Effects of ultrasonic oscillation on processing behaviors of PS,EPDM, and PS/EPDM blend

In this study, the extrusion processing behaviors of polystyrene (PS), ethylene–propylene–diene terpolymer (EPDM), and their blend (PS/EPDM, 80/20) were studied by using a special ultrasonic oscillation extrusion system developed in our laboratory. The die pressure and volume flow rate were measured at different ultrasonic intensities and screw rotation speeds. The dependences on ultrasonic intensity of die pressure, volume flow rate, and apparent viscosity of polymers, as well as die swell at the same screw rotation speed were investigated. The effects of screw rotation speed on the processing behaviors of polymers and their blend at the same ultrasonic intensity were also studied. The experimental results showed that in the presence of ultrasonic irradiation, the processibilities of polymers and their blend were improved. Their possible mechanism is discussed in this article. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1856–1863, 2006     

Carbon black‐reinforced dynamically cured EPDM/PP thermoplastic elastomers. I. Morphology,rheology, and dynamic mechanical properties

The structure development, rheological behavior, and viscoelastic properties of carbon black‐filled dynamically vulcanized thermoplastic elastomers based on the ethylene–propylene–diene terpolymer (EPDM) and polypropylene (PP) with the ratio range of 50/50 to 80/20 were studied and compared with similar but unfilled samples. Two‐phase morphology was observed at all ratios for the dynamically cured samples in which rubber particles are dispersed in the thermoplastic matrix. Carbon black distribution in each phase and damping behavior was found to be dependent upon the mixing condition and route of carbon black feeding. However, carbon black tends to stay mainly in the rubber phase, which leads to increase in the viscosity difference and, therefore, increase in the rubber particle size. Tensile strength and rupture energy increased with carbon black loading. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1127–1137, 2000     

EPDM／PP共混物的形态结构与性能

用透射电镜分析比较了EPDM／PP共混物硫化前后的形态结构及力学和加工性能,讨论了共混设备、硫化体系对EPDM／PP共混物硫化前后形态结构及力学与加工性能的影响,揭示了共混物形态结构与力学及加工性能的关系。     

Dynamic mechanical properties of polypropylene‐g‐maleic anhydride and ethylene–propylene–diene terpolymer blends: Effect of blend preparation methods

In this work, we attempted two different ways of processing to improve interfacial adhesion of polypropylene (PP) and ethylene–propylene–diene terpolymer (EPDM) by introducing maleic anhydride (MAH); In one way, the in situ grafting and dynamic vulcanization (ISGV) were performed simultaneously from PP and EPDM with MAH in the presence of dicumyl peroxide (DCP) in an intensive mixer. In another way, PP was first grafted with MAH and then the PP‐g‐MAH was blended with EPDM in the intensive mixer in the presence of DCP by the dynamic vulcanization (DV). It was found that the glass transition temperatures (T_gs) of both PP and EPDM phases were shifted to higher temperature as the EPDM content increased for the blends prepared by both IGSV and DV methods, mainly due to the crosslinking of EPDM. The higher T_gs and larger storage moduli were observed for the blends prepared by the ISGV method than those prepared by the DV method, while the morphology showed that the size reduction of dispersed particles in latter blends was larger than that of the former blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2777–2784, 2000     

动态硫化SBR/PP共混物力学性能的研究

研究了不同共混比,不同类型SBR及不同硫化体系对动态硫化SBR／PP共混物力学性能的影响,试验结果表明,SBR／PP共混物的最佳共混比为60／40,E－SBR／PP共混物的力学性能稍好于S－SBR／PP共混物;采用硫黄硫化体系的共混物的力学性能优于采用过氧化物和酚醛树脂硫化体系的共混物;动态硫化SBR／PP共混物的交联密度低于静态硫化SBR母炼胶的交联密度。     

Determination of monomer sequence distribution in EPDM by 13C‐NMR: Third monomer effects

The methods for sequencing ethylene–propylene copolymers (EPMs) by ¹³C‐NMR were extended to account for third monomer effects. The equations for calculating the ethylene content and monomer sequence distribution in EPMs were corrected for the presence of the third monomers 1,4 hexadiene, 2‐ethylidene‐5‐norbornene, and 5,8‐dicyclopentadiene that display resonances that overlap with the main chain EPM carbons. These corrections dramatically reduce the standard deviation among equivalent calculation methods. We also examined the effects of experimental conditions on the sequencing data including the choice of solvent, Cr³⁺ doping, and the presence of the nuclear Overhauser effect. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 523–530, 1999     

交联剂对动态硫化PP／EPDM中PP晶体及EPDM形态结构的影响

针对ＰＰ／ＥＰＤＭ动态硫化中有机过氧化物交联剂Ａ用量对试样拉伸,弯曲和冲击等性能所产生的较大的影响,采用偏光显微镜研究了不同交联剂Ａ用量下动态硫化ＰＰ／ＥＰＤＭ中连续相ＰＰ的晶体结构和分散相ＥＰＤＭ的形态结构特征。     

