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     

Preparation and properties of peroxide dynamically vulcanized polypropylene/ethylene‐propylene‐diene monomer/zinc dimethacrylate thermoplastic olefin

Attempts were made to prepare the polypropylene (PP) /ethylene‐propylene‐diene monomer (EPDM) blends with zinc dimethacrylate (ZDMA) via peroxide dynamic vulcanization. PP was melt‐mixed with EPDM and ZDMA at different compositions (PP/EPDM/ZDMA, i.e., 70/30/0, 70/30/3, 70/30/6, and 70/30/9, w/w/w) using an internal mixer at 50 rpm rotor speed. The addition of ZDMA improved the rheological properties of the resulting materials in the melt state. The morphological studies revealed that the addition of ZDMA led to an improvement of size reduction and distribution uniformity for crosslinked EPDM phase. ZDMA showed a positive effect on the mechanical properties of the PP/EPDM/ZDMA composites, particularly on the toughness and extensibility. With the incorporation of ZDMA, the izod impact strength and the elongation of PP/EPDM/ZDMA composites increased from 41 kJ/m² to 72 kJ/m² and 110% to 495%, respectively. The crystallization behaviors analysis indicated that the addition of ZDMA promoted the nucleation process of PP but the crystallinity of the PP phase was decreased at the meantime. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Morphological structure and surface properties of maleated ethylene propylene diene monomer/organoclay nanocomposites

The phase morphology and surface properties of some maleated ethylene propylene‐diene/organoclay nanocomposites (EPDM‐g‐MA/OC) were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and contact angle measurements. The effect of organoclay and/or compatibilizing agent [maleic anhydride‐grafted polypropylene (PP‐g‐MA)] on the properties of the EPDM‐g‐MA nanocomposites was investigated. The quality and uniformity of nanoclay dispersion were analyzed by SEM and AFM images. The experimental results showed an intercalate structure and biphasic morphology for the binary blends based on EPDM and clay. The surface properties of the studied composites are significantly influenced by the presence of a compatibilizing agent—PP‐g‐MA. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Study on the morphology,static and dynamic mechanical properties of (styrene butadiene rubber/ethylene propylene diene monomer/organoclay) nanocomposites vulcanized by the gamma radiation

Blends of styrene‐butadiene rubber/ethylene–propylene‐diene monomer (SBR/EPDM) with and without organoclay (OC) were prepared by melt mixing method. Then the samples were vulcanized by gamma radiation in comparison to conventional sulfur curing system. Characterization by X‐ray diffraction analysis, atomic force microscopy, and Field emission scanning electron microscopy revealed the intercalation structure and good dispersion of the OC in prepared nanocomposites. In addition to this, by increasing the absorbed dose of radiation and using OC, reduction in solvent uptake, increase in crosslink density and improvement of mechanical and dynamic–mechanical properties were observed. Comparison of the tensile strength of irradiated nanocomposite with the sulfur cured one's displayed the synergistic effect of the OC and gamma radiation on tensile properties of SBR/EPDM blend. Mooney–Rivlin plot confirmed the increase in crosslink density and interaction between rubbers due to presence of OC and increasing absorbed dose. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43581.     

Effects of the compatibilizer structural parameters on microstructural formation in ethylene–propylene–diene monomer rubber/ethylene–propylene–diene monomer rubber‐g‐maleic anhydride/organoclay nanocomposites

Nanocomposite vulcanizates based on ethylene–propylene–diene monomer rubber (EPDM) and organically modified montmorillonite with improved mechanical and barrier properties were prepared via a melt‐mixing process in the presence of maleic anhydride grafted ethylene–propylene–diene monomer rubber (EPDM‐g‐MAH) as an interfacial compatibilizer. The effects of the EPDM Mooney viscosity as the matrix and also the compatibilizer molecular weight and its maleation degree on the developed microstructure were also studied. The annealing of the vulcanized nanocomposites based on a low‐Mooney‐viscosity EPDM matrix and low‐Mooney‐viscosity EPDM‐g‐MAH enhanced the flocculation of the dispersed clay platelets; this implied that the flocculated structure for the clay nanolayers was more thermodynamically preferred in these nanocomposites. This was verified by the decrease in the oxygen permeability of the nanocomposite vulcanizates with increasing annealing time. The tendency of the clay nanosilicate layers to flocculate within the matrix of EPDM was found to be influenced by the clay volume fraction, the maleation degree, and also, the Mooney viscosity of the compatibilizer. Interfacially compatibilized nanocomposites based on high‐molecular‐weight EPDM exhibited a more disordered dispersion of the clay nanolayers, with a broadened relaxation time spectra; this was attributed to the higher shearing subjected to the mix during the melt‐blending process. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

