Effect of dynamic cross‐linking on melt rheological properties of polypropylene/ethylene‐propylene‐diene rubber blends

Study of melts rheological properties of unvulcanized and dynamically vulcanized polypropylene (PP)/ethylene‐propylene‐diene rubber (EPDM) blends, at blending ratios 10–40 wt %, EPDM, are reported. Blends were prepared by melt mixing in an internal mixer at 190°C and rheological parameters have been evaluated at 220°C by single screw capillary rheometer. Vulcanization was performed with dimethylol phenolic resin. The effects of (i) blend composition; (ii) shear rate or shear stress on melt viscosity; (iii) shear sensitivity and flow characteristics at processing shear; (iv) melt elasticity of the extrudate; and (v) dynamic cross‐linking effect on the processing characteristics of the blends were studied. The melt viscosity increases with increasing EPDM concentration and decreased with increasing intensity of the shear mixing for all compositions. In comparison to the unvulcanized blends, dynamically vulcanized blends display highly pseudoplastic behavior provides unique processing characteristics that enable to perform well in both injection molding and extusion. The high viscosity at low shear rate provides the integrity of the extrudate during extrusion, and the low viscosity at high shear rate enables low injection pressure and less injection time. The low die‐swell characteristics of vulcanizate blends also give high precision for dimensional control during extrusion. The property differences for vulcanizate blends have also been explained in the light of differences in the morphology developed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1488–1505, 2000     

Effect of dynamic crosslinking on impact strength and other mechanical properties of polypropylene/ethylene‐propylene‐diene rubber blends

The deformation and fracture behavior of several dynamic vulcanizate blends of isotactic polypropylene with ethylene‐propylene‐diene rubber (EPDM) was examined and compared with those of uncrosslinked blends of PP/EPDM. These blends were prepared by melt mixing in an internal mixer at 190°C in a composition range of 10–40 wt % EPDM rubber. The variation in yield stress, the strength of fibrils of the craze, and the number density of the EPDM rubber domains (morphology fixation) that are dominant factors for enhancing interfacial adhesion and toughness in dynamic vulcanizate blends were evaluated. The ductility and toughness of these materials were explained in light of the composition between crack formation and the degree of plastic deformation through crazing and shear yielding. The physicomechanical properties including the hardness, yield stress, Young's modulus, percentage elongation, impact strength, flexural strength, and flexural modulus of dynamic vulcanized blends were found to be consistent and displayed higher values compared with uncrosslinked blends. The nucleation effect of the crosslinked particles and the decrease of crystallinity of the EPDM rubber were also considered to contribute to the improvement in the impact strength. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2089–2103, 2000     

Miscibility of blends of ethylene‐propylene‐diene terpolymer and polypropylene

The miscibility of polymers is not only an important basis for selecting a proper blending method, but it is also one of the key factors in determining the morphology and properties of the blends. The miscibility between ethylene‐propylene‐diene terpolymer (EPDM) and polypropylene (PP) was explored by means of dynamic mechanical thermal analysis, transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). The results showed that a decrease in the PP content and an increase of the crosslinking density of EPDM in the EPDM/PP blends caused the glass‐transition temperature peaks of EPDM to shift from a lower temperature to higher one, yet there was almost no variance in the glass‐transition temperature peaks of PP and the degree of crystallinity of PP decreased. It was observed that the blends prepared with different mixing equipment, such as a single‐screw extruder and an open mill, had different mechanical properties and blends prepared with the former had better mechanical properties than those prepared with the latter. The TEM micrographs revealed that the blends were composed of two phases: a bright, light PP phase and a dark EPDM phase. As the crosslinking degree of EPDM increased, the interface between the phases of EPDM and PP was less defined and the EPDM gradually dispersed in the PP phase became a continuous phase. The results indicated that EPDM and PP were both partially miscible. The mechanical properties of the blends had a lot to do with the blend morphology and the miscibility between the blend components. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 315–322, 2002     

Thermal and mechanical properties of silicon rubber/cis‐polybutadiene rubber/ethylene–propylene–diene monomer blends

