To obtain a given structure in 3D building-up modes, it is necessary to use optimal surfacing modes that determine the amount of heat input in local areas. For this purpose, aluminum bronze was surfacing onto a deformed base and the structure and its characteristics in the surfacing and heat-affected zones were studied by the EBSD method. The heterogeneity of the formation of the structure in each selected zone is established, which indicates the heterogeneity of heat input in local areas of the material in one mode of surfacing. For typical cases of crystallization, a molecular dynamics simulation of crystallization processes with different heat input to the base with characteristics specified based on experimental data was carried out. It has been established that the amount of heat input determines the degree of melting and the inherited defectiveness of growing crystals. The formation of misorientation boundaries and crystallization centers of new grains is determined by the conditions of joint growth of grains with given crystallographic parameters of the computational model. Numerical calculations agree with the experimentally observed results.

Grazing incidence X-Ray Diffraction spectroscopy was employed to characterize crystallinity of Iron, Nickel, Copper and Tungsten, prepared by sparking discharge process in presence of 0.4 T magnetic field at ambient temperature 25 °C. Iron thin film preserved crystallinity even after one year of ageing. Nickel exhibit higher crystallinity when sparked in nitrogen gas flow from the one sparked in oxygen. Tungsten was successfully crystalized after just 40 minutes of sparking inside of magnetic field.

Crystallization behavior of hexadecane (C₁₆H₃₄), octadecane (C₁₈H₃₈), eicosane (C₂₀H₄₂), and docosane (C₂₂H₄₆) dispersions of similar mean droplet diameter (x_50.2 ≈ 15 µm) was investigated in quiescent systems and compared to crystallization under mechanical stress. In quiescent systems, the required supercooling decreased with increasing chain length of the alkanes to initiate crystallization. Crystallization of alkane dispersions under mechanical stress resulted in similar onset crystallization supercooling, as during quiescent crystallization. Increase of mechanical stress did not affect the onset crystallization supercooling within alkane dispersions.

This paper deals with the viscoelastic behavior during crystallization and melting of semicrystalline polymers with the aim of later modeling the residual stresses after processing in case where crystallization occurs in quasi static conditions (in additive manufacturing for example). Despite of an abundant literature on polymer crystallization, the current state of scientific knowledge does not yet allow ab initio modeling. Therefore, an alternative and pragmatic way has been explored to propose a first approximation of the impact of crystallization and melting on the storage and the loss moduli during crystallization-melting-crystallization cycle. An experimental approach, combining DSC, optical microscopy and oscillatory shear rheology was used to define macroscopic parameters related to the microstructure. These parameters have been integrated into a phenomenological model. Isothermal measurements were used to describe the general framework, and crystallization at a constant cooling rate was used to evaluate the feasibility of a general approach. It can be concluded that relying solely on the crystalline fraction is inadequate to model the rheology. Instead accounting for the microstructure at the spherulitic level could be more useful. Additionally, the results obtained from the experiments help to enhance our understanding of the correlations between crystallization kinetics and its mechanical effects.

Crystallization of glass through conventional thermal annealing in a furnace is a well-understood process. However, crystallization by femtosecond (fs) laser brings another dimension to this process. The pulsed nature of the irradiation necessitates a reevaluation of parameters for optimal crystallization and to understand the particularities in the case of using fs laser. This includes adjusting the laser pulse energy, the repetition rate, and the writing speed to either initiate nucleation or achieve substantial crystal growth. Therefore, a key challenge to this work is to establish reliable calculations for understanding the relation of the size of the crystallized region with respect to an ongoing transition (e.g., solid-to-solid, liquid-to-solid), and accounting for the aforementioned laser parameters. In this context and based on previous work, we simulate a temperature distribution (in space and time) to model the thermal treatment at any point in the glass. By setting the condition that the temperatures are between the glass transition and melting temperature, we can deduce the crystallized region size to be compared with experimental observations. For that purpose, the knowledge of the beam width at the focal point and of the absorbed beam energy fraction are critical inputs that were extracted from experiments found in the literature. After that, management of the crystallization process and the width of the crystallization line can be achieved according to pulse energy e.g. crystallite size, and also the effect of the scanning speed can be understood. Among the main conclusions to highlight, we disclose the laser conditions that determine the extent of the crystallized area and deduce that it is never interesting to increase the pulse energy too much but rather the repetition rate for uniform crystallized line.

The pharmaceutical industry is undergoing a shift in processing methods for small-scale production (250-1000 kg/a), leading to an increased focus on continuous production research. Various concepts were developed to overcome challenges in small-scale crystallization for the production of high-quality products. However, further optimization is needed to enhance the industrial applicability of these concepts. This study aims to demonstrate the practical applicability of the Slug Flow Crystallizer (SFC) in the pharmaceutical industry by extending its use to a wider range of substance systems for small-scale API production. Employing an experimental strategy, the research seeks to rapidly assess the SFC's potential for achieving uniform, high-purity product yields, emphasizing the importance of factors such as slug flow stability, residence time distribution, and substance-specific crystallization criteria. This, coupled with our previously published model-based strategy, forms a comprehensive methodology to explore crystallization behavior and modeling for a variety of substance systems within the SFC. The ultimate goal of this study is to showcase the practicality of the SFC in the pharmaceutical industry, enabling the way for its reliable use in long-term, small-scale continuous crystallization and the production of high-quality pharmaceutical products.

Bottlebrush (BB) elastomers with water-soluble side chains and tissue-mimetic mechanical properties are promising for biomedical applications like tissue implants and drug depots. This work investigates the microstructure and phase transitions of BB elastomers with crystallizable polyethylene oxide (PEO) side chains by real-time synchrotron X-ray scattering. In the melt, the elastomers exhibit the characteristic BB peak corresponding to the backbone-to-backbone correlation. Upon crystallization of the side chains, the intensity of the peak decays linearly with crystallinity, and eventually vanishes due to BB packing disordering within intercrystalline amorphous gaps. This behavior of the bottlebrush peak differs from an earlier study of BBs with poly(ε-caprolactone) side chains, explained by stronger backbone confinement in the case of PEO, a high-crystallinity polymer. Microstructural models based on 1D SAXS correlation function analysis suggest crystalline lamellae of PEO side chains separated by amorphous gaps of monolayer-like BB backbones.

Recently, there has been a lot of interest in the phenolics of pomegranate peels because of their health-promoting effects. The incorporation of encapsulated phenolic extracts in functional foods, beverages, and dietary supplements can enhance their nutritional and health benefits. This paper aims to provide an overview of the encapsulation of pomegranate peel phenolic extract by co-crystallization, focusing on the properties of the encapsulated extract. Pomegranate peel extract encapsulated in sucrose by co-crystallization at conditions determined in our previous work is characterized by evaluating its properties; moisture content, bulk density, solubility, hygroscopicity, color, degree of encapsulation by thermograms, crystallinity by X-ray scattering, microstructure by scanning electron microscope, and storage stability in terms of total phenolic content and antioxidant activity. The co-crystallized powder had a low moisture content (0.59%) and hygroscopicity (0.011%) and a high bulk density (0.803 g/cm3) and solubility (61 s). Its total phenolic content decreased by only 0.56% after storage at 60oC for 45 days, whereas its antioxidant activity was maintained at levels higher than 84%. The differential scanning calorimetry and the X-ray scattering techniques proved the successful encapsulation in the sucrose matrix and the fact that the extract remained liquid inside the porosity of the sucrose crystals.

