Influence of α′‐/α‐crystal polymorphism on properties of poly(l‐lactic acid)

Poly(l ‐lactic acid) (PLLA) is a biodegradable and biocompatible thermoplastic polyester produced from renewable sources, widely used for biomedical devices, in food packaging and in agriculture. It is a semicrystalline polymer, and as such its properties are strongly affected by the developed semicrystalline morphology. As a function of the crystallization temperature, PLLA can form different crystal modifications, namely α′‐crystals below about 120 °C and α‐crystals at higher temperatures. The α′ modification is therefore of special importance as it may be the preferred polymorph developing at processing‐relevant conditions. It is a metastable modification which typically transforms into the more stable α‐crystals on annealing at elevated temperature. The structure, kinetics of formation and thermodynamics of α′‐ and α‐crystals of PLLA are reviewed in this contribution, together with the effect of α′‐/α‐crystal polymorphism on the properties of PLLA. © 2018 Society of Chemical Industry     

高分子材料导热性能影响因素研究进展

介绍了高分子材料导热性能影响因素研究进展，重点阐释了聚合物基体的结构特性（链结构、分子间相互作用、取向、结晶度等）、导热填料（种类、含量、形态、尺寸等）以及制备方法等对高分子材料导热性能的影响。     

Crystallization,structure, and enhanced mechanical property of ethylene-octene elastomer crosslinked with dicumyl peroxide

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.     

Blocked crystallization in capped ultrathin polymer films studied by molecular simulations

The crystallization of capped ultrathin polymer films is closely dependent on film thickness and interfacial interaction. Using dynamic Monte Carlo simulations, the crystallization behaviors of polymer films confined between two substrates were investigated. The crystallization rate of confined polymers is reduced with high interfacial interactions. Above a critical strength of interfacial interaction, polymer crystallization in the thin film is inhibited within the simulation time scales. An increase in film thickness leads to a rise in critical interfacial interaction. In thicker films, the chains have more space to change conformation to form crystal stems. In addition, there are fewer absorbed segments in confined chains for the thicker films, and thus the chains have stronger ability to adjust their conformation. Therefore an increase in film thickness can cause a reduction in the entropic barrier required for the formation of crystals and thus an increase in the critical interfacial interaction. © 2018 Society of Chemical Industry     

The formation of fibrous structure of polyamide 6 induced by the three-step forming process and its prominent reinforcement in nitrile rubber

Nitrile rubber (NBR) blends with excellent performance have always been a hot research topic in petroleum field. Due to the excellent performance and compatibility of polyamide 6 (PA6), it provides an opportunity for the preparation of high-performance NBR/PA6 blends. In this article, NBR/PA6 blends were prepared by the three-step molding process. Experimentally, it was found that PA6 has a prominent reinforcement effect in NBR matrix. The variation of this mechanical property was investigated from different aspects of the crystal structure, crystallinities, phase morphology, and so on. It can be cleared that the formation of fibrous structure of PA6 phase is the main factor for reinforcement of the polymer blends. Meanwhile, the formation mechanism of the special phase structure induced by the three-step process is deeply expounded and its structural evolution schematic is established. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47472.     

烧结时间对含铅玻璃制备微晶玻璃析晶及性能的影响

以铅玻璃与粉煤灰为原料，通过协同熔炼制备了微晶玻璃。通过XRD和SEM等手段研究了不同烧结时间下微晶玻璃的物相组成及显微结构，测定了微晶玻璃的密度、吸水率、维氏硬度和化学抗性。结果表明: 延长烧结时间对含铅玻璃加入量为40%(FG40)、50%(FG50)样品的晶相类型和晶化程度有影响，而对含铅玻璃加入量为60%(FG60)、70%(FG70)和80%(FG80)样品的影响较小。随着烧结时间延长，样品晶化程度提高，晶体长大，玻璃相减少。适宜的含铅玻璃加入量为50%~70%，对应的FG50、FG60、FG70样品最佳烧结时间分别为4 h、3 h、3 h。     

Impact of high-intensity ultrasound on physical properties and degree of oxidation of lipase modified menhaden oil with caprylic acid and/or stearic acid

