Search Results (545)

Zirconium (Zr) thin films were deposited on silicon (Si) substrates via pulsed laser deposition (PLD) using a 248 nm excimer laser. The effects of substrate temperature on film morphology and crystallinity were systematically investigated. X-ray diffraction (XRD) revealed that the Zr(100) plane exhibited the strongest orientation at 400 °C while Zr (002) was maximum at 500 °C. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) analyses demonstrated an increase in surface roughness with temperature, with the smoothest surface observed at lower temperatures and significant island formation at 500 °C due to the transition to 3D growth. At 500 °C, interdiffusion effects led to the formation of zirconium silicide at the Zr/Si interface. To further interpret the experimental findings, computational modeling was employed to analyze the transition from 2D layer-by-layer growth to 3D island formation at elevated temperatures. Using a multi-parameter kinetics-free model based on free energy minimization, the critical film thickness for this transition was determined to be ~1–2 nm, aligning well with experimental observations. A separate kinetic model of island nucleation and growth predicts that this shift is driven by the kinetics of adatom surface diffusion. Additionally, the kinetic simulations revealed that, at 400 °C, adatom diffusivity optimally balances crystallization and surface energy minimization, yielding the highest film quality. At 500 °C, the rapid increase in diffusivity leads to the proliferation of 3D islands, consistent with the roughness trends observed in SEM and AFM data. These findings underscore the critical role of deposition parameters in tailoring Zr thin films for applications in advanced coatings and electronic devices. Full article

The control of crystal form in chiral active pharmaceutical ingredients (APIs) is a critical challenge in pharmaceutical development, as differences in solid-state structure can significantly influence physical properties and manufacturing performance. Troglitazone, a molecule with two chiral centers, exists as four stereoisomers (RR, SS, RS, SR) that crystallize as two enantiomeric pairs: RR/SS and RS/SR. This study aims to elucidate the relationship between solution-state molecular interactions and crystallization behavior of these diastereomeric pairs. Antisolvent crystallization experiments were conducted for both mixed solutions containing all four isomers and solutions of individual pairs. Crystallization kinetics were monitored by HPLC, and the resulting solids were characterized by PXRD, DSC, TG, and microscopic observation. Nucleation induction times were determined over a range of supersaturation levels. To probe intermolecular interactions in solution, NOESY and targeted NOE NMR experiments were performed, and the results were compared with crystallographic data. The RS/SR crystals(H-form) consistently exhibited shorter induction times and faster crystallization rates than the RR/SS crystals (L-form), even under conditions where RR/SS solutions were more supersaturated. In mixed solutions, H-form crystallized preferentially, with L-form either remaining in solution or being incorporated into H-form crystals as a solid solution. NOESY and NOE analyses revealed intermolecular proximities between protons that are distant in the molecular structure, indicating the presence of ordered aggregates in solution. These aggregates were more structurally compatible with the H-form than with the L-form crystal lattice, as supported by crystallographic distance analysis. The results demonstrate that differences in nucleation kinetics between troglitazone diastereomers are closely linked to solution-state molecular arrangements. Understanding these relationships provides a molecular-level basis for the rational design of selective crystallization processes for chiral APIs. Full article

The understanding and control of protein crystallization are crucial in structural biology, drug development, and biomaterial design. This study introduces a unified framework for modeling and comparing crystallization kinetics using selected growth functions. Experimental datasets from the literature for four proteins, Lysozyme, Thaumatin, Ribonuclease A, and Proteinase K, under Hanging Drop and Langmuir–Blodgett conditions were analyzed. Five kinetic models, Avrami, Kashchiev, Hill, Logistic, and Generalized Sigmoid (GSM), were fitted to size–time data of the four benchmark proteins. From each fit, four descriptors were extracted: crystallization half-time, time of maximum growth, width at half-maximum, and peak growth rate. These metrics summarize crystallization dynamics and enable cross-comparison of proteins and methods. Langmuir–Blodgett templating accelerated onset and improved synchrony, though the effect varied by protein and model. Logistic, Hill, and GSM models provided consistent fits across most conditions, while Avrami and Kashchiev were more sensitive to early or late deviations. Notably, descriptor extraction remained reliable even with limited or uneven sampling, revealing kinetic regimes such as synchrony, asymmetry, or prolonged nucleation, not evident in raw data. This transferable analytical framework supports quantitative evaluation of crystallization behavior, aiding screening, process optimization, and time-resolved structural studies. Full article

