环氧树脂基体的原位增韧技术研究进展
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摘要
自20世纪初环氧树脂问世以来,其优异的胶黏性能、可加工性能、耐化学腐蚀性能等特性使环氧树脂被广泛应用于涂料、包装、电子产品的制造和封装等众多行业。近年来,环氧树脂优良的热稳定性、电绝缘性和物理、力学性能,使其作为复合材料的浸润基体在航空航天、武器装备等众多国家前沿技术领域发挥了重要的作用。采用不同新型树脂模塑传递技术对以环氧树脂为基体的复合材料进行制备与加工,得到的产品具有收缩率小、整体性均一、耐腐蚀性能优良的优点,同时可以兼顾材料对电气性能和力学性能的要求。迄今,环氧树脂在航空工业仍处于主导地位。随着世界各国航空前沿技术的竞争愈演愈烈,对航空复合材料的发展提出了更高的要求,与航空航天相关的先进复合材料制备技术也在不断丰富和完善。环氧树脂在固化时形成的三维网状立体结构,一方面显著提高了材料的物理强度、硬度,但另一方面,这种结构的形成往往伴随着过高的交联密度,进而导致材料质脆、易裂,在某些极端环境下易发生脆性断裂,限制了环氧树脂的应用和发展。因此,对环氧树脂进行增韧处理,提高最终制品的冲击强度,拓宽其应用领域,一直是航空复合材料领域的研究重点。经过多年对环氧树脂增韧改性的尝试,研究者们已取得了丰硕的成果,各种增韧方案和增韧机理的相继建立大幅拓展了环氧树脂的应用范围。目前,国内外较为成熟的对环氧树脂进行增韧的方案大多属于原位增韧的范畴,即通过在原有均匀分散的环氧树脂多相体系中引入增强相或形成一种新相,保持浸润基体内部不同相的均匀空间分布状态,最终达到对环氧树脂制品增韧的目的。其中增韧效果优异的方案主要有:(1)在环氧树脂基体中引入橡胶粒子,或是添加热致液晶聚合物、超支化聚合物、核壳结构聚合物等添加剂进行增韧;(2)通过预先设计,将环氧树脂与第二组分形成互穿/半互穿网络聚合物进行增韧;(3)添加具有特殊功能性的纳米粒子对环氧树脂基体进行增韧。对环氧树脂增韧改性的研究具有重要的理论意义和实用价值。本文对环氧树脂的发展历程进行了简要梳理,从理论研究较为成熟的宏观上对树脂体系进行增韧和近30年来发展迅速的使用纳米改性剂进行增韧两方面,对增韧效果较好的一些原位增韧技术进行了介绍,并列举了近年来报道的重要成果,同时客观评价了不同技术的优缺点。最后分析了环氧树脂增韧技术面临的问题及未来发展的方向,以期为制备轻质、高性能环氧树脂复合材料提供参考。
Since the invention of epoxy resin in the early 20 th century,due to its great properties in adhesion,machinability and chemical resistance,the epoxy resin is widely used in coating,packaging,electronic products manufacturing and other industries. In recent years,people use epoxy resin as infiltration matrix in the aerospace,arms equipment and many other national frontier technology areas and has achieved lots of research production. When people use different new resin moulding transfer techniques to prepare and process composites with epoxy resin matrix,it is easy to make the final products have some advantages like small shrinkage,uniform integrity and excellent corrosion resistance,and make the materials meet requirements for electrical and mechanical properties at the same time. Up to now,epoxy resin is still in dominant position in aviation industry.In order to promote the application of aviation industry,countries around the world have put forward higher requirements for epoxy resin,and the related advanced composite material preparation technology has been constantly enriched and improved. Epoxy resin forms a three-dimensional network structure in curing process. In one hand,it improves the physical strength and hardness of the materials significantly. In the other hand,high crosslinking density also makes materials brittle and easy to crack. Therefore,it has always been the focus of research in the field of aeronautical composites about how to improve toughness of epoxy resin. Researchers have made great achievements after attempting in toughening epoxy resin for many years. Various toughening schemes and mechanisms have been established successively,which expands the application of epoxy resin greatly.Most of the mature schemes for toughening epoxy resin belong to the category of in-situ toughening at present. A new phase can be formed by adding reinforcing phase into the epoxy resin polyphase system,the uniform spatial distribution of different phases in the infiltrating matrix will improves toughness as the result. Some of the most effective toughening schemes are:( i) toughening epoxy resin by adding rubber particles,thermotropic liquid crystal polymer,hyperbranched polymer,core-shell polymer and so on;( ii) preparing a interpenetrating/semi-interpenetrating polymer networks with epoxy resin and another phase to toughen through pre-design;( iii) adding nanoparticles with special functions to toughen epoxy resin matrix. The research on toughening modification of epoxy resin has important theoretical significance and practical value in general.In this paper,the development of epoxy resin was briefly reviewed through two aspects: the mature macroscopic system and the rapid development of nano-modifiers in recent 30 years. Some in-situ toughening technologies with great effect were described in detail,and enumerate the important results published in recent years to support. The paper also evaluated the advantages and disadvantages of different technologies objectively. At the end of this paper,the problems faced by the toughening technology of epoxy resin and the future development direction are analyzedto provide reference for the preparation of light and high performance epoxy resin composites.
