Kinetics of Crystallisation of Polymers - A Review

2002 ◽  
Vol 18 (3) ◽  
pp. 195-215 ◽  
Author(s):  
P. Sajkiewicz
Keyword(s):  
Critical Size ◽  
Crystallization Rate ◽  
Relaxation Effect ◽  
Steady State Condition ◽  
Potential Barriers ◽  
Classical Models ◽  
External Conditions ◽  
Thermal Nucleation ◽  
Athermal Nucleation ◽  
Kinetics Of

A review covering nucleation modes and models of polymer crystallization kinetics. The classical models assume the rate of crystallization to be related to temperature only. For materials exhibiting low molecular mobility, e.g., polymers, time effects appear justified. Ziabicki's model (51-53) allows the rate to be related to time. In thermal nucleation, this relation stems from the delay of the steady-state condition to become established under specific external conditions. The athermal mechanism of nucleation produces another time effect. It involves no potential barriers to be overcome by a cluster to become a nucleus and proceeds only on account of the change in the criterion for the nucleus stability (critical size) as external conditions are modified. Experiments showed the (iso and non-isothermal) crystallization rate to be directly related to time. The underlying phenomenon involves the athermal nucleation occurring on crystal residues left in the melt and the relaxation effect upon subsequent thermal nucleation. The applicability of Ziabicki's model is demonstrated.

scholarly journals Isothermal Crystallization Kinetics of Poly(ethylene oxide)/Poly(ethylene glycol)-g-silica Nanocomposites

Polymers ◽  
2021 ◽  
Vol 13 (4) ◽  
pp. 648
Author(s):  
Xiangning Wen ◽  
Yunlan Su ◽  
Shaofan Li ◽  
Weilong Ju ◽  
Dujin Wang
Keyword(s):  
Molecular Weight ◽  
Ethylene Oxide ◽  
Crystallization Kinetics ◽  
Isothermal Crystallization ◽  
Crystallization Rate ◽  
Poly Ethylene Glycol ◽  
Isothermal Crystallization Kinetics ◽  
Poly Ethylene Oxide ◽  
Poly Ethylene ◽  
Kinetics Of

In this work, the crystallization kinetics of poly(ethylene oxide) (PEO) matrix included with poly(ethylene glycol) (PEG) grafted silica (PEG-g-SiO2) nanoparticles and bare SiO2 were systematically investigated by differential scanning calorimetry (DSC) and polarized light optical microscopy (PLOM) method. PEG-g-SiO2 can significantly increase the crystallinity and crystallization temperature of PEO matrix under the non-isothermal crystallization process. Pronounced effects of PEG-g-SiO2 on the crystalline morphology and crystallization rate of PEO were further characterized by employing spherulitic morphological observation and isothermal crystallization kinetics analysis. In contrast to the bare SiO2, PEG-g-SiO2 can be well dispersed in PEO matrix at low P/N (P: Molecular weight of matrix chains, N: Molecular weight of grafted chains), which is a key factor to enhance the primary nucleation rate. In particular, we found that the addition of PEG-g-SiO2 slows the spherulitic growth fronts compared to the neat PEO. It is speculated that the interfacial structure of the grafted PEG plays a key role in the formation of nuclei sites, thus ultimately determines the crystallization behavior of PEO PNCs and enhances the overall crystallization rate of the PEO nanocomposites.

Non-Isothermal Crystallization Kinetics of Graphene Oxide-Carbon Nanotubes Hybrids / Polyamide 6 Composites

2019 ◽  
Vol 41 (3) ◽  
pp. 394-394
Author(s):  
Zhi Qiang Wang Zhi Qiang Wang ◽  
Yong Ke Zhao and Xiang Feng Wu Yong Ke Zhao and Xiang Feng Wu
Keyword(s):  
Carbon Nanotubes ◽  
Graphene Oxide ◽  
Cooling Rate ◽  
Crystallization Kinetics ◽  
Isothermal Crystallization ◽  
Crystallization Rate ◽  
Polyamide 6 ◽  
Degree Of Crystallinity ◽  
Isothermal Crystallization Kinetics ◽  
Kinetics Of

