Crystallization Step Research Articles

Crystal Step‐Induced Uniform and Rapid Deposition on Zinc Anodes

AbstractAqueous Zn‐ion batteries have emerged as promising candidates for large‐scale energy storage owing to their high safety and low cost. However, dendrite growth and side reactions compromise the stability of the Zn anode in practical applications. Here, a novel Zn anode featuring well‐designed crystal steps along the (002) facets, referred to as Step‐Zn is introduced. The intersections of the (002) and (100) planes in these crystal steps create preferential adsorption sites for Zn2⁺ ions, promoting initial electro‐epitaxial growth of Zn that uniformly covers the crystal steps. This process effectively regulates subsequent Zn deposition, ensuring fast reaction kinetics and smooth morphology without dendrite formation. Consequently, the unique Step‐Zn anode exhibits excellent cycle life over 6000 times at 3 mA cm−2 and low greatly reduced polarization voltage under high areal currents and capacities. Integrated with activated carbon (AC) cathode, the Step‐Zn||AC full cell demonstrates excellent durability over 10 000 cycles at 5 A g−1. This work offers valuable insights into controlling Zn deposition modes by engineering the surface microstructure of Zn anodes with greatly extended cycling stability.

Monitoring the dynamics of nanozeolite formation by combined in situ coherent small angle X-ray scattering techniques

Understanding the dynamics of zeolite formation is key to synthesising high-quality zeolitic materials with controllable properties, in order to develop more efficient and performant materials. X-ray photon correlation spectroscopy (XPCS) using coherent X-rays offers new possibilities for in situ observation of nano to micron-scale fluctuation dynamics during crystal growth. An in situ cell, which is capable of collecting time-resolved coherent X-ray scattering data under hydrothermal conditions has been developed and used to study, by in situ XPCS combined with small and wide angle X-ray scattering, zeolite formation and dynamics. Analysis of the results using two-time correlations enables to accurately identify the successive growth and crystallisation steps, revealing the dissolution process of the LTA topology during the SOD growth. This approach opens a powerful new avenue for studying the dynamics of nanomaterials formation, phase transitions and growth processes under in situ conditions that will enable profound insights into the nanoscale synthesis mechanisms.

Step height measurement of monoatomic silicon crystal lattice steps with a commercial atomic force microscope

Abstract Precise control of advanced materials relies on accurate dimensional metrology at the sub-nanometre scale. At this scale, the accuracy of scanning probe microscopy (SPM) has been limited by the lack of traceable transfer standard artefacts with calibration structures of suitable dimensions. With the adoption in 2019 of the silicon crystal lattice spacing as a secondary realization of the metre in the International System of Units (SI), SPM users have direct access to a realization of the SI metre at the sub-nanometre level by means of the step height of self-assembled monatomic lattice steps that can form on the surface of silicon crystals. A key challenge of successfully adopting this pathway is establishing the need for established protocols to minimize measurement errors and artifacts in routine laboratory use.
In this study, step height measurements of monoatomic lattice steps in an ordinal/staircase structure on a Si(111) crystal surface have been derived from images acquired with a commercially available, research-level atomic force microscope (AFM). Measurement results derived from AFM images using three different SPM image processing and analysis software packages are compared. Significant sources of measurement uncertainty are identified; principally the contribution from the dependence on scan direction. The calibration of the
AFM derived from this measurment was used to traceably measure the sub-nanometre lattice steps on a silicon carbide crystal surface to demonstrate the viability of this calibration pathway.

Improved Extraction of Crocin and Comprehensive Evaluation of its Physicochemical, Biological, and Functional Properties

