Effect of rubber content on mechanical properties and heat shrinkage of ethylene vinyl acetate copolymer blended with epoxidized natural rubber

Ethylene vinyl acetate (EVA, 18 mol % vinyl acetate) and epoxidized natural rubber (ENR, 50 mol % epoxidation) were blended in an internal mixer and compared to EVA. Dicumyl peroxide (DCP) was used as a curing agent. The blends consisted of 10–50 wt % of ENR and were compared with crosslinked EVA in terms of heat shrinkage, mechanical properties, and degree of crystallinity. It is found that the blends showed a decrease in mechanical properties with increasing ENR content because DCP was not a good vulcanizing agent of ENR. The addition of ENR did not affect heat shrinkability of EVA. The maximum heat shrinkage obtained was 80% for EVA and the blends. ENR did not affect thermal properties of EVA investigated by the differential scanning calorimetry. The X‐ray diffractometry showed discrepancy in degree of crystallinity before and after specimen stretching and after heat shrinking. It is believed that ENR particles decreased molecular orientation of EVA resulting in a decrease in degree of crystallinity but the remained orientation was sufficient for heat shrinking. The blend showed better extrudability than EVA after increasing take‐up speed. Therefore, the extruded tube prepared from the blend provided higher heat shrinkage than EVA tube. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Cure characteristics,morphology, mechanical properties,and aging characteristics of silicone rubber/ethylene vinyl acetate blends

Silicone rubber/ethylene vinyl acetate (SR/EVA) rubber mixes with different ratios were prepared by using dicumyl peroxide (DCP) and benzoyl peroxide (BP) as curing agents. The vulcanization characteristics such as cure kinetics, activation energy, and cure rate of the blends were analyzed. The effects of blend ratio and curing agents on the mechanical properties such as stress–strain behavior, tensile strength, elongation at break, tear strength, relative volume loss, hardness, flex crack resistance, and density of the cured blends have been investigated. Almost all the mechanical properties have been found to be increased with increase in EVA content in the blends particularly in DCP‐cured systems. The increment in mechanical properties of the blends with higher EVA content has been explained in terms of the morphology of the blends, attested by scanning electron micrographs. Attempts have been made to compare the experimental results, from the evaluation of mechanical properties, with relevant theoretical models. The aging characteristics of the cured blends were also investigated and found that both the DCP‐ and BP‐cured blends have excellent water and thermal resistance. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1069–1082, 2006     

Epoxidized natural rubber/epoxy blends: Phase morphology and thermomechanical properties

Epoxidized natural rubbers (ENRs) were prepared. ENRs with different concentrations of up to 20 wt % were used as modifiers for epoxy resin. The epoxy monomer was cured with nadic methyl anhydride as a hardener in the presence of N,N‐dimethyl benzyl amine as an accelerator. The addition of ENR to an anhydride hardener/epoxy monomer mixture gave rise to the formation of a phase‐separated structure consisting of rubber domains dispersed in the epoxy‐rich phase. The particle size increased with increasing ENR content. The phase separation was investigated by scanning electron microscopy and dynamic mechanical analysis. The viscoelastic behavior of the liquid‐rubber‐modified epoxy resin was also evaluated with dynamic mechanical analysis. The storage moduli, loss moduli, and tan δ values were determined for the blends of the epoxy resin with ENR. The effect of the addition of rubber on the glass‐transition temperature of the epoxy matrix was followed. The thermal stability of the ENR‐modified epoxy resin was studied with thermogravimetric analysis. Parameters such as the onset of degradation, maximum degradation temperature, and final degradation were not affected by the addition of ENR. The mechanical properties of the liquid‐natural‐rubber‐modified epoxy resin were measured in terms of the fracture toughness and impact strength. The maximum impact strength and fracture toughness were observed with 10 wt % ENR modified epoxy blends. Various toughening mechanisms responsible for the enhancement in toughness of the diglycidyl ether of the bisphenol A/ENR blends were investigated. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39906.     

