Crystallization Phenomena Research Articles

Crystal Evolution of Amorphous Poly(lactic acid) During Simultaneous Multi‐step Tensile Deformation and Annealing

ABSTRACTThe cold‐crystallization and crystal evolution of amorphous poly(lactic acid) (PLA) are analyzed during multistep tensile deformation and annealing at 70°C using in situ synchrotron wide‐angle X‐ray scattering (WAXS) measurements. The 2D‐WAXS diffraction pattern reveals that the PLA crystalline structure forms perpendicular to the draw direction. The annealing process lets to a rearrangement of the crystalline structure, while the stretching causes crystal contraction. Both WAXS and FTIR analyses confirm that the crystals developed through stretching and annealing are in the α′‐form. The crystallinity of PLA increases with higher deformation strains and longer annealing times. The orientation degree of both crystalline and amorphous phases of PLA, as indicated by the Hermans orientation factor and dichroic ratio of 956 cm−1 band (evaluated by WAXS and polarized FTIR analysis, respectively) also increase. The enhanced cold‐crystallization ability of PLA is attributed to the synergistic effect of tensile deformation and annealing, rather than either technique alone. The unusual crystallization phenomenon observed during multistep tensile deformation coupled with annealing provides valuable insights into the crystallization and crystal evolution of PLA.

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.

Graphene Nanoplatelet Induced Microphase Separation in Poly(ether-block-amide)s

The inclusion of graphene nanoplatelets (GNP) in segmented block copolymers offers a route to manipulate microphase separation for tailoring the mechanical properties of thermoplastic elastomers. GNP loading, lateral size, surface chemistry, interactions with the copolymer hard (HS) and soft (SS) segments and the relative ratio of HS:SS determine the mechanical properties achievable. To test this hypothesis, two different GNPs with similar surface chemistry but which differed in lateral dimensions by one order of magnitude (GNP1, ∼2μm and GNP2, ∼20μm) were melt mixed with three different poly(ether-block-amide)s (PE-b-A)s with variable HS and SS content from high to low. The inclusion of the larger lateral sized GNP2 had a more pronounced effect on PE-b-A morphology as it was more effective at hindering SS chain mobility resulting in microphase separation and suppression of the glass transition temperature (Tg) of the PE-b-A with the largest SS content. At low loadings GNP2 preferentially locates to the HS region, inducing reorganisation of this phase resulting in increased microphase separation. Strain induced crystallisation (SIC) phenomena were also observed for the lowest HS content PE-b-A, behaviour not evident for the PE-b-A with the largest HS content as the SS are not long enough to allow SIC. Inclusion of GNP2 to the PE-b-A with the largest HS content resulted in the largest increase in Young’s modulus (E) of 46%, tensile strength (σ) of 37% and elongation at break (ε) of 53% relative to the unfilled polymer.

Evolution mechanism of Ti(C,N)-based cermet microstructure under microwave sintering

Experimental studies of microwave-sintered cermets were carried out at different sintering temperatures and holding times to investigate their microstructure evolution mechanism. Results of the study show that: (1) As sintering temperature increases, main microstructure evolution mechanisms of cermets are as follows: metal-phase melting, hard-phase skeleton filling of large pores in hard-phase skeletons, secondary rearrangement of the liquid phase (the liquid phase gradually fills the space between grains), and cooling down (precipitation–crystallization–reattachment); (2) As holding time increases, main microstructure evolution mechanisms of cermets are as follows: complete filling of large pores in the hard-phase skeleton, secondary rearrangement of the liquid phase, intense dissolution precipitation enhancing the formation of core-rim phase, and secondary homogeneous arrangement of the liquid phase. The special electromagnetic effects of microwave-sintered cermets and their influence on the sintering process were analyzed. It was found that both tip-discharge effect and hot-spot effect occurring during the microwave sintering process are conducive to the sintering process. The formation process of core-rim phase of cermets was also studied. Results show that: (1) Cermets form black core–white rim–grey rim structure via dissolution–precipitation and precipitation–crystallization phenomena; (2) Cermets form white core–grey rim structure through agglomeration of small particles, dissolution–precipitation, and precipitation–crystallization phenomena.

