TIME-DEPENDENT MORPHOLOGY OF POLYETHYLENE-POLYPROPYLENE BLENDS

The effect of time-temperature treatment on morphology of polyethylene-polypropylene (PE-PP) blends wasstudied to establish a relationship between thermal history, morphology and mechanical properties. Polypropylene (PP)homopolymers were used to blend with various polyethylenes (PE), including high density polyethylene (HDPE), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE), and very and ultra low density polyethylene(VLDPE and ULDPE). The majority of the blends were prepared at a ratio of PE:PP = 80:20, while blends of PP and LLDPEwere prepared at various compositions. Thermal treatment was carried out at temperatures between the crystallizationtemperatures of PP and PEs to allow PP to crystallize first from the blends. On cooling further, PE crystallized too. A verydiffuse PP spherulite morphology in the PE matrix was formed in some partially miscible blends when PP was less than 20%by mass. Droplet-matrix structures were developed in other blends with either PP or PE as dispersed domains in a continuousmatrix, depending on the composition ratio. The scanning electron microscopy (SEM) images displayed a fibrillar structureof PP spherulite in the LLDPE-PP (80:20) and large droplets of PP in the HDPE-PP (80:20) blend, providing larger surfacearea and better bonding in the LLDPE-PP (80:20) blends. This explains why the blends with diffuse spherulite morphologyshowed greater improvement in tensile properties than droplet-matrix morphology blends after time-temperature treatment.     

Studies on the Crystallization Behavior of Polypropylene Solid Phase Grafted Maleic Anhydride

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聚丙烯/凹凸棒土纳米复合材料结晶形态和形貌研究

采用熔融共混的方法 ,制备聚丙烯 凹凸棒土纳米复合材料 .通过X射线衍射 (XRD)分析凹凸棒土在聚丙烯复合材料中晶面间距的变化以及对聚丙烯晶型的影响 ,结果表明凹凸棒土在复合材料中晶面间距没有变化 ;聚丙烯晶型没有发生变化但晶粒尺寸增加了 .用示差扫描量热法 (DSC)分析聚丙烯复合材料的结晶度的变化 ,发现凹凸棒土的加入使复合材料的结晶温度提高 ,结晶速率增大 ,结晶度增加 .用偏光显微镜(POM)观察凹凸棒土对聚丙烯球晶的影响 ,结果表明凹凸棒土的加入起到了成核剂的作用 ,使得聚丙烯球晶尺寸减小 ,当凹凸棒土的加入量到 10 %左右时 ,观察不到完整的球晶 .利用扫描电子显微镜 (SEM)和原子力显微镜 (AFM)观察凹凸棒土在聚丙烯中的分散 ,发现凹凸棒土在聚丙烯基体中分散比较均匀 ,但呈无序分布 .     

Morphology and non-isothermal crystallization of dynamically vulcanized PP/EPDM blends in situ compatibilized via magnesium dimethacrylate

Polypropylene/ethylene-propylene-diene rubber (PP/EPDM) blends in situ compatibilized by magnesium dimethacrylate (MDMA) were fabricated via peroxide-induced dynamic vulcanization. Scanning electron microscope observation indicated that the size of cross-linked EPDM particles decreased with incorporation of MDMA. Polarizing Optical Microscope (POM) analysis suggested that the spherulite size of PP phase decreased sharply with incorporation of MDMA during dynamic vulcanization. The Pseudo-Avrami, Ozawa and Mo's models were applied to analyze the non-isothermal crystallization kinetics of the composites. The analyzed data indicated that the crosslinked EPDM particles and homopolymerized MDMA acted as heterogeneous nucleating agents, which enhanced the crystallizability and decreased the spherulite size of the PP phase. In addition, the non-isothermal crystallization activation energy (ΔE) was calculated through the Kissinger and Friedman methods, and the ΔE value was found increase with incorporation of MDMA.     