Crocin, as a valuable metabolite of saffron, encompasses numerous nutritional, pharmacological, and medicinal properties suitable for different applications. This study aimed to effectively extract crocin compounds with high yield and quality from saffron stigma and comprehensively investigate their various physicochemical and functional properties. To this end, the modified solvent extraction method was used for crocin extraction and its different functional and physicochemical properties were investigated using various characterization techniques. The functional and biological properties of the resultant crocins in terms of antioxidant activity, antibacterial potency, anti-tyrosinase property, and cytotoxicity were investigated. According to the results, a high extraction yield and purity for extracted samples (19.6% and 13.4% production yield and 78% and 98.4% purity in the first and second crystallization steps, respectively) were obtained using the green, environmentally friendly, and sustainable crystallization method. The coloring index, bitterness, and aromatic power of the extracted crocin were comparable with the standard crocin. Morphological, structural, and thermal properties of the extracted crocin from different analytical methods confirmed its preserved composition and structure through the solvent extraction process. Moreover, a desired antioxidant activity by the DPPH, superoxide, hydroxyl radical scavenging, and reducing power assays were observed for resultant crocin products. In the antibacterial and cytotoxicity assays, a 5 mg/mL minimum inhibitory concentration (against Gram-positive and Gram-negative bacteria) and more than 95% cell viability (toward the NIH 3T3 cell line) were recorded, respectively. A potent anti-tyrosinase activity (IC50 = 73.93 μg/mL) with a significant reduction in the melanin production of the B16F10 cell line also was noticed for the obtained crocin products.

Protocrystallinity of Monodispersed Ultra-Small Templated Mesoporous Silica Nanoparticles.

Monodisperse and semi-faceted ultra-small templated mesoporous silica nanoparticles (US-MSNs) of 20-25 nm were synthesized using short-time hydrolysis of tetraethoxysilane (TEOS) at room temperature, followed by a dilution for nucleation quenching. According to dynamic light scattering (DLS), a two-step pH adjustment was necessary for growth termination and colloidal stabilization. The pore size was controlled by cetyltrimethylammonium bromide (CTAB), and a tiny amount of neutral surfactant F127 was added to minimize the coalescence between US-MSNs and to favor the transition towards internal ordering. Flocculation eventually occurred, allowing us to harvest a powder by centrifugation (~60% silica yield after one month). Scanning transmission electron microscopy (STEM) and 3D high-resolution transmission electron microscopy (3D HR-TEM) images revealed that the US-MSNs are partially ordered. The 2D FT transform images provide evidence for the coexistence of four-, five-, and sixfold patterns characterizing an "on-the-edge" crystallization step between amorphous raspberry and hexagonal pore array morphologies, typical of a protocrystalline state. Calcination preserved this state and yielded a powder characterized by packing, developing a hierarchical porosity centered at 3.9 ± 0.2 (internal pores) and 68 ± 7 nm (packing voids) of high potential for support for separation and catalysis.

Process development in Quality‐by‐Design paradigm for anti‐solvent aided crystallization: impact of crystallization parameters on particle morphology and dissolution behaviour of Dexlansoprazole active pharmaceutical ingredient

AbstractBACKGROUNDIn this work, a process development study for the crystallization step of dexlansoprazole API has been demonstrated under the Quality‐by‐Design (QbD) paradigm. Dexlansoprazole (crystalline) samples prepared under different crystallization conditions of reactor temperature and addition time of anti‐solvent were subjected to solid‐state characterization with variety of analytical techniques, including X‐ray powder diffraction (XRPD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic vapour sorption (DVS), scanning electron microscopy (SEM), particle size distribution (PSD) by laser diffraction and intrinsic dissolution rate (IDR).RESULTSThe crystalline samples were observed to have identical polymorphic phase integrity but differed in their physical characteristics. The particle size distribution and microscopy data collectively elucidated the particle growth kinetics and the extent of agglomeration could be correlated to crystallization conditions, namely reactor temperature and addition time of anti‐solvent. The intrinsic dissolution rate of samples was in good agreement with the morphological properties.CONCLUSIONAn empirical model has been proposed for intrinsic dissolution rate correlating with crystallization process parameters. In conclusion, it was possible to elucidate the impact of crystallization parameters on the solid‐state behaviour of dexlansoprazole for development of appropriate pharmaceutical dosage forms. © 2024 Society of Chemical Industry (SCI).

In-situ observation of DL-alanine crystallization from a laser-trapped dense liquid droplet as a heterogeneous nucleation site

Abstract Nucleation from an aqueous solution is an important step in crystallization which controls the physicochemical properties of crystalline materials. Although dense liquid droplets are considered as a precursor of a crystal in the two-step nucleation model, their actual role is unclear. Our in-situ microscopic observations of the crystallization of DL-alanine from a dense liquid droplet trapped by laser tweezers show that liquid droplets play the role of a substrate, facilitating heterogeneous nucleation, rather than a precursor of a crystal.

