Study of the Carbonization behavior of Polyimide Materials

摘要

聚酰亚胺(PI)材料具有优异的力学性能、热性能和耐紫外辐照、耐化学腐蚀等性能特点，作为工程塑料广泛应用于工业领域，如飞机零部件，电子包装、粘合剂和复合材料的基体材料等。其独特的芳杂环结构和非常高的碳含量，使其成为制备碳材料的重要前驱体之一。本项工作的研究重点即是对聚酰亚胺材料的碳化行为进行研究。主要内容包括以下四个方面:
　　1.通过改变化学结构对聚酰亚胺/金属复合薄膜的碳化性能的研究。将均苯四甲酸二酐(PMDA)与4,4-二胺基二苯醚(ODA)在N，N-二甲基乙酰胺(DMAc)溶液中进行合成得到聚酰胺酸（PAA）溶液，掺入乙酰丙酮铁(Ⅲ)(AAI)后，碳化温度由600℃升至1600℃。碳膜的碳化过程和性质变化通过X射线衍射(XRD)和扫描电镜(SEM)紧密追踪。
　　2.研究PMDA/ODA体系PI/Fe复合薄膜的制备、表征和热降解以及Fe粒子的形成过程。PI/Fe复合薄膜的热稳定性和热降解动力学参数通过N2保护的热重分析(TGA)进行研究。
　　3.含不同金属催化剂的聚酰亚胺/金属复合膜的碳化性能研究。将3，3’，4，4’-联苯四酸二酐(BPDA)与对苯二胺(PDA)在DMAc溶液中进行合成得到PAA，再将铁或镍与所得溶液进行混合后涂膜，升温碳化，可以得到碳化产物。炭化过程和碳膜的性质可以通过XRD和SEM进行跟踪，在碳化过程中，膜中的铁络合物和镍团簇的尺寸在600℃到1600℃的升温过程中发生明显的生长。
　　4.几种体系PI碳化过程的研究以及多种性质的测量，包括热性能、尺寸、电导率以及其他性能的变化。
　　结果发现，聚酰亚胺膜内部的金属络合物能够促进聚酰亚胺基体的碳化过程。不同的金属材料能够赋予薄膜特定的电性能和磁性能。金属纳米粒子的晶型转变主要发生在600到1600℃的范围内。Fe粒子与PI基体之间的强相互作用对复合材料的热转变行为和磁性产生了重要影响。

目录

声明

ABSTRACT

摘要

Table of contents

Table of Figures

Table of Tables

Chapter One Introduction

1．1 Background

1．2 Objects of the Thesis

1．3 Innovative points of research

1．4 Literature Review

1．4．1 Polyimide-a high-performance polymer

1．5 Applications of polyimides

1．5．1 Polyimides in Electronics Industry

1．5．2 Polyimides in Optoelectronic industry

1．5．3 Polyimides in aerospace industry

1．6 Applications of polyimide composites

1．6．1 Application in Aerospace Industries

1．6．3 Other high performance applications

1．8 Carbonization of polyimide film

1．9 Overview

Chapter Two Polyimides—Chemistry and Structure

2．2 Two-step method for polyimide synthesis

2．2．1 Formation of PAA

2．2．2 Effect of monomer reactivity

2．2．3 The effect of reaction conditions and solvents on the synthesis polyimide

2．2．4 Side reactions and other factors involved in polyimide synthesis

2．2．5 Thermal imidization of a poly(amic acid)

2．2．6 Chemical imidizafion of the PAA

2．3 one step method：high temperature solution polymerization

2．4 Structure-property relationships in linear aromatic polyimides

2．4．2 Polyimide chain-chain interactions

2．4．3 Effect of chain length of the ether diamines on the glass transition

2．4．4 Effect of isometic attachment of the diamines

2．4．5 Effect of the dianhydride structure on the glass transition temperature

2．4．6 Effect of chain structure on the crystallinity

2．4．7 Crystallization behavior from the melt

2．4．8 Polyimide Composites

Chapter Three Characterization and Study on the Thermal Degradation of Carbonized Polyimide(PMDA／ODA)／Fe Composite Films

3．1 Introduction

3．2．Experimental

3．2．1．Materials

3．2．3．Carbonization of PI and PI-Fe composite films

3．2．4．Characterization

3．3．Results and discussion

3．3．1．XRD Test

3．3．2．Raman Spectroscopy measurement

3．3．3．SEM of PI and PI-Fe composite films with different carbonization temperature

3．3．4 Thermal Properties Study of Polyimide／Fe Composite Films

3．3．5．Electrical Conductivity

3．3．6 Magnetic properties

3．4．Summary

Chapter Four Carbonization behavior of polyimide films hybrid with different metal catalyst

4．1 Introduction

4．2．Experimental

4．2．1 Materials

4．2．2．Preparation of PI-Fe and PI-Ni composite film

4．2．3．Carbonization of PI-Fe and PI-Ni composite films

4．2．4．Characterization

4．3 Results and discussion

4．3．1．XRD measurement

4．3．2 Raman Spectroscopy measurement

4．3．3 SEM and TEM of PI-Fe and PI-Ni composite films with different carbonization temperatures

4．4 Properties films

4．4．1 Electrical conductivity

4．4．2 Magnetic properties

4．5 Summary

Chapter Five Conclusion

References

Papers submitted for publication

Acknowledgements

Author’s Declaration

Brief introduction of the supervisor

Author’s resume