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     

BIIR/EPDM/OMMT纳米复合材料的结构与性能研究

选择实验室自制有机蒙脱土(OMMT),采用机械共混法制备了溴化丁基橡胶/三元乙丙橡胶/OMMT(BIIR/EPDM/OMMT)纳米复合材料。利用X射线衍射分析(XRD)和扫描电子显微镜分析(SEM)考察了复合材料的亚微观结构,表明成功制备出了BIIR/EPDM/OMMT纳米复合材料;不同OMMT含量的复合材料的力学性能测试结果表明:当OMMT用量为5份时,拉伸强度和撕裂强度分别提高了44%和43%;另外对纳米复合材料的硫化特性及表观交联密度进行了对比分析。     

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     

Preparation and structure and mechanical properties of poly(styrene‐b‐butadiene)/clay nanocomposites

Star‐shaped and linear block thermoplastic poly(styrene‐b‐butadiene) copolymer (SBS)/organophilic montmorillonite clays (OMMT) were prepared by a solution approach. The intercalation spacing in the nanocomposites and the degree of dispersion of nanocomposites were investigated by X‐ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. The mechanical properties, dynamic mechanical properties, and thermal stability of these nanocomposites were determined. Results showed that SBS chains were well intercalated into the clay galleries and an intercalated nanocomposite was obtained. The mechanical strength of nanocomposites with the star‐shaped SBS/OMMT were significantly increased. The addition of OMMT also gave an increase of the elongation, the dynamic storage modulus, the dynamic loss modulus, and the thermal stability of nanocomposites. The increase of the elongation of nanocomposites indicates that SBS has retained good elasticity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3430–3434, 2004     

Mechanical and physicochemical properties of electron beam irradiated rubber/clay nanocomposites

Effect of electron beam irradiation on the mechanical and physicochemical properties of both styrene butadiene rubber (SBR)/clay and ethylene propylene diene monomer (EPDM)/clay nanocomposites containing clay contents from 3 to 10 phr prepared by melt blending method has been investigated. The prepared composites were subjected to electron beam irradiation doses of up to 150 kGy to induce radiation curing, whereas the mechanical properties in terms of tensile strength (TS), tear strength (Ts), and elongation at break (E_b) were studied as a function of irradiation dose and clay content. TS and Ts increased with increasing irradiation dose up to 100 kGy, they were decreased with further increase in dose. An increase in TS and Ts for SBR and EPDM nanocomposites containing various organomodified montmorillonite (OMMT) contents (3–5 phr) was noticed, whereas a decrement behavior was observed at higher OMMT content. The elongation at break decreased continuously with both irradiation dose and OMMT content. The crosslink density for either EPDM or SBR samples increases with increasing irradiation dose up to 150 kGy and by increasing clay content up to 5 phr, whereas it decreases at higher clay content (7–10 phr). At 5 phr OMMT and 100 kGy irradiation, SBR nanocomposites showed higher TS and Ts than EPDM nanocomposites, while the crosslink density of SBR is lower. POLYM. COMPOS., 34:1600–1610, 2013. © 2013 Society of Plastics Engineers     

Compatibilization of poly(lactic acid)/ethylene‐propylene‐diene rubber blends by using organic montmorillonite as a compatibilizer

This work focuses on phase morphology and properties of immiscible poly(lactic acid)/ethylene‐propylene‐diene rubber (PLA/EPDM) blends compatibilized with organic montmorillonite (OMMT). Effect of OMMT loading on phase morphology, mechanical properties, and blown film bubble stability was investigated. Transmission electron micrographs show that a large number of OMMT nanolayers locate at interfacial region between PLA and EPDM phase, as well as in EPDM phase due to higher affinity of OMMT with EPDM. Scanning electron micrographs show that EPDM domain size decreases largely with increasing OMMT loading, which is associated with reduction of interfacial energy and inhibition of coalescence by the OMMT locating at the interface, acting as an emulsifier to enwrap the discrete domains. As OMMT loading increases from 0 to 1 phr, elongation at break increases from 20.4 to 151.7% and notched impact strength is enhanced from 8.2 to 31.7 kJ?m^?2. The reduced EPDM domain is the main reason for enhanced toughness of PLA/EPDM/OMMT samples according to crazing with shear yielding mechanism. However, with more than 2 phr of OMMT, the toughness decreases largely due to excessive stress concentration and OMMT aggregation. Attempts were made to produce ductile films from the PLA/EPDM/OMMT nanocomposites by using blown film extrusion. Improvement in blown film bubble stability and tensile ductility of PLA/EPDM/OMMT films also shows that OMMT is an efficient compatibilizer, as well as a processing aid for PLA/EPDM blends. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44192.     

