Crystallization Rate Research Articles

The Effect of the Surface Treatment on TiO2 Particles When Used as a Filler on Crystallization and Mechanical Properties of Polylactic Acid Composites. Case of Study: Silane Coupling Agents and Dicarboxylic Acids Were Used as Surface Modifiers

ABSTRACT This article analyzes the effect of the type of surface modification (using silane coupling agents and dicarboxylic acids) on titanium dioxide particles used as fillers in polylactic acid composites, which were exposed to a photodegradative process. The thermomechanical properties of the composites were analyzed; it was found that the silane coupling agent with Imidazole allowed the composites to have Young’s modulus values 60% lower than the composite without filler. On the other hand, the crystallization rate was 30% higher for composites with azelaic Acid attached to TiO2 particles than for composites without filler at a cooling rate of 5°C min−1. Once degraded composites containing azelaic acid were the least brittle, with a minor increment in Young’s Modulus compared to pure polylactic acid composites. When a mixture of modified titanium dioxide particles (with imidazole and either azelaic acid or pimelic acid) was used, there was a synergistic effect regarding photostability.

Gypsum Crystals Formed by the Anhydrite–Gypsum Transformation at Low Temperatures: Implications for the Formation of the Geode of Pulpí

Determining the mechanisms of the formation of giant crystals is a challenging subject. Gypsum, calcium sulfate dihydrate (CaSO4·2H2O), is known to form crystals larger than one meter in several locations worldwide. These selenite crystals grow at different temperatures, either in sedimentary or hydrothermal systems. The famous selenite crystals of the geode of Pulpí (Almería, Spain) are known to have grown at a temperature T = 20 ± 5 °C and have been proposed to form in a subaqueous environment by a self-feeding mechanism triggered by anhydrite dissolution and the ripening of microcrystalline gypsum, enhanced by oscillations in temperature. This paper reports the monitored crystallization of gypsum crystals, from anhydrite powder dissolution, inside airtight evaporation-free reactors under oscillating low temperatures (15 °C < T < 25 °C). These crystals are clearly smaller than the ones in the Pulpí mine but exhibit similar habits (i.e., single blocky crystals and twins following the 100 twinning law). The growth rate of gypsum single crystals has been measured to be between 3.8 and 35.3 µm/day. Noteworthy, we document the occurrence of the 100 contact twinning law of gypsum, which is the most widespread twinning law in natural environments but never univocally reported in laboratory experiments. The selection of the 100 contact twinning law has been correlated to the low supersaturation values obtained in the experiment, where the concentration in these long-duration experiments can be safely assumed to be the equilibrium concentration, i.e., 0.3 (at 25 °C) ≤ SI ≤ 0.4 (at 15 °C). We discuss the relevance of our experiment for forming the gypsum crystals of Pulpí in the framework of the geological history of Pulpí mineralization. These laboratory model experiments contribute to a deeper understanding of mineral nucleation and growth processes in natural environments.

Study on the uniaxial tensile mechanical behavior of two-dimensional single-crystal aluminum nitride

Abstract To investigate the tensile behavior and mechanical properties of single-crystal aluminum nitride (AlN) at the microscopic level, molecular dynamics simulations were used to study the effects of crystal orientation, strain rate, environmental temperature, and hole defect size on fracture strength, fracture mechanism, and potential energy during uniaxial tensile. The results show that the tensile strength of AlN in the [100] crystal direction is stronger. The anisotropic behavior characteristics of Al-N bonds fracture mechanism, crack growth rate, and cracking degree are significant when stretched along the [100], [010], and [110] crystal directions. Under high temperature condition, the lattice structure undergoes changes, causing grain boundaries to move and slip. This facilitates the breaking of bonds, leading to a decrease in tensile strength and a reduction in stored potential energy. Hole defects cause more lattice damage, reducing the energy required for Al-N bonds breakage and facilitating the propagation of microcracks. Additionally, it was found that the strain rate affects the stress-strain behavior of the model. An increase in strain rate leads to an increase in breaking stress, and the rapid deformation of AlN results in more energy being stored in the lattice in the form of potential energy. Therefore, the tensile strength and potential energy are improved.