Monitoring and preservation of stone cultural heritage using a fuzzy model for predicting salt crystallisation damage

In this study, a fuzzy model is presented for predicting the possibility of degradation due to salt crystallisation cycles. The formalization of the proposed model has been based on the multivariable approach which considers environmental data (such as temperature, solar radiation, wind speed, rain quantity, relative humidity), characteristic inflection points of specific salts and stone features derived from laboratory characterizations (including mechanical properties, porosity, and mineralogical composition). Modeling results have been compared with experimental data elaborations acquired by monitoring a semi-confined archaeological site situated in the city of Cagliari (Munatius Irenaus cubicle), revealing substantial alignment in the degradation kinetics trends. Moreover, the achieved outcomes show the remarkable capability to identify salt crystallisation phenomenon type (efflorescence or subflorescence).

In-situ cryogenic X-ray diffraction analysis of Poly(dimethylsiloxane) oil and film

Understanding the phase transitions and crystallographic characteristics of polysiloxane materials poses a significant challenge. To address this issue, a custom cryogenic chamber has been developed and integrated with a laboratory X-ray diffraction apparatus, enabling the execution of in-situ temperature-dependent X-ray diffraction (XRD) analyses across the cooling and heating cycles. Through the utilization of diverse sample holders, the real-time monitoring of crystallization and melting phenomena in both linear poly(dimethylsiloxane) (PDMS) oil and crosslinked PDMS film has been made feasible. Notably, high-quality X-ray diffraction data, encompassing 13 diffraction lines, are successfully acquired for the first time for linear PDMS oil at 153K. Subsequent crystallographic examination has revealed a tetragonal unit cell characterized by lattice parameters a = b = 8.3379 Å, c = 11.9284 Å, and space group I 41, suggesting the adoption of a fourfold helical conformation by two polymer chains, each comprising four monomer units, within the lattice structure. This improved and versatile X-ray instrumentation presents clear advantages over conventional commercial powder X-ray diffractometers, which is anticipated to provide a promising in-situ characterization approach for investigating the low-temperature behaviors of liquid or oil materials.

Crystallization Morphology and Self-Assembly of Polyacrylamide Solutions During Evaporation

This study investigates the crystallization and self-assembly phenomena of polyacrylamide (PAM) solutions during evaporation. While traditional thin-film fabrication methods such as spin coating and drop casting are commonly used, this study utilizes a simple evaporation approach to gain insights into the self-assembly processes of PAM solutions. We examined PAM solutions with varying concentrations (1%, 2%, and 5%) and observed the resulting crystalline structures and morphological changes during evaporation. Spectroscopic absorbance measurements were employed to analyze concentration gradients and crystallization patterns. The findings reveal that the concentration gradient during evaporation significantly impacts the crystallization behavior of PAM solutions. The 2% solution exhibited the clearest and most regular crystalline patterns, whereas the 1% and 5% solutions displayed more complex and irregular morphologies. These observations provide new insights into how solution concentration influences PAM crystallization, contributing to a better understanding of polymer thin-film self-assembly. The novelty of this study lies in exploring PAM self-assembly through controlled evaporation, offering valuable insights for the development of polymer films.

Ab Initio Molecular Dynamics Simulations of Phosphocholine Interactions with a Calcium Oxalate Dihydrate (110) Surface.

