乙烯基笼型倍半硅氧烷/聚丙烯纳米复合材料热降解动力学

用热重分析(TGA)法研究了乙烯基笼型倍半硅氧烷(V-POSS)/聚丙烯纳米复合材料的热降解动力学.采用Kim-Park,Flynn-Wall-Ozswa和Friedman三种方法计算了共混物的降解反应活化能,结果说明,当V-POSS加入质量分数分别为4%、8%、12%和16%、升温速率为5℃/min时材料热降解起始温...     

双峰中密度聚乙烯/高压聚乙烯共混物的流变行为与力学性能

用毛细管流变仪研究了双峰中密度聚乙烯(BMDPE)及其与高压聚乙烯(LDPE)共混物熔体的流变行为。讨论了共混物的组成、剪切应力、剪切速率及温度对熔体流变行为的影响和挤出膨胀比，测定了不同配比熔体的非牛顿指数(n)，熔融指数(MI)。测定了共混物的屈服应力、断裂应力和断裂伸长率。证明共混物的强度随双峰中密度聚乙烯含量的增加而提高，为BMDPE的加工和使用提供了依据。     

V-POSS/UPR非等温固化动力学与物理性能

为了提高不饱和聚酯树脂(UPR)的性能，本文中以乙烯基笼型倍半硅氧烷(V-POSS)改性不饱和聚酯树脂，用非等温 DSC法研究了UPR和5% V-POSS/UPR体系的固化反应动力学以及表观反应活化能与转化率之间的关系，测定了玻璃钢层压板的力学性能和电性能。结果表明，加入V-POSS固化反应E_a随反应程度增加而降低，通过使用两参数Šesták-Berggren(S-B)模型描述固化反应过程，得到了反应动力学方程。当V-POSS质量分数为5%时玻璃钢层压板拉伸强度达到最大值，提高了17.6 MPa，冲击强度随V-POSS加入量增加而降低，但在10%时冲击强度有所上升。层压板电性能随 V-POSS加入量增加而提高，其中体积电阻率和表面电阻率提高1～2个数量级。     

MPE/LLDPE/LDPE共混熔体的流变学

研究了不同比例共混的茂金属聚乙烯（MPE），线性低密度聚乙烯（LLDPE）及高压聚乙烯（20％固定质量配比的LDPE）熔体的流变学行为，讨论了共混物组成，剪切速率和剪切应力以及温度对熔体流变曲线，熔体粘度和膨胀比的影响，为MPE的共混改性加工提供了理论依据，不同共混比的熔体均为假塑性流体，共混熔体的假塑性随LDPE／LLDPE的增多而增强，共混熔体的转变应力和非牛顿指数随LDPE／LLDPE的增加而降低，对加工的敏感性提高，加工性能得到改善。     

线性双峰聚乙烯/高压聚乙烯/线性低密度聚乙烯共混物的流变行为与力学性能

研究了线性双峰聚乙烯(LBPE)、高压聚乙烯(LDPE)与线性低密度聚乙烯(LLDPE)共混物熔体的流变行为和力学性能。讨论了共混物的组成、剪切应力和剪切速率对熔体粘度和膨胀比的影响。结果说明,共混物熔体为假塑性流体,LBPE含量为70％时熔体粘度最大,含量高于60％时挤出胀大变小,含量高于40％时力学强度增大。     

聚(3-羟基丁酸酯-co-4-羟基丁酸酯)/POSS共混体系的性能

采用熔融模压法分别制备了聚(3-羟基丁酸酯-co-4-羟基丁酸酯)[P(3HB-co-4HB)]和两种多面体笼型硅氧烷(POSS)[八异丁基倍半硅氧烷(OIBS)和八氨基苯基倍半硅氧烷(OAPS)]的共混物,考察了不同含量的OIBS,OAPS对共混体系性能的影响。结果表明,两种POSS都起到成核剂的作用。OIBS,OAPS的质量分数小于1%时,可以提高体系结晶温度,力学性能;随着OIBS,OAPS质量分数的提高,成核性有所增加,但因分散性变差,体系热稳定性和力学性能变差。由于OAPS的活泼氨基可与P(3HB-co-4HB)发生化学反应,改性效果较OIBS优。     

环氧乙烯基笼型倍伴硅氧烷/P(3HB-co-4HB)复合材料的制备与降解性能

采用熔融共混法制备了环氧乙烯基笼型倍半硅氧烷(EOVPOSS)与聚(3-羟基丁酸酯-co-4-羟基丁酸酯)[P(3HB-co-4HB)]的复合材料,考察了不同含量的EOVPOSS对共混体系力学性能和降解性能的影响。结果表明,当添加的EOVPOSS含量为1%时,共混材料的力学性能最优,同时其在土壤及脂肪酶中的降解性能最佳。     

