Enhanced Crystallization Kinetics Research Articles

Synergetic effect of microfluidic flow and ultrasonication on chains pre-ordering in conjugated polymer solution

Multi-physical fields solution processing strategy provides a universal and facile way to prepare various conjugated polymer (CP) films and high-performance devices, whereas the hierarchical structures evolution and crystallization of the polymer chains are elusive particularly under the far-from-equilibrium state in solution. In this work, we employed a combined microfluidic flow and ultrasonication strategy (FU) for CP solution processing and found a pronounced synergetic effect of these fields in promoting the pre-ordering of chains in solution. This conformation order and anisotropy of the solution were revealed by using UV–Vis absorption, polarized optical microscopy (POM) and cryogenic transmission electron microscopy (Cryo-TEM) characterizations. A non-classical nucleation model for the conjugated polymer crystallization in the procedure of non-equilibrium solution processing was confirmed. The roles of microfluidic flow and ultrasonication on the chain aggregation and crystallization were addressed with the aim of a multi-physical simulation based on pressure acoustics streaming, fluid heat transfer and thermoviscous boundary layer impedance. Compared to pristine solutions, the FU strategy showed improved solution anisotropy and crystallization kinetics, substantially giving rise to a larger crystallinity in films and much increased mobilities for the organic field-effect transistor (OFET) devices by more than an order of magnitude. With an appropriate balance between the solvation and interchain interactions, the FU processing strategy is universal for regulation of chains conformation and aggregation in conjugated polymer solution.

Facile synthesis of mesoporous ZSM-5 aided by sonication and its application for VOCs capture

Application of ultrasound power to the mother liquor is popular pretreatment for zeolite synthesis which offers a simple way of accelerating crystallization process and finetuning the properties of nanocrystalline zeolites. In this work, sonication-aided synthesis of mesoporous ZSM-5 at low temperature and ambient pressure was systematically studied, in an attempt to reach efficient and benign synthesis of zeolites with hierarchical pore structure, which has wide applications as catalysts and sorbents. The effects of sonication duration, power density, sonication temperature and seeding on the crystallization of ZSM-5 were investigated. The obtained samples were characterized by XRD, SEM, BET and VOCs capture. High quality mesoporous ZSM-5 can be obtained by a facile 5 d synthesis at 363 K, much faster than conventional hydrothermal synthesis. The reduced synthesis time was mainly attributed to the enhanced crystallization kinetics caused by the fragmentation of seeds and nuclei, while sonication radiation had little impact on the nucleation process. Compared with control sample, mesoporous ZSM-5 prepared by sonochemical method had higher surface area and mesoporosity which demonstrated improved adsorption performance for the capture of isopropanol.

Laser sintering of PA12 particles studied by in-situ optical, thermal and X-ray characterization

The microstructure of products manufactured by selective laser sintering (SLS) is known to be highly dependent on various process and material parameters. The latter thus also affect the final part properties. While most work has focused on ex-situ characterization of the printed parts, little is known about the time-dependent microstructure development during sintering. In this work, we present direct observations of the microstructural evolution during laser sintering of polyamide 12 (PA12) particle doublets by in-situ synchrotron wide angle X-ray diffraction (WAXD), using our in-house developed laser sintering setup. Simultaneously, the neck growth between the particles and the temperature are captured via optical and infrared microscopy. We show that isothermal crystallization experiments under quiescent conditions are not sufficient to describe crystallization in a non-isothermal process like SLS. The enhanced crystallization kinetics in small particles suggests that both temperature and flow play a role. This finding was corroborated by the critical Weissenberg numbers estimated from rheological reptation and Rouse time scales. Furthermore, a microstructure survey has been carried out by microtoming thin slices of the sintered doublets. Both optical and atomic force microscopy reveal significant differences in the crystalline structure of the laser-affected zone as compared to the un-sintered region.

