Crystallization Behavior in Poly(propylene) Containing Wollastonite Microfibrils

The structure development and crystallization behavior of poly(propylene) (PP) filled with wollastonite mineral was studied with respect to different particle sizes of the filler. The decrease in particle size led to increase in crystallization rates and decrease of crystallization half time, indicating greater nucleation efficiency for smaller sizes of the wollastonite particles. This was also reflected in the higher crystallinity values obtained for small filler particles. The WAXD analysis of PP/wollastonite revealed significant changes in the relative intensity of certain peaks (110 reflection) at small particle size, indicating preferential growth of PP on wollastonite. The exact co‐relationship of nucleation rate/crystallization rate and the additive particle size (d) was determined which showed that for any given concentration of the additive, it was proportional to (1/d)³.     

Direct preparation of battery-grade lithium carbonate via a nucleation–crystallization isolating process intensified by a micro-liquid film reactor

With the lithium-ion battery industry booming, the demand for battery-grade lithium carbonate is sharply increasing. However, it is difficult to simultaneously meet the requirements for the particle size and the purity of battery-grade lithium carbonate. Herein, the nucleation–crystallization isolating process (NCIP) is applied to prepare battery-grade lithium carbonate without any post-treatment procedure. The nucleation process is intensified by a micro-liquid film reactor (MLFR), where the feedstock solution is subject to intensive shear force and centrifugal force. The feedstock solutions are mixed rapidly and a large number of nuclei form instantly in the MLFR. After nucleation, the crystallization process is achieved in another reactor. A few new nuclei form in the crystallization process. The nucleation intensification in the MLFR is verified by computational fluid dynamics (CFD) simulations and experimental results. The particle size distribution is narrower and the impurity residue in the products is far lower than that prepared by a traditional precipitation method. The effects of nucleation and crystallization on the particle size distribution and purity were investigated. In the optimized operation parameters, the particle size distribution of the Li₂CO₃ product is D₁₀ = 2.856 μm, D₅₀ = 5.976 μm, and D₉₀ = 11.197 μm, and the purity is 99.73%, both of which meet the requirements of battery-grade Li₂CO₃. Moreover, the lithium recovery rate is increased to 88.21% compared to that prepared by a traditional precipitation method (79.0%). This work provides an alternative way for the preparation of high-purity chemicals by process intensification.     

Membrane assisted cooling crystallization: Process model,nucleation, metastable zone,and crystal size distribution

The membrane assisted cooling crystallization was proposed and investigated by the simulation and experiments. The developed process model concerned the supersaturation evolution on the membrane interface, the combined nucleation rate in the crystallizer. The impact of different membrane on reducing the nucleation barrier was investigated by introducing the metastable zone width theory. The influence of membrane distillation conditions on the crystal nucleation and growth kinetic was uncovered based on the simulation and experiments results. The experimental results indicated that membrane assisted cooling mode with optimized profiles did improve the crystal size distribution and crystal habit comparing with conventional cooling mode. Terminal coefficient of variation decreased from 55.4 to 33.9 under similar mean crystal growth rate, 2.27 × 10^?7 m s^?1 (conventional cooling) and 1.98 × 10^?7 m s^?1 (membrane assisted cooling). Finally, the brief summary on the advantages and key issues of this propose membrane assisted crystallization operation were concluded. © 2015 American Institute of Chemical Engineers AIChE J, 62: 829–841, 2016     

