Preparation and characterization of nanocomposites based on thermoplastic elastomers from rubber–plastic blends

In the present work, thermoplastic elastomer (TPE)–clay nanocomposites (TPN) based on different rubber–plastic blends from ethylene–octene copolymer [Engage]–Polypropylene and brominated poly(isobutylene‐co‐paramethyl styrene)–nylon 6 were prepared by melt blending. Hexadecyltrimethylammonium bromide and octadecyl amine‐modified sodium montmorillonite were used as organoclays. The nanocomposites were prepared by adding the nanoclay separately into the rubber and plastic phases. The TPNs were characterized with the help of transmission electron microscopy (TEM) and X‐ray diffraction. The X‐ray diffraction peaks observed in the range of 3–10° for the modified clays disappeared in the thermoplastic elastomeric nanocomposites. TEM photographs showed exfoliation and intercalation of the clays in the range of 20–30 nm in the particular phase where the clay was added. Excellent improvement in mechanical properties like tensile strength, elongation at break, and modulus was observed on incorporation of the nanoclays in the rubber phase of TPN. When the nanoclay was added to the plastic phase, the mechanical reinforcement is comparatively poorer due to partial destruction of the crystallinity. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1645–1656, 2006     

Influence of various crosslinking systems on the mechanical properties of gas phase EPDM/PP thermoplastic vulcanizates

Dynamically cured thermoplastic elastomers or thermoplastic vulcanizates (TPVs) are widely used nowadays for their unique characteristics. In this paper, gas phase ethylene–propylene–diene terpolymer (GEPDM)/Polypropylene (PP) TPVs with various crosslinking systems have been extensively studied to optimize the curative level in each crosslinking system with special reference to their mechanical properties. Optimized systems were compared for heat aging, recyclability, crosslink density, morphology studies, and dynamic mechanical analysis. Crosslinking by peroxide in the presence of triallyl cyanurate as a coagent gives best overall performance with reference to excellent heat aging behavior, tension set, and compatibility between GEPDM and PP. Conventional EPDM/PP system was also compared with GEPDM/PP system. GEPDM/PP system was found to exhibit better behavior in all respects. Significant correlations were obtained between delta torque values obtained from Moving Die Rheometer and modulus or cross link density of TPVs irrespective of the nature of crosslinking agent. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5463–5471, 2006     

Sustainable bionanocomposite from d,l‐lactide/δ‐valerolactone triblock and bionanowhiskers: Preparation,characterization, and properties

Bionanocomposites were prepared using d ,l ‐lactide–δ‐valerolactone–d ,l ‐lactide triblock and unmodified and modified cellulose nanowhiskers (CNs) at different loadings (0, 2, 4, 8 wt %). Poly(δ‐valerolactone) chains were grafted on CNs for modification. These were characterized by various techniques. The broadening of OH (hydroxyl) stretching region and the presence of low‐intensity peaks at 1064 cm^?1 for C? O/C? C stretching vibration and 1426 cm^?1 for bending vibration of CH₂ group_, were evident in Fourier transform infrared spectra of the nanocomposites. The increase in crystallinity was noticed as the amount of nanowhiskers was increased. The nanowhiskers having the width in the range of 80–300 nm were uniformly dispersed in the triblock matrix. The tensile strength and modulus increased by 130% and 50% respectively at 8 wt % of filler loading. The storage modulus, loss modulus, complex viscosity, and tan δ values increased with increased filler loading. Further improvement in mechanical properties was observed with the modified CNs. The modulus mapping from atomic force microscopy confirmed the effective reinforcement behavior of the nanowhiskers. Scaffold fabrication using the bionanocomposite exhibited porous nature, having a homogeneous dispersion of CNs on the surface of the scaffold. The 3‐(4,5‐Dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay confirmed the suitability of the composite material for scaffold application. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 135, 46035.     

New polymeric blends from hydrogenated styrene–butadiene rubber and polyethylene

New thermoplastic elastomeric blends based on hydrogenated styrene–butadiene rubber (HSBR) and low-density polyethylene (LDPE) were prepared by the melt blending technique. The rheology, structural and mechanical properties were measured as a function of blend composition. The HSBR/LDPE blend had a higher tensile strength, modulus, and work-to-break with low elongation at break compared with those of pure HSBR. X-ray diffraction studies demonstrated co-crystallisation and a remarkable increase in the degree of crystallinity. The improvement in the mechanical properties and the uniform morphology were correlated with the interfacial adhesion and compatibilisation of the HSBR/LDPE blend through ethylene segments. The experimental results for the HSBR/LDPE blends were compared with those for HSBR/high-density polyethylene (HDPE) and SBR/LDPE blends. The mechanical properties of the HSBR/LDPE blend were found to be superior. The results were explained on the basis of morphology and interaction.     

