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

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

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

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

动态硫化EPDM／PP热塑性弹性体相态结构及其力学行为

研究动态硫化ＥＰＤＭ／ＰＰ热塑性弹性体相态结构及其力学行为。结果表明：动态硫化ＥＰＤＭ／ＰＰ共混物相态是ＥＰＤＭ橡胶以颗粒状分布在ＰＰ连续相中,这种相态结构一般不随橡塑比的变化而改变,但ＥＰＤＭ橡胶颗粒的形态变化显著。动态硫化ＥＰＤＭ／ＰＰ共混物,在橡塑比小于２５／７５,共混物具有类似橡胶应力－应变特征。     

The Effect of Dicumyl Peroxide Vulcanization on the Properties & Morphology of Polypropylene/Ethylene-Propylene Diene Terpolymer/Natural Rubber Blends

ABSTRACT

This article discusses some properties such as tensile properties, chemical and oil resistance, gel content, crystallinity, and morphology of polypropylene (PP)/ethylene-propylene diene terpolymer (EPDM)/natural rubber (NR) blends. Dicumyl peroxide (DCP) was applied as a crosslinking agent. In terms of tensile properties, peroxide vulcanized blend shows higher tensile strength and tensile modulus (stress at 100% elongation, M₁₀₀) as compared with the unvulcanized blend. The elongation at break of the peroxide vulcanized blend is higher for the blend with NR rich content compared with the EPDM rich content. The improvements in chemical and oil resistance as well as gel content of peroxide vulcanized blends have also proved the formation of crosslinks in the rubber phase. Scanning electron microscopy (SEM) micrographs from the surface extraction of the blends support that the crosslinks have occurred during dynamic vulcanization. Dynamical vulcanization with DCP has decreased the percent crystallinity of blends that can be attributed to the formation of crosslinks in the rubber.     

The Effect of Dynamic Vulcanization on the Properties of Polypropylene/Ethylene-Propylene Diene Terpolymer/Natural Rubber (PP/EPDM/NR) Ternary Blend

The effects of dynamic vulcanization on the process development and some properties, such as tensile properties, swelling index, gel content, crystallinity, and morphology, of the polypropylene (PP)/ethylene-propylene diene terpolymer (EPDM)/natural rubber (NR) blends were investigated. Dynamically vulcanized blends show higher stabilization torque than unvulcanized blends. In terms of tensile properties, the tensile strength and tensile modulus (stress at 100% elongation, M₁₀₀) of the vulcanized blends have been found to increase as compared with the unvulcanized blends, whereas the elongation at break is higher in the blend with richer EPDM content. These results can be attributed to the formation of cross-linking in the rubber phase. The formation of cross-links in the rubber phase has also been proved by swelling index and gel content. The percentage of crystallinity of the blends is decreased by dynamic vulcanization. Scanning electron microscopy (SEM) micrographs from the surface extraction of the blends support that the cross-links occurred during dynamic vulcanization.     

Effect of dynamic cross-linking on mixing torque behavior and tensile yield behavior of isotactic polypropylene (iPP) / ethylene-propylene diene rubber (EPDM) /nitrile rubber (NBR) elastomeric blends

The mixing torque behavior of ter blends of isotactic-polypropylene (iPP) with ethylene-propylene diene rubber (EPDM)/Nitrile rubber (NBR) was studied with the help of Rheometer using resole type phenolic resin as a cross-linking agents. Systematic changes with varying blend composition were observed in stress-strain behavior in the yield region viz., width of yield peak, work of yield, yield stress and yield strain. Analysis of yield stress data was made on the basis of various mathematical expressions of first power and two-thirds power laws of blend composition dependence and the porosity model. It led to consistent result from the expressions about the variation of stress concentration effect in both uncross-linked and cross-linked blend systems. With the aid of scanning electron microscopy (SEM) shapes and sizes of dispersed elastomer phase (EPDM / NBR) domains at varying blend compositions were studied.     

In‐situ ultrasonic compatibilization of unvulcanized and dynamically vulcanized PP/EPDM blends

Dynamically vulcanized PP/EPDM blends were treated by high‐intensity ultrasonic waves during extrusion. These blends were compared with unvulcanized PP/EPDM blends that were treated by ultrasound during extrusion and then dynamically vulcanized. Die pressure and power consumption were measured. The effects of different gap sizes, ratio of components, and number of ultrasonic horns were investigated. The rheological properties, morphology and mechanical properties of the blends with and without ultrasonic treatment were compared. The results obtained indicated that ultrasonic treatment induced thermo‐mechanical degradation, causing enhanced molecular transport and chemical reactions at the interfaces, thus leading to in‐situ compatibilization, which is evident by the morphological and mechanical property studies. Processing conditions were established for enhanced in‐situ compatibilization of the PP/EPDM blends that were either originally dynamically vulcanized and then ultrasonically treated or first treated and then dynamically vulcanized. Polym. Eng. Sci. 44:2019–2028, 2004. © 2004 Society of Plastics Engineers.     