High Resolution Study of Micrometer Particle Detachment on Different Surfaces

In an effort to identify particle initial motion prior liftoff interactions of micrometer glass beads (10–100 μm) on glass, ceramic, and hardwood substrates were investigated experimentally. Particles were deposited on the lower surface of a 10 cm² wind tunnel by gravitational settling. Air flows were imposed from an open entrance at average velocities up to 16 m/s. Individual particle trajectories obtained by high-speed imaging reveal three different types of motion: rolling/bouncing (saltation caused by the movement of hard particles over an uneven surface in a turbulent flow of air), immediate liftoff (particles completely leave the surface with no or minimal initial rolling/bouncing) and complex motion (particles travel with rolling/bouncing motion on the surface for a certain distance before final liftoff). Surface roughness significantly affects the particle initial motion prior to liftoff. The majority of particle trajectories from the glass substrate were parallel to the surface with complex motion. Hardwood substrates took the longest time for initial particle movement (t >1 s) causing a more rapid liftoff. The ceramic substrate showed the most rolling/bouncing motion, for 80% of the particles. The detachment percentage initially follows an exponentially increasing trend for a period of ～1 s, followed by a plateau phase for a period of 5 s. Changing the velocity, substrate, and particle size significantly affects particle detachment. Incorporating the different types of particle motion prior to liftoff into detachment mode models, and understanding how their relative contributions change with different particle and substrate materials, can potentially yield improved predictive capabilities.

Copyright 2013 American Association for Aerosol Research     

Quantitative evaluation of fractionated and homogeneous nucleation of polydisperse distributions of water-dispersed maleic anhydride-grafted-polypropylene micro- and nano-sized droplets

The nucleation processes in waterborne Maleic Anhydride-grafted-Polypropylene micro- and nano-droplet suspensions have been studied. Compared to a previous report on this topic, an extended set of samples in combination with improved particle size distribution data of the samples have been used, which are both essential for the advancement of the analysis.Self-nucleation was utilized to ensure that the observed lowered fractionated crystallization (peak) temperatures – down to the extremely low value of 34 °C – are due to a lack of seeds in the droplets, which seeds for the polypropylene system used are normally active at the heterogeneous crystallization temperature of approximately 110 °C. An unusual self-nucleation behavior was observed in case of samples having a large amount of small droplets, requiring an extremely low self-nucleation temperature in order to suppress all crystallization at the lowest temperatures. Such behavior was observed for block copolymers but has not been reported so far for droplets dispersed in an immiscible matrix, polymeric or not. Another unusual behavior was observed for some self-nucleation temperatures for which apparently two different populations of self-nuclei are created that are suggestive of the α₁ and α₂ crystal structures of isotactic polypropylene.Next, two new methods are presented to quantify various crucial parameters of the nucleation process: one estimates the density of nucleants acting at different temperatures from the combination of dynamic DSC data and particle size distribution (PSD) data, and the other one focuses on the nature of the nucleation mechanism using both isothermal DSC data and PSD data, quantifying the nucleation rate at different temperatures. For the present MA-g-PP dispersions the latter method leads to the conclusion that the lowest crystallization temperatures reflect sporadic nucleation, probably by way of volume (homogeneous) nucleation.In the field of polymer crystallization, polymer dispersions are usually treated as being monodisperse, even though that is rarely the case. This simplification is inadequate for the present calculations, which is why polydispersity has been taken into account in order to quantify the density of nucleants and the kinetics of nucleation. Though in the present study DSC data are used for the calculations, the methods developed can be easily adapted to other techniques like time-resolved X-ray, rheometry and dilatometry.     

Effect of silicon dioxide on crystallization and melting behavior of polypropylene

The crystallization and melting behavior of isotactic polypropylene (iPP) and polypropylene copolymer (co‐PP) containing silicon dioxide (SiO₂) were investigated by differential scanning calorimeter (DSC). SiO₂ had a heterogenous nucleating effect on iPP, leading to a moderate increase in the crystallization temperature and a decrease in the half crystallization time. However, SiO₂ decreased the crystallization temperature and prolonged the half crystallization time of co‐PP. A modified Avrami theory was successfully used to well describe the early stages of nonisothermal crystallization of iPP, co‐PP, and their composites. SiO₂ exhibited high nucleation activity for iPP, but showed little nucleation activity for co‐PP and even restrained nucleation. The iPP/SiO₂ composite had higher activation energy of crystal growth than iPP, indicating the difficulty of crystal growth of the composite. The co‐PP/SiO₂ composite had lower activation energy than co‐PP, indicating the ease of crystal growth of the composite. Crystallization rates of iPP, co‐PP, and their composites depended on the nucleation. Because of its high rate of nucleation, the iPP/SiO₂ composite had higher crystallization rate than iPP. Because of its low rate of nucleation, the co‐PP/SiO₂ composite had lower crystallization rate than co‐PP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1889–1898, 2006     

