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     

Thermoplastic elastomers based on recycled high‐density polyethylene,ethylene–propylene–diene monomer rubber,and ground tire rubber

High‐performance thermoplastic elastomers (TPEs), based on recycled high‐density polyethylene (HDPE^R), olefinic type ethylene–propylene–diene monomer rubber (EPDM), and ground tire rubber (GTR) treated with bitumen, were prepared by using dynamic vulcanization technology, and their structure–property relationships were investigated. It was established that special pretreatment of GTR by bitumen confers outstanding mechanical properties on the resulting TPEs. TPEs, containing GTR pretreated by bitumen, exhibit thermal behavior similar to that of the HDPE^R/EPDM basic blend in the temperature region up to about 340°C. Rheological measurements showed that bitumen acts as an effective plasticizer for the GTR‐containing TPEs. SEM, DSC, and DMTA results revealed improved adhesion between the particles of GTR treated by bitumen and the surrounding thermoplastic matrix, compared to that of the untreated GTR particles. It was concluded that bitumen acts as an effective devulcanizing agent in the GTR treatment stage. In the following steps of TPE production, bitumen acts simultaneously as a curing agent for the rubber components (EPDM/GTR) and as a compatibilizer for the blend components. GTR‐containing TPEs, prepared by extrusion technology, were reprocessed (by passing through the extruder six times) without any observable changes in their tensile properties, thermal stability, and melt viscosity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 659–671, 2005     

Polyamide 6/maleated ethylene–propylene–diene rubber/organoclay composites with or without glycidyl methacrylate as a compatibilizer

Polyamide 6 (PA6)/maleated ethylene–propylene–diene rubber (EPDM‐g‐MA)/organoclay (OMMT) composites were melt‐compounded through two blending sequences. Glycidyl methacrylate (GMA) was used as a compatibilizer for the ternary composites. The composite prepared through via the premixing of PA6 with OMMT and then further melt blending with EPDM‐g‐MA exhibited higher impact strength than the composite prepared through the simultaneous blending of all the components. However, satisfactorily balanced mechanical properties could be achieved by the addition of GMA through a one‐step blending sequence. The addition of GMA improved the compatibility between PA6 and EPDM‐g‐MA, and this was due to the reactions between PA6, EPDM‐g‐MA, and GMA, as proved by Fourier transform infrared analysis and solubility (Molau) testing. In addition, OMMT acted as a compatibilizer for PA6/EPDM‐g‐MA blends at low contents, but it weakened the interfacial interactions between PA6 and EPDM‐g‐MA at high contents. Both OMMT and GMA retarded the crystallization of PA6. The complex viscosity, storage modulus, and loss modulus of the composites were obviously affected by the addition of OMMT and GMA. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Blends of polyamide 6 with low‐density polyethylene compatibilized with ethylene–methacrylic acid based copolymer ionomers: Effect of neutralizing cations

Blends of polyamide 6 with low‐density polyethylene compatibilized with sodium‐, zinc‐, and lithium‐neutralized ethylene—methacrylic acid ionomers were investigated at 11, 33, and 55 wt % neutralization of the ionomers. Blends of polyamide 6 with low‐density polyethylene without a compatibilizer had poor properties characteristic of incompatible polymer–polymer blends. After the addition of a compatibilizer, tensile properties improved, the modulus drop associated with melting increased to higher temperatures, and the dispersed phase size decreased. The improvement of the mechanical properties and thermomechanical properties was less with the acid copolymer than with the ionomers. Overall, ionomers neutralized with sodium, zinc, or lithium showed little difference in their compatibilization efficiency. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

Thermostimulative shape‐memory effect of reactive compatibilized high‐density polyethylene/poly(ethylene terephthalate) blends by an ethylene–butyl acrylate–glycidyl methacrylate terpolymer

High‐density polyethylene (HDPE)/poly(ethylene terephthalate) (PET) blends were prepared by means of melt extrusion with ethylene–butyl acrylate–glycidyl methacrylate terpolymer (EBAGMA) as a reactive compatibilizer. The effects of the EBAGMA and PET contents, recovery temperature, and stretch ratio on the thermostimulative shape‐memory behavior of the blends were studied. The results show that the addition of EBAGMA to the HDPE/PET blends obviously improved the compatibility and the shape‐memory effects of the blends. The response temperature was determined by the melting point of HDPE, and the shape‐recovery ratio of the 90/10/5 HDPE/PET/EBAGMA blend reached nearly 100%. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Poly(ethylene‐co‐methacrylic acid)–lithium ionomer as a compatibilizer for poly(ethylene terephthalate)/linear low‐density polyethylene blends

