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Phase-change memory emerges as a top contender for non-volatile data storage applications. We report here a systematic change in local structure and crystallization kinetics of binary GeTe thin films using temperature-dependent resistivity measurements, which offers single-stage crystallization at around 187 °C, corroborated with x-ray diffraction. Furthermore, the change in chemical bonding upon crystallization is determined through x-ray photoelectron spectroscopy core level spectra, which reveals the existence of Ge and Te components that align with the GeTe crystal structure. Also, an investigation was carried out employing a UV–Vis–NIR spectrophotometer to explore the evolution of optical bandgaps (E g) , Tauc parameter (B) representing the local disorder, and Urbach energy (E u) of the GeTe material, as it undergoes the transition from a disordered amorphous state to a crystalline state. As crystallization progresses, a consistent shift of E g from 0.92 to 0.70 eV corresponds to as-deposited amorphous at room temperature and crystalline at 250 °C, respectively. In addition, the reduction in E u (from 199.87 to 141.27 meV) and a sudden increase of B around crystallization temperature is observed upon increasing temperature, indicating direct observation of enhanced medium-range order and distortion in short-range order, respectively, in GeTe thin films, revealing improved structural and optical properties. These enhancements make the GeTe material ideal for data storage applications of phase-change memory for next-generation computing technology. [ABSTRACT FROM AUTHOR]

The development of Ge-rich GeSbTe (GGST) alloys significantly enhanced the high-temperature stability required for Phase-Change Memory technology. Previous studies on Ge enrichment in GeSbTe (GST) materials with Sb-over-Te ratio lower than one (Sb / Te < 1) highlighted the segregation into cubic Ge and cubic GST phases. Such a segregated cubic GST phase is metastable and presents a polycrystalline structure with disordered grain boundaries that could lead to structural relaxation and then to drift phenomena. In this work, using resistivity measurements, Raman spectroscopy, and in situ x-ray diffraction analyses, we demonstrate for the first time to our knowledge that GGST with Sb/Te higher than one (Sb / Te > --> 1) upon annealing leads to the direct formation of a GST hexagonal phase featuring a high growth speed, bypassing the cubic metastable phase. Combined with Ge enrichment, the increased value of the activation energy of the nucleation of Sb / Te > --> 1 GGST alloys ensures a high stability of the amorphous phase. Finally, nitrogen introduction further stabilizes the system against the crystallization, without compromising the high crystalline growth speed and the formation of the stable GST hexagonal phase in alloys with Sb / Te > --> 1. These results demonstrate the possibility to tune the crystalline structure of the segregated phases in Ge-rich GeSbTe alloys, combining the stability at high temperature of the amorphous phase with the high crystallization speed and uniformity (with larger grains) of a targeted GST phase. [ABSTRACT FROM AUTHOR]

Upon osmotic compression, rotationally symmetric faceted colloidal particles can form translationally ordered, orientationally disordered rotator mesophases. This study explores the mechanism of rotator-to-crystal phase transitions where orientational order is gained in a translationally ordered phase, using rotator-phase forming truncated cubes as a testbed. Monte Carlo simulations were conducted for two selected truncations (s), one for s = 0.527 where the rotator and crystal lattices are dissimilar and one for s = 0.572 where the two phases have identical lattices. These differences set the stage for a qualitative difference in their rotator–crystal transitions, highlighting the effect of lattice distortion on phase transition kinetics. Our simulations reveal that significant lattice deviatoric effects could hinder the rotator-to-crystal transition and favor arrangements of lower packing fraction instead. Indeed, upon compression, it is found that for s = 0.527, the rotator phase does not spontaneously transition into the stable, densely packed crystal due to the high lattice strains involved but instead transitions into a metastable solid phase to be colloquially referred to as "orientational salt" for short, which has a similar lattice as the rotator phase and exhibits two distinct particle orientations having substitutional order, alternating regularly throughout the system. This study paves the way for further analysis of diffusionless transformations in nanoparticle systems and how lattice-distortion could influence crystallization kinetics. [ABSTRACT FROM AUTHOR]

In materials science, chiral perovskites stand out due to their exceptional optoelectronic properties and the versatility in their structure and composition, positioning them as crucial in the advances of technologies in spintronics and chiroptical systems. This review underlines the critical role of synthesizing and growing these materials, a process integral to leveraging their complex interplay between structural chirality and distinctive optoelectronic properties, including chiral-induced spin selectivity and chiroptical activity. The paper offers a comprehensive summary and discussion of the methods used in the synthesis and growth of chiral perovskites, delving into extensive growth techniques, fundamental mechanisms, and strategic approaches for the engineering of low-dimensional perovskites, alongside the creation of novel chiral ligands. The necessity of developing new synthetic approaches and maintaining precise control during the growth of chiral perovskites is emphasized, aiming to enhance their structural chirality and boost their efficiency in spin and chiroptical selectivity.

Water can be vitrified if it is cooled at high rates, which makes it possible to outrun crystallization in so-called no man's land, a range of deeply supercooled temperatures where water crystallizes rapidly. Here, we study the reverse process in pure water samples by flash melting amorphous ice with microsecond laser pulses. Time-resolved electron diffraction reveals that the sample transiently crystallizes despite a heating rate of more than 5 × 106 K/s, even though under the same conditions, vitrification can be achieved with a similar cooling rate of 107 K/s. Moreover, we observe different crystallization kinetics for amorphous solid water and hyperquenched glassy water. These experiments open up new avenues for elucidating the crystallization mechanism of water and studying its dynamics in no man's land. They also add important insights into the laser melting and revitrification processes that are integral to the emerging field of microsecond time-resolved cryo-electron microscopy. [ABSTRACT FROM AUTHOR]

In material processing and handling processes, premixed interlayer often replace the ideal Ni/Al interface, which would become a new origin of alloying reaction. This work investigates shock-induced reaction mechanism and kinetics of premixed Ni/Al nanolaminates with molecular dynamics simulations and theoretical analysis. The reaction is found to be driven by the crystallization evolution in premixed interlayer and the diffusion of premixed atoms. Among them, multi-stage reaction patterns are strongly manifested by the crystallization evolution characteristics. Specifically, "crystallization-dissolution-secondary growth" and "crystallization-dissolution" of B2 phase respectively correspond to the solid-state and solid-liquid reaction cases, where crystallizations are fitted well by Johnson–Mehl–Avrami kinetics model. Interestingly, the different growth mechanisms of B2 grain are revealed, namely nuclei coalescence and atomic diffusion. Moreover, the analysis of microscopic diffusion theory indicates a certain non-random diffusion nature for solid-state reaction initiation, but near-purely random diffusion for solid-liquid reaction initiation. The diffused Al atoms possess a limited diffusion coefficient and enhanced diffusion correlation, resulting in extremely slow mixing rate in Ni layer. In addition, the influence law of Ni concentration in premixed interlayer on reactivity parameters can be quantitatively described by a quadratic function. [ABSTRACT FROM AUTHOR]

The phase transition temperature and crystallization kinetics of phase-change materials (PCMs) are crucial characteristics for their performance, data retention, and reliability in memory devices. Herein, the crystallization behavior and kinetics of a compositionally optimized, N-doped Ge-rich Ge–Sb–Te alloy (GGST) in the slow crystallization regime are systematically investigated using synchrotron x-ray diffraction (XRD) in situ during heat treatment. Uniform thin films (50, 25, 10, and 5 nm) of initially amorphous N-doped GGST are investigated. The specimens were heated up to 450 °C at a rate of 2 °C/min to estimate crystallization onsets by quantifiying the crystallized quantity during material transformation from the XRD patterns. Subsequent isothermal anneals have been performed to assess crystallization behavior and activation energies. Nucleation-controlled crystallization that progresses in two steps is observed, together with the emergence of Ge preceding cubic Ge2Sb2Te5, with a mild dependence of crystallization temperature on film thickness that is inverse to what has been observed in other systems. Ge and GST crystallization may be described occurring in three-time stages: (i) an incubation period; (ii) a fast growth period; and (iii) a very slow-growth period. Very high activation energies (between 3.5 and 4.3 eV) for each phase are found for the incubation time t0. The activation energy for Ge in the fast growth regime is close to the one reported for the crystallization of pure Ge films. In the case of Ge, the incubation time is strongly thickness-dependent, which may have important consequences for the scaling of memories fabricated with this class of materials. [ABSTRACT FROM AUTHOR]

