有机硅自修复材料

有机硅自修复材料在可穿戴装备、智能涂层等领域有广泛应用。本文分别从外援型和本征型两大类介绍了有机硅自修复材料的特点、修复机理和最新研究进展。在外援型有机硅自修复材料中,主要介绍了利用光引发自由基反应、缩合固化、硅氢加成等有机硅特异性反应实现自修复。在本征型有机硅自修复材料中介绍了利用Diels-Alder反应、酰腙键、酯键、Schiff base结构等可逆化学反应,金属-配体配位作用以及氢键、π-π堆叠作用等超分子作用,实现自修复功能的途径及特点;除此之外还介绍了最小化表面自由能、巯基与纳米银之间的键合作用和重构反应等有机硅自修复实例。最后,本文指出了有机硅自修复材料面临的问题并对今后的发展方向进行了展望。     

基于非共价键的本征型自修复聚合物材料及其应用

自修复材料作为一种拥有结构上自愈合能力的智能材料近年来得到了快速发展。具备自修复性能的聚合物材料主要包括外援型和本征型。由于本征型自修复聚合物材料具有潜在的自修复能力,且能实现多次修复,所以该领域对于本征型自修复聚合物材料的关注越来越多。由氢键、π-π堆积、疏水作用、离子作用和主客体作用等非共价键力形成的本征型自修复聚合物体系不需要或需要极少外界能量就能实现快速、高效修复。这将是实现节约能源,社会可持续发展的重要途径。本文以不同类型的非共价键为线索,综述了近年来基于非共价键的本征型自修复聚合物材料的发展及其应用,并展望了其未来的发展方向。     

基于超分子聚合物的自修复材料

材料的自修复功能对于材料应用具有重要的意义,如键组装/解组装常数、键的方向和链的弛豫时间等因素会影响自修复效率。根据提供修复功能的物质构成形式,可以分为外援型自修复材料和本征型自修复材料,其中本征型自修复材料是当前的热点方向,在本征型自修复材料中,超分子自修复材料以其独特的可逆性组装,以及在快速、可逆、多重响应方面的优势而成为研究重点。本文重点阐述了基于不同结合效应的超分子自修复聚合物的研究进展,并对今后的研究方向作了展望,认为材料的耐环境性能能否达标是未来能否获得应用的关键因素之一。     

微胶囊自修复材料的修复反应

受自然界生物可以自动愈合伤口的启发,科学家设计出能够自动修复损伤的自修复材料。由于微胶囊体系的制备工艺简单、应用范围广、对多种损伤形式均可修复,受到了科学家的广泛关注。其主要修复过程为:裂纹扩展使微胶囊破裂,微胶囊内的修复剂流到微裂纹处,在催化剂作用下修复剂发生聚合反应从而修复微裂纹。这一过程中修复反应是实现材料自修复的关键,它必须能够在室温下将低粘度液体转变为坚韧的热固性高聚物。本文综述了针对微胶囊自修复材料的修复反应,重点介绍了环烯烃的开环易位聚合、环氧树脂的开环聚合、溶剂的再固化、点击化学四类反应。其中,点击化学由于简单高效的特点成为设计自修复材料的新方法,包括叠氮化物-炔烃反应、共轭二烯和亲二烯体反应、疏基-烯反应、疏基-氰酸酯反应等。通过对比分析修复反应的机理和自修复效率的影响因素,指出各种修复反应的优点和局限性,并对微胶囊自修复材料的发展趋势进行展望。     

微胶囊填充型自修复聚合物及其复合材料

微胶囊填充型自修复聚合物及其复合材料是近年来高分子科学界的研究热点之一。本文介绍了含有微胶囊聚合物复合材料自修复的概念和机理,综述了近5年来针对不同基体材料的微胶囊自修复研究情况,包括环氧树脂、乙烯基酯树脂、纤维增强环氧树脂复合材料、弹性体以及聚甲基丙烯酸甲酯等基体材料。本文同时介绍了微胶囊的芯材和壁材、微胶囊的粒径、修复时间和压强等因素对复合材料自修复性能的影响,以及自修复效果的评价方法。最后对微胶囊填充型自修复聚合物及其复合材料的研究前景进行了展望。     

自愈合聚合物材料的研究进展Ⅰ.传统修复方法及热固性自愈合材料的制备和表征

自愈合聚合物材料是受自我修复生物体系的触发而发展的,这是一个新兴迷人的研究领域,可以明显拓宽聚合物材料的工作寿命和广泛应用的安全性.参考近年来的文献资料,文章着重介绍了传统的修复聚合物材料的方法,以及各种热固性自愈合材料的制备和表征,其中最主要的制备方法是中空纤维法和微胶囊法.     

