Curing process and kinetics of CMC/E44/DDM systems

DONG Hongxing; ZHAO Qingchen; ZHANG Jin; CHEN Ye; YUE Guojun; LIU Wenxin; LIU Jinsong; LIU Lijia; ZHANG Chunhong

doi:10.3969/j.issn.0438-1157.2014.11.025

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Curing process and kinetics of CMC/E44/DDM systems

更新时间：2025-12-10

- Curing process and kinetics of CMC/E44/DDM systems
- CIESC Journal Issue 11, Pages: 4392-4399(2014)
- 作者机构：
  
  1. 哈尔滨工程大学材料科学与化学工程学院超轻材料与表面技术教育部重点实验室高分子材料研究中心,黑龙江,哈尔滨,150001
  2. 中国航天科工集团第六研究院359厂,内蒙古,呼和浩特,010000
  3. 中粮生化能源(肇东)有限公司, 黑龙江肇东,151100
- 作者简介：
- 基金信息：
- DOI：10.3969/j.issn.0438-1157.2014.11.025
  CLC： 641
- Online First：05 November 2014，
  
  Published：05 November 2014
- 稿件说明：
移动端阅览
DONG Hongxing, ZHAO Qingchen, ZHANG Jin, et al. Curing process and kinetics of CMC/E44/DDM systems[J]. CIESC Journal, 2014, (11): 4392-4399.
DOI：

DONG Hongxing, ZHAO Qingchen, ZHANG Jin, et al. Curing process and kinetics of CMC/E44/DDM systems[J]. CIESC Journal, 2014, (11): 4392-4399. DOI： 10.3969/j.issn.0438-1157.2014.11.025.

摘要

采用红外光谱和非等温DSC法研究了羧甲基纤维素(CMC)/E44环氧树脂/4

4'-二氨基二苯基甲烷(DDM)体系的固化过程和动力学.红外光谱研究表明

CMC可促使E44/DDM体系在固化过程中生成更多的聚醚结构.DSC非等温固化反应动力学研究表明

CMC的加入在反应初始阶段降低了E44/DDM体系的反应活化能

促进固化反应的进行.采用等转化率法和自催化模型对固化反应的过程进行研究

建立动力学方程.由Starink等转化率法获得E44/DDM和CMC/E44/DDM体系的活化能随转化率的变化情况.E44/DDM体系的活化能随转化率升高而显著降低;CMC/E44/DDM体系的活化能随转化率升高变化不明显

在相同含量时

相对分子质量高的CMC体系活化能高.采用SB自催化模型研究E44/DDM和CMC/E44/DDM体系的固化过程并获得模型参数.对CMC/E44/DDM体系

SB模型对实验结果拟合较好;对E44/DDM体系

SB模型和实验结果吻合效果较差.由于E44/DDM体系活化能随固化度有显著变化

因此采用改进的变活化能自催化模型描述其实验现象

结果显示该法获得的模型能够较好地描述实验现象.动力学模型的建立能够为工艺参数的选择和工艺窗口优化提供理论依据.

Abstract

The influence of sodium carboxy methyl cellulose (CMC) on the curing process of epoxy resin E44 with 4

4'-diamino diphenyl methane (DDM) was studied by using infrared spectra and thermal analytical methods. Infrared spectra indicated that the CMC contributed to forming more polyether structures during the curing process. The study of non-isothermal curing kinetics by differential scanning calorimeters (DSC) showed that CMC accelerated curing reaction of E44/DDM and reduced reaction activation energy in the initial reaction stage. The iso-conversional method and the autocatalytic model were used to analyze the curing process of E44/DDM and CMC/E44/DDM systems respectively. A kinetic model was built. The changes of activation energy (E) versus conversion (a) were obtained by the Starink's iso-conversional method for E44/DDM system and CMC/E44/DDM systems respectively. The activation energy (E) of E44/DDM system was reduced obviously with increasing conversion. When CMC content was the same

activation energy of the CMC system with high molecular weight was higher than that with low molecular weight. However

for the CMC/E44/DDM system

as the degree of conversion increased

variation of E was not obvious. The SB (m

n) autocatalytic kinetic model was used to describe the curing reaction process of the studied system. The model parameters were calculated by using the Levenberg-Marquardt method. The SB model showed a good agreement with experimental data of CMC/E44/DDM system. However

the SB model showed a relatively bad agreement with experimental data of E44/DDM system. An E variable autocatalytic kinetic model was proposed to describe the curing process of E44/DDM system due to the obvious change of activation energy and the model parameters calculated with the Levenberg-Marquardt method. Compared with the SB model

this model showed a better agreement with the experimental data of E44/DDM system. The results of the research provide theoretical basis for improvement of manufacturing process and optimization of processing window.

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