Crosslinking of polyolefin elastomer (POE, ENGAGE™ 8480) with Dicumyl Peroxide (DCP) can have effects on its crystallization dynamics, crystal structure, and properties. The POE crosslinked uniformly has significantly lower crystalline ability than the one with only amorphous phase crosslinked, which, in turn, has weaker crystalline ability than neat POE. The crystallinity and melting point depend on how the POE is crosslinked. The neat POE and POE crosslinked in amorphous phase only, are investigated with DSC and in‐situ tensile/synchrotron radiation (WAXD/SAXS). In situ tensile/synchrotron X‐ray during a uniaxial stretching process indicates that severe crystal fragmentation is observed at a strain around 45%, and with further increase in strain. The stress in the crosslinked POE is significantly larger than neat POE. For both samples, crystal orientation increases sharply within the strain range up to 88% where orientation‐induced new crystals aligned in stretching direction are observed. The long period increases more in stretching direction for the crosslinked POE, consistent with larger stress in this sample, and the stress difference is more pronounced at large strains (27.3 vs. 10.9 MPa at a strain 435%). Permanent set of the crosslinked POE is smaller, consistent with less oriented crystals observed after the test for permanent set.
The difference in compatibility at the molecular level can lead to a change of microphase separation structure of thermoplastic polyurethanes blend systems, which will improve their thermal and mechanical properties. In this study, TDI-polyester based TPU was blended with MDI-polyether-based TPU and MDI-polyester based TPU, with different ratios. In the blend system, the obvious reduction of the melting temperature of the high-temperature TDI-polyester based TPU component indicates its hard segments can be mutually integrated with the other component. For TDI-polyester based TPU/MDI-polyether based TPU blends, their similar hard segment ratio and similar chemical structure of the soft segment give the molecular chains of the two components better compatibility. The aggregation structure of the two kinds of chains can rearrange at the molecular level which makes the hard domains mutually integrate to form a new phase separation structure with larger phase region distance. As a result, the yield strength of this blend increased by almost 143% when the elongation at break was only reduced by 12%. In contrast, the other group of blends still partly maintain their respective micro domains, forming a weak interface and leading to a decreased of elongation at break.
A novel, effective approach to improve the cutting and chipping resistance (CCR) of carbon black (CB)filled styrene butadiene rubber (SBR) composite was reported in this study. CCR of SBR was dramatically improved more than 30% by addition of 4 phr nanodispersed clay (NC), while not decreasing the stress at 100% and the Shore A hardness of the composite. The curing characteristics, loss tangent (tan d), and the strength of filler network of the composites were further measured by a Disk Oscillating Rheometer and a rubber processing analyzer, respectively. It was found that the addition of NC led to a slightly lower crosslink density, higher tan d, and stronger filler network, which contributed to the higher CCR. Therefore, the novel layered NC is more efficient in improving CCR when compared with CB. The results are expected to promote the application of NC in rubber industry.
The dynamic crosslinking method has been widely used to prepare rubber/plastic blends with thermoplastic properties, and the rubber phase is crosslinked in these blends. Both polyolefin elastomer (POE) and ethylene-propylene-diene monomer rubber (EPDM) can be crosslinked, which is different from usual dynamic crosslinking components. In this paper, dynamic crosslinked POE/EPDM blends were prepared. For POE/EPDM blends without dynamic crosslinking, EPDM can play a nucleation role, leading to POE crystallizing at a higher temperature. After dynamic crosslinking, the crosslinking points hinder the mobility of POE chains, resulting in smaller crystals, but having too many crosslinking points suppresses POE crystallization. Synchrotron radiation studies show that phase separation occurs and phase regions form in non-crosslinked blends. After crosslinking, crosslinking points connecting EPDM and part of POE chains, enabling more POE to enter the EPDM phase and thus weakening phase separation, indicates that dynamic crosslinking improves the compatibility of POE/EPDM, also evidenced by a lower β conversion temperature and higher α conversion temperature than neat POE from dynamic mechanical analysis. Moreover, crosslinking networks hinder the crystal fragmentation during stretching and provide higher strength, resulting in 8.3% higher tensile strength of a 10 wt% EPDM blend than neat POE and almost the same elongation at break. Though excessive crosslinking points offer higher strength, they weaken the elongation at break.
Moony viscosity of ethylene-propylene-diene monomers (EPDMs) can have effect on the crystallization dynamics, structure, and properties of EPDM/polypropylene (PP)-based thermoplastic vulcanizates (TPVs). TPVs with two different Moony viscosities are prepared via a twin-screw extruder, respectively. Crosslinked EPDM with lower Moony viscosity has a higher crosslinking density and the nucleation effect of its crosslink point improves the crystallization ability of PP in TPV, leading to PP phase crystallization at higher temperatures. For TPV with an EPDM of higher Moony viscosity, it has higher crystallinity and the EPDM phase crystallized earlier. Synchrotron radiation studies show that the EPDM with low Moony viscosity has no obvious crystalline structure, and the prepared TPV has an obvious phase separation structure, while the TPV with higher Mooney viscosity of the EPDM does not exhibit obvious phase separation, indicating that the longer EPDM chains have better compatibility with PP in TPV, also evidenced by the almost disappearance of the PP glass transition peak in TPV, from the dynamic mechanical analysis. The longer EPDM chains in TPV provide more physical entanglement and better interaction with PP molecules, resulting in a stronger strain hardening process, longer elongation at break, and higher tensile stress in TPV.
Nano-silica (SiO2) has been widely used to fill rubbers (crosslinked) and usual polyolefin elastomers (POEs). SiO2 filled POE with crystalline structure can also be crosslinked. Crystallization, structure, and mechanical properties of crosslinked POE/SiO2 composites can be affected by SiO2. In this paper, crosslinked POE/SiO2 composites were obtained through two different methods: dynamic crosslinking in molten state and static crosslinking. For the non-crosslinked and static crosslinked composites, SiO2 had a more significant effect on the nucleation in non-crosslinked POE than in static crosslinked POE. For the dynamic crosslinked composite, SiO2 and crosslinking points hindered the mobility of POE chains and suppressed the POE crystallization, resulting in smaller and fewer crystals. Dynamic mechanical analysis showed that the SiO2 and POE were compatible, as evidenced by the lower tan(δ) value in SiO2-filled samples. The latter was more consistent with the higher tensile strength and elongation at break for the non-crosslinked and static crosslinked composites than for the non-filled samples. However, the dynamic crosslinked composite exhibited the worst elongation at break, resulting from the lowest number of crystals and shortened molecular chains due to the shearing that occurred during crosslinking process. The SiO2 had no observable effect on the permanent deformation of samples.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.