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追踪山梨糖醇修饰的纳米硅:用于聚(L-乳酸)的纳米成核。

Trace sorbitol-modified nano-silica: Towards nano-nucleation for poly(L-lactic acid).

机构信息

Department of Materials Science and Engineering, Beijing Technology and Business University, Beijing 100048, China.

Department of Materials Science and Engineering, Beijing Technology and Business University, Beijing 100048, China.

出版信息

Int J Biol Macromol. 2024 Aug;274(Pt 1):133236. doi: 10.1016/j.ijbiomac.2024.133236. Epub 2024 Jun 17.

Abstract

Nucleating agents, especially those with small particle sizes, are preferred to boost the nucleation density and crystallinity of poly(lactic acid) (PLA) due to its weak crystallization capability. Organophilicly modified nanofillers hardly alter the nucleation and crystallinity of non-isothermally crystallized PLA. Herein, nano-silica adsorbed trace D-sorbitol (m-SiO) as a heterogeneous nucleating agent was melt-mixed with poly(L-lactic acid) (PLLA), and the isothermal and non-isothermal crystallization behavior, as well as crystallization kinetics, were investigated. Transmission electron microscopy (TEM) revealed that m-SiO was uniformly dispersed in the PLA matrix as 100-300 nm clusters. Differential scanning calorimetry (DSC) and polarized optical microscopy (POM) showed that the nucleation rate and density of the non-isothermally crystallized PLLA/m-SiO composites were significantly improved. Despite the fact that m-SiO does not raise the overall non-isothermal crystallization rate, the crystallization temperature and crystallinity of the PLLA/3%m-SiO composite increased from 97.2 °C and 6.8 % for neat PLLA to 108.2 °C and 48.6 % (10 °C/min cooling rate), respectively. The Avrami exponent n of isothermal crystallization remains unchanged, while the crystallization rate increases dramatically. Both isothermal and non-isothermal crystallization have increased activation energies. The heat deflection temperature increased from 59 °C of neat PLLA to 152 °C with a 50 % increase in impact strength.

摘要

成核剂,尤其是那些粒径较小的成核剂,由于其结晶能力较弱,优先用于提高聚乳酸(PLA)的成核密度和结晶度。亲有机改性纳米填料几乎不会改变非等温结晶 PLA 的成核和结晶度。在此,吸附痕量 D-山梨醇的纳米二氧化硅(m-SiO)作为异相成核剂与聚 L-乳酸(PLLA)熔融共混,研究了等温结晶和非等温结晶行为及结晶动力学。透射电子显微镜(TEM)显示,m-SiO 在 PLA 基体中均匀分散,形成 100-300nm 的团聚体。差示扫描量热法(DSC)和偏光显微镜(POM)表明,非等温结晶 PLLA/m-SiO 复合材料的成核速率和密度显著提高。尽管 m-SiO 并未提高整体非等温结晶速率,但 PLLA/3%m-SiO 复合材料的结晶温度和结晶度从纯 PLLA 的 97.2°C 和 6.8%分别提高到 108.2°C 和 48.6%(10°C/min 冷却速率)。等温结晶的 Avrami 指数 n 保持不变,而结晶速率显著增加。等温结晶和非等温结晶的活化能均有所增加。热变形温度从纯 PLLA 的 59°C 提高到 152°C,冲击强度提高了 50%。

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