Effects of EPDM‐g‐MAH compatibilizer and internal mixer processing parameters on the properties of NR/EPDM blends: An analysis using response surface methodology

This study evaluates the effects of ethylene‐propylene‐diene‐monomer grafted maleic anhydride (EPDM‐g‐MAH) and internal mixer melt compounding processing parameters on the properties of natural rubber/ethylene‐propylene‐diene rubber (NR/EPDM) blends. Using Response Surface Methodology (RSM) of 2⁵ two‐level fractional factorial, we studied the effects of NR/EPDM ratio, mixing temperature, Banbury rotor speed, mixing period, and EPDM‐g‐MAH contents in NR/EPDM blends. The study found that the presence of EPDM‐g‐MAH in NR/EPDM blends had a predominant role as a compatibilizing agent, which affected the processability and properties of the final material. We also determined the model fitting with constant determination, R² of 99.60% for tensile strength (TS) response with a suggested combination of mixing process input parameters. The reproducibility of the proposed mixing strategy was then confirmed through model validation with a minor deviation at +2.303% and higher desirability of 0.960. This study is essential in providing a process design reference for NR/EPDM blends preparation by melt‐blending and the role of a compatibilizer from the systematic Design of Experiment (DOE) approach. The experimental findings were further supported with swelling and cross‐link density measurements, differential scanning calorimetry analysis, and observation of fracture morphology using a scanning electron microscope. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42199.     

Blending of NR/BR/EPDM by reactive processing for tire sidewall applications. I. Preparation,cure characteristics and mechanical properties

EPDM incorporated into blends of natural rubber/butadiene rubber (NR/BR) improves ozone resistance. In this work, the inferior mechanical properties of NR/BR/EPDM blends generally obtained by conventional straight mixing are overcome by utilizing a reactive processing technique. The entire amount of curatives, based on a commonly employed accelerator N‐cyclohexyl‐2‐benzothiazole sulfenamide (CBS) and sulfur, is first added into the EPDM phase. After a thermal pretreatment step tuned to the scorch time of the EPDM phase, the modified EPDM is mixed with premasticated NR/BR. The reactive blend vulcanizates show a significant improvement in tensile properties: tensile strength and elongation at break, as compared to those prepared by straight mixing, in both gum and carbon black‐filled blends. The increase of tensile properties in gum and filled reactive blend vulcanizates does suggest that the reactive processing technique leads to more homogeneous blends due to, either a better crosslink distribution, or more homogeneous filler distribution, or both. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103:2538–2546, 2007     

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     

Improved mechanical properties of NR/EPDM blends by controlling the migration of curative and filler via reactive processing technique

Simple blending of natural rubber/ethylene–propylene–diene rubber (NR/EPDM) generally results in inferior mechanical properties because of curative migration and their differences for filler affinity. In this work, the 70/30 and 50/50 NR/EPDM blends prepared by reactive processing techniques were investigated and compared with the simple, nonreactive blends. The reactive blend compounds were prepared by preheating EPDM, containing all curatives to a predetermined time related to their scorch time prior to blending with NR. For the 70/30 gum blends, four types of accelerators were studied: 2,2‐mercaptobenzothiazole (MBT), 2,2‐dithiobis‐ (benzothiazole) (MBTS), N‐cyclohexyl‐2‐benzothiazolesulfenamide (CBS), and N‐tert‐butyl‐2‐benzothiazolesulfenamide (TBBS). When compared with the simple blends, the reactive blends cured with CBS and MBTS showed a clearly improved tensile strength whereas the increase of tensile strength in the blends cured with TBBS and MBT was marginal. However, a dramatic improvement of ultimate tensile properties in the reactive 50/50 NR/EPDM blends cured with TBBS was observed when compared with the simple blend. For the N‐550‐filled blends at the blend ratios of 70/30 and 50/50, the reactive‐filled blends prepared under the optimized preheating times demonstrated superior tensile strength and elongation at break over the simple blends. The improved crosslink and/or filler distribution between the two rubber phases in the reactive blends accounts for such improvement in their mechanical properties. This is shown in the scanning electron micrographs of the tensile fractured surfaces of the reactive blends, which indicate a more homogeneous blend. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Cure efficiency of dodecyl succinic anhydride as a cross‐linking agent for elastomer blends based on epoxidized natural rubber

