Thermal aging of bentonite‐filled ethylene propylene diene monomer composites

Bentonite‐filled ethylene propylene diene monomer (EPDM/Bt) composites were prepared using two roll mill compounding method and the effect of Bt loading on the thermal aging, swelling resistance and crosslink density of EPDM/Bt composites were studied. The effect of in situ addition of different silane coupling agents (SCAs) on the above properties at optimum Bt loading of EPDM/Bt composite was also investigated. Thermal aging test results show that the tensile strength and tensile modulus at 100% elongation (M100) increase initially for 2 days aged composites and decrease slightly after 4 days of aging, meanwhile the elongation at break (E_b) decrease gradually with aging period as compared to the unaged composites. Upon aging, swelling resistance increase initially indicating increased crosslink density of EPDM/Bt composite due to post‐curing and reduced after 4 days of aging due to crosslink destruction and EPDM chain scissioning. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4419–4427, 2013     

Optimization of hybrid oil/water-swelling ethylene/propylene/diene monomer compounds

Hybrid swell packers are rubber products capable of swelling in (saline) water and hydrocarbon oils, by exploiting the hydrocarbon diffusion properties of an nonpolar elastomer with the osmotic swelling of a water absorbent (WA). In this study, a variety of modified natural and synthetic WAs and mixtures thereof have been screened in a rubber compound with respect to swelling in decalin, demineralized, and saline water, respectively. We aimed at achieving high and fast swelling in all used media. Mixing of the various WAs in an ethylene/propylene/diene monomer (EPDM)/carbon black masterbatch at an addition level of 75 phr did not pose any problems, although it was found that the WAs did affect the sulfur vulcanization. Decalin swelling of the vulcanizates is very fast, reaching high equilibrium swelling within 1.5 days. Swelling in demineralized or saline water is much slower, with up to 300% swelling in water and up to 100% swelling in saline water. Significant leaching of the organic WA from the EPDM vulcanizates to the water phase occurs. Some combinations of WAs show synergetic effects for swelling in water. To our knowledge, such a systematic study of hybrid swelling elastomers constitutes a novelty in the open literature.     

Natural rubber/ethylene propylene diene blends for high insulation iron crossarms

This research studied the composition and behavior of natural rubber (NR) and ethylene propylene diene monomer (EPDM) blends at various carbon black concentrations (0–30 phr) in terms of electrical resistivity, dielectric breakdown voltage testing, and physical properties. The blends having electrical properties suitable for application in high‐insulation iron crossarms were selected for investigation of compatibility and increased physical properties. The effect of the homogenizing agent concentration on improvement of compatibility of blends was studied by scanning electron microscopy, pulsed nuclear magnetic resonance spectroscopy, and rheology techniques. We also examined mechanical properties such as tensile strength, tear strength, elongation at break, and hardness. The NR/EPDM blends filled with a fixed concentration of silica were investigated for ozone resistance. A carbon black content as high as 10 phr is still suitable for the insulation coating material, which can withstand electrical voltage at 10 kVac. Addition of the homogenizing agent at 5 phr can improve the mechanical compatibility of blends, as evidenced by the positive deviation of shear viscosity of the rubber blend, that is, the calculated shear viscosity being higher than that of experimental data. Moreover, the pulsed NMR results indicated that the spin‐spin relaxation (T₂) of all three components of the rubber blend was compressed upon the addition of the homogenizing agent. The ratio of NR/EPDM in the blend to best resist the ozone gas is 80/20 with the addition of silica of 30 phr into the blend. Also, the NR/EPDM filled with silica had a decreased change in thermal and mechanical properties of blends after thermal aging. The synergistic effect of silica content and high NR content (80) in 20 phr EPDM could improve antioxidation by ozone in the absence of a normal antioxidant for natural rubber. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3401–3416, 2004     

Thermomechanical devulcanization of ethylene propylene diene monomer rubber and its application in blends with high-density polyethylene

