PA1212的结晶动力学研究

采用DSC方法研究了PA1212的非等温和等温结晶动力学。Avrami方程可以适用PA1212的等温结晶过程,其Avrami指数为2．51～2．87,等温结晶活化能为-131．9 kJ/mol;在非等温结晶过程中,结晶速率随降温速率的增大而提高,综合利用Avrami方程和Ozawa方程得到Avrami指数与Ozawa指数的比值为1．31～1．49,非等温结晶活化能为-87．96 kJ/mol。结果表明,与其他聚酰胺相比,PA1212较容易结晶。     

聚对苯二甲酸丙二醇酯的非等温结晶动力学研究

采用DSC研究了聚对苯二甲酸丙二醇酯(PTT)在不同等速降温速率下的结晶过程,并利用由等温Avrami方程推导得到的两种不同的等速降温非等温结晶方程,研究了其结晶动力学,得出PTT的成核方式为异相成核,同时利用拟和法计算了PTT的结晶能力,发现在同等条件下PTT的结晶能力大于PET。     

聚甲醛等温结晶动力学研究

采用差示扫描量热法(DSC)研究了纯聚甲醛和加入成核剂氮化硼(BN)的聚甲醛等温结晶动力学,采用Avrami方程和L H方程得到了在不同结晶温度下的K、t1/2、n和σe值,探讨了成核剂BN对聚甲醛的结晶成核作用。实验证明,加入氮化硼后,聚甲醛的结晶峰温度和起始结晶温度提高,结晶过程为异相三维生长过程,结晶速率明显加快,半结晶时间和表面自由能下降,说明BN是一种较好的成核剂。     

动态硫化EPDM/PP热塑性弹性体等温结晶行为研究

采用差示扫描量热仪（DSC）对比研究了聚丙烯（PP）和动态硫化三元乙丙橡胶/聚丙烯热塑性弹性体（EPDM/PPTPV）的等温结晶行为,并用Avrami方程对其进行等温结晶动力学分析。结果表明,在相同的结晶温度下,EPDM/PPTPV比PP结晶更快。2种试样的等温结晶行为符合Avrami方程,在相同的结晶温度下,TPV的Avrami指数n比PP的低,半结晶时间t_1/2比PP的低,结晶速率常数k比PP的高。     

PTT的等温与非等温结晶动力学研究

采用DSC方法对聚对苯二甲酸丙二酯进行等温与非等温结晶动力学研究,利用不同动力学模型对其结晶过程进行分析.结果表明,在等温结晶过程中,Avrami指数n和半结晶时间随着结晶温度的升高而增大,结晶速率常数K随着结晶温度的升高而减小;在非等温结晶的过程中,结晶动力学常数Zc和相对过冷度△Tc随着降温速率的提高而上升,Avr...     

PET/PTT共混聚酯的等温结晶行为

使用差示扫描量热仪(DSC)研究不同比例的PET/P1T共混聚酯在205℃的等温结晶行为,并使用Avrami方程对其等温结晶过程进行研究.结晶半周期t1/2,总结晶速率常数k和Avrami指数n的变化表明:在共混体系中,对于PET和PTT而言,另一组分的加入都会对结晶产生阻碍作用,PET与P1T相互影响成核与晶体生长机理.     

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。     

聚丙烯/六钛酸钾复合材料的等温结晶动力学研究

采用硅烷偶联剂KH-550对针状六钛酸钾晶须(PTW)的表面进行修饰改性,并利用熔融共混法制备改性后的产物与聚丙烯的复合材料。利用差示扫描量热仪(DSC)分析聚丙烯(PP)/六钛酸钾(K_2Ti_6O_(13))复合材料的等温结晶行为,相关结晶动力学参数可使用Avrami方程计算。结果表明:PP和PP/K_2Ti_6O_(13)复合材料的等温结晶行为在较大的区域内适合用Avrami方程描述;在相同的结晶温度下,PP/K_2Ti_6O_(13)复合材料的半结晶时间(t_(1/2))较纯PP更短,Avrami指数(n)较纯PP更大,说明六钛酸钾晶须的加入能促进PP基体结晶,生成更多二维盘状结构;而对于纯PP和PP/K_2Ti_6O_(13)复合材料,结晶温度(T_c)的提高,使得半结晶速率(G_(1?2))降低,结晶度(X_c)提高。     

聚丙烯/碱式硫酸镁晶须复合材料等温结晶动力学研究

采用月桂酸(LA)对碱式硫酸镁晶须(MOSw)进行改性,将改性产物LA-MOSw与聚丙烯(PP)熔融共混制成复合材料。利用差示扫描量热法(DSC)考察了纯PP及PP/MOSw、PP/LA-MOSw复合材料的等温结晶行为,并进一步通过Avrami方程计算得到相关等温结晶动力学参数。结果表明:在相同结晶温度下,PP/LAMOSw复合材料具有较短的半结晶时间(t_(1/2))及较小的Avrami指数(n),说明加入LA-MOSw能促进PP基体结晶,生成更多二维盘状结晶;但MOSw的加入则会抑制PP的结晶,而诱导生成更多的三维球状结晶。Arrhenius方程及Hoffman-Lauritzen模型分析结果表明,LA-MOSw促进PP结晶的原因主要在于LAMOSw的引入降低了PP基体的结晶活化能(ΔE)与成核参数(K_t),使PP基体成核结晶变得更加容易。     

