Threshold tensile strength and modulus of carbon-black-filled rubber vulcanizates

The threshold tensile strength and modulus of carbon-black-filled natural rubber and styrenebutadeine rubber vulcanizates have been determined. N-220, N-330, N-375, N-550 and N-660 carbon blacks at various loadings have been used. The threshold strength varies between 0.4 MPa for gum vulcanizate to 3 Mpa for 50 phr loaded samples. Both the threshold strength and modulus are dependent on the nature and loading of the filler. The theoretical and experimental values of threshold strength and modulus are in good agreement.     

The role of tackifiers on the auto-adhesion behavior of EPDM rubber

The article describes the effect of hydrocarbon (HC) and coumarone-indene (CI) resin tackifiers on autohesion behavior of ethylene propylene diene polymethylene (EPDM) rubber. The viscoelastic behavior and nature of compatibility of EPDM/tackifier blends were studied by means of dynamic mechanical analysis. Furthermore, scanning electron microscopy and atomic force microscopy were used to understand the compatibility of the EPDM/tackifier blends. The HC tackifying resin modified the viscoelastic properties of the EPDM rubber in such a way that it behaved as a plasticizer at lower frequency by reducing the storage modulus and filler at higher frequency by increasing the storage modulus. On the contrary, the CI modified EPDM rubber did not show similar behavior; the modulus enhanced throughout the entire frequency range. The viscosity of the matrix was found to be highly governed by the compatibility as well as amount of tackifier present in the blend. In order to explain the tack behavior, several tack governing factors such as green strength, creep compliance, entanglement molecular weight, relaxation time, self-diffusion coefficient, and monomer friction coefficient (ζ₀) were investigated. The tack strength increased with HC tackifier loading up to 24 parts per hundred grams of rubber (phr), beyond which a plateau region was observed. A maximum of 196% improvement was observed at 24 phr HC loaded sample as compared to gum EPDM rubber devoid of tackifier. Conversely, there was a marginal improvement of tack strength (36%) up to 8 phr loading for the system containing CI, beyond which it dropped.     

挤出法乙丙橡胶/蒙脱土纳米复合材料制备和表征

采用一种新型的有机土蒙脱土(OMM T),通过熔融挤出法制备出了具有优异性能的乙丙橡胶/OMM T复合材料,并与炭黑补强体系进行了对比。透射电子显微镜考察表明,所制备的乙丙橡胶/OMM T纳米复合材料为剥离型结构;力学性能测试结果表明,当有机土含量仅为3份时,复合材料硫化胶的扯断强度是纯胶体系的5.2倍,比同量的高耐磨炭黑增强体系的硫化胶也提高了284%,与加入15份高耐磨炭黑的硫化胶相当;有机土体系撕裂强度也明显高于炭黑体系。还利用门尼黏度测试表征了材料的加工性能。     

Sm_2O_3/EPDM复合材料的硫化特性及力学性能

文中研究了Sm2O3/EPDM复合材料的硫化特性及力学性能。主要涉及硫化温度、偶联剂对体系硫化特性的影响;氧化钐及偶联剂含量对体系力学性能的影响。研究表明,随Sm2O3含量的增加,硫化焦烧时间变长,氧化钐对三元乙丙橡胶(EPDM)体系的力学性能有一定的增强效果,当氧化钐含量为40份时,力学性能最优。用KH-845-4偶联剂处理的氧化钐能够促进体系的硫化,体系的力学性能得到进一步的改善。     

三元乙丙橡胶耐磨性能研究

研究了生胶品种、硫化体系、填充体系和加工助剂等因素对三元乙丙橡胶耐磨性能的影响。实验结果表明:胶种选用高乙烯含量,高门尼粘度的非充油型乙丙橡胶,硫化体系采用硫磺/硫载体并用的有效硫磺硫化体系,填充体系采用高结构炭黑N220以及Si-69改性过的气相法白炭黑AS-200并用体系,同时配合0.5份左右的爽滑粉,都能有效提高EPDM胶料的耐磨性能。     

