Thermoplastic natural rubber based on polyamide‐12: Influence of blending technique and type of rubber on temperature scanning stress relaxation and other related properties

Thermoplastic natural rubber based on polyamide‐12 (PA‐12) blend was prepared by melt blending technique. Influence of blending techniques (i.e., simple blend and dynamic vulcanization) and types of natural rubber (i.e., unmodified natural rubber (NR) and epoxidized natural rubber (ENR)) on properties of the blends were investigated. It was found that the simple blends with the proportion of rubber ～ 60 wt % exhibited cocontinuous phase structure while the dynamically cured blends showed dispersed morphology. Furthermore, the blend of ENR exhibited superior mechanical properties, stress relaxation behavior, and fine grain morphology than those of the blend of the unmodified NR. This is attributed to chemical interaction between oxirane groups in ENR molecules and polar functional groups in PA‐12 molecules which caused higher interfacial adhesion. It was also found that the dynamic vulcanization caused enhancement of strength and hardness properties. Temperature scanning stress relaxation measurement revealed improvement of stress relaxation properties and thermal resistance of the dynamically cured ENR/PA‐12 blend. This is attributed to synergistic effects of dynamic vulcanization of ENR and chemical reaction of the ENR and PA‐12 molecules. Furthermore, the dynamically cured ENR/PA‐12 blend exhibited smaller rubber particles dispersed in the PA‐12 matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Development of novel elastomeric blends containing natural rubber and ultra-low-density polyethylene

This study sought to develop novel elastomeric compounds using natural rubber (NR) and ultra-low-density polyethylene (ULDPE). Blends were prepared by means of a two-roll mill for three ratios (70/30, 60/40, and 50/50 NR/ULDPE). Conventional vulcanization was performed in a compression mold. The physical and mechanical properties of the blend were determined according to ASTM standards. The results were compared with those obtained from NR blended with styrene-butadiene rubber (SBR). The morphological examinations with scanning electron microscopy indicated that ULDPE was compatible with NR; thus, the addition of a compatibilizer was not necessary. The cocontinuous phase was dominant in the NR/ULDPE blend containing 50 and 60 wt % NR. The tensile properties, tear resistance, and aging resistance of the NR/ULDPE blends were found to be superior to those of NR/SBR blends. On the other hand, the abrasion and flex cracking resistances of the NR/ULDPE blend were inferior to those exhibited by SBR blends but the Mooney viscosity and resilience of both blends fell in the same range. However, the addition of dicumyl peroxide appeared to have caused crosslinking of the ULDPE phase in the blend, which in turn increased the tensile properties and abrasion and aging resistance. The properties of the tertiary NR/SBR/ULDPE blend were investigated as well. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 650–660, 2001     

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.     

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     

Rheological properties,oil, and thermal resistance in sulfur‐cured CPE/NR blends

The use of natural rubber (NR) for partly substituting elastomeric chlorinated polyethylene (CPE) was carried out. Sulfur curing was used to vulcanize NR phase in the blends. Mechanical, rheological, and thermal aging properties as well as oil resistance of the blends were investigated. The amount of NR in blends significantly affects properties of the blends. With NR content in blends up to 20 wt %, tensile properties are similar to those of the pure CPE, even after either oil immersion or thermal aging. Rheological properties of CPE/NR blends determined from the rubber process analyzer (RPA 2000) and parallel‐plate rheometer are controlled strongly by the blend composition. The viscoelastic behavior of pure CPE and the blends with CPE as a major component is governed by the viscous response, which could be seen from the high damping factor, particularly at high strain, the short linear viscoelastic range, and the high degree of pseudoplasticity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1129–1135, 2004     

Nanoclay distribution and its influence on the mechanical properties of rubber blends

The distribution of modified and unmodified nanoclays inside the rubber phases of immiscible rubber–rubber blends composed of nonpolar–polar natural rubber (NR)/epoxidized natural rubber (ENR) and nonpolar–nonpolar NR/polybutadiene rubber (BR) was investigated for the first time. The distribution of clays at various loadings in the blends was calculated from the viscoelastic properties of the blends. For example, in the 50 : 50 NR/ENR blend, 42% Cloisite 30B migrated to the NR phase, and 58% went to the ENR phase. However, in the same blend, only 7% Cloisite Na⁺ was found in the NR phase, and 93% was found in the ENR phase. Again, in the 50 : 50 NR/BR blends, the NR phase contained 85% Cloisite 30B, whereas 55% Cloisite Na⁺ migrated to the NR phase. All these observations were explained with the help of viscosity, X‐ray diffraction, and morphology analyses. The effect of the distribution of the clay on the mechanical properties was also discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Microwave absorbing rubber composites containing carbon black and aluminum powder