自修复高分子材料近五年的研究进展

自修复材料的概念源于对生物体自愈合现象的仿生研究,该类材料在受到损伤时可进行自修复并恢复一定程度的力学等性能。对高分子材料而言,其受机械力损伤后一般发生大分子链均裂或异裂而使材料产生微裂纹,此类微裂纹很难探测,而微裂纹的产生往往会引起高分子材料失效,因此快速修复微裂纹对诸多工程领域的高分子材料来讲尤为重要。本文从外源型及本征型自修复高分子材料两个方面,综述了近五年自修复高分子材料的研究进展,并对其今后发展进行了展望。     

锂离子电池自修复聚合物电解质的研究进展

自修复材料可以修复其在外界环境因素作用下产生的局部创伤或微裂纹,大大延长材料的使用寿命.将自修复聚合物作为固态聚合物电解质应用于锂离子电池,可以显著提高锂离子电池的循环稳定性和安全性,延长使用寿命.本文首先概述了自修复聚合物材料的发展历程和修复机理,然后按超分子相互作用和动态共价键分类总结了本征型自修复聚合物电解质应用于锂离子电池的研究进展,最后对自修复聚合物电解质存在的问题和未来的发展方向做出了展望,为下一代高安全性、高性能和长使用寿命的锂离子电池的研究提供借鉴.     

自修复有机硅材料的制备策略

近年来，通过仿生生命体自我修复损伤这一现象而研制的自修复材料，可有效延长材料的使用寿命、提高材料的使用安全性、降低资源浪费，具有巨大的发展潜力。其中，自修复有机硅材料因兼具自我修复的功能和有机硅材料的优异性能，已成为当下的研究热点。由于外界刺激条件如紫外光、温度等是材料实现损伤自我修复的外在驱动力，在很大程度上影响着材料的修复效能，且不同的刺激条件具有不同的优缺点和应用领域。因此，本文将基于自修复过程中外界刺激因素的不同，对自修复有机硅材料尤其是近五年来的最新研究成果进行综述，从外援型和本征型自修复有机硅材料两方面入手，以本征型自修复有机硅材料为重点，并对自修复有机硅材料今后的发展进行了分析展望。     

自修复超疏水涂层材料研究进展

超疏水涂层材料具有自清洁、减阻、防雾、防黏附等特点,被广泛应用于防腐涂层、管道运输、油水分离等领域。但超疏水涂层材料在使用过程中由于物理磨损和化学腐蚀等原因易使其丧失超疏水性能,限制了其在工业中的实际应用,因此自修复超疏水涂层材料应运而生,且成为近年来的研究热点。本文综述了自修复超疏水涂层材料的最新研究进展,总结并对比了外援型自修复超疏水涂层材料和本征型自修复超疏水涂层材料的优缺点,同时对该领域的未来发展前景进行了简要展望。     

Self-Healing Polymer Composites: Prospects,Challenges, and Applications

Self-healing polymer composites possess the inherent ability to heal the damage event autonomically or non-autonomically with external intervention. These advanced materials can be commercialized if the challenges and limitations of different self-healing mechanisms are well known and considered. These include capsule-based healing systems, vascular healing systems, and intrinsic healing systems. To date, most of the reviews have studied and reported on different self-healing mechanisms including their response to impact, fatigue, and corrosion tests. This review focuses mostly on extrinsic and intrinsic self-healing polymer composites which have been reported during the past five years by comparing their healing efficiency, advantages, and challenges in the prospect of their future development as well as their possible applications across various industries such as aerospace, automobile, coating, electronics, energy, etc.     

Design and synthesis of self-healing polymers

Self-healing polymers represent a class of materials with built-in capability of rehabilitating damages. The topic has attracted increasingly more attention in the past few years. The on-going research activities clearly indicate that self-healing polymeric materials turn out to be a typical multi-disciplinary area concerning polymer chemistry, organic synthesis, polymer physics, theoretical and experimental mechanics, processing, composites manufacturing, interfacial engineering, etc. The present article briefly reviews the achievements of the groups worldwide, and particularly the work carried out in our own laboratory towards strength recovery for structural applications. To ensure sufficient coverage, thermoplastics and thermosetting polymers, extrinsic and intrinsic self-healing, autonomic and non-autonomic healing approaches are included. Innovative routes that correlate materials chemistry to full capacity restoration are discussed for further development from bioinspired toward biomimetic repair.     

The Potential of Microencapsulated Self-healing Materials for Microcracks Recovery in Self-healing Composite Systems: A Review

The autonomic self-healing materials based on microcapsules have made major advancements for the repairing of microcracks in polymers and polymer composite systems. Self-healing encapsulated materials have the inborn ability to heal polymeric composites after being damaged by chemical and mechanical progressions. These intelligent micro-encapsulated self-healing materials possess great capabilities for recovering the mechanical as well aesthetic properties and barrier properties of the polymeric structures. Based on real world observations and experimental data, it is believed that microcracks and microcracking in polymeric materials can result because of many chemical and physical routes and is one of the foremost critical issues for polymeric materials. Especially in polymeric coatings, these microcracks can lead towards disastrous failure, and conventional healing systems like patching and welding cannot be used to repair microcracks at such a micro-level. Self-healing materials, especially, capsule based self-healing materials is a new field sought as an alternative to the conventional repairing techniques, requiring no manual intrusion and uncovering. This review covers the basic and major aspects of the microencapsulated self-healing approach like the effect of synthesis parameters on the size of microcapsules, healing efficiency determination, and the potential of the existing developed microencapsulated agents.     