三元乙丙橡胶/聚丙烯动态硫化热塑性弹性体的相态结构

用扫描电镜研究了三元乙丙橡胶(EPDM)聚/丙烯(PP)动态硫化热塑性弹性体(TPV)相态结构的形成过程,探讨了交联密度、制备工艺、螺杆转速对EPDM/PP TPV相态结构的影响。结果表明,采用以酚醛树脂为硫化剂的动态硫化工艺制备的EPDM/PP TPV,其相态结构实现了由EPDM和PP组成的双连续相到以EPDM为分散相、PP为连续相的转变;当硫化剂用量为7份时,橡胶相硫化速率和交联密度最大;当螺杆转速为180 r/m in时,反应性挤出工艺较之密炼机工艺制备的EPDM/PP TPV的橡胶粒子更细小、分散更均匀。     

Morphology and mechanical properties of polypropylene/organoclay nanocomposites

Polypropylene (PP) nanocomposites were prepared by melt intercalation in an intermeshing corotating twin‐screw extruder. The effect of molecular weight of PP‐MA (maleic anhydride‐ modified polypropylene) on clay dispersion and mechanical properties of nanocomposites was investigated. After injection molding, the tensile properties and impact strength were measured. The best overall mechanical properties were found for composites containing PP‐MA having the highest molecular weight. The basal spacing of clay in the composites was measured by X‐ray diffraction (XRD). Nanoscale morphology of the samples was observed by transmission electron microscopy (TEM). The crystallization kinetics was measured by differential scanning calorimetry (DSC) and optical microscopy at a fixed crystallization temperature. Increasing the clay content in PP‐ MA330k/clay, a well‐dispersed two‐component system, caused the impact strength to decrease while the crystallization kinetics and the spherulite size remained almost the same. On the other hand, PP/PP‐MA330k/clay, an intercalated three‐component system containing some dispersed clay as well as the clay tactoids, showed a much smaller size of spherulites and a slight increase in impact strength with increasing the clay content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1562–1570, 2002     

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     

Structure and mechanical properties of nanodispersed fibrous silicate‐reinforced ethylene–propylene–diene monomer nanocomposites

In this study, ethylene–propylene–diene monomer (EPDM)/fibrillar silicate (FS) nanocomposites were successfully prepared by mechanically blending EPDM with FS, which was modified by silane coupling agent KH570 containing methacryloxy group. The effects of silane content and modified FS on the dispersion of FS and mechanical properties of the composites were investigated. The impact of water in FS on mechanical properties of the composites was also evaluated. The results showed that modified FS could be dissociated into nanofibers dispersing evenly in the EPDM matrix by increasing substantially the loading of silane through the mechanical blending. The optimum loading level of silane coupling agent was up to 24 phr/100 phr FS. Silane KH570 could improve the dispersion of FS and strengthen nanofibers–rubber interfacial adhesion even at the loading of as high as 50 phr FS, making FS to exhibit excellent reinforcement to EPDM. Too much FS could not be completely dissociated into nanofibers, slowing down further improvement. The EPDM/FS composites exhibited the similar stress–strain behavior and obvious mechanical anisotropy with short microfiber‐reinforced rubber composites. With the increase in silane coupling agent and modified FS, the number of nanofibers increased because of the exfoliation of FS microparticles; thus, the mechanical behaviors would become more obvious. It was suggested that the free water in FS should be removed before mechanically blending EPDM with FS because it obviously affected the tensile properties of the composites. Regardless of whether FS was dried or modified, the EPDM/FS composites changed little in tensile strength after soaked in hot water. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of ethylene‐1‐butene copolymer on tensile properties and toughness of polypropylene/mica/organoclay hybrid nanocomposites

In this study, polypropylene (PP) was reinforced using 1 wt% organically modified‐grafted mica (OMGM) and various levels of Cloisite15A (C15A), 0–3 wt%. For OMGM preparation, polypropylene graft maleic anhydride (PP‐g‐MAH) was grafted onto diacetone acryl amid modified mica. The results showed the highest impact strength enhancement of 68% and Young's modulus of 12% for hybrid nanocomposite containing 1 wt% OMGM and 0.5 wt% C15A when compared to neat PP. In order to considerably improve the impact strength of PP with advantage of elastic modulus enhancement, PP was melt blended with above‐mentioned amounts of OMGM and C15A and different contents of ethylene‐1‐butene copolymer (EBR), 0–10 wt%. The dispersion of low‐ and high‐aspect ratio layered silicate tactoids and EBR nanoparticles in the polymer matrix was studied using transmission electron microscopy. The effect of EBR level on the crystallization behavior, tensile properties, impact strength, and fracture toughness of the resultant toughened hybrid nanocomposite was investigated. The presence of EBR nanoparticles did not show any sufficient effect on the melting and crystallization temperatures of the toughened PP and hybrid nanocomposites. However, the impact results indicated that the addition of EBR to neat PP remarkably increased the toughness while sharply decreased its Young's modulus. The incorporation of 7 wt% EBR in the hybrid nanocomposite containing 1 wt% OMGM and 0.5 wt% C15A considerably enhanced impact strength 119% and 30% in comparison to neat PP and its hybrid nanocomposite, respectively. Additionally, the incorporation of EBR nanoparticle in the presence of the silicate layered nanoparticles prevented significant decreasing in Young's modulus of the matrix. J. VINYL ADDIT. TECHNOL., 25:117–126, 2019. © 2018 Society of Plastics Engineers     

