodine molecules. To understand structure–property relationships in these hybrid materials, it is essential to have benchmark structural and physical data for the parent triiodide salt component. Herein, we report the structure and thermal properties of eight new triiodide salts, three of which exhibit polymorphism: tetrapentylammonium triiodide (1a and 1b), tetrahexylammonium triiodide (2), trimethylphenylammonium triiodide (3), trimethylbenzylammonium triiodide (4), triethylbenzylammonium triiodide (5), tri-n-butylbenzylammonium triiodide (6), 3-methylbenzothizolium triiodide (7a and 7b), and 2-chloro-1-methylpyridinium triiodide (8a and 8b). The structural features of the triiodide anion, Raman spectroscopic analysis, and melting and thermal decomposition behavior of the salts, as well as a computational analysis of the polymorphs, are discussed. The polymorphic pairs here are distinguished by symmetric versus asymmetric triiodide anions, as well as different packing patterns. Computational analyses revealed more subtle differences in their isosurface plots. Importantly, this study provides reference data for these new triiodide salts for comparison to hybrid cocrystals and deep eutectic solvents formed from their combination with various organoiodines. Full article

As a part of our effort to establish reliable thermodynamic data for amino acids, the heat capacity and phase behavior are reported for two stable polymorphs (α and γ) of glycine (aminoacetic acid, CAS RN: 56-40-6). Prior to heat capacity measurement, thermogravimetric analysis and X-ray powder diffraction were performed to determine decomposition temperatures and initial crystal structures, respectively. The literature heat capacities obtained by adiabatic calorimetry are available in the temperature interval (7–304). The literature data were used for validating performance of our relaxation (heat-pulse) calorimeter, which was used for measurement of the heat capacity of α-glycine in the temperature interval (2–267) K. The crystal heat capacities of the α- and γ-glycine were extended towards higher temperatures using Tian–Calvet calorimetry in the temperature interval (262–358) and power compensation DSC in the temperature interval (310–449) K. As a result, reference heat capacities and thermodynamic functions for the crystalline phase from 0 K up to 450/435 K for α/γ-glycine were developed. The literature heat capacities for β-glycine over the range 0 K to 295 K were treated in the same manner in order to provide thermodynamic data for all three polymorphs existing at the atmospheric pressure. Full article

To meet the expectations of European consumers, who prioritize agro-environmental factors and local resources, the substitution of fats (palm, coconut, shea) and achieving a balanced fatty acid profile in spreadable fats are gaining more attention. The crystallization at 4 °C of a lipid blend composed of rapeseed oil, anhydrous dairy fats, and emulsifiers was studied using a multi-scale approach (DSC and X-ray diffraction techniques) to understand the emergence of polymorphic structures. Although the addition of PUFA from rapeseed oil reduces the atherogenicity and thrombogenicity indices in the blend, controlling the cooling kinetics influences the shapes (needles and spherulites) and sizes of the crystalline structures (small crystals form at a cooling rate of 1 °C min⁻¹, while larger crystals form at higher rates of 5 and 10 °C min⁻¹). The crystallization behavior revealed differences in polymorphic forms at 4 °C in the blend, with a transition to different forms occurring more rapidly compared to dairy fat (stop-and-return method). The study shows crystalline coexistence (α, β′, and β) in a 2L lamellar structure, with the β′ form being predominant. This structure is ideal for formulating a spreadable product, offering good spreadability (SFC < 32% at 10 °C), mouthfeel, and nutritional benefits compared to butter. Full article

Describing fat phase behavior is of significant interest for food and non-food applications. One recognized approach to understand the behavior of complex fatty systems is to simplify the fat matrix and to emphasize only the main triacylglycerol (TAG) components. In this context, the kinetic phase behavior and phase transformation paths of binary mixtures of selected saturated monoacids (trilaurin (LaLaLa), trimyristin (MMM), and tripalmitin (PPP)) and of mixed saturated triacylglycerols containing lauric (La) and myristic (M) acids (MMLa and LaLaM) typical from lauric fats were investigated. Kinetic phase diagrams were constructed based on DSC heating thermograms (fast cooling and reheating at 5 °C min⁻¹) and powder X-ray diffraction data. The investigated binary kinetic phase diagram presented an apparently typical eutectic behavior, with a eutectic point that varies depending on the blend composition. Introducing mixed saturated TAGs (MMLa or LaLaM) in binary blends led to a shift in the position of the eutectic point. Considering the binary blends made of LaLaLa, it was shifted from X_LaLaLa = 0.7 in the LaLaLa–MMM system to X_LaLaLa = 0.5 for the LaLaLa–MMLa mixture, and to X_LaLaLa = 0.25 for the LaLaLa–LaLaM blend. Finally, the blend made of the two mixed TAGs (MMLa–LaLaM) also presented a complex non-ideal behavior. Full article

Akimotoite, ilmenite-type MgSiO₃ high-pressure polymorph can be stable in the lower-mantle transition zone along average mantle and subducting slab geotherms. Significant amounts of Al₂O₃ can be incorporated into the structure, having the pyrope (Mg₃Al₂Si₃O₁₂) composition. Previous studies have investigated the effect of Al₂O₃ on its crystal structure at nearly endmember compositions. In this study, we synthesized high-quality ilmenite-type Mg₃Al₂Si₃O₁₂ phase at 27 GPa and 1073 K by means of a Kawai-type multi-anvil press and refined the crystal structure at ambient conditions using a synchrotron X-ray diffraction data via the Rietveld method to examine the effect of Al₂O₃. The unit-cell lattice parameters were determined to be a = 4.7553(7) Å, c = 13.310(2) Å, and V = 260.66(6) ų, with Z = 6 (hexagonal, R$\overline{3}$). The volume of the present phase was placed on the akimotoite-corundum endmember join. However, the refined structure showed a strong nonlinear behavior of the a- and c-axes, which can be explained by Al incorporation into the MgO₆ and SiO₆ octahedral sites, which are distinctly different each other. Ilmenite-type Mg₃Al₂Si₃O₁₂ phase may be found in shocked meteorites and can be a good indicator for shock conditions at relatively low temperatures of 1027–1127 K. Full article

This is an overview of recent findings on the structural changes observed upon heating, including crystallization processes in conventional metallic glasses, bulk metallic glasses, and their corresponding supercooled liquids. This paper encapsulates the various crystallization behaviors in metallic glasses by primary, eutectic, and polymorphous mechanisms, highlighting the complexity and diversity of the nucleation and growth mechanisms involved. Mechanically induced room-temperature crystallization is also discussed. Full article