LOW TEMPERATURE CRYSTALLIZATION BEHAVIOR OF NR BY DYNAMIC MECHANICAL ANALYSIS

ABSTRACT A fundamental study of low temperature crystallization of NR gum polymer (raw elastomer) was conducted using dynamic mechanical analysis (DMA) in oscillatory shear rheology mode. Isothermal crystallization was followed using DMA for crystallization temperatures ranging from −15 to −35 °C, with the maximum rate of crystallization noted at −25 °C. After the isothermal crystallization (annealing) for times from 6 to 9 h, DMA heating scans revealed two melting transitions (α and β) with locations that depended on the prior annealing temperature. The locations of these melting transitions were comparable with literature results for melting peaks by differential scanning calorimetry. At temperatures above these melting transitions, we identified two additional relaxations in the DMA heating trace that did not depend on the prior crystallization history. We also found evidence of the melt memory effect in polymer crystallization, which is discussed. During annealing at −25 °C, high cis-1,4 IR showed considerably slower and lower extent of crystallization than NR and crosslinked NR did not show noticeable crystallization within the 12-h experiment.

Transition state of matter in the fluctuation model of crystal growth

Two mechanisms of the effect of the transition state of building particles (activated complexes according to S. Arrhenius) on the crystal growth rate within the framework of the fluctuation model of dislocation crystal growth are discussed. Transition state clusters adsorbed on the surface of the growing face perform the function of an impurity that lowers the surface energy of the crystal at the time moments between free energy fluctuations. Thus, the transition state of the crystallizing substance by the first mechanism affects the relaxation rate of the secondary adsorption of impurities and shortens the time period of attachment of building particles to the crystal face. Other clusters formed in solution reduce the number of free particles and under conditions of low concentration of the building substance are able to decrease the crystallization rate. Nevertheless, in a natural multicomponent crystallization environment, at low concentrations of building material, significant thermal effect of crystallization and small deviations from equilibrium, the role of the transition state in crystal growth is generally insignificant.

Supramolecular Interactions as Key in Racemic Resolution: New Insights into the (SSi)‐ and (RSi)‐Diastereomers of (1R,2S,5R)‐Methyl(1‐naphthyl)‐phenylmenthoxysilane of Sommer

AbstractA highly selective approach with high yields of two diastereomeric silicon‐stereogenic menthoxysilanes, (RSi)‐3 and (SSi)‐3, introduced by Sommer et al., could be established as well as investigated in detail using different analytical tools. Single‐crystal X‐ray diffraction analysis was used to examine the different crystallization rates while Hirshfeld surface analysis was applied to extend supramolecular interactions in the solid state which showed stronger hydrogen bridges for the faster crystallizing diastereomer (SSi)‐3. In addition, similar ground‐state energies haven been found for both diastereomers by DFT calculations. Subsequent NMR studies showed stable Si‐configurations wherein epimerization only started after more than 4 hours at 110 °C. Access to both diastereomers with opposite configuration at the stereogenic silicon center is achievable in high yields and high stereochemical purity using only naturally occurring (−)‐menthol as a reagent.

Removal of Residual Additive Enabling Perfect Crystallization of Photovoltaic Perovskites

Achieving high‐efficiency perovskite solar cells (PSCs) hinges on the precise control of the perovskite film crystallization process, often improved by the inclusion of additives. While dimethyl sulfoxide (DMSO) is traditionally used to manage this process, its removal from the films is problematic. In this work, methyl phenyl sulfoxide (MPSO) was employed instead of DMSO to slow the crystallization rate, as MPSO is more easily removed from the perovskite structure. The electron delocalization associated with the benzene ring in MPSO decreases the electron density around the oxygen atom in the sulfoxide group, thus reducing its interaction with PbI2. This strategy not only sustains the formation of a crystallization‐slowing intermediate phase but also simplifies the elimination of the additive. Consequently, the optimized PSCs achieved a leading power conversion efficiency (PCE) of 25.95% along with exceptional stability. This strategy provides a novel method for fine‐tuning perovskite crystallization to enhance the overall performance of photovoltaic devices.