This manuscript investigates the dispersion of cetyltrimethylammonium bromide (CTAB) treated cellulose nanocrystals (CNCs) in polypropylene (PP) by melt mixing. FTIR spectra of CTAB-modified CNCs and unmodified CNCs in a PP matrix were used to evaluate the surface treatments. The surface energies and morphologies of CTAB surface modified CNCs in polypropylene (PP) were used to interpret the effects of nanoparticle dispersion on the crystallization and rheological and mechanical properties of the PP matrix.

The hydrothermal synthesis of aluminophosphate molecular sieve type AlPO4-11 was processed from chemicals containing psueudobohemite, 85% phosphoric acid, water, and di-isopropylamine as templating agent. The crystallization of the samples was studied by taking samples in times from 2 to 74 hours. The obtained white powder products have been characterized by XRD patterns, FT-IR spectra, thermogravimetric data, scanning electron microscopy and pH measurement of the mother liquor. The pore volume, as determined from TG and DTG curves, was ca. 0.17 cm3g-1. The crystallization process of the aluminophosphate exhibited in its initial phase a behavior of first order reaction with a specific velocity constant of ca. 0.25 h-1, as determined from XRD and FT-IR data.

Polymer-derived ceramic (PDC) based coatings like Si-C-N and their derivatives are gaining importance day by day in N/MEMS and aerospace due to their thermos-mechanical stability and conductivity. The crystallized, amorphous, and near amorphous morphology of SiCN nanocomposite coatings based on deposition conditions requires thorough investigation for appropriate utilization as they lead to differences in mechanical properties (quantified using nanoindentation in this case). A 4-stage model was proposed based on Raman spectroscopy due to the N₂-Ar pressure variations during the deposition process of SiCN coatings by magnetron sputtering. The integral intensity of the G (graphitic), disorder (D), and tetrahedral (T) peaks namely I_G, I_D, and I_T were calculated after the deconvolution of the spectra. The sp² domain size and defect parameters were evaluated and correlated with the hardness and different bond formation involving Si, C, and N. Image analysis revealed the atomic migration involved during the growth process leading to crystallization along with the formation of voids and defects. The observations were supported by FTIR and TEM-SAED analysis. The outcomes provide a foundation causing an urge to develop similar models with further elemental additions and correlate with various physical properties.

The utilization of natural waxes to form oleogels has emerged as a new and efficient technique for structuring liquid edible oil into solid-like structures for diverse food applications. The objective of this study was to investigate the interaction between sunflower wax (SW) and monoglycerides (MGs) in olive oil oleogels and to assess their physical characteristics and storage stability. To achieve this, pure SW and a combination of SW with MGs in a 1:1 ratio were examined within a total concentration range of 6-12% w/w. The formed oleogels were characterized based on their microstructure, melting and crystallization properties, textural characteristics, and oxidative stability during storage. All the oleogels were shelf-stable, and as the concentration increased, the hardness of the oleogels also increased. The crystals of SW oleogels were long needle-like, while the combination of SW and MGs led to the formation of crystal aggregates and rosette-like crystals. The differential scanning calorimetry and FTIR showed that the addition of MGs led to different crystal structures. The oxidation results revealed that oleogels had low peroxide and TBARS values throughout the 28-day storage. These results provide useful insights about the utilization of SW and MGs oleogels for potential applications in the food industry.

In this paper, a quick and efficient method for preparation of scopolamine hydrobromide with high purity was introduced, named as magnetic field induced crystallization. Based on the solubility difference between scopolamine and scopolamine hydrobromide, salifying crystallization was selected and then treated with the synergistic effect of magnetic field to achieve the aim of scopolamine purification. The effects of crystallization solvents and magnetic field intensity on the crystallization process of scopolamine hydrobromide, as well as the influnence of magnetic field on the crystal growth direction were investigated. The results revealed that after treatment under magnetic field, the shortened induction time (25.64%-75.46%), the increased purity of crystals (0.95%-2.92%) and the improved recovery rate (4.51%-10.78%) were achieved. Furthermore, we also found that magnetic field could destroy the hydrogen bond in the solution, and change the physical properties of the mother liquid, so as to promote the nucleation formation and crystal growth. The above experiments suggested that the external magnetic field has the potential to be a feasible method for scopolamine preparation.

We summarize how to obtain protein crystals from which better diffraction images can be obtained. In particular, we describe in detail the quality evaluation of the protein sample, the crystallization methods and crystallization conditions, the flash-cooling protection of the crystal, and the crystallization under a microgravity environment.

The encapsulation of bacteria in emulsion droplets offer various advantages over other conventional methods of encapsulation such as improvement in bacterial viability and may served as microenvironments for bacterial growth. Nevertheless, changes in temperature may affect bacterial viability and droplet stability. In this study, the encapsulation of bacteria in single water-in-oil (W/O) and double water-in-oil-in-water (W1/O/W2) emulsions was investigated under cold storage with a study on temperature-modulated release. The microencapsulation of bacteria in emulsion droplets was achieved by using a flow-focusing microfluidic device. Droplets stability was determined by measuring changes in droplets size and creaming behaviour at different temperatures. Thermal properties of the samples were determined by using differential scanning calorimetry while the release of bacteria with change in temperature was determined by measuring colony form unit (CFU) of the released bacteria and fluorescence microscopy. Higher bacterial viability was observed for encapsulated samples as compared to free cells indicating the ability of emulsion system in improving the bacterial viability during cold temperature storage. Crystallization temperature was lowered in the presence of bacteria, but the melting temperature was similar with or without bacteria. Storage in freezing temperatures of -20°C and -80°C leads to an extensive droplet destabilization with immediate release of encapsulated bacteria upon thawing in which temperature modulated release of encapsulated bacteria was achieved. This study provides an overview of the potential application of emulsion droplets for encapsulation and controlled release that is beneficial for various applications such as food and pharmaceuticals.

This study provides an in-depth examination of the binary system of n-Nonadecane and 1-Octadecanol, representative of plant cuticular waxes. It emphasizes the crystallization and phase transitions in this hydrocarbon mixture. Using Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared (FTIR) spectroscopy, the research uncovers detailed thermal properties and phase behaviors. The findings reveal the distinct phase transitions and enthalpy changes of each component in the binary system. This research is significant for its implications in under-standing the structural properties of plant waxes. Such insights are crucial for enhancing the effi-ciency of fertilizer and pesticide absorption in plant leaves, with broad applications in bionics and materials science. This study not only furthers the understanding of identifying specific phase transitions for each compound, facing challenges in detecting subtle changes using DSC. The re-search enhances understanding of plant cuticle waxes through FTIR analysis, revealing intricate molecular interactions and structural complexities. but also opens avenues for improved agri-cultural practices and material engineering, potentially influencing future innovations in these fields.

