Effect of Electron Beam Irradiation on the Kinetics of Non-isothermal Crystallization of Nylon 66

The non-isothermal crystallization kinetics was studied by differential scanning calorimetric analysis on nylon 66 and e-beam irradiated nylon 66 at different cooling rates. The Modified Avrami equation, the Ozawa equation and the Combined Avrami-Ozawa equation were applied to study the kinetics of non-isothermal crystallization of nylon 66. The crystallization behavior of pristine nylon 66 polymer was compared with that of e-beam irradiated nylon 66 and observed that the kinetics of non-isothermal crystallization of nylon66 was affected largely upon e-beam irradiation. E-beam irradiation not only decreased the crystallization temperature of nylon 66, but influenced the mechanism of nucleation and crystal growth and reduced the overall crystallization rate of nylon 66 also. The crystallization activation energy calculated by the Kissinger method for irradiated nylon 66 was lower than that of pristine nylon 66.     

Study of Isothermal Crystallization Kinetics of 5CB with Differential Scanning Calorimetry and Broadband Dielectric Spectroscopy

The isothermal crystallization kinetics of 4-n-pentyl-4–cyanobiphenyl (5CB) has been studied with Differential Scanning Calorimetry (DSC) and Dielectric Relaxation Spectroscopy (DRS). 5CB is a well characterized material which makes it ideal for a dielectric and thermal comparative study. The effect that isothermal crystallization exerts on the behavior of relaxation processes α and δ by cooling the isotropic liquid below the nematic phase or through the process of cold crystallization by heating it from the supercooled state is explored by comparing the DRS and DSC. Furthermore, by employing the Avrami equation, we compare the ability to probe the crystallization with each technique.     

An investigation of the crystallization kinetics of zeotype SAPO-34 crystals synthesized by hydrothermal and sonochemical methods

The kinetics study of SAPO-34 crystallization from a gel containing morpholine as a structure directing agent (SDA) was investigated by means of X-ray diffraction (XRD) patterns in order to determine the kinetics parameters, i.e. induction times, rate constants, frequency factors, and activation energies for the induction and growth stages. The kinetics data of growth period were determined by using the Avrami–Erofeev nucleation growth model. SAPO-34 molecular sieves were synthesized by using both sonochemical-assisted hydrothermal and conventional hydrothermal heating at temperatures of 180, 200, and 220 °C to elucidate the influence of crystallization method on the crystallization kinetics of SAPO-34. The activation energy values indicated that the crystal growth mechanism was enhanced for samples synthesized sonochemically, whereas the induction energy was not greatly affected by using sonication process. Also, the kinetic compensation effect (KCE) was considered in order to obtain the isokinetic temperature.     

Isothermal and temperature-cycling retrogradation of high-amylose corn starch: Impact of sonication on its structural and retrogradation properties

In this study, the effects of sonication and temperature-cycled storage on the structural properties and resistant starch content of high-amylose corn starch were investigated. Sonication induced a partial depolymerization of the molecular structures of amylopectin and amylose. Sonication treatment induced the appropriate structural changes for retrogradation. Although the relative crystallinity of sonicated starch was lower than that of non-sonicated starch, sonicated starch after retrogradation showed much higher relative crystallinity than non-sonicated starch. Regardless of sonication treatment, temperature-cycled storage resulted in a higher degree of retrogradation than isothermal storage, but the rate of retrogradation was greater in sonicated starch than in non-sonicated starch, as supported by retrogradation enthalpy, the Avrami constant, and relative crystallinity. The highly developed crystalline structure in sonicated starches due to retrogradation was reflected by the large amount of resistant starch.     

动态扭振法在树脂固化研究中的最新应用

用计算机全自动控制的LHX-Ⅱ型树脂固化仪对热固性树脂基蒙脱土纳米复合材料、热塑性树脂PMMA基蒙脱土纳米复合材料以及聚合物互穿网络等体系进行了固化反应的研究。借用Avrami理论来处理树脂基纳米复合材料的固化行为,求取固化反应表现动力学参数。     

Determination of avrami parameters of hydroxyapatite and β-wollastonite in bioactive phosphor—Silica glasses

The properties of biologically active glasses in the system SiO₂?P₂O₅?MgO?CaO were studied. Crystalline hydroxyapatite (HA) and β-wollastonite (β-W) were used after heat treatment (1100°C). The influence of the glass particle size (0.071–2.5 mm) and of glass powder (d ₅₀=15.1 μm) on the behaviour of the products during differential thermal analysis was followed. These analyses indicated that the β-W probably originates from surface nucleation, and HA from bulk nucleation. The differentiation was confirmed by calculation of the Avrami parameters (n) with the Pi-loyan-Borchardt analytical method. For HA and β-W, the calculated values ofn were 2.96 and 1.91. The surface-nucleated glasses exhibited predominant bidimensional crystal growth.     

