PBT非等温结晶动力学

用差示扫描量热法研究聚对苯二甲酸丁二酯（PBT）的非等温结晶动力学，并分别用Ozawa,Jeziorny和考虑综合因素法来处理PBT的非等温结晶数据。结果表明，PBT非等温结晶过程与Ozawa动力学方程相吻合，但不符合用Jeziorny方法处理的Avrami动力学方程；综合考虑温度和结晶程度对聚合物结晶速度的影响。PBT非等温结晶过程符合结晶动力学方程。     

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...     

含氟PET的非等温结晶动力学

通过分子设计,在聚对苯二甲酸乙二酯(PET)大分子主链上同时引入耐热性的芳杂酰亚胺环和含氟基团。以六氟二酐和氨基十一酸为原料,通过热环化反应合成酰亚胺二酸,再用制备的酰亚胺二酸单体按照不同配比和对苯二甲酸二甲酯、乙二醇按一定比例调节投料比进行酯化缩聚反应,合成一系列含氟PET。利用差示扫描量热(DSC)法研究了聚合物非等温结晶行为,发现纯PET的结晶能力最强,随着含氟量的增加,结晶能力减弱。采用Jeziorny法分析了纯PET和含氟PET的非等温结晶动力学,发现结晶速率常数随着含氟链段的加入而减小,表明含氟链段的加入降低了PET的结晶能力。     

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。     

聚丁二酸丁二醇酯的等温结晶动力学研究

采用差示扫描量热仪(DSC)对聚丁二酸丁二醇酯(PBS)的等温结晶动力学进行了研究,并用Avrami方程对实验数据进行了量化分析。研究结果表明:在等温结晶时,PBS倾向于以均相成核的三维生长方式结晶,并通过偏光显微镜进行了验证;同时,随着结晶温度的升高,PBS的结晶速率常数K值下降,半结晶时间t1/2延长。     

有光和半消光尼龙6切片的非等温结晶动力学研究

采用差示扫描量热仪研究了尼龙6(PA 6)有光切片和半消光切片的非等温结晶行为,用Jeziorny法和Liu法对其动力学进行了分析,并用Friedman方程计算了非等温结晶活化能(E)。结果表明:二氧化钛的加入对PA 6切片的结晶起到促进作用,提高了其结晶速率;少量二氧化钛的加入对PA 6切片的晶体生长方式没有很大影响,PA 6半消光切片的E的平均值较有光切片的低约13.1 k J/mol。     

硅橡胶的结晶行为及动力学研究

采用差示扫描量热（DSC）仪测试硅橡胶在温度变化过程中的热行为,并对硅橡胶的非等温结晶动力学和等温结晶动力学进行研究。结果表明：硅橡胶在升温过程中存在冷结晶现象;在降温过程中,结晶峰温度随着降温速率的增大向低温方向移动;等温结晶温度越低,结晶速率越快;Mo法和Avrami法分别适用于硅橡胶的非等温结晶动力学和等温结晶动力学分析。     

聚乳酸/纳米SiO_2复合材料的非等温冷结晶行为

利用表面固定伯胺分子层的纳米SiO2粒子(NH2-SiO2)与Cu2+构成氧化-还原体系,引发N,N-二甲基丙烯酰胺(DMAAm)的自由基接枝聚合,得到表面包覆聚合物的纳米SiO2杂化粒子(P-SiO2),采用差示扫描量热法(DSC)研究了NH2-SiO2和P-SiO2对聚乳酸(PLA)非等温冷结晶行为的影响,并用莫志深法对PLA及其复合材料的非等温冷结晶动力学进行了分析。结果表明:PLA和PLA/SiO2复合材料的非等温冷结晶过程均可用莫志深动力学方程来描述;两种SiO2在PLA中均起到了较好的冷结晶促进剂的作用;较之于NH2-SiO2,纳米杂化粒子P-SiO2的结晶促进效果更加明显。     