Crystallization often occurs in the laser welding of amorphous alloys, reducing the amorphous alloys’ properties. So, it is necessary to simulate the temperature field curve of the welding area by computer and then determine the power and laser moving speed of laser welding. In this paper, the temperature field curve of Zr41.2Ti13.8Cu12.5Ni10Be22.5(Vit1) amorphous alloy in laser welding is obtained by finite element analysis. The continuous heating curve (CHT) of Vit1 is fitted by the Vogel-Fulcher-Tammann (VFT) equation and the Kissinger equation. If the temperature field curve intersects with the CHT curve, crystallization occurs. The experiment results show that the VFT equation can be used to predict the crystallization of Vit1 better in laser welding. The tem-perature and welding time are increased by using low welding speed. Therefore, the temperature of the weld zone cannot fall in time, resulting intersection of the temperature field curve and the CHT curve. So, crystallization can be avoided if the welding speed is controlled within a rea-sonable range, and the highest temperature is kept under the CHT curve.

In the current research work, electrical resistance tomography (ERT) was employed for crystallization process monitoring and visualization. A first-of-its-kind MATLAB-based interactive GUI application “ERT-Vis” is presented. Two case studies involving varied crystallization methods were undertaken. The experiments involving calcium carbonate reactive (precipitative) crystallization for the high conductivity solution-solute media and the cooling crystallization for sucrose crystallization representing the lower conductivity solution-solute combination were designed and performed. The software successfully provided key insights regarding the process progress in both crystallization systems. It could detect and separate the crystal agglomerations in the low as well as high conductivity solutions using visual analytics tools provided. The performance and utility of the software were studied using a software evaluation case study involving domain experts. Participant feedback indicated that ERT-Vis software helps in reconstructing images instantaneously, interactively visualizing, and evaluating the output of the crystallization process monitoring data.

The Sanshui Basin (SSB) is located at the northern continental margin of the South China Sea and characterized by a continental rift basin. The bimodal volcanic rocks in SSB record the early Cenozoic magmatic activity in the South China Block, on the magmatic evolution process of bimodal volcanic rocks are poorly understood. Clinopyroxenes in bimodal volcanic rocks in the SSB provide an opportunity to investigate the magma process during magma ascent. We classified nine types of clinopyroxene phenocrysts according to the different compositions and textures types in cogenetic basalt-trachyandesite-comenditic trachyte, the composition of unzoned clinopyroxene have an evolution sequence of diopside- hedenbergite- aegirine with the decrease of Mg#, and the trace element contents of unzoned clinopyroxenes also increase systematically during magma evolution, indicating that the genesis of clinopyroxene dominated by fractional crystallization in a closed magma system; however, the clinopyroxenes with reverse zoning and multiple zoning record the process of magma mixing and recharge indicating an open magma system. Whilst fractional crystallization is the dominated process, magma mixing, recharge, and crystal settling complicate magma evolution. Thermobarometric calculations show that clinopyroxene phenocrysts in bimodal volcanic rocks of SSB are distributed in the whole crust during magma ascent. We have established a magma plumbing system, which provides a new constrain for the complex magmatic evolution history in the SSB by detailed mineral-scale analysis.

Presently, nano-crystallization is widely accepted for increasing the solubility and biological barrier permeability of poorly soluble drugs. It improves the bioavailability of therapeutic agents, increasing the effectiveness for treating diseased conditions, and could be safely administered by oral, parenteral, or transdermal routes. Drug nanocrystals are drug particles coated with a thin polymer layer to enhance their stability and could be decorated with ligands for active targeting. In addition, nanocrystals, due to their morphological properties, improve cell internalization. Therefore, passive targeting by high cellular uptake and retention in the mononuclear phagocyte system (MPS) may be expected. Drug nanocrystals are formulated by either top-down or bottom-up methods and could be scaled up for industrial manufacturing. In the past few decades, nanocrystal formulation has been increasingly studied to overcome the limitations of BCS Class II and IV chemotherapeutic agents. The study of cytotoxic effects of drug formulation on cell lines gives an insight for estimating its in-vivo biodistribution. This review highlights the role of morphology, stabilizer, and ligand conjugation on drug targeting and cellular uptake in cancer cells, as well as a brief discussion on nanocrystal production.

As a special class of “green” elastomers, thermoplastic vulcanizates (TPVs) have been widely used in industries due to the combination of the excellent resilience of conventional elastomers and the easy recyclability of thermoplastics. Here, the morphology evolution of TPVs based on polyamide 6/ethylene-propylene-diene rubber (PA6/EPDM) blends was investigated by varying the content of the curing agent, phenolic resin (PF). With the incorporation of 6 wt% PF, the gel content of the EPDM phase reaches a high value of 49.6wt% and a typical sea-island structure is formed with EPDM domain in a micro-nano size. The dynamic rheology behaviors of TPVs showed that with the curing degree of EPDM phase increasing, a denser network of EPDM particles is formed in PA6 matrix. Also, a lower crystal degree and crystal peak temperature are observed, indicating that the presence of a growth restriction of PA6 crystal plate induced by a thinner plastic layer between the adjacent EPDM particles. However, the crystal form of PA6 is not changed with the increasing curing degree of the EPDM phase. This study provides an effective strategy to realize a new kind of TPVs, which can be easily introduced into industrial applications.

: The crystallization conditions from the solution play an important role in determining the mor-phology, phase composition, and photovoltaic properties of perovskite films. Post-processing of the obtained films can have a crucial role in increasing the grain size of perovskite and enhancing its crystallinity. It has been shown that the formation of crystal nuclei can be utilized to accelerate crystallization. In this case, crystallization occurs through the growth of seed crystals created in the solution, enabling the formation of relatively large crystals. For the deposition of CH3NH3PbI3 hybrid halide perovskite films from a solution of the perovskite in dimethylformamide the spin coating technique was employed. Pre-crystallization was achieved by annealing the films at a temperature of 100 or 110 °C. The dissolution process involved adding a drop of dimethylformamide onto the substrate surface and allowing it to partially dissolve the perovskite film. Subsequently, residual solvent was removed through spin coating. The mor-phological analysis of the perovskite film surface after recrystallization at temperatures ranging from 80 to 130 °C was performed. The infrared transmission spectra of the obtained perovskite films were investigated, and their light absorption characteristics were studied through transmission spectra. The perovskite structure in the obtained films was confirmed by the peaks observed in the X-ray diffraction patterns.