Investigation on morphology and mechanical properties of polyamide 6/maleated ethylene‐propylene‐diene rubber/organoclay composites

Maleated ethylene‐propylene‐diene rubber (EPDM‐g‐MA) toughened polyamide 6 (PA6)/organoclay (OMMT) nanocomposites were prepared by melt blending. The role of OMMT in the morphology of the ternary composites and the relationship between the morphology and mechanical properties were investigated by varying the blending sequence. The PA6/EPDM‐g‐MA/OMMT (80/20/4) composites prepared by four different blending sequences presented distinct morphology and mechanical properties. The addition of OMMT could obviously decrease viscosity of the matrix and weaken the interfacial interactions between PA6 and EPDM‐g‐MA when blending EPDM‐g‐MA with a premixed PA6/OMMT nacocomposite, resulting in the increase of rubber particle size. The final mechanical properties are not only determined by the location of OMMT, but also by the interfacial adhesion between PA6 and EPDM‐g‐MA. Having maximum percentage of OMMT platelets in the PA6 matrix and keeping good interfacial adhesion between PA6 and EPDM‐g‐MA are beneficial to impact strength. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

In situ reactive compatibilization and reinforcement of peroxide dynamically vulcanized polypropylene/ethylene‐propylene‐diene monomer tpv by zinc dimethacrylate

This work demonstrates an approach of in situ reactive compatibilization between polypropylene (PP) and ethylene‐propylene‐diene monomer (EPDM) by using ZDMA as a compatibilizer and, simultaneously, as a very strong reinforcing agent. With 7phr ZDMA in the PP/EPDM (30/70, w/w) thermoplastic vulcanizate (TPV), the tensile strength and elongation at break were increased from 5.3 MPa and 222% up to 11.2 MPa and 396%, respectively. Increasing the PP concentration further improved mechanical properties of the TPVs with ZDMA. This tremendous reinforcing as well as the compatibilization effect of the ZDMA was understood by polymerization of ZDMA and ZDMA reacting with EPDM and PP during peroxide induced dynamic vulcanization. A peculiar nano‐composite structure that the crosslinked rubber particles were “bonded” by a transition zone which containing numerous of nano‐particles with dimensions of about 20–30 nm was observed from transmission electron microscopy (TEM). Scanning electron microscopy (SEM) results showed that increase of PP/EPDM ratio reduced the size of crosslinked EPDM particles. Moreover, we found that the ZDMA reinforced EPDM particles resulted in a higher tan δ peak temperature for EPDM phase and built “filler‐filler”‐like networking in the PP melt. POLYM. COMPOS. 34:1357–1366, 2013. © 2013 Society of Plastics Engineers     

Comprehensively improved mechanical properties of silane crosslinked polypropylene/ethylene propylene diene monomer elastomer blends

The properties and structure of silane crosslinked polypropylene (PP)/ethylene propylene diene monomer (EPDM) elastomer blends had been carried out. Fourier transform infrared spectroscopy and gel content tests were employed to evaluate the crosslinking reaction of PP/EPDM blends. Crosslinking efficiency of PP/EPDM blends was investigated using thermogravimetric analysis, differential scanning calorimeter, dynamic mechanical analysis, dynamic rheology, and tensile testing. Tanδ curves of silane crosslinked PP/EPDM blends exhibited an obvious “gel point” originated from the formation of dynamic crosslinking network. The blend corresponding to the “gel point” presented comprehensively improved mechanical properties. These results demonstrated that characteristic rheological parameters showed close correlations with key mechanical properties of silane crosslinked PP/EPDM blends. Scanning electron microscopy images illustrated that crosslinking had remarkably changed the morphologies of PP/EPDM blends. The large deformation mechanism of these blends had been suggested.     