Effects of Composition and Dynamic Vulcanization on the Rheological Properties of PP/NBR Blends

Summary Rheological behavior of isotactic polypropylene (PP) and nitrile rubber (NBR) blends, in the composition range of 10–30-wt % NBR content were studied, with special reference to the effect of blend ratio, dynamic vulcanization and compatibilization. All blends were prepared in a twin-screw extruder. Capillary Rheometry was employed. Pseudoplastic behavior of blends was favored by increasing rubber content. The incorporation of NBR into PP lowered activation energies. Compatibilization of unvulcanized blends did not produce significant changes on flow behavior. Dynamically vulcanized blends provide unique processing characteristics that enable to perform well in both injection molding and extrusion. Received: 8 October 2002/Revised version: 3 March 2003/Accepted: 4 March 2003 Correspondence to M. Hernández     

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

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

EPDM/iPB共混型热塑弹性体的制备与性能

通过对比不同共混比的EPDM/iPB共混体系动态硫化与未硫化的力学性能研究发现,动态硫化后的EPDM/iPB体系的性能明显优于未硫化的,当EPDM/iPB的配比为60/40、动态硫化的时间为6min时,综合性能较好;同时,研究了硫化剂和硫化时间等因素对EPDM/iPB力学性能的影响,结果表明:采用DCP/S作为硫化剂、...     

Evidences of solvent‐induced miscibility in polychloroprene‐co‐ethylene‐propene diene terpolymer blends

Solvent dependent changes in the compatibility behavior of Polychloroprene/Ethylene–propylene–diene terpolymer blends (CR/EPDM) have been investigated using dilute solution viscometry and solvent permeability analysis. To predict the compatibility of rubber blends of different compositions in solvents of different cohesive energy densities, Huggins interaction parameter (ΔB), hydrodynamic interaction (Δη) and Sun's parameter (α) were evaluated from the analysis of the specific and reduced viscosity data of two and three‐component polymer solutions. Miscibility criteria were not satisfied for CR/EPDM blends over the entire composition range in toluene, xylene, and carbon tetrachloride (CCl₄), however, a narrow miscibility domain was observed in chloroform (CHCl₃) for CR/EPDM/CHCl₃ system. These results were further corroborated with the analysis of heat of mixing (ΔH_m) and polymer–polymer interaction parameter (χ₁₂), for all rubber blend compositions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Morphology prediction and the effect of core‐shell structure on the rheological behavior of PP/EPDM/HDPE ternary blends

In this work, the morphologies of polypropylene (PP)/ethylene‐propylene‐diene (EPDM) rubber/high density polyethylene (HDPE) 70/20/10 blends were studied and compared with the predictions of the spreading coefficient and minimum free energy models. The interfacial tension of PP/HDPE, PP/EPDM, and HDPE/EPDM blends were obtained by fitting the experimental dynamic storage modulus data to Palierne's theory. The prediction results showed core‐shell morphology (core of HDPE and shell of EPDM) in PP matrix. The PP/EPDM/HDPE blends were respectively prepared by direct extrusion and lateral injection method. Core‐shell morphology (core of HDPE and shell of EPDM) could be obtained with direct extrusion corresponding to the predicted morphology. The morphology of PP/EPDM/HDPE blends could be effectively controlled by lateral injection method. For PP/EPDM/HDPE blend prepared by lateral injection method, HDPE and EPDM phase were dispersed independently in PP matrix. It was found that the different morphology of PP/EPDM/HDPE blends prepared by two methods showed different rheological behavior. When the core‐shell morphology (core of HDPE and shell of EPDM) appeared, the EPDM shell could confine the deformation of HDPE core significantly, so the interfacial energy contribution of dispersed phase on the storage modulus of blends would be weaken in the low frequency region. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Tensile properties and morphology of the dynamically cured EPDM and PP/HDPE ternary blends

The tensile properties and morphology of the polyolefin ternary blends of ethylenepropylene–diene terpolymer (EPDM), polypropylene and high density polyethylene were studied. Blends were prepared in a laboratory internal mixer where EPDM was cured in the presence of PP and HDPE under shear with dicumyl peroxide (DCP). For comparison, blends were also prepared from EPDM which was dynamically cured alone and blended with PP and HDPE later (cure–blend). The effect of DCP concentration, intensity of the shear mixing, and rubber/plastics composition was studied. The tensile strength and modulus increased with increasing DCP concentration in the blends of EPDM-rich compositions but decreased with increasing DCP concentration in blends of PP-rich compositions. In the morphological analysis by scanning electron microscopy (SEM), the small amount of EPDM acted as a compatibilizer to HDPE and PP. It was also revealed that the dynamic curing process could reduce the domain size of the crosslinked EPDM phase. When the EPDM forms the matrix, the phase separation effect becomes dominant between the EPDM matrix and PP or HDPE domain due to the crosslinking in the matrix.     