[Display omitted] • Eh-pH diagram of K-S-Fe-H 2 O system is established to analyze the iron removal. • Controlling high potential and a certain pH value are good for jarosite process. • Efficient and selective iron removal from acid solution has been achieved. • Regular ellipsoidal particles of jarosite with even particle size are obtained. • The crystallization mechanism and kinetics of jarosite formation are analyzed. Aerospace magnetic material scraps are abundant in cobalt and nickel. Sulfuric acid leaching process is an efficient method for extracting them. But it is a non-selective process, a significant amount of iron dissolves in the solution. This study focuses on the selective removal of iron from this solution using the jarosite process. E h -pH diagram of K-S-Fe-H 2 O system was established. Based on thermodynamic analysis, H 2 O 2 is used to oxidize Fe2+ into Fe3+, achieving efficient and selective removal of iron from the solution containing cobalt and nickel. The optimal conditions are as follows: temperature 95°C, K 2 SO 4 dosage coefficient 1.5, seed dosage 10 g/L, time 90 min, pH 1.76, and endpoint pH controlled at approximately 3. Under these conditions, the iron removal efficiency is above 99%, while the loss ratios of cobalt and nickel are below 2%. The product is characterized by XRD and SEM-EDS. Results indicate that the product is jarosite ((K,H 3 O)Fe 3 (SO 4) 2 (OH) 6), exhibiting an ellipsoid structure with the mean particle size in the range of 0.2–5.0 μm. Temperature, pH value and seed dosage significantly affect reaction rate, particle size and crystallinity, and K 2 SO 4 dosage mainly affects reaction rate and the morphology of jarosite. The jarosite crystallization kinetics can be described by the Avrami equation, with an Avrami index (n) of approximately 2.5 and the apparent activation energy of 42.68 kJ/mol. [ABSTRACT FROM AUTHOR]

Perovskite light‐emitting diodes (PeLEDs) present potential applications for next‐generation displays due to their excellent luminescent properties and solution processing. The formamidinium‐caesium lead bromide (FAxCs1−xPbBr3) mixed cation strategy is one of the primary methods to achieve high‐performance of Cs‐dominate PeLEDs system. However, the inhomogeneous distribution of cations is detrimental to the photoelectronic performance of Cs‐dominated PeLEDs. Here, in mixed FA/Cs perovskite films, it is observed that Cs, Br and trace Pb elements precipitated on the surface of the perovskite films. It is found that the segregation of cations is induced by the uncontrollable crystallization process of Cs/FA cations. By introducing biuret additive, the hydrogen bonding interaction of biuret and FA cation balances crystallization rate, which therefore significantly improves the crystal quality and cations distribution of perovskite films. As a result, green PeLEDs with a high external quantum efficiency of 28.8% are obtained, and represent five times enhancement in half‐life time (T50) of 2.48 h at an initial luminance of 100 cd m−2 relative to the control device. The results help to understand the relationship between cationic distribution and PeLEDs properties, offering significant insights for modulating the performance of PeLEDs. [ABSTRACT FROM AUTHOR]

The non-isothermal crystallization kinetics of the pure ethylene-methyl acrylate copolymer (EMA) and EMA/chloroprene rubber (CR) thermoplastic vulcanizate (TPV) prepared by dynamic vulcanization were extensively investigated using differential scanning calorimetry (DSC). The Avrami method modified by the Jeziorny, the Ozawa and the Mo methods were employed to characterize the non-isothermal crystallization process. The results indicated that the Avrami method modified by the Jeziorny and Mo methods effectively characterized the non-isothermal crystallization behavior of both pure EMA and EMA/CR TPV, while the behavior could not be described by the Ozawa modification method. [ABSTRACT FROM AUTHOR]

Recent interest in thermoplastic composites for aerospace applications is driven by the need for high-volume manufacturing of materials that display excellent mechanical, thermal, and solvent resistive properties. Specifically, a large component of the composite properties of thermoplastic composites are highly dependent on the crystalline fraction of the semi-crystalline polymer matrix of the reinforced system. This work investigates the melting behavior of poly (ether ketone ketone) (PEKK) and the influence of temperature and fiber on crystallization kinetics and morphology of (PEKK) composites utilizing, differential scanning calorimetry, Velaris-Sefaris modelling, and polarized optical microscopy (POM). Annealing temperatures of 380°C and above were required to fully erase crystalline ordering in the PEKK matrix. Furthermore, carbon fibers accelerated crystallization kinetics in PEKK at a range of temperatures observed via DSC, and Velaris- Sefaris modelling implied a shift from bulk to surface induced nucleation by the addition carbon fiber to the PEKK matrix, reducing activation energy of crystallization events. This nucleation behavior was visually confirmed through POM with observation of transcrystalline domains nucleated from the surface of a single carbon fiber. [ABSTRACT FROM AUTHOR]

The crystallization thermal stability plays an essential role in affecting thermal stress of glass-ceramic sealant for long-term planar-type solid oxide fuel cells (SOFC) to prevent fuel leakage during operation. Due to the lack of systematic research on regulating the stable performance of glass-based sealant with the working time at operation temperature, herein, the effect of MgO on crystallization kinetics, phase stability, and thermal and mechanical properties of MgO–BaO–CaO–Al 2 O 3 –B 2 O 3 –SiO 2 (MBCABS) glass-ceramic has been firstly analyzed at heat-treatment of 750 °C with working time of 1∼1000h in this work. Subsequently, the relationship evolution of crystallization thermal stability-coefficient of thermal expansion (CTE) match-thermal stress was established by Finite Element Method (FEM). The main reasons for the decrease of CTE of MBCABS glass-ceramics with low-content MgO are the precipitation of hexagonal BaAl 2 Si 2 O 8 phase and the transformation of hexagonal BaAl 2 Si 2 O 8 to low-CTE monoclinic BaAl 2 Si 2 O 8 phase, bring about that the Von Mises thermal stress of sealant itself and interface having tripled at 1000h (more than 200 MPa) according to FEM simulation results. The thermal stable and high-CTE BaMgSiO 4 , Ba 8 Mg 16 Si 16 O 56 , and BaCa 2 Mg(SiO 4) 2 phases crystallized in MBCABS glass-ceramics with high-content MgO, therefore the maximum stress at all time parameters was below 100 MPa for 1∼1000h. This study was useful for identifying the optimal phase option and CTE matching of glass-based sealant for efficient and stable long-term operation of solid oxide fuel cells. [ABSTRACT FROM AUTHOR]

The performance of perovskite cells closely relies on the quality of films, leading to a special focus on crystallization manipulation and defect control. In this study, a novel approach using 1D metal‐free perovskites, specifically DABCO‐NH4Cl3, is proposed to facilitate the crystallization process of 3D FAPbI3 perovskites, while simultaneously addressing surface defects. Analysis of crystallization kinetics reveals that the introduction of 1D metal‐free perovskites provides numerous nucleation sites, effectively slowing down crystal growth rates and resulting in the formation of uniform, large‐grain perovskite films. Furthermore, the organic groups present in 1D perovskites play a crucial role in passivating defects within the perovskite structure. The synergistic impact of these factors enables the perovskite to achieve an efficiency of 24.72% while demonstrating exceptional stability. This research offers a promising approach for controlling perovskite crystallization, leading to the development of high‐efficiency and stable perovskite materials. [ABSTRACT FROM AUTHOR]