We use ab initio modeling (CASTEP) to help elucidate the crystallization phenomena and chemistry behind kidney stone composition and formation. To explore the stone formation process, we have constructed a surface model of calcium oxalate dihydrate-the mineral most commonly found in patients with hypercalciuria and modeled stone growth, by simulating further calcium oxalate adsorption onto the surface (-7.446 eV, -0.065 eV/atom). Furthermore, urine analysis of kidney stone patients has previously revealed that their urine contains higher concentrations of phospholipids compared to healthy individuals. Therefore, to investigate the interactions between urinary macromolecules and the growing crystal surfaces at an atomic level, we have performed ab initio molecular dynamics simulations of phosphocholine adsorption on calcium oxalate surfaces. We have shown that the phosphocholine headgroups become entrapped within the growing crystal and the lowest energy structures (-18.008 eV, -0.0396 eV/atom) are those where the calcium oxalate dihydrate surfaces have become disrupted, with reorganization of their crystallographic structure. Urinary calculi (kidney stones) are a common ailment affecting around 10% of the world's population and resulting in nearly 90,000 finished consultant episodes (FCE) each year in the United Kingdom [Hospital Episode Statistics, Admitted Patient Care-England, 2011-12 NHS Digital, 2021-2022. https://digital.nhs.uk/data-and-information/publications/statistical/hospital-admitted-patient-care-activity/hospital-episode-statistics-admitted-patient-care-england-2011-12].

Effect of Fe2O3 addition on synthesis of diamond single crystal under high-pressure and high-temperature conditions

The influence of Fe2O3 addition on the growth characteristics of synthetic diamonds under high-temperature and high-pressure conditions was systematically investigated in this work. Utilizing Fe2O3 as an oxygen source within the Fe-Ni-C-O system, oxygen-containing diamond single crystals were synthesized. The role of the oxygen atoms during the growth of large-sized diamonds with the {111} face as the growth surface was also analyzed. In addition, the morphology, growth rate, internal nitrogen content, and crystal quality of the crystals were examined. From our analysis, it was demonstrated that an increase in Fe2O3 addition leads to a reduction in the size of the synthetic crystals and a gradual decrease in the growth rate. The diamonds with complete crystal forms exhibited no significant change in color, and all appeared yellow. When the addition exceeded a threshold, cracks appeared around the seed crystal at about 0.3 mm, resulting in a cracked crystal phenomenon. A further increase in the Fe2O3 addition resulted in the skeleton crystal, and the crystal color turned black. Fourier Transform Infrared Spectroscopy (FTIR) measurements were also conducted, indicating that the introduction of oxygen atoms increases the nitrogen content in the crystals, which in turn aggregates in the form of C-centered nitrogen. The Raman spectroscopy results showed that as Fe2O3 addition in the crystals increases, more impurities are introduced, leading to an increase in the diamond stress and a shift in the diamond Raman peak, along with an increase in the full width at half maximum. The photoluminescence (PL) characterization results indicated that with the increase of the Fe2O3 addition, the intensity of the photoluminescence peaks of NV− centers and W8 centers was enhanced, which is related to the increase in the internal C-centered nitrogen content of the crystals. From the acquired results, it was proven that Fe2O3 addition has a significant impact on the synthesis of diamond single crystals. Our work provides valuable pieces of experimental evidence for exploring the formation mechanism of natural diamonds.

Dynamic flexoelectric instabilities in nematic liquid crystals.

Electrohydrodynamic phenomena in liquid crystals constitute an old but still very active research area. The reason is that these phenomena play the key role in various applications of liquid crystals and due to the general interest of the physical community in out-of-equilibrium systems. Nematic liquid crystals (NLCs) are ideally representative for such investigations. Our article aims to study theoretically the linear NLCs dynamics. We include into consideration orientation elastic energy, hydrodynamic motion, external alternating electric field, electric conductivity, and flexoelectric polarization. We analyze the linear stability of the NLC film, determining dynamics of perturbations with respect to the homogeneous initial state of the NLC. For the purpose we compute eigenvalues of the evolution matrix for a period of the external alternating electric field. These eigenvalues determine the amplification factors for the modes during the period. The instability occurs when the principal eigenvalue of the evolution matrix becomes unity by its absolute value. The condition determines the threshold (critical field) for the instability of the uniform state. It turns out that one might expect various types of the instability, only partially known and investigated in the literature. Particularly, we find that the flexoelectric instability may lead to two-dimensionally space-modulated patterns exhibiting time oscillations. This type of the structures was somehow overlooked in the previous works. We formulate conditions needed for the scenario to be realized. We hope that the results of our work will open the door to a broad range of further studies. Of especial importance would be a comprehensive understanding of the role of various material parameters and nonlinear effects which is a key step for the rational design of NLCs exhibiting the predicted in this publication multidimensional oscillating in time patterns.

