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Creators/Authors contains: "Miyoshi, Toshikazu"

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  1. Free, publicly-accessible full text available March 15, 2023
  2. Free, publicly-accessible full text available February 15, 2023
  3. Abstract

    The evergrowing plastic production and the caused concerns of plastic waste accumulation have stimulated the need for waste plastic chemical recycling/valorization. Current methods suffer from harsh reaction conditions and long reaction time. Herein we demonstrate a non-thermal plasma-assisted method for rapid hydrogenolysis of polystyrene (PS) at ambient temperature and atmospheric pressure, generating high yield (>40 wt%) of C1–C3hydrocarbons and ethylene being the dominant gas product (Selectivity of ethylene,SC2H4 > 70%) within ~10 min. The fast reaction kinetics is attributed to highly active hydrogen plasma, which can effectively break bonds in polymer and initiate hydrogenolysis under mild condition. Efficient hydrogenolysis of post-consumer PS materials using this method is also demonstrated, suggesting a promising approach for fast retrieval of small molecular hydrocarbon modules from plastic materials as well as a good capability to process waste plastics in complicated conditions.

  4. Stereoregularity significantly influences the crystallization, mechanical, and thermal properties of polymers. In this work, we investigate crystallization behaviors and molecular dynamics of atactic (a)-, isotactic (i)-, and syndiotactic (s)-hydrogenated poly(norbornene) (hPNB)s by using small-angle X-ray scattering and solid-state (ss) NMR. a-hPNB exhibits a much higher crystallinity (Φc) (82%) and long period (L) (80 nm) than i- and s-hPNB (50–55% and 17–21 nm). Moreover, in the s-hPNB crystalline region, chain dynamics is not thermally activated up to the melting temperature (Tm), while in the crystalline regions of i- and a-hPNB, small amplitude motions occur in a slow dynamic regime of 10–2–102 s. The molecular dynamics follows Arrhenius behavior in a-hPNB up to the crystal–crystal transition temperature (Tcc), while these dynamics are surprisingly saturated in i-hPNB under these conditions. Temperature dependence of the molecular dynamics leads to different crystal–crystal transitions between i- and a-hPNBs: i-hPNB changes the trans conformation to the gauche one due to the localized bond rotations where chain dynamics is restricted, whereas a-hPNB keeps a nearly trans conformation and conducts fast chain dynamics due to the amplified C–C bond rotations in the high-temperature phase. Such fast chain dynamics leads to unique crystallization behaviors of hPNB, specifically in the atacticmore »configuration due to configurational disorder coupled with conformational flexibility.« less
  5. Poly(vinylidene fluoride) (PVDF) and its random copolymers exhibit the most distinctive ferroelectric properties; however, their spontaneous polarization (60–105 mC m −2 ) is still inferior to those (>200 mC m −2 ) of the ceramic counterparts. In this work, we report an unprecedented spontaneous polarization ( P s = 140 mC m −2 ) for a highly poled biaxially oriented PVDF (BOPVDF) film, which contains a pure β crystalline phase. Given the crystallinity of ∼0.52, the P s for the β phase ( P s,β ) is calculated to be 279 mC m −2 , if a simple two-phase model of semicrystalline polymers is assumed. This high P s,β is invalid, because the theoretical limit of P s,β is 185 mC m −2 , as calculated by density functional theory. To explain such a high P s for the poled BOPVDF, a third component in the amorphous phase must participate in the ferroelectric switching to contribute to the P s . Namely, an oriented amorphous fraction (OAF) links the lamellar crystal and the mobile amorphous fraction. From the hysteresis loop study, the OAF content was determined to be ∼0.28, more than 50% of the amorphous phase. Because of the highmore »polarizability of the OAFs, the dielectric constant of the poled BOPVDF reached nearly twice the value of conventional PVDF. The fundamental knowledge obtained from this study will provide a solid foundation for the future development of PVDF-based high performance electroactive polymers for wearable electronics and soft robotic applications.« less
  6. In response to the stringent requirements for future DC-link capacitors in electric vehicles (EVs), it is desirable to develop dielectric polymer films with high-temperature tolerance (at least 105 °C) and low loss (dissipation factor, tan δ < 0.003). Although the biaxially oriented poly(ethylene terephthalate) (BOPET) film has an alleged temperature rating of 120 °C, its dielectric performance in terms of breakdown strength and lifetime cannot satisfy the stringent requirements for power electronics in EVs. In this work, we carried out a structure–electrical insulation property relationship study to understand the working mechanism for various PET films, including a commercial BOPET film, an amorphous PET (AmPET) film, and two annealed PET films (AnPET, i.e., cold-crystallized from AmPET). Structural analyses revealed a uniform edge-on crystalline orientation in BOPET with the a* axis in the film normal direction. Meanwhile, a high content of the rigid amorphous fraction (RAF) was identified for BOPET, which resulted from biaxial stretching during processing. On the contrary, AnPET films had a random crystal orientation with lower RAF contents. From dielectric breakdown and lifetime studies, the high-crystallinity AnPET film exhibited better electrical insulation than BOPET, and AmPET had the worst electrical insulation. Electrical conductivity results revealed that the high RAF contentmore »in BOPET led to reasonably high breakdown strength and long lifetime only at low temperatures (<100 °C). Meanwhile, PET crystals were more insulating than the amorphous phase, whether mobile, rigid, or glassy. In particular, the flat-on lamellae in the AnPET film were more effective than the edge-on lamellae in BOPET in blocking the conduction of charge carriers (electrons and impurity ions). This understanding will help us design high-temperature semicrystalline polymer films for DC-link capacitors in EVs.« less