Reflux esophagitis, a treatment for gastric ulcers known as Ilaprazole (Ila), is not stable during storage and handling at room temperature, requiring storage at 5 degrees celsius. In this study, to address these issues with Ila, coformers rich in oxygen (O) and hydroxyl (OH) groups capable of forming hydrogen bonds with were selected. These coformers included Xylitol (Xyl), Meglumine (Meg), Nicotinic acid (Nic), L-Aspartic acid (Asp), and L-Glutamic acid (Glu). A 1:1 physical mixture of Ila and each coformer was prepared, and the potential for cocrystal for-mation was predicted using differential scanning calorimetry (DSC) screening. The results indi-cated the potential for cocrystal formation in the Ila/Xyl physical mixture. Subsequently, Ila and Xyl were mixed in ethyl acetate (EA) in a 1:1 ratio, and after 28 hours of slurry, the formation of Ila/Xyl cocrystal was confirmed through solid-state CP/MAS 13C NMR spectrum analysis, showing intermolecular hydrogen bonding and conformational changes. Furthermore, the 1:1 ratio of Ila/Xyl cocrystal was confirmed through solution-state NMR (1H, 13C, and 2D) molecular structure analysis. To assess the stability of Ila/Xyl cocrystal at room temperature, it was stored and com-pared with Ila at 25±2°C and relative humidity (RH) of 65±5% over three months. The results showed that the purity of Ila/Xyl cocrystal remained at 99.8% from the initial purity of 99.75% over the three months, while Ila was predicted to decrease from an initial 99.8% purity to 90% after three months. Additionally, at 25±2°C and RH 65±5%, a specific impurity B in Ila/Xyl cocrystal was observed to be 0.03% over three months, whereas Ila was predicted to increase from an initial 0.032% to 2.28% after three months. To evaluate the dissolution rate of Ila/Xyl cocrystal, a formulation was prepared and compared with Ila at pH 10, with a dosage equivalent to 10mg of Ila. The results showed that Ila/Xyl cocrystal reached 55% within 15 minutes and 100% within 45 minutes, while Ila was predicted to reach 32% at 15 minutes and 100% only after 60 minutes. However, overall, the Ila/Xyl cocrystal showed results equivalent to or exceeding the dissolution rate of Ila. Therefore, it is predicted that the Ila/Xyl cocrystal will maximize its effectiveness as a more convenient crystal structure for formulation development, allowing storage and preservation at room temperature without the need for the problematic 5°C refrigeration during ambient con-ditions and storage, addressing the issues associated with Ila.

The crystallization conditions from the solution play an important role in determining the mor-phology, phase composition, and photovoltaic properties of perovskite films. Post-processing of the obtained films can have a crucial role in increasing the grain size of perovskite and enhancing its crystallinity. It has been shown that the formation of crystal nuclei can be utilized to accelerate crystallization. In this case, crystallization occurs through the growth of seed crystals created in the solution, enabling the formation of relatively large crystals. For the deposition of CH3NH3PbI3 hybrid halide perovskite films from a solution of the perovskite in dimethylformamide the spin coating echnique was employed. Pre-crystallization was achieved by heating films at a temperature of 100 or 110 °C. The dissolution process involved adding a drop of dimethylformamide onto the substrate surface and allowing it to partially dis-solve the perovskite for 30-40 seconds. Subsequently, residual solvent was removed through spin coating. The recrystallization process was carried out by heating films at the temperature range of 80 to 130 °C. The morphological analysis of the perovskite film surfaces after recrystallization at tem-peratures ranging from 80 to 130 °C was performed. The infrared transmission spectra of the obtained perovskite films were investigated, and their light absorption characteristics were studied through transmission spectra. The perovskite structure in the obtained films was con-firmed by the peaks observed in the X-ray diffraction patterns.

Crystallization is a significant procedure in the manufacturing of many pharmaceutical and solid food products. In-situ Electrical Resistance Tomography (ERT) is a novel Process Analytical Tool (PAT) to provide a cheap and quick way to test, visualize, and evaluate the progress of crystallization processes. In this work, the spatial accuracy of the non-conductive phantoms in low conductivity solutions was evaluated. Gauss-Newton, Linear Back Projection, and iterative Total Variation reconstruction algorithms were used to compare the phantom reconstructions for tap water, industrial-grade saturated sucrose solution, and demineralized water. Cylindrical phantom measuring 10 mm in diameter and a cross-section area of 1.5 % of the total beaker area was detected at the center of the beaker. Two phantoms with a 10 mm diameter were visualized separately in non-central locations. The quantitative evaluations were done for the phantoms with radii ranging from 10 mm to 50 mm in demineralized water. Multiple factors such as ERT device and sensor development, FEM mesh density and simulations, image reconstruction algorithms, number of iterations, segmentation methods, and morphological image processing methods were discussed and analyzed to achieve spatial accuracy. The development of ERT imaging modality for the purpose of monitoring crystallization in low conductivity solutions was performed satisfactorily.

Biocompatible and biodegradable poly(butylene succinate-co-adipate) (PBSA)/hexadecylamine-modified PPZn (m-PPZn) nanocomposites were prepared using a melt mixing process. Experimental results of wide-angle X-ray diffraction and transmission electron microscopy revealed that the stacking layers of the m-PPZn were partially intercalated and partially exfoliated into the PBSA polymer matrix. The isothermal crystallization kinetics of PBSA/m-PPZn nanocomposites were studied at the temperature range of 62−70 °C and the half-time for crystallization of 3 wt % PBSA/m-PPZn nanocomposite was reduced by 27−35% compared with that of pure PBSA. This finding suggests that the incorporation of m-PPZn might cause the heterogeneous nucleation and the subsequent crystallization growth, which enhances the isothermal crystallization rate of PBSA/m-PPZn nanocomposite. The biodegradation rates of PBSA using Lipase from Pseudomonas sp. increase as the contents of m-PPZn increase. The degradation behavior of the neat PBSA investigated using the change of weight-average molecular weight belongs to exo-type hydrolysis activity. It is necessary to point out that the change of degree of crystallinity and degradation rate are almost linearly proportional to the loading of hexadecylamine-modified PPZn. This finding would provide an important information for the manufacturing biodegradable PBSA nanocomposites.

The article delves into the intricate phase transitions of 1-Octadecanol and n-Nonadecane within a binary system, unveiling dynamic structural changes under varying conditions. Through Fouri-er-transform infrared (FTIR) analysis, specific molecular vibrations were identified, shedding light on the molecular composition and interactions. The study highlights the challenges in detecting subtle phase transitions and emphasizes the individuality of molecular behaviours in closely related compounds. The findings underscore the complexity of phase transitions in binary systems and advocate for a nuanced approach to studying molecular structures and behaviours. Addi-tionally, the research contributes valuable insights into the molecular dynamics of Organic Polymer Functional Adsorption Materials, offering implications for synthetic waxy layers in plant epidermis.

In this paper, a polyacrylic elastomer latex with butyl acrylate (BA) as the core and methyl methacrylate (MMA) copolymerized with glycidyl methacrylate (GMA) as the shell, named poly(BA-MMA-GMA) (PBMG), was synthesized by seeded emulsion polymerization. Cellulose nanocrystal (CNC) was dispersed in the polyacrylic latex to prepare PBMG/CNC dispersions with different CNC contents. The dried product was mixed with polylactic acid (PLA) to fabricate PLA/PBMG/CNC blends. The addition of PBMG and PBMG/CNC improved the mechanical properties of the PLA matrix. Differential scanning calorimetry (DSC) was used to investigate the non-isothermal crystallization kinetics. The Avrami equation modified by Jeziorny, and the Ozawa, and Mo’s equations were used to analyze the nonisothermal crystallization kinetics of PLA and its blends. Analysis of crystallization halftime of nonisothermal conditions indicated that the overall rate of crystallization increased significantly at 1 wt% content of CNC. This seemed to result from the increase of nucleation density and the acceleration of segment movement in the presence of CNC component. This phenomenon was verified by polarizing microscope observation.

The evaporation of polymer solution droplet is an important in solution-based polymer film fabrications, such as inkjet print, spray coatings, and droplet casting etc. In this work, we investigated the effect of droplet size, solvent evaporation rate, and concentration on “coffee-ring” effect, crystal nucleation, polymorphism, and morphology of dried poly (vinylidene fluoride) (PVDF) solution droplets with atomic force microscopy (AFM) method. We found that the crystal structure, morphology and crystal distribution in the center and edge regions of dried PVDF droplets were different due to “coffee-ring” effect. The “coffee-ring” effect of dried PVDF droplets was mainly composited of accumulated crystals at the edge region of droplet, which was mainly made by crystallization of migrated chains. The interplay between migration of chains, crystallization and solidification of PVDF droplets significantly influenced the formation of “coffee-ring”. In addition, our results showed that the decrease of droplet size and controlling solvent evaporation rate were effective ways to improve the PVDF β-phase nucleation and decrease crystal size.

