Poly(p-phenylene sulfide)/liquid crystalline polymer blends. II. Crystallization kinetics

The crystallization kinetics of blends made of poly(p-phenylene sulfide) (PPS) with a liquid crystalline polymer (LCP) was studied. The blends were found to be immiscible by dynamic mechanical thermal analysis (DMTA). Results of non-isothermal and isothermal crystallization experiments made by differential scanning calorimetry (DSC) showed that both components had their crystallization temperatures increased; also the LCP melting temperature was found to increase in the blends. It was concluded that the addition of LCP to the PPS increased the PPS overall crystallization rate due to heterogeneous nucleation. The fold interfacial free energy, σ_e of the PPS in the blends was observed not to vary with composition. © 1996 John Wiley & Sons, Inc.     

Non-Isothermal Crystallization of High-Impact Polystyrene/Poly(Phenylene Sulfide) Blends

The morphology of isothermally crystallized poly(phenylene sulfide) (PPS) and a blend combining it with high-impact polystyrene (HIPS) were observed through a polarized optical microscope equipped with a CSS450 hot-stage. The crystalline superstructure of PPS is mainly spherulite, and it was found that the presence of HIPS has little influence on the morphology of PPS, but decreases the nucleation rate of PPS. The effect of HIPS on the non-isothermal crystallization of PPS was investigated by differential scanning calorimetry (DSC). The maximum and onset crystallization temperatures for the HIPS/PPS blend were about 10°C lower than those of neat PPS, which indicates that the crystallization of PPS was retarded by HIPS. The Ozawa model was used to analyze the non-isothermal crystallization kinetics of PPS and its blends. The Avrami exponent values of neat PPS were higher than those of its blend, which shows that the presence of HIPS changed both the nucleation rate and the crystallization rate of PPS.     

Thermal and crystallization behavior of engineering polyblends. II. Unfilled polyphenylene sulfide with poly(ethylene terephthalate)

The melting and crystallization behavior of blends of poly(phenylene sulfide) (PPS) with poly(ethylene terephthalate) (PET) has been investigated. The component polymers in the blend exhibited separate crystallization peaks and overlapping melting peaks. The nonisothermal DSC scans indicated that the crystallization parameters for PET become modified to a greater extent than do those for PPS in the blends. The PET crystallization peak became narrower with a higher heat of crystallization, suggesting a faster rate of crystallization as a result of blending with PPS. The isothermal crystallization studies revealed that the nucleation of PPS is facilitated by the presence of PET. This contention has been substantiated by polarized light microscopic observations. The spherulites of PPS were found to be smaller in the blends as compared to those in neat PPS. This enhancement in the nucleation of PPS has been attributed to the possibilities of chemical interactions between the component polymers. On the other hand, the increase in the rate of crystallization of PET has been attributed to the heterogeneous nucleation provided by the alreadycrystallized PPS. The melt crystallized blends exhibited slightly higher heats of fusion compared to the values computed from the rule of proportional additivity. © 1994 John Wiley & Sons, Inc.     

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。     

石墨烯对聚苯硫醚非等温结晶行为的影响研究

通过熔融共混法制备了聚苯硫醚(PPS)/石墨烯(G)复合材料,采用扫描电子显微镜、差示扫描量热仪研究了PPS/G复合材料的断面形貌及非等温结晶过程,利用莫志深方程、Dobreva方程和Kissinger方程分析了非等温结晶动力学行为。结果表明:石墨烯质量分数低于0.5%时,其在PPS基体中具有较好的分散性;石墨烯起到了异相成核作用,使PPS/G程、Dobreva方程和Kissinger方程则进一步验证了石墨烯的引入促进了PPS/G复合材料的结晶。     

Rheological behavior and thermal stability of poly(phenylene sulfide)/vectra-B950 blends

Blends of polyphenylene sulfide (PPS) with a commercial, wholly aromatic, liquid crystalline polymer (LCP), Vectra-B950, have been prepared by melt-blending. Their rheological behavior has been studied in order to determine if the LCP displays a processing aid ability, and under what conditions it gives rise to potentially reinforcing fibrils dispersed in the PPS matrix. The problem of the thermal stability of PPS/LCP blends, which has been considered by some authors as the main obstacle to the production of usable materials due to the evolution of gaseous substances during processing, has been discussed. © 1994 John Wiley & Sons, Inc.     