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     

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     

Novel preparation and properties of EPDM/montmorillonite nanocomposites

This article reports on a novel route to develop ethylene–propylene–diene rubber (EPDM)/montmorillonite nanocomposites Modification of the MMT was carried out with maleic anhydride (MA), which acts as the intercalation agent for MMT and the vulcanizing agent for EPDM matrix, as well as the compatibilizer for the EPDM and MMT phases. The effect of MA‐modified MMT in nanocomposites was investigated by focusing on three major aspects: structural analysis, thermal properties, and material properties. The d‐spacings of both the MA modified MMT and exfoliated nanocomposites were investigated by X‐ray diffraction (XRD), and the morphology of these nanocomposites was examined by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Dynamic mechanical analysis confirms the constraint effect of exfoliated MMT layers on EPDM chains, which benefited the increased storage modulus, increased glass transition temperature. Thermogravimetric analysis indicates that there is some enhancement in degradation behavior between the nanocomposites and EPDM matrix. The nanocomposites exhibit great improvement in tensile strength and modulus, as well as elongation‐at‐break. The effects of MA addition on the formation of nano‐metric reinforcement and on the mechanical properties of nanocomposites are discussed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 2578–2585, 2006     

Preparation and properties of new EPDM/vermiculite nanocomposites

Novel nanocomposites based on ethylene‐propylene‐diene rubber (EPDM) and maleic anhydride‐modified vermiculite (VMT) were prepared. Maleic anhydride (MA) acts both as the intercalation agent for VMT and as a vulcanizing agent for EPDM matrix. It also acts as a compatibilizer for EPDM and VMT phases. From analysis by X‐ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), the silicate layers of the VMT were exfoliated and dispersed uniformly in the EPDM matrix as monolayers. The thermal properties of the nanocomposites were investigated by dynamic mechanical thermal analysis and thermogravimetric analysis; a strong rubber‐filler interaction in the nanocomposites was manifested in the measured temperature range by the result of storage modulus. At the same time, there was some enhancement in degradation behavior between the nanocomposites and EPDM matrix. The nanocomposites exhibited a great improvement in tensile strength and modulus, as well as elongation at break. Finally, the effects of MA addition on the formation of nanometric reinforcement and on the mechanical properties of nanocomposites are discussed. POLYM. COMPOS., 26:706–712, 2005. © 2005 Society of Plastics Engineers     

Studies on the viscoelasticity of poly(trimethylene terephthalate)/poly(ethylene–octene)/organomontmorillonite nanocomposites

The viscoelasticity of poly(trimethylene terephthalate)/maleinized poly(octene‐ethylene) copolymer/organomontmorillonite (OMMT) nanocomposites were investigated at both liquid and glassy states by using the rotational rheometer and dynamic mechanical analysis, respectively. The viscoelasticity results suggest that OMMT has many important influences on the structure, modulus, toughness, and cold‐crystallization of the nanocomposites. The OMMT has a strip‐like sheet morphology in the polymer matrix and when OMMT content increases to 4 wt%, the physical network‐like structure begins to form in the nanocomposites. The pseudoplasticity of the melts is increased by OMMT. In addition, the complex viscosity, storage modulus, and viscous behavior of the melts are increased with increasing OMMT content. The creep resistance of the nanocomposites is improved by OMMT, and it plays an important role on reinforcing the melts. The stress relaxation of the melts suggests that the nanofillers can not only enhance the interfacial interactions of the nanocomposites but also inhibit the recovery of the polymer chain segments. At glassy state, the nanocomposites' storage modulus increases with increasing OMMT content. As glass transition occurs, the loss factor and loss modulus suggest that OMMT toughens the polymer matrix. At rubber‐elastic state, OMMT depresses the cold‐crystallization of the polymer matrix due to its limitation effect on the motion of molecular chains. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Effect of organic modifiers and silicate type on filler dispersion,thermal, and mechanical properties of ABS‐clay nanocomposites

Acrylonitrile–butadiene–styrene (ABS)–clay composite and intercalated nanocomposites were prepared by melt processing, using Na‐montmorillonite (MMT), several chemically different organically modified MMT (OMMT) and Na‐laponite clays. The polymer–clay hybrids were characterized by WAXD, TEM, DSC, TGA, tensile, and impact tests. Intercalated nanocomposites are formed with organoclays, a composite is obtained with unmodified MMT, and the nanocomposite based on synthetic laponite is almost exfoliated. An unintercalated nanocomposite is formed by one of the organically modified clays, with similar overall stack dispersion as compared to the intercalated nanocomposites. T_g of ABS is unaffected by incorporation of the silicate filler in its matrix upto 4 wt % loading for different aspect ratios and organic modifications. A significant improvement in the onset of thermal decomposition (40–44°C at 4 wt % organoclay) is seen. The Young's modulus shows improvement, the elongation‐at‐break shows reduction, and the tensile strength shows improvement. Notched and unnotched impact strength of the intercalated MMT nanocomposites is lower as compared to that of ABS matrix. However, laponite and overexchanged organomontmorillonite clay lead to improvement in ductility. For the MMT clays, the Young's modulus (E) correlates with the intercalation change in organoclay interlayer separation (Δd₀₀₁) as influenced by the chemistry of the modifier. Although ABS‐laponite composites are exfoliated, the intercalated OMMT‐based nanocomposites show greater improvement in modulus. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

环氧树脂改性聚乳酸/低熔点尼龙6/蒙脱土纳米复合材料结构与性能

通过熔融共混法制备了环氧树脂改性聚乳酸 (ePLA)/低熔点尼龙6 (LMPA6)/蒙脱土纳米复合材料。XRD和DSC结果表明,结晶度随着有机蒙脱土（OMMT）加入量的增加呈先增加后减小的趋势。流变行为结果表明,ePLA/LMPA6/OMMT纳米复合材料的黏性响应占主导地位,另外,随着OMMT加入量的增加,储能模量和损耗模量也增加。阻隔性能测试结果表明,OMMT的加入能够有效地改善纳米复合材料的阻隔性能。热重结果表明,OMMT的加入能够显著提高纳米复合材料的热稳定性能。TEM测试结果表明,OMMT加入量较少时,OMMT容易在基体中形成均一的纳米结构。力学性能分析表明,随着OMMT质量分数的增加,纳米复合材料的拉伸强度、断裂伸长率和冲击强度均出现先上升后下降的趋势,且当OMMT质量分数为3%时,纳米复合材料的力学性能均达到最大值,与未加OMMT时相比,分别提高了9.7%、37.8%和35.9%。     

聚酰胺6/环氧树脂改性蒙脱土纳米复合材料的制备与性能

采用环氧树脂改性蒙脱土（MMT）得到有机化蒙脱土（OMMT）,再用熔融插层法制备了聚酰胺6 （PA6）/ OMMT纳米复合材料。采用X射线衍射仪、透射电子显微镜、万能材料试验机、热重分析仪等研究了PA6/OMMT复合材料的形态结构、力学性能和热稳定性。结果表明,经环氧树脂改性得到的OMMT的层间距明显增加,从未改性的1.22 nm增加到5.13 nm,并以纳米尺度分散于PA6基体中;随着OMMT含量的增加,PA6/ OMMT复合材料的强度和模量增加,热变形温度提高,其拉伸强度可达76 MPa,弯曲模量达到3.462 GPa,热变形温度为134 ℃;PA6/ OMMT复合材料失重10 %时的温度为422 ℃,比纯PA6的406 ℃提高了16 ℃,改善了PA6的热稳定性。     

Structure and mechanical properties of nanodispersed fibrous silicate‐reinforced ethylene–propylene–diene monomer nanocomposites

In this study, ethylene–propylene–diene monomer (EPDM)/fibrillar silicate (FS) nanocomposites were successfully prepared by mechanically blending EPDM with FS, which was modified by silane coupling agent KH570 containing methacryloxy group. The effects of silane content and modified FS on the dispersion of FS and mechanical properties of the composites were investigated. The impact of water in FS on mechanical properties of the composites was also evaluated. The results showed that modified FS could be dissociated into nanofibers dispersing evenly in the EPDM matrix by increasing substantially the loading of silane through the mechanical blending. The optimum loading level of silane coupling agent was up to 24 phr/100 phr FS. Silane KH570 could improve the dispersion of FS and strengthen nanofibers–rubber interfacial adhesion even at the loading of as high as 50 phr FS, making FS to exhibit excellent reinforcement to EPDM. Too much FS could not be completely dissociated into nanofibers, slowing down further improvement. The EPDM/FS composites exhibited the similar stress–strain behavior and obvious mechanical anisotropy with short microfiber‐reinforced rubber composites. With the increase in silane coupling agent and modified FS, the number of nanofibers increased because of the exfoliation of FS microparticles; thus, the mechanical behaviors would become more obvious. It was suggested that the free water in FS should be removed before mechanically blending EPDM with FS because it obviously affected the tensile properties of the composites. Regardless of whether FS was dried or modified, the EPDM/FS composites changed little in tensile strength after soaked in hot water. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