By means of X-ray computed microtomography (XCMT) the existence of a developed microporous structure having an average pore diameter of ~3.5 μm and pore content of ~1.1 vol.% has been revealed in unirradiated polytetrafluoroethylene (PTFE). It has been found that the combined action of gamma radiation (absorbed dose per PTFE of ~170 kGy) and high temperatures (327-350 °C) leads to the disappearance of the microporous structure and the formation of several large pores with sizes from 30 to 50 μm in the bulk of thermal-radiation modified PTFE (TRM-PTFE). It has been established by X-ray diffraction (XRD) analysis that the thermal-radiation modification of PTFE leads to an increase in the interplanar spacings, the degree of crystallinity and volume of the unit cell, as well as to a decrease in the size of crystals and the X-ray density of the crystalline phase in comparison with the initial polymer. It is assumed that the previously established effect of improving the deformation-strength and tribological properties of the TRM-PTFE can be due not only to the radiation cross-linking of polymer chains but also to the disappearance of the micropore system and to the ordering of the crystalline phase of PTFE.

We report interfacial crystallization in droplets of saline solutions placed on superhydrophobic surfaces and liquid marbles filled with the saline. Evaporation of saline droplets deposited on superhydrophobic surface resulted in the formation of cup-shaped millimeter-scaled residues. The formation of the cup-like deposit is reasonably explained within the framework of the theory of the coffee-stain effect, namely, the rate of heterogeneous crystallization along the contact line of the droplet is many times higher than in the droplet bulk. Crystallization within evaporated saline marbles, coated with lycopodium particles, depends strongly on the evaporation rate. Rapidly evaporated saline marbles yielded dented shells built of a mixture of colloidal particles and NaCl crystals. We relate the formation of these shells to the interfacial crystallization promoted by hydrophobic particles coating the marbles, accompanied with the upward convection flows supplying the saline to the particles, serving as the centers of interfacial crystallization. Convective flows prevail over the diffusion mass transport for the saline marbles heated from below.

This study analyzed the structural changes of semicrystalline polylactide (PLA) in the form of spun-bonded mulching nonwoven, during outdoor composting. The investigation was carried out at the microstructural, supramolecular and molecular levels using scanning electron microscopy (SEM), wide-angle X-ray diffraction (WAXD) and the viscosity method, respectively. The results showed the varying degree of influence of the climatic condition, prepared compost mixtures and time on the molecular, supramolecular and micromorphological structure of PLA spun-bonded mulching nonwoven and its degradation rate. The obtained experimental results revealed how the popular outdoor composting method, realized under two different European climatic conditions (in Poland and in Bulgary), affects the degradation of PLA nonwoven, designed for agriculture use.

This study explored the feasibility of fluoride removal from simulated semiconductor industry wastewater and its recovery as calcium fluoride using fluidized bed crystallization. The continuous reactor showed best performance (>90% fluoride removal and >95% crystallization efficiency) at a calcium to fluoride ratio of 0.6 within first 40 days of continuous operation. The resulting particle size increased by more than double during this time along with a 36% increase in the seed bed height indicating deposition of CaF2 onto the silica seed. The SEM-EDX analysis showed the size and shape of the crystals formed along with high amount of Ca-F ions presence. The purity of the CaF2 crystals were determined to be 91.1% though ICP-OES analysis. Following the continuous experiment, different process improvement strategies are explored. The addition of excess amount of calcium resulted in an additional 6% fluoride removal, however, compared to this single stage process, a two-stage approach was found to be better strategy to achieve a low effluent fluoride concentration. The fluoride removal reached 94% with this two-stage approach under optimum condition of 4 + 1 h HRT combinations and a [Ca2+]/[F-] ratio of 0.55 and 0.7 for the two reactors, respectively. CFD simulation showed the impact of inlet diameter, bottom-angle shape and width and height ratio of the reactor on mixing inside reactor and possibility of further improvement in reactor performance by optimizing the FBR configuration.

This article reports a protocol on the application of Amp-TB2 (single-amphibole ther-mobarometry; [1]) based on detailed electron microprobe analyses performed on homogeneous natural standards and synthetic glasses, and amphibole crystals (mostly phenocrysts) of volcanic products erupted by Bezymianny volcano during its activity through time. The application of this protocol is facilitated by a new version of the model (Amp-TB2.1.xlsx) including an equation to identify heterogeneous domains (disequilibrium; not suitable for thermobarometric constraints) and homogenous (equilibrium) zones within amphibole crystals, which can be used to quantify the physico-chemical parameters (i.e., pressure, P; temperature, T; volatile content in the melt, H2Omelt; oxygen fugacity, fO2) of “steady-state” magmatic crystallization. Application examples of the protocol, showing detailed core-rim microprobe data and physico-chemical parameter variations in representative amphibole phenocrysts of Bezymianny are also reported. The depth (and P) estimated by Amp-TB2.1 for this volcano are compared to seismic tomography results. Amp-TB2.1 results mainly shows (1) that Bezymianny is characterized by a very dynamic feeding system where the magma is stored at shallow crustal levels before recent activity periods characterized by climatic events and (2) that the pre-eruptive depth of magma storage generally increases with the age of the investigated products.

Pathological calcifications may consist of calcium oxalate (CaOx), hydroxyapatite phosphate (HAP), and brushite (BRU). The objective of this study was to evaluate the effect of phytate (inositol hexakisphosphate, InsP6), InsP6 hydrolysates, and individual lower InsPs (InsP5, InsP4, InsP3, and InsP2) on the crystallization of CaOx, HAP and BRU in artificial urine. All of the lower InsPs seem to inhibit the crystallization of calcium salts in biological fluids, although our in vitro results showed that InsP6 and InsP5 were stronger inhibitors of CaOx crystallization, and InsP5 and InsP4 were stronger inhibitors of BRU crystallization. For the specific in vitro experimental conditions we examined, the InsPs had very weak effects on HAP crystallization, although it is likely that a different mechanism is responsible for HAP crystallization in vivo. For example, calciprotein particles seem to have an important role in the formation of cardiovascular calcifications in vivo. The experimental conditions that we examined partially recapitulated the in vivo conditions of CaOx and BRU crystallization, but not the in vivo conditions of apatite crystallization.

The crystal nucleation and overall crystallization kinetics of cross-linked poly(ε-caprolactone) was studied experimentally by fast scanning calorimetry in a wide temperature range. With an increasing degree of cross-linking, both the nucleation and crystallization half-times increase. Concurrently, the glass transition range shifts to higher temperatures. In contrast, the temperatures of the maximum nucleation and the overall crystallization rates remain the same independent of the degree of cross-linking. The cold crystallization peak temperature generally increases as a function of heating rate, reaching an asymptotic value near the temperature of the maximum growth rate. A theoretical interpretation of these results is given in terms of classical nucleation theory. In addition, it is shown that the average distance between the nearest cross-links is smaller than the estimated lamellae thickness, which indicates the inclusion of cross-links in the crystalline phase of the polymer.