PP/EPDM-g-MAH/Al(OH)_3/FA复合体系流变性能研究

以毛细管流变仪研究了粉煤灰(FA)改性聚丙烯/三元乙丙橡胶接枝马来酸酐/Al(OH)_3/FA[PP/EPDM-gMAH/Al(OH)_3/FA]阻燃复合体系的流变行为,讨论了复合材料的组成、剪切应力和剪切速率及温度对熔体流变行为、熔体黏度的影响,测定了不同配比的复合材料熔体的非牛顿指数(n)和挤出膨胀比。结果表明:PP/EPDM-g-MAH/Al(OH)_3/FA熔体为假塑性流体,表观黏度随着剪切速率增加而降低。当FA的含量在0%~25%范围内时,共混物的n1,且在5%和20%处有2个极大值点,表观黏度呈先增后减再增的趋势;FA可降低共混熔体的粘流活化能,但适量FA仍可保证温敏性不会降低太大,复合材料的挤出胀大现象随FA增加有所降低。     

聚对苯二甲酸乙二醇酯-聚酰胺嵌段共聚物/聚酰胺6共混物的流变性能

通过熔融共混挤出的方法,制备了不同共聚比例的聚对苯二甲酸乙二醇酯-聚酰胺嵌段共聚物(PET-PA)与聚酰胺6(PA6)的共混物,采用毛细管流变仪对PET-PA/PA6共混物的流变性能进行了研究。结果表明,PET-PA/PA6共混物熔体为剪切变稀的非牛顿流体。随温度升高,PET-PA/PA6共混物熔体的表观黏度下降,非牛顿指数增大,表观黏度对剪切速率的敏感性减小,因此升高温度能改善共混物熔体的流动性能。随PET-PA中PA共聚比例的增加,PET-PA/PA6共混物的黏度减小,非牛顿指数增大,这为开发酸性染料可染聚酯纤维提供了参考。     

含笼型倍半硅氧烷的丙烯酸酯芯壳聚合物的合成及在改性聚氯乙烯中的应用

合成了具有不同甲基丙烯酰氧丙基笼型倍半硅氧烷(MAP-POSS)含量和不同芯壳比的丙烯酸酯芯壳聚合物(ACR)树脂,并用透射电子显微镜研究了ACR乳胶粒子的形态;用动态力学谱仪研究了聚氯乙烯(PVC)/ACR共混物的动态力学性质;测试了PVC/ACR共混物的塑化行为和力学性能。结果表明,MAP-POSS在ACR芯中参与接枝和交联反应;MAP-POSS加入量为单体质量5%和10%时,壳层有最高的玻璃化转温度;芯/壳比为1∶1时,ACR粉末效果较好;PVC/ACR共混物材料塑化时间随ACR的含量增加而缩短,而塑化扭矩增大;ACR加入量为m(ACR)/m(monomer)=11/100时共混材料具有最大的冲击强度,较未加时提高了72.9%,比不含增塑剂的纯PVC提高了3.41倍。     

SiO2纳米粒子填充PS/PMMA共连续共混物的应力松弛行为

采用流变测试和扫描电子显微镜技术,考察了亲水性SiO2纳米粒子对具有共连续结构的聚苯乙烯(PS)/聚甲基丙烯酸甲酯(PMMA)(体积比50/50)共混物在步阶剪切应变下应力松弛行为的影响。研究表明,PS/PMMA共混物呈现两步应力松弛行为,即来源于本体聚合物的较快的松弛以及来源于界面的较慢的松弛。SiO2粒子的加入细化了共混物的形态尺寸,加速了共混物第二阶段的松弛行为。同时,实验结果进一步表明,填充共混物应力松弛行为的加快主要是由于SiO2的加入引起形态细化造成的,而并非组分粘弹性的变化。     

PTT/EPDM-g-MAH/mPE共混体系的相形态与流变行为

研究了聚对苯二甲酸丙二酯/马来酸酐接枝三元乙丙橡胶/茂金属聚乙烯共混体系(PTT/EPDM-g-MAH/mPE)的相形态和流变行为。结果表明,增容剂EPDM-g-MAH可以明显改善PTT与mPE的相容性,但含量超过4%时分散相的数目增加、尺寸增大。PTT/EPDM-g-MAH/mPE共混物熔体为假塑性流体,表观黏度随剪切速率的增加而降低;当EPDM-g-MAH的含量在0%~16%范围内时,共混物的非牛顿指数先减小后增加再减小;表观黏度、粘流活化能先增加后减小,并在4%时出现极值。     

Microstructural,thermal and rheological correlations to mechanical response of polyamide-6(glass filled)/polyetherimide blend: effect of ethylene-octene copolymer on toughening of blend

