Mechanical properties of thermoplastic elastomers based on silicone rubber and an ethylene–octene copolymer by dynamic vulcanization

Thermoplastic vulcanizates (TPVs) are a special class of thermoplastic elastomers that are generally produced by the simultaneous mixing and crosslinking of a rubber with a thermoplastic polymer at an elevated temperature. Novel peroxide‐cured TPVs based on blends of silicone rubber and the thermoplastic Engage (an ethylene–octene copolymer) have been developed. These TPVs exhibit very good overall mechanical and electrical properties. With an increasing concentration of dicumyl peroxide, the tensile strength, modulus, and hardness of the TPVs increase, whereas the elongation at break decreases. Significant correlations have been obtained from oscillating disc rheometer torque values with various physical properties, such as the modulus and tension set of the TPVs. The aging characteristics and recyclability of the silicone‐based TPVs are also excellent. Scanning electron microscopy photomicrographs of the TPVs have confirmed a dispersed phase morphology. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Shear flow behavior and oil distribution between phases in thermoplastic vulcanizates

The high rate shear flow behavior and the morphology of five different oil‐extended polypropylene (PP)/ethylene‐propylene‐diene monomer (EPDM) thermoplastic vulcanizate blends were investigated with the melt flow rate (MFR) of the PP varying from 0.7 to 20. The ratio of rubber to PP is 70 : 30 in three of the thermoplastic vulcanizates (TPVs) and 50 : 50 in the other two TPVs. The distribution of the high‐temperature oil between the PP melt and the rubber is a key parameter because this will affect the viscosity of the PP/oil medium. The object of this study was to estimate the matrix composition in each of the TPVs at processing temperatures and to compare the shear viscosity of the effective matrix with that of the TPV. To this end, several PP/oil mixtures were prepared and their viscosity curves were correlated with the neat PP melt viscosity curves by means of shift factors varying with oil concentration. The oil distribution between the PP and rubber phases was estimated from TEM micrographs of the TPV blends. The results show that the PPs are mixed with oil to different proportions in the different TPVs and the viscosity curves of these mixtures exhibit the same trends in magnitude as the corresponding TPV viscosity curves. Hence, the shear flow of TPVs can be understood more readily in terms of the effective PP/oil medium flow behavior than in terms of the neat PP melt flow. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 113–121, 2004     

The structure and physical properties of polypropylene and thermoplastic olefin nanocomposites containing nanosilica

The morphology and physical properties of thermoplastic olefin blend (TPO) based nanocomposites containing nanosilica are reported. Addition of maleated PP resulted in improved filler dispersion within the PP matrix, where the filler resided exclusively. This separated morphology resulted in selective reinforcement of the PP matrix without compromising ductility, as demonstrated by mechanical property characterization. The tensile moduli, impact and flexural properties of TPO/nanosilica composites showed improvements at low loadings of nanosilica, indicating a good balance of stiffness and toughness. The addition of nanosilica into the TPOs decreased the size of the dispersed elastomer phase, which was a factor in the observed improvements of impact strength. Silane-modified nanosilica dispersed more efficiently in the polymer matrix, giving rise to improved impact properties of the TPO composites, compared to the unmodified filler.     

Effects of compounding procedure on morphology development,melt rheology,and mechanical properties of nanoclay reinforced dynamically vulcanized EPDM/polypropylene thermoplastic vulcanizates

New nanocomposite thermoplastic vulcanizates (TPVs) comprising dynamically cross‐linked nanoscale EPDM rubber particles dispersed throughout the polypropylene (PP) matrix have been prepared by both batch and continuous melt blending of PP with EPDM in the presence of vulcanizing ingredients, nanoclay and maleated EPDM (EPDM‐g‐MA) as compatibilizer. X‐ray diffraction, linear melt viscoelastic measurement, and tensile mechanical behavior results revealed that the developed microstructure is strongly affected by the type of the melt compounding process as well as the route of material feeding. When EPDM phase was precompounded with a vulcanizing agent, nanoclay, and EPDM‐g‐MA prior to the melt blending with PP, not only nanosize cross‐linked rubber particles appeared uniformly throughout the PP continuous phase, but also the melt blending leads to the significant enhancement of the mechanical properties compared with counterpart samples prepared by one‐step melt mixing process. Also better dispersion of nano layers in the rubber compound before melt blending with PP results in higher mechanical properties of the resulted TPV. POLYM. ENG. SCI., 56:914–921, 2016. © 2016 Society of Plastics Engineers     