It is reported that the solvent environment exerts a significant influence on the property of perovskite precursor solution and resultant film, which is more pronounced in more complex low‐dimensional perovskites. Four solvent additives with varying basicity are introduced to instigate a tug‐of‐war among bonding interactions, thereby exploring the systematic effect of the solvent environment on the growth of quantum wells and the photoelectric properties of the resultant low‐dimensional perovskite films. A governing principle that diverges significantly from those previously documented for three‐dimensional perovskites is elucidated in low‐dimensional perovskites. When coordination interactions predominate in the solvent environment, the emergence of a two‐dimensional GA2PbI4 transitional phase is fostered to facilitate subsequent transformation into the desirable ACI phase, and the perovskite crystallization kinetics is retarded to improve the film quality. Hence, the highest power conversion efficiency (PCE) of 22.73% is obtained for GA(MA)nPbnI3n+1 (n = 5) based solar cells with a p‐i‐n structure. The PCE achieved in this work is a record among the reported low‐dimensional perovskite solar cells. [ABSTRACT FROM AUTHOR]

Two‐step sequential deposition of perovskite films is proven efficient and compatible with large‐scale production. Nevertheless, its critically regulated environmental humidity often remains a burden, hindering its applications in reproducible fabrication of perovskite solar cells (PSCs). Herein, by introducing a water ethyl acetate (W‐EA) solution treatment before annealing, improved perovskite crystallinity and homogeneity in FA0.95‐xMAxCs0.05PbI3 films without additional composition regulation is achieved. In situ Grazing‐incidence Wide‐angle X‐ray Scattering experiments highlighted accelerated crystallization kinetics in W‐EA‐treated films, leading to high‐quality perovskite formation. PSCs based on this method reached an optimal power conversion efficiency of 25.01% and demonstrated enhanced moisture resistance, retaining 88% efficiency after 1000 h in ambient conditions. This W‐EA treatment simplifies the fabrication process, greatly reducing the need for controlled humidity, and offers insights into the role of water in perovskite film crystallization, with significant implications to produce high‐performance PSCs. [ABSTRACT FROM AUTHOR]

The widespread use of traditional petroleum‐based plastics is causing significant environmental pollution for example microplastics issues, due to its non‐biodegradability. Poly (lactic acid) (PLA) as a representative biodegradable polymer is a promising candidate to replace petroleum‐based plastics in some fields of disposable packaging materials and tableware. In this work, in order to improve the poor crystallization, mechanical and heat resistance performances of PLA, styrene–acrylonitrile‐glycidyl methacrylate (SAG) as a chain extender and octamethylenedicarboxylic dibenzoylhydrazide (ST‐NAB3) as a heterogeneous nucleating agent (HNA) were added simultaneously into PLA matrix. The chain‐extended PLA (CPLA) with branch structures had smaller crystal sizes and higher crystal density, compared with those of pure PLA. In addition, thanks to the nucleation effect of ST‐NAB3 and the development of "shish‐kebab", this tendency became more pronounced in CPLA/HNA systems. It was worth mentioning that, CPLA with the ST‐NAB3 content of 1 wt% (CPLA‐1) possessed the highest crystallinity of 43.6%. Meanwhile, CPLA‐1 had the best impact strength and heat deformation temperature of 38.9 kJ/m2 and 91.3°C respectively, which had increased by 11.3 kJ/m2 and 32.4°C contrast to pure PLA. On the whole, this study proposed a simple and effective method, which provided a new possibility for PLA modification research. [ABSTRACT FROM AUTHOR]

High‐resolution numerical simulations of the injection molding process are crucial for precise process and part behavior prediction and tool fabrication. However, the complex flow behavior with high shear rates, rapid cooling as well as the nonlinear material properties post many challenges, and efficient high‐resolution numerical analysis is still subject to research. This study presents a simplified numerical description of the polymer flow and cooling during the injection phase, aiming for efficient and yet accurate simulations of the process. The in‐house finite‐element solver XNS is used to simulate the polymer and air flows, as a two‐phase flow, using the level‐set method. The injected polymer is characterized as a shear‐thinning flow using the non‐Newtonian Cross‐Williams‐Landel‐Ferry rheology model. To reduce the computational time, other polymer model effects such as a precise crystallization kinetics model during the injection phase have been neglected as a result of the findings of a previous study. Heading towards more efficient computations, we use a space‐time discretization, which has a higher convergence rate than commonly used time discretizations and can allow future mesh refinement in time, particularly convenient for our application. The results of the simulation are compared to the propagation of the flow front in an injection molding process of a plate part. The flow front is traced in‐situ by three aligned infrared sensors that detect the temperature increase from the mold wall. The time of flow front propagation between two sensors is in good agreement with experimental results. The peak temperature is calculated lower as compared to the experiment; however the temperature gradients are in good agreement validating the numerical model presented here. [ABSTRACT FROM AUTHOR]

Controlling the cooling rate experienced by a material during a manufacturing process is a challenge and a major issue. Industrial processing techniques are very diverse and may involve a whole range of cooling rates, which are sometimes extremely high for small and/or thin manufactured parts. For polymers, the cooling rate has consequences on both the microstructure and the time-dependent properties. The common cooling rates associated with conventional calorimetric measurements are generally limited to a few tens of degrees per minute. This work combines several calorimetric techniques (DSC, modulated-temperature DSC, stochastically-modulated DSC and Fast Scanning Calorimetry) to estimate the critical cooling rate required to melt-quench fast-crystallizing polyesters to their fully amorphous state, based on the example of a series of poly(alkylene trans-1,4-cyclohexanedicarboxylate) (PCHs) with a number of methylene groups in the main structure of the repeating unit n C H 2 varying from 3 to 6. The even-numbered ones require faster cooling rates (about 3000 K s−1 for n C H 2 = 4, between 500 and 1000 K s−1 for n C H 2 = 6) compared to the odd-numbered ones (between 50 K min−1 and 100 K s−1 for n C H 2 = 3, between 10 and 30 K min−1 for n C H 2 = 5). [ABSTRACT FROM AUTHOR]

Fiber-reinforced thermoplastic composites (FRTPs) are gaining increasing attention and widespread use in engineering applications due to their high specific strength and stiffness, excellent toughness, and recyclability. The mechanical properties of these composites are closely tied to their crystallization process, making it crucial to accurately describe this phenomenon. Existing theoretical models for analyzing the non-isothermal crystallization of thermoplastic composites often face challenges relating to the complexity of obtaining multiple parameters and the difficulty of achieving a final relative crystallinity of 1. To address these issues, this paper introduces a novel functional form of the crystallization rate parameter K(T), tailored for engineering applications, and proposes an improved Mampel model. This model assumes K(T) to be zero before the onset of crystallization and also to be linearly dependent on temperature thereafter, ensuring that the final relative crystallinity reaches 1. The model requires only two easily accessible parameters: the initial crystallization temperature (Ts) and the linear slope (k). The simplicity of the model makes it particularly well suited to engineering applications. This provides a straightforward and effective tool for describing the non-isothermal crystallization kinetics of fiber-reinforced thermoplastic composites. [ABSTRACT FROM AUTHOR]