Structure–property relationship of electron‐beam‐modified EPDM rubber

Electron‐beam‐initiated grafting of trimethylolpropane triacrylate (TMPTA) onto the bulk ethylene propylene diene monomer (EPDM) was carried out with varying concentrations of TMPTA at a constant irradiation dose of 100 kGy and over a wide range of irradiation doses (0–500 kGy) at a fixed concentration (10%) of TMPTA. The rubber was also modified in the bulk by tripropylene glycol diacrylate (TPGDA, 10%) and tetramethylol methane tetraacrylate (TMMT, 10%) at an irradiation dose of 100 kGy. The modified rubbers were characterized by IR spectroscopy, crosslinking density measurements, and mechanical, dynamic mechanical, and electrical properties. The IR studies indicated increased peak absorbances at 1730, 1260, and 1019 cm⁻¹ due to increased 〉CO and C O C concentrations up to certain levels of TMPTA and irradiation dose. These are accompanied by an increase in the crosslinking density. The tensile strength of the samples increases gradually with increasing both the concentration of the monomer and radiation dose up to a certain level. The values of the modulus also increase at the expense of the elongation at break. An increase in the number of double bonds from two in the case of the diacrylate to four in the case of the tetraacrylate also brings about an increase in the tensile strength and moduli values. The elongation at break, however, decreases. The DMTA measurements indicate changes in the glass transition temperature, T_g, and tan δ_max on modification. The T_g shifts to a higher temperature with a simultaneous lowering of the tan δ_max values as the TMPTA level is increased. A similar trend is observed when the irradiation dose is increased and the nature of the monomer changes from di‐ to tetraacrylate. The dielectric loss tangent registers an increase on modification by irradiation of TMPTA while the permittivity is decreased. All the results could be explained on the basis of the structural modification and crosslinking density. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 323–337, 2000     

Hysteresis loss in filled rubber vulcanizates and its relationship with heat generation

A relationship between heat generation of filled rubber vulcanizates and hysteresis loss, specific heat, thermal conductivity, modulus, filler loading, structure, and surface area of the filler, the temperature difference between application temperature and glass transition temperature, frequency, temperature difference between the wall and the environment, stress, and stroke amplitude were developed. Styrenebutadiene rubber (SBR) and natural rubber (NR) vulcanizates were used that had variations of loading of carbon black, silica, resin and coupling agent, types of filler, level of curatives, and cure time. The derived equation was verified with a set of a few unknown SBR and NR vulcanizates, and also by varying the stress and stroke amplitudes in the heat generation experiment. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1541–1555, 1997     

New composites based on short melamine fiber reinforced epdm rubber

Melamine fibre is a new category of advanced synthetic fiber having superior heat and flame resistance with decomposition temperature above 350°C. It suitability as a reinforcing fiber for ethylene propylene diene terpolymer, abbreviated as EPDM rubber, where ‘M’ stands for polymethylene chain, was investigated. It has been observed that tensile strength and stress at 100% strain of EPDM‐melamine fiber composites increase with the addition of a three‐component dry bonding system, comprising hexamethylene tetramine (hexa), resorcinol, and hydrate silica, abbreviated HRH system. Moreover, the fiber‐filled composites anisotropy in stress‐strain properties due to preferential of the short fibers along the milling direction (longitudinal), which is substantiated by the results of swelling and fractography studies. Aging causes an increase in the modulus, tensile strength and hardness of the composites. The fractographs show an increase in interfacial adhesion between the fibers and the matrix during aging, which is further confirmed by the reduction in tan δ peak height of the aged composites during dynamic mechanical studies. Atomic Force Microscopy (AFM) studies reveal the formation of an interphase with the addition of bonding agents and a better fiber‐matrix adhesion due to aging. AFM images also confirm the role of dry bonding systems in improving the fiber‐matrix adhesion of the aged vulcanizates. The composite modulus has been theoretically calculated using the well‐known Halpin‐Tsai equation. It is found that in the transverse direction, observed modulus values are greater than the calculated values, while in the longitudinal direction, the experimental modulus values are found to be lower than the calculated values for both unaged and aged composites owing to some degree of anisotropy in fiber orientation.     