Poly(ethylene terephthalate) (PET)/linear low‐density polyethylene (LLDPE) blends (75/25), with contents of poly(ethylene‐co‐methacrylic acid) partially neutralized with lithium (PEMA–Li) that were systematically changed from 0 to 45% relative to the LLDPE, were obtained by direct injection molding in an attempt to (1) ameliorate the performance of the binary blend and (2) find the best compatibilizer content. PEMA–Li did not modify the PET or LLDPE amorphous‐phase compositions or the crystalline content of PET. However, PEMA–Li did lead to a nucleation effect and to the presence of a second smaller and less perfect crystalline structure. PET induced a fractional crystallization in LLDPE that remained in the presence of PEMA–Li and reduced the crystallinity of LLDPE. The ternary blends showed two similar dispersed LLDPE and PEMA–Li phases with small subparticles, probably PET, inside. The compatibilizing effect of PEMA–Li was clearly shown by the impressive increase in the break strain, along with only small decreases in the modulus of elasticity and in the tensile strength. With respect to the recycling possibilities of LLDPE, a ternary blend with the addition of 22.5% PEMA–Li, which led to very slight modulus and yield stress decreases with respect to the binary blend and a break strain increase of 480%, appeared to be the most attractive. However, the highest property improvement appeared with the addition of 37.5% PEMA–Li, which led to elasticity modulus and tensile strength decreases of only 9%, along with a very high break strain increase (760%). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1322–1328, 2003     

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     

Preparation and performances of ethylene–propylene–diene terpolymer/acrylic rubber reinforced with a dough‐modeling compound

A novel composite was prepared by the addition of a dough‐modeling compound (DMC) reinforcement and an ethylene–propylene–diene terpolymer (EPDM)/acrylic rubber (ACM) matrix. We studied the DMC/EPDM/ACM mass ratio and vulcanizing process by testing the tensile strength, Shore A hardness, elongation at break, and wear and thermal properties. The results show that the mechanical properties, thermal properties, and wear resistance of the composites were good when the DMC/EPDM/ACM mass ratio was 70/25/75 and the cure conditions were 180°C under 10 MPa for 25 min. The crosslinking structure of the composites was studied by IR, and this further proved the interaction between DMC, ACM, and EPDM. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical properties of high‐density polyethylene/scrap rubber powder composites modified with ethylene–propylene–diene terpolymer,dicumyl peroxide,and silicone oil

The effect of ethylene–propylene–diene terpolymer (EPDM), dicumyl peroxide (DCP), and dimethyl silicone oil on the mechanical properties of high‐density polyethylene (HDPE) composites filled with 60 mesh cryogenically scrap rubber powder (SRP) was studied. The addition of 10 wt % EPDM, 0.2 wt % DCP, and 4 wt % dimethyl silicone oil significantly increased both the impact strength and elongation at break of the HDPE/SRP composites. After the modification, the impact strength increased by 160%, and the elongation at break increased by 150% for the composites containing 40 wt % SRP. The impact load–time curves showed that the increase of impact energy for the modified composites was attributed to the increase of the maximum force at yield point and the ductile deformation after yielding. The rheological behavior, dynamic mechanical properties, and morphology observation suggested that an enhanced adhesion between SRP and polymer matrix formed in the modified HDPE/SRP composites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2020–2027, 2003     

Use of zinc‐neutralized ethylene/methacrylic acid copolymer ionomers as blend compatibilizers for nylon 6 and low‐density polyethylene

The effect of the composition on the morphologies and properties of uncompatibilized and compatibilized blends of nylon 6 and low‐density polyethylene were studied over a wide range of weight fractions. The uncompatibilized blends had substantially reduced mechanical properties after mixing, and this was almost certainly due to poor interfacial adhesion between the two polymers. The addition of a zinc‐neutralized poly(ethylene‐co‐methacrylic acid) ionomer (Surlyn® 9020) as a compatibilizer improved the mechanical properties in comparison with those of the material blended without the compatibilizer. The clearest evidence of this improvement came from dynamic mechanical studies; for selected blends with high polyethylene contents, the drop in the modulus corresponding to the transition of a solid to a melt occurred at higher temperatures with the added compatibilizer. This improvement in the properties was accompanied by a reduction in the dispersed‐phase size due to the interaction between the ionic part of the ionomer and the amide groups of nylon 6, especially when nylon 6 was the dispersed phase of the blend. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 620–629, 2003     

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     

Thermoplastic elastomers based on epoxidized natural rubber and high‐density polyethylene blends: Effect of blend compatibilizers on the mechanical and morphological properties

Epoxidized natural rubber (ENR) with a level of epoxide groups of 20 mol % was prepared via the performic epoxidation method. It was then used to blend with high‐density polyethylene (HDPE) at various blend ratios. Three types of blend compatibilizers were prepared. These included a graft copolymer of HDPE and maleic anhydride (MA; i.e., HDPE‐g‐MA) and two types of phenolic modified HDPEs using phenolic resins SP‐1045 and HRJ‐10518 (i.e., PhSP‐PE and PhHRJ‐PE), respectively. We found that the blend with compatibilizer exhibited superior tensile strength, hardness, and set properties to that of the blend without compatibilizer. The ENR and HDPE interaction via the link of compatibilizer molecules was the polar functional groups of the compatibilizer with the oxirane groups in the ENR molecules. Also, another end of the compatibilizer molecules (i.e., HDPE segments) was compatibilizing with the HDPE molecules in the blend components. The blend with compatibilizer also showed smaller phase morphology than the blend without compatibilizer. Among the three types of the blend compatibilizer, HDPE‐g‐MA provided the blend with the greatest strength and hardness properties but the lowest set properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and properties of ethylene–propylene–diene rubber/organomontmorillonite nanocomposites