Melt fracture and wall slip of thermoplastic vulcanizates

Thermoplastic vulcanizates (TPVs) are blends of polypropylene (PP) (thermoplastic phase) and ethylene propylene diene monomer (EPDM) rubber (rubber phase) in which a high content of rubber EPDM is cross-linked and dispersed in a thermoplastic matrix (PP) in the presence of oil (lubricant) and filler. Depending on the molecular characteristics of the constituent polymers, the level of curing and the amount of cross-linked rubber, their processing (extrusion) exhibits various difficulties such as melt fracture (extrudate distortions). In this study, a number of different TPVs with various characteristics, including the degree of curing and amount of cross-linked rubber are examined in capillary extrusion at two different temperatures (190°C and 205°C) relevant to real processing. First, the effect of the temperature on the yield stress is investigated using rheological measurements. Consequently, the flow behavior of the TPVs in capillary flow is studied concluding that TPVs slip massively (nearly plug flow) due to the presence of lubricant and the vulcanized rubber phase. Although there is little slip observed in PP samples, EPDMs themselves exhibit severe slip and melt fracture. As a consequence, the TPV samples essentially follow the slip behavior of EPDMs. Finally, the melt fracture analysis of several TPVs has shown that with increase of temperature and amount of cross-linked rubber, the severity of TPVs' surface defects increases accordingly.     

Dynamically vulcanized blends of polypropylene and ethylene octene copolymer: Influence of various coagents on thermal and rheological characteristics

The present study focuses on the influence of the three structurally different coagents, namely triallyl cyanurate (TAC), trimethylol propane triacrylate (TMPTA) and N,N′‐m‐phenylene dimaleimide (MPDM) on the thermal and rheological properties of thermoplastic vulcanizates (TPVs) based on the polypropylene (PP) and ethylene octene copolymer (EOC). Depending on the structure and reactivity, different coagents show different behaviors. All the TPV compositions were made by melt mixing method in a Haake Rheomix at 180°C. Rheological properties have also been evaluated at the same temperature. Viscoelastic properties of the TPVs were analyzed by a dynamic oscillatory rheometer in the melt state in a Rubber Process Analyzer (RPA 2000). Morphologically, TPVs consist of dense crosslinked rubber domains dispersed in a continuous thermoplastic matrix. The crosslinked rubber particles have a tendency to form agglomerates and build local clusters which undergo disintegration by shearing. A variety of rheological characteristics such as Payne effect, shear rate sensitivity, modulus recovery and dynamics of relaxation were studied by performing strain sweep, frequency sweep and stress relaxation tests. Among the various coagents taken for investigation, MPDM‐based TPVs show improved dynamic functions (complex modulus and complex viscosity) and lower rate of stress relaxation over TAC, TMPTA and the control sample without any coagent. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Study on the microstructure and properties of bromobutyl rubber (BIIR)/polyamide‐12 (PA12) thermoplastic vulcanizates (TPVs)

In this study, polyamide‐12 (PA12)/brominated isobutylene‐isoprene (BIIR) TPVs with good mechanical properties and low gas permeability were prepared by dynamic vulcanization in a twin‐screw extruder. The effects of three kinds of compatibilizers on the microstructure and properties of BIIR/PA12 TPV were studied. The compatibility between BIIR and PA12 was improved when maleated hydrocarbon polymeric compatibilizer is added. The reaction between maleic anhydride and amine in polyamide leads to the in situ formation of hydrocarbon polymer grafted polyamide which subsequently can be used to lower the interfacial tension between BIIR and polyamide. The compatibilizing effect of maleic anhydride modified polypropylene (PP‐g‐MAH) on BIIR/PA12 blends is the best among these compatibilizers because the surface energy of PP‐g‐MAH is very close to that of BIIR. The dispersed rubber phase of the blend compatibilized by PP‐g‐MAH shows the smallest size and more uniform size distribution, and the resulting TPVs show the best mechanical properties. The effects of fillers on the properties of BIIR/PA12 TPV were also investigated. The size of the BIIR phase increases with the increase in the content of CaCO₃. The modulus and tensile strength of TPVs increased with the increase in the content of CaCO₃ because of the reinforcing effect of CaCO₃ on TPVs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43043.     