Influence of carbon‐based nanofillers on the electrical and dielectric properties of ethylene vinyl acetate nanocomposites

A comparative study of ethylene vinyl acetate nanocomposites based on expanded graphite, multiwalled carbon nanotubes, and carbon nanofibers has been carried out to investigate the effect of different carbon nanofillers on the electrical properties of the corresponding composites. The composites were prepared by ultrasonic dispersion of fillers in ethylene vinyl acetate solution, followed by casting and compression molding. The dependence of AC conductivity and dielectric constant on the frequency and filler concentration was investigated. Carbon nanofibers provided maximum conductivity as well as lowest percolation threshold (8.2 vol%) compared to expanded graphite and multiwalled carbon nanotubes filled composites. The improvement in both electrical conductivity and dielectric constant was attributed to the high filler aspect ratio and the formation of conducting networks. The relationship of dielectric constant with filler volume fraction for all the composite systems is estimated using a power law. The pressure sensing capability of the composites at respective percolation thresholds was also compared. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

The role of tackifiers on the auto-adhesion behavior of EPDM rubber

The article describes the effect of hydrocarbon (HC) and coumarone-indene (CI) resin tackifiers on autohesion behavior of ethylene propylene diene polymethylene (EPDM) rubber. The viscoelastic behavior and nature of compatibility of EPDM/tackifier blends were studied by means of dynamic mechanical analysis. Furthermore, scanning electron microscopy and atomic force microscopy were used to understand the compatibility of the EPDM/tackifier blends. The HC tackifying resin modified the viscoelastic properties of the EPDM rubber in such a way that it behaved as a plasticizer at lower frequency by reducing the storage modulus and filler at higher frequency by increasing the storage modulus. On the contrary, the CI modified EPDM rubber did not show similar behavior; the modulus enhanced throughout the entire frequency range. The viscosity of the matrix was found to be highly governed by the compatibility as well as amount of tackifier present in the blend. In order to explain the tack behavior, several tack governing factors such as green strength, creep compliance, entanglement molecular weight, relaxation time, self-diffusion coefficient, and monomer friction coefficient (ζ₀) were investigated. The tack strength increased with HC tackifier loading up to 24 parts per hundred grams of rubber (phr), beyond which a plateau region was observed. A maximum of 196% improvement was observed at 24 phr HC loaded sample as compared to gum EPDM rubber devoid of tackifier. Conversely, there was a marginal improvement of tack strength (36%) up to 8 phr loading for the system containing CI, beyond which it dropped.     

Effect of various nanofillers on thermal stability and degradation kinetics of polymer nanocomposites

Structure of nanofillers and their subsequent interaction with a polymer is very important in determining thermal stability of polymer nanocomposite. In this paper, we tried to correlate structure of various 0, 1 and 2 dimensional nanofillers with the thermal stability of hydrogenated nitrile butadiene rubber (HNBR) nanocomposites. Organically modified and unmodified layered silicates such as montmorillonite (Cloisite Na+, Cloisite 30B and Cloisite 15A), rod-like fibrous filler (sepiolite) and spherical nanoparticles (nanosilica) were chosen for this purpose. A significant improvement in thermal stability (obtained by thermogravimeric analysis and differential scanning calorimetry) was observed for silica-filled nanocomposites. However, the activation energy of the nanocomposites calculated by different kinetic methods (both non-isothermal and isothermal methods) was found to be significantly high for sepiolite, 30B and silica-filled nanocomposites. The results were explained with the help of structure of the nanofillers, their interaction with the elastomer and the subsequent dispersion, as measured by X-ray diffraction, transmission electron microscopy and atomic force microscopy. From these analyses it was concluded that organically modified montmorillonite, sepiolite and nanosilica increase the thermal stability of the nanocomposite to a great extent due to the interaction of the reactive groups on the surface of these fillers with the polymer and high thermal stability of these inorganic fillers. Finally, degradation mechanism of HNBR in presence of the nanofillers at severe operating temperatures was investigated with the help of FTIR spectroscopy.