Study on the relaxation of polystyrene,ethylene–propylene diene monomer,and the blends of polystyrene with ethylene–propylene diene monomer by thermally stimulated current

A thermally stimulated current (TSC) was used to study the relaxation of polystyrene (PS), the ethylene–propylene diene monomer (EPDM), and the grafted copolymer of EPDM with styrene (EPDM-g-St). The effect of the measuring conditions on the relaxation of PS is discussed. Some relaxation parameters of PS, EPDM, and EPDM-g-St were calculated in two different ways. In addition, the TSC spectra of PS/EPDM and PS/EPDM-g-St showed that PS/EPDM was an immiscible system, but there existed a special interaction between the plastic phase and the rubber one in PS/EPDM-g-St blends. The compatibility of PS blends was evaluated in terms of their compositions. The results of inverse gas chromatography (IGC) agreed well with those of the TSC measurements. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1199–1204, 1998     

Dynamically vulcanized blends of polypropylene and ethylene‐octene copolymer: Comparison of different peroxides on mechanical,thermal, and morphological characteristics

Thermoplastic vulcanizates (TPVs) are prepared by the dynamic vulcanization process, where crosslinking of an elastomer takes place during its melt mixing with a thermoplastic polymer under high shear. TPVs based on polypropylene (PP) with different grades of ethylene‐octene copolymers (EOC) were prepared with a coagent assisted peroxide crosslinking system. The effect of dynamic vulcanization and influence of various types and concentrations of peroxide were mainly studied on the basis of the mechanical, thermal, and morphological characteristics. Three structurally different peroxides, namely dicumyl peroxide (DCP), tert‐butyl cumyl peroxide (TBCP), and di‐tert‐butyl peroxy isopropyl benzene (DTBPIB) were investigated. The mechanical properties of the TPVs are primarily determined by the extent of crosslinking in the EOC and the degree of degradation in the PP phase. Among all peroxides used DCP gives best overall properties with low‐molecular‐weight EOC, whereas TBCP shows best property level with high‐molecular‐weight EOC‐based TPVs. These can be explained on the basis of the molecular characteristics of EOC and the nature of the peroxide used. Differential scanning calorimetery (DSC) and morphological analysis reveal that PP and EOC are a thermodynamically immiscible system. The melting endotherm was studied to determine the influence of various peroxides on crystallinity of the PP phase. Tensile fracture patterns were also analyzed to study the failure mechanism of the samples. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

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     

Characteristics of ethylene propylene diene monomer rubber/organoclay nanocomposites resulting from different processing conditions and formulations

Several parameters which affect the nanocomposite formation in a sulfur‐cured ethylene propylene diene rubber (EPDM) containing 10 phr organoclay (montmorillonite modified with octadecylamine; MMT–ODA), were investigated. The parameters varied were linked to processing (mixer type, temperature) and rubber recipe (compatibilizer, accelerator). Increasing temperature and high shear mixing (internal mixer instead of open mill) improved the mechanical performance of the rubber nanocomposites. A more pronounced effect was achieved by using polar EPDM rubbers (maleic anhydride and glycidyl methacrylate grafted version) as compatibilizer. Among the accelerators, zinc diethyldithiocarbamate proved to be most suitable. The microstructure of the rubber/organoclay systems was studied by X‐ray diffraction, transmission electron microscopy and scanning electron microscopy. Organoclay intercalation/exfoliation was accompanied by its more or less severe confinement (reaggregation, deintercalation). This was traced to a partial or full removal of the ODA intercalant from the clay galleries via the formation of a zinc complex in which amine groups of the ODA and sulfur participated. Copyright © 2004 Society of Chemical Industry     

Structure and properties of peroxide dynamically vulcanized polypropylene/ethylene–propylene–diene/zinc dimethacrylate composites

Peroxide dynamically vulcanized thermoplastic olefin (TPO) based on polypropylene (PP)/ethylene–propylene–diene (EPDM) loaded with zinc dimethacrylate (ZDMA) was prepared. The addition of ZDMA improved the complex viscosity of the resulting materials in the melt state significantly, as determined from oscillatory rheology analyses. Dynamic mechanical analysis (DMA) and transmission electron microscopy (TEM) examinations were performed to evaluate the structure of the PP/EPDM/ZDMA composite. Atomic force microscope (AFM) and scanning electron microscopy (SEM) were used to study the morphology. The degree of crystallinity was evaluated using X‐ray diffraction method (XRD). The results revealed that incorporation of ZDMA resulted in a size reduction of the rubber droplets and improved the compatibility between rubber and PP phases. The nanoparticles of the polymerized ZDMA (PZDMA) served as an effective nucleating agent for the crystallization of PP. The rheological properties and mechanical properties were improved by ZDMA. Particularly, the izod impact strength of the PP/EPDM/ZDMA (80/20/6, w/w) composite is nearly 2 times higher than the PP/EPDM (80/20, w/w) and 12 times higher than the PP; besides, the elongation at break of the PP/EPDM/ZDMA (80/20/6, w/w) is 3 times higher than that of the PP/EPDM (80/20, w/w) and 6 times higher than the PP. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers