Microkinetics of Lamellar Crystallization in a Long Chain Polymer

1972 ◽  
Vol 45 (5) ◽  
pp. 1315-1333 ◽  
Author(s):  
E. H. Andrews ◽  
P. J. Owen ◽  
A. Singh
Keyword(s):  
Growth Rate ◽  
Chemical Composition ◽  
Crystallization Rate ◽  
Lamellar Thickness ◽  
Trans Content ◽  
Lamellar Crystal ◽  
Chain Polymer ◽  
Secondary Nucleus ◽  
Chemical Crosslinks ◽  
Kinetics Of

Abstract The growth kinetics of single crystal lamellae grown from poly(isoprene) melts have been determined by thin film electron microscopy which also reveals the relevant microstructure. The growth rate of a continuous lamellar crystal is independent of the length of the crystal and (in the absence of crosslinks) depends only upon temperature and the chemical composition of the polymer. The temperature dependence is closely similar to that observed for bulk crystallization and spherulite growth, with a maximum crystallization rate around —24° C. The growth rate at a given temperature is extremely sensitive to the chemical composition of the poly(isoprene), being for a polymer containing 10 per cent trans-poly(isoprene) one thousandth of that for pure cis-poly(isoprene). Between these extremes the logarithm of the growth rate decreases linearly with increasing trans content. A similar effect is produced by the introduction of chemical crosslinks instead of trans units. These effects are attributed to a reduction in the probability of formation of the ‘secondary nucleus’, whose size can be calculated from the experimental data. The secondary nucleus is found to correspond to three molecular folds and this agrees well with an independent estimate obtained, by using thermodynamical theory, from the dependence of lamellar thickness on temperature.

Microkinetics of lamellar crystallization in a long chain polymer

1971 ◽  
Vol 324 (1556) ◽  
pp. 79-97 ◽  
Keyword(s):  
Growth Rate ◽  
Chemical Composition ◽  
Crystallization Rate ◽  
Lamellar Thickness ◽  
Lamellar Crystal ◽  
Chain Polymer ◽  
Secondary Nucleus ◽  
Independent Estimate ◽  
Chemical Crosslinks ◽  
Kinetics Of

The growth kinetics of single crystal lamellae grown from polyisoprene melts have been determined by thin film electron microscopy which also reveals the relevant microstructure. The growth rate of a continuous lamellar crystal is independent of the length of the crystal and (in the absence of crosslinks) depends only upon temperature and the chemical composition of the polymer. The temperature dependence is closely similar to that observed for bulk crystallization and spherulite growth, with a maximum crystallization rate around — 24 °C. The growth rate at a given temperature is extremely sensitive to the chemical composition of the polyisoprene, being for a polymer containing 10% trans -polyisoprene one thousandth of that for pure cis -polyisoprene. Between these extremes the logarithm of the growth rate decreases linearly with increasing trans content. A similar effect is produced by the introduction of chemical crosslinks instead of trans units. These effects are attributed to a reduction in the probability of formation of the ‘secondary nucleus’, whose size can be calculated from the experimental data. The secondary nucleus is found to correspond to three molecular folds and this agrees well with an independent estimate obtained, by using thermodynamic theory, from the dependence of lamellar thickness on temperature.

Kinetics of polymer crystallization - II. Growth régimes

1988 ◽  
Vol 416 (1851) ◽  
pp. 463-476 ◽  
Keyword(s):  
Growth Rate ◽  
Continuum Model ◽  
Continuum Limit ◽  
Polymer Chains ◽  
Lamellar Crystal ◽  
Folding Rate ◽  
Edge Roughness ◽  
State Growth ◽  
Kinetics Of ◽  
The Continuum

From the models of paper I, exact expressions are found for the steady-state growth rate of a portion of the edge of a lamellar crystal in terms of the number of polymer segments M in the portion, the nucleation rate α on the edge and the folding rate v of polymer chains. Both hexagonal and square crystal structures are analysed. Simpler expressions are given in various limiting cases or régimes. One such régime is the continuum model of Bennett et al. (J. statist. Phys . 24, 419 (1981)). We find that the growth rates in our models differ substantially from this continuum limit when edge roughness is significant. The continuum growth rate provides an exact upper bound on the growth rate in Frank’s model (Frank, F. C. J. Cryst. Growth 22, 233 (1974)), which is sometimes exceeded by Frank’s approximation.

