Barium Titanate-reinforced Acrylonitrile-Butadiene Rubber: Synergy Effect of Carbon-based Secondary Filler

Acrylonitrile rubber(NBR) composites filled with barium titanate(BT) were prepared using an internal mixer and a two-roll mill. Also, a secondary filler, namely carbon nanotubes(CNT), was added in order to find a potential synergistic blend ratio of BT and CNT. The cure characteristics, tensile and dielectric properties(dielectric constant and dielectric loss) of the composites were determined. It was found that NBR/BT composites with CNT secondary filler, at a proper BT:CNT ratio, exhibited shorter scorch time(t_(s1)) and cure time(t_(c90)) together with superior tensile properties and reinforcement efficiency, relative to the one with only the primary filler. In addition, the NBR/BT-CNT composite with 80 phr BT and 1-2 phr CNT had dielectric constant of 100-500, dielectric loss of 12-100 and electrical conductivity below 10~(-4) S/m together with high thermal stability. Thus, with a proper BT:CNT mix and filler loading, we can produce mechanically superior rubber composites that are easy to process and low-cost, for flexible dielectric materials application.     

Radiation Vulcanization of Nitrile Butadiene Rubber/Butadiene Rubber Blends

Blends of nitrile butadiene rubber (NBR) with butadiene rubber (BR) with varying ratios have been prepared. Vulcanization of prepared blends has been induced by ionizing radiation of gamma rays with varying dose up to 250 kGy. Physical properties, namely soluble fraction and swelling number have been followed up using toluene as a solvent. Mechanical properties, namely tensile strength, tensile modulus at 100% elongation and elongation at break have been followed up as a function of irradiation dose, as well as blend composition. Thermal stability of blends was studied by TGA. The result indicated that the addition of NBR has improved the properties of NBR/BR blends. Also, NBR/BR blend is thermally stable than BR alone.     

Preparation of polypropylene/ethylene‐propylene‐diene terpolymer/nitrile rubber ternary thermoplastics vulcanizates with good mechanical properties and oil resistance by core‐shell dynamic vulcanization

As the most successful commercialized thermoplastic vulcanizates (TPVs), polypropylene (PP)/ethylene propylene rubber (EPDM) TPVs exhibit poor oil resistance. In this work, we prepared PP/EPDM/butadiene acrylonitrile rubber (NBR) ternary TPVs with good oil resistance using core‐shell dynamic vulcanization. According to the theoretical analysis of the spreading coefficient and the transmission electron microscopy results, the rubber phases exhibited a special core‐shell structure, in which the cross‐linkedNBR‐core was encapsulated by the EPDM‐shell. The core‐shell structure effectively improved the interfacial compatibility between PP and NBR phase as the EPDM‐shell could avoid the direct contact of them, thus improving the mechanical properties of the TPVs. For example, the PP/EPDM/NBR (40/30/30) ternary TPV showed enhanced tensile strength of 12.57 MPa, compared with 10.71 MPa of PP/EPDM (40/60) TPV and 11.11 MPa of PP/NBR (40/60) TPV, respectively. Moreover, the oil resistance of the TPVs was also improved. Compared with PP/EPDM TPV, the change rates in mass, volume, tensile strength and elongation at break of PP/EPDM/NBR TPV after oil immersion decreased by 42.18%, 48.69%, 52.68% and 28.77%, respectively.     

Comparative study on the effect of partial replacement of silica or calcium carbonate by bentonite on the properties of EPDM composites

The effects of the partial replacement of silica or calcium carbonate (CaCO₃) by bentonite (Bt) on the curing behaviour, tensile and dynamic mechanical properties and morphological characteristics of ethylene propylene diene monomer (EPDM) composites were studied. EPDM/silica/Bt and EPDM/CaCO₃/Bt composites containing five different EPDM/filler/Bt loadings (i.e., 100/30/0, 100/25/5, 100/15/15, 100/5/25 and 100/0/30 parts per hundred rubber (phr)) were prepared using a laboratory scale two-roll mill. Results show that the optimum cure (t₉₀) and scorch (t_S2) time decreased, while the cure rate index (CRI) increased for both composites with increasing Bt loading. The tensile properties of EPDM/CaCO₃/Bt composites increased with the replacement of CaCO₃ by Bt from 0 to 30 phr of Bt. For EPDM/silica/Bt composites, the maximum tensile strength and E_b were obtained at a Bt loading of 15 phr, with enhanced tensile modulus on further increase of Bt loading. The dynamic mechanical studies revealed a strong rubber-filler interaction with increasing Bt loading in both composites, which is manifested by the lowering of tan δ at the glass transition temperature (Tg) for EPDM/CaCO₃/Bt composites and tan δ at 40 °C for EPDM/silica/Bt composites. Scanning electron microscopy (SEM) micrographs proved that incorporation of 15 phr Bt improves the dispersion of silica and enhances the interaction between silica and the EPDM matrix.     

