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使用线性和非线性等转化率方法研究玻璃纤维增强环氧树脂复合材料的热解动力学行为

Pyrolysis Kinetic Behaviour of Glass Fibre-Reinforced Epoxy Resin Composites Using Linear and Nonlinear Isoconversional Methods.

作者信息

Yousef Samy, Eimontas Justas, Striūgas Nerijus, Praspaliauskas Marius, Abdelnaby Mohammed Ali

机构信息

Department of Production Engineering, Faculty of Mechanical Engineering and Design, Kaunas University of Technology, LT-51424 Kaunas, Lithuania.

Department of Materials Science, South Ural State University, Lenin Prospect 76, 454080 Chelyabinsk, Russia.

出版信息

Polymers (Basel). 2021 May 11;13(10):1543. doi: 10.3390/polym13101543.

Abstract

Due to the increasing demand for glass fibre-reinforced epoxy resin composites (GFRC), huge amounts of GFRC waste are produced annually in different sizes and shapes, which may affect its thermal and chemical decomposition using pyrolysis technology. In this context, this research aims to study the effect of mechanical pre-treatment on the pyrolysis behaviour of GFRC and its pyrolysis kinetic. The experiments were started with the fabrication of GFRC panels using the vacuum-assisted resin transfer method followed by crushing the prepared panels using ball milling, thus preparing the milled GFRC with uniform shape and size. The elemental, proximate, and morphology properties of the panels and milled GFRC were studied. The thermal and chemical decomposition of the milled GFRC was studied using thermogravimetric coupled with Fourier-transform infrared spectroscopy (TG-FTIR) at different heating rates. Meanwhile, the volatile products were examined using TG coupled with gas chromatography-mass spectrometry (GC-MS). The TG-FTIR and TG-GC-MS experiments were performed separately. Linear (Kissinger-Akahira-Sunose (KAS), Flynn-Wall-Ozawa (FWO), and Friedman) and nonlinear (Vyazovkin and Cai) isoconversional methods were used to determine the pyrolysis kinetic of the milled GFRC based on thermogravimetry and differential thermal gravimetry (TG/DTG). In addition, the TG/DTG data of the milled GFRC were fitting using the distributed activation energy model and the independent parallel reactions kinetic model. The TG results showed that GFRC can decompose in three stages, and the main decomposition is located in the range 256-500 °C. On the other hand, aromatic benzene and a C-H bond were the major functional groups in the released volatile components in FTIR spectra, while phenol (27%), phenol,4-(1-methylethyl) (40%), and p-isopropenylphenol (34%) were the major compounds in GC-MS analysis. Whereas, the kinetic results showed that both isoconversional methods can be used to determine activation energies, which were estimated 165 KJ/mol (KAS), 193 KJ/mol (FWO), 180 KJ/mol (Friedman), 177 KJ/mol (Vyazovkin), and 174 KJ/mol (Cai).

摘要

由于对玻璃纤维增强环氧树脂复合材料(GFRC)的需求不断增加,每年都会产生大量尺寸和形状各异的GFRC废料,这可能会影响其采用热解技术进行的热分解和化学分解。在此背景下,本研究旨在研究机械预处理对GFRC热解行为及其热解动力学的影响。实验首先采用真空辅助树脂传递法制备GFRC板,然后使用球磨将制备好的板粉碎,从而制备出形状和尺寸均匀的磨碎GFRC。研究了板和磨碎GFRC的元素、近似和形态特性。使用热重联用傅里叶变换红外光谱(TG-FTIR)在不同加热速率下研究磨碎GFRC的热分解和化学分解。同时,使用热重联用气相色谱-质谱联用仪(GC-MS)检测挥发性产物。TG-FTIR和TG-GC-MS实验分别进行。基于热重分析和微商热重分析(TG/DTG),采用线性(基辛格-赤平-ose(KAS)、弗林-沃尔-小泽(FWO)和弗里德曼)和非线性(维亚佐夫金和蔡)等转化率方法来确定磨碎GFRC的热解动力学。此外,使用分布活化能模型和独立平行反应动力学模型对磨碎GFRC的TG/DTG数据进行拟合。TG结果表明,GFRC可在三个阶段分解,主要分解发生在256-500°C范围内。另一方面,芳香苯和C-H键是FTIR光谱中释放的挥发性成分中的主要官能团,而苯酚(27%)、4-(1-甲基乙基)苯酚(40%)和对异丙烯基苯酚(34%)是GC-MS分析中的主要化合物。而动力学结果表明,两种等转化率方法均可用于确定活化能,其估计值分别为165 KJ/mol(KAS)、193 KJ/mol(FWO)、180 KJ/mol(弗里德曼)、177 KJ/mol(维亚佐夫金)和174 KJ/mol(蔡)。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bbb9/8151623/60341732dd3e/polymers-13-01543-g001.jpg

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