Crystallisation behaviour of high density polyethylene blends with bimodal molar mass distribution: 2. Non-isothermal crystallisation

Crystallisation of high density polyethylene (HDPE) blends with broad bimodal molar mass distribution was investigated by differential scanning calorimetry (DSC) under non-isothermal conditions. The blends were prepared by blending a high molar mass PE (M_w=330 kg/mol, M_w/M_n=4.8) and a low molar mass linear PE (M_w=34 kg/mol, M_w/M_n=10) in different ratios in xylene solution. The samples were analysed by the normal DSC at different crystallisation rates and by a thermal fractionation technique.The blends and their parent polymers behaved according to general expectations i.e., crystallinity and density decreased when the molar mass of the samples increased. Additionally, non-linear relationships between MM and different analysed parameters were found. Small addition of the high molar mass parent polymer to the low molar mass parent polymer increased crystallisation temperature, although the general trend was decreasing. Furthermore, a complicated relationship between the reciprocal of crystallisation half-time and sample composition was found. The value increased first with increasing molar mass, reached a maximum when the average molar mass of the blend was between 150 and 200 kg/mol and then decreased. The detected maximum correlated with the broadest molar mass distribution of the blends. The crystallinities and densities of the blends with the broadest molar mass distribution also deviated from the linear correlation between them and molar mass. The Avrami index under non-isothermal conditions was analysed with a method developed by Harnisch and Muschik. The results indicated that thermal nucleation and spherical growth regimes are present in all studied materials.     

Crystallisation behaviour of high density polyethylene blends with bimodal molar mass distribution 1. Basic characteristics and isothermal crystallisation

Isothermal crystallisation of high density polyethylene (HDPE) blends and their parent polymers was investigated. The blends having broad bimodal molar mass distributions and various compositions were prepared by blending a high molar mass (M_w=330 kg/mol, M_w/M_n=4.8) and a low molar mass HDPE (M_w=34 kg/mol, M_w/M_n=10) in different ratios in xylene solution. The blends and their parent components were characterised by size-exclusion chromatography, dynamic rheological and density measurements. Crystallisation kinetics were studied using a polarised light microscope equipped with an in-house built hot stage and by differential scanning calorimetry. The Avrami theory was applied for crystallisation kinetics analysis. Such crystallisation kinetics parameters as nucleation rate, nucleation density, the Avrami index and cystallisation rate contant were determined for the blends and their parent polymers.According to the results obtained an increasing polydispersity of the sample had a slight increasing effect on the Avrami index, indicating gain in prevalence of the thermal nucleation over the athermal one. In all samples nucleation density increased continuously during crystallisation verifying that the presence of a certain thermal nucleation was typical for all the materials studied. Both the crystallisation rate constant and the nucleation rate decreased with increasing molar mass of the sample. The nucleation density increased proportionally to the increase in average molar mass and the values were larger at lower crystallisation temperatures.The formed supermolecular structure was found to be sensitive to the blend composition and crystallisation temperature. Irregular banded or non-banded spherulites were observed in the materials. Banding of spherulites was typical for the samples having higher average molar mass. The superstructures observed in this work were smaller and vaguer than the superstructures reported in the earlier studies of polyethylene materials having similar average molar mass but narrow molar mass distribution.     

Cure behavior of epoxy resin/montmorillonite/imidazole nanocomposite by dynamic torsional vibration method

Flory’s gelation theory, the non-equilibrium thermodynamic fluctuation theory and the Avrami equation have been used to predict the cure behavior of epoxy resin/organo-montmorillonite (Org-MMT)/imidazole intercalated nanocomposites at various temperatures and Org-MMT loadings. The theoretical prediction is in good agreement with the experimental results obtained by a dynamic torsional vibration method. The results show that the addition of Org-MMT reduces the gelation time t_g and increases the rate of the curing reaction, the value of the kinetic constant k. The half-time t_1/2 of cure after the gel point decreases with increasing of cure temperature, and the value of n is around 3 at lower temperature (<90 °C) and decreases to ∼2 as the temperature increases. The addition of Org-MMT has no obvious effect on the apparent activation energy of the cure reaction. There is no special curing process required for the formation of an epoxy resin/Org-MMT/imidazole intercalated nanocomposite.     

Effect of sample size on isothermal crystallization measurements performed in a differential scanning calorimeter: A method to determine avrami parameters without sample thickness effects

Isothermal crystallization studies of low-density polyethylene (LDPE) and high-density polyethylene (HDPE) using differential scanning calorimetry (DSC) were performed using different sample thicknesses to determine the effect of non-ideal heat-transfer. Polyethylene was chosen because of its importance, its extensive coverage in the literature, and its fast crystallization kinetics. Thermal gradients were found to significantly affect the measured crystallization exotherm; slower crystallization rates were observed for thicker samples measured at lower temperatures (greater supercoolings). Differences between different sample thicknesses disappeared at higher temperatures, consistent with finite heat-transfer rates being responsible for the effect. A power-compensation and a heat-flux DSC were used; these experiments also enabled the determination that the performance of the latter was acceptable for this study. Finally, thickness-independent Avrami parameters have been calculated.