PA1212-b-PEG嵌段共聚物的合成和非等温结晶动力学研究

采用DSC方法研究了PA1212-b-PEG在不同降温速率下的结晶过程,并利用Avrami方程研究了其非等温结晶动力学。在非等温结晶过程中,随着降温速率的增大,结晶温度向低温偏移。综合利用Avrami方程得到Avrami指数为4,说明结晶是以异相成核,三维生长。     

半芳香族聚酰胺6T/6I/6的合成及其非等温结晶动力学研究

采用成盐、高温溶液缩聚两步法成功制备了半芳香族聚酰胺（PA）6T/6I/6。通过傅里叶变换红外光谱（FTIR）、氢核磁共振（¹H⁃NMR）分析了其分子链结构,并对其力学性能进行了测试表征,利用差示扫描量热法（DSC）对PA6T/6I/6的非等温结晶动力学进行了研究,使用Jeziorny法、Oazawa法和莫志深法修正的Avrami方程分别分析了PA6T/6I/6的非等温结晶行为。结果表明,通过Jeziorny法处理发现结晶过程分为主期结晶和次期结晶2个阶段,主期结晶阶段Avrami指数在1.08~1.09之间,晶体为异相成核,呈一维针状生长,次期结晶阶段Avrami指数在2.13~2.21之间,晶体为二维片状生长方式;Ozawa法处理曲线相关性低,表明不适用于描述PA6T/6I/6的非等温结晶过程;莫志深法修正的Avrami方程能较好地描述结晶过程,a值在0.89~0.90之间,F（T）值在7.24~15.85之间;采用Kissinger方程计算求得PA6T/6I/6的非等温结晶活化能为-294.17 kJ/mol。     

s-PB/TPI釜内原位聚合共混物的非等温结晶动力学

采用2种负载型催化体系在反应釜内原位合成了间同聚丁二烯（s-PB）及s-PB/反式-1,4-聚异戊二烯（TPI）（80/20）共混物。用DSC方法研究了s-PB及共混物的非等温结晶行为,结果表明：Jeziorny修正的Avrami法和Mo法对s-PB及s-PB/TPI（80/20）共混物的非等温结晶行为有较好的适用性,Ozawa法则存在一定的缺陷。s-PB及其共混物的结晶活化能分别为-253 kJ/mol和-310 kJ/mol。TPI的加入降低了s-PB的结晶速率,使得共混物的结晶活化能绝对值增大。     

PA 6非等温结晶动力学研究

用差示扫描量热法研究了聚酰胺(PA)6的非等温结晶动力学,并分别用Ozawa法、Jeziorny法和莫志深方程法处理PA 6的非等温结晶行为。结果表明:Ozawa法和Jeziorny法均不能很好地描述PA 6非等温结晶过程;莫志深方程结合Avrami和Ozawa方程,可很好地描述PA 6非等温结晶过程;PA 6的结晶受温度的影响较大,一旦成核,结晶可在短时间内发展得比较完善。     

生物基尼龙56的等温结晶性能研究

采用差示扫描量热仪和带有热台的偏光显微镜对生物基尼龙56的等温结晶性能进行了研究。用Avrami方程对等温结晶过程及其动力学进行了分析,得出Avrami指数(n值)在2.30~3.37之间,推测其晶体生长方式为三维球状生长;采用Arrhenius方程计算了生物基尼龙56的等温结晶活化能(ΔE)为-99.04 kJ/mol。偏光显微镜研究证实了上述推测,同时发现球晶半径与结晶时间呈线性关系,求得了球晶的生长速率。     