Crystallization kinetics of two polyesters with different main chain rigidity

The crystallization kinetics of two polyesters, poly(p-phenylene sebacate) (PPS) and poly(p-phenylene isophthalate) (PPI), have been investigated by DSC. The nonisothermal data indicate that the relative crystallization rate of PPI was slower than that of PPS due to the more rigid nature of the PPI the chains. The isothermal crystallization data were analyzed by the Avrami equation, 1 − X_(t) = exp(−ktⁿ). PPS exhibited Avrami exponent (n), values of about 4, indicating that its isothermal crystallization followed a process of homogeneous nucleation, spherical growth and a growth type of interface control. PPI exhibited Avrami exponent values of about 3 indicating its isothermal crystallization followed a process of homogeneous nucleation, a possible disc growth geometry and an interface control growth type. Possibly, the bending structure and rigid nature of PPI forced its growth to follow a three dimensional growth during crystallization.     

Crystallization and melt behavior of magnesium hydroxide/polypropylene composites modified by functionalized polypropylene

The crystallization and melting behavior of Mg(OH)₂/polypropylene (PP) composites modified by the addition of functionalized polypropylene (FPP) or acrylic acid (AA) and the formation of in situ FPP were investigated by DSC. The results indicated that addition of FPP increased crystallization temperatures of PP attributed to the nucleation effect of FPP. The formation of in situ FPP resulted in a reduced crystallization rate, melting point, and degree of crystallization because of the decreased regularity of the PP chain. For the Mg(OH)₂/PP composites, addition of Mg(OH)₂ increased the crystallization temperatures of PP attributed to a heterogeneous nucleation effect of Mg(OH)₂. Addition of FPP into Mg(OH)₂/PP composites further enhanced the crystallization temperatures of PP. It is suggested that there is an activation of FPP to the heterogeneous nucleation effect of Mg(OH)₂ surface. The addition of AA also increased the crystallization temperatures of PP in Mg(OH)₂/PP composites, but crystallization temperatures of PP were not influenced by the AA content, a phenomenon explained by the heterogeneous nucleation effect of the Mg(OH)₂ surface activated by FPP and AA. A synergistic effect on crystallization of PP in Mg(OH)₂/PP composites further increased the crystallization temperatures of PP. However, the crystallization temperatures of Mg(OH)₂/PP composites modified by in situ FPP were lower than those of Mg(OH)₂/PP composites modified by the addition of FPP or AA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91:3899–3908, 2004     

Crystallization and melt behavior of Mg(OH)2/PP composites modified by functionalized polypropylene

The crystallization and melting behavior of Mg(OH)₂/PP composites modified by the addition of functionalized polypropylene (FPP) or acrylic acid (AA) and the formation of in situ FPP were investigated by DSC. The results indicated that addition of FPP increased the crystallization temperatures of PP because of the nucleation effect of FPP. The formation of in situ FPP resulted in a reduced crystallization rate, melting point, and degree of crystallization attributed to the decreased regularity of the PP chain. For Mg(OH)₂/PP composites, the addition of Mg(OH)₂ increased the crystallization temperatures of PP resulting from a heterogeneous nucleation effect of Mg(OH)₂. The addition of FPP into Mg(OH)₂/PP composites further enhanced the crystallization temperatures of PP. It is suggested that there is an activation of FPP to the heterogeneous nucleation effect on the Mg(OH)₂ surface. The addition of AA also increased the crystallization temperatures of PP in Mg(OH)₂/PP composites, although the crystallization temperature of PP was not influenced by the AA content, which is explained by the heterogeneous nucleation effect of the Mg(OH)₂ surface activated by FPP and AA. A synergistic effect on the crystallization of PP in Mg(OH)₂/PP composites further increased the crystallization temperatures of PP. However, The crystallization temperatures of Mg(OH)₂/PP composites modified by in situ FPP were lower than those of Mg(OH)₂/PP composites modified by addition of either FPP or AA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3610–3621, 2004     