EPDM/NR并用胶的复合交联

采用硫黄硫化体系和过氧化物（硫化剂DCP）硫化体系对EPDM／NR并用胶实施复合交联，研究并用比和复合交联体系对胶料的硫化特性、物理性能和耐热老化性能的影响。结果表明，在大部分并用比下，复合交联可以改善胶料的硫化特性；在硫化剂DCP和助交联剂TAIC的用量均为2份、EPDM／NR／ENR并用比为30／68．5／1．5时，并用胶的物理性能优良；以NR为主的并用胶在复合交联时硫化剂DCP和助交联剂TAIC的用量宜取1～2份。     

The effect of mercapto‐modified ethylene–vinyl acetate (EVA) on curing parameters,mechanical properties,and thermal properties of vulcanized styrene–butadiene rubber (SBR)/EVA blends

The effect of EVA functionalized with mercapto groups (EVALSH) on the compatibilization of SBR and EVA copolymer blends was investigated in vulcanized systems based on sulfur or dicumyl peroxide (DCP). The presence of EVALSH resulted in an improvement of the tensile properties, indicating the reactive compatibilizing effect of this compound. The best mechanical performance was achieved with the sulfur‐curing system for both compatibilized and noncompatibilized blends. The blend systems were also analyzed by scanning electron microscopy, differential scanning calorimetry, and dynamic‐mechanical analysis. The crystallinity of the EVA phase was significantly affected by the presence of the EVALSH, whereas no substantial change was detected on the damping properties or the glass transition temperature of the SBR phase. Considering the aging properties, the presence of EVALSH increases the thermal stability of the blends vulcanized with DCP. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 239–249, 2002     

EPDM/ENR共混胶力学性能的研究

探讨了三元乙丙橡胶(EPDM)和环氧化天然橡胶(ENR)的共混比、加料顺序、硫化体系对EPDM/ENR共混物的硫化特性、力学性能和耐热空气老化性能的影响。结果表明,共混比不同,共混胶的性能均有差异,且共混物的力学性能低于单组分的线性加和值,但综合比较而言,当EPDM/ENR=40/60时共混胶的力学性能较好;在所研究的四种加料顺序中,以配合剂先与EPDM制成母炼胶后再与ENR共混的这一种加料顺序下所得的共混物硫化胶的力学性能最好;采用半有效硫化体系所制得的共混物硫化胶的力学性能较好。     

Effect of dynamic vulcanization on properties and morphology of nylon/SAN/NBR blends: A new compatibilization method of nylon/ABS blends

Dynamically vulcanized blends of nylon, styrene–acrylonitrile copolymer (SAN), and nitrile–butadiene rubber (NBR) were examined for mechanical properties, Shore D hardness, Vicat softening temperature, impact process, and phase morphology. The effect of a curing system such as phenolic formaldehyde resins (PF), dicumylperoxide (DCP), and a sulfur system on the mechanical properties of the nylon/SAN/NBR blends was studied, and dynamic vulcanization with a PF system was found to lead to outstanding toughness of the blends. The effect of PF content on the mechanical properties, Shore D hardness, and heat resistance of the nylon/SAN/NBR blends was also investigated. With increasing PF content the notched‐impact strength and Vicat softening temperature (VST) of the nylon/SAN/NBR (50/25/25) blends evidently improved, but tensile strength and Shore D hardness of the blends changed slightly. It can be concluded that the nylon/SAN/NBR (50/25/25) blends dynamically vulcanized by high‐content PF can attain excellent comprehensive mechanical properties, especially supertoughness, at room temperature. SEM was used to investigate the effect of dynamic vulcanization on disperse‐phase particle size, particle size distribution, and phase morphology. It was obvious that disperse‐phase particle size decreased with an increasing PF content. Thermal behavior and miscibility of dynamically vulcanized nylon/SAN/NBR with PF were investigated by DMTA. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2057–2062, 2003     