Efficient estimation of crystal filterability using the discrete element method and the Kozeny-Carman equation

A new method is proposed for efficiently predicting filter cake resistance as a function of crystal size distribution. The method is useful for the preliminary design of processes where an economic tradeoff is encountered between a crystallization step and a filtration step. In that case it is necessary to estimate the filter cake resistance repeatedly as a function of crystal size distribution for the process design and optimization. The method is faster than CFD-DEM and more precise than the random packing assumption. The proposed method is validated using published experimental data. To demonstrate the proposed method, an integrated crystallization-filtration process of ammonium alum is simulated and analyzed. The results show that by increasing the residence time of ammonium alum crystals in the crystallizer from 15 min to 60 min, the crystal cake resistance can be reduced by 42% and the filter area can be reduced by 23%.

Defect-regulated synthesis of ZrB2 powders via carbon thermal reduction and elucidation of its hot-pressing densification mechanism

Through defect modulation, ZrB2 powder was controllably synthesized using the carbon thermal reduction (CTR) method, with boron powder serving as a novel additive. Thermodynamic data for the ZrO2-B2O3-C system in the presence of boron were calculated using HSC thermodynamic software. Additionally, TG-DSC thermal analysis combined with XRD was used to investigate the reaction process. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) were used to analyze the defect structure and grain surface characteristics of the reaction products. The results indicate that the reaction of B with ZrO2 and C exothermically alters the nucleation environment of ZrB2 grains. The helical dislocations generated act as a source of crystal growth steps, promoting the growth of smooth interfaces and leading to a transformation of the ZrB2 grain growth mechanism. Quantitative calculations of the dislocation density of ZrB2 powders, using the convolutional multiple whole profile fitting (CMWP-fit), suggest that the inclusion of boron as an additive can modulate the defect concentration of the products. ZrB2 powders with varied dislocation densities were achieved through meticulously controlled synthesis methods, followed by subsequent densification via hot pressing sintering. The results indicated that the relative density of ZrB2 ceramics increased from 83.9 % to 96.7 % as the dislocation density of the powder increased from 2.7 × 1013 m−2 to 7.6 × 1014 m−2 with the rise in boron content from 0 wt% to 3 wt%. In addition, the defects create extra sintering-driving forces that induce a shift in the densification mechanism from grain boundary diffusion to dislocation slip during hot-pressing sintering. This shift results in an increase in the apparent activation energy from 105 kJ/mol to 210 kJ/mol.

Interaction of microorganisms with carbonates from the micro to the macro scales during sedimentation: Insights into the early stage of biodegradation

The assembly process of Organic Matter (OM) from single molecules to polymers and the formation process of Ca–CO3 ion-pairs are explored at the micro-scale, and then the relationship between OM and carbonate based on the results of microbially-induced carbonate precipitation (MICP) laboratory experiments is established at the macro-scale. Molecular dynamics (MD) is used to model the assembly of OM (a) in an aqueous solution, (b) on surfaces of calcite (10 1‾ 4) crystals and (c) on defective calcite (101‾ 4) crystal surfaces. From the MICP experiments, carbonate minerals containing abundant OM were precipitated and were characterized by Scanning Electron Microscopy (SEM), X-Ray Diffractometry (XRD) and Fourier Transform Infrared Spectroscopy (FTIR). The results of the MD show that OM is assembled into polymers in all three simulation systems. Although the Ca–CO3 ion-pairs and OM were briefly combined, the aggregation assembly of OM molecules and the precipitation of carbonate calcium are not related in the long run. The highly specific surface area of the defective calcite shows an increase in the adsorption of OM. The van der Waals forces, which are primarily responsible for controlling the assembly of OM molecules, increase with the degree of aggregation. According to the MICP experiments, OM is enriched on the mineral surfaces, and more OM is found at the steps of defective crystals with their larger surface areas. Through MD and MICP laboratory experiments, this work systematically describes the interaction of OM and carbonate minerals from the micro to the macro scales, and this provides insight into the interaction between OM and carbonates and biogeochemical processes related to the accumulation of OM in sediments.

