PP/POE共混物的毛细管和转矩流变行为

利用高压双管毛细管流变仪和Haake转矩流变仪研究了聚丙烯(PP)/乙烯-辛烯共聚物(POE)体系的流变行为,探讨了转速、剪切速率、温度及共混物的组成对熔体流变行为的影响。结果表明,两种方法所测得的熔体流变学结果基本一致,共混物熔体表现为假塑性流变行为。随着POE含量的增加,PP/POE共混物熔体的表观黏度和非牛顿指数表现为负偏差行为,粘流活化能则表现出正负偏差行为,说明PP与POE之间存在一定的相容性。     

PP/POE共混物的热行为与晶态结构

采用双螺杆挤出机熔融共混制备了不同组成的聚丙烯(PP)/乙烯-辛烯弹性体(POE)共混物,利用差示扫描量热仪、偏光显微镜和广角X射线衍射系统研究了共混物的热行为与晶态结构。结果表明PP与POE之间具有一定的相容性,POE的异相成核作用提高了共混物中PP的结晶温度和结晶速率,有效地诱导β晶型PP的形成,增大了共混物中α晶型和β晶型PP的晶面表观厚度。另一方面,由于POE与PP之间存在较强的相互作用,POE大分子链使PP分子链的扩散和堆积受阻,从而导致PP/POE共混物总结晶度的降低。     

PTT/POE-g-MAH共混合金的流变行为和结晶熔融性能

利用毛细管流变仪、热台偏光显微镜(POM)和差示扫描量热仪(DSC),分别研究了聚对苯二甲酸丙二酯(PTT)/马来酸酐接枝乙烯-辛烯共聚物(POE-g-MAH)共混合金的流变行为、结晶形态和热性能。结果表明,PTT/POE共混合金熔体为假塑性流体,POE组分含量越高,共混合金对剪切速率变化越敏感,表观黏度降低越多,POE有一定的增塑作用;由于POE与PTT间的相互作用,共混合金从熔体结晶时形成的PTT晶体尺寸明显减小,但体系起始结晶温度升高,结晶速度加快。在Tg以上,由于POE的影响,PTT组分的冷结晶焓变迅速减小。当POE组分含量超过4%时,体系中出现POE的聚集体,相分离明显。     

自动铺放成型热塑性复合材料的非等温结晶动力学研究

利用差示扫描量热仪结合Avrami方程研究玻璃纤维增强聚丙烯复合材料自动铺放成型过程非等温结晶动力学,推导非等温结晶动力学模型,并通过构建冷压辊下方铺层的冷却模型,将结晶动力学模型和传热模型相结合,设定自动铺放成型过程中的冷却条件,探讨冷却速率及冷却时间对基体材料结晶行为的影响,求解出不同冷却速率下的最大铺放速率。研究结果表明:铺层树脂基体的结晶度随冷却速率的增大而依次减小;随着冷却速率的提高,树脂结晶起始温度和结晶完成温度均向低温方向移动,且树脂相对结晶度随温度变化规律接近反S形曲线;自动铺放成型实验件的压缩强度及层间剪切强度随着铺层结晶度的增大基本呈增大趋势,而冲击强度与铺层结晶度的变化趋势完全相反,随着结晶度的增大,材料韧性越差。     

采用紫外光刻电铸技术的微型腔注塑成型

针对复杂微型腔制作的难点,基于紫外光刻电铸(UV-LIGA)技术和掩膜腐蚀的方法加工了细胞皿微型腔。以聚丙烯(PP)进行单因素充模流动工艺试验,通过极差分析,研究了注射速率、模具温度、熔体温度、保压压力和保压时间对微制品成型质量的影响规律。注射速率对提高充填率起主要作用,模具温度和熔体温度是次要因素,而保压压力和保压时间相对其它因素对充填质量影响较差,但必须保持在一个较高的水平。在获取优化工艺参数后,获得合格的制品。因此基于UV-LIGA技术和掩膜腐蚀的方法制作复杂结构微型腔对于微注塑成型是可行的。     