Structure and properties of dynamically cured EPDM/PP blends

The structure and properties of polyolefin blends of ethylene–propylene–diene terpolymer (EPDM) and polypropylene were studied. Blends were prepared in a laboratory internal mixer where EPDM was cured with PP under shear with dicumyl peroxide (DCP) at different shear conditions (blend–cure). Blends were also prepared for comparison from EPDM which were dynamically cured in the absence of PP and blended later (cure–blend). The effect of DCP concentration, intensity of the shear mixing, and rubber/plastic composition were studied. In blend–cure, the melt viscosity increased with increasing DCP concentration in blends of 75% EPDM and 25% PP, but it decreased with increasing DCP concentration in blends of 75% PP and 25% EPDM. In cure–blend, however, the melt viscosity increased with increasing DCP concentration for all compositions. The melt viscosity decreased with increasing intensity of the shear mixing presumably due to the formation of the smaller segregated microdomain of the crosslinked EPDM gels in both blend–cure and cure–blend materials. The crystallization rate was higher in EPDM/PP blends than in PP homopolymer. The crystallization rates for various blending conditions were also compared.     

Properties and morphologies of elastomer blends modified with EPDM‐g‐poly[2‐dimethylamino ethylmethacrylate]

The graft copolymerization of 2‐dimethylamino ethylmethacrylate (DMAEMA) onto ethylene propylene diene mononer rubber (EPDM) was carried out in toluene via solution polymerization technique at 70°C, using dibenzoyl peroxide as initiator. The synthesized EPDM rubber grafted with poly[DMAEMA] (EPDM‐g‐PDMAEMA) was characterized with ¹H‐NMR spectroscopy, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA). The EPDM‐g‐PDMAEMA was incorporated into EPDM/butadiene acrylonitrile rubber (EPDM/NBR) blend with different blend ratios, where the homogeneity of such blends was examined with scanning electron microscopy and DSC. The scanning electron micrographs illustrate improvement of the morphology of EPDM/NBR rubber blends as a result of incorporation of EPDM‐g‐PDMAEMA onto that blend. The DSC trace exhibits one glass transition temperature (T_g) for EPDM/NBR blend containing EPDM‐g‐PDMAEMA, indicating improvement of homogeneity. The physico‐mechanical properties after and before accelerated thermal aging of the homogeneous, and inhomogeneous EPDM/NBR vulcanizates with different blend ratios were investigated. The physico‐mechanical properties of all blend vulcanizates were improved after and before accelerated thermal aging, in presence of EPDM‐g‐PDMAEMA. Of all blend ratios under investigation EPDM/NBR (75/25) blend possesses the best physico‐mechanical properties together with the best (least) swelling (%) in brake fluid. Swelling behavior of the rubber blend vulcanizates in motor oil and toluene was also investigated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of Copolymer Composition and Curing on Toughness of Isotactic Polypropene Blended Together with Metallocene‐EPDM and Ethene/Propene/Vinylcyclohexane Terpolymers

Ethene/propene terpolymers containing either 1‐vinylcylohexene‐4 (VCHen) or vinylcyclohexane (VCHan) as termonomer component were prepared using MAO‐activated rac‐Me₂Si(2‐MeBenz[e]Ind)₂ZrCl₂ (MBI). Propene content was varied between 26 and 72 wt.‐% with less than 1 mol‐% termonomer incorporation. Blends containing 85 vol.‐% isotactic polypropene (i‐PP) and 15 vol.‐% of the two EP terpolymer families were prepared by melt‐compounding in a twin‐screw kneader at 200°C to examine the role of sulfur‐mediated crosslinking of the unsaturated EPDM terpolymer phase in comparison to the corresponding blends containing non‐crosslinked saturated EP/VCHan terpolymers. The observed glass temperature (T_g) depression of the T_g of EP(D)M phases with respect to the T_g of the corresponding bulk EP(D)M was attributed to the presence of thermally induced stresses in both blend systems. Blends of i‐PP with crosslinked EPDM showed smaller T_g depression with respect to those of iPP/EPM blends containing non‐crosslinked EP and EPM dispersed phases. Morphology differences were detected for i‐PP/EPM and dynamically vulcanized i‐PP/EPDM blends by means of atomic force microscopy (AFM). The crosslinked i‐PP/EPDM blends exhibited significantly improved low temperature toughness as compared to the corresponding non‐crosslinked i‐PP/EPM blends. Curing of the EPDM elastomer phase in i‐PP/EPDM (85 vol.‐%/15 vol.‐%) blends afforded significantly improved toughness/stiffness balance and a wider toughness window with respect to the corresponding i‐PP/EPM and i‐PP/EP blends without sulfur‐cured rubber phases.     