Considering the properties of silicon rubber, ethylene–propylene–diene monomer (EPDM), and cis‐polybutadiene rubber (BR), a blend made by a new method was proposed in this article; this blend had thermal resistance and good mechanical properties. The morphology of the blend was studied by SEM, and it was found that the adhesion between the phases of BR, EPDM, and polysiloxanes (silicon rubber) could be enhanced, and the compatibility and covulcanization were good. The influence of the mass ratio of peroxide and silica on the mechanical properties and thermal resistance of the blend was studied. The results showed that the mechanical properties and thermal resistance of the blend were improved when silicon rubber/BR/EPDM was 20/30/50, dicumyl peroxide/sulfur was 2.5/2.5, and the amount of silica was 80 phr. The integral properties of rubber blend had more advantages than did the three rubbers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4462–4467, 2006     

Physical and mechanical behavior of single‐walled carbon nanotube/polypropylene/ethylene–propylene–diene rubber nanocomposites

The effects of the incorporation of single‐walled carbon nanotubes (SWNTs) on the physical and mechanical properties of thermoplastic elastomers based on blends of isotactic polypropylene (iPP) and ethylene–propylene–diene rubber (EPDM) are described. A marked decrease of the half‐time of PP–EPDM crystallization and a sensible increase of the overall crystallization rate were observed in the presence of SWNTs. These results confirmed the expected nucleant effect of nanotubes on the crystallization of polypropylene. This effect was not linearly dependent on the SWNTs' content, showing a saturation of the nucleant effect at high nanotube concentrations. Dynamic mechanical analysis results showed a significant and controversial change of the mechanical behavior of the PP–EPDM/SWNT composites depending on the nanotube content. In particular, the storage modulus increased at the lowest incorporation of SWNTs, whereas a further increase of nanotubes led to a reduction of the storage modulus with respect to the pristine polymer matrix. Raman spectroscopy and scanning electron microscopy were successfully applied to demonstrate that in the composite films, the changes in the crystallization kinetics and mechanical properties could be explained in terms of the changes of the distance between nanotubes in bundles after a different intercalation of the polymer matrix. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2657–2663, 2003     

Mechanical and morphological properties of white rice husk ash filled polypropylene/ethylene‐propylene‐diene terpolymer thermoplastic elastomer composites

The performance of white rice husk ash (WRHA) as filler for polypropylene (PP)/ethylene‐propylene‐diene terpolymer (EPDM) thermoplastic elastomer (TPE) composites was investigated. The composites with different filler loadings were prepared in a Brabender plasticorder internal mixer. Both unvulcanized and dynamically vulcanized composites were prepared. Mixing and vulcanization processes of the composites were monitored through the typical Brabender torque‐time curves. The mechanical properties and morphology of the composites were also studied. The Brabender torque curves revealed that the dynamic vulcanization process employed was successful and incorporation of filler has no adverse effect on the processibility of the composites. Incorporation of WRHA improves the tensile modulus and flexural modulus and lowers tensile strength, elongation at break, tear strength, and toughness of both types of composites. Dynamic vulcanization significantly enhances the mechanical and TPE properties of the composites. Dynamic mechanical analysis (DMA) study revealed the existence of two phases in both types of composites. It further shows that neither dynamic vulcanization nor filler agglomeration has played a prominent role in the compatibility of the composites. Thermogravimetric investigation shows that dynamic vulcanization or WRHA loading has not adversely affected the thermal stability of the composites. The scanning electron micrographs provide evidence for the tendency to form filler agglomerates with increasing filler loading, better filler dispersion of dynamically vulcanized composites over unvulcanized composites, and effective vulcanization of elastomer phase of the composites in the presence of filler. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 438–453, 2002     

Influence of processing conditions on dual‐phase continuous blend system of thermoplastic polyurethane with ethylene‐propylene‐diene monomer elastomer