We report on space-selective crystallization of congruent and polar Sr2TiSi2O8 crystals in a stoichiometric SrO-TiO2-SiO2 glass induced by (1030 nm, 300 fs) femtosecond laser irradiation. This allows us to compare with non-congruent laser induced crystallization of polar LiNbO3, in non stoichiometric Li2O-Nb2O5-SiO2 glass and gain information on the mechanism of nanocrystals orientation with the laser polarization that we pointed out previously. Using scanning electron microscopy (SEM), Second-harmonic generation (SHG) and electron backscattered diffraction (EBSD), we studied the laser induced crystallization according to the laser processing parameters (pulse energy, pulse repetition rate, scanning speed). We found 1) a domain where the laser track is filled with crystals not perfectly textured (low energy), 2) a domain where an amorphous volume remain surrounded by a crystallized shell (high energy). This arises from Sr out-diffusion and may gives rise to crystallization of both SrTiO3 and Sr2TiSi2O8 phases at low speed. In the one-phase domain (at higher speed), it is found the possibility to elaborate a tube with a perfect fresnoite texture. Significant difference in size and morphology whereas crystallization threshold remains similar are discussed based on glases thermal propeties. Contrarily to Li2O-Nb2O5-SiO2 (LNS) glass, no domain of oriented nanocrystallization controlled by the laser polarization has been found in SrO-TiO2-SiO2 (STS) glass, which is attributed to the larger crystallization speed in STS glass. No nanogratings have also been found that is likely due to the congruency of the glass.

Calcium carbonate cements have been synthesized by mixing amorphous calcium carbonate and vaterite powders with water to form a cement paste and study how mechanical strength is created during the setting reaction. In-situ XRD was used to monitor the transformation of ACC and vaterite phases into calcite and a rotational rheometer was used to monitor the strength evolution. There are two characteristic time scales of the strengthening of the cement paste. The short timescale of the order 1 hour is controlled by smoothening of the vaterite grains, allowing closer and therefore adhesive contacts between the grains. The long timescale of the order 10-50 hours is controlled by the phase transformation of vaterite into calcite. This transformation is, unlike in previous studies using stirred reactors, found to be mainly controlled by diffusion in the liquid phase. The evolution of shear strength with solid volume fraction is best explained by a fractal model of the paste structure.

A recently developed thermodynamic theory for the determination of the driving force of crystallization and the crystal–melt surface tension is applied to the ice–water system employing the new Thermodynamic Equation of Seawater TEOS-10. The deviations of approximative formulations of the driving force and the surface tension from the exact reference properties are quantified, showing that the proposed simplifications are applicable for low to moderate undercooling and pressure differences to the respective equilibrium state of water. The TEOS-10 based predictions of the ice crystallization rate revealed pressure-induced deceleration of ice nucleation with an increasing pressure, and acceleration of ice nucleation by pressure decrease. This result is in, at least, qualitative agreement with laboratory experiments and computer simulations. Both the temperature and pressure dependencies of the ice–water surface tension were found to be in line with the le Chatelier–Braun principle, in that the surface tension decreases upon increasing degree of metastability of water (by decreasing temperature and pressure), which favors nucleation to move the system back to a stable state. The reason for this behavior is discussed. Finally, the Kauzmann temperature of the ice–water system was found to amount TK=116K, which is far below the temperature of homogeneous freezing. The Kauzmann pressure was found to amount pK=-212MPa, suggesting favor of homogeneous freezing upon exerting a negative pressure on the liquid. In terms of thermodynamic properties entering the theory, the reason for the negative Kauzmann pressure is the higher mass density of water in comparison to ice at the melting point.

Amorphous germanium films on non-refractory glass substrates were annealed by ultrashort near-infrared (1030 nm, 1.4 ps) and mid-infrared (1500 nm, 70 fs) laser pulses. Crystallization of germanium irradiated at a laser energy density (fluence) range from 25 to 400 mJ/cm2 under single-shot and multi-shot conditions was investigated using Raman spectroscopy. The dependence of the fraction of the crystalline phase on the fluence was obtained for picosecond and femtosecond laser annealings. The regimes of almost complete crystallization of germanium films over the entire thickness are obtained (from the analysis of Raman spectra with excitation of 785 nm laser). The possibility of scanning laser processing is shown, which can be used to create films of micro and nanocrystalline germanium on flexible substrates.

A new Pd(II) complex of the previously reported ligand N,N′-bis[(2,2′-dihydroxybiphen-3-yl)methyl]-N,N′-dimethylethylenediamine (L) was obtained from a DMF/H2O mixture. It differs from a Pd(II) complex of L previously obtained by sole DMF. The roles in the solid state assembly of solvent molecules and molecular conformation (driven by specific transition metal ions) were studied by comparing six complexes of L containing different metal centers (Ni(II), Cd(II), Cu(II), Pd(II)). Hirshfeld surface analysis, 2D fingerprint plots and energy frameworks calculations were used to investigate the intermolecular interactions within the crystal packing of the six complexes. As suggested by interaction energies, Pd(II) and Ni(II) complexes arrange to form ribbons, while Cd(II) and Cu(II) complexes form 3D networks. Interactions between complexes and solvent molecules in the previous Pd(II) complex are replaced by complex-complex interactions in the new Pd(II) complex, while BuOH and MeOH are interchangeable in the interactions within the crystal packing of the two Ni(II) complexes. Finally, solvent molecules are not involved in the crystal packing of the Cu(II) complex. The present study suggested that the solid state assembly of these systems is mainly driven by the molecular conformation, that depends in turn by the metal ion involved, while the solvent only plays a minor role.

In this study, four kinds of animal bone marrow powders were extracted with n-hexane using the Soxhlet extraction method. Polyunsaturated fatty acids were enriched by urea inclusion and low temperature crystallization method, then were further evaluated antioxidant and antibacterial activities. These results showed that the oil composition of the n-hexane extracts of four kinds of animal bone marrow primarily consisted of palmitic acid (18.57–31.01%), stearic acid (3.6–20.95%), and oleic acid (40.22–58.69%). The ratios of saturated fatty acids (SFA)/unsaturated fatty acids (UFA) were 1/1.417, 1/1.327, 1/2.140, and 1.285/1 for sheep, bovine, horse, and camel bone marrow oil, respectively. The SFA/UFA ratios determined by the urea inclusion method were 1/1.518, 1/1.390, 1/2.037, and 1.216/1, respectively. The SFA/UFA ratios according to the low temperature crystallization method with acetone were 1/1.920, 1/2.141, 1/2.360, and 1/1.157 for sheep, bovine, horse, and camel bone marrow oil, respectively. These enrichment methods effected the concentrations of UFAs from the camel bone marrow oil. Among the methods, the low temperature crystallization method effectively enriched the UFAs. All four bone marrow oils exhibited strong antioxidant and antimicrobial activities. The horse bone marrow oil showed the strongest antioxidant activity. Both antioxidant and antimicrobial activity improved after enrichment of the UFAs. These results lay a theoretical basis for application bone marrow oil resources in food and medicine.