Ethylene–propylene–diene rubber (EPDM)/organomontmorillonite (OMMT) nanocomposites were prepared with a maleic anhydride grafted EPDM oligomer as a compatibilizer via melt intercalation. X‐ray diffraction and transmission electron microscopy indicated that the silicate layers of OMMT were exfoliated and dispersed uniformly as a few monolayers in nanocomposites. The change in the crystallization behavior of the nanocomposites was examined. The nanocomposites exhibited great improvements in the tensile strength and tensile modulus. The incorporation of OMMT gave rise to a considerable reduction of tan δ and an increase in the storage modulus. Moreover, the solvent resistance of the nanocomposites increased remarkably. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 440–445, 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     

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     

Characterization of ethylene–propylene rubber and ethylene–propylene–diene rubber networks

The stress–strain (S/S) and the swelling equilibrium behavior in a series of ethylene propylene rubber (EPR) and ethylene propylene diene monomer (EPDM) networks were investigated and the results were employed to evaluate the effects of varying the cure conditions on the crosslinking efficiency in these networks. The S/S curve of completely swollen vulcanizates is in agreement with the predictions of rubber elasticity theory, while that of dry or partially swollen vulcanizates is fully described by the Mooney-Rivlin equation. ? values determined in benzene were found to vary linearly with v_r (v_r = equilibrium volume fraction of rubber in swollen sample). Crosslinking efficiency, moles of crosslinks produced per moles of crosslinking agent used, ranges from 3.7 in peroxide-cured EPDM (55% wt ethylene and 2.6% unsaturation) to 0.15 in similarly cured EPR (43% ethylene). Efficiency in the latter system improves to 0.6 by addition of a coagent (sulfur) to the cure formula. Crosslinking efficiency in EPDM (55% ethylene) was found to increase in the order: peroxide- > resin- > sulfur-cured. In the EPDM sulfur vulcanizates, changing the terpolymer in the cure formula resulted in significant changes in the crosslinking efficiency.     

Interaction of crosslinked ethylene–propylene–diene terpolymer blends with chlorinated organic penetrants

The sorption and diffusion of halogenated hydrocarbon penetrants through different ethylene–propylene–diene terpolymer (EPDM) blends, such as EPDM/natural rubber, EPDM/bromobutyl rubber, and EPDM/styrene butadiene rubber (50/50 w/w), were studied. The diffusion coefficient of halogenated penetrants fell in the range 1.5–14.52 × 10^?7 cm²/s in the temperature range of 25–60°C. Transport data were affected by the nature of the interacting solvent molecule rather than its size and also by the structural variations of the EPDM blends. 1,2‐Dichloroethane showed a lower mass uptake compared to other penetrants. The temperature dependence of the transport coefficient was used to estimate the activation parameters, such as the activation energy of diffusion (E_D) and the activation energy of permeation (E_p) from Arrhenius plots. The activation parameters for E_D of aliphatic chlorinated organic penetrants was in the range 7.27–15.58 kJ/mol. These values fell in the expected range for rubbery polymers, well above their glass‐transition temperature. Also, the thermodynamic parameters, such as enthalpy and entropy, were calculated and fell in the range 2–15 kJ/mol and 3–54 J/mol/K, respectively. Both first‐ and second‐order transport kinetics models were used to investigate the transport kinetics, and first‐order kinetics were followed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1366–1375, 2003     

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     

Rheological properties and morphology of compatibilized poly(butylene terephthalate)/linear low‐density polyethylene alloy

The rheological behavior of PBT/LLDPE and PBT/LLDPE‐g‐AA blends [where PBT is poly(butylene terephthalate), LLDPE is linear low‐density polyethylene, and AA is acrylic acid] under a capillary flow was investigated with a capillary rheometer. The Utracki equation was used to describe the viscosity–composition dependence of PBT/LLDPE and PBT/LLDPE‐g‐AA blends at low shear stresses. However, at high shear stresses, this equation was not suitable for these blending systems. There existed a maximum on the curves of the entrance pressure drop versus the blending compositions, and the interlayer slip factor β in the Utracki equation was related not only to the shear stress but also to the elasticity difference of the two blending components. Morphological observations indicated that at high shear rates, there existed two different morphologies at different positions of the extrudates, and this was the reason that the Utracki equation failed. Near the wall of the capillary, low‐viscosity PBT stratified, and this resulted in an additional decrease in the viscosities of the blending systems. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 206–213, 2003