Natural rubber–ethylene‐propylene‐diene rubber covulcanization: Effect of reinforcing fillers

Filled covulcanizates of elastomer blend comprising natural rubber (NR) and ethylene‐propylene‐diene rubber (EPDM) of commercial importance were successfully prepared by using a multifunctional rubber additive; namely, bis(diisopropyl)thiophosphoryl disulfide (DIPDIS). A Two‐stage vulcanization technique further improved the physicochemical properties of the blend vulcanizates by restricting, through the formation of polar rubber bound intermediates, the migration of curative and filler from lower to highly unsaturated rubber. Scanning electron microscopy studies indicate homogeneity and coherency in the morphology of the two‐stage vulcanizates. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1001–1010, 2002; DOI 10.1002/app.10361     

Novel method for preparation of carboxylated nitrile rubber–natural rubber blends using bis(diisopropyl)thiophosphoryl polysulfides

Bis(diisopropyl)thiophosphoryl trisulfide (DIPTRI) and bis(diisopropyl)thiophosphoryl tetrasulfide (DIPTET) are successfully used as a novel coupling agent and accelerator, respectively, to covulcanize an elastomer blend comprising polar carboxylated nitrile rubber (XNBR) and nonpolar natural rubber (NR). These compounds are capable of forming a chemical link between these dissimilar rubbers to produce a technologically compatible blend as judged by a swelling experiment. The blend vulcanizates thus produced exhibit enhanced physical properties that can further be improved by adopting the two‐stage vulcanization technique and also by judicious selection of the NR:XNBR ratio. The blend morphology assessed by scanning electron microcroscopy micrographs accounts for significant improvement in the physical properties of the blend vulcanizates, particularly in two‐stage vulcanization. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1725–1736, 2001     

Dynamic mechanical analysis of ethylene–propylene–diene monomer rubber and styrene–butadiene rubber blends

The effects of blend ratio, crosslinking systems, and fillers on the viscoelastic response of ethylene–propylene–diene monomer (EPDM)/styrene–butadiene rubber (SBR) blends were studied as functions of frequency, temperature, and cure systems. The storage modulus decreased with increasing SBR content. The loss modulus and loss tangent results showed that the EPDM/SBR blend vulcanizate containing 80 wt % EPDM had the highest compatibility. Among the different cure systems studied, the dicumyl peroxide cured blends exhibited the highest storage modulus. The reinforcing fillers were found to reduce the loss tangent peak height. The blend containing 40 wt % EPDM showed partial miscibility. The dispersed EPDM phase suppressed the glass‐transition temperature of the matrix phase. The dynamic mechanical response of rubbery region was dominated by SBR in the EPDM–SBR blend. The morphology of the blend was studied by means of scanning electron microscopy. The blend containing 80 wt % EPDM had small domains of SBR particles dispersed uniformly throughout the EPDM matrix, which helped to toughen the matrix and prevent crack propagation; this led to enhanced blend compatibility. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of diisopropyl thiophosphoryl‐N‐oxydiethylene sulfenamide and some disulfidic compounds in the covulcanization of NR–EPDM blends

Synergistic combinations of diisopropyl thiophosphoryl‐N‐oxydiethylene sulfenamide (DIPTOS) with some disulfide accelerators or sulfur donors improve the physical properties of NR–EPDM blend vulcanizates. Various combinations of DIPTOS with dibenzothiazyl disulfide (MBTS), tetramethyl thiuram disulfide (TMTD), bis(N‐oxydiethylene) disulfide (ODDS) and bis(diisopropyl) thiophosphoryl disulfide (DIPDIS) were used in this study. DIPTOS when used alone produces NR vulcanizates with a moderate range of physical properties, whereas in conjunction with MBTS and DIPDIS it exhibits significant mutual activities. Morphological studies of the tensile‐fractured surfaces of the blend vulcanizates by scanning electron microscopy corroborate the physical data. Copyright © 2003 Society of Chemical Industry     

Microstructure and miscibility of acrylonitrile–butadiene rubber/ethylene–propylene–diene monomer blends studied by positron annihilation spectroscopy

The free‐volume properties and miscibility of ethylene–propylene–diene monomer/acrylonitrile–butadiene rubber blends with poly(vinyl chloride) used for compatibilization were investigated with positron annihilation lifetime spectroscopy and Doppler broadening of annihilation radiation. The results showed that the ortho‐positronium annihilation lifetimes and intensities as well as the S parameter had a linear relationship with a negative slope as a function of the weight percentage of acrylonitrile–butadiene rubber, which indicated the miscibility of the blend. The filling effect of silica on the free‐volume properties of an ethylene–propylene–diene monomer/acrylonitrile–butadiene rubber (75/25) blend was also examined. On the other hand, a correlation between the size and concentration of the free‐volume holes and the electrical and mechanical properties of the aforementioned blends was established. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

