不同碳黑含量<strong>PMMA</strong>的热降解行为和动力学分析

doi:10.11901/1005.3093.2021.457

材料研究学报

2022, Vol. 36

Issue (11): 837-844 DOI: 10.11901/1005.3093.2021.457

研究论文

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不同碳黑含量PMMA的热降解行为和动力学分析

龙庆, 王传洋(

)

苏州大学机电工程学院苏州 215021

Thermal Degradation Behavior and Kinetics Analysis of PMMA with Different Carbon Black Contents

LONG Qing, WANG Chuanyang(

)

School of Mechanical and Electric Engineering, Soochow University, Suzhou 215021, China

引用本文:

龙庆, 王传洋. 不同碳黑含量PMMA的热降解行为和动力学分析[J]. 材料研究学报, 2022, 36(11): 837-844.
Qing LONG, Chuanyang WANG. Thermal Degradation Behavior and Kinetics Analysis of PMMA with Different Carbon Black Contents[J]. Chinese Journal of Materials Research, 2022, 36(11): 837-844.

全文: PDF(3903 KB) HTML

摘要:

用熔融共混法制备不同碳黑(CB)含量的聚甲基丙烯酸甲酯(PMMA)材料，根据固态反应动力学研究了这种材料的热降解行为。在不同升温速率的非等温热重分析(TGA)实验的基础上用Friedman、FWO、KAS和Freeman-Carroll四种方法构建了不同碳黑含量PMMA的热降解动力学模型，并将TGA实验数据与求解模型对比验证了模型的可靠性。结果表明：添加碳黑使PMMA的热分解温度和活化能提高，碳黑含量(质量分数)为0.1%时达到峰值；随着碳黑含量的提高PMMA的活化能先增大后减小，其最大提高量为17.76 kJ·mol^-1，表明加入碳黑能在一定程度上提高PMMA的热稳定性。

关键词 ：有机高分子材料, 热降解动力学模型, 聚甲基丙烯酸甲酯, 碳黑, 活化能

Abstract：

Polymethyl methacrylate (PMMA) with different carbon black (CB) contents were prepared by melt blending. Based on the solid-state reaction kinetics, the thermal degradation behavior of PMMA with different CB contents was explored. Through non-isothermal thermogravimetric analysis (TGA) experiments under the conditions of different heating rates, the thermal degradation kinetic models of PMMA with different CB contents were built by four methods, including Friedman, FWO, KAS and Freeman-Carroll. The accuracy of models was verified by comparing with TGA experiments. The results show that PMMA with CB has higher thermal decomposition temperature and activation energy compared with pure PMMA. The PMMA with 0.1% CB presents the highest thermal stability. The activation energy of PMMA first rises and then falls down with increasing CB content, and the maximum increment is 17.76 kJ·mol^-1, which proves that adding CB improves the thermal stability of PMMA to a certain extent.

Key words： organic polymer materials thermal degradation kinetic model polymethyl methacrylate carbon black activation energy

收稿日期: 2021-08-13

ZTFLH:

TQ325.7

基金资助:国家自然科学基金(52075354)

作者简介: 龙庆，女，1997年生，硕士生

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https://www.cjmr.org/CN/10.11901/1005.3093.2021.457 或 https://www.cjmr.org/CN/Y2022/V36/I11/837

表1 PMMA的物理性能

图1 在不同升温速率下PMMA/0% CB的热稳定性曲线

图2 升温速率为5℃/min掺碳黑PMMA的热稳定性

图3 PMMA/0% CB四种等转化率曲线

表2 Friedman、FWO、KAS方法下不同碳黑含量PMMA的活化能E

表3 Freeman-carroll法下不同碳黑含量下PMMA的反应级数n

β/℃·min^-1	A $× 1012$ /min^-1
	C_CB/%
	0	0.05	0.1	0.15	0.2	0.25
5	2.8856	4.0788	87.2426	1.9197	20.8827	3.2088
10	2.8823	4.2802	88.1820	1.9237	21.2166	3.1756
15	2.7539	4.2433	94.9790	1.9435	20.1800	2.8766
20	2.7710	4.1112	82.3381	1.7478	19.1612	3.3272
Average value	2.8232	4.1784	88.1854	1.8837	20.3601	3.1471

表4 不同碳黑含量PMMA的指前因子A

图4 不同碳黑含量的PMMA热降解模型验证，升温速率为5℃/min

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