The purpose of this research was to determine the effect of high-intensity ultrasound (HIU) on physical properties, degree of oxidation, and oxidative stability of structured lipids (SLs). Caprylic acid (C) and stearic acid (S) were incorporated into menhaden oil using Lipozyme® 435 lipase to obtain five samples: (1) LC 20 (menhaden oil with 20% of C), (2) LC 30 (menhaden oil with 30% C), (3) LS 20 (menhaden oil with 20% S), (4) LS 30 (menhaden oil with 30% S), and (5) Blend C (menhaden oil with 16.24% C and 13.04% S). Samples were crystallized for 90 min at the following temperatures: (1) LC 20 at 15.5°C, (2) LC 30 at 17.5°C, (3) LS 20 at 24°C, (4) LS 30 at 30°C, and (5) Blend C at 18.0°C, and HIU was applied at the onset of crystallization. Physical properties, degree of oxidation, and oxidative stability were evaluated in sonicated and nonsonicated samples. All SLs had statistically higher G′ after sonication. Sonicated LS 30, LC 30, and Blend C had a higher melting enthalpy than the nonsonicated ones, while enthalpy values in sonicated LS 20 and LC 20 samples were not statistically different than the nonsonicated ones. No significant difference between sonicated and nonsonicated samples was observed in peroxide values (1.2 ± 0.1 meq/kg, p > 0.05) and in the oxidative stability index (6.3 ± 0.2 h, p > 0.05). These results showed that HIU was effective at changing physical properties without affecting the oxidation of the samples.     

Effect of comb-type copolymer on crystallization of paraffin from waxy oils and methyl ethyl ketone (MEK) -toluene dewaxing

In this research, maleic anhydride-α-octadecene copolymer and its derivative with phenylethylamine was synthesized and its effect on the crystallization of paraffins was investigated. This derivative, when added into second cut of vacuum gas oil and forth cut of vacuum gas oil, increases the size and improves aggregation of paraffin crystals observed by polarizing light microscopy, increases onset temperature and enthalpy of paraffin crystallization determined by differential scanning calorimetry, improves the dewaxing efficiency with dosage of 100?ppm explored by MEK-toluene dewaxing.     

The overall crystallization behavior of polyethylene/wax blends as phase change materials for thermal energy storage: A mini review

This review paper deals with the overall crystallization behavior of polyethylene/wax blends as phase change materials (PCMs) for thermal energy storage with the determination of their thermal properties. The addition of molten wax to the polyethylenes decreases the crystallization and melting temperatures of the blends. However, incorporating fillers to the polyethylene/wax blends can either decrease or increase the crystallization and melting temperatures of the composites depending on the filler type. The normalized enthalpy values of linear low-density polyethylene showed no significant change when increasing the wax content. On the contrary, the normalized enthalpy values of the wax in the blends were lesser than that of pure wax and increased with increasing wax content. Since the wax in the blend had a lower crystallinity compared to pure wax, this influences its effectiveness as a PCM for thermal energy storage. The effect of different polyethylenes on the wax morphology gave rise to enhance phase separation when wax was blended to high-density polyethylene as compared to the other polyethylenes. On the contrary, the effect of various waxes on the morphology of polyethylene resulted in different morphologies due to the molecular weight of the wax used and the structure of the polyethylene chain. The addition of fillers to the polyethylene (PE)/wax samples resulted in enhanced phase separation. The overall isothermal crystallization rate and the equilibrium melting temperature of PEs in the PEs/wax blends were depressed by wax addition due to the wax dilution effect.     

Synergistic effects of modified TiO2/multifunctionalized graphene oxide nanosheets as functional hybrid nanofiller in enhancing the interface compatibility of PLA/starch nanocomposites

The aim of this study is to investigate the synergistic effects of modified TiO₂/multifunctionalized graphene oxide nanosheets at different ratios on the interface compatibility between starch and poly(lactic acid) (PLA). To this end, silanylated nano-TiO₂ (MTiO₂, 1 and 2%) and alkylated maleic anhydride grafted graphene oxide (f-GO, 0.1, 0.2, and 0.4%) at different combinations are blended with the PLA-starch composites using solution blending technique. Then, the synergistic effects of MTiO₂ and f-GO on PLA/starch matrix are investigated in terms of the morphology, crystallinity, structural characterization, thermal stability, dynamic mechanical, and antiaging properties, and the related mechanisms. The Raman and Fourier transform infrared spectroscopy spectra verify the successful synthesis of the two modified nanofillers (f-GO and MTiO₂) and the formation of strong hydrogen bond within the PLA-starch nanocomposites. Due to the strong interfacial interaction and the synergistic effect from the combination of 1% MTiO₂ and 0.2% f-GO, obvious improvement was observed in PLA-starch versus other nanocomposites in terms of morphology, thermal stability, surface hydrophobicity, storage modulus, ultraviolet-shielding capacity, and aging-resistance. Furthermore, differential scanning calorimeter (DSC), isothermal crystallization kinetic, and X-ray diffraction analysis demonstrate that f-GO and the M-TiO₂ significantly synergize in enhancing the crystallization rate and crystallinity of PLA/starch matrix. These results provide novel insights for constructing high-performance nanocomposites and facilitate their applications in food packaging.