Lithium-oxygen batteries (LOBs) are limited by sluggish oxygen redox kinetics and cathode instability. Herein, we report a cobalt particle catalyst encapsulated in nitrogen-doped carbon (Co@NC) with a three-dimensional hierarchical architecture, synthesized via a chitosan-derived hierarchical porous carbon framework. This innovative design integrates uniformly dispersed ultra-thin carbon shells (11.7 nm), pyridinic nitrogen doping, and Co particles (1.41 μm) stabilized through carbon-support electronic coupling. The hierarchical porosity facilitates rapid O₂/Li⁺ mass transport, while pyridinic N sites act as dual-function electrocatalytic centers for Li₂O₂ nucleation and charge transfer kinetics. Co@NC achieves 11,213 mAh g⁻¹ at 200 mA g⁻¹ (126.5% higher than nitrogen-doped carbon) and maintains 1.54 V overpotential (500 mAh g⁻¹). These metrics outperform benchmark catalysts, addressing kinetic and stability challenges in LOBs. The study advances electrocatalyst design by integrating structural optimization, heteroatom doping, and electronic coupling strategies for high-performance metal–air batteries. Full article

Cyclic Solvent Injection (CSI) is a method for enhanced heavy oil recovery, offering a reduced environmental impact. CSI processes typically involve fluid flow through both wormholes and the surrounding porous media in reservoirs. Therefore, understanding how foamy oil behavior differs between bulk phases and porous media is crucial for optimizing CSI operations. However, despite CSI’s advantages, limited research has explained why foamy oil, a key mechanism in CSI, displays weaker strength and stability in bulk phases than in porous media. To address this gap, three advanced visual micromodels were employed to monitor bubble behavior from nucleation through collapse under varying porosity with a constant pressure reduction. A sandpack depletion test in a large cylindrical model further validated the non-equilibrium bubble-reaction kinetics observed in the micromodels. Experiments showed that, under equivalent operating conditions, bubble nucleation in porous media required less energy and initiated more rapidly than in a bulk phase. Micromodels with lower porosity demonstrated up to a 2.5-fold increase in foamy oil volume expansion and higher bubble stability. Moreover, oil production in the sandpack declined sharply at pressures below 1800 kPa, indicating the onset of critical gas saturation, and yielded a maximum recovery of 37% of the original oil in place. These findings suggest that maintaining reservoir pressure above critical gas saturation pressure enhances oil recovery performance during CSI operations. Full article

In this work, zeolite LTA (Linde Type A) was synthesised from natural clay as a novel adsorbent for copper and lead ions removal from water effluents. The applied process allowed the reuse of kaolin, as natural clay, for the production of zeolite LTA through a stepwise process, which involved the formation of metakaolin. The results of characterisation showed the formation of crystalline cubic crystals of zeolite with a mean dimension of 2–3 microns, indicating the successful nucleation and development of the LTA zeolite phase. Batch adsorption studies were carried out to study the removal ability of zeolite LTA by testing Cu²⁺ and Pb²⁺ ions. Effects of contact time, pH, and adsorbent dosage were investigated. At pH > 5, the removal efficiency for both metals exceeded 95%. As the zeolite dosage increases from 2 to 10 g/L, the removal effectiveness for both metals markedly enhances (>95% at 10 g/L for lead ions and >90% at 10 g/L for copper ions). The adsorbent showed a higher adsorption capacity in removing lead compared to copper (Q_m = 81.5 mg/g for Pb²⁺ and 67.5 mg/g for Cu²⁺). The adsorption process was well described by the pseudo-second-order kinetic model, while the Langmuir isotherm adequately depicted the equilibrium behavior. Notably, the kinetics revealed distinct contributions from chemisorption and physisorption, with the AOAS model effectively quantifying their respective roles in metal ion removal. The findings revealed that prepared zeolite LTA acts as an efficient adsorbent to remove heavy metals. Full article

