PTT/PE共混体系结品动力学及结晶形态研究

采用差示扫描量热法(DSC)研究了聚对苯二甲酸乙二醇酯/聚乙烯(PTT/PE)共混体系的非等温结晶动力学,通过热台偏光显微镜(POM)对共混物在等温条件下的结晶形态进行了研究.结果发现:PTT/PE共混体系各样品的结晶峰温度随着冷却速率的提高而下降,而半结晶时间t1/2随着冷却速率的提高而提高;结晶动力学常数Zc随着冷却速率的提高而下降,表明共混体系的结晶速率随着冷却速率的提高而降低;在POM观察的时间范围内各样品的球晶尺寸随着时间的延长而增大,PTT/PE(30/70)共混体系在190℃结晶时,球晶尺寸较大,即球晶生长较快.     

PET/PTT共混体系的非等温结晶动力学研究

采用DSC方法研究了PET/PTT共混体系的非等温结晶动力学,研究发现:PET/PTT共混体系各样品的结晶峰温度和半结晶时间t1/2随着冷却速率的提高而下降;结晶动力学常数Zc随着冷却速率的提高而增加,表明共混体系的结晶速率随着冷却速率的提高而增大;Zc随着PTT含量的增加而逐渐减小,在其含量达40%￣50%时出现了最小值。     

PET/PTT合金结晶形态的研究

采用XP-201热台偏光显微镜研究了对苯二甲酸乙二醇酯（PET）/对苯二甲酸丙二醇酯（PTT）合金等温结晶时的结晶形态及影响因素。研究结果表明：随着等温结晶温度的升高,PET/PTT(40/60)合金的结晶诱导期变长;在观察的时间范围内各样品的球晶尺寸随着时间的延长而增大;随着PTT含量的增加,样品球晶的线生长速率增大,球晶尺寸增大;对比不同温度下等温结晶的球晶形态,PET/PTT(100/0)样品在190℃结晶时球晶尺寸最大, PET/PTT(40/60)样品和PET/PTT(100/0)样品在180℃结晶时球晶尺寸最大; PET/PTT(0/100)样品等温结晶时呈现出了复杂的条带球晶。     

POM与POM/TPU共混物非等温结晶动力学的研究

利用差示扫描量热仪对聚甲醛（POM）非等温结晶动力学进行了研究,并考察了热塑性聚氨酯弹性体(TPU)的加入对POM结晶动力学的影响。通过几种理论模型分析了非等温结晶数据。结果表明, Jeziorny法、莫志深法能够成功描述POM及POM/TPU共混体系的非等温结晶过程。POM的Avrami指数n稍大于POM/TPU共混物的。半结晶时间t1/2与动力学速率参数Zc的值表明POM与POM/TPU共混物的结晶速率随冷却速率的增加而增大,但相同冷却速率下POM的结晶速率要快于POM/TPU共混物。由Kissinger法估算的POM与POM/TPU共混物的活化能分别为513.5、390.5 kJ/mol。     

聚酯PTT及PTT/PBT共混体系的结晶形态

选取均聚物聚对苯二甲酸丙二醇酯(PTT)及PTT/聚对苯二甲酸丁二醇酯(PBT)共混物为研究对象,以偏光显微镜(POM)和X射线衍射(XRD)为研究手段探讨了均聚物PTT的结晶形态,以及结晶温度、共混物的组成、等温结晶时间等因素对PTT/PBT共混物结晶形态和性能的影响。结果表明,PTT形成环带球晶的条件是155℃,PTT/PBT共混物的结晶尺寸由于PBT的引入而变小,在PTT质量分数小于60%以后就不能产生环带球晶;PTT/PBT共混物结晶时是两个组分各自结晶,并且相互竞争,使其生成环带球晶的关键是结晶组分的结晶速率要和非结晶组分之扩散速率相匹配。     