尼龙612/6共聚物的表征与非等温结晶动力学研究

以尼龙612盐和己内酰胺为原料,采用熔融聚合的方法合成了尼龙612/6共聚物,采用傅里叶红外光谱仪(FTIR)、核磁共振氢谱仪(1HNMR)、偏光显微镜(PLM)对其相关结构进行表征,并分别用Jeziorny修正的Avrami方程、Ozawa方程、莫志深法进行非等温结晶动力学分析。结果表明:尼龙612结晶过程为二次成核,成核后沿着晶核二维盘状生长;而尼龙612/6共聚物的结晶过程为一次均相成核,晶核形成后沿晶核二维盘状与三维球状生长;莫志深法分析结果对应参数a基本保持一致,说明Avrami指数n与Ozawa指数m之间确实存在一定的数量关系,F(T)的变化表明,要在单位时间内达到更高的结晶度需提高降温速率,同时相同结晶度下尼龙612的结晶速率远大于尼龙612/6共聚物;采用Kissinger方程计算得出尼龙612及其共聚物的非等温结晶活化能ΔE分别为-433.29 kJ/mol、-94.12 kJ/mol。     

聚酰胺11/白炭黑纳米复合材料的非等温结晶动力学研究

采用原位聚合法制备了聚酰胺11（PA11）及PA11/白炭黑纳米复合材料,利用差示扫描量热仪研究了PA11及其纳米复合材料的非等温结晶过程,用经Jeziorny修正的Avrami方程、Mo法对其非等温结晶动力学进行了研究,计算并得到了非等温结晶动力学参数。结果表明,Avrami方程和Mo法都适用于处理PA11及其纳米复合材料的非等温结晶过程;在其非等温结晶过程中,PA11及其纳米复合材料都包括初期结晶和二次结晶两个阶段;Mo法表明,复合材料的结晶速率比PA11的小。此外,用Huffman-Lauritzen理论计算了PA11及其纳米复合材料非等温结晶的结晶活化能,结果表明,纳米复合材料的结晶活化能的绝对值小于PA11。     

T-ZnOw和POE改性聚丙烯的非等温结晶动力学

用 DSC 考察了 PP、PP/POE 和 PP/POE/T-ZnOw 复合材料的非等温结晶行为,并用 Jeziorny 法、Ozawa 法和莫志深法计算了复合材料的非等温结晶动力学参数,发现 Jeziorny 法和莫志深法能很好地分析 PP 及其复合材料的非等温结晶行为,而 Ozawa 方程则不适用。分析结果表明:POE 和 T-ZnOw 的加入起到了异相成核的作用,提高了PP 基体的结晶速率,其中 T-ZnOw 的作用更为明显。Kissinger 公式的分析结果显示 PP 的结晶活化能（339.94 kJ/mol）大于 PP/POE（262.03 kJ/mol）和 PP/POE/T-ZnOw（259.79 kJ/mol）复合材料的结晶活化能。     

无规抗冲共聚聚丙烯的非等温结晶动力学

在Spheripol工艺中试装置上制备了丙丁无规抗冲共聚聚丙烯（记作PP-1）和乙丙丁无规抗冲共聚聚丙烯（记作PP-2），对两种聚丙烯的非等温结晶行为进行了研究，针对无规抗冲共聚聚丙烯实际生产过程中的结晶特点，分别结合Caze法和Mo法提出的理论对非等温结晶动力学Ozawa模型进行了修正。结果表明：采用修正过的两种方法更加符合无规抗冲共聚聚丙烯实际生产过程中的非等温结晶行为。采用Caze法修正Ozawa模型后求出的PP-1和PP-2的Avrami指数分别为2.44,2.37，说明乙烯单体的引入并不会使PP-1的成核机理和生长方式发生改变。采用Mo法修正Ozawa模型后求出的动力学参数F(T)在同一相对结晶度下PP-1小于PP-2，表明在同一时间内PP-2要达到某一结晶度所需冷却速率更大；采用Kissinger法计算的PP-1和PP-2的结晶活化能分别为11.12,14.14 kJ/mol，进一步证实了上述结果。     

PEEK/CF复合材料的非等温结晶动力学研究

利用差示扫描量热仪(DSC)研究了聚醚醚酮(PEEK)和PEEK/碳纤维(CF)复合材料的非等温结晶行为,采用Avrami,Ozawa和Mo方程对PEEK/CF复合材料的非等温动力学进行分析,获得相关非等温动力学参数,并利用Kissinger方程计算其结晶活化能。结果表明:Avrami方程和Mo方程能很好描述PEEK/CF复合材料的非等温结晶过程;PEEK/CF复合材料的非等温结晶活化能为79.99kJ/mol。     