Melt-spun PA6/TiO₂ fibers with TiO₂ modified by silane coupling agents KH550 and KH570 at 0, 1.6, and 4 wt% provide a practical testbed to address three fiber-centric gaps: transferable interphase quantification, interphase-resolved indications of compatibility, and a reproducible kinetics–structure–property link. This work proposes, for the first time at fiber scale, a four-phase partition into crystal (c), crystal-adjacent rigid amorphous fraction (RAF-c), interfacial rigid amorphous fraction (RAF-i), and mobile amorphous fraction (MAF), and extracts an interfacial triad consisting of the specific interfacial area (S_v), polymer-only RAF-i fraction expressed per composite volume (Γ_i), and interphase thickness (t_i) from SAXS invariants to establish a quantitative interphase-structure–property framework. A documented SAXS/DSC/WAXS workflow partitions the polymer into the above four components on a polymer-only basis. Upon filling, Γ_i increases while RAF-c decreases, leaving the total RAF approximately conserved. Under identical cooling, DSC shows the crystallization peak temperature is higher by 1.6–4.3 °C and has longer half-times, indicating enhanced heterogeneous nucleation together with growth are increasingly limited by interphase confinement. At 4 wt% loading, KH570-modified fibers versus KH550-modified fibers exhibit higher α-phase orientation (Hermans factor f(α): 0.697 vs. 0.414) but an ~89.4% lower α/γ ratio. At the macroscale, compared to pure (neat) PA6, 4 wt% KH550- and KH570-modified fibers show tenacity enhancements of ~9.5% and ~33.3%, with elongation decreased by ~31–68%. These trends reflect orientation-driven stiffening accompanied by a reduction in the mobile amorphous fraction and stronger interphase constraints on chain mobility. Knitted fabrics achieve a UV protection factor (UPF) of at least 50, whereas pure PA6 fabrics show only ~5.0, corresponding to ≥16-fold improvement. Taken together, the SAXS-derived descriptors (S_v, Γ_i, t_i) provide transferable interphase quantification and, together with WAXS and DSC, yield a reproducible link from interfacial geometry to kinetics, structure, and properties, revealing two limiting regimes—orientation-dominated and phase-fraction-dominated. Full article

During deepwater drilling operations, when influx gas invades the wellbore, gas hydrates may form through the combination of the gas with free water in the drilling fluid under favorable temperature and pressure conditions. This process can alter the physical properties and flow behavior of the wellbore fluid, potentially leading to safety incidents. To prevent natural gas hydrate formation, mitigate wellbore blockages caused by hydrates, and address the associated safety hazards, this study conducted laboratory experiments to investigate hydrate formation and remediation under multiple deepwater drilling conditions. The hydrate formation boundaries for four different drilling fluid systems—seawater-based bentonite mud, seawater polymer mud, Plus/KCl mud, and HEM mud—were determined for varying well depths and pressure–temperature conditions, and corresponding trend lines were fitted. Key results reveal that a higher carbon content promotes hydrate formation, and the phase equilibrium curves also reveal significant differences among the four drilling fluids. The hydrate aggregation states and blockage processes were clarified for three typical drilling scenarios: drilling, well killing, and drilling suspension. Hydrate formation risk is negligible during normal circulation but increases dramatically during well-killing operations, significantly shrinking the safe operational window. A comparative analysis identified that adding 1% P(M-VCL), a kinetic hydrate inhibitor, to the drilling fluid was the most effective solution, demonstrating superior performance in delaying hydrate nucleation and preventing agglomeration. The study established a complete formation–inhibition–remediation approach for hydrate management in deepwater drilling, thereby enhancing operational safety and efficiency. Full article

Cracks in concrete dam tunnels compromise structural safety, watertightness, and durability, while conventional repair materials such as epoxy and cement impose environmental burdens. This study investigates biomineralization methods, namely Microbially Induced Calcium Carbonate Precipitation (MICP) and Enzyme-Induced Carbonate Precipitation (EICP), for repairing fine cracks in a large hydropower dam tunnel. Laboratory tests and field applications were conducted by injecting urea–calcium solutions with Sporosarcina pasteurii for MICP and soybean-derived urease for EICP, applied twice daily over three days. Both techniques achieved effective sealing, with precipitation efficiencies of 93.75% for MICP and 84.17% for EICP. XRD analysis revealed that MICP produced a mixture of vaterite and calcite, reflecting biologically influenced crystallization, whereas EICP yielded predominantly calcite, the thermodynamically stable phase. SEM confirmed that MICP generated irregular layered clusters shaped by microbial activity, while EICP formed smoother spherical and more uniform deposits under enzyme-driven conditions. The results demonstrate that MICP provides higher efficiency and localized nucleation control, while EICP offers faster kinetics and more uniform deposition. Both methods present eco-friendly and field-applicable alternatives to conventional repair, combining technical performance with environmental sustainability for hydraulic infrastructure maintenance. Full article