The recycling of ethylene propylene diene monomer (EPDM) rubber remains a challenge, as its cross-linked structure cannot be broken down reversibly. Devulcanization may offer a breakthrough; however, a 100% decrease in cross-link density (CLD) with no chain degradation has never been reported. In this research, sulfur- and peroxide-cured EPDM rubbers of known compositions were devulcanized on a two-roll mill and in an internal mixer. The CLD of both rubber samples decreased by around 85%, while the sol content of the peroxidic devulcanizate was considerably higher than that of the sulfuric devulcanizate (23% vs. 3%). Horikx's theory revealed that sulfur-cured samples showed excellent selectivity for cross-link scission, while peroxide-cured samples suffered degradation. Uncured, cured, and devulcanized rubber samples were mixed into high-density polyethylene at various compositions. Large EPDM rubber contents impaired the mechanical properties of the blends, indicating insufficient adhesion between the two phases. Compounds containing originally uncured rubber mixtures had the most beneficial mechanical properties.     

Naturally occurring halloysite nanotubes for enhanced durability of natural rubber/ethylene propylene diene monomer rubber vulcanizate

A facile approach of using halloysite nanotubes (HNTs) was proposed to address the durability performance demands of natural rubber (NR)/ethylene propylene diene monomer rubber (EPDM) blends and to protect them from the deleterious effects of the service environment including ozone, chemicals, abrasion, and cyclic loading. The introduction of HNTs substantially improved the stability of NR/EPDM when exposed to ozone (over fourfold enhancement with the addition of 5 phr HNTs). Moreover, the HNT-filled NR/EPDM vulcanizates offered approximately 66% reduction in the solvent-mediated swelling in comparison to the unfilled sample. Fatigue life studies showed that the HNT-reinforced NR/EPDM composite could withstand 30% more cycles to failure than the un-reinforced NR/EPDM blend. The effect of various HNT loading on the morphological, mechanical, physical, and rheological properties of nanocomposite vulcanizates based on NR/EPDM was also investigated. The morphological investigations revealed that the introduction of HNT into the NR/EPDM rubber matrix caused a rough morphology in fracture surface and a well-dispersed structure was obtained with the addition of up to 5 phr of HNTs. These findings were further supported by rheological, mechanical, and thermodynamical results.     

Study on isotactic polypropylene/zinc‐neutralized sulfonated ethylene propylene diene monomer rubber/CaCO3 ternary blends

The morphological structure and mechanical properties of isotactic polypropylene (PP)/zinc‐neutralized sulfonated ethylene propylene diene monomer rubber (Zn? SEPDM)/CaCO₃ blends were studied. PP/Zn? SEPDM/CaCO₃ blends were prepared through two different sequences. A: Blending PP with Zn? SEPDM, then adding CaCO₃; B: Blending Zn? SEPDM with CaCO₃, then adding PP. The blending sequence has substantial influence on the mechanical properties. SEM micrographs and X‐ray photoelectron spectrometry indicate that the CaCO₃ filler is encapsulated by Zn? SEPDM in those blends prepared through sequence B, which caused an extra increase of impact strength. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1635–1640, 2004     

Studies on electrically conductive composites of ethylene propylene diene monomer rubber and steel fibers