双辊共混法制备EPDM/OMMT纳米复合材料

自制一种有机改性蒙脱土(OMMT),采用双辊共混法与三元乙丙橡胶复合,得到了具有高强度、低硬度等超常力学性能的乙丙橡胶/有机蒙脱土纳米复合材料。透射电镜观察表明,制备出了半剥离型纳米复合材料,力学性能测试显示,在低填充量(15份以下)时,纳米复合材料的各项力学性能远超过同含量下高耐磨碳黑体系的。在填充量为10份时,有机土填充体系的断裂强度为15.85 MPa,是碳黑填充体系(6.57 MPa)的2.4倍,是纯橡胶体系(2.05 MPa)的7倍多;撕裂强度也高于碳黑体系和纯胶体系的;而此时纳米复合材料的邵A硬度仅为58.5,比相同强度下碳黑补强体系的低近10。     

Quantitative mapping of surface elastic moduli in silica-reinforced rubbers and rubber blends across the length scales by AFM

The surface elastic moduli of silica-reinforced rubbers and rubber blends were investigated by atomic force microscopy (AFM)-based HarmoniX material mapping. Styrene–butadiene rubbers (SBR) and ethylene–propylene–diene rubbers (EPDM) and SBR/EPDM rubber blends with varying concentrations of silica nanoparticles (0, 5, 10, 20, 50 parts per hundred rubber, phr) were prepared to investigate the effect of different composition on the resulting morphology, filler distribution and elastic moduli of a specific rubber or rubber blend sample. For SBR, the elastic modulus values varied from 0.5 MPa for unfilled SBR to 5 MPa for 50 phr reinforced SBR with the increase in the concentration of filler. For EPDM, the corresponding values increased from 1.4 MPa for unfilled EPDM to 4.5 MPa for 50 phr reinforced EPDM. Local stiff and soft domains in silica-reinforced SBR and EPDM rubbers and rubber blends were identified by HarmoniX AFM imaging. While the stiff silica particles show modulus values as high as 2 GPa, the rubber matrix reveals modulus values in the range of ca. 30 MPa for the rubber blends to ca. 300 MPa for the unfilled rubbers. The lower value of elastic modulus of the EPDM phase in the blend, compared to the blank EPDM compound can be attributed to the presence of Sunpar oil in the compound which has a very good affinity with EPDM and decreases the rubber modulus. The elastic moduli maps revealed an increase of the areal fraction of silica particles showing an intrinsic surface modulus value with rising silica content in the compound preparation mixture. HarmoniX AFM measurements revealed the formation of larger silica aggregates in EPDM in contrast to SBR where isolated silica particles were observed. For silica-reinforced rubber blends a phase separation into a soft (ca. 40 MPa) and a significantly harder phase could be observed (ca. 500 MPa–1.5 GPa) indicating the incorporation of silica particles in the SBR phase. Using HarmoniX AFM imaging significantly higher surface elastic moduli were observed compared to those obtained by bulk tensile testing. Possible reasons for the observed differences between bulk modulus values and those measured by AFM are discussed in detail, including the aspect of different averaging procedures like inherent to surface probing by AFM versus bulk tensile testing, different filler distributions in SBR and EPDM and the AFM modulus calibration procedures.     

Characterization of polyethylene/EPDM/silicon dioxide multicomponent composites by solid-state dynamic mechanical spectroscopy

Various composites of polyethylene, ethylene propylene diene rubber (EPDM), and filler are milled and analysed by solid-state dynamic mechanical spectroscopy. The filler used is silicon powder with an oxidized surface. This filler is a model for materials with siliceous surfaces. The torsion pendulum measurements show that the multicomponent composites exhibited complex viscoelastic behaviour. For composites of polyethylene and silicon dioxide, there is evidence of particle-particle interactions. In composites which include polyethylene, rubber and filler, interactions of the polyethylene and especially of the rubber with the filler surface are significant. Treatment of the filler surface with gamma-aminopropyltriethoxysilane (-APS) or gamma-methacryloxypropyltrimethoxysilane (-MPS) has a significant influence on the resultant composite dynamic mechanical spectrum. Maleic anhydride grafting of the EPDM rubber also changes the character of the composites. These composites appear to exhibit complex morphologies, which may be controlled to a certain extent by filler surface treatment and grafting to the rubber. There is evidence for a chemical reaction between the maleic anhydride modification of the EPDM and -APS during processing on the roll mill. Prediction of the composite properties using the extended van der Poel model is qualitatively useful.     