Multifunctional peroxide as alternative crosslink agents for dynamically vulcanized epoxidized natural rubber/polypropylene blends

Commonly used dicumyl peroxide (DCP) in combination with coagent, triallyl cyanurate (TAC), as a crosslinking agent is well acceptable for dynamically vulcanized rubber phase of thermoplastic vulcanizates (TPVs). However, it generally produces volatile decomposition products, which cause a typical unpleasant smell and a blooming phenomenon. In this work, influence of two types of multifunctional peroxides: 2,4‐diallyloxy‐6‐tert‐butylperoxy‐1,3,5‐triazine (DTBT) and 1‐(2‐tert‐butylperoxyisopropyl)‐3‐isopropenyl benzene (TBIB), on properties of TPVs based on epoxidized natural rubber (ENR)/polypropylene (PP) blends were investigated. The conventional peroxide/coagent combinations, i.e., DCP/TAC and tert‐butyl cumyl peroxide (TBCP)/α‐methyl styrene (α‐MeS) were also used to prepare the TPVs for a comparison purpose. The TPVs with multifunctional peroxide, DTBT, provided good mechanical properties and phase morphology of small dispersed vulcanized rubber domains in the PP matrix which were comparable with the DCP/TAC cured TPVs. However, the TPVs with TBIB/α‐MeS and TBCP/α‐MeS showed comparatively low values of the tensile properties as well as rather large phase morphology. The results were interpreted by three main factors: the kinetic aspects of the various peroxides, solubility parameters of respective peroxide/coagent combinations in the ENR and PP phases, and the tendency to form unpleasantly smelling byproducts. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Automotive applications of thermoplastic vulcanizates

Thermoplastic vulcanizates (TPVs) are special classes of thermoplastic elastomers, in which dynamic vulcanization of the rubber phase takes place during melt mixing with a semicrystalline thermoplastic matrix phase at elevated temperature. This review article focus on the different types of thermoplastic vulcanizates (TPVs) from various elastomer and thermoplastic blends that are suitable for the automotive applications purpose. A detailed study of the various TPVs based on polypropylene-ethylene propylene diene rubber (PP-EPDM) and polypropylene-ethylene α-olefin has been focused and their application in the automobile sector has been summarized. Most of the commercially available TPVs are PP-EPDM based. Limited applications of that TPVs in high heat and oil resistant application purposes requires new generation of TPVs. High performance TPVs or super TPVs are new generation TPVs that exhibit high heat resistance as well as excellent oil resistance property suitable for automotive under-the-hood applications. Therefore TPVs based on XNBR-PA12, HNBR-PA12 and FKM-PA6 system has also been explored in details in this study and the possibility of the use of those TPV system has been focused for the high temperature application purpose in the automobile sector where high and oil resistant application properties is the prime concern.     

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.     

Thermoplastic vulcanizates based on maleated natural rubber/polypropylene blends: Effect of blend ratios on rheological,mechanical, and morphological properties

Maleated natural rubber (MNR) was prepared and used to formulate thermoplastic vulcanizates (TPVs) based on various MNR/PP blends. The influence of mixing methods on the TPVs properties was first studied. We found that mixing all ingredients in an internal mixer provided the TPVs with better mechanical properties. The final mixing torque, shear stress, and shear viscosity of the TPVs prepared with various blend ratios of MNR/PP increased with increasing levels of MNR in the blends. This may be attributed to higher shear viscosity of the pure MNR than that of the pure PP. Furthermore, as evidenced in SEM micrographs, the TPVs are two phase morphologies with dispersed small vulcanized rubber domains in the PP matrix. Therefore, the higher content of PP caused the more molten continuous phase of the flow during mixing and rheological characterization. Tensile strength and hardness of the TPVs increased with increasing levels of PP, while the elongation at break decreased. Furthermore, the elastomeric properties, in terms of tension set, increased with increasing levels of MNR in the blends. This may be attributed to decreasing trends in the size of vulcanized rubber particles dispersed in the PP matrix with an increasing concentration of MNR. POLYM. ENG. SCI. 46:594–600, 2006. © 2006 Society of Plastics Engineers.     