CNTs/PPG/PP复合材料的非等温结晶行为

采用差示扫描量热法(DSC)研究了碳纳米管(CNTs)加入量和降温速率对CNTs/接枝马来酸酐聚丙烯(PPG)/聚丙烯(PP)复合材料(CNTs/PPG/PP)的非等温结晶过程的影响,并采用Jeziorny法对DSC结果进行动力学分析。结果表明:当降温速率为20℃/min时,加入CNTs可提高复合材料的结晶温度,当CNTs加入量为1.0%(wt,质量分数)条件下,复合材料的结晶峰温度为117.6℃,比未加CNTs时提高了2.0℃,CNTs的加入同时还使得复合材料结晶度增大,结晶速率加快,且均随着CNTs加入量的增加而增大;CNTs起到了异相形核作用,改变了PP基的形核方式和晶体长大方式;降温速率的增大使得复合材料将在更低的温度下结晶,结晶度增大。     

POE与HDPE对PP的协同增韧改性

以两种高密度聚乙烯(HDPE)和三种聚烯烃弹性体(POE)为增韧剂,对聚丙烯(PP)进行共混改性,探讨增韧剂结构和含量对PP韧性和流动性能的影响规律,获得了最佳混合比。实验发现:POE和HDPE有增韧效果,POE的效果优于HDPE;但降低其熔体质量流动速率(MFR)。当POE:HDPE:PP为25:15:60时,三元复合体系的简支梁缺口冲击强度为74.21KJ·m~(-2),较纯PP提高了13倍。     

微结构塑件的注塑充填尺度效应

微尺度聚合物熔体流动具有明显的尺度效应,模具温度和注射速率是微注塑充填流动的关键影响因素。文中采用微细电火花铣削技术设计分别制造了一模八腔的带有200μm和300μm微孔的注塑模具。以聚丙烯(PP)进行单因素充模流动工艺实验,研究了模具温度和注射速率对直径为200μm和300μm微圆柱充填高度影响规律。结果表明,当模具温度为30℃和注射速率为60%时,直径200μm微圆柱孔的充填高度小于直径300μm微圆柱孔的充填高度,且Ⅰ型腔的微圆柱充填高度大于Ⅱ的充填高度。随着模具温度升高和注射速率增加,2种微孔充填高度差在减小,Ⅰ型腔和Ⅱ型腔之间的充填高度差值也在减小。可见,升高模具温度和增加注射速率可以减少微尺度效应对微圆柱孔充填高度的影响,同时,还可以减小流动不平衡程度。     

注塑工艺参数和超声外场对聚丙烯制件结晶结构的影响

针对模腔内熔体温度对制件冷却过程中其内部分子的凝聚结构及结晶形态的影响,通过自行设计制造的带有热电偶传感器和超声外场的注塑成型实验系统,采用单因素实验方法,通过测量PP制件成型过程中模腔不同位置处的熔体温度同时利用X射线衍射法,对制件内部微观结构形态的检测分析,研究了不同工艺参数和超声功率变化,对制件内部分子凝聚态结构的影响。结果表明,模腔内熔体峰值温度的升高及降温时间的延长,有利于制件内部分子形成结晶结构;但过高的熔体温度则不利于结晶结构的形成。适当增大超声功率能够有效促进制件内部分子生成结晶结构,使其结晶度提高;但过高的超声功率会使制件的结晶度下降。试验工艺参数条件下,施加600 W超声功率时,制件获得平均48.06%的最高结晶度,有效地提高了制件的力学性能。     

尺寸效应对多型腔注射成型过程影响的可视化实验

利用可视化注塑模具和高速摄像机对注塑成型过程中熔体在型腔内的充填不平衡现象进行了动态观察,探讨了尺寸效应对熔体充填型腔速率及充填平衡性的影响。实验结果表明,熔体的充填平衡性与型腔的厚度有关,根据实验结果可以较好地描述熔体注射成型过程中充填不平衡现象的产生规律,为薄壁及微细尺寸下的精密注射成型技术的发展提供实验依据。     

