Physico-mechanical properties and automotive fuel resistance of EPDM/ENR blends containing hybrid fillers

This research aimed to investigate the effect of blend ratios on cure characteristics, mechanical and dynamic properties, morphology and automotive fuel resistance of ethylene-propylene diene rubber (EPDM) and epoxidized natural rubber (ENR) blends containing carbon black and calcium carbonate hybrid filler. The composition of EPDM/ENR blends varied were 100/0, 70/30, 50/50, 30/70 and 0/100 %wt/wt. All ingredients used for preparing each blended compound, except for the curatives, were mixed in a kneader. Thereafter, the compound was further mixed with curatives on a two-roll mill and then were vulcanized together with shaped by compression molding before determining cure characteristics, mechanical properties, morphology and weight swelling ratio in three automotive fuels; gasohol-91, diesel and engine oils. The results indicated that Mooney viscosity and cure time of EPDM/ENR blends tended to decrease with increasing ENR content, while cure rate index and crosslink density increased. Tensile strength of all EPDM/ENR blends is lower than that of the individual EPDM and ENR. This is attributed to the incompatibility between nonpolar and polar nature of EPDM and ENR, respectively, supporting by the glass transition temperature form dynamic mechanical thermal analysis (DMTA) and scanning electron micrographs (SEM). Owing to the differences in polarity of automotive fuels and rubbers, weight swelling of EPDM/ENR vulcanizates decreased in diesel and engine oils, but increased in gasohol-91 with increasing in ENR content.     

Development of butyl rubber nanocomposites in presence and absence of compatibiliser

Abstract

Chlorobutyl rubber nanocomposites containing organically modified nanoclay (CI-C) were prepared by solution mixing. The nanoclay used in this study was Cloisite 20A. The obtained nanocomposites were incorporated in butyl rubber (IIR) with sulphur as a curing agent. Morphology, curing characteristics, mechanical and gas barrier properties of the nanocomposites were analysed. The morphological studies proved the partial exfoliation along with agglomeration of nanoclay platelets in chlorobutyl rubber, and further incorporation of CI-C in IIR matrix enhance the exfoliation of the nanoclay platelets. Curing study demonstrated shorter scorch time, cure time and increase in maximum torque for the nanoclay loaded IIR compound in the presence of chlorobutyl rubber as a compatibiliser compared to pure and IIR-nanoclay compound without compatibilisers. Dynamic mechanical thermal analysis results showed tremendous improvement in storage modulus and decrease in tan?δ value for the one containing a compatibiliser. This particular compound exhibited substantial improvement in mechanical and gas barrier properties.     

Influence of modified natural rubber and structure of carbon black on properties of natural rubber compounds

Carbon black‐filled natural rubber composites were prepared using various types of natural rubber: unmodified natural rubber, epoxidized natural rubber with two levels of epoxy groups at 25 and 50 mol % [epoxidized natural rubber (ENR)‐25 and ENR‐50], and maleated natural rubber. Two types of carbon black (HAF and ECF) with different structure and surface area were used. The functional groups present in natural rubber and carbon black were characterized by FTIR and ¹H‐NMR. Furthermore, cure characteristics, mechanical, morphological, and electrical properties of composites and gum rubber compounds were investigated. It was found that the presence of polar functional groups in rubber molecules and the different structures of carbon black significantly affected the cure characteristics and mechanical properties. This is attributed to physical and chemical interactions between carbon black surfaces and rubber molecules. It was also found that natural rubber filled with ECF showed the highest Young's modulus and hardness, which is due to the high‐surface area and structure of the ECF causing an increase in the degree of entanglement between rubber chains and carbon black particles. Frequency dependency of the dielectric constant, loss tangent, and AC conductivity was also investigated. An increase in dielectric constant, loss tangent, and AC conductivity was observed in the ENR/ECF composites. High‐carbon black loading level caused network formation of these conductive particles, increasing the AC conductivity of the composites. POLYM. COMPOS. 2012. © 2012 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。     

Preparation of Silica‐Based Rubber Compounds without the Use of a Silane Coupling Agent through the Use of Epoxidized Natural Rubber