Investigating the disentanglement of long chain branched polypropylene under different shear fields

AbstractMany experimental results have revealed that entanglement networks of molecular chain would undergo the orientation, deformation, and breakdown under the condition with shear field, forming a new conformation with much reduced entanglement interactions with the surrounding medium. In this work, the role of shear mode on the disentanglement of chains was investigated to give us some guidance for designing a new polymer melts disentanglement machine to optimize the processability of polymers by reducing viscosity. Results showed that the intensity of the generated shear modification depends on shear procedure during treatment, ramping‐up shear has the most efficient influence on molecular chains disentanglement due to the absence of shear banding, resulting in a higher molecular weight between entanglements Me and much lower entanglement density. Besides, the reduced entanglement density enabled the higher chain mobility, which greatly enhanced crystallization kinetics during non‐isothermal and isothermal crystallization.

Crystallization of Cocoa Butter in Cocoa Powder

AbstractCocoa powder quality is determined by its color, flavor, dispersion, and flow properties, which can be controlled via tempering. Design of a cocoa powder tempering profile, however, requires that the mechanism of cocoa butter crystallization in cocoa powder be fully understood. Low‐fat (8–12%) and high‐fat (20–24%) cocoas were sourced from two commercial manufacturers at varying degrees of alkalization and compared with two commercial cocoa butters. Unrefined paired cocoa powders and cocoa butters sampled from the hydraulic press were also evaluated. Isothermal crystallization kinetics and polymorphism of cocoa powders and cocoa butters were compared at 18, 21, and 24 °C using a direct time‐domain nuclear magnetic resonance method, differential scanning calorimetry, and x‐ray diffraction. Crystallization was also studied under dynamic tumbling conditions. It was found that cocoa butter in cocoa powder was nucleated by the cocoa powder matrix and transitioned to higher‐stability polymorphs more rapidly than bulk cocoa butters. High‐fat cocoas also exhibited enhanced crystallization kinetics relative to low‐fat cocoas, showing that differences in the cocoa microstructure may influence crystallization behavior. Notably, alkalization did not significantly affect the crystallization behavior of most cocoa powders. Finally, it was found that tumbling conditions led to crystallization of βV and that caking, especially of high‐fat cocoas, could be reduced by a static low‐temperature hold step prior to tumbling. Overall, these results demonstrated that crystallization of cocoa butter in cocoa powder is influenced both by the intrinsic attributes of the cocoa powder as well as the conditions of the tempering process.

Crystalline nanocellulose/thermoplastic polyester composites prepared by in situ polymerization

In situ polymerization by polycondensation was implemented to disperse crystalline nanocellulose (CNC) in poly(ethylene succinate) (PESu). The in situ polymerization technique resulted in good dispersion of the CNC nanoparticles in the PESu matrix. The polymerization kinetics were altered with increasing CNC content, causing a decrease in the polymer molecular weight. The addition of CNC particles having a large aspect ratio resulted in significant increases in the viscosity of the resulting composites, and significantly enhanced crystallization kinetics. PESu containing well‐dispersed 0.25 wt% CNC maintained the tensile properties of the matrix, demonstrating that at these very low loadings the CNC acts as an efficient nucleating agent, without compromising the mechanical properties and biodegradability POLYM. ENG. SCI., 59:989–995, 2019. © 2019 Society of Plastics Engineers

Enhanced Crystallization Kinetics of PLLA by Ethoxycarbonyl Ionic Liquid Modified Graphene

To investigate the performance of graphene (Gra) modified with ethoxycarbonyl ionic liquid (IL), chain mobility and crystallization kinetics of poly(L-lactic acid) (PLLA), a series of PLLA nanocomposites have been prepared using solution-cast method. IL can improve the dispersion of Gra in PLLA matrix and the samples containing IL have higher growth rate of PLLA spherulite than neat PLLA does. PLLA/IL/Gra and PLLA/2Gra exhibit the same relaxation strength and time of αN relaxation that corresponds to the longest normal mode motion at 110−140 °C. PLLA/IL/Gra shows a faster crystallization rate than PLLA/2Gra does, which might be attributed to the Gra-imidazolium cation interaction in IL modified Gra, the significant dispersion effect of IL at Gra surface, and the increase of nuclei density of PLLA/IL/Gra.