Cure characteristics and properties of NBR composites filled with co‐precipitates of black liquor and montmorillonite

Acrylonitrile‐butadiene rubber (NBR) composites filled with co‐precipitates of black liquor and montmorillonite (CLM) were prepared by mechanical mixing on a two‐roll mill. The cure characteristics, mechanical properties, thermal properties, and thermo‐oxidative aging properties of NBR/CLM composites were evaluated. Scanning electron microscopy and transmission electron microscopy showed that the filler particles were well dispersed in the NBR/CLM composites. The scorch time and optimum cure time increase with increasing filler loading. A remarkable enhancement in tensile strength, elongation at break, 300% modulus, and shore “A” hardness was also observed. When the loading of CLM was 40 parts per hundred rubbers, it showed about seven times increase in tensile strength, about 1.8 times increase in elongation at break, about three times increase in 300% modulus, and about 1.3 times increase in shore A hardness, respectively, as compared with those of pure cured NBR. Thermal properties and thermal oxidative aging properties, in general, were also improved with loading of this novel filler. Copyright © 2011 John Wiley & Sons, Ltd.     

Use of carbon black as a reinforcing nano-filler in conductivity-reversible elastomer composites

This study presents an innovative approach to the production of reinforced elastomer composites filled with carbon black Printex XE-2B, using the calendering process and ionic liquids (ILs) as dispersing agents. The effect of Printex XE-2B on the mechanical and electrical properties of acrylonitrile-butadiene rubber (NBR) composites was compared to that of conventional carbon black Humex N339. It was found that the highly structured Printex XE-2B significantly enhanced both the mechanical and electrical properties of the NBR composites, in contrast to standard Humex N339. To obtain uniform filler dispersion in the polymer matrix, several different ILs were employed as dispersing agents. The application of ILs had a considerable effect on the properties of the prepared composites, due to the improved dispersion of the filler particles in the composite matrix, which favored the formation of ‘conductive paths.’ Importantly, the prepared NBR/Printex XE-2B/IL composites were found to have reversible and repeatable electrical properties following exposure to chloroform vapors.     

Effect of carbon nanofibers on mechanical and electrical behaviors of acrylonitrile‐butadiene rubber composites

Recently, carbon nanofibers have become an innovative reinforcing filler that has drawn increased attention from researchers. In this work, the reinforcement of acrylonitrile butadiene rubber (NBR) with carbon nanofibers (CNFs) was studied to determine the potential of carbon nanofibers as reinforcing filler in rubber technology. Furthermore, the performance of NBR compounds filled with carbon nanofibers was compared with the composites containing carbon black characterized by spherical particle type. Filler dispersion in elastomer matrix plays an essential role in polymer reinforcement, so we also analyzed the influence of dispersing agents on the performance of NBR composites. We applied several types of dispersing agents: anionic, cationic, nonionic, and ionic liquids. The fillers were characterized by dibutylphtalate absorption analysis, aggregate size, and rheological properties of filler suspensions. The vulcanization kinetics of rubber compounds, crosslink density, mechanical properties, hysteresis, and conductive properties of vulcanizates were also investigated. Moreover, scanning electron microscopy images were used to determine the filler dispersion in the elastomer matrix. The incorporation of the carbon nanofibers has a superior influence on the tensile strength of NBR compared with the samples containing carbon black. It was observed that addition of studied dispersing agents affected the performance of NBR/CNF and NBR/carbon black materials. Especially, the application of nonylphenyl poly(ethylene glycol) ether and 1‐butyl‐3‐methylimidazolium tetrafluoroborate contributed to enhanced mechanical properties and electrical conductivity of NBR/CNF composites.     

Design of PP/EPDM/NBR TPVs with tunable mechanical properties via regulating the core-shell structure

In this work, polypropylene (PP)/ethylene-propylene-diene monomer (EPDM)/butadiene acrylonitrile rubber (NBR) TPVs with different EPDM/NBR ratios were prepared by the core-shell dynamic vulcanization. The relationship between the core-shell structure and mechanical properties of the TPVs were thoroughly investigated. The formation of core-shell structure by adding NBR is conducive to the mechanical properties of the TPVs. The ratio of EPDM to NBR has an important effect on the structure and performances of the final products, and there is a critical ratio for this effect change. Transmission electron microscope (TEM), tensile test, reprocessing test, ageing test, rheological behavior test and stress relaxation were used to characterize the morphology and properties of the TPVs in detail. It was found that when the ratio of EPDM/NBR was 2:4, the tensile strength increased by ~14% compared with PP/EPDM TPV without NBR. Meanwhile, the reprocessing properties, rheological characteristics and instantaneous tensile deformation, etc. all exhibited sudden changes at this critical ratio.     