Effect of cure systems on shrinkability of polyolefin–EPDM blends

Effects of cure systems on shrinkability of polyolefin and EPDM blends have been studied as a function of cure time and amount of elastomers added. During measurement one of the parameters is kept constant while the other varies. The shrinkability of the blends increases with the increase in cure time when elastomer content is fixed. Similarly, at constant cure time higher loading of elastomer increases the shrinkability of the blends. Samples stretched under high temperature show higher shrinkability than those stretched under room temperature. Dicumylperoxide (DCP) is a more effective curing agent for making a particular set of blends more shrinkable than the sulfur. The changing morphological pattern with DCP-cured shrunk samples from those of sulfur cured samples is corroborated by the SEM studies where the elastomer phase appears to be globular in nature. The crystallinity of the blend depends on the dose and type of the elastomer used in polyolefin. The curing efficiency of the elastomerphase depends on the polyolefin used as blend partner. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 597–603, 1998     

Characterization of epoxidized natural rubber/ethylene vinyl acetate (ENR‐50/EVA) blend: Effect of blend ratio

Epoxidized natural rubber/Ethylene vinyl acetate copolymer (ENR‐50/EVA) blends with different ratios were prepared by using a Haake internal mixer. The effect of the blend ratio on the processing, tensile properties (such as tensile strength, elongation at break, Young's modulus and stress–strain behavior), morphology, dynamic mechanical properties, and thermal properties has been investigated. The tensile properties increase with the increase of EVA content, whereas the stabilization torque increases with the increase of ENR‐50 content in the blend. In 40:60 and 50:50 blend of ENR‐50/EVA, both the phases exist as continuous phases, producing a co‐continuous morphology. At these blend ratio, the drastic change in properties were noted, indicating that the phase inversion occurs. The results on dynamic mechanical properties revealed that the blends are compatible. Blending of ENR‐50 and EVA lead to the improvement in thermal stability and 50:50 blend ratios is the most stable blend. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1504–1515, 2006     

The use of EVA-containing mercapto groups in natural rubber-EVA blends. II. The effect of curing system on mechanical and thermal properties of the blends

Natural rubber (NR)-poly(ethylene-co-vinyl acetate) (EVA) blends have been studied by incorporation of mercapto-modified EVA (EVASH) combined with dicumyl peroxide (DCP) as a curing agent. The mechanical, thermal, and morphological properties of NR-EVA blends as functions of blend composition and compatibilizer and/or curative additions were investigated. An EVASH-DCP combined system leads to the greatest improvement in tensile strength when EVA is dispersed within the NR matrix. Higher performance on Shore A hardness was also achieved with this combined system. For blends characterized by NR domains dispersed in the EVA matrix, the efficiency of pure DCP in improving the tensile strength is higher. Morphological observations and selective extraction experiments indicate the cross-linking of NR phase in both systems. A cross-linking of the EVA phase is also suggested by DCP or an EVASH-DCP combined system, based on the decreasing degree of crystallinity of this phase. © 1996 John Wiley & Sons, Inc.     

动态交联PP/EVA共混物的制备与性能研究

本文将动态交联技术应用于PP/EVA共混体系中,制得动态交联PP/EVA共混物。采用Hakke转矩流变仪研究了动态交联对PP/EVA共混物扭矩的影响;研究了DCP和EVA含量对共混物力学性能的影响;考察了动态交联共混物的维卡软化点。结果表明：加入DCP后,PP/EVA共混物扭矩先升后降,DCP的添加量为EVA含量的1%为宜。随EVA用量的增加,动态交联EVA/PP共混物的冲击强度大幅提高,但拉伸强度有所降低。少量经动态交联的EVA颗粒可以促进共混物中PP的结晶, 提高共混物的维卡软化点。     

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     

The Effect of Epoxidized Natural Rubber (ENR-50) or Polyethylene Acrylic Acid (PEA) as Compatibilizer on Properties of Ethylene Vinyl Acetate (EVA)/Natural Rubber (SMR L) Blends