Blends of a highly epoxidized natural rubber (ENR50) with unmodified natural rubber (NR) and ethylene propylene elastomers (EPDM) were produced to evaluate the mixing and curing characteristics. Dodecyl succinic anhydride was used to cross‐link the ENR50 component and the reactivity was assessed by monitoring the evolution of the torque in an oscillatory co‐axial cylinder rheometer, as well as by DSC thermal analysis. A physical model was used to obtain a single parameter for the reactivity of the system, which corresponds to the rate constant for first order curing reactions. Although the blends were thermodynamically immiscible, displaying no significant change in T_g, the components were well dispersed at microscopic level. Better mechanical properties were obtained for blends with EPDM. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41448.     

NR/SBR/organoclay nanocomposites: Effects of molecular interactions upon the clay microstructure and mechano‐dynamic properties

Nanocomposites based on (70/30) blends of natural rubber (NR), styrene‐butadiene rubber (SBR), and organoclay (OC) have been prepared successfully via melt‐mixing process. Effects of the extent of polymers/clay interactions upon the developed microstructure, fatigue life, and dynamic energy loss by the nanocomposites have been investigated. Maleated EPDM (EPDM‐g‐MAH) and epoxidized NR (ENR50) were employed as compatibilizer. Nanocomposites were characterized by means of X‐ray diffractometer (XRD), transmission electron microscope (TEM), scanning electron microscope, atomic force microscopy, root mean square, and dynamic mechanical thermal analysis. EPDM‐g‐MAH showed more potential in enhancing dispersion of the clay nanolayers and their interaction with rubber phases. More potential for separating and dispersing the clay nanoplatelets with better interface enhancement was exhibited by EPDM‐g‐MAH as compatibilizer. This was consistent with higher resistance towards large strain cyclic deformations along with more heat build‐up characteristics showed by EPDM‐g‐MAH based nanocomposites especially at compatibilizer/organoclay ratio of 3. Pronounced non‐terminal behavior within low frequency region was also observed for melt storage modulus of this nanocomposite, indicating higher extent of intercalation/exfoliation microstructure with reinforced interfaces than the nanocomposite generated by ENR50. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influences of the phenolic curative content and blend proportions on the properties of dynamically vulcanized natural rubber/acrylonitrile–butadiene–styrene blends

The vulcanization of natural rubber (NR)‐blended acrylonitrile–butadiene–styrene (ABS) was carried out with a phenolic curing agent by a melt‐mixing process. The NR compound was first prepared before blending with ABS. The effects of the phenolic curative contents (10, 15, and 20 phr) and blend proportions (NR/ABS ratio = 50 : 50, 60 : 40, and 70 : 30) on the mechanical, dynamic, thermal, and morphological properties of the vulcanized NR/ABS blends were investigated. The tensile strength and hardness of the blends increased with increasing ABS content, whereas the elongation at break decreased. The strength property resulting from the thermoplastic component and the vulcanized NR was an essential component for improving the elasticity of the blends. These blends showed a greater elastic response than the neat ABS. The thermal stability of the blends increased with increasing ABS component. Scanning electron micrographs of the blends showed a two‐phase morphology system. The vulcanized 60 : 40 NR/ABS blend with 15‐phr phenolic resin showed a uniform styrene‐co‐acrylonitrile phase dispersed in the vulcanized NR phase; it provided better dispersion between the NR and ABS phases, and this resulted in superior elastic properties. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42520.     