原位交联改性PP/POE共混物的等温结晶行为

采用热塑性聚烯烃弹性体(POE)作为增韧材料,以过氧化二异丙苯(DCP)为交联剂制备了PP/POE共混物。利用差示扫描量热仪(DSC)和偏光显微镜(PLM)研究了PP/POE共混物等温结晶行为,并用Avrami方程分析了PP/POE共混物结晶动力学。结果表明,POE的加入能起到异相成核的作用,加快了PP的结晶成核速率。Avrami指数在1.93～3.09,DCP的引入对聚丙烯(PP)的成核与生长机理影响不大,但其原位交联作用阻碍了PP分子链的运动,使得PP结晶速率降低,结晶时间延长。     

PP/POE共混体系脆韧转变的定量研究

研究了乙烯-1-辛烯共聚物(POE)对两种不同型号的聚丙烯(PP)的增韧情况。结果显示,对不同性质的基体PP,出现脆韧转变所需的弹性体POE含量不同;根据逾渗模型,应用不同的计算公式,定量地求得了两种PP/POE体系分别出现脆韧转变时的临界基体层厚度Tc。     

Blends of PP/PE co‐octene for modified atmosphere packaging applications

The aim of this work was to obtain films of polypropylene (PP)/polyethylene co‐octene (POE) blends and study the influence of their composition and mixing conditions on final morphology and ultimate properties (thermal, mechanical, oxygen and water vapour transmission rates). Scanning electron microscopy showed segregation of POE domains in the PP matrix. Thermal analysis indicated that the addition of POE modified neither the melting temperature nor the crystallinity of PP in the pressed films. It was found that permeabilities of films were mainly related to POE content rather than morphological features. For the maximum POE concentration used (40%), the oxygen permeability increased up to ∼100% from that of neat PP. A similar trend was found for water vapour permeability. Rigidity of blends dropped significantly with the addition of POE although their ductility slightly increased when compared to pure PP. No significant effect of blend preparation conditions on these properties was found. Mechanical and permeability characteristics of films make them very attractive to be used for MAP of fresh produce such as apple, blueberry and mushroom. Copyright © 2011 John Wiley & Sons, Ltd.     

固相剪切碾磨制备聚丙烯/废旧橡胶/聚烯烃弹性体复合材料

利用固相剪切碾磨技术在常温下制备了聚丙烯(PP)/废旧轮胎橡胶(GTR)/聚烯烃弹性体(POE)复合材料。采用力学性能测试、差热分析(DSC)和扫描电镜(SEM)对固相剪切碾磨制备的GTR/POE复合粉体和相应PP/GTR/POE复合材料进行表征和分析,研究了碾磨次数和GTR/POE含量对PP/GTR/POE复合材料结构与性能的影响。结果表明,对固相剪切碾磨方法制备的PP/GTR/POE复合材料,GTR和POE被有效粉碎和均匀分散,其冲击强度和断裂伸长率比常规熔融共混方法制备的复合材料高;增加GTR/POE共碾磨复合粉体的含量或增加碾磨次数均可提高冲击强度和断裂伸长率。     

聚丙烯/聚烯烃弹性体/硅灰石复合材料的制备与热学力学性能

采用熔融共混的方法制备聚丙烯(PP)/聚烯烃弹性体(POE)/硅灰石(Wollastonite)复合材料,利用万能材料试验机、悬臂梁冲击机、差热扫描量热仪(DSC)和扫描电镜(SEM)研究了聚烯烃弹性体和硅灰石对聚丙烯的力学性能及热性能的影响。结果表明,POE弹性体对PP有很好的增韧作用,提高了PP的冲击强度,硅灰石在一定程度上有增强的作用,提高了PP/POE的拉伸强度;POE和硅灰石使复合材料的结晶温度有所提高,但使熔点有所降低。当POE占3%(质量分数,下同),硅灰石占3%时,复合材料的热学、力学性能最优,冲击强度比纯PP高出15.4%,拉伸强度高出2.6%,结晶温度高出5℃。     