In the present work, we extend the investigation on the influence of processing conditions on the morphology, the mechanical properties, and the rheology of the blends of thermoplastic polyurethane (TPU) and ethylene–propylene–diene monomer elastomer (EPDM). Scanning and transmission electron microscopies show that the dual‐phase continuous morphology of the blends was strongly dependant on the EPDM composition, processing temperature, and the shear rates. The network structure of the EPDM domain in TPU matrix became finest and most regular for the blends containing 7 wt % EPDM. It was also found that high shear rate favored the formation of the perfect network structure. Furthermore, the blends prepared at 180°C present finer and more perfect network structure than those at the other processing temperatures. The competition of compatible and incompatible segments of TPU with EPDM during melt blending plays an important role in development of the dual‐phase continuous morphology. This was reflected through the influence of processing conditions on the rheological properties, and was also verified by the Davies equation's prediction. The tensile properties present a significant improvement with addition of EPDM, and obtained the optimum value for the blends containing 7 wt % EPDM. The influence of different processing parameters on the mechanical properties is associated with their influence on the morphology, and better tensile properties are obtained in the processing conditions, in which, the finer and more perfect network structure of EPDM domain is presented. These facts confirm that the dual‐phase continuous morphology is the main advantage for higher tensile strength, elongation at break, and Young's modulus can be well controlled by different processing conditions for the improvement of mechanical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5472–5482, 2006     

Polyhydroxybutyrate/acrylonitrile‐g‐(ethylene‐co‐ propylene‐co‐diene)‐g‐styrene blends: Their morphology and thermal and mechanical behavior

Polyhydroxybutyrate (PHB) is a biodegradable bacterial polyester emerging as a viable substitute for synthetic, semicrystalline, nonbiodegradable polymers. An elastomer terpolymer of acrylonitrile‐g‐(ethylene‐co‐propylene‐co‐diene)‐g‐styrene (AES) was blended with PHB in a batch mixer and in a twin‐screw extruder to improve the mechanical properties of PHB. The blends were characterized with differential scanning calorimetry, dynamic mechanical analysis, scanning electron microscopy, and impact resistance measurements. Despite the narrow processing window of PHB, blends with AES could be prepared via the melting of the mixture without significant degradation of PHB. The blends were immiscible and composed of four phases: poly(ethylene‐co‐propylene‐co‐diene), poly(styrene‐co‐acrylonitrile), amorphous PHB, and crystalline PHB. The crystallization of PHB in the blends was influenced by the AES content in different ways, depending on the processing conditions. A blend containing 30 wt % AES presented impact resistance comparable to that of high‐impact polystyrene, and the value was about 190% higher than that of pure PHB. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of anhydride‐modified ethylene–propylene–diene rubber and ethylene–vinyl acetate copolymers on the compatibilization of nitrile rubber/ethylene–propylene–diene rubber blends

The effects of maleic anhydride modified ethylene–propylene–diene rubber (EPDMMA) and maleic anhydride modified ethylene–vinyl acetate (EVAMA) on the compatibilization of nitrile rubber (NBR)/ethylene–propylene–diene rubber (70:30 w/w) blends vulcanized with a sulfur system were investigated. The presence of EPDMMA and EVAMA resulted in improvements of the tensile properties, whereas no substantial change was detected in the degree of crosslinking. The blend systems were also analyzed with scanning electron microscopy and dynamic mechanical thermal analysis. The presence of EVAMA resulted in a blend with a more homogeneous morphology. The compatibilizing effect of this functional copolymer was also detected with dynamic mechanical analysis. A shift of the glass‐transition temperature of the NBR phase toward lower values was observed. The presence of EPDMMA and EVAMA also increased the thermal stability, as indicated by an improvement in the retention of the mechanical properties after aging in an air‐circulating oven. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2408–2414, 2003     

Dynamic mechanical and morphological behavior of blends of polystyrene and poly[acrylonitrile‐g‐(ethylene‐co‐propylene‐co‐diene)‐g‐styrene] prepared by in situ polymerization of styrene