Electrically conductive composites comprised of ethylene propylene diene monomer (EPDM) rubber and steel fibers were prepared by an open mill mixing method. Fibers of two distinctly different lengths (5 mm and several meters) were used and the influence of these fibers on electrical conductivity, mechanical, thermal, and physical properties of the composites was investigated. Composites with different compositions were prepared by varying the loading levels of fibers from 20–100 phr (parts per hundred parts of rubber). Homogeneity of the composites was determined using scanning electron microscopy. Further analysis included the measurement of resistance, hardness, tensile strength, tear strength, rebound resilience, etc. The results of the analysis revealed that the addition of steel fibers rendered conductivity to the otherwise insulating EPDM rubber even at small loading levels, however, the length appears to have negligible effect on conductivity. In case of short fibers, the resistance of composites was observed to decrease from > 40 MΩ (Initial value of EPDM rubber) to 25 KΩ at a loading level of 20 phr with a further significant decrease of the order of 10³, that is around 18 Ω at 100 phr. Composites with long fibers exhibited resistance in the range of 15 kΩ–70 Ω at loading levels between 30 and 100 phr. The conductivity of the sample is observed to be altered negligibly on ageing. Mechanical properties such as hardness, tensile, and tear strength were observed to be enhanced in case of composites except resilience which decreased by 29 % in comparison to EPDM rubber. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal stability and ablation properties study of aluminum silicate ceramic fiber and acicular wollastonite filled silicone rubber composite

The thermal stability and ablation properties of silicone rubber filled with silica (SiO₂), aluminum silicate ceramic fiber (ASF), and acicular wollastonite (AW) were studied in this article. The morphology, composition, and ablation properties of the composite were analyzed after oxyacetylene torch tests. There were three different ceramic layers found in the ablated composite. In the porous ceramic layer, the rubber was decomposed, producing trimers, tetramers, and SiO₂. ASF and part of AW still remained and formed a dense layer. The SiO₂/SiC filaments in the ceramic layer reduced the permeability of oxygen, improving the ablation properties of the composites. The resultant ceramic layer was the densest, which acted as effective oxygen and heat barriers, and the achieved line ablation rate of the silicone composite were optimum at the proportion of 20 phr/40 phr (ASF/AW). Thermogravimetric analysis (TGA) confirmed that thermal stability of the composites was enhanced by the incorporation of ASF and AW. The formation of the ceramic layer was considered to be responsible for the enhancement of thermal stability and ablation properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39700.     

Investigation of novel polyanilines as new antioxidants for ethylene propylene diene monomer rubber composites

Oxidative aging is a significant deterioration process that affects the performance and durability of rubber materials in various applications. Therefore, this study focuses on the development of new antioxidants-based on polyaniline for ethylene propylene diene monomer (EPDM) rubber to enhance its resistance to oxidative aging. The novel polyanilines were prepared using in situ polymerization method and characterized using Fourier transforms infrared (FTIR) and thermogravimetric analysis (TGA). FTIR illustrates the success synthesis of polyanilines as it shows their characteristic functional groups. The thermal stability of the formed polyanilines is discussed through TGA and derivative of thermogravimetry (DTG) curves. The curves prove the good thermal stability of the synthesized polymers. The prepared polyaniline compounds were mixed to carbon black filled-EPDM rubber composites using a roll mill and then vulcanized using sulfur curing process. Accelerated aging tests for the prepared EPDM rubber composites were conducted to evaluate the effectiveness of the antioxidants. Moreover, their impact on rheometer, mechanical, and swelling properties was studied. The results showed that the EPDM samples with the prepared polyaniline compounds exhibited improved oxidative properties compared to the EPDM sample with commercial antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline. These findings suggest that the novel antioxidants have the potential to enhance the durability and performance of EPDM rubber in various applications.     

Ablation properties of aluminum silicate ceramic fibers and calcium carbonate filled silicone rubber composites

The ablative performance of aluminum silicate ceramic fiber (ASF) and calcium carbonate (CaCO₃) filled silicone rubber composites prepared through a two‐roll mill was examined. The properties of the composites were investigated by thermogravimetry, thermal conductivity measurements, and oxyacetylene torch testing. After the material was burnt, the structure and composition of the char were analyzed by Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy (SEM). The results of the ablation test showed that the ablation resistance improved greatly in an appropriate filler scope. Combined with SEM, it was proven that a firm, dense, and thermal insulation layer, which formed on the composites surface during the oxyacetylene torch test, was a critical factor in determining the ablation properties. Thermogravimetric analysis revealed that the thermal stability of the composites was enhanced by the incorporation of ASF and CaCO₃. The thermal conductivity measurements showed that the silicone rubber composites had a very low thermal conductivity ranging from 0.206 to 0.442 W m^?1 K^?1; this significantly prevented heat from transferring into the inner matrix at the beginning of the burning process. The proportion of 20/40 phr (ASF/CaCO₃) was optimum for improving the ablation resistance of the silicone rubber composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41619.     

