The Behaviour of Styrene Butadiene Rubber/Acrylonitrile Butadiene Rubber Blends in the Presence of Chlorinated Hydrocarbons

The behaviour of styrene butadiene rubber/acrylonitrile butadiene rubber (SBR/NBR) blends in the environment of chlorinated hydrocarbons, such as carbon tetrachloride, chloroform and dichloromethane, in the temperature range 32–52°C has been investigated. Sulphur, dicumyl peroxide and a mixed system consisting of sulphur and peroxide were used as the vulcanising systems for the matrix. The effects of vulcanising agents, blend composition, solvents and temperature on the sorption characteristics were studied. The sulphur-vulcanised systems exhibited the highest solvent uptake and those with dicumyl peroxide as the vulcanising agent the lowest. This difference has been explained on the basis of the nature of cross links established between the polymer chains during vulcanisation. The solvent uptake increased with an increase in SBR content in the blends when carbon tetrachloride was used as the penetrant, whilst it decreased with SBR content when chloroform and dichloromethane were used as the probes. This behaviour has been explained on the basis of the polarity difference of the solvents. For a given blend system, the solvent uptake was maximum when dichloromethane was used as the solvent and minimum when carbon tetrachloride was used. This has been accounted for in terms of the difference in the size of the penetrants. The intrinsic diffusion coefficient, permeation coefficient, cross link density and interaction parameter were estimated from the sorption data. Thermodynamic parameters such as enthalpy and free energy changes were also calculated. These values indicate that the sorption process in the present systems is exothermic and is more spontaneous in sulphur-vulcanised systems. The experimental results, when compared with different theoretical diffusion models, have been found to be closer to Robeson’s and Maxwell’s models.     

Mass transfer characteristics of natural rubber/ethylene vinyl acetate blends

The transport behavior of natural rubber/ethylene vinyl acetate (NR/EVA) blends has been investigated using aromatic hydrocarbons as probe molecules, in the temperature range of 26–56°C. It has been observed that the solvent uptake decreases with increase in the EVA content of the blends. The blends were crosslinked by three systems, viz. sulfur, dicumyl peroxide (DCP), and a mixture consisting of sulfur and peroxide. The DCP crosslinked system exhibited the lowest solvent uptake. The differences in the transport behavior of the blends, crosslinked by different modes, has been described in terms of the nature of crosslinks introduced between the macromolecular chains during vulcanization. The mechanism of transport has been found to deviate from the regular Fickian behavior, observed with conventional rubbers, with an increase in EVA in the blends. The dependence of the transport coefficients on blend composition, crosslinking systems, nature of penetrants, and temperature was studied. The blend–solvent interaction parameter, enthalpy, and entropy of sorption have also been estimated from the transport data. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2691–2702, 2003     

Molecular Sorption by Heterogeneous Natural Rubber/Poly(ethylene-co-vinyl acetate) Blend Systems

The sorption of n-alkanes, viz. hexane, heptane and octane by cross-linked natural rubber/poly(ethylene-co-vinyl acetate) (NR/EVA) blends has been studied at 28, 38, 48 and 58°C, with special reference to the effects of EVA content, cross-linking systems, penetrant nature and temperature. The solvent transport was found to decrease with increase in EVA content in the blends. The effects of blend ratio on the transport characteristics have been correlated with the phase morphology of the blends, using scanning electron micrographs and optical micrographs. Among the three vulcanising systems, viz. sulphur (S), dicumyl peroxide (DCP) and a mixed system (S + DCP) employed for the matrix, the DCP cross-linked blends exhibited the lowest solvent uptake. Octane has been found to show higher interaction with the blends than hexane and heptane, probably owing to the closer solubility parameter values. The computed transport coefficients, viz. diffusion coefficient and permeability coefficient, were found to decrease with increase in EVA content in the blends. At room temperature, the mechanism of diffusion was found to deviate slightly from the regular Fickian trend for all blend systems. The blend–solvent interaction parameter and the activation energy for transport were also determined from the sorption data.     

