Effect of ultrasound on extrusion of polypropylene/ethylene–propylene–diene terpolymer blend: Processing and mechanical properties

The effects of ultrasonic irradiation on extrusion processing and mechanical properties of polypropylene (PP)/ethylene–propylene–diene terpolymer (EPDM) blends are examined. Results show that appropriate irradiation intensity can prominently decrease die pressure and apparent viscosity of the melt, increase output, as well as increase toughness of PP/EPDM blends without harming rigidity. In case the blends are extruded with ultrasonic irradiation twice, the impact strength of the blend rises sharply at 50–100 W ultrasonic intensity, and amounts to more than 900 J/m, 1.5 times as high as that of blend without ultrasonic irradiation. Scanning electron microscopy observation shows that with ultrasonic irradiation, morphology of uniform dispersed EPDM phase and good adhesion between EPDM and PP matrix was formed in PP/EPDM blend. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3519–3525, 2003     

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     

Structured polymer blends: 2. Processing of polypropylene/EDPM blends: controlled rheology and morphology fixation via electron beam irradiation

Electron beam irradiation has been used to improve the processability of polypropylene/ethylene-propylenediene monomer (PP/EPDM) blends (controlled rheology) in combination with fixation of morphology by inducing crosslinks in the dispersed EPDM phase. An optimum morphology for impact toughening has been obtained via extrusion-blending high molecular weight PP with EPDM. Upon irradiation before subsequent processing (injection moulding) this morphology is fixated, whereas the viscosity of the blend decreases as a result of chain scission of the PP matrix. Impact strength and elongation at break of these irradiated blends are better than those of blends of low molecular weight PP with EPDM, which possess comparable overall viscosity.     

Mechanical properties,morphological structure,and thermal behavior of dynamically photocrosslinked PP/EPDM blends

A dynamically photocrosslinked polypropylene (PP)/ethylene–propylene–diene (EPDM) rubber thermoplastic elastomer was prepared by simultaneously exposing the elastomer to UV light while melt‐mixing in the presence of a photoinitiator as well as a crosslinking agent. The effects of dynamic photocrosslinking and blend composition on the mechanical properties, morphological structure, and thermal behavior of PP/EPDM blends were investigated. The results showed that after photocrosslinking, tensile strength, modulus of elasticity, and elongation at break were improved greatly. Moreover, the notched Izod impact strength was obviously enhanced compared with corresponding uncrosslinked blend. Scanning electron microscopy (SEM) morphological analysis showed that for uncrosslinked PP/EPDM blends, the cavitation of EPDM particles was the main toughening mechanism; whereas for dynamically photocrosslinked blends, shear yielding of matrix became the main energy absorption mechanism. The DSC curves showed that for each dynamically photocrosslinked PP/EPDM blend, there was a new smaller melting peak at about 152°C together with a main melting peak at about 166°C. Dynamic mechanical thermal analysis (DMTA) indicated that the compatibility between EPDM and PP was improved by dynamic photocrosslinking. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3371–3380, 2004     

Silica‐reinforced dynamically vulcanized ethylene–propylene–diene monomer/polypropylene thermoplastic elastomers: Morphology,rheology, and dynamic mechanical properties

Attempts were made to prepare dynamically crosslinked ethylene–propylene–diene monomer/polypropylene (EPDM/PP, 60/40 w/w) blends loaded with various amounts of silica as a particulate reinforcing agent. The dispersion of silica between the two phases under mixing conditions, and also extent of interaction, as the two main factors that influence the blend morphology were studied by scanning electron microscopy. Increasing the silica concentration led to the formation of large‐size EPDM aggregates shelled by a layer of PP. Dynamic mechanical thermal analysis performed on the dynamically cured silica‐loaded blend samples showed reduction in damping behavior with increasing silica content. Higher rubbery‐like characteristics under tensile load were exhibited by the silica‐filled EPDM/PP‐cured blends. However, increasing the silica level to 50 phr led to the enhancement of interface, evidenced by increases in the tensile modulus and extensibility of the blend compared with those of the unloaded sample. Addition of a silane coupling agent (Si69) into the mix improved the mechanical properties of the blend, attributed to the strengthening of interfacial adhesion between the PP matrix and silica‐filled EPDM phase. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2000–2007, 2004     

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     

Influence of phase modifiers on morphology and properties of thermoplastic elastomers prepared from ethylene propylene diene rubber and isotactic polypropylene

A series of thermoplastic elastomers (TPEs) were prepared from a binary blend of ethylene propylene diene rubber (EPDM) and isotactic polypropylene (iPP) using different types of phase modifiers. The influence of sulphonated EPDM, maleated EPDM, styrene‐ethylene‐co‐butylene‐styrene block copolymer, maleated PP, and acrylated PP as phase modifiers showed improved physico‐mechanical properties (like maximum stress, elongation at break, moduli, and tension set). Scanning electron and atomic force microscopy studies revealed better morphologies obtained with these phase modified EPDM‐iPP blends. The dependence of the phase modifier type and concentration was optimized with respect to the improvement in physical properties and morphology of the blends. Physical properties, dynamic mechanical properties, and morphology of these blends were explained with the help of interaction parameter, melt viscosity, and crystallinity of the blends. Theoretical modeling showed that Kerner, Ishai‐Cohen, and Paul models predicted the right morphology–property correlation for the prepared TPEs. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.     