PP/CNFs复合材料非等温结晶动力学研究

采用聚丙烯蜡乳液(PP-wax)改性纤维素纳米微纤(CNFs),再通过HAKKE转矩流变仪熔融混合制备了聚丙烯(PP)/CNFs复合材料。利用差示扫描量热仪(DSC)研究了改性CNFs对PP非等温结晶行为的影响,并分别用Jeziorny、Ozawa和Mo模型对数据进行了处理。结果表明:改性CNFs对PP结晶的影响主要由改性剂PP-wax决定。一方面,低分子量PP-wax降低了PP基体的规整性,抑制了PP的成核,使得PP结晶温度下降;另一方面,PP-wax提升了基体PP分子链的运动能力,使PP晶体的生长速度加快,进而提高了PP基体的结晶速率。另外,Kissinger公式计算结果表明,CNFs的引入降低了PP结晶的活化能。     

原位复合阻燃尼龙6的非等温动力学研究

采用差示扫描量热法研究了原位聚合反应制备阻燃尼龙6的非等温结晶行为,用Jeziorny法和莫志深法对其动力学过程进行了分析。结果表明:由于阻燃剂起到异相成核作用,使晶核的生长变快,提高了阻燃尼龙6的结晶温度和成核速率。随降温速率的增加,其结晶峰从高温向低温方向移动,峰形变宽,结晶时间缩短。同时阻燃剂在尼龙6分子链中存在相互作用力,阻碍了尼龙6分子链在结晶过程中的运动,导致结晶活化能提高,晶体生长速度下降,结晶度降低。     

Studies on the phase structure,mechanical, rheological properties,and nonisothermal crystallization kinetics of the PEN/SCF composites

Short carbon fiber reinforced poly(ethylene 2,6‐naphthalate) composites (PEN/SCF) were prepared by twin‐screw extruder. The structure, mechanical, rheological properties, and nonisothermal crystallization kinetics of the composites were investigated by scanning electron microscope, universal tester, and differential scanning calorimetry. The results suggest that there is better interaction between SCF and PEN matrix, which leads to an increase in the tensile strength, Young's modulus, and impact strength of the composites with proper contents of SCF. Rheological behavior of the PEN/SCF composites melt is complicated, combining a dilate fluid at lower shear rate and a pseudoplastic fluid at higher shear rate. Moreover, the flow activation energy of the composites suggests that the melt with more SCF has higher sensitivity to the processing temperature. In conclusion, the composite with 5–10 wt % content of SCF has better properties. The Avrami equation modified by Jeziorny and Ozawa theory was used, respectively, to fit the primary stage of nonisothermal crystallization of various composites. The Avrami exponents n are evaluated to be 2.6–3.1 for the neat PEN and 3.4–4.8 for PEN/SCF composites, and the SCF served as nucleation agent accelerates the crystallization rate of the composites, and more the content of SCF faster the crystallization rate. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Isothermal and nonisothermal crystallization kinetics of nylon-11

Analysis of the isothermal, and nonisothermal crystallization kinetics of Nylon-11 is carried out using differential scanning calorimetry. The Avrami equation and that modified by Jeziorny can describe the primary stage of isothermal and nonisothermal crystallization of Nylon-11. In the isothermal crystallization process, the mechanism of spherulitic nucleation and growth are discussed; the lateral and folding surface free energies determined from the Lauritzen–Hoffman equation are ς = 10.68 erg/cm² and ς_e = 110.62 erg/cm²; and the work of chain folding q = 7.61 Kcal/mol. In the nonisothermal crystallization process, Ozawa analysis failed to describe the crystallization behavior of Nylon-11. Combining the Avrami and Ozawa equations, we obtain a new and convenient method to analyze the nonisothermal crystallization kinetics of Nylon-11; in the meantime, the activation energies are determined to be −394.56 and 328.37 KJ/mol in isothermal and nonisothermal crystallization process from the Arrhonius form and the Kissinger method. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2371–2380, 1998     

Isothermal and nonisothermal melt‐crystallization kinetics of syndiotactic polystyrene