The present study represents a new concept: the possibility of preparing a rubber compound filled with silica without the use of a silane coupling agent. For this purpose two different types of silica have been compounded with two different grades of epoxidized natural rubber (ENR) without the use of a silane coupling agent. The mechanical and other properties of the resulting compounds have been compared with two reference compounds prepared from natural rubber (NR) and silica with and without the addition of a silane coupling agent bis‐(triethoxysilylpropyl)tetrasulfane (TESPT). It is shown that by using ENR as rubber component together with silica, it is possible without the use of coupling agents to achieve significantly improved mechanical properties with respect to similar NR compounds without coupling agents. The reason for these improvements lies in the polar nature of ENR which interacts strongly with the silica surface by hydrogen bonding mechanism. This does not happen when NR or another non‐polar rubber component is used. Thus, in this latter case the use of silane coupling agents to make the silica surface more non‐polar and hydrophobic is needed to have a good reinforcing effect and overall performances from the composite studied.     

Studies on novel dual filler based epoxidized natural rubber nanocomposite

Carbon black (N‐330), organically modified nanoclay (NC) based ternary, particulate nanocomposites comprising of epoxidized natural rubber matrix having 25 mol% of epoxy group (ENR‐25) were prepared in an open two‐roll mill. Investigations of cure characteristics, dynamic mechanical, tensile, thermal, and morphological characteristics were conducted using Rheometric analysis, Dynamic Mechanical Analysis (DMA), mechanical property evaluation, Thermo‐gravimetric analysis (TGA), High Resolution Transmission Electron Microscopy (HR‐TEM), respectively, to derive the interrelation among the developed nanostructures inside the composite, crosslinking density, performance properties obtained there from. A satisfactory level of correlation was obtained among various results, which indicated the formation of “nanounit” comprising of N‐330 and NC inside ENR‐25 matrix. To optimize the nanostructures, ENR based compounds containing various combinations of NC and N‐330 was prepared. Thorough and systematic structure‐property analyses were performed on those composites. Optimum stoichiometric combination of N‐330 and NC inside the ENR‐25 matrix was derived (ratio of N‐330 and nanoclay in wt% = 20:15), which showed synergistic effect of one filler upon another that was ultimately reflected in their dynamic mechanical and tensile properties. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Effects of epoxidized natural rubber (ENR‐50) and processing parameters on the properties of NR/EPDM blends using response surface methodology

The effects of epoxidized natural rubber (ENR‐50) and processing parameters on the properties of natural rubber/ethylene–propylene–diene rubber (NR/EPDM; 70 : 30 phr) blends were studied. The compounds were prepared by melt compounding method. Using response surface methodology of two‐level full factorial, the effects of ENR‐50 contents (?1 : 5 phr; +1 : 10 phr), mixing temperature (?1 : 50°C; +1 : 110°C), rotor speed (?1 : 40 rpm; +1 : 80 rpm), and mixing time (?1 : 5 min; +1 : 9 min) in NR/EPDM blends were evaluated. Cure characteristics and tensile properties were selected as the responses. The significance of factors and its interaction was analyzed using ANOVA and the model's ability to represent the system was confirmed using the constant of determination, R² with values above 0.90. It was found that the presence of ENR‐50 has the predominant role on the properties of NR/EPDM blends. The addition of ENR‐50 significantly improved cure characteristics and tensile strength up to 5.12% and 6.48% compared to neat NR/EPDM blends, respectively. These findings were further supported by swell measurement, differential scanning calorimetry, and scanning electron microscopy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40713.     