基体PP分子量及分散相含量对分散相形态的影响

采用凝胶渗透色谱仪(GPC)、扫描电子显微镜(SEM)、转矩流变仪研究了基体分子量和分散相含量对聚丙烯(PP)/乙烯-辛烯共聚物(POE)共混体系分散相形态的影响。研究表明,当固定分散相POE含量时,随着基体PP分子量的降低,基体黏度降低,POE/PP的两相黏度比变大,导致分散相粒径大小和分布宽度增加。当固定基体分子量(M-w=148021),POE/PP两相黏度比不变时,增加分散相POE含量,分散相粒径大小及分布宽度均随其含量的增加先增大后趋于平台区。     

Fracture resistance improvement of polypropylene by joint action of core-shell particles and nucleating agent

As a serial work about the fracture resistance improvement of polypropylene (PP), this work reports the joint effect of core-shell particles and nucleating agent (NA) on the microstructure and fracture resistance of PP. Core-shell particles were prepared through melt blending of ethylene-octene copolymer (POE) and calcium carbonate (CaCO₃). Different NA, i.e. α-form NA (P-tert-butylbenzoic acid-Al, MD-NA-28) and β-form NA (aryl amides compound, TMB-5) were introduced into PP matrix to control the crystalline structure. The phase morphology of POE and the distribution of CaCO₃ were characterized by using scanning electron microscope (SEM), and the crystallization behavior of PP matrix were investigated by using differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD) and polarization optical microscope (POM). The mechanical properties were obtained through universal tensile measurement and notched Izod impact measurement. Surprisingly, the results show that through addition of so-called core-shell particles and NA simultaneously, the fracture resistance of PP can be dramatically improved.     

Characterisation of the thickness of transition layer and its relation to mechanical properties of polypropylene/poly(ethylene-co-octene) blends

Poly(ethylene-co-octene) (POE) was mixed into polypropylene (PP) by an internal mixer, which was installed on on-line small-angle laser light scattering (SALLS) device. A new parameter called the thickness (d) of transition layer was introduced to describe the compatibility of PP/POE blends in both dynamic and static states. Using the correlation distance, a_c (it was indicative of the dimension of the dispersed phase pellets), d was calculated for the PP/POE blends based on the SALLS theory. The results indicated that the average values of d increased with increasing concentration of dispersed phase and had a maximum value at 40/60(PP/POE) for the blends. And the values of d showed much more violent fluctuation and were much larger at the early stage of mixing, but at a later stage d leveled off and approached to steady state. In addition, the relationships between the thickness of transition layer and mechanical properties were studied. It showed that the notched Izod impact strength and the average values of d of PP/POE blends increased with increasing of POE concentration, while the Young's modulus and flexural modulus decreased. The results indicated that SALLS method was an effective method to deal with diffuse transition layer of PP/POE blends and d was indeed a valid parameter to describe compatibility.     

PP/POE/高岭土三元复合材料的力学及热性能

研究了高岭土和乙烯-辛烯共聚物弹性体(POE)填充聚丙烯(PP)制备的PP/POE/高岭土三元复合材料的力学和热力学性能。结果表明,POE和高岭土不能提高PP的拉伸强度,但高岭土可以显著提高PP/POE的杨氏模量。POE降低了PP的弯曲强度和弯曲模量,但PP/POE/高岭土三元复合材料的弯曲强度和弯曲模量显著高于PP/POE和PP。POE和高岭土可以显著提高PP的冲击强度,当高岭土和POE的填充份数分别为10份和5份时,PP/POE/高岭土复合材料的冲击强度最大。高岭土的添加可以提高PP的结晶温度,加快PP的结晶速率,促进PP的异相成核。合适含量的高岭土可以提高PP的熔融温度,改善PP的耐热性能。