New double negative and positive temperature coefficients of conductive EPDM rubber TiC ceramic composites

In this paper, we have successfully prepared ethylene-propylene-diene monomer (EPDM)/TiC composites as thermistors, with new double negative and positive temperature coefficients of conductivity (NTCC/PTCC). EPDM composites loaded with 50 phr HAF carbon black and different concentrations of TiC were prepared. This study focuses on the effect of TiC content on the vulcanization process, the network structure and the electrical and thermal properties of EPDM/TiC composites. The effect of TiC on the network structure was evaluated e.g. the curing process, the characteristic time constant during vulcanization, the volume fraction of rubber, gel fraction, interparticle distance between conductive particles, the extent of TiC reinforcement in the rubber matrix and molecular weight between cross-linking through experimental and affine-phantom models. The effects of TiC content on the percolation theory, electrical conductivity, conducting mechanism of conductivity, conducting hysteresis and I-V characteristics were also studied, as well as its TiC on the (NTCC/PTCC), thermoelectric power, dielectric constant and thermal conductivity. Stability and reproducibility of the thermal cycles for heating element applications was tested. Specific heat and the amount of heat transfer by radiation and convection as a function of TiC content was calculated using both the calorimetric technique and a theoretical model. It was proved that TiC improves the network structure, electrical and thermal properties of EPDM composites for practical applications.     

Maleic-anhydride grafted EPM as compatibilising agent in NR/BR/EPDM blends

Incorporation of approximately 30 phr Ethylene-Propylene-Diene rubber (EPDM) into natural rubber (NR)/butadiene rubber (BR) is a means to achieve non-staining ozone resistance for tire sidewall applications. However, due to incompatibility of the elastomers and heterogeneous filler distribution in each of the rubber phases, the mechanical properties deteriorate. In the present work, maleic-anhydride modified EPM (MAH-EPM) is added as a compatibilising agent between NR/BR and EPDM. The addition of 5 phr of MAH-EPM results in significantly improved tensile and tear strength when compared to a straight NR/BR/EPDM blend. These improvements can mainly be attributed to a compatibilising effect of MAH-EPM, resulting in a more homogeneous phase distribution, but in particular a much better homogeneous carbon black distribution over the different rubber phases. In addition, ionic crosslinks are introduced into the blends by interaction of MAH-EPM with zinc oxide.     

Comparison of cure,mechanical, electric properties of EPDM filled with Sm2O3 treated by different coupling agents

Composites based on ethylene–propylene–diene rubber (EPDM) were prepared. EPDM was reinforced with 100 phr Sm₂O₃ treated with coupling agents: stearic acid (SA), isopropyl tri(dioctylphosphate) titanate (NDZ102), bis-[-3-(triethoxysilyl)propyl]tetrasulfide (KH845-4), and N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane (SG-Si602), respectively. Cure, mechanical and electrical properties of the composites were investigated. It was found that carboxyl in coupling agents could retard EPDM cure while amino groups, PO bonds and S atoms could accelerate EPDM cure. Amino groups enhanced composite mechanical properties by forming additional rigid C–C linkages, whilst S atoms boosted composite mechanical properties by generating flexible S–C linkages. PO bonds might be subject to cleavage during vulcanization and form flexible P–C linkage. Thus, composites with NDZ102 and KH845-4 treated filler exhibited better mechanical properties than that with SG-Si602 treated filler. In addition, treatment of filler could reduce composite electrical properties due to interfacial improvement.     

Effect of polyfunctional monomers on properties of radiation crosslinked EPDM/waste tire dust blend

In this study, waste tire dust is recycled as filler and blended with ethylene-propylene diene monomer (EPDM) rubber. Three different polyfuntional monomers (PFMs) are incorporated into the standard formulation and irradiated under electron beam at different doses up to maximum of 100 kGy. The combined effects of PFMs and absorbed dose on the physical properties of EPDM/WTD blend are measured and compared with sulfur crosslinked formulation. Thermogravimetric analysis showed that radiation developed better crosslinked network with higher thermal stability than sulfur crosslinked structure. The physical properties of radiation crosslinked blend are similar to the sulfur crosslinked blend. The absence of toxic chemicals/additives in radiation crosslinked blends made them an ideal candidate for many applications such as roof sealing sheets, water retention pond, playground mat, sealing profile for windows etc.     

