Viscoelastic behavior of polypropylene/nitrile rubber thermoplastic elastomer blends: Application of Kerner's models for reactively compatibilized and dynamically vulcanized systems

The viscoelastic properties of binary blends of nitrile rubber (NBR) and isotactic polypropylene (PP) of different compositions have been calculated with mean‐field theories developed by Kerner. The phase morphology and geometry have been assumed, and experimental data for the component polymers over a wide temperature range have been used. Hashin's elastic–viscoelastic analogy principle is used in applying Kerner's theory of elastic systems for viscoelastic materials, namely, polymer blends. The two theoretical models used are the discrete particle model (which assumes one component as dispersed inclusions in the matrix of the other) and the polyaggregate model (in which no matrix phase but a cocontinuous structure of the two is postulated). A solution method for the coupled equations of the polyaggregate model, considering Poisson's ratio as a complex parameter, is deduced. The viscoelastic properties are determined in terms of the small‐strain dynamic storage modulus and loss tangent with a Rheovibron DDV viscoelastometer for the blends and the component polymers. Theoretical calculations are compared with the experimental small‐strain dynamic mechanical properties of the blends and their morphological characterizations. Predictions are also compared with the experimental mechanical properties of compatibilized and dynamically cured 70/30 PP/NBR blends. The results computed with the discrete particle model with PP as the matrix compare well with the experimental results for 30/70, 70/30, and 50/50 PP/NBR blends. For 70/30 and 50/50 blends, these predictions are supported by scanning electron microscopy (SEM) investigations. However, for 30/70 blends, the predictions are not in agreement with SEM results, which reveal a cocontinuous blend of the two. Predictions of the discrete particle model are poor with NBR as the matrix for all three volume fractions. A closer agreement of the predicted results for a 70/30 PP/NBR blend and the properties of a 1% maleic anhydride modified PP or 3% phenolic‐modified PP compatibilized 70/30 PP/NBR blend in the lower temperature zone has been observed. This may be explained by improved interfacial adhesion and stable phase morphology. A mixed‐cure dynamically vulcanized system gave a better agreement with the predictions with PP as the matrix than the peroxide, sulfur, and unvulcanized systems. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1417–1432, 2004     

Toughness mechanism in polypropylene composites: Polypropylene toughened with elastomer and calcium carbonate

Polypropylene (PP) was modified with elastomer or CaCO₃ particles of two different sizes (1 μm and 50 nm) in various volume fractions. The dispersion morphology and mechanical properties of the two systems were investigated as functions of the particle size and volume fraction of the modifier. The brittle‐to‐tough transition occurred when the matrix ligament thickness was less than the critical ligament thickness, which was about 0.1 μm for the PP used here, being independent of the type of modifier. At the same matrix ligament thickness, the improvement of the toughness was obviously higher with the elastomer rather than with CaCO₃, but adding CaCO₃ increased the modulus of PP. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1656–1662, 2004     

Formation of β‐iPP in isotactic polypropylene/ethylene–propylene rubber blends: Effects of preparation method,composition, and thermal condition

The effects of preparation method, composition, and thermal condition on formation of β‐iPP in isotactic polypropylene/ethylene–propylene rubber (iPP/EPR) blends were studied using modulated differential scanning calorimeter (MDSC), wide angle X‐ray diffraction (WAXD), and phase contrast microscopy (PCM). It was found that the α‐iPP and β‐iPP can simultaneity form in the melt‐blended samples, whereas only α‐iPP exists in the solution‐blended samples. The results show that the formation of β‐iPP in the melt‐blended samples is related to the crystallization temperature and the β‐iPP generally diminishes and finally vanishes when the crystallization temperature moves far from 125 °C. The phenomena that the lower critical temperature of β‐iPP in iPP/EPR obviously increases to 114 °C and the upper critical temperature decreases to 134 °C indicate the narrowing of temperature interval, facilitating the formation of β‐iPP in iPP/EPR. Furthermore, it was found that the amount of β‐iPP in melt‐blended iPP/EPR samples is dependent on the composition and the maximum amount of β‐iPP formed when the composition of iPP/EPR blends is 85:15 in weight. The results through examining the effect of annealing for iPP/EPR samples at melt state indicate that this annealing may eliminate the susceptibility to β‐crystallization of iPP. However, only α‐iPP can be observed in solution‐blended samples subjected to annealing for different time. The PCM images demonstrate that an obvious phase‐separation happens in both melt‐blended and solution‐blended iPP/EPR samples, implying that compared with the disperse degree of EPR in iPP, the preparation method plays a dominant role in formation of β‐iPP. It is suggested that the origin of formation of β‐iPP results from the thermomechanical history of the EPR component in iPP/EPR. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1704–1712, 2007     

