Exploring the thermomechanical properties of peroxide/co-agent assisted thermoplastic vulcanizates through temperature scanning stress relaxation measurements

Temperature scanning stress relaxation (TSSR) measurement of peroxide vulcanized polymer blends of polypropylene (PP) and ultrahigh molecular-EPDM (UHM-EPDM) rubber has been performed to study the thermomechanical behavior of thermoplastic vulcanizates (TPVs). Co-agents play crucial roles in the enhancement of properties of TPVs. Different types of co-agents (Triallyl cyanurate-TAC; N, N-m-phenylene-dimaleimide-HVA2; zinc dimethacrylate-ZDMA; and in-situ formed zinc dimethacrylate-ZMA) have been explored in this work. TSSR study shows that higher T50 and T90 values have been achieved in ZMA co-agent assisted-TPV. Higher TSSR-index (RI) value was also found for the same co-agent ZMA, indicating higher elastic behavior. TSSR result supports the mechanical and rheological properties, and it is found that the ZMA and ZDMA show higher mechanical strength. Cross-linked-density calculated by modified Flory–Rehner equation and the cross-link-density as obtained from TSSR method have been compared and the trend was found to be the same. Stress relaxation study shows the slow relaxation-phenomena of the ZMA-TPV with slowest relaxation-time (θr) than the other TPVs, which correlates with superior material strength. Thermogravimetric analysis proves that there is a difference in degradation temperature of the blends at approximately 5–10°C. Ultrahigh molecular weight-EPDM/PP based TPVs reveal superior thermomechanical and physico-mechanical properties with ZMA and ZDMA co-agent over TAC and HVA2. These ultrahigh molecular weight-EPDM based TPVs can be used in automotive seals/strips, hoses, bellows, and 2 K-molds for automotive applications

Devulcanization of ethylene-propylene-diene monomer rubber waste. Effect of diphenyl disulfide derivate as devulcanizing agent on vulcanization, and devulcanization process

A systematic study was performed to understand the effects of the devulcanizing agent dibenzamido diphenyl disulfide (DBD) on the vulcanization and devulcanization process of a sulfur-cured ethylene-propylene-diene monomer (EPDM) rubber. The influence of DBD on vulcanization was investigated by mixing DBD with virgin rubber and curative system. The devulcanization of rubber waste was achieved with varying amounts of DBD ranging from 0.4 to 13.8 wt% and temperatures from 150 to 200°C. The quality of vulcanizates and devulcanizates was evaluated by rheometer tests, temperature scanning stress relaxation measurements, and analysis of mechanical properties. During vulcanization, DBD acts as an accelerator in the presence of sulfur. When accelerators are added, the scorch time increases, and the cure rate decreases. Thus, DBD acts as a retarder. In the presence of activators, DBD leads to a significant reduction of crosslink density. This results in composites with high elongation at break and poor compression set values. The efficiency of the devulcanization of rubber waste depends strongly on DBD concentration and temperature. The monosulfidic crosslinks are cleaved by low concentrations of DBD, while polysulfidic crosslinks require higher concentrations. These results show that DBD is effective as a devulcanizing agent and degrades the network below 200°C

Influence of Filler from a Renewable Resource and Silane Coupling Agent on the Properties of Epoxidized Natural Rubber Vulcanizates

Rice husk ash (RHA) was used as a reinforcing filler in epoxidized natural rubber (ENR) with various loading levels (0, 10, 20, and 30 phr), and silica filled ENR was also studied for comparison. The effects of RHA content on cure characteristics, mechanical properties, dynamic mechanical properties, and thermoelastic behavior of the filled ENR composites were investigated. It was found that the incorporation of RHA significantly affected the cure characteristics and mechanical properties. That is, the incorporation of RHA caused faster curing reactions and increased Young’s modulus and tensile strength relative to the unfilled compound. This might be attributed to the metal oxide impurities in RHA that enhance the crosslinking reactions, thus increasing the crosslink density. Further improvements in the curing behavior and the mechanical properties of the filled composites were achieved by in situ silanization with bis(triethoxysilylpropyl) tetrasulfide (Si69). It was found that the rubber-filler interactions reinforced the composites. This was indicated by the decreased damping characteristic (tan ⁡δ) and the other changes in the mechanical properties. Furthermore, the ENR composites with Si69 had improved filler dispersion. Temperature scanning stress relaxation (TSSR) results suggest that the metal oxide impurities in RHA promote degradation of the polymer network at elevated temperatures

Temperature scanning stress relaxation of an autonomous self-healing elastomer containing non-covalent reversible network junctions

In this work, we report about the mechanical relaxation characteristics of an intrinsically self-healable imidazole modified commercial rubber. This kind of self-healing rubber was prepared by melt mixing of 1-butyl imidazole with bromo-butyl rubber (bromine modified isoprene-isobutylene copolymer, BIIR). By this melt mixing process, the reactive allylic bromine of bromo-butyl rubber was converted into imidazole bromide salt. The resulting development of an ionic character to the polymer backbone leads to an ionic association of the groups which ultimately results to the formation of a network structure of the rubber chains. The modified BIIR thus behaves like a robust crosslinked rubber and shows unusual self-healing properties. The non-covalent reversible network has been studied in detail with respect to stress relaxation experiments, scanning electron microscopic and X-ray scattering.publishedVersionPeer reviewe

Temperature Scanning Stress Relaxation of an Autonomous Self-Healing Elastomer Containing Non-Covalent Reversible Network Junctions

In this work, we report about the mechanical relaxation characteristics of an intrinsically self-healable imidazole modified commercial rubber. This kind of self-healing rubber was prepared by melt mixing of 1-butyl imidazole with bromo-butyl rubber (bromine modified isoprene-isobutylene copolymer, BIIR). By this melt mixing process, the reactive allylic bromine of bromo-butyl rubber was converted into imidazole bromide salt. The resulting development of an ionic character to the polymer backbone leads to an ionic association of the groups which ultimately results to the formation of a network structure of the rubber chains. The modified BIIR thus behaves like a robust crosslinked rubber and shows unusual self-healing properties. The non-covalent reversible network has been studied in detail with respect to stress relaxation experiments, scanning electron microscopic and X-ray scattering