Molecular transport of aliphatic hydrocarbons through styrene butadiene rubber/ethylene vinyl acetate blends

Polymer blends based on styrene butadiene rubber and ethylene vinyl acetate (EVA) were prepared. The sorption and diffusion of four aliphatic hydrocarbons through the blends were investigated with temperatures of 26–56°C. Sulfur, dicumyl peroxide (DCP), and a mixed system consisting of sulfur and DCP (mixed) were used as crosslinking agents for the blends. Of the three systems, the peroxide vulcanized blends were found to exhibit the lowest penetrant uptake. The aliphatic liquid penetration through the matrix decreased with an increase in the EVA content in the blends, which was attributed to the semicrystalline nature of the EVA matrix. The experimental observations were correlated with the morphology of the blends. Diffusion and permeation coefficients were calculated from the sorption data. A slight deviation from the Fickian trend was observed for the mechanism of transport with an increase in the EVA content in the blends. The molecular mass between crosslinks and thermodynamic parameters of sorption were determined from swelling data. The experimental observations were compared with different theoretical models. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2884–2897, 2006     

Molecular transport of aromatic hydrocarbons through crosslinked styrene-butadiene rubber membranes

Molecular transport of aromatic hydrocarbons through crosslinked SBR has been carried out in the temperature range (25–65°C). SBR has been vulcanized by four different vulcanizing techniques viz., conventional, efficient, dicumyl peroxide and a mixture consisting of sulfur and peroxide. SBR vulcanized with EV system showed highest solvent uptake tendency and that vulcanized with peroxide showed the lowest. The influence of penetrant size on sorption behaviour of SBR has been examined. The thermodynamic constants such as standard entropy, standard enthalpy and first-order kinetic rate constant have been evaluated. A correlation between theoretical and experimental sorption results was evaluated. The polymer—solvent interaction parameter (χ) was also computed from the diffusion data.     

Sorption and diffusion of acrylonitrile monomer through crosslinked nitrile rubber

As the first step for the preparation of interpenetrating polymer networks from nitrile rubber and polyacrylonitrile, the sorption and diffusion of acrylonitrile monomer through nitrile rubber crosslinked by three different vulcanization systems—conventional (CV), dicumyl peroxide (DCP), and a mixture consisting of sulfur and peroxide (mixed)—were studied in the temperature interval of 30–70°C. Kinetic curves have been generated for these systems to compute diffusion and sorption coefficients. The equilibrium sorption is found to be maximum for the CV system. The molar mass between crosslinks (M_c) has estimated and compared with affine and phantom models. It was found that the M_c values follow the affine model. The diffusion coefficient values are highest for DCP and lowest for CV. It was observed that the kinetics of liquid sorption followed an anomalous behavior. The temperature dependence of the transport parameters was followed by an Arrhenius relationship, from which the activation energy for diffusion, permeation, and sorption were calculated. It is found that temperature activates diffusion in all cases. The polymer–solvent interaction parameter was determined. The amount of polysulfidic linkages in the rubber network was also estimated. The experimental results were compared with theoretical predictions. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 941–952, 2000     

The swelling behavior of interpenetrating polymer networks composed of polyurethane and unsaturated polyester

The kinetics of swelling and the sorption performance were observed for the polymer compositions with interpenetrating polymer networks made up of polyurethane and unsaturated polyester during their exposure to chlorobenzene at 25°C. It was found that the rates for solvent transport and solvent absorption processes were controlled by the chemical composition of the formulation studied. On the basis of the observed swelling process, parameters could be assessed which were specific for the mass transfer process, i.e., diffusion coefficient, sorption coefficient, and permeability coefficient. Moreover, an attempt was made to evaluate structural parameters that describe topology of the obtained networks. It was found that the increasing share of polyurethane in the composition reduced crosslinking density in the polyester network that resulted in faster diffusion of the solvent and higher sorption capacity for the solvent. The higher the styrene content in the composition, the higher the crosslinking density in the system, and hence the diffusion of solvent and its sorption inside the polymer network was much more difficult. In the scanning electron microscope analysis of samples, which had been subjected to swelling, no leaching was observed for any phase present in the system, despite phase separation for both the components. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3511–3519, 2006     