The influence of nano silica particles on gamma-irradiation ageing of elastomers based on chlorosulphonated polyethylene and acrylonitrile butadiene rubber

The goal of this work was to study gamma irradiation ageing of rubber blends based on acrylonitrile butadiene rubber (NBR) and chlorosulphonated polyethylene rubber (CSM) reinforced by silica nano particles. The NBR/CSM compounds (50: 50, w/w) filled with different content of filler (0–100 phr) were crosslinked by sulfur. The vulcanization characteristics were assessed using the rheometer with an oscillating disk. The vulcanizates were prepared in a hydraulic press. The obtained materials were exposed to the different irradiation doses (100, 200, 300 and 400 kGy). The mechanical properties (hardness, modulus at 100% elongation, tensile strength and elongation at break) and swelling numbers were assessed before and after gamma irradiation ageing.     

Properties of rubber filled with montmorillonite with various surface modifications

Layered silicate/natural rubber composites were prepared by direct polymer melt intercalation. Na‐montmorillonite Kunipia‐F and its organic derivates (organo‐clays) prepared by ion exchange were used as clay fillers. Silica (SiO₂) Ultrasil VN3, a filler commonly used in the rubber industry, was used in combination with clay fillers. The effect of clay or organo‐clay loading from 1 up to 10 phr without (0 phr) or with silica (15 phr) showed significant improvement of the tensile properties (stress at break, strain at break and modulus M100). Modification of montmorillonite by three alkylammonium cations with the same length of alkylammonium chain (18 carbons) and different structure resulted in altered reinforcing and plasticizing effects of the filler in composites with rubber matrix. Copyright © 2011 John Wiley & Sons, Ltd.     

Enhanced thermal conductivity and mechanical properties of polymeric composites through formation of covalent bonds between boron nitride and rubber chains

Hexagonal boron nitride (BN) platelets, also known as white graphite, are often used to improve the thermal conductivities of polymeric matrices. Due to the poor interfacial compatibility between BN platelets and polymeric matrices, in this study, polyrhodanine (PRd) was used to modify BN platelets and prepared functionalized BN-PRd platelets, thereby enhancing the interfacial interaction between the thermal conductive filler and polymeric matrix. Then, BN-PRd platelets were dispersed into the nitrile butadiene rubber (NBR) matrix to yield high thermally conductive composites. The presence of N? C═S groups in PRd allowed the combination of PRd and NBR chains containing stable covalent bonds via vulcanization reaction. The thermal conductivity of the as-prepared 30 vol% BN-PRd/NBR composite reached 0.40 W/mK, representing an increment of 135% over pure NBR (0.17 W/mK). In addition, the largest tensile strength of NBR composite containing 30 vol% BN-PRd platelets was 880% times of pure NBR. The 30 vol% BN-PRd/NBR composite also displayed a relatively high dielectric constant (9.35 at 100 Hz) and a low dielectric loss tangent value (0.07 at 100 Hz), indicating their usefulness as dielectric flexible materials of microelectronics. In sum, the simplicity and good efficiency of formation of covalent bonds between boron nitride and rubber chains look very promising for large-scale industrial production of high thermally conductive composites.     

Gamma radiation curing of nitrile rubber/high density polyethylene blends

Nitrile butadiene rubber (NBR) was mixed with high density polyethylene (HDPE) thermoplastics with different ratio namely (100/20), (100/40), (100/60) and (100/80). The obtained blends were subjected to gamma irradiation with varying dose from 50 to 250 kGy. The induced crosslinking and hence the improvement in the different properties were followed up as a function of irradiation dose. Mechanical properties as tensile strength, tensile modulus at 50 % elongation, elongation at break percent, permanent set and hardness were carried out as a function of irradiation dose and blend ratio. Moreover, physical properties namely, gel fraction % and swelling number were found to improve with the increase of irradiation dose up to 250 kGy and with the increase of the content of HDPE in blend. Moreover, presence of NBR enhances the shrinking properties of the obtained blend which can be used as a good heat shrinkable material.     