Infrared analysis and Izod impact testing of multicomponent polymer composites: polyethylene/ EP D M /filler systems

Various multicomponent polyethylene/rubber/filler composites have been characterized by diffuse reflectance infrared spectroscopy (DRIFT) and notched lzod impact testing. This work is part of a study which also included solid state and melt state dynamic mechanical testing of the same composites. The fillers used were an oxidized silicon powder and calcium carbonate. Fillers were also treated with coupling agents gamma -ami nopropyltriethoxysilane (-APS) and gamma -methacryloxypropyltrimoethoxysilan8 (-MPS). The rubbers were ethylene propylene diene (EPDM) rubber and a maleic anhydride grafted EPDM (EPDM-MA). DRIFT is useful for investigating the structure of these multicomponent composites on the molecular level. The DRIFT technique was used to confirm the presence of -MPS in the final composites treated with that coupling agent. The structure of the maleic anhydride functionality of @ maleic anhydride grafted EPDM was also determined. The DRIFT analysis detected a reaction between the maleic anhydride modification of the EPDM and -APS during processing on the roll mill to form the cyclic imide structure. This is useful in interpreting a great deal of the dynamic mechanical results. The lzod impact testing shows that impact properties of both the oxidized silicon powder and calcium carbonate composites are improved by rubber addition. The use of EPDM-MA results in greater improvement than EPDM. This is likely due to greater filler-rubber interactions in the case of EPDM-MA which leads to encapsulation of the filler by the rubber due to favourable interfacial interactions. Comparison of the storage modulusG at room temperature and lzod impact values was made for the PE/rubber/filler composites and the PE/filler and PE/rubber composites investigated in this study. Proper design of multiconmponent PE/rubber/filler composites may clearly result in higher modulus and higher impact strength than that which is available with two phase PE/filler or PE/rubber systems.     

过氧化物硫化三元乙丙橡胶的高温硫化过程模拟

通过橡胶加工分析仪探讨了采用2种一级唯象动力学方程模拟过氧化物高温硫化三元乙丙橡胶(EPDM)的可行性。结果表明,该模型与实测曲线之间具有良好的相关性,随着硫化温度的升高,过氧化物硫化EPDM橡胶的交联反应程度和断链反应程度均增大,反应速率加快。当温度低于195℃时,交联反应的活化能与断链反应的活化能基本相等;当高于195℃时,交联反应的活化能降低,而断链反应活化能的大小依赖于温度变化。并且发现高温硫化EPDM硫化胶拉伸储能模量(E’)的频率依赖性明显增强,硫化时间长短也会影响分子链的松弛行为。     

Effect of chemical blowing agent on cell structure and mechanical properties of EPDM foam, and peel strength and thermal conductivity of wood/NR composite–EPDM foam laminates

Melt-laminates of wood/natural rubber (wood/NR) composite and ethylene-propylene diene rubber (EPDM) foam were prepared by compression molding technique. Two different forms of 4,4′oxybis(benzenesulfonylhydrazide) (OBSH) blowing agent were used; pure OBSH (designated as OBSH) and ethylene-propylene bound OBSH (designated as EPR–b-OBSH). The effect of the OBSH concentration on the cell structures and mechanical properties of EPDM foam, and the peel strength and thermal conductivity of wood/NR composite–foamed EPDM laminates was examined. It was found that the EPR–b-OBSH gave EPDM foam with greater number of cell structures, higher porosities and resistances to water penetration on the foam surface. However, the EPDM with EPR–b-OBSH agent had worse elastic recovery as compared to that with OBSH due to deformation of cell structures after prolonged compression loading. The recommended concentrations for EPR–b-OBSH and OBSH blowing agents were 3.0 and 5.0 phr, respectively, for the optimum interfacial adhesion and low thermal conductivity.     