POM /TPU共混物非等温结晶动力学研究

采用差示扫描量热法(DSC}研究了不同冷却速率下聚甲醛( POM)以及POM/热塑性聚氨酷弹性体(TPU)共混物的非等温结晶过程,分别采用Jeziorny法、Ozawa法和Mo法进行处理。结果表明:随着冷却速率的增大,POM及其共混物的结晶峰都变宽,结晶峰值温度(Tc)都降低;在相同冷却速率下,POM /TPU共混物的Tc。较纯POM有所提高;Jeziorny法和Mo法处理非等温结晶过程比较理想,而由于次级结晶的存在Ozawa法并不适用;Jeziorny法和Mo法处理所得的数据表明,TPU的加人能够提高POM的结晶速率,减小半结晶时间(t1/2),并且导致POM的结晶成核和生长发生了改变。     

聚丙烯/共聚酯/蒙脱土复合材料结晶行为的研究

采用热台偏光显微镜研究了聚丙烯(PP)/共聚酯(COPET)以及PP/COPET/蒙脱土(MMT)复合材料等温结晶时的结晶形态,结果表明:两样品均呈现清晰的球晶所特有的黑十字消光图像,PP/COPET/MMT复合材料的球晶尺寸比PP/COPET样品的球晶尺寸大大减小。采用差示扫描量热法对PP/COPET以及PP/COPET/MMT复合材料的非等温结晶行为进行了研究,结果表明:随着MMT含量的增加,复合材料样品的结晶初始温度和结晶峰温基本呈现逐渐降低趋势,结晶放热焓随MMT含量增加先增加后减小;在不同的降温速率下结晶,两种样品结晶峰温均随降温速率的增大而降低,结晶放热焓也随着结晶速率的增大而降低。采用Jeniorny法处理了PP/COPET和PP/COPET/MMT样品的非等温结晶过程,得出了两体系的结晶速率总体上随着冷却速率的增加而加快,为多维结晶生长体系。     

微型注塑条件下PLA/POM共混物的形貌及结晶行为

采用微型注塑加工技术制备了聚乳酸(PLA)/聚甲醛(POM)共混物微型注塑试样,利用扫描电子显微镜(SEM)、差示扫描量热(DSC)仪和偏光显微镜(PL M)研究了微注塑加工过程中注射速率和模具温度对PLA/POM微型注塑试样的形貌及结晶行为的影响。结果表明,微型注塑加工条件下,PLA/POM共混物为相容体系;注射速率对POM的结晶行为影响更大,提高注射速率更有利于POM分子链的取向及取向程度的增加,导致POM的熔点和PLA/POM共混物微型注塑试样的结晶度提高;提高模具温度明显增加PLA的热焓松弛峰温度,同时还导致PLA冷结晶温度和熔点的降低以及POM熔点的增加,这与较高模温条件下PLA分子链较易规整排列以及PLA较高的玻璃化转变温度有关。此外,PLA/POM共混物微型注塑试样中PLA形成的晶体类型与等温结晶的温度有关,相对较低温度的等温结晶条件有利于PLA/POM共混物微型注塑试样形成环带球晶。微型注塑条件下,PLA/POM共混物微型注塑试样的中PLA形成的晶体类型与冷却方式有关。     

聚丙烯/聚苯乙烯/膨润土共混体系的结晶性能和热性能研究

通过偏光显微镜(PLM)和光学解偏振仪对聚丙烯/聚苯乙烯/膨润土三元共混体系的结晶形态和等温结晶速率进行了研究。结果表明:共混体系所形成的球晶比纯聚丙烯(PP)所形成的球晶尺寸小,聚苯乙烯(PS)/膨润土(Garamite)复合粒子的加入导致PP的结晶成核和生长发生了改变,加快了PP的结晶速率。同时采用差示扫描量热仪(DSC)对该三元共混体系的热性能进行了研究,结果表明,随着膨润土含量的增加,共混体系熔融温度变高,结晶温度变高,结晶度下降。     