PS/AES blends were prepared by in situ polymerization of styrene in the presence of AES elastomer, a grafting copolymer of poly(styrene‐co‐acrylonitrile) – SAN and poly(ethylene‐co‐propylene‐co‐diene)–EPDM chains. These blends are immiscible and present complex phase behavior. Selective extraction of the blends' components showed that some fraction of the material is crosslinked and a grafting of PS onto AES is possible. The morphology of the noninjected blends consists of spherical PS domains covered by a thin layer of AES. After injection molding, the blends show morphology of disperse elastomeric phase morphology in a rigid matrix. Two factors could contribute to the change of morphology: (1) the stationary polymerization conditions did not allow the mixture to reach the equilibrium morphology; (2) the grafting degree between PS and AES was not high enough to ensure the morphological stability against changes during processing in the melting state. The drastic change of EPDM morphology from continuous to disperse phase has as consequence a decrease in the intensity of the loss modulus peaks corresponding to the EPDM glass transition. However, the storage modulus at temperatures between the glass transition of EPDM and PS/SAN phases does not change significantly. This effect was attributed to the presence of the SAN rigid chains in the AES. © 2009 Wiley Periodicals, Inc. Journal of Applied Polymer Science, 2009     

Rheological behavior and processability of polypropylene blends with rubber ethylene propylene diene terpolymer

A study of the dynamic complex and steady shear viscosity of isotactic polypropylene (iPP), ethylene–propylene diene terpolymer rubber (EPDM) and three different blends of both polymers are presented over a range of temperatures and frequencies. Moreover, the processability of these materials is studied through torque measurements during blend mixing. The results obtained show that the viscosity gradually increases with rubber content in the blend and decreases with both temperature and frequency. Plots of η″ versus η′ (Cole–Cole plots) show that the blend with the lower rubber content (25%), has a certain rheological compatibility with neat PP. Furthermore, torque curves measured during blend mixing confirm these results, demonstrating that the blend with 25% of elastomer has a similar behavior of iPP during processing. To analyze the morphological structure of the blends, a dynamic mechanical analysis of the solid state is also presented. It is observed that the blends have two distinct values of T_g close to the corresponding values of the pure polymers, confirming that this type of blends based on a semicrystalline polymer and an amorphous elastomer forms a two‐phase system with a limited degree of miscibility between both components. In addition, the polymer present with the higher concentration forms the continuous phase and controls the rheological properties of the blend. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1–10, 2001     

Influence of the clay modification and compatibilizer on the structure and mechanical properties of ethylene–propylene–diene rubber/montmorillonite composites

Ethylene–propylene–diene rubber (EPDM)/montmorillonite (MMT) composites were prepared through a melt process, and three kinds of surfactants with different ammonium cations were used to modify MMT and affect the morphology of the composites. The morphology of the composites depended on the alkyl ammonium salt length, that is, the hydrophobicity of the organic surfactants. Organophilic montmorillonite (OMMT), modified by octadecyltrimethyl ammonium salt and distearyldimethyl ammonium salt, was intercalated and partially exfoliated in the EPDM matrix, whereas OMMT modified by hexadecyltrimethyl ammonium chloride exhibited a morphology in which OMMT existed as a common filler. Ethylene–propylene–diene rubber grafted with maleic anhydride (MAH‐g‐EPDM) was used as a compatibilizer and greatly affected the dispersion of OMMT. When OMMTs were modified by octadecyltrimethyl ammonium chloride and distearydimethyl ammonium chloride, the EPDM/OMMT/MAH‐g‐EPDM composites (100/15/5) had an exfoliated structure, and they showed good mechanical properties and high dynamic moduli. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 638–646, 2004     

Compatibilization of nitrile‐butadiene rubber/ethylene‐propylene‐diene monomer blends by mercapto‐modified ethylene‐vinyl acetate copolymers