The effect of epoxidized natural rubber (ENR) or polyethylene acrylic acid (PEA) as a compatibilizer on properties of ethylene vinyl acetate (EVA)/natural rubber (SMR L) blends was studied. 5 wt.% of compatibilizer was employed in EVA/SMR L blend and the effect of compatibilizer on tensile properties, thermal properties, swelling resistance, and morphological properties were investigated. Blends were prepared by using a laboratory scale of internal mixer at 120°C with 50 rpm of rotor speed. Tensile properties, thermal properties, thermo-oxidative aging resistance, and oil swell resistance were determined according to related ASTM standards. The compatibility of EVA/SMR L blends with 5 wt.% of compatibilizer addition or without compatibilizing agent was compared. The EVA/SMR L blend with compatibilizer shows substantially improvement in tensile properties compared to the EVA/SMR L blend without compatibilizer. Compatibilization had reduced interfacial tension and domain size of ethylene vinyl acetate (EVA)/natural rubber (SMR L) blends.     

Effect of surface modification of silicon carbide nanoparticles on the properties of nanocomposites based on epoxidized natural rubber/natural rubber blends

Improvement of the properties of rubber nanocomposites is a challenge for the rubber industry because of the need for higher performance materials. Addition of a nanometer‐sized filler such as silicon carbide (SiC) to enhance the mechanical properties of rubber nanocomposites has rarely been attempted. The main problem associated with using SiC nanoparticles as a reinforcing natural rubber (NR) filler compound is poor dispersion of SiC in the NR matrix because of their incompatibility. To solve this problem, rubber nanocomposites were prepared with SiC that had undergone surface modification with azobisisobutyronitrile (AIBN) and used as a filler in blends of epoxidized natural rubber (ENR) and natural rubber. The effect of surface modification and ENR content on the curing characteristics, dynamic mechanical properties, morphology and heat buildup of the blends were investigated. The results showed that modification of SiC with AIBN resulted in successful bonding to the surface of SiC. It was found that modified SiC nanoparticles were well dispersed in the ENR/NR matrix, leading to good filler‐rubber interaction and improved compatibility between the rubber and filler in comparison with unmodified SiC. The mechanical properties and heat buildup when modified SiC was used as filled in ENR/NR blends were improved. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45289.     

EPDM/POE共混橡胶耐热老化性能研究

以三元乙丙橡胶(EPDM)和热塑性弹性体(POE)并用为主体材料,采用不同配方设计和硫化工艺制得了耐热老化性能优良的共混胶.探讨了过氧化二异丙苯(DCP)、烯丙基异氰脲酸酯(TALC)和硫磺(S)不同用量对EPDM/POE共混胶的力学性能、热老化性能的影响.结果表明,从并用POE改性来提高EPDM耐热方面考虑,以过氧化物DCP硫化为主,加入部分TAIC和少量硫磺有助于两者的共硫化,得到的共混胶具有良好的耐热老化性能.     

Thermoplastic vulcanizates based on epoxidized natural rubber/polypropylene blends: Effect of epoxide levels in ENR molecules

Epoxidized natural rubbers (ENR) with various levels of epoxide groups were prepared. Thermoplastic vulcanizates based on 75/25 ENRs/PP blends with Ph‐PP compatibilizer were later prepared by dynamic vulcanization using sulfur curing system. Influence of various levels of epoxide groups on rheological, mechanical morphological properties, and swelling resistance of the TPVs was investigated. It was found that the mixing torque, apparent shear stress, apparent shear viscosity, tensile strength, and hardness properties increased with increasing levels of epoxide groups in the ENR molecules. This may be attributed to increasing level of chemical interaction between the methylol groups of the Ph‐PP molecules and polar functional groups of the ENR molecules. Also, the PP segments in the Ph‐PP molecules are capable of compatibilizing with the PP molecules used as a blend composition. In SEM micrographs, we observed finer dispersion of vulcanized rubber domains as increasing levels of epoxide contents. This corresponds to increasing trend of strength and hardness properties of the TPVs. An increasing trend of tension set and a decreasing trend of elongation at break were observed as increasing levels of epoxide groups in the ENR molecules. This is because of higher rigidity of the vulcanized ENR phase with higher epoxide groups. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3046–3052, 2006     