Effects of compounding procedure on morphology development,melt rheology,and mechanical properties of nanoclay reinforced dynamically vulcanized EPDM/polypropylene thermoplastic vulcanizates

New nanocomposite thermoplastic vulcanizates (TPVs) comprising dynamically cross‐linked nanoscale EPDM rubber particles dispersed throughout the polypropylene (PP) matrix have been prepared by both batch and continuous melt blending of PP with EPDM in the presence of vulcanizing ingredients, nanoclay and maleated EPDM (EPDM‐g‐MA) as compatibilizer. X‐ray diffraction, linear melt viscoelastic measurement, and tensile mechanical behavior results revealed that the developed microstructure is strongly affected by the type of the melt compounding process as well as the route of material feeding. When EPDM phase was precompounded with a vulcanizing agent, nanoclay, and EPDM‐g‐MA prior to the melt blending with PP, not only nanosize cross‐linked rubber particles appeared uniformly throughout the PP continuous phase, but also the melt blending leads to the significant enhancement of the mechanical properties compared with counterpart samples prepared by one‐step melt mixing process. Also better dispersion of nano layers in the rubber compound before melt blending with PP results in higher mechanical properties of the resulted TPV. POLYM. ENG. SCI., 56:914–921, 2016. © 2016 Society of Plastics Engineers     

Influence of nanoclay‐carbon black hybrid fillers on cure and properties of natural rubber compounds

The influence of organically modified nanoclay‐carbon black (CB) hybrid filler on the curing behavior of natural rubber (NR) was explored in this investigation. Here an effort was paid to understand the curing kinetics of organomodified nanoclay filled rubber compounds. On the basis of two different types of modified clay, NR nanocomposites were prepared and cured by a conventional vulcanization system. A faster curing rate and lower torque values were found when the modification was done by quaternary ammonium compounds. The activation energy of the rubber curing process decreased with the incorporation of nanoclay. In addition, it was revealed that the quaternary ammonium compounds used as modifier in the clay show a plasticization effect. Additionally, X‐ray diffraction studies indicated, that the basal spacing of the clay minerals was increased in both cases after incorporation in the rubber matrix. The dynamic mechanical analysis using a strain sweep mode showed that the Payne effect decreases because of an improved dispersion of CB induced by the presence of nanoclay. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

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     

Rheological and curing properties of reactive blending products of epoxidised natural rubber and cassava starch

Abstract

Epoxidised natural rubber (ENR) has been prepared and used as a blending ingredient together with a compatibiliser for blending of natural rubber (air dry sheet, ADS) and cassava starch. Mooney viscosities of the blends were quantified at 100°C and rheological properties in terms of shear stress and shear viscosity were plotted against shear rates. The results showed that pure ENR gave a lower Mooney viscosity, shear stress, and shear viscosity than blends with cassava starch. Mooney viscosity, shear stress, and shear viscosity for the blends increased with increasing levels of starch. At the same level of cassava starch blended, the highest values of these quantities were observed for the blends with ENR. The blend of ADS with ENR as a compatibiliser showed lower values than those of ENR itself, but higher than those of ADS with the starch. The results are described in terms of the level of chemical interaction between polar groups in ENR and in cassava starch. Curing behaviour for compounds of ENR, ADS, and ADS with ENR as a compatibiliser were studied. The results found that ENR exhibited a long delay (～ 10 min) before the vulcanisation took place compared with 1 min for ADS compounds. In the curing curve for ENR, an equilibrium value at maximum torque was not found indicating that the stiffness of the ENR compounds still increased with increasing testing time until 60 min. Stiffness of the ENR compounds also increased with increasing levels of cassava starch.     

Effects of hygrothermally decomposed polyurethane on the curing and mechanical properties of carbon black‐filled epoxidized natural rubber vulcanizates

Hygrothermally decomposed polyurethane (HD‐PUR) was mixed up to 20 phr in epoxidized natural rubber (with 50 mol % epoxidation; ENR50) recipes, and the curing and mechanical behaviors were studied. Mechanical testing of the ENR50/HD‐PUR vulcanizates determined the tensile, tear, compression‐set, hardness, abrasion, hysteresis, and resilience properties. No significant changes were observed in the tensile properties with the incorporation of HD‐PUR. The ENR50 compounds showed an increase in compression set with increasing HD‐PUR content. Rubbers cured by a semi‐efficient vulcanization system gave the best overall performance. A further improvement in curing and mechanical properties was achieved by the carbon black grade N330 being replaced with a more active grade (N375). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2265–2276, 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。     

Various nano-particles influences on structure,viscoelastic, Vulcanization and mechanical behaviour of EPDM nano-composite rubber foam