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.

Kinetics of non-isothermal melting and crystallization of gamma-irradiated isotactic polypropylene

e-Polymers ◽  
2003 ◽  
Vol 3 (1) ◽  
Author(s):  
Emanuel Nedkov ◽  
Tatyana Dobreva
Keyword(s):  
Constant Temperature ◽  
Isotactic Polypropylene ◽  
Crystallization Rate ◽  
Melting Rate ◽  
Isothermal Kinetics ◽  
Lamellar Thickness ◽  
Scanning Calorimetry ◽  
Gamma Irradiated ◽  
Kinetics Of ◽  
Melting And Crystallization

Abstract The non-isothermal kinetics of melting and crystallization of gamma-irradiated isotactic polypropylene were investigated by differential scanning calorimetry. At constant temperature the melting rate increased with the dose. During the melting, the average lamellar thickness, the free surface energy and the transport energy through the phase boundary reduced with increasing the dose. The crystallization rate decreased with increasing dose at constant temperature. Mixed α-γ spherulites were grown during crystallization. The non-isothermal crystallization rate expressed, in fact, the rate of secondary nucleation of the lamellae in the spherulites and their growth. Raising the irradiation doses led to a decrease of the crystallization temperature. A critical dose of irradiation of about 200 kGy was found, where the dependences of the calculated kinetic parameters underwent an important change. This change could be successfully connected with the effect of radiation annealing and melting.

Isolation, identification and in silico study of native cellulase producing bacteria

2019 ◽  
Vol 17 ◽  
Author(s):  
Farzane Kargar ◽  
Mojtaba Mortazavi ◽  
Mahmood Maleki ◽  
Masoud Torkzadeh Mahani ◽  
Younes Ghasemi ◽  
...  
Keyword(s):  
Growth Rate ◽  
Bacillus Cereus ◽  
16S Rdna ◽  
Enzyme Production ◽  
Rational Design ◽  
Cellulase Production ◽  
Bacillus Species ◽  
Bacillus Sp ◽  
Chain Polymer ◽  
Bacillus Toyonensis

Aims: The purpose of this study was to screen the bacteria producing cellulase enzymes and their bioinformatics studies. Background: Cellulose is a long-chain polymer of glucose that hydrolyzes by cellulases to glucose molecules. In order to design the new biotechnological applications, some strategies have been used as increasing the efficiency of enzyme production, generating cost-effective enzymes, producing stable enzymes and identification of new strains. Objective: On the other hand, some bacteria special features have made them suitable candidates for the identification of the new source of enzymes. In this regard, some native strains of bacteria were screened. Method: These bacteria were grown on a culture containing the liquid M9 media containing CMC to ensure the synthesis of cellulase. The formation of a clear area in the culture medium indicated decomposition of cellulose. In the following, the DNA of these bacteria were extracted and their 16S rDNA genes were amplified. Result: The results show that nine samples were able to synthesize cellulase. In following, these strains were identified using 16S rDNA. The results show that these screened bacteria belonged to the Bacillus sp., Alcaligenes sp., Alcaligenes sp., and Enterobacter sp.conclusionThe enzyme activity analysis shows that the Bacillus toyonensis, Bacillus sp. strain XA15-411 Bacillus cereus have produced the maximum yield of cellulases. However, these amounts of enzyme production in these samples are not proportional to their growth rate. As the bacterial growth chart within 4 consecutive days shows that the Alcaligenes sp. Bacillus cereus, Bacillus toyonensis, Bacillus sp. strain XA15-411 have a maximum growth rate. The study of the phylogenetic tree also shows that Bacillus species are more abundant in the production of cellulase enzyme. These bioinformatics analyses show that the Bacillus species have different evolutionary relationships and evolved in different evolutionary time. Other: However, for maximum cellulase production by this bacteria, some information as optimum temperature, optimum pH, carbon and nitrogen sources are needed for the ideal formulation of media composition. The cellulase production is closely controlled in microorganisms and the cellulase yields appear to depend on a variety of factors. However, the further studies are needed for cloning, purification and application of these new microbial cellulases in the different commercial fields as in food, detergent, and pharmaceutical, paper, textile industries and also various chemical industries. However, these novel enzymes can be further engineered through rational design or using random mutagenesis techniques.

