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聚乳酸/酸处理纤维素纳米晶体基生物纳米复合材料的热降解动力学。

Thermal degradation kinetics of polylactic acid/acid fabricated cellulose nanocrystal based bionanocomposites.

机构信息

Department of Chemical Engineering, Indian Institute of Technology Guwahati, Assam-781039, India.

出版信息

Int J Biol Macromol. 2017 Nov;104(Pt A):827-836. doi: 10.1016/j.ijbiomac.2017.06.039. Epub 2017 Jun 23.

Abstract

Cellulose nanocrystals (CNC) are fabricated from filter paper (as cellulosic source) by acid hydrolysis using different acids such as sulphuric (HSO), phosphoric (HPO), hydrochloric (HCl) and nitric (HNO) acid. The resulting acid derived CNC are melt mixed with Polylactic acid (PLA) using extruder at 180°C. Thermogravimetric (TGA) result shows that increase in 10% and 50% weight loss (T, T) temperature for PLA-CNC film fabricated with HNO, HPO and HCl derived CNC have improved thermal stability in comparison to HSO-CNC. Nonisothermal kinetic studies are carried out with modified-Coats-Redfern (C-R), Ozawa-Flynn-Wall (OFW) and Kissinger method to predict the kinetic and thermodynamic parameters. Subsequently prediction of these parameter leads to the proposal of thermal induced degradation mechanism of nanocomposites using Criado method. The distribution of E calculated from OFW model are (PLA-HPO-CNC: 125-139 kJmol), (PLA-HNO-CNC: 126-145 kJmol), (PLA-HSO-CNC: 102-123 kJmol) and (PLA-HCl-CNC: 140-182 kJmol). This difference among E for the decomposition of PLA-CNC bionanocomposite is probably due to various acids used in this study. The E calculated by these two methods are found in consonance with that observed from Kissinger method. Further, hyphenated TG-Fourier transform infrared spectroscopy (FTIR) result shows that gaseous products such as CO, CO, lactide, aldehydes and other compounds are given off during the thermal degradation of PLA-CNC nanocomposite.

摘要

纤维素纳米晶体(CNC)是由滤纸(作为纤维素源)通过酸水解用不同的酸如硫酸(HSO)、磷酸(HPO)、盐酸(HCl)和硝酸(HNO)制备的。所得的酸衍生的 CNC 与聚乳酸(PLA)在 180°C 下使用挤出机熔融共混。热重(TGA)结果表明,与 HSO-CNC 相比,用 HNO、HPO 和 HCl 衍生的 CNC 制备的 PLA-CNC 薄膜的 10%和 50%重量损失(T,T)温度提高,热稳定性得到改善。采用修正的 Coats-Redfern(C-R)、Ozawa-Flynn-Wall(OFW)和 Kissinger 法进行非等温热动力学研究,以预测动力学和热力学参数。随后,根据 Criado 方法,通过预测这些参数,提出了纳米复合材料热诱导降解的机制。由 OFW 模型计算得到的 E 的分布为(PLA-HPO-CNC:125-139 kJmol)、(PLA-HNO-CNC:126-145 kJmol)、(PLA-HSO-CNC:102-123 kJmol)和(PLA-HCl-CNC:140-182 kJmol)。PLA-CNC 生物纳米复合材料分解中 E 的这种差异可能是由于本研究中使用的各种酸。由这两种方法计算得到的 E 与 Kissinger 法观察到的一致。此外,联用 TG-傅里叶变换红外光谱(FTIR)结果表明,在 PLA-CNC 纳米复合材料的热降解过程中会释放出 CO、CO、丙交酯、醛等气态产物。

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