ABSTRACT

In this study, the effect of various nano-particle type and concentration on the structure, curing, viscosity variation during vulcanisation, and mechanical characteristics of ethylene–propylene–diene monomer (EPDM) rubber foam is reported. Three types of nanoparticle with various dimensional aspects (1D carbon nanotubes, 2D nano clay, and 3D nano silica) are employed to investigate their effect on the fabrication of EPDM rubber foam. It is observed that the properties of the foams were efficiently influenced by the nano-particle shapes and content in the matrix. Nanoparticles may increase cell density and change cell structures. In addition, they can change the curing behaviour of foam rubber by affecting curing rate and scorch time of rubber. In the end, mechanical properties of EPDM foam rubbers investigated by experimental tests and implementing few empirical and constitutional mechanical models. It is very helpful to use suitable nanoparticle to achieve desired properties out of fabricated foams.     

The Effect of Filler Loading and Epoxidation on Paper-Sludge-Filled Natural Rubber Composites

The effect of filler loading and epoxidation on curing characteristics, dynamic properties, tensile properties, morphology, and rubber-filler interactions of paper-sludge-filled natural rubber compounds have been studied. Two different types of natural rubber, SMR L and ENR 50, having 0% and 50% of epoxidation and conventional vulcanization were used. Paper sludge was used as a filler and the loading range was from 0 to 40 phr. Compounding was carried out using a laboratory-sized two-roll mill. The scorch time for both rubber compounds decreased with filler loading. The cure time was found to decrease with increasing filler content for SMR L vulcanizates, whereas for ENR 50, the cure time seemed to be independent of the filler loading. Dynamic properties, i.e., maximum elastic torque, viscous torque, and tan delta, increase with filler loading in both grades of natural rubber. Results also indicate that both rubbers show increment in tensile modulus but inverse trend for elongation at break and tensile strength. However, for a fixed filler loading, ENR 50 compounds consistently exhibit higher maximum torque, modulus at 100% elongation, and modulus at 300% elongation, but lower elongation at break than SMR L compounds. In the case of tensile strength, ENR 50 possesses higher tensile strength than SMR L at 10 to 20 phr, but the difference is quite small at 30 and 40 phr. These findings might be associated with better rubber-filler interaction between the polar hydroxyl group of cellulose fiber and the epoxy group of ENR 50.     

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.     

Compatibilization of natural rubber–polyolefin thermoplastic elastomeric blends by phase modification

Natural rubber–polyolefin (70/30) blends have been studied by incorporation of modified rubber and plastic phases with a view to make the heterogeneous phases compatible. The modified rubbers used were epoxidized natural rubber (ENR) and sulfonated ethylene–propylene diene rubber (S-EPDM) at a level of 20 parts. Other rubbers such as chlorinated polyethylene (CPE) and ethylene propylene diene rubbers (EPDM) were also used at a level of 20 parts in the natural rubber–polyethylene (NR/PE) systems. The plastic phase was chemically modified with maleic anhydride (MA) in presence of benzoyl peroxide (BPO) and used at a concentration of 10% of PE, i.e., PEm. The tensile properties such as the modulus, elongation at break, tensile strength, and hysteresis were studied. NR/ENR/PEm/PE shows the greatest improvement in tensile strength (45% over control NR/PE). NR/S-EPDM/PEm/PE also shows similar improvement, although the hysteresis loss decreases. The change in these properties could be related to the adhesive strength. This was found to be improved by the incorporation of modified rubber and modified plastic phases. The best adhesion values have been obtained with NR/ENR/PEm/PE and NR/S-EPDM/PEm/PE. Thus, a correlation between tensile and adhesive strength was obtained for all the systems. The increase in adhesive strength is due to chemical reactions between the various phases. Probable chemical reactions have been suggested. Morphological observations show that the phases are interpenetrating, and this is consistent with the increased tensile strength. The natural rubber–polypropylene (NR/PP) systems do not offer good strength properties with the modified PP and modified rubbers. The adhesive strength also decreases with the incorporation of the modified system. The hysteresis properties show some improvement.     