Effect of PMR‐POI on the melt behavior and isothermal crystallization of poly(phenylene sulfide)

The crystallization behavior of neat PPS and PPS in blends with PMR‐POI prepared by melt mixing were investigated by differential scanning calorimetry (DSC). It was found that POI was an effective nucleation agent of the crystallization for PPS. The enthalpy of crystallization of PPS in the blends increased compared with that of neat PPS. During isothermal crystallization from melt, the dependence of relative degree of crystallinity on time was described by the Avrami equation. It has been shown that the addition of POI causes an increase in the overall crystallization rate of PPS; it also changed the mechanism of nucleation of the PHB crystals from homogeneous nucleation to heterogeneous nucleation. The equilibrium melting temperature of PPS and PPS/POI blends were determined. The analysis of kinetic data according to nucleation theories shows that the increase in crystallization rate of PPS in the composite is due to the decrease in surface energy of the extremity surface. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 436–442, 2002     

Isothermal crystallization of pure and glass fiber reinforced poly(phenylene sulfide) composites

The isothermal crystallization of poly(phenylene sulfide) (PPS) and its glass fiber (GF) reinforced composite has been investigated by differential scanning calorimetry (DSC) and polarized optical microscope (POM) equipped with a hot stage. During the isothermal crystallization process of PPS the Avrami exponent value decreases with time, indicating the change of crystallization mechanism and presence of mixed growth mechanism (bidimensional and three‐dimensional growth of crystals). The presence of GF greatly accelerates the bulk crystallization rate of PPS and changes the crystalline morphology of PPS from the spherulites to transcrystallization. And the reason for development of transcrystallization is considered to be relevant with the compatibility of the interface between GF and PPS. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers     

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.     

纤维级聚苯硫醚的非等温结晶及热降解性能

通过差示扫描量热法(DSC)和热重分析法(TGA),测试了两种不同的纤维级聚苯硫醚(PPS)树脂的结晶和热分解过程,并用Khanna法、Ozawa法和Jeziorny法分析了两种PPS的非等温结晶动力学性质。结果表明:Ozawa方程、Jeziorny方程都可以很好地描述PPS的非等温结晶过程,并求出了相应的动力学参数;比较了两种PPS热性能之间的差异,认为相对分子质量影响PPS的热性能。     

Thermal and crystallization behavior of engineering polyblends. I. Glass reinforced polyphenylene sulfide with polyethylene terephthalate

The thermal and crystallization behavior of blends of glass fiber reinforced polyphenylene sulfide (PPS) with polyethylene terephthalate (PET) has been reported. The blends showed two overlapping melting peaks and two separate crystallization peaks. The heat of crystallization of PPS was found to decrease continuously with increasing PET content, whereas the heat of crystallization of PET was found to increase with increasing PPS content. This indicates that the degree of crystallinity of PPS is reduced whereas that of PET is increased as a result of blending. It is interesting to note that the combined heats of fusion of the blends were marginally higher than those calculated by proportional additivity rule in spite of the drop in the heat of crystallization of PPS. The temperature onset of crystallization of PET in the blends shifted to higher temperature whereas there was no significant change in the crystallization temperature of PPS. The increase in the temperature of crystallization of PET indicates enhanced nucleation. The isothermal crystallization studies of the component polymers revealed that both the component polymers crystallized at a relatively faster rate in the blend. The crystallization rate of PPS was found to increase significantly with increasing PET content. A significant increase in the rate of crystallization of PET was also observed in the blends. The acceleration of crystallization rate of PET in the blends was more pronounced as compared to that of PPS. The acceleration in the PET crystallization rate was attributed to the presence of glass fibers and crystallized PPS.     

Crystallization kinetics of two polyesters with different main chain rigidity

The crystallization kinetics of two polyesters, poly(p-phenylene sebacate) (PPS) and poly(p-phenylene isophthalate) (PPI), have been investigated by DSC. The nonisothermal data indicate that the relative crystallization rate of PPI was slower than that of PPS due to the more rigid nature of the PPI the chains. The isothermal crystallization data were analyzed by the Avrami equation, 1 − X_(t) = exp(−ktⁿ). PPS exhibited Avrami exponent (n), values of about 4, indicating that its isothermal crystallization followed a process of homogeneous nucleation, spherical growth and a growth type of interface control. PPI exhibited Avrami exponent values of about 3 indicating its isothermal crystallization followed a process of homogeneous nucleation, a possible disc growth geometry and an interface control growth type. Possibly, the bending structure and rigid nature of PPI forced its growth to follow a three dimensional growth during crystallization.     