Effects of peroxide and gamma radiation on properties of devulcanized rubber/polypropylene/ethylene propylene diene monomer formulation

Mechanical and thermal properties of devulcanized rubber (DR)/polypropylene (PP)/ethylene propylene diene monomer blends (EPDM) were studied at various concentrations of dicumyl peroxide (DCP) and gamma radiation doses. The blends showed improved mechanical properties for vulcanized sample. The coupling of DR/PP/EPDM with different proportions of DCP was investigated by X‐ray diffraction and scanning electron microscopy techniques. Evaluation of the developed blends, unirradiated and gamma irradiated, was carried out using elastic modulus, tensile strength, elongation at break, thermogravimetric analysis, kinetic analysis, and DSC measurements. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40611.     

环氧化天然橡胶共交联改性EPDM/NR共混物的性能

将三元乙丙橡胶(EPDM)与环氧化天然橡胶(ENR)共交联改性后,再与天然橡胶(NR)共混,考察了ENR共交联改性EPDM/NR共混胶的硫化特性、硫化胶的物理机械性能、溶胀指数和耐热空气老化性能,并对该硫化胶进行了差示扫描量热分析。结果表明,EPDM经过ENR共交联改性后与NR共混,ENR共交联改性EPDM/NR共混胶的交联程度明显提高,各相达到了同步交联,硫化胶的综合性能得到了显著改善。     

Effect of hybrid filler (HNTs‐phthalocyanine) on the thermal properties and flammability of diene rubber

Rubber is an essential polymer widely used in the auto‐industry. We report a method for the synthesis of zinc phtalocyanine (ZP), chloroalumino phthalocyanine (CP), and their hybrid fillers obtained by the synthesis of the two phtalocyanines in the presence of halloysite nanotubes (HNTs). The hybrid fillers were characterized by means of microscopic, thermal, and particle size measurement analysis. The effect of these fillers on the properties of diene rubbers were assessed in comparison with a physical mixture of halloysite and ZP or CP pigment. The dispersion degree of hybrid fillers inside an elastomeric matrix (rubber) was assessed with the atomic force microscopy. The influence of the hybrid fillers on the thermal and mechanical properties and flammability of butadiene‐acrylonitrile (NBR) and butadiene‐styrene (SBR) rubbers was assessed by analyzing the measurement results obtained by means of thermogravimetric analysis, differential scanning calorimetry, Zwick Tensile testing, FAA micro‐calorimeter, and oxygen index determination. We found that regardless of the spatial network structure of NBR and SBR rubbers, the incorporation of hybrid fillers into the matrix of the elastomers showed an improvement in their thermal and mechanical properties as well as a significant reduction in flammability. The improvement is attributed to the smaller size and much better dispersion of HZ and HC in relation to the particles of phthalocyanine. The colored composites of NBR rubber, containing hybrid filler (HZ or HC), showed an increase in the heat capacity compared to the uncolored samples, which can increase safety by facilitating the processes of self‐extinguishing. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42593.     