NR/EPDM 的共硫化

利用环氧化天然橡胶(ENR)与天然橡胶(NR)和三元乙丙橡胶(EPDM)均有很好相容性的特点，采用硫化促进剂预混工艺对NR／EPDM并用胶实施共硫化。考察了其对NR／EPDM并用胶的硫化特性、硫化胶的物理机械性能和耐热空气老化性能的影响。结果表明：本工艺确实能改善NR／EPDM的共硫化性能，所得硫化胶物理性能较好且操作简单。     

One‐step latex compounding method for producing composites of natural rubber/epoxidized natural rubber/aminosilane‐functionalized montmorillonite: enhancement of tensile strength and oil resistance

Montmorillonite (Mt) was intercalated with cetyltrimethylammonium bromide and functionalized with three types of aminosilane (3‐aminopropyltrimethoxysilane, n‐(2‐aminoethyl)‐3‐aminopropyltrimethoxysilane and 3‐[2‐(2‐aminoethylamino)ethylamino]propyltrimethoxysilane). The modified Mt was compounded with natural rubber (NR)/epoxidized natural rubber (ENR) via one‐step latex compounding. The effect of the modified Mt content on the oil resistance and mechanical properties of the NR/ENR/modified Mt composites was investigated. The X‐ray diffraction patterns of the composites showed partial intercalation/exfoliation of the modified Mt in the rubber matrix. Cryogenic fracture and X‐ray fluorescence results revealed highly dispersed modified Mt in the composites in the presence of 10 phr ENR. All three aminosilane groups slightly improved the oil resistance, with the long‐alkyl‐length group producing the greatest improvement. The addition of a small amount of modified Mt improved both oil resistance and tensile strength by increasing in the average diffusion path length in the NR matrix and enhancing the interaction between the modified Mt and the epoxide groups in ENR. The addition of 1.0 phr of modified Mt increased the tensile strength by 18% and decreased the elongation at break by 12% compared with a neat NR/ENR blend. © 2017 Society of Chemical Industry     

Optimization of accelerators on curing characteristics,tensile, and dynamic mechanical properties of (natural rubber)/(recycled ethylene‐propylene‐diene‐monomer) blends

The migration of sulfur from natural rubber (NR) compound to the ground waste ethylene‐propylene‐diene monomer (EPDM) rubber phase may have caused the cure incompatibility between these two rubbers. Optimization of accelerators had been adopted to overcome the cure incompatibility in NR/(R‐EPDM) blends as well as to get increased curative distribution. In this study, blends of NR and R‐EPDM were prepared. The effect of accelerator type on curing characteristics, tensile properties, and dynamic mechanical properties of 70/30/NR/(R‐EPDM) blend was investigated. Four types of commercial accelerators were selected [ie, N‐tert‐butyl‐2‐benzothiazyl‐sulphonamide , N‐cyclohexyl‐benzothiazyl‐sulfenamide (CBS), tetramethylthiuram disulfide, and 2‐mercaptobenzothiazol]. It was found that the tensile strength of the blends cured in the presence of CBS was relatively higher than the other three accelerators. Scanning electron micrographs of CBS‐cured NR/(R‐EPDM) blends exhibited more roughness and cracking path, indicating that higher energy was required toward the fractured surface. The high crosslinking density observed from the swelling method could be verified from the storage modulus (E′) and damping factor (tan δ) where (tetramethylthiuram disulfide)‐cured NR/(R‐EPDM) blends provided a predominant degree of crosslinking followed by N‐tert‐butyl‐2‐benzothiazyl‐sulphonamide , CBS, and 2‐mercaptobenzothiazol, respectively. J. VINYL ADDIT. TECHNOL., 21:79–88, 2015. © 2014 Society of Plastics Engineers     

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。     

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     

Novel ternary blends of natural rubber/linear low-density polyethylene/thermoplastic starch: influence of epoxide level of epoxidized natural rubber on blend properties

