Effects of the ethylene–propylene–diene monomer microstructural parameters and interfacial compatibilizer upon the EPDM/montmorillonite nanocomposites microstructure: Rheology/permeability correlation

Attempts have been made to investigate the effects of ethylene–propylene–diene monomer (EPDM) rubber structural parameters on the developed microstructure, mechanical properties, rheology, and oxygen gas permeability of EPDM/organically modified montmorillonite (O‐MMT) nanocomposite samples prepared via melt mixing. Maleic anhydride grafted EPDM (EPDM‐g‐MAH) has been employed as an interfacial compatibilizer. The influence of the EPDM melt viscosity and chain linearity on the extent of exfoliation of the clay nanolayers has been evaluated through the calculation of the nanolayer aspect ratio (length/thickness) with the Halpin–Tsai model. The results are consistent with the X‐ray diffraction patterns of the samples. The flocculation of the clay nanolayers has been found to be more probable when O‐MMT is mixed with highly branched, low‐molecular‐weight EPDM. More exfoliation occurs when EPDM rubber with a high molecular weight but low branching is used. This has been confirmed by more nonlinear melt rheology behavior and broadening of the retardation time spectra. Maleated EPDM has been shown to be effective in enhancing the molecular intercalation of the clay nanolayers and the prevention of flocculation in both low‐molecular‐weight and high‐molecular‐weight EPDM matrices. Dynamic melt rheology measurements have revealed nonterminal behavior within the low‐frequency range by interfacially compatibilized molten samples with an EPDM‐g‐MAH/clay ratio of 3, regardless of the matrix molecular weight and chain linearity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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     

Functionalization of ethylene–propylene–diene monomer rubber with maleic anhydride in the melt state through high‐shear stress‐induced initiation

The functionalization reactions of ethylene–propylene–diene monomer rubber (EPDM) with maleic anhydride (MAH) in melt state through high‐shear‐stress‐induced initiation by an increase in the screw rotation speed of the twin‐screw extruder and through compounded initiation by the addition of some initiator and an increase in the screw rotation speed were investigated. The results show that, with increasing screw rotation speed and reaction temperature, the percentage grafting and melt flow rate of the functionalized products (EPDM‐g‐MAH) were noticeably increased, and the viscosity‐average molecular weight decreased, which implied that the grafting reaction consisted of the chain scission and grafting reaction of the produced macroradicals with MAH. In the presence of a certain peroxide initiator, the crosslinking reaction during melt extrusion was suppressed by an increase in the screw rotation speed. The percentage grafting of EPDM‐g‐MAH amounted to 1.1%, its melt flow rate was between 0.3 and 4.0 g/10 min, and its gel content was less than 1.0%, depending on the screw rotation speed and reaction temperature. Impact testing and scanning electron microscopy showed that the functionalized product prepared through the high shear stress‐induced initiation had a higher blocking activity with the amide terminated of PA66 than that prepared through the peroxide initiation or through the compound initiation, and the impact strength of the PA66/EPDM blends, improved by the high‐shear‐stress‐induced product was noticeably higher than those of the peroxide‐initiated product or the compound‐initiated one. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

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     

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     

Oil‐absorptive polymeric networks based on dispersed oleophilized nanolayers of laponite within ethylene–propylene–diene monomer vulcanizates

Oil‐absorptive polymeric nanocomposites were prepared through the melt blending of soft oleophilic ethylene–propylene–diene monomer and stearyl acrylate as a hydrophobic monomer in the absence and presence of different loadings of untreated and oleophilized laponites with quaternary ammonium salts of n‐alkylamines of different chain lengths (C10, C12, and C16) with dicumyl peroxide as a vulcanizing agent. The samples were then vulcanized at 152°C according to the determined rheometric characteristics to produce nanocomposite vulcanizates of an exfoliated type with limited cavities as revealed by X‐ray diffraction and scanning electron microscopy. The produced vulcanizates were evaluated as oil‐absorptive polymeric networks and proved to be efficient oil sorbents of moderate activity. The oil absorptivity was examined with respect to the stearyl acrylate grafting, the types of oleophilizing agents of clay in comparison with the bare clay, and the clay loading and crosslink density. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

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.     