Interaction of n-alkanes with crosslinked cis-1,4-polybutadiene

Permeation of n-alkanes through cis-1,4-polybutadine crosslinked using conventional, efficient, and peroxide vulcanizing systems was studied by a gravimetric method. Four alkanes from n-hexane to n-nonane were used. In n-octane, the studies were conducted in the temperature range of 27–70°C.The sorption data was used to estimate the diffusion and permeability coefficients, the activation energy for diffusion and permeation, the entropy and enthalpy of sorption, polymer–solvent interaction parameter, and the degree of crosslinking. The various parameters estimated indicate that permeability of the membranes depends more on the degree of crosslinking than on the nature of crosslinks. Increase in permeant chain length was found to lower permeability. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2404–2413, 2001     

Effect of adhesion on the equilibrium swelling of natural rubber-aluminium powder composites

Equilibrium swelling of natural rubber composites containing aluminium powder has been investigated in a series of aromatic hydrocarbon solvents, such as benzene, toluene, xylene, and mesitylene. These composites were vulcanized by four vulcanizing systems, viz. conventional, efficient, dicumyl peroxide, and a mixture, consisting of sulfur and dicumyl peroxide. In each system, the effect of aluminium powder with and without bonding agent was studied. The results showed that addition of bonding agent reduced the swelling considerably, and its effect is more pronounced in the conventional system due to increased adhesion. The dependence of the diffusion coefficient on the crosslinking system and the solvent–polymer interaction parameter were calculated from diffusion data. These results are also indicative of the improved adhesion with hexa-resorcinol–silica bonding system in these composites. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2427–2438, 1998     

Influence of static and dynamic crosslinking techniques on the transport properties of ethylene propylene diene monomer rubber/poly (ethylene-co-vinyl acetate) blends

The transport characteristics of dynamically and statically cross-linked Ethylene Propylene Diene Monomer/poly (ethylene-co-vinyl acetate) (EPDM/EVA) blends have been examined in the temperature interval of 28–58 °C using benzene, toluene and xylene as probe molecules. The dynamically vulcanized blends exhibited enhanced properties on the sorption and diffusion features compared to the corresponding statically vulcanized blends. In both the cases, as the EVA content increased in the blends, the solvent uptake decreased. The experimental observations have been correlated with the phase morphology of the blends, using scanning electron micrographs. The crystallinity of the blends was studied using X-ray diffraction patterns. Among the three vulcanising systems, viz, sulphur, dicumyl peroxide (DCP), and a mixture consisting of sulphur and peroxide, employed for the matrix, the DCP cross linked system exhibited the lowest solvent uptake. The molar mass between cross links and the diffusion coefficients have been computed to complement the observed sorption behaviour.     

Effect of prevulcanization on the rheological behavior of natural rubber/styrene butadiene rubber latex blends

The effect of prevulcanization on the rheological behavior of natural rubber (NR), styrene butadiene rubber (SBR) latices, and their blends was studied with special reference to shear rate, blend ratio, vulcanizing systems, prevulcanization time, and accelerator systems. The NR latex showed a sharp increase in viscosity with increase in prevulcanization time due to high extent of crosslinking. However, SBR latex showed marginal effect on viscosity with prevulcanization time due to its low dry rubber content and low degree of unsaturation. Blends showed variations in viscosity according to the change in composition. The use of a single accelerator was found to have marked influence on the viscosity of the blends compared with a combination of accelerators. Swelling experiments were carried out in order to determine the crosslink density of the blends. The viscosity changes have been correlated with the crosslinking density of the latices and their blends. © 1996 John Wiley & Sons, Inc.     

Transport studies of peanut shell powder reinforced natural rubber composites in aromatic solvents

This article investigates the transport behavior of three aromatic organic solvents, viz. benzene, toluene, and xylene in natural rubber (NR) composite membranes containing peanut shell powder (PSP) as filler at different temperatures by conventional weight‐gain experiments. PSP used in compounding the NR was processed in two particle sizes. The solvent swelling characteristics of NR composites containing both untreated and alkali‐treated fillers were investigated. The computed sorption characteristics were discussed in terms of PSP content, particle size, nature of solvent, and temperature. All the NR‐PSP composites were found to decrease with the uptake of aromatic solvents than NR, but the effect was more significant in the case of alkali‐treated PSP composites. Furthermore, the uptake of solvent decreased with decrease in penetrant size. The estimated Arrhenius activation energies (E_D) for the processes of sorption, diffusion, and permeation showed that E_D was generally highest in xylene at the filler contents investigated. The thermodynamic parameters of the sorption process were also evaluated. The relationship between the transport behavior and the morphology of the system was examined. The mechanism of diffusion is found to be close to Fickian trend in toluene and xylene and Fickian trend in benzene. Comparison between theoretical and experimental diffusion results was made to understand the mechanism of diffusion. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Complex-forming polymeric sorbents with macromolecular arrangement favorable for ion sorption