Effect of hot air aging on properties of EPDM/SmBO3/EVA and EPDM/ATO/EVA composites

Ethylene–propylene–diene rubber (EPDM)/samarium borate (SmBO₃)/ethylene‐vinyl acetate (EVA) copolymer and EPDM/antimony‐doped tin oxide (ATO)/EVA composites are aged at 150°C for different intervals. Surface modification is used to improve filler to matrix interphase. The main aim is to investigate the effect of filler type and vinyl acetate (VA) content in EVA on stability of EPDM composites. It is found that acidic ATO particles can lower pH level of EPDM composites and then promote the degradation of acetic acid during aging. Moreover, when VA content exceeds 14 wt %, the instable VA content causes more acetic acids escape during aging. With the increasing of aging time, EPDM/SmBO₃ control and EPDM/SmBO₃/EVA composites tend to become darker while EPDM/ATO and EPDM/ATO/EVA composites would become yellow. And the color change is correlated well with the variation of carbonyl index. The chemical crosslink points prevent crystals in EVA from melting at aging temperature (150°C), and the variation of crosslink density influences the crystallinity during aging. The tendency of tensile strength is well consistent with that of swelling ratios, and electric properties are correlated with increased polar groups and crystallinity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Optimized processing conditions for the preparation of dynamically vulcanized EPDM/PP thermoplastic elastomers containing PP resins of various melt indexes

We have investigated the mechanical and morphological properties of un‐vulcanized and dynamically vulcanized ethylene propylene diene terpolymer/polypropylene (EPDM/PP) thermoplastic elastomers prepared under various processing conditions and possessing various compositions. After melt‐blending EPDM and PP resins twice in a twin‐screw extruder, the values of tensile strength (σ_f) of the un‐vulcanized EPDM/PP samples were at most equal to that of the pure EPDM specimen, but were much lower than those of the pure PP specimens. The elongations at break (ε_f) of the un‐vulcanized EPDM/PP samples were, however, dramatically higher than those of their respective virgin PP resins, and they improved significantly upon increasing the shear viscosity (η_s) of the PP resins. The tensile properties of the dynamically vulcanized EPDM/PP samples were significantly better than those of the corresponding un‐vulcanized EPDM/PP specimens. Similar to the behavior of the un‐vulcanized EPDM/PP specimens, the tensile properties of the dynamically vulcanized EPDM/PP specimens were optimized when prepared at a screw rate of 115 rpm. Morphological analysis revealed that the un‐vulcanized and dynamically vulcanized EPDM/PP specimens both featured many EPDM domains finely dispersed in continuous PP matrices. Such domains were present on the surfaces of the dynamically vulcanized EPDM/PP specimens; the relative sizes of the vulcanized EPDM domains were minimized when the vulcanized EPDM/PP specimens were prepared at the optimal screw rate (115 rpm). In fact, under these conditions, the average sizes of the vulcanized EPDM domains decreased upon increasing the values of η_s of the PP resins used to prepare the vulcanized EPDM/PP specimens. To understand these interesting tensile and morphological properties of the un‐vulcanized and dynamically vulcanized EPDM/PP specimens, we measured the rheological properties of the base polymers and performed energy‐dispersive x‐ray (EDX) analyzes of the compositions of the un‐vulcanized and dynamically vulcanized EPDM/PP specimens. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of cashew nut shell liquid as a plasticizer on cure characteristics,processability, and mechanical properties of 50 : 50 NR/EPDM blends: A comparison with paraffin oil

50 : 50 natural rubber (NR) and ethylene–propylene–diene monomer rubber (EPDM) blends were prepared with different contents of cashew nut shell liquid (CNSL), a natural product obtained from the shells of the cashew nut, as a plasticizer. For comparison, a commercial paraffin oil plasticizer was also used. The effect of plasticizer content on the cure characteristics, processability, and mechanical properties such as tensile strength, elongation at break, and Young's modulus before and after ageing was investigated. Scanning electron microscopy (SEM) was used to observe the blend morphology. The results indicated that the CNSL plasticizer resulted in lower Mooney viscosity and lower cure time of the 50 : 50 NR/EPDM blends. The incorporation of CNSL into 50 : 50 NR/EPDM blends improved tensile strength and elongation at break but decreased Young's modulus. On addition of CNSL the resistance of the blends to heat and weathering ageing improved. Scanning electron micrographs revealed that the morphology of the blend plasticized with CNSL is finer and more homogeneous compared with the blend plasticized with paraffin oil. Overall results indicate that CNSL can be used as a cheaper plasticizer to replace paraffin oil in NR/EPDM blends with improved processability and mechanical properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