Interaction of self‐nucleation and the addition of a nucleating agent on the crystallization behavior of isotactic polypropylene

The relationship between heterogeneous or homogeneous nucleation and self‐nucleation of polypropylene (PP) and PP nucleated by an organic phosphate salt (PPA) was studied by DSC. For pure PP, it homogeneously nucleated during cooling after melting at the selected temperature (T_s) of 170–200°C for 3 min, but at the T_s of 160–168°C self‐nucleation occurred; PPA only nucleated heterogeneously at the T_s of 168–200°C, and there existed self nucleation at the T_s of 160–168°C. The double melting peaks of PP and PPA at the T_s of 162°C were observed. Once the self‐nucleation occurred, the change of the crystallization temperature and heat of fusion of PP is more significant than that of PPA with the change of the T_s, depending upon the crystallization conditions. Results were explained by homogeneous nucleation, heterogeneous nucleation, self‐nucleation, and annealing crystallization. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 78–84, 2001     

Crystallization Behavior of Amorphous Si2BC3N Ceramic Monolith Subjected to High Pressure

The crystallization behavior of amorphous Si₂BC₃N monoliths by heating at 1000°C–1400°C and 5 GPa was investigated with the special attention to the nucleation mechanisms of β‐SiC and BN(C) phases. Nanoscale puckered structures arising in particle bridging areas were found and its evolution behavior well reflected the nucleation process of nanocrystallites. The temperature‐dependent crystallization of amorphous Si₂BC₃N monoliths at 5 GPa passes through four stages: The material remains amorphous below 1100°C. It undergoes partial phase segregation (1100°C–1200°C), followed by initiation of nucleation (1200°C–1250°C), and then nucleation and growth of β‐SiC and turbostratic BN(C) crystallites (>1250°C). The first principles calculation indicates the nucleation precedence of BN(C) phase over β‐SiC. BN(C) nucleates preferentially at bridges between ceramic particles causing SiC to concentrate in particle interiors thus forming capsule‐like structures.     

Isothermal crystallization kinetics of silk fibroin fiber‐reinforced poly(ε‐caprolactone) biocomposites

BACKGROUND: Poly(ε‐caprolactone) (PCL) has attracted great attention due to its wide applications for pharmaceutical controlled released systems and implanted polymer devices. In this study, silk fibroin fiber (SF) obtained from degumming treatment of silk was used to prepare novel reinforced PCL biocomposites. The isothermal crystallization behavior of these composites was investigated using differential scanning calorimetry measurements. RESULTS: With a decrease of isothermal crystallization temperature (T_c) and an increase of fiber filler, the crystallization time of the SF/PCL composites becomes shorter, the crystallization rate constant (K) increases and the Avrami exponent (n) gradually decreases (being between 1 and 2). The crystallization of PCL and SF/PCL composites occurs in the same regime. With the gradual addition of fiber, lateral surface free energy (σ) is nearly unchanged, but fold surface free energy (σ_e) decreases. CONCLUSION: Heterogeneous nucleation is dominant and different growth morphologies coexist during the isothermal crystallization process of the SF/PCL hybrid systems. Although the introduction of SF obviously increases the overall crystallization rate of PCL, the growth rate constant and nucleation constant of PCL are reduced because of the confinement effect of fiber network structures on the molecular mobility of polymer molecular chains. Copyright © 2009 Society of Chemical Industry     