Crosslinked polymeric sorbents with macromolecular arrangement favorable for sorption of copper ions have been obtained obtained on the base of copolymer of diethyl ester of vinylphosphonic acid with acrylic acid. The general principle involves interaction of linear polymer and sorbing ions in solution where the segments of the macromolecules are still mobile enough, subsequent fixation of optimal ion uptake conformations of macromolecules by crosslinking of metal polymer complexes, and removal of ions from crosslinked sorbent. Such treatment increases the exchange capacity of the sorbents more than twice and improves essentially its kinetic characteristics in comparison with the same copolymer crosslinked by conventional methods without special arrangement of macromolecules. The rate of the uptake on the sorbents with macromolecular arrangement favorable for ion sorption first increases with increase in the degree of crosslinking and then decreases. Apparently the jise of the crosslinking degree leads to more rigid fixation of the optimum ion uptake conformations of the macromolecules' segments. Further increase of the crosslinking degree alongside with fixation prevents ions from diffusion into the sorbent.     

Diffusion and sorption of organic liquids through polymer membranes. II. Neoprene,SBR, EPDM,NBR, and natural rubber versus n-alkanes

Diffusion and sorption of n-alkanes (C₆–C₁₀) through commercial polymer membranes such as neoprene, styrene butadiene rubber, ethylene propylene diene terpolymer, nitrile butadiene rubber, and natural rubber have been studied from 25 to 60°C. The diffusion results have been explained in terms of the size of liquid molecules and the diffusion mechanism was found to follow the Fickian trend. Nitrile butadiene rubber and neoprene showed much smaller values of diffusivities and sorption constants than the other polymer membranes. Arrhenius parameters for the activated diffusion process and the thermodynamic quantities for the process of equilibrium sorption have been estimated.     

Solvent Transport Characteristics of Thermoplastic Elastomer Blends Based on Nylon and NBR

Transport characteristics of chlorinated hydrocarbon through Nylon/NBR (Acrylonitrile Butadiene Rubber) blend has been investigated with special reference to the effect of blend ratio, compatibilizer and effect of dynamic crosslinking. An attempt has been made to correlate the diffusion characteristics with morphology of the blend. Fine and uniform distribution of the dispersed domains with a stable morphology were obtained by dynamic vulcanization. Depending on the composition, blends show dispersed/matrix and co‐continuous phase morphologies. The various transport parameters such as diffusion coefficient (D), permeation coefficient (P) and sorption coefficients (S) were evaluated at different diffusion conditions such as temperature and percentage of compatibilizer. The equilibrium solvent uptake decreases with an increase in the concentration of NBR in the blends. Finally thermodynamic parameters were evaluated from the diffusion data. POLYM. ENG. SCI., 57:231–236, 2017. © 2016 Society of Plastics Engineers     

Diffusion mechanism of byproducts resulting from the peroxide crosslinking of polyethylene

In this study, a polyethylene grade used for applications in the insulation of energy cables was crosslinked by the peroxide crosslinking route. The impact of dicumyl peroxide (DCP) crosslinking on the polymer microstructure was studied. The different byproducts formed during the crosslinking reaction [acetophenone, α‐cumyl alcohol, and α‐methyl styrene (aMS)] were identified and quantified. Another molecule, 2,4‐diphenyl‐4‐methyl‐1‐pentene, regarded as an aMS dimer, was detected for the first time. Some amounts of residual DCP were also detected. A detailed study of the diffusion mechanism of each byproduct under different desorption conditions (e.g., samples exposed to vacuum or atmospheric conditions) and temperatures was performed. The diffusion coefficient values were determined and are discussed as a function of the desorption conditions and byproduct characteristics. Through this study, essential diffusion parameters were provided as a first step for further modeling development to allow the definition of optimized desorption conditions for a large range of sample geometries and thicknesses. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44525.     