Phase morphology and thermomechanical analysis of poly(styrene‐co‐acrylonitrile)/ethylene–propylene–diene monomer blends: Uncompatibilized and reactively compatibilized blends with two mixing sequences

The phase morphology developing in immiscible poly(styrene‐co‐acrylonitrile) (SAN)/ethylene–propylene–diene monomer (EPDM) blends was studied with an in situ reactively generated SAN‐g‐EPDM compatibilizer through the introduction of a suitably chosen polymer additive (maleic anhydride) and 2,5‐dimethyl‐2,5‐di‐(t‐butyl peroxy) hexane (Luperox) and dicumyl peroxide as initiators during melt blending. Special attention was paid to the experimental conditions required for changing the droplet morphology for the dispersed phase. Two different mixing sequences (simple and two‐step) were used. The product of two‐step blending was a major phase surrounded by rubber particles; these rubber particles contained the occluded matrix phase. Depending on the mixing sequence, this particular phase morphology could be forced or could occur spontaneously. The composition was stabilized by the formation of the SAN‐g‐EPDM copolymer between the elastomer and addition polymer, which was characterized with Fourier transform infrared. As for the two initiators, the blends with Luperox showed better mechanical properties. Scanning electron microscopy studies revealed good compatibility for the SAN/EPDM blends produced by two‐step blending with this initiator. Dynamic mechanical thermal analysis studies showed that the two‐step‐prepared blend with Luperox had the best compatibility. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A comparison of white rice husk ash and silica as fillers in ethylene–propylene–diene terpolymer vulcanizates

White rice husk ash (WRHA) and silica filled ethylene–propylene–diene terpolymer (EPDM) vulcanizates were prepared using a laboratory size two‐roll mill. Curing characteristics and physical properties of vulcanizates were studied with respect to the filler loading and filler type. Filler loading was varied from 0–50 parts per hundred resin (phr) at 10 phr intervals. Curing was carried out using a semi‐efficient vulcanization system in a Monsanto rheometer. Enhancement of the curing rate was observed with increasing WRHA loading, whereas the opposite trend was observed for silica‐filled vulcanizates. It was also indicated by the maximum torque and Mooney viscosity results that WRHA offers processing advantages over silica. Compared to the silica‐filled vulcanizates, the effect of filler loading on the physical properties of WRHA‐filled vulcanizates was not significant. According to these observations, WRHA could be used as a diluent filler for EPDM rubber, while silica can be used as a reinforcing filler. © 2001 Society of Chemical Industry     

Compatibilizing effect of ethylene–propylene–diene grafted maleic anhydride terpolymer on the blend of polyamide 66 and thermal liquid crystalline polymer

Polyamide 66–thermal liquid crystalline polymer (PA66/TLCP) composites containing 10 wt% TLCP was compatibilized by ethylene–propylene–diene‐grafted maleic anhydride terpolymer (MAH‐g‐EPDM). The blending was performed on a twin‐screw extrusion, followed by an injection molding. The rheological, dynamic mechanical analysis (DMA), thermal, mechanical properties, as well as the morphology and FTIR spectra, of the blends were investigated and discussed. Rheological, DMA, and FTIR spectra results showed that MAH‐g‐EPDM is an effective compatibilizer for PA66/TLCP blends. The mechanical test indicated that the tensile strength, tensile elongation, and the bending strength of the blends were improved with the increase of the content of MAH‐g‐EPDM, which implied that the blends probably have a great frictional shear force, resulting from strong adhesion at the interface between the matrix and the dispersion phase; while the bending modulus was weakened with the increase of MAH‐g‐EPDM content, which is attributed to the development of the crystalline phase of PA66 hampered by adding MAH‐g‐EPDM. POLYM. COMPOS., 27:608–613, 2006. © 2006 Society of Plastics Engineers     

Effect of bis(diisopropyl)thiophosphoryl disulfide on the covulcanization of styrene–butadiene rubber and ethylene–propylene–diene (monomer) blends