氧化钕填充聚丙烯的等温结晶动力学研究

用ＤＳＣ法研究了氧化钕微粉填充聚丙烯的等温结晶动力学．结果表明，加入少量氧化钕可明显提高聚丙烯的基体结晶速率和结晶度，降低球晶径向生长的单位面积表面自由能；从Ａｖｒａｍｉ和Ｈｏｆｆｍａｎ理论出发都可得出稀土氧化物Ｎｄ２Ｏ３填充聚丙烯后可明显改变聚丙烯的结晶行为．     

马来酸酐接枝聚丙烯的等温结晶动力学研究

用ＤＳＣ法追踪了马来酸酐接枝聚丙烯的等温结晶过程，讨论了马来酸酐降低聚丙烯球晶径向生长自由能，提高结晶速率，但降低聚丙烯结晶度的物理和化学机制．同时探讨了马来酸酐的接枝对球晶生长和成核机制的影响．     

聚丙烯与SBS嵌段共聚物共混时的结晶行为

用偏光显微镜,小角光散射,动态力学测量和DSC等方法研究了聚丙烯和SBS共混物的结晶行为。结果表明,SBS的混入可以降低聚丙烯的结晶程度和阻碍球晶的形成,因而有利于提高聚丙烯塑料的抗冲击性能。从DSC实验也看到共混物中的聚丙烯具有较高的结晶速率。     

聚丙烯催化合金的结晶行为研究

近 1 0年来 ,Montell公司发展的聚丙烯催化合金 (Polypropylene catalloy,PP-c)技术受到广泛关注 .该技术采用具有特定结构的催化剂粒子 ,在适当的聚合条件下 ,得到具有一定大小、形状及内部形貌的聚合物粒子 .由 PP-c技术获得的材料性能可以在非常宽的范围内进行调节 ,其呈现出的高强度可以与工程塑料相比拟 ,柔性可以与聚乙烯相媲美 [1] .结晶性聚合物的结晶度、球晶尺寸等因素对其机械性能 ,尤其是冲击韧性具有重要的影响[2 ,3] .改性聚丙烯的结晶行为及其与物理机械性能之间的关系一直备受关注 .对于纯聚丙烯、聚丙烯与橡胶的共混物…     

New understanding on the memory effect of crystallized iPP

In this study, recovery processes of isotactic polypropylene(iPP) melted spherulites at 135 °C after melting at higher temperatures(170 °C–176 °C) were investigated with polarized optical microscopy and Fourier transform infrared spectroscopy. The recovery temperature was fixed to exclude the interference from heterogeneous nuclei. After melting at temperatures between 170 °C and 174 °C, the melted spherulite could recover back to the origin spherulite at low temperatures. Interestingly, a distinct infrared spectrum from iPP melt and crystal was observed in the early stage of recovery process after melting at low temperatures, where only IR bands resulting from short helices with 12 monomers or less can be seen, which indicates that the presence of crystal residues is not the necessary condition for the polymer memory effect. Avrami analysis further indicated that crystallization mainly took place in melted lamellae. After melting at higher temperatures, melted spherulite cannot recover. Based on above findings, it is proposed that the memory effect can be mainly ascribed to melted lamellae, during which crystalline order is lost but conformational order still exists. These conformational ordered segments formed aggregates, which can play as nucleation precursors at low temperatures.     

Stabilization and modification op polyolefins used in medical articles

The thermo and radiation aging of polyolefins and their blends were studied. It was shown that near the inversion point of phase there is the most marked interaction between continuous and dispersed components of blend. This interaction results in an improvement of blend stability higher than expected. The investigation of the influence of supermolecular structure of PP stability revealed the small spherulite samples are more stable under irradiation in air than large spherulite ones. The possibility of obtaining composites of polyolefins and silicon liquids urns shown.     