Enhanced crystallization kinetics of bacterially synthesized poly(3-hydroxybutyrate-co-3-hydroxyhexanate) with structural optimization of oxalamide compounds as nucleators

Bacterially synthesized poly (3-hydroxybutyrate-co-3-hydroxyhexanate) (PHBH) has attracted much attention as biodegradable plastics and potential biomaterials. However, the crystallization rate of PHBH is very low, which limits its application in plastic field. Herein, oxalamide compounds (OXAn) with a formula of C6H5NHCOCONH(CH2)nNHCOCONHC6H5 (n = 2, 4, 8, 12) were tailor-made as nucleators to improve the crystallization behaviors of PHBH. The effect of aliphatic spacer length of OXAn, i.e., -(CH2)n-on the nucleation behavior was investigated. The OXAn would assemble into shish-like superstructures and PHBH crystals preferred to grow on the surfaces of the shish. The crystallization rate of PHBH/OXAn blends increased with the spacer length of OXAn up to n = 8 and then leveled off, which trend was consistent with the nucleation activity (Ψ) and the nucleation constant (Kg) of the OXAn. Meanwhile, the OXAn increased the nuclei density of the PHBH while inhibited its secondary crystallization, resulting in a superior and steady mechanical performance of PHBH materials. This work provides a scientific approach to design the optimal structure of OXAn as nucleators for PHBH materials, which may broaden the application range of PHBH materials.

Insights into crystallization and melting of high density polyethylene/graphene nanocomposites studied by fast scanning calorimetry

Graphene nanoplatelets (5 wt%) with different diameters (5 and 25 × 10−6 m in diameter, 6 × 10−9 m in thickness) filled high density polyethylene nanocomposites were prepared by the melt-mixing method and the effect of graphene nanoplatelets on the polymeric matrix are then investigated by X-ray diffraction, polarized light microscopy, differential scanning calorimetry, fast scanning calorimetry, and rheology. Polarized light microscopy revealed that graphene nanoplatelets of 5 × 10−6 m promote the decrease in the size of the spherical aggregates during crystallization compared to larger nanoplatelets. From rheological measurements, it was found that even though the viscosity of the nanocomposites with increasing filler diameter was increased significantly compared to the neat polymer, the processability of these materials was not affected. Several melting events for neat high-density polyethylene and graphene nanocomposites were observed by fast scanning calorimetry associated with the small imperfect crystals grown at large supercooling, the nucleation efficiency and the diameter size of the filler. The activation energy values versus the relative extent of crystallization revealed that graphene nanoplatelets block the movement of the molecular segments and make crystallization difficult, especially at the final stage of the process. Based on this work, it can be concluded that the nanocomposite with the smaller diameter showed the most enhanced crystallization kinetics as graphene increased the number of nucleation sites, while the larger ones hindered the melted molecules in reaching full isotropization above the melting temperature.

Nucleation Enhancement in Stereodefective Poly(l-lactide) by Free Volume Expansion Resulting from Low-Temperature Pressure CO₂ Preconditioning.

Nucleation enhancement in a highly stereodefective poly(l-lactide) (PLLA) with an optical purity of 88% by low-temperature pressure (0 and 35 °C under 2 MPa) CO2 preconditioning was investigated using differential scanning calorimetry (DSC), infrared (IR) spectroscopy, polarized optical microscopy (POM) as well as positron annihilation lifetime spectroscopy (PALS). Despite the preconditioning of the melt-quenched films for 2 h, IR results indicated that no trace of mesophase was generated and the samples remained in the glassy state. However, judging from the results of DSC, IR, and POM, when compared to the untreated sample, both the treated ones showed a significantly enhanced crystal nucleation effect, resulting in the corresponding greatly enhanced crystallization kinetics. Moreover, owing to the existence of the retrograde vitrification, the conditions of the previous low-pressure CO2 conditioning affected the nucleation enhancement effect. When compared to the case of 35 °C, the much lower temperature of 0 °C was more effective for nucleation enhancement. The PALS results indicated that the enlarged free volume, which resulted from the CO2 conditioning, largely accounted for the formation of locally ordered structures, providing many more potential nucleation sites for forming critical nuclei and thus the resulting enhanced crystallization kinetics in glassy PLLA. The present results have implications in understanding the nucleation enhancement effect, in particular in stereodefective PLLA systems, which possess extremely low crystallization ability and are thus probably too problematic to be evaluated by conventional methods.