(Invited) 2D Liquid Crystals of Aligned Semiconducting Carbon Nanotubes at Liquid-Liquid Interfaces

Carbon nanotubes transport more electricity per area than silicon and more easily switch between on and off states with lower voltage, making them exciting for future, fast, low-energy logic and high-speed, linear RF devices. For nanotubes to offer the highest performance, they must be aligned in one direction in a single layer so that electricity can quickly and efficiently flow through them. This has been a long-standing challenge.This talk will present on recent, yet-to-be published advances at the University of Wisconsin on assembling and aligning dense arrays of polymer wrapped semiconducting carbon nanotubes via 2D liquid crystal (2D-LC) phenomena at liquid-liquid interfaces. Topics will include: (1) the direct visualization of 2D-LCs of nanotubes at liquid-liquid interfaces via in situ polarized optical microscopy; (2) the assembly of nanotubes at density of > 250 nanotubes μm-1 at liquid-liquid interfaces; (3) the post-alignment and post-deposition removal of polymer wrapper via oxidation at room-temperature; and (4) field effect transistor studies incorporating all of the above.

Programmable Carbon Nanotube Networks: Controlling Optical Properties Through Orientation and Interaction.

The lattice geometry of natural materials and the structural geometry of artificial materials are crucial factors determining their physical properties. Most materials have predetermined geometries that lead to fixed physical characteristics. Here, the demonstration of a carbon nanotube network serves as an example of a system with controllable orientation achieving on-demand optical properties. Such a network allows programming their optical response depending on the orientation of the constituent carbon nanotubes and leads to the switching of its dielectric tensor from isotropic to anisotropic. Furthermore, it also allows for the achievement of wavelength-dispersion for their principal optical axes - a recently discovered phenomenon in van der Waals triclinic crystals. The results originate from two unique carbon nanotubes features: uniaxial anisotropy from the well-defined cylindrical geometry and the intersection interaction among individual carbon nanotubes. The findings demonstrate that shaping the relative orientations of carbon nanotubes or other quasi-one-dimensional materials of cylindrical symmetry within a network paves the way to a universal method for the creation of systems with desired optical properties.

Study on water-salt phase transition of saline soils during freezing

As the temperature decreases, when the freezing temperature is reached, the solution in the pores of saline soil undergoes ice crystallization and salt crystallization phenomena. Theoretical and experimental studies have been carried out in order to investigate the behaviour of water-salt phase transitions within the pores of saline soils. Firstly, the theoretical expression for the initial crystallization radius is given from the thermodynamic theory by considering the interphase chemical potential equilibrium and the Young-Laplace equation, and the relationship between the initial crystallization radius and temperature as well as the initial salt content is analyzed. Then, a theoretical model to predict the pore solution content and crystal content was developed in conjunction with the Van Genuchten soil-water characteristic curve model, and the water-salt phase transition behaviour of saline soils was analyzed by numerical calculations. Finally, the validity of the theoretical model was verified by a saline soil freezing test. The results show that the water-salt phase transition behaviour of the solution within the pores of saline soils is affected by temperature and initial salt content, and the water-salt phase transition behaviour mainly occurs at the early stage of freezing. Salt lowers the freezing temperature of the soil; the higher the salt content, the lower the freezing temperature, and the presence of salt inhibits the growth of ice crystals. As the temperature decreases, the precipitation of ice salt crystals during the phase transition of the soil pore solution reduces the soil porosity and decreases the channels for ion migration, resulting in a gradual increase in the soil pore volume ratio.