Novel degradable materials based on ternary blends of natural rubber (NR)/linear low-density polyethylene (LLDPE)/thermoplastic starch (TPS) were prepared via simple blending technique using three different types of natural rubber (i.e., unmodified natural rubber (RSS#3) and ENR with 25 and 50 mol% epoxide). The evolution of co-continuous phase morphology was first clarified for 50/50: NR/LLDPE blend. Then, 10 wt% of TPS was added to form 50/40/10: NR/LLDPE/TPS ternary blend, where TPS was the particulate dispersed phase in the NR/LLDPE matrix. The smallest TPS particles were observed in the ENR-50/LLDPE blend. This might be attributed to the chemical interactions of polar functional groups in ENR and TPS that enhanced their interfacial adhesion. We found that ternary blend of ENR-50/LLDPE/TPS exhibited higher 100 % modulus, tensile strength, hardness, storage modulus, complex viscosity and thermal properties compared with those of ENR-25/LLDPE/TPS and RSS#3/LLDPE/TPS ternary blends. Furthermore, lower melting temperature (T _m) and heat of crystallization of LLDPE (?H) were observed in ternary blend of ENR-50/LLDPE/TPS compared to the other ternary blends. Also, neat TPS exhibited the fastest biodegradation by weight loss during burial in soil for 2 or 6 months, while the ternary blends of NR/LLDPE/TPS exhibited higher weight loss compared to the neat NR and LLDPE. The lower weight loss of the ternary blends with ENR was likely due to the stronger chemical interfacial interactions. This proved that the blend with ENR had lower biodegradability than the blend with unmodified NR.     

Mechanical properties and blend compatibility of natural rubber –chlorosulfonated polyethylene blends

Natural rubber (NR) was blended with chlorosulfonated polyethylene (CSM) with various formulation and blend ratios (NR/CSM: 80/20 –20/80, wt/wt). Rubber blends were prepared by using a two‐roll mill and vulcanized in a compression mold to obtain the 2 mm‐thick sheets. Tensile properties, tear resistance, thermal aging resistance, ozone resistance, and oil resistance were determined according to ASTM. Compatible NR/CSM blends are derived from certain blends containing 20–30% CSM without adding any compatibilizing agent. Tensile and tear strength of NR‐rich blends for certain formulations show positive deviation from the rule of mixture. Thermal aging resistance depends on formulation and blend ratio, while ozone and oil resistance of the blends increase with CSM content. Homogenizing agents used were Stuktol®60NS and Epoxyprene®25. Stuktol®60NS tends to decrease the mechanical properties of the blends and shows no significant effect on blend morphology. Addition of 5–10 phr of epoxidized natural rubber (ENR, Epoxyprene® 25) increases tensile strength, thermal aging resistance, and ozone resistance of the blends. It is found that ENR acts as a compatibilizer of the NR/CSM blends by decreasing both CSM particle size diameter and α transition temperature of CSM. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 127–140, 2006     

Interaction Between Fumed-Silica and Epoxidized Natural Rubber

Epoxidized natural rubber (ENR)/fumed silica vulcanizates were prepared by mechanical mixing method. Fumed silica content can affect mechanical properties of the composites, and ten parts per hundreds of rubber (phr) fumed silica lead to the best tensile strength. The interaction between ENR and fumed silica was characterized by Kraus equation, crosslink density (tested by NMR), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA) and scanning electron microscope (SEM). The results showed that the dispersion of silica in ENR was better than in natural rubber (NR), hydrogen bond was produced between ENR and fumed-silica in ENR/silica blends, and glass transition temperature of ENR/silica vulcanizate was higher than pure ENR vulcanizate. TGA and DMA confirmed that there was intense interaction between ENR and silica.     

Studies on blends of natural rubber and ethylene propylene diene rubber modified with phosphorylated cardanol prepolymer: Processability,physico‐mechanical properties,and morphology

The melt processability and physico‐mechanical properties of blends of natural rubber (NR) and ethylene propylene diene rubber (EPDM) containing different dosages (0–10 phr) of phosphorylated cardanol prepolymer (PCP) were studied in unfilled and china‐clay‐filled mixes. The plasticizing effect of PCP in the blends was evidenced by progressive reduction in power consumption of the mixing and activation energy for melt flow with an increase in the dosage of PCP. The PCP‐modified blend vulcanizates showed higher tensile properties and tear strength despite a decrease in the chemical crosslink density (CLD) index. This is presumably due to the formation of a crosslinked network structure of PCP with the rubbers and improved dispersion of the filler particles in the rubber matrix, as evidenced by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Thermogravimetric analysis showed an increase in thermal stability of the blend vulcanizate in presence of 5 phr of PCP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5123–5130, 2006     