Effect of pulverized coal/carbon black hybrid fillers on mechanical properties and thermal stability of styrene butadiene rubber composites

Pulverized coal (coal) possesses a layered structure similar to graphite and is a potential reinforcing filler. In this paper, ball milling is used to reduce the particle diameter of coal. The coal is modified with KH-560 to obtain K-COAL and prepared K-COAL/styrene-butadiene rubber (SBR) composites. In addition, carbon black (CB) is modified to obtain CB-Si69, K-COAL and CB-Si69 are added to SBR in different ratios to prepare COAL/CB/SBR composites. The results show that the addition of K-COAL can improve the vulcanization performance, thermal stability, and mechanical properties of SBR composites, but the reinforcing effect is weak. In the COAL/CB/SBR composites, the vulcanization and mechanical properties of the composites gradually increase with the increase of CB, while those of the thermal stability decrease. The tensile strength of the 10 phr COAL/30 phr CB/SBR composite is 24.1 MPa, which is elevated by 1105% and 205% compared with the pure SBR and 40 phr K-COAL/SBR composites, respectively. The composites maintain high elasticity while the tensile strengths are greatly improved, and the mechanical properties are significantly enhanced. In conclusion, this paper provides a reference for the clean utilization of coal and shows new possibilities for finding new fillers to replace CB.     

Evaluation of the salt leaching method for the production of ethylene propylene diene monomer rubber foams

The thermomechanical behavior of ethylene propylene diene monomer (EPDM) foams produced with the salt leaching method has been investigated and compared with the behavior of EPDM foams obtained from conventional blowing agents. Moreover, the salt-leaching process has been optimized to minimize salt residues and the influence of different parameters (such as average particle size and particle size distribution) has been investigated. Scanning electron microscopy and density measurements highlighted that salt-leaching leads to the formation of open-cell porosity with cell dimensions of around 60 to 80 μm, while foams obtained with the two traditional foaming agents lead to closed-cell porosity. Compression set values indicate that the behavior of the foams produced with salt leaching are more similar to the unfoamed rubber, characterized by higher elasticity and low residual deformation. Two theoretical models were successfully applied to the compression curves (Mooney-Rivlin and Exponential-Logarithmic) and they highlighted the effect of foaming on the properties of EPDM rubber and in particular the higher chain extensibility obtained through the salt leaching foaming method.     

Thermal and mechanical properties of dough modeling compound reinforced ethylene propylene diene monomer/silicon rubber composites

Ethylene propylene diene monomer (EPDM)/silicon rubber composite was prepared by adding dough‐modeling compound (DMC). EPDM/silicon rubber is the matrix of the composite, and DMC is a disperse phase (reinforced phase). The morphology of the composite was studied by scanning electron microscopy, and it was found that the compatibility of DMC/EPDM/silicon rubber composite was good. The influence of the DMC and peroxide curing agents on the mechanical and thermal properties were studied. The results showed that the mechanical and thermal properties of the composite were best, when DMC/EPDM/silicon rubber was 80/25/75. The thermal properties of the composite prepared with added equivalent dicumyl peroxide was better than those with added benzoperoxide, but Shore A hardness and elongation at break are unchangeable. The integral properties of DMC reinforced EPDM/silicon rubber composite was much better than three raw materials. POLYM. COMPOS. 27:621–626, 2006. © 2006 Society of Plastics Engineers     

超细全硫化粉末丁苯橡胶/三元乙丙橡胶共混物的结构与性能

制备了超细全硫化粉末丁苯橡胶(UFPSBR)/三元乙丙橡胶(EPDM)共混物,研究了其硫化特性、相态结构、动态力学性能及物理机械性能。透射电镜观察表明,无论UFPSBR与EPDM共混比如何,UFPSBR粒子始终保持为分散相。当UFPSBR用量为10份(质量)时,它在EPDM中的分散相尺寸为200 nm左右;用量较高时其分散相尺寸较大,存在大量的聚集体。动态力学分析结果显示共混物存在2个玻璃化转变温度,说明共混物存在两相结构。加工性能分析结果表明,UFPSBR粒子在EPDM基质中形成了网络结构,对EPDM基质起到了较好的增强作用,当UFPSBR与EPDM的质量共混比为50/50时,共混物的拉伸强度可达13.4 MPa。UFPSBR对EPDM的硫化特性有明显影响。     