Cure and mechanical properties of recycled NdFeB-natural rubber composites

Magnetic polymer composites containing recycled neodymium-iron-boron (NdFeB) powder and natural rubber (NR) were prepared by the two-roll mill technique. Their mechanical and cure properties were studied as a function of NdFeB loading from 0–120 phr. With increasing magnetic loading, the cure time of the NdFeB-NR composites were exponentially decreased because of the reduction of the polymer chain crosslink. The tensile strength of the NR compound, related to the cure characteristics, was reduced by 40% by the addition of 10 phr NdFeB fillers because of the inhibition of the stress-induced crystallization. However, the variation in loading from 30–90 phr has modest effects on the tensile strength as well as elongation at break and the hardness. Furthermore, recycled NdFeB-NR composites had higher modulus and lower percentage of swelling in this magnetic loading regime. Simple tests confirmed the distribution of magnetic stray field around pieces of NdFeB-NR composites.     

纳米粘土/炭黑双相填料对天然橡胶性能的影响

以有机纳米粘土替代部分炭黑,在材料内部引入形状各向异性的纳米片层,制备天然橡胶/炭黑/纳米粘土复合材料,研究了粘土含量对复合材料静态力学性能、动态力学性能、热稳定性、老化性及拉伸疲劳性能的影响。结果表明,以少量有机纳米粘土(2 phr～6 phr)替代部分炭黑可提高天然橡胶的硫化效率,增强复合材料的静态力学性能,降低动态损耗因子,提高复合材料的热稳定性、耐热空气老化性能及拉伸疲劳性能。与纯炭黑试样相比,复合材料拉伸强度最高提高91%,拉伸疲劳寿命提高31%,达55万次。     

聚丙烯酸铅/三元乙丙橡胶复合材料的制备及辐射防护性能

采用氧化铅(Pb O)与丙烯酸(HAA)经偶氮二异丁腈引发合成聚丙烯酸铅,以过氧化物为硫化体系制备了聚丙烯酸铅/三元乙丙橡胶复合材料,采用傅里叶变换红外光谱仪、X射线衍射谱仪和扫描电镜对其结构进行了分析。利用材料万能试验机测量了复合材料的拉伸强度和断裂伸长率,用邵氏硬度计测量了硬度,以及高纯锗伽马能谱仪测量了屏蔽性能。结果表明,复合材料的拉伸强度和硬度随着聚丙烯酸铅粉体含量的增加而增加;断裂伸长率随着聚丙烯酸铅粉体含量的增加而降低。复合材料对于γ射线的质量衰减系数,随着聚丙烯酸铅粉体含量的增加而提高。     

Influence of interaction promoter on the properties of thermoplastic elastomeric blends of natural rubber and polyethylene

The influence of a third component as interaction promoter on the properties of natural rubber-polyethylene thermoplastic blends, both uncured and cured, has been studied. The third component chosen has some structural similarity with polyethylene and is amorphous in nature. Ethylene propylene diene (EPDM) rubber, chlorinated polyethylene and chlorosulphonated polyethylene have been used as the third component. All the third components have better adhesion with the plastic phase and the rubber phase. The adhesive strength is highest with EPDM. The properties are improved by using the above third components both for cured and uncured blends. In comparing the properties, the strength of the composite is divided by the modulus of the composite to take care of the hard-phase contribution. The size of the dispersed domain is reduced by using the third component and is approximately 1.2 m. All the properties could be explained in terms of the strengths of the individual phases, the morphology and the adhesion between components.     

Feasible incorporation of devulcanized rubber waste in virgin natural rubber

Devulcanized rubber waste produced from end-of-life passenger tyres by continuous shear flow stage control reaction technology was used both as filler and as part of rubber in a natural rubber matrix to develop the use of the rubber compound and lower the cost. The measurements of cure characteristics, swelling behaviour, crosslink density and dynamic and mechanical properties were carried out in our laboratory. In the present study it was found that using devulcanized rubber as part of rubber yields much better properties than using it as filler. Up to 15 phr devulcanized rubber used as filler and up to as much as 50 phr devulcanized rubber used as part of rubber can be incorporated in a new product without any noteworthy deterioration in performance arising.     