Mercapto‐modified ethylene‐vinyl acetate (EVASH) has been employed as a reactive compatibilizing agent for nitrile‐butadiene rubber (NBR)/ethylene‐propylene‐diene monomer (EPDM) blends vulcanized with a sulfur/2,2′‐dithiobisbenzothiazole (MBTS) single accelerator system and a (sulfur/MBTS/tetramethylthiuram disulfide (TMTD) binary accelerator system. The addition of 5.0 phr EVASH resulted in a significant improvement in the tensile properties of blends vulcanized with the sulfur/MBTS system. In addition to better mechanical performance, these functionalized copolymers gave rise to a more homogeneous morphology and, in some cases, better aging resistance. The compatibilization was not efficient in blends vulcanized with the S/MBTS/TMTD binary system, probably because of the faster vulcanization process occurring in this system. The good performance of these EVASH samples as compatibilizing agents for NBR/EPDM blends is attributed to the higher polarity of these components that is associated with their lower viscosity. Dynamic mechanical analysis also suggested a good interaction between the phases in the presence of EVASH. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1404–1412, 2004     

Study of polypropylene/ethylene‐propylene‐diene monomer blends reinforced with sisal fibers

Thermoplastics reinforced with natural fibers have attracted much attention from researchers because of their advantages, especially regarding environmental aspects. However, poor impact strength, particularly at low temperatures, limits the application of some thermoplastics, such as polypropylene (PP). To minimize this drawback, impact modifiers have been used, including the terpolymer of ethylene‐propylene‐diene (EPDM). In this work, PP/EPDM/sisal composites of distinct compositions were investigated focusing on the effect of the alkali (NaOH) treatment of the vegetable fiber on the composites properties regarding physical, mechanical, thermal, and morphological behavior. The results indicated that flow rate decreases at higher fiber content due to flow hindering by the presence of the fibers. The addition of the fiber, in general, increased Young's modulus and strength (tensile and flexural), whereas impact strength increased for higher EPDM content. The alkali treatment was considered generally efficient in terms of mechanical properties, even though this was not found in the dynamic mechanical analysis. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Self‐reinforcing elastomer composites based on ethylene–propylene–diene monomer rubber and liquid‐crystalline polymer

In this study, the prime factor determining the size, shape, and distribution of liquid‐crystalline polymer (LCP) was the viscosity ratio at the processing conditions. The fiber‐forming capacity of the LCP depended on the viscosity of the ethylene–propylene–diene monomer rubber (EPDM). With increasing LCP content, the tensile and tear strengths did not increase, perhaps because of incompatibility between the EPDM and LCP. The hardness increased because of the hard mesogenic groups in the LCP. The percentage swelling decreased as the LCP content increased. With increasing LCP content, processability became easier because of a lower melt viscosity. The scorch time increased at higher LCP levels. A higher percentage crystallinity was observed with increasing LCP content. Scanning electron microscopy clearly showed the fiber phase formation, which was two‐dimensionally isotropic in nature, confirming fiber formation even in a shear field. The addition of LCP improved the thermal stability. The onset degradation temperatures shifted to higher values with increasing LCP content. Dynamic mechanical thermal analysis revealed that with the addition of LCP, the mechanical damping increased at its lower level. High‐temperature processing increased the effective amorphous zone. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 711–718, 2004     

Mechanism of toughening for polypropylene blended with ethylene–propylene–diene rubber following selective crosslinking

Toughening mechanism of polypropylene (PP) blended with ethylene–propylene–diene rubber (EPDM) following selective crosslinking was examined in comparison with that of blends of PP before crosslinking. The yield stress, strength of craze, and density of void which are dominant factors for enhancing toughness in PP blends were evaluated and the deformation and fracture mechanism was discussed. It was concluded that toughness of PP blended with EPDM is improved by selective crosslinking, since the improvement of the craze strength is greater than the drop in the release of the constraint of strain. © 1996 John Wiley & Sons, Inc.     