Melting behaviors, isothermal and non-isothermal crystallization kinetics of nylon 1212

Isothermal crystallization, subsequent melting behavior and non-isothermal crystallization of nylon 1212 samples have been investigated in the temperature range of 160-171 °C using a differential scanning calorimeter (DSC). Subsequent DSC scans of isothermally crystallized samples exhibited three melting endotherms. The commonly used Avrami equation and that modified by Jeziorny were used, respectively, to fit the primary stage of isothermal and non-isothermal crystallizations of nylon 1212. The Avrami exponent n was evaluated, and was found to be in the range of 1.56-2.03 for isothermal crystallization, and of 2.38-3.05 for non-isothermal crystallization. The activation energies (ΔE) were determined to be 284.5 KJ/mol and 102.63 KJ/mol, respectively, for the isothermal and non-isothermal crystallization processes by the Arrhenius' and the Kissinger's methods.     

Crystallization behavior of polyamide 11/multiwalled carbon nanotube composites

Differential scanning calorimetry (DSC) was used to investigate the isothermal and nonisothermal crystallization kinetics of polyamide11 (PA11)/multiwalled carbon nanotube (MWNTs) composites. The Avrami equation was used for describing the isothermal crystallization behavior of neat PA11 and its nanocomposites. For nonisothermal studies, the Avrami model, the Ozawa model, and the method combining the Avrami and Ozawa theories were employed. It was found that the Avrami exponent n decreased with the addition of MWNTs during the isothermal crystallization, indicating that the MWNTs accelerated the crystallization process as nucleating agent. The kinetic analysis of nonisothermal crystallization process showed that the presence of carbon nanotubes hindered the mobility of polymer chain segments and dominated the nonisothermal crystallization process. The MWNTs played two competing roles on the crystallization of PA11 nanocomposites: on the one hand, the MWNTs serve as heterogeneous nucleating agent promoting the crystallization process of PA11; on the other hand, the MWNTs hinder the mobility of the polymer chains thus retarding the crystal growth process of PA11. The activation energies of PA11/MWNTs composites for the isothermal and nonisothermal crystallization are lower than neat PA11. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Crystallization Kinetics and Mechanism of Low-Expansion Lithium Aluminosilicate Glass-Ceramics by Dilatometry

The crystallization kinetics and mechanism of a precursor glass of lithium aluminosilicate (LAS)-based commercial low-expansion glass-ceramics were investigated using a dilatometer. The isothermal crystallization behavior of β-quartz solid solution (ss) was found to obey the Avrami equation. Nonisothermal crystallization data were analyzed by the Ozawa method and modified Kissinger equation. The value of the Avrami exponent ( n ) was ∼1.5, and the apparent activation energy ( E _a) was ∼500 kJ/mol, which was close to that of the diffusion of silicon and aluminum ions as well as metal–oxygen bond strengths, suggesting a three-dimensional (3D) diffusion-controlled reaction mechanism.     

Isothermal and nonisothermal crystallization kinetics of MC nylon and polyazomethine/MC nylon composites

Crystallization kinetics of MC nylon (PA6) and polyazomethine (PAM)/MC nylon (PAM/PA6) both have been isothermally and nonisothermally investigated by different scanning calorimetry (DSC). Two stages of crystallization are observed, including primary crystallization and secondary crystallization. The Avrami equation and Mo's modified method can describe the primary stage of isothermal and nonisothermal crystallization of PA6 and PAM/PA6 composite, respectively. In the isothermal crystallization process, the values of the Avrami exponent are obtained, which range from 1.70 to 3.28, indicating an average contribution of simultaneous occurrence of various types of nucleation and growth of crystallization. The equilibrium melting point of PA6 is enhanced with the addition of a small amount of rigid rod polymer chains (PAM). In the nonisothermal crystallization process, we obtain a convenient method to analyze the nonisothermal crystallization kinetics of PA6 and PAM/PA6 composites by using Mo's method combined with the Avrami and Ozawa equations. In the meanwhile, the activation energies are determined to be ?306.62 and ?414.81 KJ/mol for PA6 and PAM/PA6 (5 wt %) composite in nonisothermal crystallization process from the Kissinger method. Analyzing the crystallization half‐time of isothermal and nonisothermal conditions, the over rate of crystallization is increased significantly in samples with a small content of PAM, which seems to result from the increased nucleation density due to the presence of PAM rigid rod chain polymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2844–2855, 2004     