Crystallization behavior of poly(N‐methyldodecano‐12‐lactam). III. Kinetics of isothermal crystallization

Differential scanning calorimetry, combined with Avrami theory, was used to investigate the kinetics of three steps of the complex crystallization process of poly(N‐methyldodecano‐12‐lactam) (MPA): (1) primary melt crystallization at respective crystallization temperature (T_c), (2) additional crystallization at 30°C, and (3) recrystallization at 54°C. Kinetics of the three steps was discussed with respect to T_c. The Avrami exponent n of primary melt crystallization decreased between 2.5 and 1.9 in the range of T_c values of ?10 to 20°C, which suggests heterogeneous nucleation, followed by two‐dimensional growth, with a larger involvement of homogeneous thermal nucleation at greater supercoolings. The crystallization rate constant k decreased with increasing T_c. The value of n = 1.5 for additional crystallization implies a two‐dimensional diffusion‐controlled crystal growth with a suppressed nucleation phase. For T_c values ranging from ?10 to 0°C and 0 to 20°C, k showed weak and quite strong decreasing dependencies on T_c, respectively. The recrystallization mechanism involved partial melting of primary crystallites and two‐dimensional rearrangement of chains into a more perfect structure. The rate of this process was almost independent of T_c. The values of activation energies were derived for the three steps of MPA crystallization using the Arrhenius equation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 279–293, 2004     

Thermal,crystallization, and dynamic rheological behavior of wood particle/HDPE composites: Effect of removal of wood cell wall composition

This study investigated the effect of removal of wood cell wall composition on thermal, crystallization, and dynamic rheological behavior of the resulting high density polyethylene (HDPE) composites. Four types of wood particle (WP) with different compositions: native wood flour (WF), hemicellulose‐removed wood particle (HR), lignin‐removed wood particle (holocellulose, HC), and both hemicellulose and lignin removed particle (α‐cellulose, αC) were prepared and compounded with HDPE using extruder, both with and without maleated polyethylene (MAPE). Results show that removal of the hemicellulose improved the thermal stability of composites, while removal of the lignin facilitated thermal decomposition. WPs acted as nucleating agents and facilitated the process of crystallization, thereby increasing the crystallization temperature and degree of crystallinity. The crystallization nucleation and growth rate of αC and HR based composites without MAPE decreased, as compared with WF based one. Composite melts with and without MAPE exhibited a decreasing order of storage modulus, loss modulus, and complex viscosity as αC > WF > HR > HC and αC > HR > WF > HC, respectively. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40331.     

Crystallization and melting behavior of nano‐CaCO3/polypropylene composites modified by acrylic acid

Nano‐CaCO₃/polypropylene (PP) composites modified with polypropylene grafted with acrylic acid (PP‐g‐AA) or acrylic acid with and without dicumyl peroxide (DCP) were prepared by a twin‐screw extruder. The crystallization and melting behavior of PP in the composites were investigated by DSC. The experimental results showed that the crystallization temperature of PP in the composites increased with increasing nano‐CaCO₃ content. Addition of PP‐g‐AA further increased the crystallization temperatures of PP in the composites. It is suggested that PP‐g‐AA could improve the nucleation effect of nano‐CaCO₃. However, the improvement in the nucleation effect of nano‐CaCO₃ would be saturated when the PP‐g‐AA content of 5 phf (parts per hundred based on weight of filler) was used. The increase in the crystallization temperature of PP was observed by adding AA into the composites and the crystallization temperature of the composites increased with increasing AA content. It is suggested that the AA reacted with nano‐CaCO₃ and the formation of Ca(AA)₂ promoted the nucleation of PP. In the presence of DCP, the increment of the AA content had no significant influence on the crystallization temperature of PP in the composites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2443–2453, 2004     