Ice nucleation temperatures and associated ice growth rates are critical parameters in defining the initial ice morphology template, which governs dry layer resistance during sublimation and therefore impacts primary drying kinetics and overall process time. In this study, we developed a through-vial impedance spectroscopy (TVIS) method to determine both ice nucleation temperature and average ice growth rate, from which future estimation of average ice crystal size may be possible. Whereas previous TVIS applications were limited to solutions containing simple, uncharged solutes such as sugars, our adapted approach enables the analysis of conductive solutions (5% sucrose with 0%, 0.26%, and 0.55% NaCl), covering osmolarities below and above isotonicity. We established that the real part capacitance at low and high frequencies—either side of the dielectric relaxation of ice—provides the following: (i) a temperature-sensitive parameter for detecting the onset of ice formation, and (ii) a temperature-insensitive parameter for determining the end of the ice growth phase (unaffected by temperature changes in the frozen solution). This expanded capability demonstrates the potential of TVIS as a process analytical technology (PAT) for non-invasive, in situ monitoring of freezing dynamics in pharmaceutical freeze-drying. Full article

Molecular dynamics (MD) simulations provide atomistic insights into nucleation and crystallization in polymers, yet interpreting their complex spatiotemporal data remains a challenge. Existing order parameters face limitations, such as failing to account for directional alignment or lacking sufficient spatial resolution, preventing them from accurately capturing the anisotropic and heterogeneous characteristics of nucleation or the surface phenomena of polymer crystallization. We introduce a novel set of local order parameters—namely, directional entropy bands— that extend scalar entropy-based descriptors by capturing first-order angular moments of the local entropy field around each particle. We compare these against conventional metrics (entropy, the crystallinity index, and smooth overlap of atomic positions (SOAP) descriptors) in equilibrium MD simulations of polymer crystallization. We show that (i) scalar entropy bands demonstrate advantages compared to SOAP in polymer phase separation at single-snapshot resolution and (ii) directional extensions (dipole projections and gradient estimates) robustly highlight the evolving crystal–melt interface, enabling earlier nucleation detection and quantitative surface profiling. UMAP embeddings of these 24–30D feature vectors reveal a continuous melt–surface–core manifold, as confirmed by supervised boundary classification. Our approach is efficient and directly interpretable, offering a practical framework for studying polymer crystallization kinetics and surface growth phenomena. Full article

Hydrate-based CO₂ sequestration is considered one of the most promising methods in the field of carbon capture, utilization, and storage. The abundant fractured environments in marine sediments provide an ideal setting for the sequestration of CO₂ hydrate. Investigating the kinetics and morphological characteristics of CO₂ hydrate formation within fractures is a critical prerequisite for achieving efficient and safe CO₂ sequestration using hydrate technology in subsea environments. Based on the aforementioned considerations, the kinetic experiments on the formation, dissociation, and reformation of CO₂ hydrates were conducted using a high-pressure visualization experimental system in this study. The kinetic behaviors and morphological characteristics of CO₂ hydrates within sandstone fractures were comprehensively investigated. Particular emphasis was placed on analyzing the effects of fracture width, type, and surface roughness on the processes of hydrate formation, dissociation, and reformation. The experimental results indicate the following: (1) At a formation pressure of 2.9 MPa, the 10 mm width fracture exhibited the shortest induction time, the longest formation duration, and the highest hydrate yield (approximately 0.52 mol) compared to the other two fracture widths. The formed CO₂ hydrates exhibited a smooth, thin-walled morphology. (2) In X-type fractures, the formation of CO₂ hydrates was characterized by concurrent induction and dissolution processes. Compared to I-type fractures, the hydrate formation process in X-type fractures exhibited shorter formation durations and generally lower hydrate yields. (3) An increase in fracture roughness enhances the number of nucleation sites for the formation of hydrates. In both fracture types (I-type and X-type), the induction time for CO₂ hydrate formation was nearly negligible. However, a significant difference in the trend of formation duration was observed under varying roughness conditions. (4) Hydrate dissociation follows a diffusion-controlled mechanism, progressing from the fracture walls towards the interior. The maximum gas production was achieved in the 10 mm-width fracture, reaching 0.24 mol, indicating optimal heat and mass transfer conditions under this configuration. (5) During the reformation process, the induction time was significantly shortened due to the “memory effect.” However, the hydrate yield after the reformation process remained consistently lower than that of the first formation, which is primarily attributed to the high solubility of CO₂ in the aqueous phase. Full article

