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Temperature-Dependent Reinforcement of Hydrophilic Rubber Using Ice Crystals
This is the first study on the impact of ice crystals on glass transition and mechanical behavior of soft cross-linked elastomers. A hydrophilic elastomer such as epichlorohydrin-ethylene oxide-allyl glycidyl ether can absorb about ∼40 wt % of water. The water-swollen cross-linked network exhibits elastic properties with more than 1500% stretchability at room temperature. Coincidently, the phase transition of water into solid ice crystals inside of the composites allows the reinforcement of the soft elastomer mechanically at lower temperatures. Young's modulus of the composites measured at -20 °C remarkably increased from 1.45 to 3.14 MPa, whereas at +20 °C, the effect was opposite and the Young's modulus decreased from 0.6 to 0.03 MPa after 20 days of water treatment. It was found that a part of the absorbed water, ∼74% of the total absorbed water, is freezable and occupies nearly 26 vol % of the composites. Simultaneously, these solid ice crystals are found to be acting as a reinforcing filler at lower temperatures. The size of these ice crystals is distributed in a relatively narrow range of 400-600 nm. The storage modulus (E′) of the ice crystal-filled composites increased from 3 to 13 MPa at -20 °C. The glass transition temperature (-37 °C) of the soft cross-linked elastomer was not altered by the absorption of water. However, a special transition (melting of ice) occurred at temperatures close to 0 °C as observed in the dynamic mechanical analysis of the water-swollen elastomers. The direct polymer/filler (ice crystals) interaction was demonstrated by strain sweep experiments and investigated using Fourier transform infrared spectroscopy. This type of cross-linked rubber could be integrated into a smart rubber application such as in adaptable mechanics, where the stiffness of the rubber can be altered as a function of temperature without affecting the mechanical stretchability either below or above 0 °C (above the glass temperature region) of the rubber.
Poly(acrylonitrile-co-butadiene) as polymeric crosslinking accelerator for sulphur network formation
The major controlling factors that determine the various mechanical properties of an elastomer system are type of chemical crosslinking and crosslink density of the polymer network. In this study, a catalytic amount of acrylonitrile butadiene copolymer (NBR) was used as a co-accelerator for the curing of polybutadiene (BR) elastomer. After the addition of this copolymer along with other conventional sulphur ingredients in polybutadiene compounds, a clear and distinct effect on the curing and other physical characteristics was noticed. The crosslinking density of BR was increased, as evidenced by rheometric properties, solid-state NMR and swelling studies. The vulcanization kinetics study revealed a substantial lowering of the activation energy of the sulphur crosslinking process when acrylonitrile butadiene copolymer was used in the formulation. The compounds were also prepared in the presence of carbon black and silica, and it was found that in the carbon black filled system the catalytic effect of the NBR was eminent. The effect was not only reflected in the mechanical performance but also the low-temperature crystallization behavior of BR systems was altered. © 2020 The AuthorsMaterials science; Materials chemistry; Crosslinking accelerator; Sulphur network; Solid state NMR; Curing kinetics; Activation energy; Acrylonitrile butadiene; Polybutadiene; Low-temperature; Crystallization. © 2020 The Authors