Covulcanization of elastomer blends constituting styrene–butadiene rubber (SBR) and ethylene–propylene–diene (monomer) rubber (EPDM) was successfully performed in the presence of reinforcing fillers like carbon black and silica by using a multifunctional rubber additive, bis(diisopropyl)thiophosphoryl disulfide (DIPDIS). The polarity of EPDM rubber was increased by a two‐stage vulcanization technique, which allowed the formation of rubber‐bound intermediates. In this way the migration of both curatives and reinforcing fillers in the EPDM–SBR blend could be controlled and cure rate mismatch could be minimized. The process significantly improved the physical properties of the blend vulcanizates. The phase morphology, as evident from the SEM micrographs, was indicative of the presence of a much more compact and coherent rubber matrix in the two‐stage vulcanizates. Different accelerator systems were studied to understand better the function and effectiveness of DIPDIS in developing homogeneity in the blends of dissimilar elastomers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1231–1242, 2004     

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     

Improvement of the compatibility of natural rubber/ethylene–propylene diene monomer rubber blends via natural rubber epoxidation

The longitudinal ultrasonic velocity, longitudinal ultrasonic absorption (attenuation coefficient), glass‐transition temperature, and Mooney viscosity for epoxidized natural rubber/ethylene–propylene diene monomer blends were measured. The variation of the longitudinal ultrasonic velocity with the blend ratios was linear, indicating a compatible system in comparison with the same system without epoxidation (natural rubber/ethylene–propylene diene monomer), which was incompatible. Also, the behavior was confirmed by heat of mixing calculations as well as Mooney viscosity measurements. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2816–2819, 2002     

Exfoliation targeted toughness enhancement in polypropylene‐blend‐ montmorillonite nanocomposites

BACKGROUND: Both exfoliated and toughened polypropylene‐blend‐montmorillonite (PP/MMT) nanocomposites were prepared by melt extrusion in a twin‐screw extruder. Special attention was paid to the enhancement of clay exfoliation and toughness properties of PP by the introduction of a rubber in the form of compatibilizer toughener: ethylene propylene diene‐based rubber grafted with maleic anhydride (EPDM‐g‐MA). RESULTS: The resultant nanocomposites were characterized using X‐ray diffraction, atomic force microscopy, scanning electron microscopy, thermogravimetric analysis, dynamic mechanical analysis and Izod impact testing methods. It was found that the desired exfoliated nanocomposite structure could be achieved for all compatibilizer to organoclay ratios as well as clay loadings. Moreover, a mechanism involving a decreased size of rubber domains surrounded with nanolayers as well as exfoliation of the nanolayers in the PP matrix was found to be responsible for a dramatic increase in impact resistance of the nanocomposites. CONCLUSION: Improved thermal and dynamic mechanical properties of the resultant nanocomposites promise to open the way for highly toughened super PPs via nanocomposite assemblies even with very low degrees of loading. Copyright © 2008 Society of Chemical Industry     

NR/SBR/organoclay nanocomposites: Effects of molecular interactions upon the clay microstructure and mechano‐dynamic properties

Nanocomposites based on (70/30) blends of natural rubber (NR), styrene‐butadiene rubber (SBR), and organoclay (OC) have been prepared successfully via melt‐mixing process. Effects of the extent of polymers/clay interactions upon the developed microstructure, fatigue life, and dynamic energy loss by the nanocomposites have been investigated. Maleated EPDM (EPDM‐g‐MAH) and epoxidized NR (ENR50) were employed as compatibilizer. Nanocomposites were characterized by means of X‐ray diffractometer (XRD), transmission electron microscope (TEM), scanning electron microscope, atomic force microscopy, root mean square, and dynamic mechanical thermal analysis. EPDM‐g‐MAH showed more potential in enhancing dispersion of the clay nanolayers and their interaction with rubber phases. More potential for separating and dispersing the clay nanoplatelets with better interface enhancement was exhibited by EPDM‐g‐MAH as compatibilizer. This was consistent with higher resistance towards large strain cyclic deformations along with more heat build‐up characteristics showed by EPDM‐g‐MAH based nanocomposites especially at compatibilizer/organoclay ratio of 3. Pronounced non‐terminal behavior within low frequency region was also observed for melt storage modulus of this nanocomposite, indicating higher extent of intercalation/exfoliation microstructure with reinforced interfaces than the nanocomposite generated by ENR50. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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

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

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