The kinetics and evolution of hydrogen-induced cracking (HIC) were modeled using a theoretical model developed by Gonzalez to calculate the individual crack growth rate and a computational algorithm based on a Poisson distribution to generate the initial spatial distribution of HIC nuclei. Additionally, the Monte Carlo method was used to model the interconnection of individual HIC cracks. The results of the computational model were compared versus experimental results of HIC induced by cathodic charging experiments in low-carbon steel plates. The model was capable of accurately emulating the kinetics of HIC, considering the first stage of nucleation and growth of randomly dispersed individual HIC cracks, followed by a second stage where the individual cracks interconnect with each other to form large cracks that subsequently grow. The study was complemented with the fractographic examination of the HIC cracks to verify if the fracture mechanism is consistent with the crack morphology and propagation mode in the proposed model. The results indicate that HIC propagation occurs by cleavage and quasi-cleavage mechanisms, with crack interconnection by ductile shear tearing, where the driving force for HIC is the accumulated hydrogen pressure within the internal HIC cracks, explaining why the crack growth rates are nearly constant in each stage of HIC growth. Full article

Objectives: Transforming poorly soluble crystalline drugs into their amorphous form is a well-established strategy in pharmaceutical science to enhance their solubility and improve their clinical efficacy. However, developing amorphous forms of organic drugs for pharmaceutical applications presents significant technical hurdles due to the lack of suitable analytical tools for the amorphization process. Carbamazepine is a crystalline BCS class II drug commonly used for epilepsy and trigeminal neuralgia, whose clinical efficacy is compromised by its low solubility and slow dissolution. Therefore, this study focuses on investigating the amorphization of carbamazepine to enhance its solubility by using a micro-droplet precipitation system. Methods: These micro-droplets serve as individual reactors, enabling homogeneous nucleation for precipitation of carbamazepine. During crystallization, carbamazepine undergoes an intermediate liquid–liquid phase transition characteristic of two-step nucleation. By varying the solvent’s composition (methanol/water), we characterized the kinetics and stability of the intermediate liquid phase under various conditions. Results: Our results indicate that carbamazepine can undergo either a one-step liquid-to-amorphous-solid phase transition or a two-step liquid-to-crystalline-solid phase transition. Notably, both transitions pass through a liquid-to-dense-liquid phase separation process starting from the supersaturated solution, where the generated intermediate phases exhibit different sizes and numbers that are influenced by the solvent and its concentration. Conclusions: Our findings not only elucidate the mechanism underlying the carbamazepine phase transition but also propose a novel method for studying the amorphous process, which could be broadly applicable to other poorly soluble pharmaceutical compounds and may be helpful to amorphous formulations production, potentially offering significant improvements in drug efficacy and patient compliance. Full article

The kinetics of insulin aggregation and fibril formation were studied in vitro using Scanning Electron Microscopy (SEM) and Fourier Transform Infrared (FTIR) spectroscopy. Our investigation centered on the protein’s morphological and structural changes to better understand the transient molecular configurations that occur during the lag phase. SEM images showed that, already at early incubation stages, a network of disordered pseudo-filaments, ranging in length between 200 and 500 nanometers, develops on the surface of large aggregates. At later stages, fibrils catalyzed by protein aggregates were observed. Principal Component Analysis (PCA) of the FTIR data identified signatures of intramolecular β-sheet secondary structures forming during the lag phase and at the onset of the exponential growth phase. These absorption bands are linked to secondary nucleation mechanisms due to their transient nature. This interpretation is further supported by a chemical equilibrium model, which yielded a reliable secondary nucleation rate constant, K₂, on the order of 10⁴ M⁻² s⁻¹. Full article