纳米SiO2对动态硫化EPDM/PP热塑性硫化胶性能的影响

采用不同硫化体系动态硫化制备三元乙丙橡胶/聚丙烯热塑性硫化胶(EPDM/PP TPVs),并在制备的过程添加不同量的纳米SiO2。结果表明酚醛树脂2402动态硫化得到的EPDM/PP TPVs性能最佳。随着纳米SiO2添加量的增加,EPDM橡胶粒子的粒径先减小后增大,当纳米SiO2的添加量为10份时,EPDM橡胶粒子的粒径达到最小。流变性能研究表明添加纳米SiO2使EPDM/PP TPVs的加工性能变差。动态机械分析仪(DMA)研究表明纳米SiO2提高了TPVs中PP相的玻璃化转变温度。当纳米SiO2的添加量为10份,TPVs的拉伸强度达到最高为23.7MPa,提高了19.1%,断裂伸长率达到最大为431%,提高了11.1%。纳米SiO2使EPDM/PP TPVs的热稳定性和耐热老化性能变好。     

Exploring the thermomechanical properties of peroxide/co-agent assisted thermoplastic vulcanizates through temperature scanning stress relaxation measurements

Temperature scanning stress relaxation (TSSR) measurement of peroxide vulcanized polymer blends of polypropylene (PP) and ultrahigh molecular-EPDM (UHM-EPDM) rubber has been performed to study the thermomechanical behavior of thermoplastic vulcanizates (TPVs). Co-agents play crucial roles in the enhancement of properties of TPVs. Different types of co-agents (Triallyl cyanurate-TAC; N, N-m-phenylene-dimaleimide-HVA2; zinc dimethacrylate-ZDMA; and in-situ formed zinc dimethacrylate-ZMA) have been explored in this work. TSSR study shows that higher T₅₀ and T₉₀ values have been achieved in ZMA co-agent assisted-TPV. Higher TSSR-index (RI) value was also found for the same co-agent ZMA, indicating higher elastic behavior. TSSR result supports the mechanical and rheological properties, and it is found that the ZMA and ZDMA show higher mechanical strength. Cross-linked-density calculated by modified Flory–Rehner equation and the cross-link-density as obtained from TSSR method have been compared and the trend was found to be the same. Stress relaxation study shows the slow relaxation-phenomena of the ZMA-TPV with slowest relaxation-time (θ_r) than the other TPVs, which correlates with superior material strength. Thermogravimetric analysis proves that there is a difference in degradation temperature of the blends at approximately 5–10°C. Ultrahigh molecular weight-EPDM/PP based TPVs reveal superior thermomechanical and physico-mechanical properties with ZMA and ZDMA co-agent over TAC and HVA2. These ultrahigh molecular weight-EPDM based TPVs can be used in automotive seals/strips, hoses, bellows, and 2 K-molds for automotive applications.     

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     

The effect of selective location of carbon nanotubes on electrical properties of thermoplastic vulcanizates

Three types of conductive thermoplastic vulcanizates (TPVs) were prepared by blending polypropylene (PP), carbon nanotubes (CNT), and carboxylic acrylonitrile butadiene ultrafine full‐vulcanized powdered rubber (xNBR‐UFPR). The CNT locations were different in these three types of TPVs, i.e., CNTs were localized in PP matrix, in the xNBR‐UFPR phase, or mainly in the interface. It had been found that TPV with CNTs localized mainly in the interface had the lowest conductive percolation threshold among these three types of TPVs. The volume resistivity of the TPV with 2 phr CNTs was as small as 220 Ω?cm. Moreover, the conductive TPV possessed good mechanical properties. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Dependence of microstructure and properties of polypropylene/bromo-isobutylene-isoprene rubber thermoplastic vulcanizates on the molding process

To explore the dependence of the microstructure and properties of thermoplastic vulcanizates (TPVs) on the molding process. The polypropylene/bromo-isobutylene-isoprene rubber thermoplastic vulcanizates (PP/BIIR-TPVs) are molded by high rate shear injection and compression molding, and the phase morphology and physical-mechanical properties of PP/BIIR-TPVs specimens are investigated. Detailed small-angle X-ray scattering, scanning electron microscopy and atomic force microscopy investigations demonstrate that the high rate shear of injection molding not only decreases the size of BIIR particles but also induces the orientation of the PP matrix and further increases its crystallinity. Subsequently, the PP/BIIR-TPVs molded by injection molding have higher tensile strength and Young's modulus, while the compression molding benefits to higher elongation at break. The mechanism regarding the effects of high rate shear during injection molding on phase morphology development of PP/BIIR-TPVs is discussed. This study guides the preparation of TPVs products with desired properties.     