The Effect of 3-aminopropyltrimethyoxysilane (AMEO) as a Coupling Agent on Curing and Mechanical Properties of Natural Rubber/Palm Kernel Shell Powder Composites

This research is conducted using palm kernel shell powder (PKS) as filler in natural rubber The effect of 3-aminopropyltrimethoxysilane as coupling agent on composites were studied at different palm kernel shell loading i.e, 0 5, 10, 15 and 20 phr The palm kernel shell was crushed and sieved to an average particle size of 5.53 μm The palm kernel shell filled natural rubber composites were prepared using laboratory size two roll mill The curing characteristics such as scorch time, cure time and maximum torque were obtained from rheometer The palm kernel shell powder filled natural rubber composites were cured at 150^oC using hot press according to their cure time Curing characteristics, tensile properties, rubber-filler interaction and morphological properties of palm kernel shell powder filled natural rubber were studied Scorch time and cure time show reduction but tensile strength, elongation at break, modulus at 100% (M100) and modulus at 300% (M300) increased with the presence of 3-aminopropyltrimethyloxysilane Rubber-filler interaction studies showed that rubber filler interaction in natural rubber filled with palm kernel shell powder improved with incorporation of 3-aminopropyltrimethyoxysilane.     

Effect of chitosan derivatives as rubber antioxidants for increasing durability

A series of chitosan derivatives, namely polydiethylamino-ethylmethacrylate-chitosan-graft-copolymer (chitosan-g-DEAEMA), polycarboxy-chitosan-graft copolymer (chitosan-g-COOH), polyvinyl alcohol chitosan-graft-copolymer (chitosan-g-VOH), and carboxymethyl-chitosan (CM-chitosan), were synthesized and investigated as antioxidants for natural rubber (NR) and acrylonitrile butadiene rubber (NBR) mixes and vulcanizates to increase their durability. The rheometric characteristics of the rubber mixes were determined using an oscillating disc rheometer. The physico-mechanical properties of the rubber vulcanized were measured before and after exposure to thermal oxidative aging. It was found that the CM-chitosan had an accelerating effect on the curing process of NR and NBR. Also, the investigated polymers enhanced the properties of rubbers (NR and NBR) especially after ageing up to 7 days compared with commercial antioxidants, such as phenyl ß-naphthylamine (PßN) and N-isopropel-Nphenyl-p-phenylene diamine (IPPD) which are used in the rubber industry. After ageing, the retained values of tensile strength, modulus at 100 % strain, and elongation at break were improved. The optimum concentration of the investigated compounds used to give good properties was found to be 1–2 parts per 100 of rubber (phr). In addition, these prepared polymers showed a decrease in the equilibrium swelling of rubber in toluene which is the proper solvent and consequently increases the crosslink density for rubbers.     

Effect of crosslinking on the properties of composites based on LDPE and conducting organic filler

New types of composites were prepared using low-density polyethylene (LDPE) filled with modified organic filler, Canadian switch grass coated with polypyrrole (PPy). The grass surface was entirely covered when 10 wt.% of pyrrole was used for the modification, as confirmed by scanning electron microscopy and infrared spectroscopy. LDPE composites filled with modified grass were prepared by melt mixing and their properties were compared with the properties of the composites filled with unmodified grass. The influence of crosslinking, induced by 1 wt.% of peroxide, on mechanical, thermal and electrical properties of the composites was investigated. Crosslinking enhanced the tensile strength of the prepared composites in the entire range of the filler content. The Young’s modulus of the composites prepared by crosslinking is slightly lowered when compared with the uncrosslinked composites if the filler content is less than 60 wt.%, for higher filler content it is increased. The conductivity of the uncrosslinked composites containing 40 wt.% of grass modified by PPy was in the range 1 × 10⁻⁶ S cm⁻¹, which is a value by 5 orders of magnitude higher than the conductivity of the crosslinked materials. The presence of PPy on grass surface leads to a reduction of crosslinking of the LDPE matrix.     

Properties of ethylene propylene diene rubber/white and black filler composites cured by gamma radiation in presence of sorbic acid

The effect of incorporating sorbic acid (SA), an echo-friendly curing agent, and silica or carbon black (CB) filler, as well as gamma irradiation on the physico-chemical, mechanical and thermal properties of ethylene propylene diene monomer rubber (EPDM) was investigated. The results indicated that the developed composites revealed improvement in the studied parameters over the untreated samples. Filler incorporation into rubber matrix has been proven a key factor in enhancing the swelling resistance, tensile strength and thermal properties of the fabricated composites. The improvement in tensile strength and modulus was attributed to better interfacial bonding via SA. Alternatively, a comparison was established between the performance of the white and black fillers. The utmost mechanical performance was reported for the incorporated ratios 10 phr SA and 40 phr white filler into a 50 kGy irradiated composite. Meanwhile, the incorporation of CB yielded better thermally stable composites than those filled with silica at similar conditions.