The control of miscibility of PP/EPDM blends by adding lonomers and applying dynamic vulcanization

The control of miscibility for isotactic polypropylene (PP) and ethylene-propylene-diene terpolymer (EPDM) has been attempted by adding poly(ethylene-comethacrylic acid) (EMA) ionomers and by applying dynamic vulcanization. The rheological properties, crystallization behavior, and morphology of the dynamically vulcanized EPDM/PP/ionomer ternary blends were investigated with a Rheometrics dynamic spectrometer (RDS), a differential scanning calorimeter (DSC), and a scanning electron microscope (SEM). Two kinds of EMA ionomers neutralized with different metal ions (Na⁺ and ZN⁺⁺) were investigated. Blends were prepared on a laboratory internal mixer at 190°C. Blending and curing were performed simultaneously, i.e., EPDM was vulcanized with dicumyl peroxide (DCP) in the presence of PP/ionomer. The composition of PP and EPDM was fixed at 50/50 by wt% and the contents of EMA ionomer were vaired from 5 to 20 parts based on the total amount of PP and EPDM. It was found that the addition of ionomers and the application of the dynamic vulcanization were effective in enhancing the miscibility of PP and EPDM. The structure of the blends was controlled by the following three component phases, i.e., the phase of the dynamially valcanized EPDM, PP, and Zn-neutralized ionomer. The ternary blends showed more miscibility than the PP/EPDM binary blend. This is due to the thermoplastic interpenetrating polymer network (IPN) of the ternary blends. The structure and properties of the ternary blends differed, depending on the types and contents of ionomer, i.e., the ternary blend containing Na-neutralized ionomer did not show a thermoplastic IPN structure clearly, even though the blend was prepared by dynamic vulcanization. The ternary blend containing Zn-neutralized ionomer clearly showed the behavior of a thermoplastic IPN when the contents of ionomer and DCP were 15 parts and 1.0 part, respectively.     

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 dynamic vulcanization on the physical,mechanical, and morphological properties of high‐density polyethylene/(natural rubber)/(thermoplastic tapioca starch) blends

Blending of high density polyethylene (HDPE), natural rubber (NR), and thermoplastic tapioca starch (TPS) have been studied. Two series of samples having 5–30 wt% of TPS were prepared: (a) unvulcanized blends (control) and (b) dynamically vulcanized HDPE/NR/TPS blends. The composition of the HDPE/NR was constant and fixed at a blend ratio of 70/30. Morphology studies by SEM showed that the TPS particles were homogeneously dispersed and well‐embedded in vulcanized HDPE/NR matrix. The SEM micrographs showed agreement with the tensile strength and elongation at break values. Tensile strength improved significanly when the HDPE/NR/TPS blends were vulcanized by using sulfur curative system. The enhancement in tensile properties is attributed to the crosslinking reaction within the NR phase. J. VINYL ADDIT. TECHNOL., 18:192–197, 2012. © 2012 Society of Plastics Engineers     

Radiation‐processed polychloroprene‐co‐ethylene–propene diene terpolymer blends: Evaluation of blend morphology,miscibility, and physical properties

The miscibility of polychloroprene rubber (CR) and ethylene–propylene–diene terpolymer rubber (EPDM) was studied over the entire composition range. Different blend compositions of CR and EPDM were prepared by initially mixing on a two‐roll mill and subsequently irradiating to different gamma radiation doses. The blends were characterized by differential scanning calorimetry, Fourier transform infrared spectroscopy, density measurement, hardness measurement, and solvent permeability analysis. The compatibility of the blends was studied by measuring the glass transition temperature and heat capacity change of the blends. The immiscibility of blends was reflected by the presence of two glass transition temperatures; however, partial miscible domains were observed due to inter diffusion of phases. Permeation data fitted best with the Maxwell's model and indicated that in CR‐EPDM blends, EPDM exists as continuous phase with CR as dispersed phase for lower CR weight fractions and phase inversion occurred in 40–60% CR region. It was observed that CR improved oil resistance of EPDM; however, the effect was prominent for blends of >20% CR content. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008