The hybrids combined by nano-materials with different dimensions usually possess much better enhancement effects than single one. Graphene oxide-carbon nanotubes hybrids / polyamide 6 composites has been fabricated. The non-isothermal crystallization kinetics of the as-prepared samples was discussed. Research results showed that increasing the cooling rate was in favor of increasing the crystallization rate and the degree of crystallinity for the as-prepared samples. Moreover, the crystallization rate was first decreased and then increased with increasing the hybrids loading. Furthermore, the crystallization mechanism was changed with increasing the crystallization temperature and the cooling rate. The nucleation and growth modes of the non-isothermal crystallization could be classified into three different types, according to the Ozawa’s theory. These complicated results could be attributed to the important role of crystallization rate as well as the simultaneous hindering and promoting effects of the as-prepared hybrids. This work has reference values for understanding the crystallization kinetics of the polyamide 6-based composites.

Kinetics of crystallization for polypropylene/polyethylene/halloysite nanotube nanocomposites

2018 ◽  
Vol 33 (4) ◽  
pp. 451-463 ◽  
Author(s):  
MY Ong ◽  
WS Chow
Keyword(s):  
Crystallization Rate ◽  
Avrami Equation ◽  
Crystallization Time ◽  
Halloysite Nanotube ◽  
Kissinger Equation ◽  
Polyethylene Blends ◽  
Instantaneous Nucleation ◽  
Half Crystallization Time ◽  
T Values ◽  
Kinetics Of

The aim of this study is to investigate the kinetics of non-isothermal crystallization of polypropylene/high-density polyethylene/halloysite nanotube (PP/HDPE/HNT) nanocomposites using three methods, that is, Avrami equation, combined Ozawa–Avrami method (hereafter called Mo model), and Kissinger equation. The Avrami exponent ( n) is in the range of 1–2 for all the PP/HDPE/HNT nanocomposites indicating instantaneous nucleation while the crystallization rate constant ( Zt) values of PP/HDPE increased with the addition of HNT. This proved that addition of HNT increases the crystallization rate. The reduction of half crystallization time ( t 1/2) for PP/HDPE as the increasing HNT loading indicates faster crystallization rate. In the Mo model, the cooling rate chosen at unit crystallization time F( T) values for PP/HDPE decreases with the addition of HNT. Kissinger equation showed that the activation energy ( E a) of crystallization for the PP/HDPE decreases with the addition of HNT. All the results demonstrated that HNT can accelerate the crystallization rate for the PP/polyethylene blends.

scholarly journals DAF1, a mutant gene affecting size control, pheromone arrest, and cell cycle kinetics of Saccharomyces cerevisiae.

1988 ◽  
Vol 8 (11) ◽  
pp. 4675-4684 ◽  
Author(s):  
F R Cross
Keyword(s):  
Saccharomyces Cerevisiae ◽  
Cell Cycle ◽  
Critical Size ◽  
Size Control ◽  
Mutant Gene ◽  
G1 Phase ◽  
Wild Type ◽  
Alpha Factor ◽  
Multiple Copies ◽  
Kinetics Of

The mating pheromone alpha-factor arrests Saccharomyces cerevisiae MATa cells in the G1 phase of the cell cycle. Size control is also exerted in G1, since cells do not exit G1 until they have attained a critical size. A dominant mutation (DAF1-1) which causes both alpha-factor resistance and small cell size (volume about 0.6-fold that of the wild type) has been isolated and characterized genetically and by molecular cloning. Several alpha-factor-induced mRNAs were induced equivalently in daf1+ and DAF1-1 cells. The DAF1-1 mutation consisted of a termination codon two-thirds of the way through the daf1+ coding sequence. A chromosomal deletion of DAF1 produced by gene transplacement increased cell volume about 1.5-fold; thus, DAF1-1 may be a hyperactive or deregulated allele of a nonessential gene involved in G1 size control. Multiple copies of DAF1-1 also greatly reduced the duration of the G1 phase of the cell cycle.