Radial growth rate of spherulites in polypropylene/barium sulfate composites

The effect of barium sulfate (BaSO₄) on the spherulite radial growth rates of isotactic polypropylene (PP) was studied by means of optical microscopy. The PP-BaSO₄ interface was modified by treating the fillers with different couple agents. The addition of BaSO₄ depresses the spherulite growth rate, and the effect is more dramatic when the interfacial interaction between the PP and BaSO₄ was enhanced. The data were analyzed with the Lauritzen-Hoffmann secondary nucleation theory, and the results demonstrated that the enhanced PP-BaSO₄ interaction promotes the particles to serve as physical crosslinking points, which hinder the movement of the polymer chains and results in a decrease of the pre-exponential factor, G₀.     

Attapulgite and ultrasonic oscillation induced crystallization behavior of polypropylene

In this article, the effect of ultrasonic oscillation on the dispersed morphology of attapulgite in polypropylene (PP) and crystallizing kinetics of PP/attapulgite composites prepared through extrusion in the presence and the absence of ultrasonic oscillation were studied. X‐ray diffraction analysis results showed that ultrasonic oscillation did not change attapulgite crystal structure during extrusion in PP/attapulgite composites. On the other hand, scanning electron microscopy and transmission electron microscope photographs indicated that ultrasonic oscillation promoted the dispersion of attapulgite particles in PP matrix. The dispersed morphology of attapulgite and ultrasound oscillation affected the crystalline form, nucleation rate, crystallization temperature, crystallinity, and spherulite size of PP crystals. PP transcrystals were formed on the attapulgite particle surface. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2300–2308, 2007     

Influence of N,N,N′,N′-tetraalkyl terephthalamide on isothermal crystallization kinetics and morphology evolution of polypropylene

The influence of N,N,N′,N′-tetraalkyl terephthalamide (TATA) on the isothermal crystallization kinetics of polypropylene (PP) was studied using differential scanning calorimetry (DSC). It was found that TATA shows a heterogeneous nucleation effect and leads to the formation of β-PP. TATA can not only shorten the crystallization time but also heighten the crystallization temperature of PP. The crystallization rate constant of PP containing TATA is larger than that of pure PP. The evolution of crystalline morphology of PP was investigated on a polarized optical microscopy (POM) equipped with a hot stage and the results showed that the introduction of TATA into PP can quicken the crystallization of PP, which is consistent with DSC results. TATA also leads to a substantial decrease in the spherulite size of PP and the boundaries of spherulites are hardly distinguished.     

Structure and properties of blends of isotactic polypropylene with ethylene-propylene oil

The structure of blends of isotactic polypropylene with ethylene-propylene oil was studied by light and atomic force microscopy, X-ray diffraction, and DSC. It was shown that the blends are heterogeneous systems which contain semicrystalline PP and oil crystallizing at low temperatures. An increase in the oil content leads to a change in the spherulite size; a decrease in the lamella size; and, accordingly, to a drop in the melting temperature of PP. The PP-oil blends are thermodynamically compatible in melt. The mechanism of PP deformation gradually varies from the ductile to the quasi-brittle mode with a significant deterioration of mechanical characteristics of the material with an increase in the oil content. The experimental results are described satisfactorily by a model of deformation of the polymer matrix alone.     

耐辐射致色聚烯烃的研究

研究了在γ射线辐照条件下受阻胺光稳定剂 (简称HALS)、各种抗氧剂对聚丙烯 (PP)和聚乙烯 (PE)的黄度 (YI)的影响。结果表明五甲基HALS比相应的四甲基HALS更能有效地阻止聚烯烃的辐射致色。抗氧剂Irganox 10 76比Irgafos16 8或IrganoxPS 80 2更有效。当抗氧剂和HALS并用时显示出协同效应 ,10 76和PDS并用时聚丙烯的黄度比单独添加 10 76或PDS的聚丙烯的黄度都低。     

Migration Study of Polypropylene (PP) Oil Blends in Food Simulants

Migration study in aqueous and olive oil food simulants was carried out on PP and its blend with oil mixture. It was found that after 10 days at 44 °C PP with oil content up to 0.83% had overall migration into olive oil less than 10 mg/dm². However, under high temperature migration test (at 110–138 C for 4 hours), the overall migration into olive oil was large for both the virgin PP and all its blends. The overall migration in water, 10% ethanol, and 3% acetic acid was smaller than those in olive oil under both migration test conditions. DSC and density measurement showed that addition of oil in PP led to smaller spherulite size and increased degree of crystallinity in the pure PP part. Small decrease in tensile strength in the oil blends was also observed but there was no significant change in tensile strength after migration test.     