Morphological features and crystallization behavior of the conductive composites of poly(trimethylene terephthalate)/graphene nanosheets

ABSTRACTPoly(trimethylene terephthalate) (PTT) composites filled with well‐dispersed graphene nanosheets (GNSs) were prepared through a coagulation method. The effects of increased GNS concentration on variations in the structure and properties of the PTT matrix, such as its electrical conductivity, crystallization kinetics, melting behavior, and crystal morphology, were investigated. Several analytical techniques were used, including electrical conductivity measurement, differential scanning calorimetry, Fourier transform infrared spectroscopy, wide‐angle X‐ray diffraction, polarized light microscopy, transmission electron microscopy (TEM), and thermo‐gravimetric analysis (TGA). Electrical conductivity increased from 1.8 × 10−17 S/cm for neat PTT to 0.33 ± 0.23 S/cm for PTT/GNS composites with 2.97 vol % GNS content. Percolation scaling laws were applied, and then threshold concentration and exponent were determined. In the case wherein liquid nitrogen was used to quench the melt, a mesomorphic phase was formed despite the extremely short crystallization time after adding high GNS contents. PTT crystallization rate increased with the gradual addition of GNSs. The enhanced crystallization kinetics was attributed to the high nucleation ability of GNSs to induce epitaxially grown lamellae on their surfaces, as revealed by TEM. PTT nuclei were randomly developed on the GNS surface to form the lamellae. However, crystallinity reached its maximum value near the electrical percolation threshold because the PTT chain mobility was confined after the GNS–GNS network formed. The growth of PTT banded spherulites in the bulk was still observed for composites with high GNS content, and TGA results revealed that the GNS‐filled PTT composites had excellent thermal stability. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43419.

Enhanced crystallization kinetics of poly(lactide) with oxalamide compounds as nucleators: effect of spacer length between the oxalamide moieties

Crystallization kinetics of poly (lactide) were enhanced by using oxalamide compounds as nucleators and the nucleation efficiency can be well tailored by tuning the aliphatic spacer length between the oxalamide moieties.

Poly(lactic acid)-Based in Situ Microfibrillar Composites with Enhanced Crystallization Kinetics, Mechanical Properties, Rheological Behavior, and Foaming Ability.

Melt blending is one of the most promising techniques for eliminating poly(lactic acid)'s (PLA) numerous drawbacks. However, success in a typical melt blending process is usually achieved through the inclusion of high concentrations of a second polymeric phase which can compromise PLA's green nature. In a pioneering study, we introduce the production of in situ microfibrillar PLA/polyamide-6 (PA6) blends as a cost-effective and efficient technique for improving PLA's properties while minimizing the required PA6 content. Predominantly biobased products, with only 3 wt % of in situ generated PA6 microfibrils (diameter ≈200 nm), were shown to have dramatically improved crystallization kinetics, mechanical properties, melt elasticity and strength, and foaming-ability compared with PLA. Crucially, the microfibrillar blends were produced using an environmentally friendly and cost-effective process. Both of these qualities are essential in guarantying the viability of the proposed technique for overcoming the obstacles associated with the vast commercialization of PLA.

Highly Enhanced Crystallization Kinetics of Poly(l-lactic acid) by Poly(ethylene glycol) Grafted Graphene Oxide Simultaneously as Heterogeneous Nucleation Agent and Chain Mobility Promoter

Nanofillers can act as effective heterogeneous nucleation agents for semicrystalline polymers; however, it never facilitates the crystal growth. In the current work, we proposed a facile strategy to enhance the crystallization kinetics of poly(l-lactic acid) (PLLA) by simultaneously accelerating the crystal nucleation and growth. Herein, we synthesized poly(ethylene glycol) (PEG) grafted graphene oxide (GO) (PEGgGO). Pronounced effects of PEGgGO on the crystalline morphology and crystallization rate of PLLA were explicitly clarified by direct morphological observation and quantitative crystallization kinetics analysis. The results manifested that, in contrast to the unmodified GO, PEGgGO desirably dispersed in PLLA and also preserved the high nucleation ability. More importantly, the flexible PEG chains on GO served as a chain mobility promoter and boosted the crystal growth rate of PLLA. Compared to the PLLA/GO nanocomposite containing 0.5 wt % GO, the nucleation density and crystal growth rate of the PLLA/PEGgGO one were increased by 110% and 14.3% at the crystallization temperature of 130 °C, respectively, leading to 52.2% relative augment in the final crystallinity. Our proposed methodology offers the flexibility of fabricating the polymer nanocomposits with well-dispersed nanofillers and also high crystallinity, by which the step toward the high-performance nanocomposites will be further.