Two-dimensional self-healing hydrogen-bond-based supramolecular polymer film

A monolayer hydrogen-bond-based supramolecular polymer (HSP) film has self-healing properties at the two-dimensional limit after destroyed by tip of atomic force microscopy and it can also modify the SiO₂ dielectric for copper phthalocyanine field effect transistor with improved mobility.     

氧化石墨烯/聚合物复合水凝胶的研究进展

氧化石墨烯是一种具有单原子厚度的二维材料, 具有优异的力学性能和良好的水分散性, 其表面有大量的含氧官能团. 将氧化石墨烯引入水凝胶体系中可以提高水凝胶的机械性能, 丰富其刺激响应的类型. 目前, 氧化石墨烯水凝胶在高强度、 吸附、 自愈合及智能材料等很多领域均有出色的表现. 氧化石墨烯水凝胶的研究已有10年的历史. 本文总结了氧化石墨烯水凝胶的制备方法, 归纳了智能氧化石墨烯水凝胶在光热响应、 pH响应和自愈合3个方面的响应机理和研究进展, 并综合评述了其在高强度水凝胶、 生物医学、 智能材料和污水处理等方面的应用前景.     

A Fast and Room-temperature Self-healing Thermal Conductive Polymer Composite

Thermal conducting materials may be damaged during long-term use, resulting in the increase of thermal resistance and therefore inefficient heat dissipation. The introduction of self-healing ability may solve this problem, but the realization of fast and room-temperature selfhealing in thermal conducting composites is quite challenging. Herein, we choose a flexible poly(dimethylsiloxane) polymer material(PDMSCOOH) as the matrix and graphene nanosheets as the thermal conductive filler to prepare a new kind of thermal conductive polymer composite(PDMS-COOH-CG) that can quickly self-heal at room temperature. The thermal conductivity of PDMS-COOH-CG10 with 10% of graphene content is 0.48 W·m~(-1)·K~(-1), which is 16 times that of PDMS-COOH(0.03 W·m~(-1)·K~(-1)). At room temperature, self-healing efficiency of PDMS-COOHCG10 based on tensile strength can be 53.8% for 30 s and 84.6% for 24 h. Dynamic infrared thermal imaging dipicted that after 2 min of selfhealing at room temperature, the thermal conduction temperature near the damage was basically restored to the level of the pristine sample.     

Thermo-reversible MWCNTs/epoxy polymer for use in self-healing and recyclable epoxy adhesive

A self-healing and recyclable carbon tube/epoxy adhesive was prepared by epoxy monomer with Diels-Alder(DA) bonds, diethylenetriamine and polyethyleneimine modified multi-wall carbon nanotubes(MWCNTs). The self-healing and recyclable ability was attained by thermally reversible Diels-Alder reaction between furan and maleimide in the epoxy monomer. By controlling the molar ratio of furfuryl glycidyl ether and 4,4′-methylenebis(N-phenylmaleimide), the glass transition temperature and mechanical properties of MWCNTs/epoxy adhesives were varied. The self-healing properties of MWCNTs/epoxy polymers were evaluated by lap shear experiment and the results showed that the MWCNTs/epoxy adhesives exhibited enhanced mechanical properties and excellent self-healing ability under heat stimulus. The healing efficiency was related to the molecule mobility and the conversion of DA reaction between furan and maleimide. The MWCNTs/epoxy adhesives also displayed excellent recyclable ability by transforming into soluble polymer under heating. These materials offer a wide range of possibilities to produce materials with healing and recyclable ability and have the potential to bring great benefits to our daily lives by enhancing the safety, performance, and lifetime of products.     

PREFACE

正We are delighted to present this special-themed issue of the Chinese Journal of Polymer Science(CJPS) devoted to the recent advances in self-healing polymeric materials. Selfhealing has been recognized as one of the most attractive topics for advanced polymers in the past few years, enabling their reworkability, durability and reliability.     

非晶固体高分子表面的低温流动特性

高分子低温加工是材料领域重大挑战。相较于本体分子,位于材料表面高分子链的玻璃化转变温度降低、黏度减小、塑性增强,为高分子材料低温加工提供了可能途径。本文总结了近年来对非晶固体高分子表面分子运动的研究成果,从表面分子动力学的角度阐述了高分子表面低温流动性的起源及其影响因素,举例介绍了表面低温流动特性在高分子材料低温粘结、自愈合以及加工成型等方面的应用,并对未来研究及前景进行了展望。希望通过本文加深对高分子表面低温流动行为的认识和理解,促进高分子材料加工和成型新方法和新概念的发展。