Glass Crystallization Research — A 36-Year Retrospective. Part I,Fundamental Studies

Over the past 36 years, our research has mainly focused on the crystallization kinetics and properties of glasses and glass-ceramics. A sampling of the most conclusive papers are reviewed here and include the following topics: the effects of liquid phase separation on crystal nucleation; tests and development of models of crystal nucleation, growth, and overall crystallization; metastable phase formation; surface crystallization; glass stability against devitrification; glass-forming ability; possible correlations between the molecular structure and the nucleation mechanism; sintering with concurrent surface crystallization; and diffusional processes that control crystallization. We conclude that despite significant advancement in the knowledge about several aspects of phase transformations in glasses that resulted from our own research and of other groups, which is not described in this review, glass crystallization remains an open, rich field to be explored.     

Effect of sepiolite on the crystallization behavior of biodegradable poly(lactic acid) as an efficient nucleating agent

To enhance the crystallization kinetics of poly(lactic acid) (PLA), fibrous sepiolite was explored for nucleating the crystallization of PLA. PLA/sepiolite nanocomposites were prepared via the melt‐extrusion method. The effect of sepiolite on the crystallization behavior, spherulite growth and crystal structure of PLA were investigated by means of differential scanning calorimetry (DSC), polarized optical microscope (POM), wide angle X‐ray diffraction (WAXD), Fourier transform infrared (FTIR), and scanning election microscope (SEM). On the basis of DSC and POM results, the overall crystallization kinetics of PLA/sepiolite nanocomposites were significantly enhanced leading to higher crystallinity and nucleation density, faster spherulite growth rate (G) and lower crystallization half‐time (t_1/2) compared with the neat PLA. Under non‐isothermal conditions, the PLA blend comprising 1.0 wt% of sepiolite still revealed two crystallization peaks upon cooling at a rate of 35°C/min. Above phenomena strongly suggested that sepiolite was an effective nucleating agent for PLA. FTIR and WAXD analyses confirmed that the crystal structure of PLA matrix was the most common α‐form. SEM micrographics illustrated the fine three‐dimensional spherulite structures with the lath‐shape lamellae regularly arranged in radial directions. POLYM. ENG. SCI., 55:1104–1112, 2015. © 2014 Society of Plastics Engineers     

Role of the particle size of graphite-like boron nitride in nucleation of cubic boron nitride

The influence of the reduced radius of grains of the graphite-like hexagonal boron nitride (h-BN) on the nucleation of the cubic boron nitride (c-BN) during synthesis from an initiator solution at a high pressure is analyzed. The colloidal mechanism of nucleation is confirmed experimentally. It is shown that there is a correlation between the nucleus sizes of the hexagonal boron nitride and the pressure of the onset of nucleation of the cubic boron nitride. The effect of these sizes of the hexagonal boron nitride on the concentration of crystal nuclei of the cubic boron nitride is studied. The kinetic nucleation curves are obtained. It is demonstrated that the concentration of crystallization centers depends on the thermodynamic and kinetic parameters, as well as on the particle size of the graphite-like hexagonal boron nitride. Original Russian Text ? S.P. Bogdanov, 2008, published in Fizika i Khimiya Stekla.     

Effect of Ultrasonic Irradiation on the Probability of Primary Nucleation of L-Arginine Hydrochloride

Most of the amino acids that are utilized as medical raw materials and food additives show polymorphism. To improve the functionality of amino acid crystals, an effective method of polymorph control is required in the crystallization process. Here, primary nucleation of L-arginine hydrochloride by ultrasonication was investigated. L-Arginine hydrochloride exhibits polymorphism, and it crystallizes into three distinct crystal forms. A cooling crystallization experiment was performed, and nucleation of each polymorph upon ultrasonication was observed. In addition, the nucleation was analyzed using the nucleation probability theory. The results indicate that ultrasonic irradiation would significantly induce the nucleation of a particular polymorph.