PHBV/PEA共混物结晶行为的研究

采用偏光显微镜(POM)和差示扫描量热仪(DSC)深入研究了不同配比的聚己酸戊酸共聚酯/聚己二酸乙二醇酯(PHBV/PEA)共混体系在不同结晶温度下的结晶形貌、结晶热力学以及结晶动力学。结果表明:随着结晶温度的升高,PHBV/PEA共混物中PHBV的球晶尺寸和环带间距均有所增大;随着PEA含量的增加,PHBV球晶尺寸增大,结构更加开放,同时共混物中PEA组分受PHBV组分的影响,由原来的大球晶变成了细小的碎晶。此外,同纯PHBV和纯PEA相比,PHBV/PEA共混体系中两种组分的结晶速率均有所降低。     

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...     

PVDF/PMMA共混物非等温结晶动力学和晶体结构

通过差示扫描量热仪（DSC）、X射线衍射仪（XRD）对纯聚偏氟乙烯（PVDF）和PVDF/聚甲基丙烯酸甲酯（PMMA）共混物在不同降温速率下的非等温结晶行为和晶体结构进行表征和分析,并采用Jeziorny法和莫志深法研究了各组样品的非等温结晶动力学。结果表明,PMMA含量过多（PVDF/PMMA质量比为6/4和5/5）会完全抑制PVDF结晶;对于纯PVDF和可结晶的共混物（PVDF/PMMA质量比为9/1、8/2、7/3）样品,随着PMMA含量的增加,共混物结晶温度先升高后降低,结晶速率先少许增大后减小,说明少量PMMA起异相成核作用,可促进共混物结晶,而大量PMMA可明显阻碍分子重排,抑制其结晶;PMMA的加入可促进共混物晶体结构向低维转变;共混物晶体结构主要是α晶型,PMMA含量的增加不改变共混物的晶型,且使共混物结晶度先增大后减小。     

Crystallization and melting behaviour of polypropylene ‘catalloys’

The crystallization and melting behaviour of polypropylene ‘catalloys’ (PP‐cats) as well as pure polypropylene (PP) were investigated using differential scanning calorimetry. The results showed that, for PP‐cats and PP, a single melting peak of PP appeared under slow cooling rate. When the cooling rate is fast enough in the non‐isothermal case, or the crystallization temperature is relatively high in the isothermal case, a shoulder peak appears in front of the melting peak with increasing ethylene content in PP‐cats. It is believed that this shoulder is induced by recrystallization of crystals initially formed during non‐isothermal or isothermal crystallization. When the ethylene component in PP‐cats reached a certain level, there existed a melting peak of polyethylene (PE) crystallized during the cooling process. Polarized optical microscopy (POM) showed that the spherulites formed by PP‐cats were much smaller and had less perfect morphology compared with that formed by pure PP at the same cooling rate. And with the increase of the cooling rate, the spherulites could not be clearly observed. Copyright © 2004 Society of Chemical Industry     

Study on the crystal morphology and melting behavior of isothermally crystallized composites of short carbon fiber and poly(trimethylene terephthalate)

The spherulites of the short carbon fiber(SCF)/poly (trimethylene terephthalate) (PTT) composites formed in limited space at designed temperatures, and their melting behaviors were studied by the polarized optical microscopy, atomic force microscopy (AFM), and scanning electron microscopy (SEM), respectively. The results suggest that SCF content, isothermal crystallization temperatures, and the film thicknesses influence the crystal morphology of the composites. The dimension of the spherulites is decreased with increasing SCF content, but whether banded or nonbanded spherulites will form in the composites is not dependent on SCF content. However, the crystal morphology of the composites depends strongly on the temperature. When the isothermal crystallization temperatures increase from 180°C to 230°C, the crystal morphology of SCF/PTT composites continuously changes in the following order: nonbanded → banded → nonbanded spherulites. Discontinuous circle lines form in the film when the film thickness increases from 30 to 60 μm. Basing on the SEM observation, it is found that these circle lines are cracks formed due to the constriction difference of the different parts of the spherulites. These cracks are formed when the film is cooled from the isothermal crystallization temperature to the room temperature at a slow cooling rate; while they will disappear gradually at different temperatures in the heating process. The crack will appear/disappear first around the center of the spherulite when the film was cooled/heated. The nontwisted or slightly twisted lamellas will reorganize to form highly twisted lamellas inducing apparent banded texture of the spherulites.     