Exploring the effect of hemp fibers’ addition on the properties of PLA/PPAd biodegradable blends

Poly(lactic acid) (PLA) is a compostable aliphatic polymer with enhanced strength and toughness, and it is a promising material for packaging products. Polymer blending is a financially feasible and easy way to upgrade its properties, such as its slow degradation and crystallization rates and its modest elongation, and thus, make it more adaptable. Furthermore, the use of natural fibers as fillers can reinforce the biobased character of the final composite materials and enhance their antioxidant activity values, a crucial property of polymers that are addressed for active packaging. Herein, the influence of the addition of hemp fibers (HF) on the features of poly(lactic acid)/poly(propylene adipate) blends containing 85/15 w/w PLA/PPAd, was investigated. The utilization of a poly(lactic acid)-co-poly(propylene adipate) block copolymer (cop) as a compatibilizer was also examined. The thermal, morphological and mechanical assets of the composite materials were evaluated with the implementation of multiple techniques. The addition of HF enhanced the hydrophobicity and biodegradation of the composites, render them as candidates for several applications. Furthermore, the introduction of the compatibilizer successfully increases the adhesion between the polymeric matrices and the HF, resulting in enhanced properties.

Bilateral Embedded Anchoring via Tailored Polymer Brush for Large-Area Air-Processed Blue Light-Emitting Diodes.

Perovskite light-emitting diodes (PeLEDs) that can be air-processed promises the development of displaying optoelectronic device, while is challenged by technical difficulty on both the active layer and hole transport layer (HTL) caused by the unavoidable humidity interference. Here, we propose and validate that, planting the polymer brush with tailored functional groups in inorganic HTL, provides unique bilateral embedded anchoring that is capable of simultaneously addressing the n phases crystallization rates in the active layer as well as the deteriorated particulate surface defects in HTL. Exemplified by zwitterionic polyethyleneimine-sulfonate (PEIS) in present study, its implanting in NiOx HTL offers abundant nuclei sites of amino and sulfonate groups that balance the growth rate of different n phases in quasi-2D perovskite films. Moreover, the PEIS effectively nailed the interfacial contact between perovskite and NiOx, and reduced the particulate surface defects in HTL, leading to the enhanced PLQY and stability of large-area blue perovskite film in ambient air. By virtue of these merits, present work achieves the first demonstration of the air-processed blue PeLEDs in large emitting area of 1.0 cm2 with peak external quantum efficiency (EQE) of 2.09 %, which is comparable to the similar pure-bromide blue PeLEDs fabricated in glovebox.

Shish-kebab formation in the micro-injection molding of polyethylene: In-situ synchrotron small angle X-ray scattering study

The structural formation and evolution in high density polyethylene (HDPE) during the micro-injection molding process were investigated as a function of the mold temperature and injection speed utilizing an in situ synchrotron small angle X-ray scattering (SAXS) technique in conjunction with a portable micro-injection molding setup. It was found that shish-kebab structures were formed in all cases. The beginning of occurrence of shish is not much affected by the mold temperature, but the onset of the formation of kebab crystals is strongly dependent on the mold temperature. This mold temperature dependence of the kinetics of shish-kebab formation is attributed to the interplay between the crystallization rate in the outer layer and the formation rate of the shish-like structure, which was further evidenced by the multilayered structure of molded samples via ex situ microfocus scanning SAXS and wide angle X-ray diffraction (WAXD) measurements. On the other hand, the injection speed affects the long period of oriented lamellae and the dimension of the shish-like structure only slightly but influences the kinetics of structural formation evidently. The larger the injection speed, the earlier occurrence of oriented lamellae and shish formation is observed.

Removal of Residual Additive Enabling Perfect Crystallization of Photovoltaic Perovskites.