水性聚氨酯的结晶动力学参数及其在鞋用胶黏剂的应用

以聚己二酸1,4-丁二醇酯（PBA）、六亚甲基二异氰酸酯（HDI）和异佛尔酮二异氰酸酯（IPDI）为主要原料,制备了不同软段分子量和不同硬段含量的水性聚氨酯（WPU）乳液。采用DSC技术表征了WPU胶膜在非等温和等温条件下的结晶行为,并以莫志深方程和Avrami方程为模型,对WPU胶膜的结晶行为进行了研究。WPU胶膜的非等温结晶动力学分析结果表明,随着WPU相对结晶度的增加,非等温结晶动力学参数F（T）增大,说明适当提高活化温度可提高WPU胶黏剂的结晶速率和初黏强度;WPU胶膜的等温动力学分析结果表明,不同软段分子量和不同硬段含量的WPU胶膜的等温结晶动力学参数t_1/2与相应WPU胶黏剂的开放时间存在对应关系,即t_1/2较大者,相应WPU胶黏剂的开放时间较长。     

Crystallization of running filament in melt spinning of polypropylene

The crystallization kinetics of the running filament in melt spinning have been studied for three cases: isothermal crystallization of an isotropic melt, non-isothermal crystallization of an isotropic melt, and non-isothermal crystallization of a non-isotropic melt. Both the temperature and the orientation dependences of nucleation rate and growth rate are estimated for polypropylene. Calculated curves for non-isothermal crystallization of a non-isotropic melt with partial high orientation closely approximate the experimental data. In particular, the experimental data are best explained by crystallization with two-dimensional growth. The crystallization processes in melt spinning may be governed by localized molecular orientation of the supercooled melt in the initial stage.     

聚苯硫醚/碳纳米管复合材料的非等温结晶性能

利用双螺杆挤出机制备了纤维用聚苯硫醚/多壁碳纳米管(PPS/MWCNTs)复合材料。通过差示扫描量热法(DSC)研究了不同降温速率下纯PPS以及PPS/MWCNTs复合材料的非等温结晶过程,并运用Ozawa模型进行了非等温结晶动力学分析。结果表明:降温速率对PPS/MWCNTs复合材料的结晶性能有很大的影响,当降温速率为20℃/min时,PPS/MWCNTs复合材料的结晶能力及相对结晶度最大;MWCNTs在PPS结晶过程中起异相成核剂的作用,使PPS/MWCNTs复合材料的结晶温度较纯PPS升高。     

聚苯硫醚/碳纳米管复合材料等温结晶性能研究

利用双螺杆挤出机制备了聚苯硫醚(PPS)/多壁碳纳米管(MWCNTs)复合材料,然后通过差示扫描量热法(DSC)研究了纯PPS以及PPS/MWCNTs复合材料的等温结晶过程,并运用Avrami模型对纯PPS以及PPS/MWCNTs复合材料的等温结晶动力学进行分析。研究结果表明,MWCNTs的加入明显缩短了PPS的半结晶期,提高了结晶速率;Avrami模型能够较好地描述PPS及PPS/MWCNTs复合材料的等温结晶动力学。     

聚苯硫醚的等温结晶动力学

采用光学解偏振法结晶速率仪研究了聚苯硫醚(PPS)的等温结晶动力学.结果表明:PPS的结晶速率随结晶温度的升高,先增大后减小,并在160℃左右达到最大结晶速率,约为0.471 7 s-1.PPS的Avrami指数为2.20～2.93,表明PPS是以异相成核或非热成核的方式三维生长形成球状结晶.在偏光显微镜放大400倍的...     

Study on polymerization of acrylonitrile with methylacrylate and itaconic acid in mixed solvent

Isothermal crystallization kinetics were investigated by differential scanning calorimetry (DSC) for poly(p-phenylene sulfide) (PPS) doped with amorphous carbon or crystalline graphite particles. Both types of carbon forms have been found to affect the crystallization behavior of PPS to different extents. The crystalline graphite particles have a more pronounced effect on the overall rate as well as mechanisms of PPS crystallization than do the amorphous carbon particles. Relative contributions and competition from crystallizations of two different crystals in the later-stage crystallization of PPS have been found to cause the phenomenon of deviation from linearity in the Avrami plots. A sequential crystallization model has been shown to describe well the crystallization behavior of the PPS doped with the particles. © 1995 John Wiley & Sons, Inc.     

聚苯硫醚/玻璃微珠复合材料体系的相容性及非等温结晶动力学研究

采用熔融共混挤出法制备了聚苯硫醚(PPS)/玻璃微珠(GB)复合材料,考察了PPS/GB复合材料的相容性、结晶形态,并采用Ozawa方程和R-t关系法研究了复合材料的非等温结晶动力学。结果表明,PPS/GB复合材料在熔融状态下两相之间有良好的相容性,而在固态条件下随着GB含量增加存在分散不均匀现象。复合体系中PPS主要生成球晶,GB在PPS基体中起异相成核作用,加速其结晶。Ozawa方程和R-t关系法能较好地描述复合材料的非等温结晶动力学。