Numerical study on rubber compounds made of reactivated ethylene propylene diene monomer for fiber reinforced elastomeric isolators

A huge amount of rubber waste coming from tire industry or other sources (eg, weather strips producers) has attracted interest from researchers to investigate the possibility of recycling used rubber for various products, particularly in construction sector. This article presents a series of experimental and numerical investigations to evaluate the feasibility of regenerated synthetic rubber ethylene propylene diene monomer (EPDM) for production of a building seismic isolation system. Four rubber blends using two different sources of regenerated EPDM are considered in this study. The mechanical properties of the recycled rubber under study are evaluated through uniaxial tensile and relaxation tests, considering the accelerated aging effect. Based on several hyperelasticity and viscosity models of rubber available in the literature, several numerical test simulations on rubber compounds and on a prototype of fiber reinforced elastomeric isolators (FREIs) are performed. The test results reveal that the proposed regenerated EPDM compounds can be particularly suitable for the production of unbonded FREIs, especially because they are able to exhibit low/moderate tensile stresses at high-shear strain. The results also show that not all regenerated rubber blends fulfill the durability requirements of rubber for seismic isolation after accelerated aging tests. The durability of the specimens seems to be mainly affected by the choice of the regenerated rubber source.     

Thermal and scanning electron microscopy/energy‐dispersive spectroscopy analysis of styrene–butadiene rubber–butadiene rubber/silicon dioxide and styrene–butadiene rubber–butadiene rubber/carbon black–silicon dioxide composites

Silica as a reinforcement filler for automotive tires is used to reduce the friction between precured treads and roads. This results in lower fuel consumption and reduced emissions of pollutant gases. In this work, the existing physical interactions between the filler and elastomer were analyzed through the extraction of the sol phase of styrene–butadiene rubber (SBR)–butadiene rubber (BR)/SiO₂ composites. The extraction of the sol phase from samples filled with carbon black was also studied. The activation energy (E_a) was calculated from differential thermogravimetry curves obtained during pyrolysis analysis. For the SBR–BR blend, E_a was 315 kJ/mol. The values obtained for the composites containing 20 and 30 parts of silica per hundred parts of rubber were 231 and 197 kJ/mol, respectively. These results indicated an increasing filler–filler interaction, instead of filler–polymer interactions, with respect to the more charged composite. A microscopic analysis with energy‐dispersive spectroscopy showed silica agglomerates and matched the decreasing E_a values for the SBR–BR/30SiO₂ composite well. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2273–2279, 2005     

Utilization of fly ash acid residue as a reinforcing filler in ethylene propylene diene monomer rubber

Fly ash acid residue (FAAR), a by‐product of circulating fluidized bed fly ash extracted Al₂O₃ by acid leaching method, has been posing problems because of its disposal. The major chemical components of FAAR are amorphous SiO₂ (66.38 wt %) and unburned carbon (20 wt %). Attempts were made for its application as a reinforcing filler for ethylene propylene diene monomer (EPDM) rubber in this article. Surface modification for FAAR by silane coupling agent (Si69) was carried out. The effect of surface modification and unburned carbon existing in FAAR on the performance of FAAR was characterized by Fourier transform infrared and dispersibility test. The results indicated that surface modification could reduce the hydrophilicity of FAAR and unburned carbon also had positive effect on the dispersion of FAAR particles in kerosene. The effect of partial replacement of carbon black by FAAR on the curing behavior, mechanical properties, and morphological characteristics of EPDM rubber was also studied. It was proved that with partial replacement of carbon black by FAAR, the cure time (t₉₀) and maximum torque (M_H) of EPDM composites increased with the content of FAAR. The mechanical properties were significantly improved when 15 wt % of carbon black was replaced by FAAR. SEM micrographs confirmed that surface modification can improve the compatibility between FAAR and rubber matrix. Unburned carbon existing in FAAR was also beneficial to the interface bonding. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013