Two‐step sequential deposition is a widespread technique for the fabrication of perovskite films, renowned for its better control of the crystallization process. However, achieving a well‐controlled and complete reaction of PbI2 by organic ammonium salts remains a key challenge. Previous studies have predominantly focused on regulating the properties of the PbI2 layer while paying less attention to the high reactivity of organic ammonium salts. In this study, the natural molecule anethole is first explored to control perovskite crystallization during two‐step sequential deposition, focusing on the reactivity modulation of organic formamidine ion (FA+). It is demonstrated that FA+ exhibits strong hydrogen bond interactions with anethole, inhibiting the high reactivity of FA+ and effectively delaying the rapid reaction between FAI and PbI2. This decelerates the crystallization kinetics of perovskite films, facilitating the orderly and complete reaction of PbI2 by FAI while suppressing detrimental δ‐phase formation. Consequently, FA‐based perovskite films with high crystallinity, preferred orientation, and low defect state density are obtained. The fabricated planar hole transport layer‐free carbon electrode perovskite solar cells deliver an efficiency of 20.41% (certified efficiency of 20.0%), which is a new record for this kind of solar cell. [ABSTRACT FROM AUTHOR]

Glass and glass ceramics are very functional materials, albeit their structural complexity. Their relevance ranges from fundamental science problems in the fields of physics, chemistry, and geoscience, to applications in health areas, engineering, or technological matters that require high performance. Enhancing our understanding of these materials' performance and refining sample preparation methods remains paramount in this field. Synchrotron facilities offer a suite of powerful techniques for the detailed characterization of glasses and glass ceramics. These methods provide valuable insights into their atomic and molecular structure, phase transformations, mechanical behavior, and thermal properties, ultimately contributing to the development of improved materials for a wide range of applications. In‐depth investigations conducted under extreme conditions of pressure and temperature have yielded pivotal insights into densification mechanisms, phase transitions, crystallization kinetics, and their consequential macroscopic properties. The emergence of fourth‐generation synchrotrons brings in a wave of novel experimental possibilities that may exert a profound influence on this field in the coming decade. In this study, we unveil a selection of the remarkable capabilities now accessible to researchers at the Brazilian Synchrotron Light Source—Sirius, within the realm of extreme methods of analysis (EMA) beamline for investigating vitreous systems under extreme conditions. [ABSTRACT FROM AUTHOR]

In this study, investigations of the non-isothermal crystallization kinetics of polyamide 6 (PA6) and PA6/m-lignin composites were conducted by differential scanning calorimetry (DSC). The crystallization kinetics of the PA6, including crystallization temperature and rate, were characterized by monitoring the heat flow during cooling. The study found that the crystallization temperature shifted to lower temperatures and the crystallization kinetics slowed down with increasing lignin. Besides, the Avrami equation modified by Jeziorny and Mo's method were used to study the non-isothermal crystallization kinetics of the neat PA6 and PA6 composites. The curve fit resulting from the modified Avrami equation was not convincing. However, Mo's method did successfully characterize the overall non-isothermal crystallization kinetics for neat PA6 and the PA6 composites. In addition, the activation energies of the non-isothermal crystallization were calculated by the Kissinger method. It was found that the PA6 composite crystallization rate increased when adding less than 10% lignin. However, the more the content of m-lignin, the slower the crystallization rate. The same conclusion was reached based on the fitting results of the non-isothermal crystallization activation energies. [ABSTRACT FROM AUTHOR]

Two copolymer polyethylenes of raised temperature resistance (PE-RT) were used to analyze their basic properties and molecular structure, including their basic physical properties, molecular weight and distribution, molecular chain structure, and aggregation structure of the product; the crystallization kinetics and other properties differences are also discussed. The results showed that the basic physical properties of the two resins were similar, but there were still some differences in molecular structure. The molecular weight of PE-RT-1 was slightly lower in the range of 500,000–1,000,000 molecular weight, and slightly higher in the range of <500,000 molecular weight than PE-RT-2. The crystallization capacity of the crystallizable part of PE-RT-2 was slightly better than that of PE-RT-1. The comonomer (1-butene) content and polymer branching degree of PE-RT-2 were higher than those of PE-RT-1. The crystallinity of PE-RT-1 products was higher than that of PE-RT-2, and the lattice structure of PE-RT-1 was more complete and had good heat resistance. In addition, the butene content of PE-RT-2 with high molecular weight was higher than those of PE-RT-1, which was more conducive to the generation of tie molecules. [ABSTRACT FROM AUTHOR]

Nucleation and growth during the crystallization process are crucial steps that determine the crystal structure, size, morphology, and purity. A thorough understanding of these mechanisms is essential for producing crystalline products with consistent properties. This study investigates the solubility of tacrolimus (FK506) in an ethanol–water system (1:1, v/v) and examines its crystallization kinetics using batch crystallization experiments. Initially, the solubility of FK506 was measured, and classical nucleation theory was employed to analyze the induction period to determine interfacial free energy ( γ ) and other nucleation parameters, including the critical nucleus radius ( r * ), critical free energy ( ∆ G * ), and the molecular count of the critical nucleus ( i * ). Crystallization kinetics under seeded conditions were also measured, and the parameters of the kinetic model were analyzed to understand the effects of process states such as temperature on the crystallization process. The results suggested that increasing temperature and supersaturation promotes nucleation. The surface entropy factor ( f ) indicates that the tacrolimus crystal growth mechanism is a two-dimensional nucleation growth. The growth process follows the particle size-independent growth law proposed by McCabe. The estimated kinetic parameters reveal the effects of supersaturation, temperature, and suspension density on the nucleation and growth rates. [ABSTRACT FROM AUTHOR]

Tin-lead halide perovskites with a bandgap near 1.2 electron-volt hold great promise for thin-film photovoltaics. However, the film quality of solution-processed Sn-Pb perovskites is compromised by the asynchronous crystallization behavior between Sn and Pb components, where the crystallization of Sn-based perovskites tends to occur faster than that of Pb. Here we show that the rapid crystallization of Sn is rooted in its stereochemically active lone pair, which impedes coordination between the metal ion and Lewis base ligands in the perovskite precursor. From this perspective, we introduce a noncovalent binding agent targeting the open metal site of coordinatively unsaturated Sn(II) solvates, thereby synchronizing crystallization kinetics and homogenizing Sn-Pb alloying. The resultant single-junction Sn-Pb perovskite solar cells achieve a certified power conversion efficiency of 24.13 per cent. The encapsulated device retains 90 per cent of the initial efficiency after 795 h of maximum power point operation under simulated one-sun illumination. The film quality of Sn-Pb perovskites is compromised by the asynchronous crystallization. Here, the authors introduce a noncovalent binding agent to target unsaturated Sn(II) solvate, achieving certified efficiency of 24.13% for operationally stable single-junction Sn-Pb perovskite solar cells. [ABSTRACT FROM AUTHOR]

Disentangling nucleation and growth in materials that crystallize on the nanosecond time scale is experimentally quite challenging since the relevant processes also take place on very small, i.e., sub‐micrometer length scales. Phase change materials are bad glass formers, which often crystallize rapidly. Here systematic changes in crystallization kinetics are shown in pseudo‐binary compounds of GeTe and Sb2Te3 and related solids subjected to short laser pulses. Upon systematic changes in stoichiometry, the speed of crystallization changes by three orders of magnitude concomitantly with pronounced changes in stochasticity. Resolving individual grains with electron backscatter diffraction (EBSD) permits to disentangle of the process of nucleation and growth. From these experiments, supported by multiphysics simulations of crystallization, it can be concluded that high crystallization speeds with small stochasticity characterize phase change materials with fast nucleation, while compounds that nucleate slowly crystallize much more stochastically. [ABSTRACT FROM AUTHOR]