On the Mechanical Properties of EPDM/CIIR Blends Cured with Reactive Phenolic Resin

Blends of ethylene propylene diene monomer rubber (EPDM) and chlorinated isobutylene isoprene rubber (chlorobutyl, CIIR) with a reactive phenolic resin as the curing agent have been prepared through conventional two-roll mill mixing. The effect of resin curing on the mechanical properties of EPDM/CIIR blends was investigated and compared with conventional curing systems. The morphology of the blends as well as their thermal and steam aging resistance has also been reported. It was found that blends with a phenolic curing system exhibited superior mechanical and thermal aging properties and have potential applications in high-temperature engineered products.     

Study of heat shrinkability of crosslinked low‐density polyethylene/poly(ethylene vinyl acetate) blends

In this study, the heat‐shrinkage property in polymer was induced by first compounding low‐density polyethylene/poly(ethylene vinyl acetate) (LDPE/EVA) blends with various amounts of peroxide in a twin‐screw extruder at about 130°C. The resulting granules were molded to shape and chemically crosslinked by compression molding. A process of heating–stretching–cooling was then performed on the samples while on a tensile machine. Shrinkability and effective parameters were also investigated using thermal mechanical analysis. The results showed that the gel fraction was higher for the sample of higher EVA content with the same amount of dicumyl peroxide (DCP). A decrease in the melting point and heat of fusion (ΔH_f), as determined from DSC, was observed with an increase in the DCP content. Studies on the heat shrinkability of the samples showed that samples stretched above the melting point had a higher shrinkage temperature than those stretched around the crystal transition temperature. The results showed that by increasing the peroxide content, the shrinkage temperature was decreased. These could be attributed to the formation of new spherulites as well as changes in the amount and the size of crystals. Furthermore, in samples elongated at 120°C (above the melting point), the rate of stretching had no effect on the shrinkage temperature. The results showed that the extent of strain had no effect on the temperature of shrinkage, but rather on the ultimate shrinkage value. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1389–1395, 2004     

复合硫化体系对ACM/NBR共混胶性能的影响

分别采用TCY/硫黄、3#硫化剂/硫黄/促进剂、皂/硫黄/促进剂3种复合硫化体系硫化ACM/NBR共混胶。研究不同复合硫化体系、TCY用量和硫黄用量对ACM/NBR共混胶硫化特性、力学性能、耐热老化性能、耐油性能和压缩永久变形性能的影响,结果表明,TCY/硫黄复合硫化体系硫化的ACM/NBR共混胶的综合性能优于3#硫化剂/硫黄/促进剂和皂/硫黄/促进剂复合硫化体系,当TCY/硫黄的用量为1.5/0.3份时,ACM/NBR共混胶具有良好的综合物理机械性能。     

Studies on blends of ethylene vinyl acetate and polyacrylic rubber with reference to their shrinkability

Preferential crosslinking was introduced in the rubber phase of a blend of ethylene vinyl acetate (EVA) and polyacrylic rubber (AR‐801). The heat shrinkability of the polymer blends was measured at room temperature (RT) and at a high temperature (HT) of 150°C. Various parameters were tried for a correlation with shrinkability. Shrinkability goes up with the increase in rubber content and is increased with increasing cure time in blends of a fixed ratio. The crystallinity of an HT (at 150°C) stretched sample was higher than that of a RT stretched sample, which was higher than that of the shrunk and original sample. The continuous cure characteristics, showed that the torque was increased with the rubber content. High temperature DSC demonstrated that the increase in AR‐801 content decreased the stability and further HT processing increased the stability. SEM showed that the rubber phase was more elongated in the HT stretched sample compared to the RT stretched sample. In the shrunk sample the rubber phase was more globular. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2088–2095, 2000