Solute interaction-driven and solvent interaction-driven liquid-liquid phase separation induced by molecular size difference.

We conducted molecular dynamics (MD) simulations in a binary Lennard-Jones system as a model system for molecular solutions and investigated the mechanism of liquid-liquid phase separation (LLPS), which has recently been recognized as a fundamental step in crystallization and organelle formation. Our simulation results showed that LLPS behavior varied drastically with the size ratio of solute to solvent molecules. Interestingly, increasing the size ratio can either facilitate or inhibit LLPS, depending on the combination of interaction strengths. We demonstrated that the unique behavior observed in MD simulation could be reasonably explained by the free energy barrier height calculated using our thermodynamic model based on the classical nucleation theory. Our model proved that the molecular size determines the change in number of interaction pairs through LLPS. Varying the size ratio changes the net number of solute-solvent and solvent-solvent interaction pairs that are either broken or newly generated per solute-solute pair generation, thereby inducing a complicated trend in LLPS depending on the interaction parameters. As smaller molecules have more interaction pairs per unit volume, their contribution is more dominant in the promotion of LLPS. Consequently, as the size ratio of the solute to the solvent increased, the LLPS mode changed from solute-related interaction-driven to solvent-related interaction-driven.

Influence of Peptoid Sequence on the Mechanisms and Kinetics of 2D Assembly.

Two-dimensional (2D) materials have attracted intense interest due to their potential for applications in fields ranging from chemical sensing to catalysis, energy storage, and biomedicine. Recently, peptoids, a class of biomimetic sequence-defined polymers, have been found to self-assemble into 2D crystalline sheets that exhibit unusual properties, such as high chemical stability and the ability to self-repair. The structure of a peptoid is close to that of a peptide except that the side chains are appended to the amide nitrogen rather than the α carbon. In this study, we investigated the effect of peptoid sequence on the mechanism and kinetics of 2D assembly on mica surfaces using in situ AFM and time-resolved X-ray scattering. We explored three distinct peptoid sequences that are amphiphilic in nature with hydrophobic and hydrophilic blocks and are known to self-assemble into 2D sheets. The results show that their assembly on mica starts with deposition of aggregates that spread to establish 2D islands, which then grow by attachment of peptoids, either monomers or unresolvable small oligomers, following well-known laws of crystal step advancement. Extraction of the solubility and kinetic coefficient from the dependence of the growth rate on peptoid concentration reveals striking differences between the sequences. The sequence with the slowest growth rate in bulk and with the highest solubility shows almost no detachment; i.e., once a growth unit attaches to the island edge, there is almost no probability of detaching. Furthermore, a peptoid sequence with a hydrophobic tail conjugated to the final carboxyl residue in the hydrophilic block has enhanced hydrophobic interactions and exhibits rapid assembly both in the bulk and on mica. These assembly outcomes suggest that, while the π-π interactions between adjacent hydrophobic blocks play a major role in peptoid assembly, sequence details, particularly the location of charged groups, as well as interaction with the underlying substrate can significantly alter the thermodynamic stability and assembly kinetics.

Quantitative in situ synchrotron X-ray analysis of the ALD/MLD growth of transition metal dichalcogenide TiS2 ultrathin films.

We present the results of a full quantitative analysis of X-ray absorption spectroscopy (XAS) performed in situ during the growth of ultrathin titanium disulfide (TiS2) films via an innovative two-step process, i.e. atomic layer deposition/molecular layer deposition (ALD/MLD) followed by annealing. This growth strategy aims at separating the growth process from the crystallization process by first creating an amorphous Ti-thiolate that is converted later to crystalline TiS2via thermal annealing. The simultaneous analysis of Ti and S K-edge XAS spectra, exploiting the insights from density functional theory calculations, allows us to shed light on the chemical and structural mechanisms underlying the main steps of growth. The nature of the bonding at the base of the interface creation with the SiO2 substrate is disclosed in this study. Evidence of a progressive incorporation of S in the amorphous Ti-thiolate is given. Finally, it is shown that the annealing step plays a critical role since the transformation of the Ti-thiolate into nanocrystalline TiS2 and the loss of S are simultaneously induced, validating the two-step synthesis approach, which entails distinct growth and crystallization steps. These observations contribute to a deeper understanding of the bonding mechanism at the interface and provide insights for future research in this field and the generation of ultra-thin layered materials.