Natural rubber (NR), epoxidized natural rubber (ENR), and chlorosulfonated polyethylene (CSM) composites filled with conductive carbon black and aluminum powder have been prepared by using a two‐roll mill. An electromagnetic interference shielding effectiveness of those rubber composites was carried out in the frequency range of 8–12GHz (X‐band microwave). The increase of filler loading enhanced shielding effectiveness of the rubber composites. Conductive carbon black was more effective in shielding than aluminum powder. Binary filler‐filled rubber composites showed higher shielding effectiveness than that of single filler‐filled rubber composites. It has been observed that the shielding effectiveness of these rubber composites could be ranked in the following order: ENR ≥ CSM > NR, whereas the mechanical properties of the rubber composites were in the order of CSM > ENR > NR. The correlation between shielding effectiveness and electrical conductivity as well as mechanical properties of the rubber composites are also discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Toughness enhancement of poly(lactic acid) by melt blending with natural rubber

Rubber toughened poly(lactic acid) (PLA) was prepared by blending with natural rubber (NR)‐based polymers. The blends contained 10 wt % of rubber and melt blended with a twin screw extruder. Enhancement of impact strength of PLA was primarily concernced. This study was focused on the effect of rubber polarity, rubber viscosity and molecular weight on mechanical properties of the blends. Three types of rubbers were used: NR, epoxidized natural rubber (ENR25 and ENR50), and natural rubber grafted with poly(methyl methacrylate) (NR‐g‐PMMA). Effect of viscosity and molecular weight of NR, rubber mastication with a two‐roll mill was investigated. It was found that all blends showed higher impact strength than PLA and NR became the best toughening agent. Viscosity and molecular weight of NR decreased with increasing number of mastication. Impact strength of PLA/NR blends increased after applying NR mastication due to appropriate particle size. DMTA and DSC characterization were determined as well. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

聚乙烯醇/天然橡胶共混物的制备及其性能研究

利用环氧化天然胶乳作为界面改性剂,采用胶乳共混法将聚乙烯醇（PVA）溶液同天然胶乳进行混溶,制备了PVA/天然橡胶（NR）的共混物,通过电子万能材料试验机、动态热机械分析仪、热老化箱和臭氧老化箱,研究了共混物力学性能、玻璃化转变温度、老化性能以及耐溶剂抽出性。结果表明,PVA的加入明显提高了NR的撕裂强度和硬度,而共混物的拉伸强度和断裂伸长率随着PVA含量的增加都出现下降的趋势;随着PVA含量的增加,NR的玻璃化转变温度呈现先增加后降低的趋势;随着PVA含量增加,共混物各试样对乙醇的耐抽出能力相差不大,对水的耐抽出能力逐步变弱。热空气老化对材料的力学性能影响明显,而臭氧老化由于时间较短,对材料的力学性能影响不明显。老化实验对材料的性能变化率影响显著。     

环氧化天然橡胶复合材料性能研究

采用新方法制备环氧化天然橡胶(ENR)/白炭黑和天然橡胶(NR)/ENR/白炭黑复合材料,并对其性能进行研究。结果表明:ENR/白炭黑复合材料的热稳定性优于ENR;在NR/ENR并用胶中加入白炭黑和硅烷偶联剂KH-550,NR/ENR/白炭黑复合材料0℃时的损耗因子(tanδ)增大,65℃时的tanδ值减小,复合材料的抗湿滑性能提高,滚动阻力减小。     

Polypropylene/natural rubber thermoplastic elastomer: Effect of phenolic resin as a vulcanizing agent on mechanical properties and morphology