PP-g-MAH增容PP/PA 6的形态结构与流变性能

研究了用马来酸酐接枝聚丙烯（PP-g-MAH)来增容聚丙烯/聚酰胺6（PP/PA6）共混物的形态结构，探讨了PP-g-MAH增容PP/P6共混物的流动行为。结果表明，PP/PA6共混物为热力学不相容的海岛型两相结构，PP-g-MAH的加入改善了PA6与P宾相容性，使两相分散均匀。用PP-g-MAH为增容剂增容PP/PA6共混物，在加工成型温度下为非牛顿流体，在PP-g-MAH质量分数为10%，PP/PA6的配比为95：5-75：25，其流动行为可用T=1580γw^0.65模型描述。     

Synthesis and evaluation of high‐performance ethylene–propylene–diene terpolymer/organoclay nanoscale composites

The main objective of this study was to synthesize and characterize the properties of ethylene–propylene–diene terpolymer (EPDM)/clay nanocomposites. Pristine clay, sodium montmorillonite (Na⁺–MMT), was intercalated with hexadecyl ammonium ion to form modified organoclay (16Me–MMT) and the effect of intercalation toward the change in interlayer spacing of the silicate layers was studied by X‐ray diffraction, which showed that the increase in interlayer spacing in Na⁺–MMT by 0.61 nm is attributed to the intercalation of hexadecyl ammonium ion within the clay layers. In the case of EPDM/16Me–MMT nanocomposites, the basal reflection peak was shifted toward a higher angle. However, gallery height remained more or less the same for different EPDM nanocomposites with organoclay content up to 8 wt %. The nanostructure of EPDM/clay composites was characterized by transmission electron microscopy, which established the coexistence of intercalated and exfoliated clay layers with an average layer thickness in the nanometer range within the EPDM matrix. The significant improvement in thermal stability and mechanical properties reflects the high‐performance nanocomposite formation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2429–2436, 2004     

Morphology and properties of PP/EPDM binary blends and PP/EPDM/nano‐CaCO3 ternary blends

In this article, the morphology, crystallization, and rheological behaviors of polypropylene (PP)/ethylene‐propylene‐diene terpolymer (EPDM) binary blend and PP/EPDM/calcium carbonate nanoparticles (nano‐CaCO₃) ternary blend were investigated. Two processing methods, i.e., direct extrusion and two‐step extrusion, were employed to prepare the PP/EPDM/CaCO₃ blend. The influence of EPDM and nano‐CaCO₃ respectively on phase morphology and properties of PP/EPDM blend and PP/EPDM/CaCO₃ blend were characterized by scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and dynamic rheometer. The crystallinity and crystallization temperature of PP/EPDM blend were improved in comparison to pure PP due to addition of EPDM, but kept invariable with the increased EPDM loading. As the EPDM content was increased, the mobility of PP molecular chains was weakened. Compared with direct extruded blend, less and finer nano‐CaCO₃ was dispersed in matrix of two‐step extruded blend. Accordingly, the increased nano‐CaCO₃ in matrix gave rise to a weaker increment in crystallinity and crystallization temperature of two‐step extruded blend, and a later platform of tanδ curve. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

聚对苯二甲酸乙二酯/聚丙烯不相容共混体系的结构流变学

通过熔融共混制备了不相容的聚对苯二甲酸乙二醇酯（PET）/聚丙烯（PP）复合体系,研究了复合体系的结构流变学。结果表明,PET/PP共混体系的不相容相形态显著影响其稳态和动态流变行为。当PP组分为分散相时,复合体系表现出动态形状松弛;当两组分呈多种相形态共存时,复合体系表现出强烈的低频区弹性响应;而当PET组分为分散相时,复合体系的剪切敏感性则相对较小。在较高剪切应力作用下,分散相液滴的凝聚是影响体系流变行为的控制因素,而在较低的剪切应力作用下,液滴的破碎则成为控制因素。     

EPDM/PP共混型热塑性硫化胶的增容研究

研究了酚醛树脂接枝改性聚丙烯(PP-g-MP)和马来酸酐接枝改性茂金属乙烯-辛烯共聚物(EOC-g-MAH)对动态硫化EPDM/PP共混型热塑性硫化橡胶(TPV)的增容作用,探讨了增容剂对TPV的物理机械性能、形态结构和流变性能的影响。结果表明,PP-g-MP能够提高EPDM/PPTPV的100%定伸应力和拉伸强度,但扯断伸长率下降;适量的EOC-g-MAH能够提高EPDM/PPTPV的拉伸强度和扯断伸长率,但100%定伸应力下降。接枝率越高,TPV的拉伸强度和扯断伸长率也越高。通过相差显微镜分析表明,加入增容剂有助于橡胶粒子的更精细、更均匀地分散,EOC-g-MAH的增容作用更佳。加入EOC-g-MAH后TPV的切敏性更显著。     

