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An appropriate processing protocol was proposed to improve the rubber elasticity of a thermoplastic polyester elastomer (TPEE). Rheology measurements at the processing temperature and thermal measurements determined the critical temperature at which small numbers of crystals exist. It was found from dynamic mechanical analyses, wide- and small-angle X-ray measurements, and electron microscope observations that cooling from the critical temperature markedly promoted the crystallization of hard segments. Moreover, tensile tests revealed that the modulus and yield stress increased. Most importantly, compared with films obtained by cooling from high temperatures, the residual strain at a fixed stress was low—i.e., the rubber elasticity was improved owing to its well-developed crystalline structure. These effects were accelerated by a more optimized process—i.e., subsequent heating at slightly below the critical temperature. The technique is noteworthy because a TPEE with high modulus generally shows poor elasticity.

金沢大学理工研究域フロンティア工学系, Raman spectroscopy has been used to reveal the microscopic structural changes of low-density polyethylene under ultraviolet irradiation. The fraction of non-crystalline consecutive trans chains (the molecular chains in the trans conformation separate from the orthorhombic crystalline phase) drastically decreases at ∼600 h, together with a decrement in the molecular weight and an increment in the crystallinity owing to chemicrystallization. This suggests that short trans chains are prolonged to form consecutive trans chains before chemicrystallization. Moreover, gradual increases of the stretching and compression stresses are observed on the trans and amorphous chains, respectively. These conformational changes are detected by Raman spectroscopy even in the early stage of photodegradation. Chemicrystallization at ∼600 h is accompanied by structural changes, such as shortening of the interchain distance of the lamellar crystals and thinning of the amorphous layer, which induce formation of surface cracks on the macroscopic specimen., Embargo Period 24 months

We prepared model polyethylene (PE) samples that contain the controlled-amounts of the high-molecular-weight component by blending a monodispersed PE into a polydispersed PE, to elucidate the influence of the high-molecular-weight component of a polymer on its mechanical properties. The strength and strain-hardening modulus were significantly enhanced by the addition of a monodispersed PE of sufficiently high molecular weight, and the critical value of Mw was determined to be ~3.0 × 105. The improved strength and strain-hardening modulus are attributed to higher amounts of inter-cluster links that bridge adjacent lamellar cluster units because these links act as stress transmitters between these units.

Triblock copolymers, poly(L-lactide)-b-poly(2-methyl-1,3-propanediyl succinate)-b-poly(L-lactide) (PLLA-b-PMPS-b-PLLA), were synthesized as new biodegradable thermoplastic elastomers by two-step polymerization. In the first step, hydroxy-telechelic poly(2-methyl-1,3-propanediyl succinate) (PMPS) was synthesized from 2-methyl-1,3-propanediol (MP, small excess) and succinic acid (SA) using two-stage reaction of esterification and simple polycondensation processes. In the second step, plant derived L-lactide (LLA) was polymerized using the bifunctional PMPS as a macroinitiator to synthesize PLLA-b-PMPS-b-PLLA triblock copolymers. The structures of the triblock copolymers as well as the PMPS macroinitiator were characterized by NMR and GPC analysis. PMPS is an amorphous polymer with Tg at lower than −24 °C. The triblock copolymers also exhibited low Tg for the PMPS segment at lower than −20 °C as well as Tm at around 150 °C for the PLLA segment. The tensile tests of the triblock copolymers demonstrated their low modulus and high elongation. The biodegradation tests of these polymers were also performed using enzymes and seawater to reveal their biodegradability.

In situ observation of the microscopic structural changes in high-density polyethylene during hot drawing was performed by incorporating a temperature-controlled tensile machine into a Raman spectroscopy apparatus. It was found that the load sharing and molecular orientation during elongation drastically changed at 50°C. The microscopic stress of the crystalline chains decreased with increasing temperature and diminished around 50°C. Moreover, the orientation of the crystalline chains was greatly promoted above 50°C. These microscopic structural changes were caused by the thermal activation of the molecular motion within lamellar crystalline chains owing to the onset of relaxation of the crystalline phase. © 2015 Elsevier Ltd. All rights reserved., Embargo Period 24 months

The microscopic mechanism of high-density polyethylene under uniaxial drawing is investigated using in situ Raman spectroscopy. From the peak shifts of the symmetric and anti-symmetric C–C stretching modes, it is found that the load sharing on the polymer chain in the yielding region is anisotropic with stretching along the chain and compression perpendicular to the chain. The orientation functions (〈P2〉 and 〈P4〉) as well as the orientation distribution function (N(θ)) are determined from the polarized Raman spectra. The molecular orientation with cold drawing is found to proceed more effectively for lower crystallinity specimens. In the yielding region, it is also found that N(θ) has a maximum at the polar angle θ = 30–70°. This peculiar behavior in the microscopic scale is explained by the preferential collapse of spherulites and the existence of lamellar clusters as the bulky mobile units.