The aim of this study is to characterize thermoplastic elastomers (TPEs) from polypropylene and natural rubber with and without phenolic resin as a vulcanizing agent. The blends containing 40–60 wt % of polypropylene were mixed in an internal mixer and pressed with a compression molding machine. TPEs without rubber vulcanization, named as unvulcanized thermoplastic natural rubber (uTPNR) were compared to TPEs containing dynamic vulcanized rubber, referred as vulcanized thermoplastic natural rubber (vTPNR). The uTPNRs illustrated cocontinuous phase morphology, whereas the vTPNRs displayed dispersed phase of vulcanized natural rubber. Tensile properties, tear strength, thermal ageing resistance, ozone resistance, tension set, hardness and swelling test in toluene, IRM 903 oil and engine oil were carried out according to ASTM. It was found that tensile and tear strength, hardness and tension set of the uTPNRs increased with increasing polypropylene content. Dynamic vulcanization improved tensile strength, elongation at break, tension set and degree of swelling of the TPEs, whereas hardness and tear strength did not show significant change after dynamic vulcanization. The vTPNRs exhibited higher ozone resistance and swelling resistance than the uTPNRs. Reprocessability of the vTPNRs was investigated and showed that tensile strength decreased at 20 and 30% and elongation at break decreased at 13 and 27% for the first and the third reprocessing respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Ethylene vinyl acetate as compatibilizer on cure characteristics and mechanical properties of (natural rubber)/(Recycled acrylonitrile‐butadiene rubber) blends

Ethylene vinyl acetate (EVA) has been used as a compatibilizer for (natural rubber)/(recycled acrylonitrile‐butadiene rubber) (NR/NBRr) blends, vulcanized by sulfur. EVA offers excellent heat, ozone, and weather resistance, whereas the vinyl acetate groups provide oil resistance to the blend. It exhibits good tear resistance and may be crosslinked. However, EVA exhibits poor low‐temperature flexibility. NBR gloves have excellent resistance to punctures, tears, and many types of chemicals, while NR has good physical and mechanical properties. NR/NBRr blends were prepared with various compositions with the EVA content fixed. Tensile properties, hardness, and swelling behavior tests were performed to determine the compatibility of NR/NBRr blends in the presence of EVA. Results indicated that incorporation of EVA into NR/NBRr blends improved tensile strength, modulus, and elongation at break compared with NR/NBRr blends without EVA. The improvement in hardness and reduction in resilience on compatibilization are due to an increase in crosslink density, which gives NR/NBRr blends better swelling resistance. Scanning electron microscopy of the fracture surfaces indicates that, with the addition of EVA in NR/NBRr blends, better adhesion between NR and NBRr was obtained, thus improving the compatibility of NR/NBRr blends. J. VINYL ADDIT. TECHNOL., 23:135–141, 2017. © 2015 Society of Plastics Engineers     

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。     

A comparison of the properties of rice husk ash,silica, and calcium carbonate filled 75 : 25 NR/EPDM blends

The effects of incorporation of three different fillers, i.e., rice husk ash (RHA), silica, and calcium carbonate (CaCO₃), over a loading range of 0–60 phr on the curing characteristics, processability, mechanical properties, and morphology of 75 : 25 natural rubber (NR)/ethylene‐propylene‐diene monomer (EPDM) blends were studied using a conventional vulcanization system. Filler loading and type influence the processability of the blends in which RHA and CaCO₃ offer better processing advantage over silica. The best improvement in the tensile and tear strength and abrasion resistance of the 75 : 25 NR/EPDM blends with additional fillers was achieved when filled with silica. However, RHA and CaCO₃ were better in resilience property compared to that of silica. The RHA filled blends showed higher failure properties and abrasion resistance but lower ozone resistance than that containing CaCO₃. Scanning electron micrographs revealed that the morphology of the blend filled with silica is finer and more homogenous compared to the blend filled with RHA and CaCO₃. According to these observations, RHA can be used as a cheaper filler to replace CaCO₃ in rubber blends where improved mechanical properties are not so critical. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of different curing systems on heat shrinkability and mechanical properties of ethylene vinyl acetate/epoxidized natural rubber blends

Ethylene vinyl acetate (EVA)/epoxidized natural rubber (ENR) blends containing 10 and 30 wt % ENR were prepared by using an internal mixer. Five different types of curing systems were employed: dicumyl peroxide (DCP), sulfur (S), phenolic resin (Ph), DCP + S, and DCP + Ph. DCP could crosslink with both EVA and ENR while S and Ph were curing agents for ENR. The DCP system provided the lowest tensile properties and tear strength because of low crosslinking in ENR phase. Addition of sulfur or phenolic resin increased the mechanical properties due to a better vulcanization of the rubber phase. The mechanical properties of the blends decreased with increasing ENR content. The rubber particle size in the blends containing 30% ENR played a more important role in the mechanical properties than the blends containing 10% ENR. ENR particle size did not affect heat shrinkability of EVA and a well vulcanized rubber phase was not required for high heat shrinkage. Furthermore, heat shrinkage of the blends slightly changed as the ENR content increased for all curing systems. With regard to the mechanical properties and heat shrinkability, the most appropriate curing system was DCP + Ph and in the case the 10 wt % ENR content produced a more favorable blend. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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.     