Influence of incorporation methods of ATH on microstructure,elastomeric properties,flammability, and thermal decomposition of dynamically vulcanized NR/PP blends

Flame‐retardant thermoplastic vulcanizates (TPVs) of natural rubber (NR)/polypropylene (PP) (60/40 wt %) blends filled with alumina trihydrate (ATH) were prepared with an internal mixer. To increase the properties of flame‐retardant NR/PP TPV, the new mixing method, stepwise masterbatch mixing (SMB) method was adopted. The effects of SMB method along with different ATH loadings on microstructure and properties of NR/PP TPVs were investigated. Conventional one‐step mixing (CV) method was also studied for comparison. Transmission electron microscopy analysis showed that different processes led to a variation in microstructural homogeneity, which imposed various effects on blend properties. The mechanical properties of TPVs changed with ATH loading, and the strength of the samples obtained from SMB method was higher than those of CV method. LOI and cone calorimetry tests revealed that the flame retardancy of NR/PP blends dramatically increased at higher ATH loading. Furthermore, the increment level of flame retardancy was accelerated in the blends produced particularly through SMB method, resulting from homogeneity of local ATH distribution in NR/PP blend. Greater combustion resistance of blends prepared from SMB route were confirmed by thermogravimetry and pyrolysis‐gas chromatography–mass spectrometry techniques. Finally, a burning mechanism between filler structure and flammability of NR/PP TPVs obtained from CV and SMB methods was discussed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46231.     

Modification of Ethylene Propylene Diene Terpolymer Rubber by Some Thermoplastic Polymers

Abstract

Blends of ethylene propylene diene terpolymer (EPDM) rubber with thermoplastic polyolefins such as low‐density polyethylene (LDPE), high‐density polyethylene (HDPE), high molecular weight polypropylene (PP), and polypropylene random copolymer grade (PP‐R) were prepared by melt mixing. The physico‐mechanical properties, equilibrium swelling in benzene, and aging properties of the binary blends were investigated, analyzing the effect of the rubber/thermoplastics ratio and the type of the thermoplastic material on these properties. The data obtained indicate that EPDM/PP‐R blend in 20/80 w/w% shows the highest physico‐mechanical properties with improved retained tensile strength at 90°C for 7 days. This blend ratio also gives excellent retained equilibrium swelling in benzene at room temperature for 7 days, although EPDM/LDPE blend in 80/20 w/w% imparts the highest retained elongation at break at 90°C for 7 days.     

Influences of blend proportions and curing systems on dynamic,mechanical, and morphological properties of dynamically cured epoxidized natural rubber/high‐density polyethylene blends

Thermoplastic elastomers (TPEs) based on dynamically cured epoxidized natural rubber/high‐density polyethylene (ENR/HDPE) blends were prepared. Influence of the process oil, blend proportion, and curing systems were investigated. It was found that the oil‐extended thermoplastic vulcanizates (TPVs) exhibited better elastomeric properties and improved ease of the injection process. Increasing the proportion of ENR caused increasing elastic response of elongation at break, tension set properties, and tan δ. It was also found that the TPV treated with phenolic resin exhibited superior mechanical properties and the smallest vulcanized rubber domains. The TPV treated with the conventional peroxide co‐agent curing system showed superior strength properties but had poor elastomeric properties. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

Effect of grafted maleic anhydride content and recyclability of dynamically cured maleated natural rubber/polypropylene blends

Maleated natural rubbers (MNRs) were prepared using various levels of maleic anhydride (MA) at 4, 6, 8, 10, and 12 phr. Dynamically cured 60/40 MNR/PP blends with phenolic‐modified polypropylene (Ph‐PP) compatibilizer at a loading level of 5 wt % of PP were prepared by melt mixing process using sulfur vulcanization system. The influence of the level of MA on properties of the thermoplastic vulcanizates (TPVs) was studied. It was found that the mixing torque, apparent shear stress, shear viscosity, tensile strength, and hardness properties increased with increasing levels of the MA or grafted succinic anhydride groups in the MNR molecules. This is attributed to an increase in chemical interaction and reaction between methylol groups in the Ph‐PP molecules and polar functional groups in the MNR molecules upon increasing levels of the grafted succinic anhydride groups. As a consequence, compatibilizing block copolymers of MNR and PP blocks were formed. The block copolymers were capable of compatibilizing with MNR and PP blend components via the respective blocks. Recyclability of the MNR/PP TPVs was also studied. It was found that, after processing through a number of cycles by injection molding and extrusion processing, the TPV exhibited marginal decreases in mechanical properties. This corresponded to slightly increasing size of the dispersed vulcanized rubber domains. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008