Achieving high-efficiency perovskite solar cells (PSCs) hinges on the precise control of the perovskite film crystallization process, often improved by the inclusion of additives. While dimethyl sulfoxide (DMSO) is traditionally used to manage this process, its removal from the films is problematic. In this work, methyl phenyl sulfoxide (MPSO) was employed instead of DMSO to slow the crystallization rate, as MPSO is more easily removed from the perovskite structure. The electron delocalization associated with the benzene ring in MPSO decreases the electron density around the oxygen atom in the sulfoxide group, thus reducing its interaction with PbI2. This strategy not only sustains the formation of a crystallization-slowing intermediate phase but also simplifies the elimination of the additive. Consequently, the optimized PSCs achieved a leading power conversion efficiency (PCE) of 25.95% along with exceptional stability. This strategy provides a novel method for fine-tuning perovskite crystallization to enhance the overall performance of photovoltaic devices.

Tunable interfacial properties of monolayer GeSb2Te4 on metal surfaces

Abstract Atomically thin monolayer (ML) GeSb 2 Te 4 (GST) holds promising prospects in non-volatile memory applications because of its high non-homogeneous crystallization rate. In GST-based devices, the interaction between GST and metals is crucial, as it affects the electronic properties. Herein, based on first-principles calculations, we investigate the interaction and Schottky barrier height of contacts formed by the combination of ML GST with various metals. It is found that the interfaces of GST with Pt, Pd, Ir and W exhibit strong interaction, characterized by large binding energies ranging from 1.394 to 1.015 eV , and the interfaces between GST and Cu, Ag and Au display weak interaction. For the seven contacts, Ag and W form Ohmic contacts with ML GST, while Cu, Au, Pd, Ir, and Pt form n-type Schottky contacts, with Schottky barrier heights ranging from 0.029 to 0.353 eV . The strong Fermi level pinning at GST-metal interface is observed with a pinning factor of 0.378. Additionally, altering the interfacial distance and optimizing the layers of GST enable a transition from Ohmic contact to Schottky contact. These findings provide crucial guidance for the design and optimization of electronic devices based on phase change materials like GST.

Synergistic Modulation of Sn2+ Oxidation and Perovskite Crystallization Induced by 4-Hydroxypyridine for Stable Lead-Free Solar Cells.

Tin perovskites present promising alternatives to lead perovskites, offering comparable optoelectronic properties alongside environmentally friendly characteristics. However, the rapid crystallization and easy oxidation of Sn2+ lead to poor film quality, further constraining the device performance. Here, 4-hydroxypyridine (4-HP) is introduced into the tin perovskite precursor for fabrication of high-quality tin perovskite films. 4-HP could modulate the colloidal size of prenucleation perovskite clusters in the precursor, thus inducing fast nucleation and retarding the crystal growth rate of tin perovskite through the formation of chemical interaction between nitrogen of pyridine and Sn2+ ions. Furthermore, the hydroxyl group on the pyridine ring contributes to suppressing the oxidation of Sn2+. As a result, the power conversion efficiency (PCE) of the devices based on 4-HP increases up to 11.3%. The stability of the unencapsulated devices shows significant improvement, retaining 100% of their initial PCEs after 2000 h of storage in N2 with 50-100 ppm of O2. This research presents a novel approach to the synchronized regulation of tin perovskite crystallization and the suppression of Sn2+ oxidation.

Influence of bottom supporting columns and cooling rate on the surface shape characteristics of sapphire substrates

The manufacturing process of sapphire substrates involves several key steps, including epitaxy, annealing, cutting, and processing. Among these, epitaxy and annealing are particularly crucial. The temperature variances along both the longitudinal and transverse axes within the furnace during the crystallization process play a significant role in determining the crystallization rate and internal structure of sapphire crystals. Furthermore, annealing sapphire serves to alleviate internal stress, enhance crystal structure, optimize physical properties, improve optoelectronic characteristics, enhance surface quality, and increase overall yield. This step is paramount in enhancing the performance and application value of sapphire materials. In order to investigate and optimize the effects of different thermal conductivities of support columns at the base and various annealing procedures on the surface characteristics of sapphire substrates, thereby improving product quality, this study conducted research by utilizing support columns made of different materials and carefully controlling the cooling rate parameters for sapphire. The findings revealed that using graphite as the base support column for the crystal furnace can reduce both the longitudinal and transverse temperature gradients within the furnace, consequently promoting crystal growth and enhancing the quality of sapphire ingots. Additionally, sapphire chips annealed using the rapid one-step annealing program exhibited the highest average warpage and bending rate variation, reaching 2.0 μm, and the average dislocation density was half that of conventionally produced chips, at 108.89 pits/cm2.