Improvement of impact property of natural fiber–polypropylene composite by using natural rubber and EPDM rubber

In this research, vetiver grass was used as a filler in polypropylene (PP) composite. Chemical treatment was done to modify fiber surface. Natural rubber (NR) and Ethylene Propylene Diene Monomer (EPDM) rubber at various contents were used as an impact modifier for the composites. The composites were prepared by using an injection molding. Rheological, morphological and mechanical properties of PP and PP composites with and without NR or EPDM were studied. Adding NR or EPDM to PP composites, a significant increase in the impact strength and elongation at break is observed in the PP composite with rubber content more than 20% by weight. However, the tensile strength and Young’s modulus of the PP composites decrease with increasing rubber contents. Nevertheless, the tensile strength and Young’s modulus of the composites with rubber contents up to 10% are still higher than those of PP. Moreover, comparisons between NR and EPDM rubber on the mechanical properties of the PP composites were elucidated. The PP composites with EPDM rubber show slightly higher tensile strength and impact strength than the PP composites with NR.     

Magnetoactive elastomeric composites: Cure, tensile, electrical and magnetic properties

Magnetically active elastomer materials were prepared by incorporating nickel powder in synthetic elastomeric matrices, polychloroprene and nitrile rubber. Cure characteristics, mechanical, electrical and magnetic properties were experimentally determined for different volume fractions of magnetoactive filler. The cure time decreases sharply for initial filler loading and the decrease is marginal for additional loading of filler. The tensile strength and modulus at 100% strain was found to increase with increase in the volume fraction of nickel due to reinforcement action. The magnetic impedance and a.c. conductivity are found to increase with increase in volume fraction of nickel as well as frequency.     

NR/CSM/biogenic silica rubber blend composites

Biogenic silica (BSi) was added at different ratios to some polymer blends of polyisoprene rubber (NR) and chlorosulphonated polyethylene rubber (CSM) cured by conventional sulfur system. The reinforcing performance of the filler was investigated using rheometric, mechanical and swelling measurements, differential scanning calorimetry (DSC), thermogravimetric (TGA) and scanning electron microscopy (SEM) analysis. There was a remarkable decrease in the optimum cure time (t_c90) and the scorch time (t_s2), which was associated with an increase in the cure rate index (CRI), with filler loading up to 30 phr in the different blend ratios. The tensile strength and hardness was 4–5 Sh-A higher in the case for the different blend compositions, while the resistance to swelling in toluene became higher. SEM photographs show that the filler is located at the interface between the different polymers which induces compatibilization in the immiscible blends. DSC scans of the filled blends showed shifts in the glass transition temperatures Tg which can be attributed to the improve interfacial bonding between filler and NR/CSM matrix. A higher thermal stability of NR/CSM/BSi composites was detected.     

Effect of montmorillonite modification on mechanical properties of vulcanized natural rubber composites

Natural rubber-clay composites were prepared by direct polymer melt intercalation. Ca-montmorillonite Jelšovy Potok (JP; Slovakia) and Na-montmorillonite Kunipia-F (KU; Japan) were ion exchanged with octadecyltrimethylammonium (ODTMA) bromide and were used as aluminosilicate fillers. Silica Ultrasil VN3 was used in amount of 15 phr as conventional filler. The effect of clay or organoclay loading from 1 up to 10 phr on the mechanical properties was evaluated from the tensile tests (stress at break, strain at break and modulus M100). Organic modification resulted in an increase of toluene uptake degree for both fillers. While an addition of unmodified KU had no effect on tensile strength and deformation at break, a reinforcing effect was observed for the mixture containing 10 phr of unmodified JP. Both ODTMA modified fillers (KU and JP) exhibited substantial increase in tensile strength and deformation at break; JP proved to be more effective compared to KU also if modified with ODTMA. The highest stress at break and strain at break values for natural rubber composites were obtained with 15 phr of SiO₂ and 10 phr of montmorillonite; however, the effect of exchangeable cation was minor.