Synergistic effect of aluminum hydroxide and nanoclay on flame retardancy and mechanical properties of EPDM composites

The composites based on ethylene–propylene–diene monomer rubber (EPDM) with aluminum hydroxide (ATH), nanoclay, vulcanizing agent, and curing accelerator were prepared by conventional mill compounding method. The thermal stability and the flame retardant properties were evaluated by thermogravimetric analysis (TGA), limiting oxygen index (LOI), UL‐94 test, cone calorimeter, and smoke density chamber tests. The results indicated that the substitution of the nanoclay in the EPDM/ATH composites increased the 50% weight loss temperature and the LOI value, and reduced the peak heat release rate (pk‐HRR), the extinction coefficient (Ext Coef), the maximal smoke density (Dm), and the whole smoke at the first 4 min (VOF4) of the test specimens. The synergistic flame retardancy of the nanoclay with ATH in EPDM matrix could imply that the formation of a reinforced char/nanoclay layer during combustion prevents the diffusion of the oxygen and the decomposed organic volatiles in the flame. The mechanical properties of the composites have been increased by replacing more of the nanoclays into the EPDM/ATH blends. The best loading of the nanoclay in EPDM/ATH composites is 3 wt %, which keeps LOI in the enough value, the V‐0 rating in the UL‐94 test, and the improved mechanical properties with better dispersion and exfoliation of the nanoclays shown by transmission electron microscopy (TEM) micrographs. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2042–2048, 2013     

Effect of epoxidized natural rubber on thermal properties,fatigue life,and natural weathering test of styrene butadiene rubber/recycled acrylonitrile‐butadiene rubber (SBR/NBRr) blends

The utilization of waste rubber powder in polymer matrices provides an attractive strategy for polymer waste disposal. Addition of recycled acrylonitrile‐butadiene rubber (NBRr) in rubber compounds gives economic (lowering the cost of rubber compounds) as well as processing advantages. In this study, the properties of styrene butadiene rubber (SBR)/NBRr blends with and without epoxidized natural rubber (ENR‐50) as a compatibilizer were determined. The results such as thermal gravimetric analysis (TGA), fatigue life, and natural weathering test of SBR/NBRr blends with and without ENR‐50 were carried out. Results showed that TG thermograms of SBR/NBRr blends with ENR‐50 show lower thermal stability compared blends without ENR‐50. The incorporation of ENR‐50 into SBR/NBRr blends has reduced char residue compared SBR/NBRr blends without ENR‐50. The incorporation of ENR‐50 in SBR/NBRr blends has increased the rigidity of the blends thus lowering the fatigue life. The increment in tensile properties retention of SBR/NBRr blends with ENR‐50 indicated the enhancement on weathering resistant. The surfaces of SBR/NBRr blends with ENR‐50 after 6 months exposure showed a minimal severity of crack compared with SBR/NBRr blends without ENR‐50. It revealed that the scale of cracks has reduced indicating well‐retaining interfacial adhesion between SBR and NBRr with the presence of ENR‐50 as a compatibilizer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of contact time and temperature on adhesion between components of rubber-polyethylene thermoplastic composites

—The effect of contact time and temperature on the adhesion between rubber and polyethylene has been studied. The degree of adhesion between natural rubber (NR) and polyethylene (PE) was varied by using physical (EPDM) and chemical interaction promoters (ENR/PE_m). It was observed that the peel strength increases with an increase in time of contact at a particular temperature. The adhesion strength varies with the square root of the contact time for all the systems with the exception of NR/PE/DCP at 75 and 100°C, EPDM/PE at 100°C, and NR/ENR/PE_m/PE at 100°C. With an increase in temperature, however, only EPDM-containing systems show higher values of adhesion between components. EPDM enhances the strength of the interface of the NR/PE joint, especially at longer contact times and higher temperatures. However, the chemical modifier is active only when the joining temperature is 150°C. On mastication of NR up to 15 min, the adhesion between natural rubber and polyethylene increases. The tack strength of NR-PE composites is increased with the introduction of physical and chemical modifiers.