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.     

Hydrophobic Cross-Linked Poly(dimethylsiloxane)-Based Sorbents for Oil Spill Applications

With the increase of industrialization and urbanization, humankind faces massive oil-based pollution due to tanker accidents, human error, and natural disasters. For this, hydrophobic sorbents are fabricated and their applications for the removal of oil from polluted water sources are investigated. These hydrophobic sorbents are prepared by the condensation reaction of poly(dimethylsiloxane) and tris[3-(trimethoxysilyl)propyl]isocyanurate cross-linker via bulk polymerization. The obtained sorbents exhibit high oil sorption capacity, fast absorption–desorption kinetics, and great reusability. Moreover, they can selectively absorb oil from the water surface, thus making them practical for water clean-up applications.     

急性炎性疾病患者乳酸林格氏液液体动力学

目的:探索炎性疾病患者的乳酸林格氏液（Ringer's lactate,RL）液体动力学特征以及炎性生物标记物是否可以作为协变量影响RL分布和排泄。方法:本研究为前瞻性队列研究。选择40例美国麻醉医师分级（ASA）I-II级，腹腔镜下择期胆囊切除术（胆囊炎组，n=20）或者腹腔镜下急诊阑尾切除术（阑尾炎组，n=20）。所有患者麻醉诱导前开始输注RL，按15 mL/kg，35 min内输毕。采用酶联免疫（enzyme-linked immunosorbent assay,ELISA）方法测定血浆炎症（TNF-α,IL-10和CRP）或者内皮损伤生物标记物（syndecan-1,SDC-1）；利用血红蛋白（Hb）稀释-时间曲线和尿量，使用Phoenix软件，采用非线性混合效应模型分析计算RL液体动力学参数和协变量的影响。结果:与胆囊炎组相比，阑尾炎组RL从组织间隙到血浆的转运速率常数（k21）显著降低（14×10-3min-1 versus 35×10-3min-1;P=0.012）。阑尾炎组C反应蛋白（CRP）升高［中位数38.1(1.8-143.6) μg/mL versus 1.3(0.1-159.0) μg/mL;P<0.001］；与清醒状态相比，麻醉期间（输液开始后30～45 min），液体从中央室中到外周室的转运速率常数（k12）显著增加（57×10-3min-1 versus 32×10-3min-1；P<0.01）。清除速率常数（k10）降低90%（0.6×10-3min-1 versus 5.3×10-3min-1;P<0.001）。无论在清醒状态还是麻醉状态下低血压均能降低液体清除；炎症或者内膜损伤的生物标记物不能作为显著影响RL液体动力学参数的协变量。结论:阑尾炎或者胆囊炎患者术前输入液体后“炎症反应的生物标记物”不是RL的液体动力学的协变量，但是两组患者中，全身麻醉期间输入液体的清除率下降。     

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     

胡萝卜丁中维生素C在热风辅助射频干燥过程中降解的动力学模型

目的研究热风辅助射频(hot air-assisted radio frequency,HA-RF)干燥过程中维生素C随温度变化的降解动力学模型。方法在6.5 cm极板间距和60℃热风系统条件下进行HA-RF干燥,重点研究胡萝卜丁中维生素C在干燥过程中的降解动力学,包括脱氢抗坏血酸(dehydroascorbic acid,DHAA)和抗坏血酸(ascorbic acid,AA)。总维生素C含量采用2,4-硝基苯肼分光光度法测定,AA采用2,6-二氯吲哚酚滴定法测定。结果HA-RF干燥过程中维生素C的降解规律符合一级可逆模型,其降解活化能为40.54 kJ/mol。DHAA活化能为35.83 kJ/mol,表明DHAA的稳定性低于AA。结论本研究使用的干燥温度为62.5~77.5℃,较高的干燥温度下维生素C降解速率较高,较低处理温度下的降解过程具有更好的模型适应度(R2>0.98)。     

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.     

Rate equation theory for the hydrogenation kinetics of Mg-based materials

A uniform solid product layer normally assumed in the shrinking-core model cannot predict the kinetic transition behavior of the H₂ adsorption reactions. In this study, the concept of a uniform solid product layer has been replaced by that of the inward growth of solid products on the solid surface. A rate equation is established to calculate the inward growth of the solid product and was implemented into the shrinking-core model to calculate the H₂ adsorption kinetics for various shapes of Mg-based materials. The prediction accuracy of the developed model is verified from the detailed experimental data. To account for the external gas diffusion around the particle and the intraparticle gas diffusion, an analytical equation is derived using the Thiele modulus method. This model can be used to analyze various kinetic aspects and to analyze the effect of change in the particle microstructure on intraparticle diffusion.