Shear-accelerated crystallization in a supercooled atomic liquid.

A bulk metallic glass forming alloy is subjected to shear flow in its supercooled state by compression of a short rod to produce a flat disk. The resulting material exhibits enhanced crystallization kinetics during isothermal annealing as reflected in the decrease of the crystallization time relative to the nondeformed case. The transition from quiescent to shear-accelerated crystallization is linked to strain accumulated during shear flow above a critical shear rate γ̇(c)≈0.3 s(-1) which corresponds to Péclet number, Pe∼O(1). The observation of shear-accelerated crystallization in an atomic system at modest shear rates is uncommon. It is made possible here by the substantial viscosity of the supercooled liquid which increases strongly with temperature in the approach to the glass transition. We may therefore anticipate the encounter of nontrivial shear-related effects during thermoplastic deformation of similar systems.

Polymorphism and transcrystallization of syndiotactic polystyrene composites filled with carbon nanotubes

Syndiotactic polystyrene (sPS) composites filled with well-dispersed multi-walled carbon nanotubes (CNTs) were readily prepared through a coagulation method. Fourier-transform infrared spectroscopy and wide-angle X-ray diffraction revealed the effect of CNTs on the polymorphism of sPS. When crystallized from the melted state, the formation of the β-form was always favored after CNT addition regardless of crystallization conditions (isothermal or non-isothermal). In the case where liquid nitrogen was used to quench the melt, the uncrystallized material that was not able to crystallize in the extremely short crystallization time crystallized in the α form upon subsequent cold crystallization. Regardless of the CNT content, the glass transition and equilibrium melting temperature of the sPS matrix were unchanged at ∼96 and 290°C, respectively. With a gradual increase in CNT loading, the sPS crystallization rate initially increased but then reached a plateau value at high CNT concentrations because of the reduction in chain mobility. Moreover, the Avrami exponent was changed from 2.8 for samples at low CNT contents to 2.0 for samples with a CNT concentration above 0.1wt.%, at which the rheological threshold was approached and a polymer-CNT hybrid network was formed. The enhanced crystallization kinetics was attributed to the high nucleating ability of CNTs to induce a transcrystalline layer (TCL) at its surface, as revealed by transmission electron microscopy. For composites with low levels of CNT, the growth of sPS spherulites in the bulk between CNTs prevailed. Provided that the CNT-related networks were developed, the two-dimensional growth of cylindrical TCL at the CNT surface became dominant and led to the expected Avrami exponent.

Enhanced crystallization kinetics in poly(ethylene terephthalate) thin films evidenced by infrared spectroscopy

The cold crystallization process in poly(ethylene terephthalate) (PET) spin-coated ultrathin films was studied by infrared spectroscopy. The conformational change associated to the formation of crystal phase during annealing at 107°C was measured in real time, by monitoring both intensity and frequency shift of trans and gauche conformer bands of the PET glycol segment. Enhancement of crystallization kinetics was observed in thin films deposited on amorphous silicon, with respect to a 20 μm thick free standing film used as reference, where the fastest kinetics was observed for the thinnest (35nm) film. Experimental findings were interpreted in terms of scarce interaction between PET films and silicon substrate, which does not provide slowing down of crystallization kinetics as observed on different substrates. This results in a dominant effect of the polymer/air interface, where faster kinetics is observed, as also confirmed by atomic force microscopy imaging, particularly on the thinnest film. Additionally, Avrami and Avramov analyses evidence a decrease of both the Avrami exponent, related to growth dimensionality, and induction time, related to delay of nucleation start, when decreasing film thickness. Therefore, the reported results enrich the description of confinement and substrate interaction effects on the cold crystallization process taking place in PET ultrathin films.