Mechanical properties and morphological structures relationship of blends based on sulfated EPDM ionomer and polypropylene

The mechanical properties and morphological structures of blends based on Zn²⁺ neutralized low degree sulfated ethylene propylene diene monomer rubber (Zn–SEPDM) ionomer and polypropylene (PP) were studied. It was found that Zn²⁺ neutralized low degree sulfated EPDM ionomer and PP blends, which are new thermoplastic elastomeric materials, have better mechanical properties than those of PP/EPDM blend. Theoretical analysis of tensile data suggests that there is an increase of the extent of interaction between PP and EPDM in the presence of a low degree of Zn²⁺, which is also an indicator of better interfacial adhesion between PP and Zn–SEPDM than that between PP and EPDM. SEM results proved that the finer dispersed phase sizes and the shorter interparticle distances are the main reasons for the improved mechanical properties of the PP/EPDM blend. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1504–1510, 2004     

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.     

Compatibilization of PP/EPDM blends by grafting acrylic acid to polypropylene and epoxidizing the diene in EPDM

In this article, ethylene–propylene–diene‐rubber (EPDM) was epoxidized with an in situ formed performic acid to prepare epoxided EPDM (eEPDM). The eEPDM together with the introduction of PP‐g‐AA was used to compatibilize PP/EPDM blends in a Haake mixer. FTIR results showed that the EPDM had been epoxidized. The reaction between epoxy groups in the eEPDM and carboxylic acid groups in PP‐g‐AA had taken place, and PP‐g‐EPDM copolymers were formed in situ. Torque test results showed that the actual temperature and torque values for the compatibilized blends were higher than that of the uncompatibilized blends. Scanning electron microscopy (SEM) observation showed that the dispersed phase domain size of compatibilized blends and the uncompatibilized blends were 0.5 and 1.5 μm, respectively. The eEPDM together with the introduction of PP‐g‐AA could compatibilize PP/EPDM blends effectively. Notched Izod impact tests showed that the formation of PP‐g‐EPDM copolymer improved the impact strength and yielded a tougher PP blend. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3949–3954, 2006     

Synergetic toughness and morphology of poly(propylene)/nylon 11/maleated ethylene‐propylene diene copolymer blends

Polypropylene (PP)/nylon 11/maleated ethylene‐propylene‐diene rubber (EPDM‐g‐MAH) ternary polymer blends were prepared via melt blending in a corotating twin‐screw extruder. The effect of nylon 11 and EPDM‐g‐MAH on the phase morphology and mechanical properties was investigated. Scanning electron microscopy observation revealed that there was apparent phase separation for PP/EPDM‐g‐MAH binary blends at the level of 10 wt % maleated elastomer. For the PP/nylon 11/EPDM‐g‐MAH ternary blends, the dispersed phase morphology of the maleated elastomer was hardly affected by the addition of nylon 11, whereas the reduced dispersed phase domains of nylon 11 were observed with the increasing maleated elastomer loading. Furthermore, a core‐shell structure, in which nylon 11 as a rigid core was surrounded by a soft EPDM‐g‐MAH shell, was formed in the case of 10 wt % nylon 11 and higher EPDM‐g‐MAH concentration. In general, the results of mechanical property measurement showed that the ternary blends exhibited inferior tensile strength in comparison with the PP matrix, but superior toughness. Especially low‐temperature impact strength was obtained. The toughening mechanism was discussed with reference to the phase morphology. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

PET/PC blends: Effect of chain extender and impact strength modifier on their structure and properties

Methylene diphenyl diisocyanate (MDI) affects the morphology, rheological, mechanical, and relaxation properties, as well as tendency to crystallize of PET in PET/PC/(PP/EPDM) ternary blends produced by the reactive extrusion. Irrespective of the blend phase structure, the introduction of MDI increases the melt viscosity (MFI dropped), resulting from an increase in the molecular weight of the polymer chains; the PET crystallinity was also reduced. MDI favors compatibility of PET with PC in PET/PC/(PP/EPDM) blends. This is explained by intensified interphase interactions on the level of segments of macromolecules as well as monomer units. The presence of MDI causes a substantial rise in the dynamic shear modulus within the high‐elastic region of PET (for temperature range between T_g,PET and that of PET cold crystallization); the processes of PET cold crystallization and melt crystallization become retarded; the glass‐transition temperatures for PET and PC become closer to each other. MDI affects insignificantly the blend morphology or the character of interactions between the disperse PP/EPDM blend and PET/PC as a matrix. PP/EPDM reduces the intensity of interphase interactions in a PET/PC/(PP/EPDM), but a rise in the degree of material heterogeneity. MDI does not change the mechanism of impact break‐down in the ternary blends mentioned above. Increased impact strength of MDI‐modified materials can be explained by higher cohesive strength and resistance to shear flow at impact loading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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

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

Mechanical Properties and Morphology of Ternary PP/EPDM/PE Blends

The ternary blends of high‐density polyethylene (PE), EPDM terpolymer and polypropylene (PP) have been used as a model low interfacial tension system to study encapsulation dynamics in ternary blends and their relation to the blends' mechanical properties. It was found that the modulus, tensile strength and impact resistance can be improved by PE addition if the PE is localized within the EPDM phase. A range of blend morphology was found depending on the PE viscosity and polymer incorporation sequence in the twin‐screw extruder. In the most favorable sequence, PE and EPDM were mixed together prior to their dispersion in the PP matrix. This practice resulted in a 50% increase in impact resistance when compared to mixing the three components in a single‐step.     