Photoactive black‐phase formamidinium lead triiodide (α‐FAPbI3) perovskite has dominated the prevailing high‐performance perovskite solar cells (PSCs), normally for those spin‐coated, conventional n‐i‐p structured devices. Unfortunately, α‐FAPbI3 has not been made full use of its advantages in inverted p‐i‐n structured PSCs fabricated via blade‐coating techniques owing to uncontrollable crystallization kinetics and complicated phase evolution of FAPbI3 perovskites during film formation. Herein, a customized crystal surface energy regulation strategy has been innovatively developed by incorporating 0.5 mol % of N‐aminoethylpiperazine hydroiodide (NAPI) additive into α‐FAPbI3 crystal‐derived perovskite ink, which enabled the formation of highly‐oriented α‐FAPbI3 films. We deciphered the phase transformation mechanisms and crystallization kinetics of blade‐coated α‐FAPbI3 perovskite films via combining a series of in‐situ characterizations and theoretical calculations. Interestingly, the strong chemical interactions between the NAPI and inorganic Pb−I framework help to reduce the surface energy of (100) crystal plane by 42 %, retard the crystallization rate and lower the formation energy of α‐FAPbI3. Benefited from multifaceted advantages of promoted charge extraction and suppressed non‐radiative recombination, the resultant blade‐coated inverted PSCs based on (100)‐oriented α‐FAPbI3 perovskite films realized promising efficiencies up to 24.16 % (~26.5 % higher than that of the randomly‐oriented counterparts), accompanied by improved operational stability. This result represented one of the best performances reported to date for FAPbI3‐based inverted PSCs fabricated via scalable deposition methods. [ABSTRACT FROM AUTHOR]

Highlights Polymer nanocomposites boast complex microstructures with instant control of final performance, including mechanical strength, thermal stability, and crystallinity. Although tremendous studies have been devoted to understanding the structure–property relation of polymer nanocomposites, the effect of simultaneous nanomaterial contents on binary polymers remains unclear. Here, we report how the microstructure and rheological characteristics are subject to change upon adding a hybrid multi‐walled carbon nanotube (CNT) and graphene nanoplatelet (GNP). We choose a refined binary system based on polypropylene (PP) as a commodity polymer with proven long‐standing applications, alongside ethylene‐butylene copolymer (EBC) with a random ethylene and butylene monomers orientation for better impact strength acquisition. Rheology and microscopy imaging support an adequate dispersion of both materials across the PP/EBC blend, similar to when a single‐particle nanocomposite is examined. Beyond investigating the heterogeneous nucleation role of CNT and GNP, the crystallinity rate and the half‐time parameter for completing the ordered transformation are calculated using the Avrami equations. The thermal stability as well as the mechanical properties of all nanocomposites reveal improved resilience under heat and external stress, leading to a rising trend in decomposition temperature, tensile strength, and modulus. Synergistic effect of hybrid CNT and GNP on the thermal stability of PP/EBC. The impact of hybrid CNT and GNP on crystallization kinetics. Improvement of the mechanical performance with CNT/GNP loading. Role of PP‐g‐MA on the dispersion and distribution of CNT and GNP. [ABSTRACT FROM AUTHOR]

It has been validated that enhancing crystallinity and passivating the deep‐level defect are critical for improving the device performance of kesterite Cu2ZnSn(S,Se)4 (CZTSSe) solar cells. Coordination chemistry interactions within the Cu‐Zn‐Sn‐S precursor solution play a crucial role in the management of structural defects and the crystallization kinetics of CZTSSe thin films. Therefore, regulating the coordination environment of anion and cation in the precursor solution to control the formation process of precursor films is a major challenge at present. Herein, a synergetic crystallization modulation and defect passivation method is developed using P2S5 as an additive in the CZTS precursor solution to optimize the coordination structure and improve the crystallization process. The alignment of theoretical assessments with experimental observations confirms the ability of the P2S5 molecule to coordinate with the metal cation sites of CZTS precursor films, especially more liable to the Zn2+, effectively passivating the Zn‐related defects, thereby significantly reducing the defect density in CZTSSe absorbers. As a result, the device with a power conversion efficiency of 14.36% has been achieved. This work provides an unprecedented strategy for fabricating high‐quality thin films by anion‐coordinate regulation and a novel route for realizing efficient CZTSSe solar cells. [ABSTRACT FROM AUTHOR]

A series of partially bio-based and biodegradable poly(propylene terephthalate-co-adipate) (PPTA) random copolymers with different components were prepared by the melt polycondensation of petro-based adipic acid and terephthalic acid with bio-based 1,3-propanediol. The microstructure, crystallization behavior, thermal properties, and enzymatic degradation properties were further investigated. The thermal decomposition kinetics was deeply analyzed using Friedman's method, with the thermal degradation activation energy ranging from 297.8 to 302.1 kJ/mol. The crystallinity and wettability of the copolymers decreased with the increase in the content of the third unit, but they were lower than those of the homopolymer. The thermal degradation activation energy E, carbon residue, and reaction level n all showed a decreasing trend. Meanwhile, the initial thermal decomposition temperature (Td) was higher than 350 °C, which can meet the requirements for processing and use. The PPTA copolymer material still showed excellent thermal stability. Adding PA units could regulate the crystallinity, wettability, and degradation rate of PPTA copolymers. The composition of PPTA copolymers in different degradation cycles was characterized by 1H NMR analysis. Further, the copolymers' surface morphology during the process of enzymatic degradation also was observed by scanning electron microscopy (SEM). The copolymers' enzymatic degradation accorded with the surface degradation mechanism. The copolymers showed significant degradation behavior within 30 days, and the rate increased with increasing PA content when the PA content exceeded 45.36%. [ABSTRACT FROM AUTHOR]

This study reports on the successful synthesis of Zn 2 P 2 O 7 glass using the conventional melt-quenching method. The state of the material has been investigated using X-ray Diffraction (XRD) and Differential Scanning Calorimetry (DSC), to verify its amorphous and glassy state with the onset of two distinct crystallization peaks. These peaks were indicative of the transition to α-Zn 2 P 2 O 7 and γ-Zn 2 P 2 O 7 phases during the annealing process, a finding that was supported by Fourier-transform infrared spectroscopy (FTIR) analysis. This marked the inaugural occasion where the stabilization of both Zn 2 P 2 O 7 phases from their respective annealed glassy state was achieved. The crystallization kinetics and associated parameters of Zn 2 P 2 O 7 glass were deeply delved into, with various models including Kissinger, Ozawa, and the Matusita-Sakka approach. The applied models elucidate the mechanisms of growth and nucleation within the glass matrix. This kinetic study provided valuable insights into the crystallization process, revealing that α-Zn 2 P 2 O 7 is both kinetically and thermally more stable than the γ-phase. However, it is less thermodynamically stable compared to the γ-phase. Besides, the study of phase transformations and crystallization kinetics was enhanced by the analysis of the Avrami index. [ABSTRACT FROM AUTHOR]

Cesium zirconium halide (e.g., Cs2ZrCl6:Te or CZCT) perovskites have garnered significant interest due to their unique optical properties. However, there have been no reports of CZCT perovskite nanoparticles (PNPs) that simultaneously offer high efficiency and thermal stability. Here, a comprehensive defect suppression strategy is reported to achieve CZCT PNPs with these attributes. First, the inner defects of CZCT perovskite microcrystals (PMCs) are minimized by controlling crystallization kinetics precisely. Second, the PNPs are obtained from PMCs via top‐down fabrication, and the surface defects of PNPs are passivated via the hydroxyl groups of alkyl‐terminated silica‐oligomer shell (ASO). The resulting CZCT@ASO PNPs show the highest photoluminescence quantum yield (PLQY) of 96% and high thermal stability among the reported conventional CZCT emitters. Finally, white light‐emitting diodes (WLEDs) are integrated by using CZCT@ASO PNPs as the down‐color converters, achieving a color coordinate of (0.31, 0.33) and a color rendering index of 86. These results demonstrate that core/shell CZCT@ASO PNPs have great potential as phosphors for lighting applications. [ABSTRACT FROM AUTHOR]