Nucleation, crystal growth, nuclei stability, and polymorph selection in supercooled tolbutamide melt.

Nucleation is an essential step of overall crystallization, yet crystal nuclei are elusive to direct observation due to their small size and transient nature. A method for assessing the nuclei size distribution and growth rate based on selective melting/dissolving was developed recently, making use of the rapid heating/cooling rate available in fast scanning calorimetry. The method was first employed to study the nuclei in the polymer poly-L-lactic acid. Here we investigate the crystal nuclei of tolbutamide, a molecular compound. We show that while the general behavior of tolbutamide is compatible with the classic nucleation theory (CNT) and is in agreement with previous results for poly-L-lactic acid, there are some peculiarities. First, tolbutamide nuclei display extreme thermal stability, surviving heating above the melting onset of the polymorph forming at the same conditions. Second, the nuclei size distribution shows a sharp cut-off at the high end of the distribution. Finally, the difference in the growth rate of nuclei and crystals of tolbutamide is even higher (about 5 orders of magnitude) than what was determined for poly-L-lactic acid previously.

Synchrotron X-ray operando study and multiphysics modelling of the solidification dynamics of intermetallic phases under electromagnetic pulses

In this paper, we used synchrotron X-ray radiography and tomography to study systematically and in operando conditions the growth dynamics of the primary Al3Ni intermetallic phases in an Al-15wt%Ni alloy in the solidification process with magnetic pulses of up to 1.5 T. The real-time observations clearly revealed the growth dynamics of the intermetallics in time scale from millisecond to minutes, including phase growth instability, side branching, fragmentation and orientation alignment under different magnetic pulse fluxes. A multiphysics numerical model was also developed to calculate the alternating and cyclic Lorentz forces and stresses acting on the Al3Ni phases and the nearby melt due to the applied pulses. Combining the results of the operando experiments and modelling, for the first time, the differential forces between the growing Al3Ni phases and the nearby melt were quantified. The forces can create slip dislocations at the growing crystal front which can further develop into nm and µm crystal steps for initiating phase branching. Furthermore, the magnitudes of the shear stresses are strongly related to the size, morphological and geometric features of the growing Al3Ni phases. Dependent on the magnitude of the shear stresses, phase fragmentation could occur in a single pulse period or in multiple pulse periods via fatigue mechanism. This systematic research work elucidate some of the long-time debated hypotheses concerning intermetallic phases growth instability and phase fragmentation in pulse magnetic fields. The research establishes a robust theoretical framework for quantitative understanding of the intermetallic phase growth dynamics in solidification under pulse magnetic fields.

Crystallization kinetics and nanoindentation studies of Cu46Zr40Ti8.5Al5.5 glassy alloy

Crystallization kinetics of Cu46Zr40Ti8.5Al5.5 metallic glass is investigated in non-isothermal and isothermal conditions. In non-isothermal condition, the crystallization activation energy is determined using Kissinger's method. Further, activation energy of reported Cu-Zr-Al metallic glasses are compared with Cu46Zr40Ti8.5Al5.5 alloy to understand the effect of Ti addition on crystallization kinetics. Detailed investigation on activation energy through the crystallization process is studied. To understand the influence of nucleation and growth mechanism during the crystallization steps, samples are heated in isothermal conditions at various annealing temperatures in supercooled liquid region to determine the local Avrami's exponent using Johnson-Mehl-Avrami equation. Additionally, small scale mechanical response is noted on metallic glass sample to determine the influence of structure on hardness and elastic modulus. Nanoindentation results showed hardness value of 5.39 ± 0.09 GPa and Young's modulus of 92.81± 0.52 GPa.