Nanocrystallization of Fe73.5Si13.5B9Nb3Cu1 soft-magnetic alloy from amorphous precursor in a magnetic field

The effect of a magnetic field on the nature of nanocrystallization from a melt-spun Fe73.5Si13.5B9Nb3Cu1 amorphous precursor has been studied with the aim of controlling microstructures and magnetic properties. Annealing for magnetic crystallization was carried out at temperatures between the Curie temperature of the amorphous phase (586 K) and that of the crystalline phase (920 K). It was found that the {110} texture component in crystallized α-Fe(Si) phase increased in importance with increasing magnetic-field strength. An X-ray diffraction analysis based on the Shultz method revealed that the magnetic field caused preferential formation of {110}-oriented nuclei. In addition, the applied field enhanced crystallization kinetics, particularly the nucleation rate. No significant difference in grain growth behavior was observed as a result of applying a magnetic field. We therefore conclude that the development of the {110} texture by magnetic crystallization is predominantly attributable to preferential nucleation, rather than preferential growth, of {110}-oriented nuclei. The saturation magnetization of nanocrystallized specimens, evaluated using a vibrating sample magnetometer (VSM), was increased by the application of a magnetic field up to 4T during nanocrystallization.

Trypsin crystallization by membrane-based techniques

To grow protein crystals is not an easy task; moreover, if we need to grow protein crystals with controlled shape, size, and size distribution, depending on their application, the mission becomes even harder. Membrane crystallization has been recognized as an interesting tool for growing protein crystals with enhanced crystallization kinetics, both in static and in forced solution flow configuration, without detrimental effects on crystal quality. In the present work, we have studied the membrane crystallization process of benzamidine inhibited trypsin from bovine pancreas (BPT), with ammonium sulphate (dissolved in Tris–HCl buffer, 0.1 M, pH 8.5), as precipitant agent. We have demonstrated that, by using the membrane crystallization technique, BPT crystals can be obtained in 24–48 h, in static configuration, and in 4–7 days, in a forced solution flow system, depending on the experimental conditions. Furthermore, the kinetics of BPT crystallization have been modulated, to control the morphological characteristics of the crystals produced, by an accurate selection of the operative parameters involved in the process. The active membrane surface and the flow rate of extraction solvent in quiescent configuration, and the solution velocity in forced convection solution experiments, were the parameters investigated. In this respect, membrane crystallization techniques have been assessed as an interesting way for growing proteins, and more specifically enzyme crystals, with high control on the final properties of the crystalline material produced, with potential fundamental implication in the field of structural biology and biotechnology.

Structure of mutant human carbonmonoxyhemoglobin C (betaE6K) at 2.0 A resolution.

Previous studies have demonstrated that in vitro crystallization of R-state liganded hemoglobin C (HbC), a naturally occurring mutant human hemoglobin (betaE6K), in high-phosphate buffer solutions provides a potential model system for the intracellular crystallization of HbC associated with chronic hemolytic anemia in CC disease. The first high-resolution crystal structure of liganded HbC is reported here. HbC was crystallized from high phosphate and the structure of the carbonmonoxy-liganded R-state form was refined at 2.0 A resolution. Crystals exhibit diffraction consistent with the tetragonal space group P4(1)2(1)2, with unit-cell parameters a = 54.16, c = 195.30 A. The structure was solved by difference Fourier techniques and refinement by simulated annealing and restrained least-squares yielded a final R of 0.183 and an R(free) of 0.238 for all 19,382 unique reflections. The side chain of betaK6 exhibits very weak electron density consistent with significant mobility within the crystalline lattice. The highly dynamic nature of the side chain could potentially support a number of specific polar interactions that might reduce the barrier to crystallization and thus result in enhanced crystallization kinetics for HbC relative to HbA. Specifically, the NZ atom of the BK6 side chain could participate in an amino-aromatic hydrogen bond with the pi-electron cloud of betaH116 in a symmetry-related tetramer. BetaK6 NZ might also interact with the main-chain carbonyl O atom of betaH117 and the carboxylate group of betaE22 from a symmetry-related tetramer.