Since the invention of epoxy resin in the early 20 th century,due to its great properties in adhesion,machinability and chemical resistance,the epoxy resin is widely used in coating,packaging,electronic products manufacturing and other industries. In recent years,people use epoxy resin as infiltration matrix in the aerospace,arms equipment and many other national frontier technology areas and has achieved lots of research production. When people use different new resin moulding transfer techniques to prepare and process composites with epoxy resin matrix,it is easy to make the final products have some advantages like small shrinkage,uniform integrity and excellent corrosion resistance,and make the materials meet requirements for electrical and mechanical properties at the same time. Up to now,epoxy resin is still in dominant position in aviation industry.In order to promote the application of aviation industry,countries around the world have put forward higher requirements for epoxy resin,and the related advanced composite material preparation technology has been constantly enriched and improved. Epoxy resin forms a three-dimensional network structure in curing process. In one hand,it improves the physical strength and hardness of the materials significantly. In the other hand,high crosslinking density also makes materials brittle and easy to crack. Therefore,it has always been the focus of research in the field of aeronautical composites about how to improve toughness of epoxy resin. Researchers have made great achievements after attempting in toughening epoxy resin for many years. Various toughening schemes and mechanisms have been established successively,which expands the application of epoxy resin greatly.Most of the mature schemes for toughening epoxy resin belong to the category of in-situ toughening at present. A new phase can be formed by adding reinforcing phase into the epoxy resin polyphase system,the uniform spatial distribution of different phases in the infiltrating matrix will improves toughness as the result. Some of the most effective toughening schemes are:( i) toughening epoxy resin by adding rubber particles,thermotropic liquid crystal polymer,hyperbranched polymer,core-shell polymer and so on;( ii) preparing a interpenetrating/semi-interpenetrating polymer networks with epoxy resin and another phase to toughen through pre-design;( iii) adding nanoparticles with special functions to toughen epoxy resin matrix. The research on toughening modification of epoxy resin has important theoretical significance and practical value in general.In this paper,the development of epoxy resin was briefly reviewed through two aspects: the mature macroscopic system and the rapid development of nano-modifiers in recent 30 years. Some in-situ toughening technologies with great effect were described in detail,and enumerate the important results published in recent years to support. The paper also evaluated the advantages and disadvantages of different technologies objectively. At the end of this paper,the problems faced by the toughening technology of epoxy resin and the future development direction are analyzedto provide reference for the preparation of light and high performance epoxy resin composites.
引文
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