Interaction of silica and carbon black fillers with natural rubber/poly(ethylene‐co‐vinyl acetate) matrix by swelling studies

The interaction of a black filler and a white filler, which are extensively used in the rubber industry, with natural rubber/poly (ethylene‐co‐vinyl acetate) (NR/EVA) blends vulcanized by DCP has been examined by equilibrium swelling technique. Blends loaded with intermediate super abrasion furnace black (ISAF) and those with silica (SiO₂), of same loading, have been used. The silica incorporated blends sorbed a higher amount of aromatic solvents, compared with the ISAF filled blends, when NR was the continuous phase. However, the silica filled systems showed lower sorption characteristics when EVA became the continuous phase. This has been explained in terms of the differences in the interaction between the filler particles and the blend components. The swelling coefficient, diffusion coefficient, and molar mass between crosslinks have been computed to complement the experimental observations. POLYM. COMPOS., 28:705–712, 2007. © 2007 Society of Plastics Engineers     

Aromatic liquid transport through filled EPDM/NBR blends

The sorption and diffusion characteristics of 70/30 ethylene propylene diene monomer rubber (EPDM)/acrylonitrile butadiene rubber (NBR) blends loaded with black fillers such as ISAF (intermediate super-abrasion furnace), HAF (high abrasion furnace) and SRF (semi-reinforcing furnace) have been investigated. The penetrants used were benzene, toluene and xylene. Filled samples have been found to show a reduced solvent uptake compared to the unfilled sample for the given blend ratio. The observations have been correlated with the morphology of the systems. Blends loaded with ISAF exhibited the lowest liquid uptake among black filled systems which has been attributed to the better filler reinforcement and enhanced crosslink density of the matrix. The extent of particulate filler reinforcement has been studied by using Kraus theory. The unfilled and filled systems have been found to exhibit non-Fickian transport behaviour. The effect of fillers on the cure and mechanical properties of the blends have also been investigated. Among the black filler loaded systems used, the ISAF mix showed the highest maximum torque value. The improvement in the cure and mechanical properties has been observed to be the highest for ISAF filled samples followed by HAF and SRF filled systems, which is in compliance with the observation from the sorption studies.     

Swelling characteristics of NR/PU block copolymers and the effect of NCO/OH ratio on swelling behaviour

A series of (NR/PU) block copolymers (BCs) was prepared from toluene diisocyanate (TDI), 1,3-butane diol (1,3-BDO), and hydroxyl-terminated liquid natural rubber (HTNR), by solution polymerisation. The swelling characteristics of the BCs were investigated. Diffusion profile in various solvents and the sorption kinetics were studied. Arrhenius and thermodynamic parameters were evaluated from the diffusion data. Finally, the influence of NCO/OH ratio on the swelling behaviour was also studied. The equilibrium sorption value (Q_∞) decreased with increasing NCO/OH ratio for all the BCs. The samples have higher uptake of solvents with solubility parameter within a small range centred about 9 (cal/cm³)^1/2. Highly polar and non-polar solvents show minimum uptake. It was observed that polarity factor predominates in the solvent transport through the present block copolymer systems. The sorption behavior is also found to vary with the NCO/OH ratio employed in the preparation of polyurethane (PU) oligomers.     

挤出过程中交联聚氯乙烯的研究

应用过氧化二异丙苯 /苯乙烯 /三乙醇胺体系在挤出过程中实现了聚氯乙烯的一步交联 ,研究了三乙醇胺和过氧化二异丙苯用量对交联产物力学性能及交联凝胶率的影响。研究发现 ,三乙醇胺对PVC交联结构的形成具有明显的促进作用。在苯乙烯用量 5 phr,三乙醇胺用量为 0 33phr时 ,过氧化二异丙苯在 0 15phr取得最佳值 ;当苯乙烯用量 5 phr,过氧化二异丙苯用量 0 15 phr时 ,三乙醇胺用量在 0 4hpr取得最佳值。交联可以使聚合物材料的力学强度得到提高