PP/EPDM热塑性弹性体结晶与熔融行为研究

采用动态光交联法制备了PP／EPDM[聚丙烯／（乙烯／丙烯／二烯）共聚物]热塑性弹性体。运用广角X射线衍射（WAXD），偏光显微镜（POM）与差示扫描量热仪（DSC）对PP的结晶形态及结晶与熔融行为进行表征。结果表明，EPDM的加入妨碍PP形成完善的球晶，而动态光交联体系中PP的球晶更不完善；动态光交联对PP的结晶温度及熔点影响不大，结晶度低于未交联体系的。     

Effects of blend composition and dynamic vulcanization on the morphology and dynamic viscoelastic properties of PP/EPDM blends

The morphology and dynamic viscoelastic properties of isotactic polypropylene (PP) blended with oil-free/oil-extended ethylene–propylene–diene (EPDM) rubbers were studied. Unvulcanized and dynamically vulcanized blends with the compositions PP/EPDM = 50/50 and = 30/70 were investigated. The morphology was observed by phase contrasted atomic force microscopy. The dynamic viscoelastic properties were determined with a rheometer of plate–plate configuration. It was shown that the rheological behavior was strongly affected by both the composition and the morphology of the blends. Significant improvement in the flowability of the dynamically vulcanized blends was observed when oil-extended EPDM was used instead of the oil-free version. It was demonstrated that the rheological properties are mostly controlled by the elastomer phase at low frequencies, while in the high-frequency range the influence of PP becomes dominant. The peculiarities in the rheological behavior of the thermoplastic elastomers (uncured blends, TPE) and thermoplastic dynamic vulcanizates (TPV, dynamically cured blends) containing oil-extended EPDMs were traced to a limited compatibility between the PP and EPDM components in the melt. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Characterization of phase morphology of polymer melts (PP/PE blends) via rheology

The viscoelastic behavior of high impact polypropylene (PP) melts, a multiphase system with an isotactic PP matrix and inclusions consisting of mainly amorphous ethylene–propylene copolymer (EP), is strongly influenced by the size of small inclusions. The dynamic moduli of such two‐phase systems (reactor products) are well described by Palierne's emulsion model. For this analysis the reactor product is separated into matrix and dispersed phase via the different solubility in xylene. This analysis also provides information on the ratio interfacial tension to particle size of the dispersed phase. With morphology data (particle size) of the solidified heterophasic samples (Transmission Electron Microscopy), we estimate the interfacial tension between PP and EP copolymer via the emulsion model of Palierne and from the relaxation time spectra according to Gramespacher and Meissner. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Mechanism of morphology development in dynamically cured EPDM/PP TPEs. I. Effects of state of cure

Attempts were made to follow and correlate morphological development with the crosslinking density, or state of cure (SOC), and the surface tension (γ) of the rubber phase in dynamically cured thermoplastic elastomers (TPEs) based on ethylene propylene diene rubber and polypropylene (PP) with 60/40 (w/w) ratios. Samples were taken from a hot running mixer without interruption and quickly quenched in liquid nitrogen both before and after the onset of vulcanization at various SOCs to carry out this process. The quick cooling of the samples prevented the coalescence and agglomeration of the dispersed rubber particles. A two‐phase morphology with the rubber particles dispersed throughout the PP matrix was observed for the uncured but frozen samples, whereas unfrozen blend samples showed a particulate cocontinuous morphology in the uncured state. An increase in the mixing torque with the SOC was observed after the addition of a curing system. This was understood to be caused by the increase in the rubber crosslinking density and also by the enhancement of the interfacial adhesion between the cured rubber phase and the PP matrix, leading to the better wetting of the two phases. Above a certain crosslinking density (SOC), γ of the rubber particles decreased through elastic shrinkage. This phenomenon, together with the breakdown of the agglomerate structure formed by the cured rubber particles, led to a decrease in the mixing torque after a maximum was passed and, finally, to a defined morphology. Based on the obtained results, a four‐stage model is proposed to describe the microstructural development in dynamically vulcanized TPEs. Dynamic mechanical thermal analysis and differential scanning calorimetry results are also used to support the model. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2531–2544, 2001     

热处理对PP/PET共混体系结晶及力学性能的影响

研究了热处理对聚丙烯(PP)/聚对苯二甲酸乙二酯(PET)共混体系结晶、熔融行为及力学性能的影响。结果表明适当地对共混体系进行热处理,可有效改善材料的拉伸性能及弯曲性能,拉伸强度及弯曲强度最大增幅分别可达13%和33%。PP/PET共混体系力学性能的增加在于体系中聚合物结晶结构的完善、结晶度的提高以及热应力的消除,其中,PP的结晶度变化较大,由处理前的37.1%增加到处理后的52.1%。