IMPROVED PROPERTIES OF METALLOCENE-CATALYZED LINEAR LOW-DENSITY POLYETHYLENE/POLYPROPYLENE BLENDS DURING ULTRASONIC EXTRUSION

Metallocene-catalyzed linear low-density polyethylene/polypropylene （mLLDPE/PP） blends were prepared by ultrasonic extrusion in this work. Their extrusion processing behaviors were estimated by online measured data, such as the die pressure and flow rate. Crystallization and mechanical properties of the blends were also investigated. The results show that the addition of PP improves the processing behaviors of mLLDPE, but has little effect on its mechanical properties. On the other hand, the addition of mLLDPE improves the impact strength of PP, but has little effect on its processing behavior. The processing behaviors and mechanical properties of mLLDPE/PP blends get further improved due to the presence of ultrasonic oscillation during extrusion. Compared with PP-rich blends, the apparent viscosity drop of mLLDPE-rich blends is more sensitive to ultrasonic oscillation. The ultrasonic oscillation affects the crystal nucleation, while barely the other crystalline behaviors of the blends.     

Application of the essential work of fracture concept to nanostructured polymer materials

The first part of the paper deals with a critical discussion of the methodical basis of essential work of fracture (EWF) concept with respect to the specimen geometry (especially the notch depth) and application to polymers. In the second part, an in situ testing device, which combines a tensile testing machine with an optical strain-field measuring system, has successfully demonstrated possibility of characterization of fracture behaviour of polystyrene-polybutadiene block copolymers and block copolymer/homopolymer blends as examples of nanostructured polymer materials. It has been shown that knowledge of the time evolution of the strain field close to the crack tips leads to a simple verification of the basic precondition for the applicability of the EWF concept, the precondition “plastic zone coalescence-before-stable crack propagation”.     

聚丙烯纤维辐射接枝进展

本文对聚丙烯纤维的辐射接枝方法、特征和机理、以及其研究进展和表征进行了扼要综述。     

Metallocene-mediated synthesis of chain-end functionalized polypropylene and application in PP/clay nanocomposites

This paper summarizes our research in the preparation of chain end functionalized isotactic polypropylene (PP) having a terminal functional group, such as Cl, OH, and NH₂. The chemistry involves metallocene-mediated propylene polymerization using rac-Me₂Si[2-Me-4-Ph(Ind)]₂ZrCl₂/MAO complex in the presence of styrene derivatives (St-f) and hydrogen, which serve as the chain transfer agents. The molecular weight of the resulting PP polymers with a terminal Cl, OH and NH₂ group (i.e., PP-t-Cl, PP-t-OH and PP-t-NH₂) are inversely proportional to the molar ratio of [St-f]/[propylene]. Despite the extremely low concentration of functional group, the high molecular weight chain end functionalized PP-t-OH and exhibit a distinctive advantage over other functional PP polymers containing side chain functional groups or long functional blocks. The terminal hydrophilic OH and cations, with good mobility and reactivity, effectively hydrogen bond and ion-exchange the cations (Li⁺, Na⁺, etc.) located between the clay interlayers, respectively. Such interactions anchor the PP chain to the clay surfaces. On the other hand, the remaining rest of the unperturbed end-tethered high molecular weight PP tail exfoliates the clay layers. This exfoliated structure is maintained even after further mixing of the PP-bearing platelets with pure neat PP polymers.     

PP/LDPE共混体系的辐射效应

研究了在多官能团单体—三烯丙基异氰脲酸酯存在下ＰＰ／ＬＤＰＥ共混体系接受γ－辐射的效果。用溶解度参数和ＴＥＭ技术评估了共混体系的相容性与多官能团单体在共混体系中的分布，并用ＳＥＭ、ＤＳＣ、动态力学等方法对共混体系相容性进行了表征。结果表明，ＰＰ／ＬＤＰＥ是不相容的共混体系，三烯丙基异氰脲酸酯主要分布在共混体系的相界面区域，辐照强化了共混体系的相间结合，增加了界面厚度，改善了共混体系的相容性。     

聚丙烯/纳米蒙脱土复合材料的结晶动力学研究

采用热分析方法，研究了聚丙烯／纳米蒙脱土复合材料（PP／CLAY）的等温结晶行为，并分别用Avrami方程和赵志英方法对所得数据进行了分析，研究结果表明，纳米蒙脱土微粒对聚丙烯等温和非等温结晶行为均有不同程度的影响，可提高聚丙烯的结晶速率并改善结晶结构。