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 thiophosphoryl compounds as accelerators and coupling agents on the vulcanization of NR‐XNBR blend

The effect of a number of thiophosphoryl compounds [viz., bis(isobutyl) thiophosphoryl di‐, tri‐, and tetrasulfides and bis(dicyclohexyl) thiophopsphoryl di‐, tri‐, and tetrasulfides] on natural rubber (NR)‐carboxylated nitrile rubber (XNBR) blend was studied. All these thiophosphoryl compounds are capable of forming interrubber links leading to covulcanized blends which exhibit a fair degree of synergism with respect to physical properties, the maximum being obtained at the 25% NR and 75% XNBR blend composition. This is an obvious claim that the blend under investigation is technologically compatible, having some degree of interrubber interaction which is enhanced in case of two‐stage vulcanization. The existence of interrubber interaction is judged by the swelling experiment. The blend morphology assessed by SEM micrographs corroborates the foregoing observations and accounts for the significant improvement in physical properties of the blend vulcanizates, particularly in two‐stage vulcanization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3286‐3299, 2002     

NR–EPDM covulcanization: A novel approach

Bis(diisopropyl)thiophosphoryl disulfide (DIPDIS) was used successfully as a novel coupling agent cum accelerator to co‐vulcanize the elastomer blend comprising highly unsaturated natural rubber (NR) and ethylene propylene diene rubber (EPDM) of low unsaturation content. The blend vulcanizates produced exhibit improved physical properties that can be further enhanced by implementing a two‐stage vulcanization technique, as well as by judicious selection of the NR‐to‐EPDM ratio. The results indicate coherency and homogeneity in the blend composition of two‐stage vulcanizates. The cure‐rate mismatch problem could thus be solved through the formation of rubber‐bound intermediates with a multifunctional rubber additive (i.e., DIPDIS), thereby restricting the curative migration from lower to highly unsaturated rubber. The blend morphology as revealed by SEM studies accounts for significant improvement in physical properties, particularly in two‐stage vulcanizates. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 800–808, 2001     

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     

Evaluation of physical and dielectric properties of chloroprene and styrene butadiene rubber blends

The influence of bis(diisopropyl) thiophosphoryl disulfide, a multifunctional rubber additive, on the curing characteristics and physical properties of polychloroprene rubber and styrene butadiene rubber blends was studied. It is evident from the study that covulcanization of SBR and CR following a two‐stage process leads to the development of improved physical properties of the vulcanizates. Dielectric and scanning electron microscopy study supports the occurrence of coherence of the dissimilar rubber blends. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1492–1504, 2005     

Mechanical and aging properties of cross‐linked ethylene propylene diene rubber / styrene butadiene rubber blends

The mechanical properties and aging characteristics of blends of ethylene propylene diene monomer (EPDM) rubber and styrene butadiene rubber (SBR) were investigated with special reference to the effect of blend ratio and cross‐linking systems. Among the blends, the one with 80/20 EPDM/SBR has been found to exhibit the highest tensile, tear, and abrasion properties at ambient temperature. The observed changes in the mechanical properties of the blends have been correlated with the phase morphology, as attested by scanning electron micrographs (SEMs). The effects of three different cure systems, namely, sulfur (S), dicumyl peroxide (DCP), and a mixed system consisting of sulfur and peroxide (mixed) on the blend properties also were studied. The stress‐strain behavior, tensile strength, elongation at break, and tear strength of the blends were found to be better for the mixed system. The influence of fillers such as high‐abrasion furnace (HAF) black, general‐purpose furnace (GPF) black, silica, and clay on the mechanical properties of 90/10 EPDM/SBR blend was examined. The ozone and water aging studies also were conducted on the sulfur cured blends, to supplement the results from the mechanical properties investigation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2606–2621, 2004     

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     

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 motional processes in polymer blends composed of isotactic polypropylene and ethylene–propylene–diene monomer rubber by broad‐line 1H‐NMR

The broad‐line ¹H‐NMR study of the polymer blend composed of isotactic polypropylene and ethylene–propylene–diene monomer rubber was carried out. The NMR measurements were performed on the samples of the polymer blend and on the components of the blend in the temperature range covering the glass‐transition regions of all studied polymers. Conclusions were drawn from the temperature dependencies of the second moment M₂ and of the data obtained by the decomposition of the spectra into the components related to the motionally distinct regions of the partially crystalline polymer. The mass fractions of the amorphous, intermediate, and crystalline domains and the widths of the spectra related to the particular phases were computed from the spectra. A double glass transition was revealed for the polymer blend. Different mechanisms of the motional processes related to the glass transition were deduced from the data. The gradual increase of the number of the chains and the enhancement of the chain mobility within noncrystalline regions of the polymer blend are responsible for the motion related to the lower glass transition and only transformation of the hindered motion into free motion was found in the temperature region of the upper glass transition. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 247–252, 2004     