Ideal nanoscale morphology of heterojunction active layer is important for the development of organic solar cells (OSCs). However, the mismatched crystalline kinetic between the polymer donor and small molecular acceptor often leads to the difficulties in controlling the morphology of the active layer. Herein, polar 1,2‐dibromo‐4,5‐difluorobenzene (DFB) and non‐polar 1,4‐dibromotetrafluorobenzene (TFB) are developed as the volatile additives for OSCs. More attractively, different from the reported volatile additives, both new volatile additives can simultaneously interact with donor and acceptor, synergistic regulating the crystallization kinetic and well‐balancing the crystallization behaviors between the polymer donor and small molecular acceptor during film formation process. Notably, due to the stronger dipole‐dipole interactions with active layer, polar DFB induces the more favorable film morphology than non‐polar TFB. As a result, the two additives‐treated PM6:Y6 devices both outperform the CN‐treated device (16.13%), and the polar DFB‐treated device deliver a higher efficiency of 17.15% than non‐polar TFB‐treated one (16.30%). With polar DFB additive, PM6:L8‐BO and PM6: BTP‐eC9 also achieve superior efficiency of 18.46% and 18.17%, respectively. This work deepens the insights of regulating crystallization kinetics and optimizing nanoscale morphology by developing simple volatile additives for further achieving high‐efficient OSCs. [ABSTRACT FROM AUTHOR]

Highlights In this paper, the reasons for the improved wear resistance of irradiation‐modified Polytetrafluoroethylene (RM‐PTFE) and its composites above the melting point were investigated from the microcrystalline point of view by using methods such as crystallization kinetics, and it was found that the linear wear rate of RM‐PTFE was only 0.3 um/km, with a 1000 times increase in wear resistance, which was due to the transformation of its crystals from flake crystals that were easily dislodged to spherical crystals that were more resistant to abrasion. It was also found that the linear wear rate of Polytetrafluoroethylene (PTFE) with coke and graphite was 0.2 and 0.1 μm/km, respectively, and the abrasion resistance was further improved, which was attributed to the lowering of spherical crystal grain size by coke and graphite, which had better mechanical properties. These studies lay the foundation for future research on the frictional wear mechanism of RM‐PTFE above the melting point. Irradiation‐modified PTFE above the melting point Wear resistance of PTFE increases 1000 times Changes in crystal morphology dramatically increase wear resistance Use of crystallization kinetics to study the crystalline form of PTFE Small grain size improves wear resistance [ABSTRACT FROM AUTHOR]

Highlights By incorporating nanomaterials into polymer matrices, nanocomposites can be produced with enhanced properties, combining the ease of processing thermoplastics with the superior physical characteristics of nanoparticles. In this study, fully bio‐based polyamide 1010 was used as the polymer matrix, with graphene oxide (GO), hexagonal‐boron nitride (h‐BN), and molybdenum disulfide (MoS2), both individually and in hybrids, serving as fillers. The tensile behavior of these nanocomposites was evaluated at room temperature and −40 °C, along with their morphology and microstructure. Results showed that the nanomaterials slightly shifted the polymer's crystallization temperature upward, indicating a small nucleating effect, but also hindered the development of crystalline domains, reducing the crystallization kinetics. Despite no change in the final crystalline form, nanocomposites with h‐BN and MoS2 showed lower microstructural order as evidenced by XRD. Regarding tensile behavior, GO provided the greatest toughening at room temperature due to its larger lateral dimensions and good chemical affinity with the matrix. However, at low temperatures, h‐BN‐based nanocomposites maintained the toughening effect better than GO‐based ones. This can be attributed to the lower order of the polymer's semi‐crystalline structure promoted by h‐BN, allowing greater energy dissipation. Surprisingly, hybrid fillers did not exhibit synergistic effects, with one nanomaterial hampering the effect of the other. However, SEM analysis indicated that the fracture mechanisms of the nanocomposites remained unchanged from the neat polymer, which makes them interesting options for applications that require desirable mechanical properties at a wide temperature range. GO showed the best toughening of polyamide 1010 at room temperature. Toughening at room temperature is mainly due to nanomaterials physical traits. Most nanofillers lowered polyamide's overall microstructural order. Toughening at −40 °C is mainly due to lower microstructural order. [ABSTRACT FROM AUTHOR]

Hybrid Perovskite materials have gone through an astonishing development due to their unique optoelectronic behavior, leading to the creation of a wide range of synthetic strategies. As the materials’ surface is found to play a crucial role with respect to the properties, e.g. hydration, stability and carrier mobilities, considerable efforts have been made to optimize the surface through various approaches. Especially the passivation of the perovskite surface attracted a lot of attention in this field, often resulting in more complex, multi‐step synthetic processes. In this study, a simple one‐step aerosol‐assisted synthetic approach is presented to obtain thiocyanate (SCN) passivated single‐crystal MAPbBr3 microcrystals. To elucidate the role of the additive in the crystallization process, mixed (pseudo‐)halide precursors are systematically investigated. The as processed, passivated microcrystals exhibit enhanced stability and charge carrier lifetimes. Additionally, a decrease in surface photovoltage, attributed to the presence of the SCN additive, is observed. Furthermore, the aerosol process is further developed resulting in a novel binary system containing MAPbBr3‐SCN perovskite microcrystals and Au nanostructures. This system serves as a promising model for further investigations into potential interactions between plasmonic and semiconducting materials, with initial results indicating prolonged charge carrier lifetimes. [ABSTRACT FROM AUTHOR]

Polylactic acid (PLA) is currently the largest volume of production and application of synthetic biodegradable polymer via bio-derived materials. However, the relaxation characteristics and very low crystallization rate determined by the hand- structure of PLA chains result in low heat-resistance temperature and troublesome demold behavior for fast extrusion and/ or injection molding process. It is well known, by introducing of nucleating agent and crystal growing accelerator, the crystallization properties of PLA materials can be improved efficiently. In the paper, the isothermal crystallization behaviors of PLA, which include the rate and temperature of crystallization, crystallinity, crystals morphologies, were systemically shown. Meanwhile, a serious of regulation strategies of isothermal crystallization kinetics of PLA materials, such as adding of biodegradable polymers, different dimension of fillers, various chain-reconstruct for PLA, processing flow fields and post-treatment, were comprehensively summarized. Additionally, the regularity strategies and next study points for PLA isothermal crystallization behavior were also presented. [ABSTRACT FROM AUTHOR]

In response to an investigation on the paths of changes in the crystallization and radial differences during the forming process of nascent fibers, in this study, we conducted numerical simulation and analyzed the changes in crystallization mechanical parameters and tensile properties through a fluid dynamics two-phase model. The model was based on the melt-spinning method focusing on melt spinning, the environment of POLYFLOW, and the method of joint simulation, coupled with Nakamura crystallization kinetics, including the development of process collaborative parameters, stretch-induced crystallization, viscoelasticity, filament cooling, gravity term, inertia, and air resistance. Finally, for nylon 6 BHS and CN9987 resin spinning, the model successfully predicted the distribution changes in temperature, velocity, strain rate tensor, birefringence, and stress tensor along the axial and radial fibers and obtained the variation pattern of fibers' crystallinity along the entire spinning process under different stretching rates. Furthermore, we also explored the effects of spinning conditions, including inlet flow rate, winding speeds, and the extrusion temperature, on the fibers' crystallization process and obtained the influence rules of different spinning conditions on fiber crystallization. Knowing the paths of changes in mechanical performance can provide important guidance and optimization strategies for the future industrial preparation of high-performance fibers. [ABSTRACT FROM AUTHOR]