Single-point substitution F97M leads to in cellulo crystallization of the biphotochromic protein moxSAASoti

To enhance the photoconversion performance of biphotochromic moxSAASoti protein, a substitution F97 M was introduced. In addition to enhancing the target properties, this substitution also resulted in the crystallization of the recombinant protein within living HeLa cells (also referred to as in cellulo crystallization). The phenomenon of protein crystallization in living cells is not unique, yet the mechanisms and application of in cellulo crystallization remain significant for further research. However, in cellulo crystallization is atypical for fluorescent proteins and detrimental for their biotechnological application. The objective of this study was to elucidate the underlying mechanisms responsible for the crystallization of moxSAASotiF97Min cellulo. For this purpose, the crystal structure of the green form of biphotochromic protein moxSAASotiF97M was determined at high resolution, which surprisingly has a space group, different from those of parent mSAASotiC21N. The analysis provided allowed to propose a mechanism of new crystal contacts formation, which might be a cause of in cellulo protein crystallization.

Oiling‐Out in Industrial Crystallization of Organic Small Molecules: Mechanisms, Characterization, Regulation, and Applications

AbstractOiling‐out is a common phenomenon in industrial crystallization processes that not only prolongs the total operating time but also leads to undesirable crystal morphology, making it challenging to control crystallization paths. This review provides a comprehensive overview of the oiling‐out phenomenon in organic small molecule crystallization. First, the formation mechanisms of oiling‐out are summarized from both thermodynamic and dynamic perspectives, providing the theoretical foundation for understanding the phenomenon. Then, the universal characterization methods for studying the oiling‐out phenomenon of organic small molecules are introduced in detail, covering both offline and online analytical tools. Moreover, the regulation strategy for oiling‐out, including solvents, impurities, seeding, temperature, and mixing methods are discussed. This paper also focuses on the application of oiling‐out in co‐assembly and crystal shape modulation. Finally, future opportunities and challenges are presented to address the current shortcomings and application bottlenecks in the study of organic small molecule oiling‐out phenomena. This review aims to provide valuable insights and guidance for researchers working on the crystallization of organic small molecules, particularly in the pharmaceutical industry, to better understand, control, and utilize the oiling‐out phenomenon.

Impurity modes in two-dimensional strongly coupled complex plasma crystals

Complex plasma fluctuation processes have been extensively studied in many aspects, especially lattice waves in strongly coupled plasma crystals, which are of great significance for understanding fundamental physical phenomena. A challenge of experimental investigations in two-dimensional strongly coupled complex plasma crystals is to keep the main body and foreign particles of different masses on the same horizontal plane. To solve the problem, we have proposed a potential well formed by two negatively biased grids to bind the negatively charged particles in a two-dimensional (2D) plane, thus achieving a 2D plasma crystal in the microgravity environment. The study of such phenomena in complex plasma crystals under microgravity environment then becomes possible. In this paper, we focus on the continuum spectrum, including both phonon and optic branches of the impurity mode in a 2D system in microgravity environments. The results show the dispersion relation of the longitudinal and transverse impurity oscillation modes and their properties. Considering the macroscopic visibility of complex mesoscopic particle lattices, theoretical and experimental studies on this kind of complex plasma systems will help us further understand the physical nature of a wide range of condensed matters.

Crystallization Kinetics of Phosphonium Ionic Liquids: Effect of Cation Alkyl Chain Length and Thermal History.

The effects of alkyl chain length on the crystallization kinetics and ion mobility of tetraalkylphosphonium, [P666,n][TFSI], (n = 2, 6, 8, and 12) ionic liquids were studied by differential scanning calorimetry (DSC) and broadband dielectric spectroscopy (BDS) over a wide temperature range. The liquid-glass transition temperature (Tg) and ion dynamics examined over a broad T range were almost insensitive to structural modifications of the phosphonium cation. In contrast, the crystallization kinetics were strongly affected by the length of the fourth alkyl chain. Furthermore, the thermal history of the sample (cold vs melt crystallization) significantly impacted the crystallization rate. It has been found that the nature of crystallization phenomena is the same across the homologous series, while the kinetic aspect differs. Finally, electric conductivity in supercooled liquid and crystalline solid phases was measured for all samples, revealing significant ionic conductivity, largely independent of the cation structure.