Silica‐reinforced dynamically vulcanized ethylene–propylene–diene monomer/polypropylene thermoplastic elastomers: Morphology,rheology, and dynamic mechanical properties

Attempts were made to prepare dynamically crosslinked ethylene–propylene–diene monomer/polypropylene (EPDM/PP, 60/40 w/w) blends loaded with various amounts of silica as a particulate reinforcing agent. The dispersion of silica between the two phases under mixing conditions, and also extent of interaction, as the two main factors that influence the blend morphology were studied by scanning electron microscopy. Increasing the silica concentration led to the formation of large‐size EPDM aggregates shelled by a layer of PP. Dynamic mechanical thermal analysis performed on the dynamically cured silica‐loaded blend samples showed reduction in damping behavior with increasing silica content. Higher rubbery‐like characteristics under tensile load were exhibited by the silica‐filled EPDM/PP‐cured blends. However, increasing the silica level to 50 phr led to the enhancement of interface, evidenced by increases in the tensile modulus and extensibility of the blend compared with those of the unloaded sample. Addition of a silane coupling agent (Si69) into the mix improved the mechanical properties of the blend, attributed to the strengthening of interfacial adhesion between the PP matrix and silica‐filled EPDM phase. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2000–2007, 2004     

Mechanical property and morphology comparison between the two blends poly(propylene)/ethylene‐propylene‐diene monomer elastomer and poly(propylene)/maleic anhydride‐g‐ethylene‐propylene‐diene monomer

The comparison of the mechanical properties between poly(propylene)/ethylene‐propylene‐diene monomer elastomer (PP/EPDM) and poly(propylene)/maleic anhydride‐g‐ethylene‐propylene‐diene monomer [PP/MEPDM (MAH‐g‐EPDM)] showed that the latter blend has noticeably higher Izod impact strength but lower Young's modulus than the former one. Phase morphology of the two blends was examined by dynamic mechanical thermal analysis, indicating that the miscibility of PP/MEPDM was inferior to PP/EPDM. The poor miscibility of PP/MEPDM degrades the nucleation effectiveness of the elastomer on PP. The observations of the impact fracture mode of the two blends and the dispersion state of the elastomers, determined by scanning electron microscopy, showed that PP/EPDM fractured in a brittle mode, whereas PP/MEPDM in a ductile one, and that a finer dispersion of MEPDM was found in the blend PP/MEPDM. These observations indicate that the difference in the dispersion state of elastomer between PP/EPDM and PP/MEPDM results in different fracture modes, and thereby affects the toughness of the two blends. The finer dispersion of MEPDM in the blend of PP/MEPDM was attributed to the part cross‐linking of MEPDM resulting from the grafting reaction of EPDM with maleic anhydride (MAH) in the presence of dicumyl peroxide (DCP). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2486–2491, 2002     

Properties of dynamically vulcanized ethylene–propylene–diene copolymer/polypropylene blends

In this study, vulcanized thermoplastic elastomers were produced through the formation of crosslinks with peroxide for different ratios of ethylene–propylene–diene copolymer to polypropylene. Mixing was performed with a twin‐screw extruder. Afterward, the yield, tensile strength, elastic modulus, elongation, Izod impact strength, hardness, melt flow index, Vicat softening point, heat deflection temperature, and density of the crosslinks were determined. The thermal transition temperatures and microstructure were determined with differential scanning calorimetry and scanning electron microscopy, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3895–3902, 2007     

Effect of melt flow on morphology and linear thermal expansion of injection‐molded ethylene–propylene–diene terpolymer/isotactic polypropylene blends

An ethylene–propylene–diene terpolymer/isotactic polypropylene blend with a structure of co‐continuous microlayers was fabricated by injection molding and was then investigated. The blend exhibited an extremely low coefficient of linear thermal expansion (CLTE) in the directions of the length and the width. As the thickness of the oriented portion increased, the CLTE was further reduced. The morphology of the co‐continuous microlayers and the thermal expansion behavior varied with the sampling positions on the injection‐molded sheets. To study the relationship between the morphology and the melt flow, the melt flow behavior during injection molding was simulated using Moldflow. Orientation of the microlayers was determined using shear flow. When the shear rate increased, the orientation state increased and the CLTE decreased. © 2015 Society of Chemical Industry