SORPTION,DIFFUSION, AND PERMEATION OF CHLORINATED HYDROCARBON VAPORS THROUGH NATURAL RUBBER,EPOXIDIZED NATURAL RUBBER,AND THEIR BLENDS

The study investigates the transport process of various chlorinated hydrocarbons through natural rubber (NR), epoxidized natural rubber (ENR), and their blends. The effect of structure and morphology of the membranes on the transport parameters has been investigated. Sorption coefficient is found to increase and the permeability coefficient shows the reverse trend with increasing epoxy content. As the mol% epoxidation increases, the polymeric network structure becomes more compact, which leads to a decrease in the diffusion coefficient, which ultimately results in a low permeation coefficient. The morphology of NR/ENR blends has been investigated by combining scanning electron microscopy with permeability measurements. The permeation coefficient is found to be minimum for the NR/ENR 70/30 composition; a 50/50 composition shows the maximum. The heterogeneous morphology of 70/30 NR/ENR blend results in the low permeability coefficient, whereas the co-continuous nature of the 50/50 composition accounts for the maximum permeability. Permeability measurements provide the most useful information about the way morphology is changing with composition of the blends and about the composition corresponding to the maximum level of co-continuity of the two phases.     

Ozone cracking and flex cracking of crosslinked polymer blend compounds

Ozone cracking and flex cracking of crosslinked elastomer blends of brominated isobutylene/para‐methylstyrene copolymer (BIMSM) and unsaturated elastomers, such as polybutadiene rubber (BR) and natural rubber (NR), are studied. This saturated BIMSM elastomer, which is a terpolymer of isobutylene, para‐bromomethylstyrene, and para‐methylstyrene, functions as the ozone‐inert phase of the blend. Ozone cracking is measured by the failure time of a tapered specimen under a fixed load in a high severity ozone oven, whereas flex cracking is ranked by the De Mattia cut growth. The ozone resistance of BIMSM/BR/NR blends is compared to that of a BR/NR blend (with or without antiozonant) at constant strain energy densities. The effects of the BIMSM content in the blend, the structural variations of BIMSM, and the network chain length between crosslinks on these two failure properties, which are important in crosslinked compounds for applications in tire sidewalls, are discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2183–2196, 2007     

Hydrogenated natural rubber blends: Aspect on thermal stability and oxidative behavior

Hydrogenated natural rubber (HNR) prepared from natural rubber (NR) is a new sustainable elastomer with excellent thermal properties. This study reports on the effect of vulcanization system and blend ratio on the thermal and oxidative resistance of HNR/NR vulcanizates. The various HNR/NR ratios vulcanized by peroxide and sulfur donor system exhibited the highest retention of tensile strength after thermal aging due to the formation of zinc‐dimethyldithiocarbamate (ZDMDC) which is an efficient antioxidant. The results from thermogravimetric analysis (TGA) indicated that the saturated structure of HNR had higher decomposition temperature and activation energy to enhance the thermal stability of HNR/NR vulcanizates. The initial and maximum decomposition temperatures of NR and HNR phases in vulcanizates were not affected by rubber blend ratio. This suggests that the decomposition pattern of HNR has no influence on another constituent. The increase in HNR content in the blends could retard the ozonolysis resulting in the surface cracking attacked by ozone. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Reclaiming of rubber by a renewable resource material (RRM). III. evaluation of properties of NR reclaim

Sulfur‐cured filled natural rubber (NR) is successfully reclaimed by using a renewable resource material (RRM) and diallyl disulfide (DADS), which is the major constituent of RRM. Reclaiming of NR vulcanizate was carried out at 60°C for 35 min in an open two‐roll mixing mill. Evaluation of the properties of NR reclaim was carried out by mixing it with virgin rubber in various proportions. The cure characteristics and mechanical properties of the virgin NR/ reclaim NR blend were studied. With increase in the proportion of reclaim rubber (RR) in virgin NR/ reclaim NR blend scorch time and optimum cure time decrease. To increase scorch time N‐cyclohexylthiophthalimide as prevulcanization inhibitor (PVI) was added in NR/RR (50/50) blend. It was found that use of 40% NR reclaim with virgin rubber resulted 83% retention of tensile strength of that of the virgin NR vulcanizate. Effect of carbon black loading was studied in NR/RR (50/50) blends. Tensile properties and swelling value of different NR/RR blends were evaluated before and after aging. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1493–1502, 2000