Three-dimensional nanocomposite networks consisting of percolated Si nanowires in a SiO₂ matrix, Si:SiO₂, were studied. The structures were obtained by reactive ion beam sputter deposition of SiO_x (x ≈ 0.6) thin films at 450 °C and subsequent crystallization using conventional oven as well as millisecond line focus laser annealing. Rutherford backscattering spectrometry, Raman spectroscopy, X-ray diffraction, cross-sectional and energy-filtered transmission electron microscopy were applied for sample characterization. While oven annealing resulted in a mean Si wire diameter of 10 nm and a crystallinity of 72 % within the Si volume, almost single-domain Si structures with 30 nm in diameter and almost free of amorphous Si were obtained by millisecond laser application. The structural differences are attributed to the different crystallization processes: Conventional oven tempering proceeds via solid state, millisecond laser application via liquid phase crystallization of Si. The 5 orders of magnitude larger diffusion constant in the liquid phase is responsible for the three times larger Si nanostructure diameter. In conclusion, laser annealing offers not only significantly shorter process times but moreover a superior structural order of nano-Si compared to conventional heating.

To improve the interfacial bonding of sisal fiber reinforced polylactide biocomposites, polylactide (PLA) and sisal fibers (SF) were melt-blended to fabricate bio-based composites via in situ reactive interfacial compatibilization with the addition of an epoxy-functionalized oligomer (ADR). The FTIR analysis and SEM characterization demonstrated that PLA molecular chain was bonded to the fiber surface and epoxy-functionalized oligomer played a hinge-like role between sisal fibers and PLA matrix, which resulted in improved interfacial adhesion between fibers and PLA matrix. The interfacial reaction and microstructures of composites were further investigated by thermal and rheological analyses, which indicated that the mobility of the PLA molecular chain in composites was restricted because of the introduction of ADR oligomer, which in turn reflected the improved interfacial interaction between SF and PLA matrix. These conclusions were further investigated by the calculated activation energies of glass transition relaxation (△Ea) of composites via dynamic mechanical analysis. The mechanical properties of PLA/SF composites were simultaneously reinforced and toughened via addition of ADR oligomer. The interfacial interaction and structure-properties relationship of composites are key points of this study.

High pressure crystallization technique has been successfully used to prepare an elusive form II of a non-steroidal anti-inflammatory drug, Mefenamic acid. Single crystal of form II was grown at 0.3 GPa from an 4:1 methanol/ ethanol mixture as a solvent using Diamond Anvil Cell. Comparison of crystal structures show that the efficient packing of MA molecules in Form II results from the structural flexibility of MA acid molecules. Compression studies performed on the single crystal of form I resulted in 14 % decrease of unit cell volume up to 2.5 GPa. No phase transition was observed up to this pressure. A reconstructive phase transition is required to induce conformational changes in the structure, which is confirmed by crystallization at high pressure results.

The structural evolution and phase composition of multi-block thermoplastic polyurethanes, with different nature of the soft segments based on poly(butylene adipate) (PBA), were analyzed during in-situ thermal treatments. A combination of synchrotron small- and wide-angle X-ray scattering, differential scanning calorimetry, thermogravimetric analysis, and FTIR spectroscopy was used to determine the influence of macrodiol nature and crystallization conditions on the polymorphic behavior of PBA. Using a new synthesis scheme, a relatively high degree of crystallinity for urethane blocks was achieved, which depends on the diisocyanate type in the structure of the soft segment. The hard segment domains impose geometrical constraints on PBA, thereby altering its crystallization process compared to the neat oligomer. Thus, crystallization after annealing at a low temperature (80 °C) is fast, predominantly yielding a metastable β-phase. When heated to 180 °C, which is higher than the hard-segment melting temperature, a phase-separated structure is observed. Subsequent crystallization is slower, favoring the formation of the stable α-PBA modification. The phase separation can be observed even after the hard block melting. A notably slow crystallization from an isotropic melt was documented after the disruption of phase separation at 230 °C.

The poor solvent crystallization of carbapenem CS-023 has been performed at 25 °C. The following results have been obtained: 1) A solvate crystal Form A (5/2 Ethanol·1/2 H2O) is recovered from 80 v/v% ethanol solution, 2) Form A transforms to Form H (4H2O) by the solid-phase transition through the solvate-free polymorph, Form A-2, and Form A also transformed to Form C (1Ethanol·3H2O) by the solvent-mediated transformation. In the present study, we found that Form C also transforms to Form H by the solid-phase transition through the solvate-free polymorph, Form C-2. The three polymorphs, Form A, H, and C, were composed of the helical-chain structures, respectively. However, there was an incomprehensible affair in the solid phase transition among the three polymorphs. Namely, Form A comprised a left-handed helix.On the other hand, Form C and Form H’s helix chains were in a left- and right-handed helix complex. The solid-phase transition of Form A into Form H suggested the switch of helicity in the solid. We attempted to explain the helicity change in the solid phase transition. As a result, it was suggested that the over-absorption of water of Form A-2 at high humidity plays a vital role in the helicity change.

Vit-106 is a promising zirconium-based alloy with high glass-forming ability and belongs to the so-called bulk metallic glasses (BMG). Workpieces with a size of around one centimeter in all three dimensions can be obtained from a BMG alloy by casting. However, further increasing the cast size decreases the cooling rate and thus induces crystallization. Selective laser melting (SLM) is a well-known technique to overcome the size limitations for BMGs because a workpiece is built by the addition of multiple melt portions where the cooling rate is kept above the critical one. Currently, BMG parts obtained by SLM suffer from partial crystallization. The present work studies the influence of SLM process parameters on partial crystallization of Vit-106 by metallography and the influence of the microstructure on mechanical properties by microhardness and wear resistance testing. Submicron crystalline inclusions are observed in an amorphous matrix of Vit-106 alloy obtained by SLM. The size and the concentration of the inclusions can be controlled by varying the laser scanning speed. It is shown that submicron crystalline inclusions formed in the amorphous matrix during SLM can favorably affect microhardness and wear resistance.

Sodium-phosphate-based glass-ceramics (GCs) are promising materials for a wide range of applications, including solid-state sodium-ion batteries, microelectronic packaging substrates, and humidity sensors. This study investigates the impact of 24-hour heat-treatments at varying temperatures on Na-Ge-P glass, with a focus on (micro)structural, electrical, and dielectric properties of prepared GCs. Various techniques such as powder X-ray diffraction (PXRD), infrared spectroscopy-attenuated total reflection (IR-ATR), and scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) are employed. With the elevation of heat-treatment temperature, crystallinity progressively rises; at 450 °C, the microstructure retains amorphous traits featuring nanometric grains, whereas at 550 °C, heat-treatment results in fully crystallized structures characterized by square-shaped micron-scale grains of NaPO3. The insight into the evaluation of electrical and dielectric properties is provided by Solid-State Impedance Spectroscopy (SS-IS), revealing a strong correlation with the conditions of controlled crystallization and observed (micro)structure. The glass-ceramic heat-treated at 450 °C achieves the highest DC conductivity of 2.30×10–8 Ω–1 cm–1 at 393 K. As the heat-treatment temperature rises, the crystallization of the NaPO3 phase depletes the glass matrix of mobile Na+ ions, resulting in a reduction in DC conductivity. Dielectric parameters also decrease with rising heat-treatment temperature, with the glass-ceramic heat-treated at 550 °C displaying the lowest permittivity of 19.37 and the dielectric loss of 0.008. This research uncovers the intricate relationship between heat-treatment conditions and material properties, emphasizing that controlled crystallization allows for precise modifications to microstructure and phase composition within remaining glassy phase, ultimately facilitating fine-tuning of material properties.