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This research was aimed to conduct solvent‐free crystallization and fractionation of virgin coconut oil (VCO). This study investigated the effect of surface contact area‐to‐volume ratio and mixing conditions on crystal characteristics. Commercially available VCO samples, extracted by different methods, were analyzed for fatty acid and triacylglycerol composition using GC–MS and UPLC–ELSD. VCO extracted through enzyme and chilling–thawing cycles exhibited higher medium chain fatty acids and medium chain triacylglycerols, which was selected for crystallization studies. Isothermal crystallization of VCO at 21°C assessed the effect of scale of crystallizer tube on cooling rate using Newton's law of cooling equation. The smaller tube (20 mm diameter) with a higher surface contact area‐to‐volume ratio produced 4.1‐fold faster cooling and a higher crystallization yield (44%) compared to the 80 mm diameter tube when no agitation was applied. Whereas mixing with a magnetic stirrer produced a large number of nuclei, generating intense crystallization heat, and rendering the crystals inseparable from liquid fraction. The process of VCO crystallization was also studied for kinetics and crystal growth mechanism using the Avrami model employing angled rotation of sample tube during non‐isothermal crystallization. Angled rotary mixing produced stable crystals and significantly increased the crystallization rate (t1/2 = 26.86 min) with polyhedral or spherulitic crystal growth (n = 3.25) compared to non‐mixing condition (t1/2 = 161.87 min) with restricted linear growth (n = 1.64). DSC analysis of VCO and its fractions obtained after crystallization using the 20 mm tube with angled rotary mixing indicated shifts in their thermogram peaks, suggesting differences in triacylglycerol compositions. Practical applications: Virgin coconut oil (VCO) is well recognized for its health‐beneficial properties, yet its application is limited due to its complex triglyceride composition. The solvent‐free crystallization method facilitates VCO fractionation into phases with different melting points without hazardous solvents. The efficacy of this process is highly dependent on temperature, cooling rate, and agitation, which affects crystal morphology and growth kinetics. This study addresses these challenges in the scarcely investigated area of VCO crystallization. The resulting fractions can be customized for specific applications based on their altered functional properties in producing baking and confectionery coatings, salad dressings, and so on. The olein fraction obtained in this study can be utilized in nutraceutical formulations targeting digestive and cognitive health, as it is reported to be rich in medium chain triglycerides. This research optimizes process conditions, suggesting an efficient method for dry‐fractionating VCO, which is significantly associated with the food and pharmaceutical industries. [ABSTRACT FROM AUTHOR]

Herein, we investigate the effect of the addition of tetra‐needle‐like zinc oxide whisker (T‐ZnOw), a novel reinforcing additive, on the melt crystallization behavior of biodegradable polybutylene adipate terephthalate (PBAT)/polylactic acid (PLA) polymer blends. PBAT and PLA were blended in a Haake mixer at a fixed weight ratio of 70/30, and the contents of T‐ZnOw varied from 0 to 7 wt%. The melt thermal properties and crystallization behavior of PBAT/PLA blends and PBAT/PLA/T‐ZnOw composites were studied using differential scanning calorimetry. The kinetics of melt crystallization have been quantitatively explained using a range of mathematical formalisms. The Avrami equation is adopted to analyze the isothermal crystallization process and kinetics of PBAT/PLA/T‐ZnOw composites. For its nonisothermal crystallization process and kinetics, the Ozawa equation cannot describe the entire process, while the Jeziomy‐modified Avrami equation can only describe the initial stage of its nonisothermal crystallization. Using Mo‐analysis, the impact of T‐ZnOw contents on the composite's nonisothermal crystallization kinetic has been thoroughly examined. Given that the PBAT/PLA blend system's crystal formation may be inhibited by T‐ZnOw, the observation demonstrates that T‐ZnOw only marginally alters this process. The work is of significant scientific value and adds a new concept to the development of sustainable thin film for packaging. Highlights: T‐ZnOw is used as a novel additive for PBAT/PLA polymer blends.The crystallization of PBAT/PLA/T‐ZnOw composite systems is thoroughly examined.T‐ZnOw marginally reduces the kinetics of the crystallization process of PBAT/PLA blends.PBAT/PLA/T‐ZnOw composites follow volume nucleation with mixed 2D/1D growth.The nonisothermal crystallization of PBAT/PLA/T‐ZnOw composites is validated by Mo‐analysis. [ABSTRACT FROM AUTHOR]

The performance of sustainable polymers can be modified and enhanced by incorporating functional groups in the backbone of the polymer chain that increases intermolecular interactions, thus impacting the thermal properties of the material. However, in-depth studies on the role of intermolecular interactions on the crystallization of these polymers are still needed. This work aims to ascertain whether incorporating functional groups able to induce intermolecular interactions can be used as a suitable systematic strategy to modify the polymer thermal properties and crystallization kinetics. Thus, amide and additional ester groups have been incorporated into aliphatic polyesters (PEs). The impact of intermolecular interactions on the melting and crystallization behavior, crystallization kinetics, and crystalline structure has been determined. Functional groups that form strong intermolecular interactions increase both melting and crystallization temperatures but retard the crystallization kinetics. Selecting appropriate functional groups allows tuning the crystallinity degree, which can potentially improve the mechanical properties and degradability in semicrystalline materials. The results demonstrate that it is possible to tune the thermal transitions and the crystallization kinetics of PEs independently by varying their chemical structure. [ABSTRACT FROM AUTHOR]

The Er3+/Yb3+ co‐doped tellurite glasses and glass‐ceramics (GCs) containing the Gd2Te6O15 phase were successfully fabricated via the conventional melting‐quenching technique followed by a crystallization regime. The Er3+/Yb3+ co‐doped tellurite glasses generated intense up‐conversion green (524 and 546 nm) and red (658 nm) emissions when stimulated by a 980 nm laser. The up‐conversion green emission intensity increased by 68 and 46 times with the increase of the Yb3+/Er3+ ratio, and the optimal Yb3+/Er3+ ratio was found to be 8:1. The surface crystallization process of the Gd2Te6O15 GCs was confirmed through analysis of crystallization kinetics and microscopic morphology. The up‐conversion luminescence and lifetime of Er3+ ions were enhanced by the precipitation of low‐phonon‐energy Gd2Te6O15 crystals. The GC sample crystallized at 480°C for 4 h showed the highest luminescence intensity. The optical thermometry properties of Er3+ ions at thermally coupled energy levels (2H11/2/4S3/2→4I15/2) were explored. The Gd2Te6O15 GCs co‐doped with 0.25 mol% Er2O3 and 2.0 mol% Yb2O3 exhibited an excellent temperature relative sensitivity (Sr) of 1.22% K−1 at 293 K and a great repeatability of 98.07%. These results suggest that the Er3+/Yb3+ co‐doped Gd2Te6O15 GCs show promise for optical thermometry. [ABSTRACT FROM AUTHOR]

Based on the Matusita–Sakka equation and the exothermic peaks in the differential thermal analysis (DTA) curves, in silicate glasses with complex crystallization processes containing the precipitation of two or more crystal phases, the effects of particle sizes on the calculations of crystal growth dimensionality and activation energy of crystal growth have been studied in depth. In crystallization processes with two or more crystal phases but one exothermic peak, 0.3 mm is considered as the boundary between the fine and the coarse particles in this type of glass. For glass samples with a particle size less than 0.3 mm, the crystal growth dimensionality is a three‐dimensional mechanism, and EG increases slightly with decreasing particle size. For glass samples with a particle size greater than 0.3 mm, the crystal growth dimensionality is a two‐dimensional mechanism, and EG increases with decreasing particle size. The EG for the fine‐particle starting material is much lower than that of the coarse‐particle starting material. In crystallization processes with two or more crystal phases and two exothermic peaks, 0.104 mm is considered as the boundary between the fine and the coarse particles in this type of glass raw material. For the first peak, in glass samples with a particle size less than 0.104 mm, the crystal growth mechanism is mainly one‐dimensional growth, and EG increases slightly with decreasing particle size. And for glass samples with particle size greater than 0.104 mm, the crystal growth mechanism is mainly two‐dimensional growth, and EG decreases with decreasing particle size. For the second peak, the crystal growth mechanism is mainly a three‐dimensional growth, and EG increases with decreasing particle size. [ABSTRACT FROM AUTHOR]