Exploring surface properties and premelting in crystals.

Crystal surfaces play a pivotal role in governing various significant processes, such as adsorption, nucleation, wetting, friction, and wear. A fundamental property that influences these processes is the surface free energy, γ. We have directly calculated γ(T) for low-index faces of Lennard-Jones (LJ), germanium, and silicon crystals along their sublimation lines using the computational cleavage technique. Our calculations agree well with experimental values for Si(111) and Ge(111), highlighting the accuracy of the method and models used. For LJ crystals, we identified a premelting onset at Tpm = 0.75Tm, marked by a sharp increase in atom mobility within the second outermost surface layer. Notably, Tpm closely aligned with the endpoint of the LJ melting line at negative pressures, Tend = 0.76Tm. We hypothesize that the emergence and coexistence of a liquid film atop the LJ crystal at Tpm < T < Tm correspond to the metastable melting line under negative pressures experienced by stretched crystal surfaces. Furthermore, our study of thin LJ crystal slabs reveals that premelting-induced failure leads to recrystallization below the homogeneous freezing limit, offering a promising avenue to explore crystal nucleation and growth at extremely deep supercoolings. Finally, no evidence of premelting was detected in the model crystals of Ge and Si, which is consistent with the experimental observations. Overall, our findings offer valuable insights into crystal surface phenomena at the atomic scale.

Probing microscale crystallization phenomena: Transforming waste slags into riches

Metal smelting and combustion of solid fuels produce significant quantities of waste slag, leading to issues such as land occupation and environmental pollution. Understanding and controlling the microscale crystallization phenomena of these slags during thermal treatment is crucial for transforming waste slags into materials suitable for carbon capture or glass ceramics. Previous research has primarily focused on macroscopic crystallization behaviors, significantly advancing the utilization of waste slags in cement clinker production. However, macroscopic results are inadequate for precisely controlling the microscale crystallization behaviors of waste slags. Here, we employed the single hot thermocouple technique to visually explore crystal growth modes, shapes, sizes, numbers, and translational rates of the crystal growth front in a representative blast furnace slag under various isothermal temperatures. The results revealed that crystals exhibited five modes as the isothermal temperature gradually increased, including equiaxed, equiaxed & columnar, columnar, columnar & planar, and planar. Moreover, the translational rate of the crystal growth front increased from 0.011 μm·s−1 to 43.7 μm·s−1 with an increase in the isothermal temperature. Simultaneously, the number of crystals decreased from around 104 to 100 μm−2. On this basis, correlations between microscale crystallization behaviors and isothermal temperature were established to fill the current gap.

Inducing a tunable skyrmion-antiskyrmion system through ion beam modification of FeGe films

Skyrmions and antiskyrmions are nanoscale swirling textures of magnetic moments formed by chiral interactions between atomic spins in magnetic noncentrosymmetric materials and multilayer films with broken inversion symmetry. These quasiparticles are of interest for use as information carriers in next-generation, low-energy spintronic applications. To develop skyrmion-based memory and logic, we must understand skyrmion-defect interactions with two main goals—determining how skyrmions navigate intrinsic material defects and determining how to engineer disorder for optimal device operation. Here, we introduce a tunable means of creating a skyrmion-antiskyrmion system by engineering the disorder landscape in FeGe using ion irradiation. Specifically, we irradiate epitaxial B20-phase FeGe films with 2.8 MeV Au4+ ions at varying fluences, inducing amorphous regions within the crystalline matrix. Using low-temperature electrical transport and magnetization measurements, we observe a strong topological Hall effect with a double-peak feature that serves as a signature of skyrmions and antiskyrmions. These results are a step towards the development of information storage devices that use skyrmions and antiskyrmions as storage bits, and our system may serve as a testbed for theoretically predicted phenomena in skyrmion-antiskyrmion crystals.