SO3NH3 crystal growth in (CH3)3SBr solution

SO3NH3 (Sulfamic acid, or SA) is known for its excellent piezoelectric and optical properties, making it valuable for various optical applications. However, it usually takes weeks to months to grow the SA single crystals with centimeter-scale size by traditional growth method from solution. In this study, we use (CH3)3SBr (Me3SBr) as an additive to enhance the growth rate of SA single crystals, and the growth time was reduced to just 48 h. The mechanism of accelerated crystallization process is attributed to the variations of electrostatic potential and binding energy on SA crystal modified by the additive. In addition, structural analysis and basic characterization on the newly grown SA are performed, and first-principles calculations provide insights into the energy band structure and phonon spectrum.

Optimizing cooling strategies in the Czochralski process for large-diameter silicon ingots

As the semiconductor industry shifts towards larger wafer sizes, such as 300 mm and 450 mm, controlling defects is crucial to ensure device performance and yield. Conversely, a high cooling rate is essential for achieving higher production rates. Therefore, finding the optimal cooling strategy is critical to maintaining high production rates while ensuring high-quality wafer production. This paper employs a simulation model to investigate the impact of various cooling strategies on point defect formation during the CZ process for 450 mm diameter silicon ingots. Using the 3D energy equation coupled with the Navier-Stokes equation and moving mesh theory, the transient CZ process is simulated, incorporating defect evaluation equations. Beside original CZ puller configuration, two cooling strategies are examined: one with a small gap and long cooling jacket (Case II) and another with a large gap and short cooling jacket (Case III), compared against a baseline setup (Case I). The simulations reveal that Case II, while enhancing the crystallization rate, increases non-uniformity. Conversely, Case III produces a flatter solid-liquid interface and lower defect concentrations, achieving a maximum Cv-Ci of 0.4 × 1014 cm−3, compared to 1.1 × 1014 cm−3 and -2.5 × 1014 cm−3 in Case I and II. These findings suggest that adjusting cooling strategies can significantly impact the quality and uniformity of large- diameter silicon ingots.

Crystallization‐correlated phase separation of polypropylene random copolymers

AbstractEthylene segments are incorporated into stereoregular propylene‐propylene‐propylene (PPP) homo‐sequences to create locally disordered ethylene‐propylene (EP) segments in polypropylene random copolymer (PPR) through a phase separation process, resulting in large quantities of spherical EP rubbery particles for improving impact toughness. However, the manipulation on size and distribution of these spherical EP rubbery phases remains insufficiently understood. In this study, the phase separation of PPR and the influence of crystallization on phase separation were investigated using rheological measurements and small‐angle x‐ray scattering (SAXS) methods. Combined with the isothermal crystallization method, phase separation was differentiated by the crystallization rate. The molecular chain states corresponding to different crystallization conditions were studied to interpret the varying rubbery particle sizes resulting from phase separation. The results showed that phase separation of EP segments from PPP is highly related to crystallization. Isothermal crystallization at temperatures ranging from 110 to 130°C leads to a high degree of phase separation due to the fast crystallization rate, as evidenced by the presence of small quantities of large pores in microscopic observations. This work provides insights into the phase separation of random copolymers and establishes correlations for manipulating the low‐temperature toughness of PPR.

Beyond the Surface: Interconnection of Viscosity, Crystal Growth, and Diffusion in Ge25Se75 Glass-Former.