Analyses of the isothermal and nonisothermal melt kinetics for syndiotactic polystyrene have been performed with differential scanning calorimetry, and several kinetic analyses have been used to describe the crystallization process. The regime II→III transition, at a crystallization temperature of 239°, is found. The values of the nucleation parameter K_g for regimes II and III are estimated. The lateral‐surface free energy, σ = 3.24 erg cm^?2, the fold‐surface free energy, σ_e = 52.3 ± 4.2 erg cm^?2, and the average work of chain folding, q = 4.49 ± 0.38 kcal/mol, are determined with the (040) plane assumed to be the growth plane. The observed crystallization characteristics of syndiotactic polystyrene are compared with those of isotactic polystyrene. The activation energies of isothermal and nonisothermal melt crystallization are determined to be ΔE = ?830.7 kJ/mol and ΔE = ?315.9 kJ/mol, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2528–2538, 2002     

PTT非等温结晶动力学研究

采用差示扫描量热仪对PTT进行非等温结晶研究。利用不同动力学模型对其结晶过程进行处理, 并将PTT与PET及PBT的非等温结晶过程进行对比。结果表明:Jeziorny方程和Ozawa方程都可以很好的 描述PTT,PET,PBT的非等温结晶过程;采用结合Avrami方程和Ozawa方程的处理方法,得到了3种聚酯的 结晶速率的大小关系:PBT>PTT>PET。通过计算Ziabicki结晶能力参数,得到3种聚酯的结晶能力的顺序 为:PBT>PTT>PET。     

湿度对单轴取向PET纤维结晶过程的影响

采用DSC研究了不同拉伸比的单轴取向PET纤维在不同湿度下的冷结晶过程。发现湿度可以诱导纤维双重结晶峰的出现。从DSC图可以看出,随着湿度的提高,结晶峰向低温移动,且分化成两个较小的结晶峰,结晶可在玻璃化转变温度之下发生。DSC数据处理结果表明,所得Avrami指数呈规律变化,由于湿度的影响,单轴取向PET纤维在低温时的结晶机理发生变化。     

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     

齐聚物对PET结晶性能的影响

运用差示扫描量热法研究了不同齐聚物含量的聚对苯二甲酸乙二酯(PET)的非等温结晶过程。结果表明:随齐聚物含量的增加,PET的熔融结晶温度向低温偏移,过冷度增大,结晶热焓增加,结晶度先增大后减小;在相同的结晶温度下,随着齐聚物含量的增加,PET的结晶温度区域逐渐变宽,半结晶周期增大,结晶速率降低。     

Isothermal and nonisothermal crystallization kinetics of partially melting nylon 10 12

Nylon 10 12, a newly industrialized engineering plastic, shows a double‐melting phenomenon during melting. Partial melts were obtained when the sample was heated to the temperature between the two melting peaks. A differential scanning calorimeter was used to monitor the energies of the isothermal and nonisothermal crystallization from the partially melted samples. During isothermal crystallization, relative crystallinity develops with a time dependence described by the Avrami equation, with the exponent n = 1.0. For nonisothermal studies, kinetics treatments based on the Avrami and Ozawa equations are presented to describe the crystallization process. It was found that the two treatments can describe the nonisothermal crystallization from the partially melted samples. The derived Avrami and Ozawa exponents are all about 1.0, which means that the partially melted samples crystallize by one‐dimensional growth, which may cause thickening of the lamellae. We calculated the crystallization activation energies for isothermal and nonisothermal crystallization from the partially melted samples. It was found that the activation energy determined by the Kissinger method was not rational, which may be attributed to the free‐nucleation process for nonisothermal crystallization from partially melted samples. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1311–1319, 2003     

聚乳酸/聚(已二酸-对苯二甲酸丁二酯)共混物的非等温结晶动力学

采用熔融挤出法制备了聚乳酸/聚(已二酸-对苯二甲酸丁二酯)共混物。利用差示扫描量热仪研究了聚乳酸及其共混体系的非等温结晶过程。用经Jeziorny修正的Avrami方程和Mo法对其非等温结晶动力学进行了分析。结果表明:Avrami方程和Mo法都适用于处理聚乳酸及其共混体系的非等温结晶过程,共混物的结晶速率大于聚乳酸的结晶速率。此外,用Huffman-Lauritzen理论计算了非等温结晶的结晶活化能,发现共混体系的结晶活化能绝对值小于聚乳酸。