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。     

Effects of Characteristics of Rubber,Mixing and Vulcanization on the Structure and Properties of Rubber/Clay Nanocomposites by Melt Blending

Summary: Three rubber‐based nanocomposites, natural rubber (NR), styrene‐butadiene rubber (SBR), and ethylene‐propylene‐diene rubber (EPDM) matrixes, were prepared with octadecylamine modified fluorohectorite (OC) by melt blending. X‐ray diffraction (XRD) revealed that the SBR/OC and EPDM/OC nanocomposites exhibited a well‐ordered intercalated structure and a disordered intercalated structure, respectively. In the case of the NR/OC nanocomposite, it exhibited an intermediate intercalated and even exfoliated structure. These results were in good agreement with transmission electron microscopy (TEM) observations. Furthermore, in the NR/OC and SBR/OC systems, the mixing process played a predominant role in the formation of nanometer‐scale dispersion structure, whereas the intercalated structure of EPDM/OC formed mainly during the vulcanization process. The tensile strength of SBR/OC and EPDM/OC nanocomposites loading 10 phr OC was 4–5 times higher than the value obtained for the corresponding pure rubber vulcanizate, which could be ascribed to the slippage of the rubber molecules and the orientation of the intercalated OC. For the strain‐induced crystallization NR, the exfoliated OC efficiently improved the modulus of the NR/OC nanocomposite relative to the pure NR. However, its hindrance on NR crystallization during the tensile process may be the main reason for the decrease in tensile strength of NR/OC.

XRD diffraction patterns of three nanocomposites containing 10 phr organoclay.     

Effect of epoxidized natural rubber on the processing behavior,tensile properties,morphology, and thermal properties of linear‐low‐density polyethylene/soya powder blends

The effect of epoxidized natural rubber (ENR) with 50 mol% epoxidation (ENR 50) on the processing behaviors, tensile properties, morphology, and thermal properties of linear‐low‐density polyethylene (LLDPE)/soya powder blends was investigated. The LLDPE was blended with various soya powder contents in a Haake internal mixer at 150°C and a rotor speed of 50 rpm for 10 min. The tensile properties were tested by using an Instron tensometer according to ISO 527. The thermal stability of the blends was determined by using a thermogravimetric analyzer (TGA). The tensile strength and elongation at the breakage point were significantly improved by the addition of ENR 50, as evidenced by morphological analysis using scanning electron microscopy (SEM). On the other hand, the tensile modulus increased with soya powder content up to 20% and decreased thereafter. The crystallinity and crystallization temperatures of the blends decreased with the incorporation of ENR, and the thermal stability of the blends was lower with higher soya powder content. However, ENR 50 improved the thermal stability of LLDPE/soya powder blends. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

TENSILE PROPERTY OF EPOXIDIZED NATURAL RUBBER/NATURAL RUBBER BLENDS

The tensile strength and elongation at break of epoxidized natural rubber (ENR) blended with natural rubber (NR) was studied. ENR 25, ENR 50, and one grade of natural rubber (SMR L) were used as the elastomers. The composition of ENR was varied from 0% to 100% rubber. The accelerated sulfur vulcanization system was used throughout the investigation. The tensile property of unaged and aged samples was determined by using the Monsanto tensometer (T10) operating at 50 cm/min. Results show that the tensile strength and elongation at break passes through a maximum at 50% ENR for both ENR25/SMR L and ENR50/SMR L blends. This positive deviation from ideality is attributed to the mutual reinforcement of ENR and NR in the blends as a result of strain-induced crystallization. This synergistic effect is more pronounced in the case of ENR 25 due to the higher crystallinity and availability of more double bonds, which is more compatible to NR compared to ENR 50/NR blends. For the aged samples, a drop in the tensile property associated to the breakdown of the polysulfidic cross-link during aging is observed. A systematic study of the effect of sulfur concentration on the percentage retention of tensile property of the ENR blends after aging reveals that percentage retention decreases with increasing sulfur loading, which, in turn, enhances the formation of the polysulfidic cross-link; thus, more breakdown is observed in the rubber vulcanizate.