Morphology and thermal properties in the binary blends of poly(propylene-co-ethylene) copolymer and isotactic polypropylene with polyethylene

The morphology and thermal properties of isothermal crystallized binary blends of poly(propylene-co-ethylene) copolymer (PP-co-PE) and isotactic polypropylene (iPP) with low molecular weight polyethylene (PE) were studied with differential scanning calorimeter (DSC), dynamic mechanical analysis (DMA), polarized optical microscopy (POM) and wide-angle X-ray diffraction (WAXD). In PP-co-PE/PE binary blends, however, the connected PE acted as a phase separating agent to promote phase separation for PP-co-PE/PE binary blends during crystallization. Therefore, the thermal properties of PP-co-PE/PE presented double melting peaks of PE and a single melting temperature of PP during melting trace; on the other hand, at cooling trace, the connected PE promoted crystallization rate because of enhanced segmental mobility of PP-co-PE during crystallization. At isothermal crystallization temperature between the melting points of iPP and PE, the binary blend was a crystalline/amorphous system resulting in persistent remarkable molten PE separated domains in the broken iPP spherulite. And then, when temperature was quenched to room temperature, the melted PE separated domains were crystallized that presented a crystalline/crystalline system and formed the intra-spherulite segregation morphology: these PE separated domains/droplet crystals contained mixed diluent PE with connected PE components. On the other hand, in the iPP/PE binary blends, the thermal properties showed only single melting peaks for both PE and iPP. Moreover, the glass transition temperature of iPP shifted to lower temperature with increasing PE content, implying that the diluent PE molecules were miscible with iPP to form two interfibrillar segregation morphologies: iPP-rich and PE-rich spherulites. In this work, therefore, we considered that the connected PE in PP-co-PE functioned as an effective phase separating agent for PP and diluent PE may be due to the miscibility between connected PE and diluent PE larger than that between PP and dispersed PE.     

Thermal properties and non‐isothermal crystallization behavior of poly(trimethylene terephthalate)/poly(lactic acid) blends

Thermal properties and non‐isothermal melt‐crystallization behavior of poly(trimethylene terephthalate) (PTT)/poly(lactic acid) (PLA) blends were investigated using differential scanning calorimetry and thermogravimetric analysis. The blends exhibit single and composition‐dependent glass transition temperature, cold crystallization temperature (T_cc) and melt crystallization peak temperature (T_mc) over the entire composition range, implying miscibility between the PLA and PTT components. The T_cc values of PTT/PLA blends increase, while the T_mc values decrease with increasing PLA content, suggesting that the cold crystallization and melt crystallization of PTT are retarded by the addition of PLA. The modified Avrami model is satisfactory in describing the non‐isothermal melt crystallization of the blends, whereas the Ozawa method is not applicable to the blends. The estimated Avrami exponent of the PTT/PLA blends ranges from 3.25 to 4.11, implying that the non‐isothermal crystallization follows a spherulitic‐like crystal growth combined with a complicated growth form. The PTT/PLA blends generally exhibit inferior crystallization rate and superior activation energy compared to pure PTT at the same cooling rate. The greater the PLA content in the PTT/PLA blends, the lower the crystallization rate and the higher the activation energy. Moreover, the introduction of PTT into PLA leads to an increase in the thermal stability behavior of the resulting PTT/PLA blends. Copyright © 2011 Society of Chemical Industry