Recent simulation studies have revealed a wealth of distinct crystal polymorphs encountered in the self-organization of polymer systems driven by entropy or free energy. The present analysis, based on the concept of self-avoiding random walks on crystal lattices, is useful to calculate upper bounds for the entropy difference of the crystals that are formed during polymer crystallization and thus provide predictions on polymorph thermodynamic stability. Here, we compare two pairs of crystals sharing the same coordination number, ncoord: hexagonal close packed (HCP) and face centered cubic (FCC), both having ncoord = 12 and the same packing density, and the less dense hexagonal (HEX) and body centered cubic (BCC) lattices, with ncoord = 8. In both cases, once a critical step length is reached, one of the crystals shows a higher number of SAWs compatible with the crystal. We explain the observed trends in terms of the bending and torsion angles corresponding to the different chain geometry as imposed by the geometric constraints of the crystal lattice.

Fiber reinforced thermoplastics (FRTP), which is reinforced with glass or carbon fibers, are used to improve the mechanical strength of injection-molded products. However, FRTP has problems such as the formation of weld lines, the deterioration of the appearance due to the exposure of fibers on the molded product surface, and the deterioration of the strength of molded products due to the fiber orientation in the molded products. We have designed and fabricated an injection mold capable of melt flow control and induction heating and cooling that has the functions of both heating and cooling the injection mold as well as the function of controlling the melt flow direction using a movable core pin. In this study, the above-mentioned mold was used for the molding of carbon fiber reinforced semi-aromatic polyamide. As a result, we found that increasing the heating temperature of the mold and increasing melt flow control volume contribute to the prevention of the generation of a weld line and the exposure of fibers on the molded product surface, as well as to the formation of a flat surface and increased bending strength. The relationships of these results with the carbon fiber orientation in the molded products and the crystallization of semi-aromatic polyamide were also examined in this study.

The self-assembly is an intriguing process of great importance in general soft matter and thus re-ceives an ever-growing scientific interest. Its most trivial example is the entropy-driven crystalli-zation of hard spheres. Past works have established the similarities and differences in the phase behavior of monomers and chains made of hard spheres. In the present work, inspired by the dif-ference in the melting points of the pure components, we study, through Monte Carlo simulations, the phase behavior of athermal mixtures composed of fully flexible polymers and individual monomers of uniform size. We analyze how the relative number fraction and the packing density affect crystallization and the established ordered morphologies. A synergetic effect is observed in the crystallization leading to synchronous crystallization of the two species. Structural analysis of the resulting ordered morphologies shows perfect mixing and thus no phase separation, which could split the system into polymer-rich and monomer-rich domains. Due to the constraints imposed by chain connectivity, the local environment of the individual spheres is systematically more spherical and more symmetric compared to the one of spheres belonging to chains. In general, increasing polymer content leads to reduction of the degree of crystallinity. According to the present findings, relative concentration is another determining factor to control the phase behavior of hard colloidal systems based on polymers.

The aim of the work is to study the effect of the 3D printing process on the microstructural and hydrophilic properties of polylactic acid (PLA) samples with various model printing patterns obtained from the black Filament PLA by sequentially applying polymer layers using the FDM (Fused Deposition Modeling) method. X-ray phase analysis revealed partial crystallization of PLA polymer chains in printed samples, which occurs under thermal and mechanical action on the original amorphous PLA filament during 3D printing to varying degrees, depending on the geometry of the pattern and the morphology of its surface. At the same time, IR spectroscopy data indicate the preservation of all intrastructural chemical bonds of polylactide. Measured at the original installation, the values of the wetting edge angles on the surface of the printed samples are in the range φ = 50-60°, which is significantly less than the right angle. This indicates the hydrophilic properties of all samples’ surface. At the same time, the influence of different geometries of model drawings in printed samples was found not only on the morphology of the samples’ surface according to SEM data, but also on its wettability.

We present results on the spontaneous crystallization of freely-jointed polymers of hard spheres obtained in an unprecedentedly long Monte Carlo (MC) simulation on a system of 54 chains of 1000 monomers. Starting from a purely amorphous configuration and after a transitory dominance of the hexagonal closed packed (HCP) polymorph, the system crystallizes in a final, stable, face centered cubic (FCC) crystal of very high perfection. Through refined metrics we gauge the degree of ordering and identify the regions of the phase transition and the corresponding morphologies. An analysis of chain conformational characteristics, of the spatial distribution of monomers and of the volume accessible to them shows that the phase transition is caused by an increase in translational entropy that is larger than the loss of conformational entropy of the chains in the crystal compared to the amorphous state. Polymer chains in the crystal adopt ideal random walk statistics as their great length renders local conformational details, imposed by the geometry of the FCC crystal, irrelevant.

The local and global order in dense packings of linear, semi-flexible polymers of tangent hard spheres are studied by employing extensive Monte Carlo simulations at increasing volume fractions. Chain stiffness is controlled by a tunable harmonic potential for the bending angle whose intensity dictates the rigidity of the polymer backbone as a function of the bending constant and equilibrium angle. The studied angles range from acute to obtuse ones, reaching the limit of rod-like polymers. We analyze how packing density and chain stiffness affect the ability of chains to self-organize at the local and global levels. The former corresponds to crystallinity as quantified by the Characteristic Crystallographic Element (CCE) norm descriptor, while the latter is computed through the scalar orientational order parameter. In all cases, we identify the critical volume fraction for the phase transition and gauge the established crystal morphologies, developing a complete phase diagram as a function of packing density and equilibrium bending angle. A plethora of structures is obtained, ranging from random hexagonal closed packed morphologies of mixed character and almost perfect face centered cubic (FCC) and hexagonal close-packed (HCP) crystals at the level of monomers, to nematic mesophases, with prolate and oblate mesogens at the level of chains. For rod-like chains, hysteresis is observed between the establishment of long-range nematic order and crystallization, while for right-angle chains both transitions are synchronized. A comparison is also provided against the analogous packings of monomeric and fully flexible chains of hard spheres.

In the present work we revise and extend the Characteristic Crystallographic Element (CCE) norm, an algorithm used to simultaneously detect radial and orientational similarity of computer-generated structures with respect to specific reference crystals and local symmetries. Based on the identification of point group symmetry elements, the CCE descriptor is able to gauge local structure with high precision and finely distinguish between competing morphologies. As test cases we use computer-generated monomeric and polymer systems of spherical particles interacting with the hard-sphere and square-well attractive potentials. We demonstrate that the CCE norm is able to detect and differentiate, between others, among: hexagonal close packed (HCP), face centered cubic (FCC), hexagonal (HEX) and body centered cubic (BCC) crystals as well as non-crystallographic fivefold (FIV) local symmetry in bulk 3-D systems; triangular (TRI), square (SQU) and honeycomb (HON) crystals, as well as pentagonal (PEN) local symmetry in thin films of one-layer thickness (2-D systems). The descriptor is general and can be applied to identify the symmetry elements of any point group for arbitrary atomic or particulate system in two or three dimensions, in the bulk or under confinement.