三元乙丙橡胶/蒙脱土纳米复合材料的制备方法与应用前景

橡胶／蒙脱土纳米复合材料的优异性能使其成为橡胶工业中富有潜力的一类新型材料。笔者综述了三元乙丙橡胶(EPDM)／蒙脱土纳米复合材料的制备方法、性能和工业应用领域等，讨论了蒙脱土片层的表面修饰、插层剂的选择以及复合材料的制备方法对材料性能的影响，并提出了三元乙丙橡胶／蒙脱土纳米复合材料这一新型橡胶材料在轮胎工业上的应用前景。     

Synergistic effects of zinc oxide in montmorillonite flame‐retardant polystyrene nanocomposites

In this study, two‐dimensional organic montmorillonite (OMMT) and one‐dimensional needlelike ZnO were used as flame retardants of polystyrene (PS). Polystyrene/organic montmorillonite (PMT) and polystyrene/organic montmorillonite/zinc oxide nanocomposites (PMZs) with different weight ratios were prepared by melt intercalation. Information on the morphologies and structures of the PS nanocomposites was obtained with Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy. The results indicate that a mixed exfoliated–intercalated structure was observed in the PMT and PMZs. Dynamic mechanical thermal analysis showed that both the storage modulus and glass‐transition temperature values of the PMT and PMZs were significantly improved compared with those of the neat PS. The mechanical property tests showed that the bending modulus values of both PM5 (PS/OMMT weight ratio = 95:5) and PMZs increased compared with that of pristine PS. PMZ1 (PS/OMMT/ZnO weight ratio = 94:5:1) provided no decrease in the tensile strength in comparison with PS. A synergistic effect was observed between OMMT and ZnO; this resulted in improvements in the flame retardancy and dynamic mechanical properties in the PMZs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43047.     

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     

Dynamic mechanical analysis of ethylene–propylene–diene monomer rubber and styrene–butadiene rubber blends

The effects of blend ratio, crosslinking systems, and fillers on the viscoelastic response of ethylene–propylene–diene monomer (EPDM)/styrene–butadiene rubber (SBR) blends were studied as functions of frequency, temperature, and cure systems. The storage modulus decreased with increasing SBR content. The loss modulus and loss tangent results showed that the EPDM/SBR blend vulcanizate containing 80 wt % EPDM had the highest compatibility. Among the different cure systems studied, the dicumyl peroxide cured blends exhibited the highest storage modulus. The reinforcing fillers were found to reduce the loss tangent peak height. The blend containing 40 wt % EPDM showed partial miscibility. The dispersed EPDM phase suppressed the glass‐transition temperature of the matrix phase. The dynamic mechanical response of rubbery region was dominated by SBR in the EPDM–SBR blend. The morphology of the blend was studied by means of scanning electron microscopy. The blend containing 80 wt % EPDM had small domains of SBR particles dispersed uniformly throughout the EPDM matrix, which helped to toughen the matrix and prevent crack propagation; this led to enhanced blend compatibility. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of exfoliated organophilic montmorillonite on the structure and conductivity of polypropylene/polyaniline composites

This study concentrates on the effect of organophilic montmorillonite (OMMT) nanolayers on conductivity, structure, morphology, and mechanical properties of the polypropylene/polyaniline (PP/PANI) composites. The composite was prepared by in situ polymerization of aniline at different composition ratios in the presence of PP powder. The structure and conductivity of ternary PP/PANI/OMMT nanocomposites were compared with those of PP/PANI composites. DC electrical conductivity measurements indicated that electrical conductivity decreased in the presence of OMMT layers. Scanning electron microscopy showed that the surface of ternary nanocomposites have more rough regions. The interaction between PANI and OMMT was confirmed by Fourier transform infrared spectroscopy. The distribution of OMMT layers in the polymer matrix, as an effective parameter on the properties of nanocomposite, was investigated and confirmed using X‐ray diffraction and transmission electron microscopy. The results showed an exfoliated array for OMMT layers in the nanocomposite structure. The shear storage modulus for PP/PANI composites was lower than that for pure PP; however, it was increased for PP/PANI/OMMT nanocomposites. The data from the tensile and izod impact strength showed that the Young's modulus and izod impact strength were increased slightly by the addition of OMMT, whereas the elongation at break was decreased. POLYM. COMPOS., 38:699–707, 2017. © 2015 Society of Plastics Engineers