聚丙烯材料聚集态结构的定量表征及其与力学性能的关系

报道了用IAS4图像分析系统研究聚丙烯材料的聚集态结构 ,表明用图像分析仪可定量表征结晶型聚合物材料球晶和第二相颗粒在基体中的形态 .通过材料聚集态结构的定量测定 ,对材料性能的变化可作出满意的解释 ,是研究结晶型高聚物结构与性能关系的有效手段     

插层聚合聚丙烯-蒙脱土纳米复合材料的微观结构形态

使用偏光显微镜，扫描电镜，透射电镜和广角X射线衍射法研究了插层聚合法制备的聚丙烯－蒙脱土（PP－MMT）纳米复合材料的微观结构和形态发展。结果表明，随着插层聚合反应的进行，较大的初级MMT粒子逐渐剥离成较小的次级粒子。次级粒子由2－20片的单个MMT片层组成，其层间充满了PP分子链。提出了插层聚合过程中PP－MMT复合材料的形态发展模型。另外，MMT的加入对PP的球晶形态也有重要影响，PP完整的球晶随MMT的加入逐渐变小和趋于扭曲甚至破坏。     

The influence of nano‐PS particle on structure evolution and electrical properties of PP/PS

The polypropylene‐g‐polystyrene (PP‐g‐PS) copolymers with different grafting ratios are used as compatibilizers to control the size of polystyrene (PS) particles at nanometer scale in polypropylene (PP) matrix. Then the PP/PS insulating nanocomposites (containing 10 wt % PS calculated from PS and PP‐g‐PS) are manufactured. With the increase in grafting ratio of PP‐g‐PS, the size of PS particle is reduced and the interfacial adhesion is enhanced. Meanwhile, the dielectric properties, DC breakdown strength and volume resistivity are increased with the decreasing of PS particle size. The spherulite size of PP is decreased and the boundary between crystals and amorphous regions is blurred or even disappears due to the presence of PS nanoparticles. This evolution of PP structure is attributed to the serious entanglements of PP and PS molecular chains. Finally, the correlation between morphological structure and electrical properties is ultimately established based on the in‐depth understanding of the molecular chain movement, crystal structure, and phase morphology. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 706–717     

纳米刚性微粒与橡胶弹性微粒同时增强增韧聚丙烯的研究

通过力学性能测试、动态力学试验、ＤＳＣ 分析以及材料断面形貌与结构分析等手段,对以纳米二氧化硅（ＳｉＯ２） 为刚性微粒、以三元乙丙橡胶（ＥＰＤＭ） 为弹性微粒组成的聚丙烯（ＰＰ）／ 纳米ＳｉＯ２／ＥＰＤＭ 的同时增强增韧效果进行了研究．结果显示,上述两种微粒可同时大幅度提高ＰＰ 的韧性、强度和模量,当ＰＰ／ 纳米ＳｉＯ２／ＥＰＤＭ 为８０／３／２０ 时,两种微粒体现较明显的协同增韧效应．纳米ＳｉＯ２ 可提高ＰＰ 的结晶温度和结晶速度,并使球晶细化．纳米ＳｉＯ２ 刚性微粒在ＰＰ连续相中以微粒团聚体形态分布,构成团聚体的平均微粒数约为６ ～７ ,其与ＰＰ基体表现出较强的结合牢度．ＰＰ／ 纳米ＳｉＯ２／ＥＰＤＭ 的综合性能已接近或达到工程塑料的性能．