Melt mixed glass-filled polyamide 6(PA6)/polyetherimide (PEI) blends were prepared in a co-rotating twin screw extruder over the entire composition range of 0–100 wt% of polyamide 6. These blends were characterized by structural, rheological, mechanical and thermal properties. Crystallization behavior and phase morphology of the blends were also investigated. The blend with the composition PA6/PEI 75/25 showed overall improved mechanical properties along with low resultant viscosity which can be processed on standard equipment. Shear viscosity along with shear stress of the blends were analyzed using shear rheometer which concluded that the blends can be processed on standard equipment due to resultant low viscosity. Scanning electron microscope micrographs revealed that the morphology of the blends showed a two phase structure in which the minor phase was dispersed as domains in the continuous phase. Polyolefin elastomer (POE) as impact modifier was added to the above composition in the range of 0–15 phr to study its effect. The thermal characteristics of PA6, PEI, and PA6/PEI blends with and without POE were investigated using DSC and TGA which revealed that the melting temperature and crystallization temperature of the blend remained unchanged while XRD results showed percent crystallinity was increased slightly. Furthermore, it can be said that the blend with composition PA6/PEI 75/25 with 10 phr impact modifier loading was suitable for high end applications because it combines the high mechanical properties of glass-filled PA6 with inherent flame-retardant property of PEI while POE overcomes the physical weakness of moisture absorption.     

Nylon-6-rubber blends

The macroscopic cavitation and yield behaviour of nylon-6/rubber blends was studied. The type of rubber (poly(butadiene), ethylene propylene copolymer (EPDM) or polyethylene (LDPE), the rubber concentration and the rubber particle size was varied. The onset of cavitation was determined by measuring the intensity of the transmitted light from an incident laser beam. Both the yield stress and the cavitation stress appeared to increase with increasing strain rate and rubber modulus. No linear relation between the shear modulus and the cavitation stress was found. The data indicate that blends with a very small particle size have a relatively high cavitation stress. In all cases, a high cavitation stress of the elastomer resulted in a high yield stress of the blend.     

Tensile dilatometry of injection-moulded HDPE/PA6 blends

In order to understand the mechanism of deformation of injection-moulded HDPE/PA6 (25 vol% /75 vol%) blends both with and without compatibilizer, the volume change has been monitored using tensile dilatometry. Dog-bone specimens were either directly moulded or cut from rectangular plaques. Both neat materials and their blends were tested. For the directly moulded dog-bone specimen, a pure shear yielding mechanism was observed for all materials tested, i.e. PA6, HDPE, and their blends in the same proportion as above. In the case of a deformable minor phase (HDPE), the dispersed phase appeared to bear its share of stress and the flow-induced orientation mimics the effect of interfacial modification. This was not the case of a rigid minor phase (glass beads) at the same concentration; the effect of surface treatment changed the mechanism of deformation from mixed mode cavitation shear yielding (45%) to almost pure shear yielding (85%). Machined specimens made of neat PA6 and HDPE deformed through pure shear yielding. The addition of 25 vol% HDPE to PA6 resulted in a mixed mode cavitation (55%)/shear yielding mechanism of deformation in the transverse direction, while in the longitudinal case, the mechanism which prevailed was almost pure shear yielding (80%). This can be attributed to the flow-induced orientation as above. When adding 10% (based on the weight of the dispersed phase) of an ionomer as a compatibilizer, the blend deformed via shear yielding (85%) and in the longitudinal direction both compatibilized and non-compatibilized blends display similar behaviour. Varying the specimen thickness by changing the mould cavity, led to a significant variation in the dilatational behaviour. Dilatometric behaviour is shown to be closely related to the morphology generated as a result of flow-induced orientation. The skin/core ratio, which is an indication of the proportion of the oriented dispersed phase to the non-oriented one, plays a key role in influencing the mechanism of deformation involved.     

Shear-induced APAP de-agglomeration

Context: Active pharmaceutical ingredient agglomerates can generate many solid product regulatory compliance issues. Objective: To study the effects of shear rate, strain, type of excipient, and grade of acetaminophen (APAP) on the process of APAP de-agglomeration. Materials and Methods: A shear-controlled environment is used to expose six different blends that consist of one of three APAP grades and one of two possible types of excipient to 10 different combinations of shear rate and strain. APAP agglomerates are sifted and weighed. Results: Finer APAP grades lead to blends with more APAP agglomerates and type of excipient only affects the de-agglomeration process for the finest APAP grade. De-agglomeration proceeds mainly as a function of strain with a minor contribution toward further de-agglomeration when larger shear rates are used. Discussion: When mechanical stress (which us proportional to shear rate) overcomes interparticle forces, de-agglomeration occurs. Higher shear rates (and stress) contribute slightly to further APAP de-agglomeration. Extended exposure to stress (strain) reduces the size and the number of agglomerates. Blends with finer APAP present more agglomerates, particularly after low strain exposure. Conclusions: This article presents a useful method for formulation and process development. Exposing blends to higher shear rates and especially to strain mitigates APAP agglomeration in blends. Finer APAP presents more agglomerates and the type of excipient used affects the degree of APAP agglomeration.