The knowledge of viscosity behavior, crystal growth phenomenon, and diffusion is important in producing, processing, and practical applications of amorphous solids prepared in different forms (bulk glasses and thin films). This work uses microscopy to study volume crystal growth in Ge25Se75 bulk glasses and thermally evaporated thin films. The collected growth data measured over a wide temperature range show a significant increase in crystal growth rates in thin films. The crystal growth is analyzed using near-surface viscosities obtained in bulks and thin films using nanoindentation and melt viscosities measured by a pressure-assisted melt filling technique. The crystal growth analysis provides information on the size of the structural units incorporated into the growing crystals, essential for estimating the diffusion coefficients and explaining the difference in crystal growth rates in bulk and thin films. The crystal growth analysis also reveals the decoupling between diffusion and viscous flow described by the Stokes-Einstein-Eyring relation. Moreover, to the authors' best knowledge, the manuscript provides the first evaluation estimation of the effective self-diffusion coefficient directly from growth data in chalcogenide glass-formers. The present data show a similar relation between diffusion coefficients (D) and crystal growth rates (u): u ≈ D0.87, which is found in several molecular glasses.

Exact analytical solution of the equations for a quasiequilibrium two-phase domain: permeability and interdendritic spacing

This study is concerned with the theoretical description of a quasi-stationary process of directional crystallization of binary melts and solutions in the presence of a quasi-equilibrium two-phase region. The quasi-equilibrium process is ensured by the fact that the system supercooling is almost completely compensated by heat released during the phase transformation. Quasi-stationarity of the process determining constancy of the crystallization rate is ensured by given temperature gradients in the solid and liquid phases. The system of heat and mass transfer equations and boundary conditions to them under these assumptions is dependent on a single spatial variable in the reference frame moving with the crystallization rate relative to a laboratory coordinate system. Exact analytical solutions to the formulated problem in parametric form are obtained. The parameter of the solution is the solid phase fraction in a two-phase region. The distributions of temperature and impurity concentration in the solid, liquid and two-phase regions of the crystallizing system, the rate of solidification, and the spatial coordinate in the two-phase region depending on the solid phase fraction in it are found. An algebraic equation for the solid phase fraction at the interface between the solid material and the two-phase region is derived. Exact analytical solutions show that the impurity concentration in the two-phase layer increases as the solid phase fraction increases. Moreover, the solid phase fraction at the interface solid phase — two phase region and its thickness increase as the temperature gradient in the solid phase and the solidification rate increase. The developed theory allows us to determine analytically the permeability of the two-phase region and a characteristic interdendritic spacing in it. Analytical solutions show that the relative permeability in the two-phase region increases from a certain value at the interface with the solid phase to unity at the interface with the liquid phase. The selection theory of stable dendritic growth allows us to determine analytically a characteristic interdendritic distance in the two-phase layer that decreases as the temperature gradient in the solid phase increases. An increase of impurity in the molten phase gives a decrease in the interdendritic spacing within a two-phase region.

Crystallization behavior of BOF slag during the cooling process towards leaching for CO2 sequestration

This work addresses the crystallization behavior and microstructure feature of the molten basic oxygen furnace (BOF) slag during a slow cooling process. The aim is to provide a reference for the modification of BOF slag for subsequent leaching of Ca as part of CO2 sequestration. Integrated analysis of XRD, SEM-EDS, and thermodynamic calculations suggest a crystallization behavior of BOF slag during the cooling process. RO phases ((Mg, Fe, Mn) O) was the equilibrium phase at a high temperature of around 1600 °C, followed at lower temperatures by the formation of Ca3SiO5 (C3S) and α-Ca2SiO4 (α-C2S). The Ca2Fe2O5 (C2F) phase forms during the latter stages of melt solidification. On the basis of the combined analysis of the leaching test results and crystallographic analysis, a future direction of modification of BOF slag is suggested that enriches Ca into the C2S and hinders the formation of C2F. However, inhibiting the generation of C2F by adjusting the cooling process alone is difficult since its crystallization rate is fast. The phase of C2F was observed in XRD and SEM even if the BOF slag was quenched from 1600 °C. Furthermore, the chemical characterization and morphological evolution of the crystalline phase of molten BOF slag during the slow cooling process was observed.