Diffusion model for deposition of epitaxial GaAs layers prepared by the MOCVD method

1991 ◽  
Vol 56 (10) ◽  
pp. 2020-2029
Author(s):  
Jindřich Leitner ◽  
Petr Voňka ◽  
Josef Stejskal ◽  
Přemysl Klíma ◽  
Rudolf Hladina
Keyword(s):  
Experimental Data ◽  
Growth Rate ◽  
Kinetic Model ◽  
Gas Phase ◽  
Substrate Surface ◽  
Deposition Process ◽  
Hydrogen Atmosphere ◽  
Epitaxial Gaas ◽  
Kinetics Of ◽  
Good Agreement

The authors proposed and treated quantitatively a kinetic model for deposition of epitaxial GaAs layers prepared by reaction of trimethylgallium with arsine in hydrogen atmosphere. The transport of gallium to the surface of the substrate is considered as the controlling process. The influence of the rate of chemical reactions in the gas phase and on the substrate surface on the kinetics of the deposition process is neglected. The calculated dependence of the growth rate of the layers on the conditions of the deposition is in a good agreement with experimental data in the temperature range from 600 to 800°C.

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.

Crystal-growth kinetics of protein single crystals along capillary tubes in the gel-acupuncture technique

1999 ◽  
Vol 55 (2) ◽  
pp. 577-580 ◽  
Author(s):  
Abel Moreno ◽  
Manuel Soriano-García
Keyword(s):  
Growth Rate ◽  
Crystal Growth ◽  
Capillary Tube ◽  
Crystal Growth Rate ◽  
Equilibrium Studies ◽  
Acta Cryst ◽  
Average Growth ◽  
X Ray Crystallography ◽  
Growing Cell ◽  
Kinetics Of

In attempts to obtain protein crystals of a sufficient size for structural studies, lack of knowledge of the physicochemical properties of protein solutions and of their crystal-growth behaviour lead to a bottleneck for drug design as well as for X-ray crystallography. Most formal investigations on crystal-growth phenomena have been focused on equilibrium studies, where the protein is soluble, and on the kinetics of crystal growth, which is related to both nucleation and crystal-growth phenomena. The aim of this work is to measure the crystal-growth rate along a capillary tube used as a growing cell. These experiments were carried out using the gel-acupuncture technique [García-Ruiz et al. (1993). Mater. Res. Bull. 28, 541–546; García-Ruiz & Moreno (1994). Acta Cryst. D50, 484–490; García-Ruiz & Moreno (1997). J. Cryst. Growth, 178, 393–401]. Crystal-growth investigations took place using lysozyme and thaumatin I as standard proteins. The maximum average growth rate obtained in the lower part of the capillary tube was about 35 Å s−1 and the minimum average growing rate in the upper part of the capillary tube was about 8 Å s−1. The crystal-growth rate as a function of the supersaturation was experimentally estimated at a constant height along the capillary tube.

Thermal Parameters, Microstructure and Porosity During Transient Solidification of Ternary Al–Cu–Si Alloys

2012 ◽  
Vol 730-732 ◽  
pp. 883-888 ◽  
Author(s):  
Daniel J. Moutinho ◽  
Laércio G. Gomes ◽  
Otávio L. Rocha ◽  
Ivaldo L. Ferreira ◽  
Amauri Garcia
Keyword(s):  
Growth Rate ◽  
Chemical Composition ◽  
Cooling Rate ◽  
Tip Growth ◽  
Thermal Parameters ◽  
Volumetric Fraction ◽  
Dendritic Network ◽  
Intermetallic Particles ◽  
Casting Length

Solidification of ternary Al-Cu-Si alloys begins with the development of a complex dendritic network typified by primary (λ1) and secondary (λ2) dendrite arm spacings which depend on the chemical composition of the alloy and on the casting thermal parameters such as the growth rate and the cooling rate. These thermal parameters control the scale of dendritic arms, the size and distribution of porosity and intermetallic particles in the casting. In this paper, λ1and λ2were correlated with experimental thermal parameters i.e., the tip growth rate and the tip cooling rate. The porosity profile along the casting length has also been experimentally determined. The volumetric fraction of pores increase with the increase in alloying Si and with the increase in Fe concentration at the regions close to the casting cooled surface.

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