聚乳酸的非等温结晶动力学研究

采用差示扫描量热仪研究了聚乳酸(PLA)样品在5种不同升温速率下的非等温结晶行为，采用Jeziorny法、Ozawa法、Mo法等分析了PLA的非等温结晶动力学。结果表明：随着升温速率的增加，PLA的熔融结晶峰向高温端移动，结晶峰变宽，结晶时间变短，同时结晶也变差。利用Jeziorny法和Mo法求得Avrami指数n和Ozawa指数m,在不同升温速率下，结晶初期的Avrami指数n和Ozawa指数m接近，均处于2～3,说明PLA的均相成核以一维方式为主、二维方式为辅；在升温速率为5～20 K/min时，结晶中期的PLA Avrami指数n>5、Ozawa指数m>3.5,均高于结晶初期的Avrami指数n与Ozawa指数m,表明PLA除了呈现均相成核的三维生长方式之外，还出现了结晶堆积的现象；当升温速率为30～40 K/min时，结晶中期的Avrami指数n和Ozawa指数m均与初期表现一致，Avrami指数n在3.5左右，Ozawa指数m为2.5～3.5,表明该条件下PLA以均相一维和二维2种方式共存结晶。应用Mo法得到的升温速率F(T)随着相对结晶度的增加而增加，表明随着结...     

Kinetics of non-isothermal cold crystallization of uniaxially oriented poly(ethylene terephthalate)

The non-isothermal equation was extended to describe non-isothermal cold crystallization kinetics of oriented polymers. The validity of the equation was examined by using a DSC crystallization curve of oriented poly(ethylene terephthalate) (PET) fibers with a constant heating rate. The double cold crystallization peaks appeared in the DSC curve. The relative degrees of crystallinity at different temperatures were analyzed by using the equation. The results show that the value of the Avrami exponent near to 1 at lower temperatures implies the bundle-like crystal growth geometry and the value of the Avrami exponent near to, 2, at higher temperatures implies the higher dimension crystal growth geometry. The first crystallization process crystallizes at faster rate than that of the isotropic sample, while the second process crystallizes at slower rate than that of isotropic sample. If a simple single process model was used, the value of the Avrami exponent, 0.77, was obtained. The result shows the simple single process model cannot describe the processes of crystallization of oriented PET fibers satisfactorily.     

Non-isothermal polymer crystallization kinetics and Avrami master curves

The kinetic crystallization model of Avrami is generally accepted as a starting point for the analysis of isothermal polymer crystallization. It is shown in this paper that, in the case of non-isothermal crystallization kinetics with constant heating or cooling rates, an apparent m -order reaction model is approximately equivalent to the nucleation and growth model of Avrami in the vicinity of the inflection points of the corresponding crystallization curves. Since the apparent m -order reaction model is defined for every real, positive apparent reaction-order m , a distinct Avrami index n , which is valid for the characterization of isothermal and non-isothermal crystallization experiments with constant heating or cooling rates, can always be related to any apparent reaction-order m . Therefore, two types of Avrami master curves, which are dependent merely on the Avrami index n and which describe the isothermal polymer crystallization thoroughly, can be obtained by performing non-isothermal experiments with constant heating or cooling rates.     

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.     

Characterization of thermal behavior and kinetics of crystallization of a thermotropic rigid-chain copolymer

Thermal analysis was employed to estimate the heat of transition, equilibrium melting temperature and surface free energy of a thermotropic liquid crystal copolyester resin (70 mol% p-hydroxybenzoic acid and 30 mol% 2,6-hydroxynaphthoic acid). Specific heats and melting and crystallization behavior were evaluated using differential scanning calorimetry (DSC). Experiments over a wide range of cooling rates indicate two different crystallization processes: a rapid crystallization process and a slow crystallization process. The kinetics of the rapid crystallization process were evaluated using a non-isothermal method. The analysis indicates that the rapid crystallization process can be suitably described by the non-isothermal Avrami equation. The Avrami exponent is found to be equal to 2, which is in agreement with the nucleation and growth mechanism of the rigid rodlike molecules. The kinetics of the slow crystallization process, which were studied using an isothermal method, indicate that the degree of crystallinity varies linearly with log(time). The equilibrium melting temperature for this process is found to be 372°C. The Arrhenius plot yields a linear relationship in the lower temperature range.     

Effect of rod-like imide unit on crystallization of copoly(ethylene terephthalate-imide)

The effect of the imide unit on the isothermal and non-isothermal crystallization, kinetics crystallization of a new family of copoly(ethylene terephthalate-imides) (called copolyesterimides or PETIs) was investigated using differential scanning calorimetry. With a combined Avrami and Ozawa equation, one can describe the non-isothermal crystallization process of copolyesterimides, and the results show the same tendency as that in the isothermal crystallization process. These studies show that the processes of crystal nucleation and growth result in mainly three-dimensional growth with a thermal nucleation. In both isothermal and non-isothermal crystallization processes, the crystallization rate of PETIs, with imide content below 0.5%, is higher than that of neat PET, while PETI-3 (0.3 mol% imide) has the highest crystallization rate. This rate is significantly enhanced over PET homopolymer. It is proposed that imide units precipitate from the melt and act as nucleating agents during the crystallization process of these novel copolyesterimides.     

SEBS-g-MAH对聚乙烯等温及非等温结晶动力学的影响

利用差示扫描量热法结合Avrami方程研究了苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物接枝马来酸酐(SEBS-g-MAH)对线型低密度聚乙烯(LLDPE)等温及非等温结晶动力学的影响。结果表明,热塑性弹性体SEBS及其接枝物的加入阻碍了LLDPE分子链的规则排列,影响了链段在结晶扩散迁移规整排列的速度,使得结晶速率变慢,对LLDPE晶体生长起了抑制作用;LLDPE/SEBS-g-MAH共混体系的半结晶时间t1/2和结晶活化能E明显增大,Avrami指数n对结晶温度有依赖性,kn值随温度的升高而减小。通过Jeziorny法对非等温结晶过程进行处理,试样的Avrami指数n值均在1.1~1.5,表明LLDPE的结晶成核机理和生长方式没有改变。