Crystallization and Melting Behaviors of Polylactic Acid/Thermoplastic Polyurethane Blends

2012 ◽  
Vol 627 ◽  
pp. 156-159 ◽  
Author(s):  
Tien Wei Shyr ◽  
Jung Yang ◽  
Chun Chieh Hu ◽  
Jian Ren Wang ◽  
Chia Hsin Tung
Keyword(s):  
Polylactic Acid ◽  
Thermoplastic Polyurethane ◽  
Crosslinking Agent ◽  
Crystallization Rate ◽  
Optical Microscope ◽  
Avrami Equation ◽  
Isothermal Crystallization Kinetics ◽  
X Ray ◽  
Structure Morphology ◽  
Kinetics Of

A series of blends were prepared by different ratios of polylactic acid (PLA) and thermoplastic polyurethane (TPU) with a crosslinking agent of dicumyl peroxide (DCP). This study focused on the crystal structure, morphology, crystallization, and melting behaviors of PLA/TPU blends using a wide angle x-ray diffractometer (WAXD), a polarizing optical microscope (POM) and a differential scanning calorimeter (DSC). A Modified Avrami equation was applied to analyze non-isothermal crystallization kinetics of PLA/TPU blends. Results show that the nucleation of PLA was enhanced by the added TPU. The spherulitic growth rate, crystallization rate, and crystallinity of the PLA/TPU blends increased with an increase of TPU content. WAXD results show that all of the crystal reflections of PLA/TPU blends related to those of PLA.

scholarly journals Monte Carlo Simulation for the Morphology and Kinetics of Spherulites and Shish-Kebabs in Isothermal Polymer Crystallization

2015 ◽  
Vol 2015 ◽  
pp. 1-10 ◽  
Author(s):  
Chunlei Ruan ◽  
Chuntai Liu ◽  
Guoqiang Zheng
Keyword(s):  
Growth Rate ◽  
Monte Carlo Simulation ◽  
Monte Carlo ◽  
Monte Carlo Method ◽  
Crystallization Rate ◽  
Polymer Crystallization ◽  
Nucleation Density ◽  
Length Growth ◽  
Average Size ◽  
Kinetics Of

Monte Carlo method is used to capture the evolution of spherulites and shish-kebabs and to predict the crystallization kinetics in isothermal polymer crystallization. Effects of nucleation density and growth rate of spherulites, nucleation density, and length growth rate of shish-kebabs, respectively, on crystallization are investigated. Results show that nucleation densities of both spherulites and shish-kebabs strongly affect crystallization rate as well as morphology. An increase in nucleation density of either spherulites or shish-kebabs leads to a quicker crystallization rate and a smaller average spherulite size. It is also shown that nucleation density of shish-kebabs has a stronger impact on crystallization rate. Growth rate of spherulites and length growth rate of shish-kebabs also have significant effect on crystallization rate and morphology. An increase in growth rate of spherulites or length growth rate of shish-kebabs also speeds up the crystallization rate; additionally, a decrease in growth rate of spherulites or an increase in length growth rate of shish-kebabs results in a more highly anisotropic shish-kebab structure and a smaller average size of spherulites. Results also show that the effect of growth rate of spherulites is more important than the effect of length growth rate of shish-kebabs on crystallization.