A novel method for preparing ultrafine molybdenum‑rhenium alloy powders

To address the issues of large particle size and poor particle size uniformity in the traditional two-step hydrogen reduction method for preparing molybdenum‑rhenium alloy powders, this study innovatively employed glucose as the carbon source and successfully prepared ultrafine molybdenum‑rhenium alloy powders through wet-wet mixing, evaporative crystallization, calcination, carbothermal pre-reduction, and hydrogen deep reduction steps. The results demonstrate that when the C/(Mo + Re) molar ratio is 0.7, the powders synthesized through carbon‑hydrogen synergistic reduction exhibit a spherical shape, with particle sizes distributed in the sub-micrometer range and an average particle size of 173 nm. The phase composition of the reduction powders consists predominantly of molybdenum, rhenium and χ phases, with a uniform distribution of alloy elements. In contrast, the powders synthesized using the traditional two-step hydrogen reduction method exhibit irregular, porous and loosely-packed structures, with particle sizes in tens of microns range and slightly larger than those of the precursor. This method is highly suitable for preparing high-purity, ultrafine, and highly homogeneous binary alloy powders, like MoRe, MoW, WRe, ect.

Precursor-directed production of water-soluble red Monascus pigments with high thermal stability via azaphilic addition reaction-based semi-synthesis

Red Monascus pigments (MPs) are a large group of polyketides from the fungus Monascus which have been widely used as food colorants. In this study, a variety of red MPs congeners were prepared to explore promising water-soluble candidates for application in liquid food formulations. The results showed that by combining the two-stage, low-pH fermentation strategy with a downstream purification step of fractional crystallization, precursors of red MPs, namely monascorubrin and rubropunctatin, were obtained with a purity of 91.9%. Then, via the azaphilic addition reaction, 18 types of red MPs congeners carrying different amino acid moieties (MPs-aa) were semi-synthesized. Compared to rubropunctamine and monascorubramine, the water solubility, pH and thermal stability of MPs-aa were improved greatly. MPs-His, MPs-Phe, MPs-Tyr and MPs-Trp were identified to be the most resistant to pasteurization. These findings provide water-soluble red MPs candidates with high thermal stability and an attractive approach for their large scale production.

Simultaneous removal of multi-nuclide (Sr2+, Co2+, Cs+, and I-) from aquatic environments using a hydrate-based water purification process

This study investigates the removal characteristics of a hydrate-based water purification process used to remove the major radionuclides monitored in nuclear accident areas. The effect of the coexistence of salt ions on the removal of radioactive materials is also evaluated. Previous studies have found existing processes such as ion exchange and membrane separation to be reliable methods for radionuclide removal from contaminated water. However, these processes cannot remove all contaminants at once and cause additional environmental problems by generating secondary wastes. In a previous study, we observed that water purification by the gas hydrate process could simultaneously remove various ions from seawater and hypersaline water in a single step without pre- or post-treatment. Therefore, the removal characteristics of Sr2+, Co2+, Cs+, and I- radionuclides are evaluated in only one context: the hydrate-based water purification process. More than 85% of the total ions were simultaneously removed regardless of the presence or absence of coexisting ions, and the time required for the removal process was about 70 min. In addition, it was observed that most of the contaminant ions were attached to hydrate crystal surfaces. Therefore, an efficient purification process is proposed that includes a hydrate crystal exterior partial dissolution step.

Physical properties of cocoa butter: effect of sucrose esters on oil migration

SummaryIt is known that emulsifiers can modify the crystallisation behaviour of fats, improving their stability. In this sense, changes in the crystallisation behaviour of cocoa butter (CB) may contribute to reducing oil migration through its crystalline structure. This study analysed the effect of adding sucrose stearate (S‐370) and sucrose behenate (B‐370) emulsifiers at different concentrations on oil migration in CB. The compatibility diagram curves indicated a miscible phase behaviour between CB and the emulsifiers S‐370 and B‐370 at concentrations of 0.1%, 0.3% and 0.5%, confirming the compatibility between its components. There is a significant difference (P ≤ 0.05) for the melting point of mixtures containing 0.3% and 0.5% of S‐370, yet we can consider that all samples reach their total melting point at 35 °C. However, the samples containing S‐370 showed a higher firmness profile than those containing B‐370, corroborating the results of compatibility and melting point. CB exhibited characteristic two‐step isothermal crystallisation at 17.5 °C, with distinct effects of the emulsifiers for each crystallisation step. S‐370 and B‐370 modify the solid dissolution process and oil migration through cocoa butter. The physical properties of CB were altered by adding S‐370 and B‐370. The oil migration process differed for each emulsifier, although diffusion, the identified migration mechanism, is the same for both.