Crystallization Kinetics of the LiBO2–Nb2O5 Glass Using Differential Thermal Analysis

The crystallization kinetics in the glass system (100− x )LiBO₂− x Nb₂O₅ (5≤ x ≤20, in molar ratio) prepared via the conventional metal-plate quenching technique have been studied by isothermal and non-isothermal methods using differential thermal analyses. X-ray powder diffraction studies carried out on heat-treated (500°C) glasses reveal the evolution of lithium niobate crystalline phase along with a minor phase of LiBO₂. The exponent n in the Jhonson–Mehl–Avrami (JMA) equation applied to the isothermal process is 2.62, which is in excellent agreement with that obtained under the non-isothermal process (2.67). The activation energies for crystal growth obtained from JMA equation under isothermal condition, modified Ozawa and Kissinger equations under non-isothermal conditions, are 293, 311, and 306 kJ/mol, respectively.     

Evaluation of nonisothermal crystallization kinetic models for linear poly(phenylene sulfide)

The nonisothermal crystallization kinetics of linear Poly(phenylene sulfide) (PPS) was studied with differential scanning calorimetry. Ozawa theory, Jeziorny model, and Mo equation were applied to describe the crystallization kinetics and to determine the crystallization parameters and mechanism of the linear PPS resin. The crystallization activation energies were also calculated using Kissinger formula and Flynn‐Wall‐Ozawa equation, respectively. According to the Ozawa model, it is found that instantaneous nucleation takes place during crystallization of PPS; the Ozawa exponent m is 3 in initial stage of crystallization; as the crystallization temperature decreases, the value of m reduces, and the growth rate of crystal almost keeps a constant. The Avrami exponent n obtained from Jeziorny model fluctuate around 1.84. Based on the Jeziorny model, the crystallization rate increases with increasing the cooling rate, but it does not change any longer when the cooling rate rise to a certain value. Mo equation also exhibits great advantages in treating the nonisothermal crystallization kinetics of PPS. The activation energy E of nonisothermal crystallization process of PPS is calculated to be −162.73 kJ/mol by the Kissinger formula, and the mean value of E determined by Flynn‐Wall‐Ozawa equation is −152.40 kJ/mol. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Ozawa方程处理PET非等温结晶动力学过程研究

采用Monte Carlo法计算机模拟在预先成核条件和不同降温速率下PET非等温结晶曲线,将模拟的结果用Ozawa方程及改进的Ozawa方程进行处理。结果表明,用Ozawa方程解析的Avrami指数与理论值相近,用改进的Ozawa方程可直接得到结晶速率常数,求出的线生长速率与理论值基本吻合。     

Isothermal and nonisothermal crystallization kinetics of a semicrystalline copolyterephthalamide based on poly(decamethylene terephthalamide)

The isothermal and nonisothermal crystallization kinetics of a semicrystalline copolyterephthalamide based on poly(decamethylene terephthalamide) (PA‐10T) was studied by differential scanning calorimetry. Several kinetic analyses were used to describe the crystallization process. The commonly used Avrami equation and the one modified by Jeziorny were used, respectively, to describe the primary stage of isothermal and nonisothermal crystallization. The Avrami exponent n was evaluated to be in the range of 2.36–2.67 for isothermal crystallization, and of 3.05–5.34 for nonisothermal crystallization. The Ozawa analysis failed to describe the nonisothermal crystallization behavior, whereas the Mo–Liu equation, a combination equation of Avrami and Ozawa formulas, successfully described the nonisothermal crystallization kinetics. In addition, the value of crystallization rate coefficient under nonisothermal crystallization conditions was calculated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 819–826, 2004