Simulation of Non-Isothermal Crystallization under Varying Cooling Rates for Polymer Melts

2011 ◽  
Vol 221 ◽  
pp. 159-164
Author(s):  
Bi Wei Qiu ◽  
Jing Bo Chen ◽  
Bin Zhang ◽  
Chang Yu Shen
Keyword(s):  
Crystallization Kinetics ◽  
Isothermal Crystallization ◽  
Specific Model ◽  
Manufacturing Processes ◽  
Cooling Rates ◽  
Isothermal Crystallization Kinetics ◽  
Model Predictions ◽  
External Conditions ◽  
Kinetics Of ◽  
Good Agreement

Traditional studies of crystallization kinetics are often limited to idealized conditions where the temperatures or the cooling rates are constant. In real manufacturing processes, however, the external conditions change continuously, which make the kinetics of crystallization dependent on instantaneous conditions, especially on changing cooling rate. To obtain the crystallization information in manufacturing processes, lots of mathematical models for the non-isothermal crystallization kinetics are raised. But most of them concentrate on constant cooling rates melts crystallization behavior and pay little attention to the condition of varying cooling rates, which is more close to actual processing conditions. Based on the thermodynamics theory of crystallization, I.J. RAO and K.R. RAJAGOPAL derived a general specific model for quiescent crystallization (it is simplified as RAO model below). In order to verify the RAO model’s simulation effect on changing cooling rates crystallization, the constant cooling rates and varying cooling rates melts crystallization of isotactic polypropylene, high density polyethylene and nylon 6 were all investigated using the DSC technique. The results showed that the model predictions and experimental results were in good agreement.

Bioceramic Drug Delivery System for Cancer Treatment and Regenerative Medicine

2016 ◽  
Vol 696 ◽  
pp. 245-249
Author(s):  
Ahmed El-Ghannam
Keyword(s):  
Drug Delivery ◽  
Growth Factors ◽  
Bone Regeneration ◽  
Critical Size ◽  
Release Kinetics ◽  
Drug Binding ◽  
Calvarial Defect ◽  
Ceramic Composition ◽  
Delivery Platform ◽  
Kinetics Of

Silica-calcium-phosphate composite (SCPC) is a drug delivery platform that has successfully demonstrated the ability to bind and release several therapeutics including antibiotics, peptides, anticancer drugs, and growth factors. It has successfully demonstrated a unique capacity for bone regeneration. The present studies address the effect of the phosphate and silicate functional groups on drug binding and controlled release kinetics of Cisplatin (Cis). Moreover, the roles of ceramic composition and resorbability on rhBMP2 release kinetics and bone regeneration in a critical size calvarial defect in rabbit is presented.

Kinetic Study on Phosphate Enrichment Behavior in CaO–SiO2–FeO–Fe2O3–P2O5 Steelmaking Slags

2018 ◽  
Vol 37 (5) ◽  
pp. 477-486
Author(s):  
Jin-yan Li ◽  
Mei Zhang ◽  
Min Guo ◽  
Xue-min Yang
Keyword(s):  
Activation Energy ◽  
Apparent Activation Energy ◽  
Crystallization Behavior ◽  
Crystallization Rate ◽  
Avrami Equation ◽  
One Dimensional ◽  
Thermal Crystallization ◽  
Steelmaking Slags ◽  
Cooling Schedules ◽  
Kinetics Of

AbstractThe iso-thermal crystallization behavior of phosphate-enriched phase has been experimentally investigated in the rapidly quenched CaO–SiO2–FeO–Fe2O3–P2O5 steelmaking slags under different cooling schedules. The experimental results indicate that increasing endpoint temperature from 1453 to 1533 K and prolonging holding time from 2 to 60 min can result in an increasing tendency of the size of phosphate-enriched phase in the shape of one-dimensional rod. The crystallization kinetics of phosphate-enriched phase in steelmaking slags has been described by Avrami equation. The Avrami constant $$n$$ was obtained to be 0.472, while the crystallization rate constant $$k$$ was recommended as $$\ln k{\rm{= 57}}{\rm{. 40 + 12,273}}{\rm{. 96}}/T - {\rm{8}}{\rm{. 25}}\,\ln T - {\rm{5}}{\rm{. 5}\times{\rm 10}^{- 3}}T$$. Thus, the apparent activation energy $$E$$ of crystallization is recommended as $$E{\rm{= 537}}{\rm{. 60}} - {\rm{206}}{\rm{. 015}}T$$ kJ/mol.

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