Cure characteristics,morphology, and mechanical properties of ethylene–propylene–diene–monomer rubber/acrylonitrile butadiene rubber blends

Blends based on ethylene–propylene–diene monomer rubber (EPDM) and acrylonitrile butadiene rubber (NBR) was prepared. Sulfur was used as the vulcanizing agent. The effects of blend ratio on the cure characteristics and mechanical properties, such as stress–strain behavior, tensile strength, elongation at break, hardness, rebound resilience, and abrasion resistance have been investigated. Tensile and tear strength showed synergism for the blend containing 30% of NBR, which has been explained in terms of morphology of the blends attested by scanning electron micrographs. A relatively cocontinuous morphology was observed for 70 : 30, EPDM/NBR blend system. The experimental results have been compared with the relevant theoretical models. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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     

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     

Effects of peroxide and phenolic cure systems on characteristics of the filled ethylene–propylene–diene monomer rubber (EPDM)

The effects of three curing systems, peroxide, peroxide–phenolic combination, and phenolic on selected properties of cured carbon black‐filled ethylene–propylene–diene monomer rubber (EPDM) were investigated. The cured rubbers immersed in hot amine solution to evaluate their suitability for seal and gasket industry at elevated temperature and amine environments. These tests were essential for evaluating the durability of the gasket in a gas refinery. The Fourier transform infrared spectroscopy spectrums revealed that the phenolic crosslink was constructed between rubber macromolecules during the curing process. The changing curing system from peroxide to peroxide–phenolic and phenolic increased the glass transition temperature of the filled cured rubbers between 3 and 5 °C. There was not any significant difference between thermogravimetric analysis thermographs of the selected cured rubbers with various cure systems and the residues ranged between 45% and 47%. Unlike of peroxide curing system, a dual phase was observed from scanning electron microscopy micrographs for peroxide–phenolic and phenolic cure systems. The phenolic cure system was not beneficial for rubber curing although, it reduced scorch time of the curing process. For the most studied mechanical properties, phenolic cure system deteriorated mechanical properties for both, aged and unaged cured rubbers. Increasing the amount of diene monomer in EPDM structure was beneficial for phenolic rubber cure system. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46213.     

Structural morphology and properties of star styrene–isoprene–butadiene rubber and natural rubber/star styrene–butadiene rubber blends

Star styrene–isoprene–butadiene rubber (SIBR) was synthesized with a new kind of star anionic initiator made from naphthalene lithium and an SnCl₄ coupled agent. The relationship between the structure and properties of star SIBR was studied. Star block styrene–isoprene–butadiene rubber (SB‐SIBR), having low hysteresis, high road‐hugging, and excellent mechanical properties, was closer to meeting the overall performance requirements of ideal tire‐tread rubber according to a comparison of the morphology and various properties of SB‐SIBR with those of star random SIBR and natural rubber/star styrene–butadiene rubber blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 336–341, 2004     

Surface segregation of polyethylene in low‐density polyethylene/ethylene–propylene–diene rubber blends: Aspects of component structure

Aspects of the molecular weight and its distribution, the branching of low‐density polyethylene (LDPE), and the molecular composition of the ethylene–propylene–diene rubber (EPDM) matrix are presented in this article in terms of their influence on the surface segregation of polyethylene (PE) in elastomer/plastomer blends. All of the PEs studied, despite different weight‐average molecular weights and degrees of branching, segregated to the surface of the LDPE/EPDM blends. Atomic force microscopy pictures demonstrated defective crystalline structures on the surface of the blends, which together with a decrease in the degrees of their bulk crystallinity and a simultaneous increase in their melting temperatures, pointed to a low molecular weight and a defective fraction of PE taking part in the surface segregation. The extent of segregation depended on the molecular structure of the EPDM matrix, which determined the miscibility of the components on a segmental level. The higher the ethylene monomer content in EPDM was, the lower was the PE content in the surface layer of the blends. The composition and structure of the surface layer was responsible for its lower hardness in comparison with the bulk of the blends studied. The surface gradient of the mechanical properties depended on the physicochemical characteristics of the components and the blend composition, which created the possibility of tailoring the LDPE/EPDM blends to dedicated applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 625–633, 2006