Phase morphology and melt rheological behavior of uncrosslinked and dynamically crosslinked polyolefin blends: role of macromolecular structure

Thermoplastic vulcanizates (TPVs) based on polypropylene (PP) with ethylene–octene copolymer (EOC) and ethylene propylene diene rubber (EPDM) have been prepared by co-agent-assisted peroxide crosslinking system. The study was pursued to explore the influence of two dissimilar polyolefin polymers having different molecular architecture on the state and mode of dispersion of the blend components and their influence on melt rheological properties. The effects of dynamic crosslinking of the PP/EOC and PP/EPDM have been compared with special reference to the concentration of crosslinking agent and ratio of blend components. Morphological analyses show that, irrespective of blend ratio, dynamic vulcanization exhibits a dispersed phase morphology with crosslinked EOC or EPDM particles in the continuous PP matrix. It was found that viscosity ratio plays a crucial role in determining the state and mode of dispersion of blend components in the uncrosslinked system. The lower viscosity and torque values of uncrosslinked and dynamically crosslinked blends of PP/EOC in the melt state indicates that they exhibit better processing characteristics when compared to corresponding PP/EPDM blends.     

Study on morphology of ternary polymer blends. II. Effect of composition

The composition effect on morphology of polypropylene/ethylene–propylene–diene terpolymer/polyethylene (PP/EPDM/PE) and polypropylene/ethylene–propylene–diene terpolymer/polystyrene (PP/EPDM/PS) ternary blends has been investigated. In all of the blends, polypropylene as the major phase was blended with two minor phases, that is, EPDM and PE or PS. From morphological studies using the SEM technique a core–shell morphology for PP/EPDM/PE and separated dispersed morphology for PP/EPDM/PS were observed. These results were found to be in agreement with the theoretical predictions. The composition of components affected only the size of dispersed phases and had no appreciable effect on the type of morphology. The size of each dispersed phase, whether it forms core or shell or disperses separately in matrix, can be related directly to its composition in the blend. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1138–1146, 2001     

Effect of dynamic crosslinking on tensile yield behavior of polypropylene/ethylene‐propylene‐diene rubber blends

Tensile yield behavior of the blends of polypropylene (PP) with ethylene‐propylene‐diene rubber (EPDM) is studied in blend composition range 0–40 wt % EPDM rubber. These blends were prepared in a laboratory internal mixer by simultaneous blending and dynamic vulcanization. Vulcanization was performed with dimethylol phenolic resin. For comparison, unvulcanized PP/EPDM blends were also prepared. In comparison to the unvulcanized blends, dynamically vulcanized blends showed higher yield stress and modulus. The increase of interfacial adhesion caused by production of three‐dimensional network is considered to be the most important factor in the improvement. It permits the interaction of the stress concentrate zone developed at the rubber particles and causes shear yielding of the PP matrix. Systematic changes with varying blend composition were found in stress‐strain behavior in the yield region, viz., in yield stress, yield strain, width of yield peak, and work of yield. Analysis of yield stress data on the basis of the various expressions of first power and two‐thirds power laws of blend compositions dependence and the porosity model led to consistent results from all expression about the variation of stress concentration effect in both unvulcanized and vulcanized blend systems. Shapes and sizes of dispersed rubber phase (EPDM) domains at various blend compositions were studied by scanning electron microscopy. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2104–2121, 2000     

Influence of coalescence and interfacial tension on the morphology of PP/HDPE compatibilized blends

In this paper, the compatibilization of polypropylene (PP)/high-density polyethylene (HDPE) blend was studied through morphological and interfacial tension analysis. Three types of compatibilizers were tested: ethylene-propylene-diene copolymer (EPDM), ethylene-vinylacetate copolymer (EVA) and styrene-ethylene/butylene-styrene triblock copolymer (SEBS). The morphology of the blends was studied by scanning electron microscopy. The interfacial tension between the components of the blends was evaluated using small amplitude oscillatory shear analysis. Emulsion curves relating the average radius of the dispersed phase and the interfacial tension to the compatibilizer concentration added to the blend were obtained. It was shown that EPDM was more efficient as an emulsifier for PP/HDPE blend than EVA or SEBS. The relative role of interfacial tension reduction and coalescence reduction to particle size reduction was also addressed. It was observed that the role of coalescence reduction is small, mainly for PP/HDPE (90/10) blends compatibilized by EPDM, EVA or SEBS. The results indicated that the role of coalescence reduction to particle size reduction is lower for blends for which interfacial tension between its components is low at compatibilizer saturation.     

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.