Clathrate hydrates are crystalline inclusion compounds wherein a water framework encages small guest atoms/molecules within its cavities. Among the others, methane clathrates are the largest fossil fuel resource still available. They can also be used to safely transport gases and can also form spontaneously under suitable conditions plugging pipelines. Understanding the crystallization mechanism is very important, and given the impossibility of experimentally identifying the atomistic path, simulations played an important role in this field. Given the large computational cost of these simulations, in addition to all-atom force fields, scientists considered coarse-grained water models. Here, we have investigated the effect of coarse-graining, as implemented in the water model mW, on the crystallization characteristics of methane clathrate in comparison with the all-atom TIP4P force field. Our analyses revealed that although the characteristics directly depending on the energetics of the water models are well reproduced, dynamical properties are off by the orders of magnitude. Being crystallization a non-equilibrium process, the altered kinetics of the process results in different characteristics of crystalline nuclei. Both TIP4P and mW water models produce methane clathrate nuclei with some amount of the less stable (in the given thermodynamic conditions) structure II phase and an excess of pentagonal dodecahedral cages over the tetrakaidecahedral ones regarding the ideal ratio in structure I. However, the dependence of this excess on the methane concentration in solution is higher with the former water model, whereas with the latter, the methane concentration in solution dependence is reduced and within the statistical error. [ABSTRACT FROM AUTHOR]

We here review mostly experimental and some computational work devoted to nucleation in amorphous ices. In fact, there are only a handful of studies in which nucleation and growth in amorphous ices are investigated as two separate processes. In most studies, crystallization temperatures Tx or crystallization rates RJG are accessed for the combined process. Our Review deals with different amorphous ices, namely, vapor-deposited amorphous solid water (ASW) encountered in many astrophysical environments; hyperquenched glassy water (HGW) produced from μm-droplets of liquid water; and low density amorphous (LDA), high density amorphous (HDA), and very high density amorphous (VHDA) ices produced via pressure-induced amorphization of ice I or from high-pressure polymorphs. We cover the pressure range of up to about 6 GPa and the temperature range of up to 270 K, where only the presence of salts allows for the observation of amorphous ices at such high temperatures. In the case of ASW, its microporosity and very high internal surface to volume ratio are the key factors determining its crystallization kinetics. For HGW, the role of interfaces between individual glassy droplets is crucial but mostly neglected in nucleation or crystallization studies. In the case of LDA, HDA, and VHDA, parallel crystallization kinetics to different ice phases is observed, where the fraction of crystallized ices is controlled by the heating rate. A key aspect here is that in different experiments, amorphous ices of different "purities" are obtained, where "purity" here means the "absence of crystalline nuclei." For this reason, "preseeded amorphous ice" and "nuclei-free amorphous ice" should be distinguished carefully, which has not been done properly in most studies. This makes a direct comparison of results obtained in different laboratories very hard, and even results obtained in the same laboratory are affected by very small changes in the preparation protocol. In terms of mechanism, the results are consistent with amorphous ices turning into an ultraviscous, deeply supercooled liquid prior to nucleation. However, especially in preseeded amorphous ices, crystallization from the preexisting nuclei takes place simultaneously. To separate the time scales of crystallization from the time scale of structure relaxation cleanly, the goal needs to be to produce amorphous ices free from crystalline ice nuclei. Such ices have only been produced in very few studies. [ABSTRACT FROM AUTHOR]

A glass-ceramic material containing nanosized crystallites is synthesized based on the natural volcanic material perlite. Using the differential thermal analysis (DTA) method, the effect of Na₂SiF₆ (a crystallization catalyst from the fluoride group) on the glass crystallization properties is studied. The characteristic glass-transition temperature 𝑇𝑔, peak crystallization temperature 𝑇𝑝, as well as the crystallization activation energy (Ec) and Avrami index (n) are determined in terms of the catalyst content in the initial composition. A decrease in the nucleation agent content is shown to increase 𝑇𝑔, 𝑇𝑝, and Ec. The effect of the crystallization catalyst content on the crystallization mechanism and glass mechanical properties is discussed.

Poly(butylene 2,5‐thiophenedicarboxylate) (PBTh) is a novel biobased semicrystalline polyester with superior thermal, mechanical, and gas barrier properties; however, the crystallization kinetics and melting behavior of PBTh have not been studied in detail so far. The crystallization kinetics of PBTh was first studied in this research. The Ozawa equation failed to describe the nonisothermal melt crystallization kinetics of PBTh due to the secondary crystallization. The crystallization activation energy value was calculated by the Friedman method, which was negative and exhibited the conversion dependence. The isothermal melt crystallization kinetics of PBTh was well described by the Avrami equation in a wide range of crystallization temperature from 84 to 120 °C. PBTh showed the fastest crystallization rate at 104 °C; moreover, the Avrami exponent value slightly varied between 2.2 and 2.7, suggesting the same crystallization mechanism within the investigated temperature range. PBTh displayed one or two melting endotherms depending on crystallization temperature, which was well explained by the melting, recrystallization, and remelting mechanism. In addition, the equilibrium melting point of PBTh was estimated to be 163.1 °C with the Hoffmann−Weeks equation. [ABSTRACT FROM AUTHOR]

We present a theory of melting kinetics of semicrystalline polymers at temperatures above the equilibrium melting temperature, by accounting for conformational entropy of chains during melting. We have derived free energy landscapes for escape of individual chains from a lamella into the amorphous phase as a function of the characteristics of the initial lamella, such as the lamellar thickness, number of chain folds, fold‐ and lateral‐surface free energies, and mean energy of a monomer inside the lamella. We show that melting of lamellae is always accompanied by a free energy barrier which is entirely entropic in origin. In terms of the parameters characterizing the lamellae and the extent of superheating, closed‐form formulas are presented for the equilibrium melting temperature, driving force for crystallization, free energy barrier height, average expulsion time of a single chain from a lamella, and the melting velocity of lamellae. The present entropic barrier theory predicts that the dependence of melting velocity on superheating is nonlinear and non‐Arrhenius, in qualitative agreement with experimental observations reported in the literature. The derived formulas open an opportunity to further explore the role of various molecular features of semicrystalline polymers on their melting kinetics. [ABSTRACT FROM AUTHOR]

Introduction of fluorescent down‐conversion layer inside perovskite solar cells (PSCs) can highly improve the ultraviolet response of the devices and the light stability. However, such a device is usually confronted with the problem of inter‐diffusion with the perovskite absorber layer, which severely limits its further development. To address this problem, herein, this work employs an interfacial dual electron transport layers (ETLs) strategy, sandwiching Cd‐CsPbCl3:Mn2+ luminescent quantum dots within gap of the ETLs, which not only reduces the interface energy level offset, but also improves the nucleation and crystallization kinetics of perovskite films and prevents their diffusion to the perovskite absorber layer. As a result, the efficient synergy effect effectively elevates both the open‐circuit voltage and fill factor of the PSCs, reaching maximum values of 1.181 V and 81.14%, respectively, finally delivering progressively increased device power conversion efficiency (PCE) of 24.32% with significantly improved light stability. To further improve the ultraviolet response, this work further adopts the strategy of dual fluorescent conversion layers inside and outside the PSCs, and finally obtains PCE of 24.63%, which is the best for various luminescent conversion cells. This work opens a new door for the development of efficient and stable photoluminescence conversion PSCs. [ABSTRACT FROM AUTHOR]