Current status of carbon fiber reinforced polymer composites recycling and re-manufacturing
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摘要: 优异性能的碳纤维增强聚合物基复合材料(CFRPs)在各领域的快速应用发展给复合材料废弃物的回收带来了挑战,尤其是碳纤维增强热固性复合材料。为有效回收碳纤维增强复合材料,促进复合材料产业的可持续发展,本文从多个角度对废弃CFRPs回收再利用研究现状进行综述,包括各回收工艺技术特点、应用领域及可降解树脂实现回收CFRPs的新策略。最后对CFRPs回收再利用技术的未来发展趋势进行了展望。Abstract: The rapid application and development of high-performance carbon fiber reinforced polymer composites (CFRPs) brought challenges for the recovery of composite waste. Recycling of carbon fiber reinforced thermoset composites has been particularly demanding. This paper reviewed the research status of CFRPs waste recycling from multiple perspectives in order to effectively promote their sustainability. Characteristics of various recycling technologies, application fields and new strategies for recycling CFRPs with biodegradable resin were reviewed. Finally, the future development trend of CFRPS recycling technology was prospected.
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Key words:
- carbon fiber /
- carbon composites /
- reinforced polymer /
- composites waste /
- recycling techniques
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图 2 (a) 过氧化氢与丙酮混合溶液降解碳纤维增强复合材料(CFRPs)[34];(b) N,N-二甲基甲酰胺(DMF)与过氧化氢混合溶液降解 CFRPs[35];(c) CFRPs中C—N键选择性断裂降解[39];(d) 硝酸、聚乙二醇和KOH实现温和条件下CFRPs降解[36];(e) 超声化学法降解CFRPs[40];(f) 过氧乙酸降解CFRPs[41]
Figure 2. (a) Degradation of carbon fiber reinforced plastics (CFRPs) by a mixture solution of hydrogen peroxide and acetone[34]; (b) Degradation of mixed solution with N, N-dimethylformamide (DMF) and hydrogen peroxide[35]; (c) Degradation by selective breakage of C—N bond in CFRPs[39]; (d) Degradation of CFRPs under mild conditions achieved by nitric acid, polyethylene glycol and KOH[36]; (e) Degradation of CFRPs by ultrasonic chemical method[40]; (f) Degradation of CFRPs by peroxyacetic acid[41]
图 3 (a) 电化学法降解废弃CFRPs技术示意图;(b) 后处理工艺红外成像;(c) 不同材料能量消耗分布超/亚临界流体法工艺条件示意图;(d) 超临界流体概述图;(e) 超临界流体回收CFRPs示意图
Figure 3. (a) Diagram of degradation of waste CFRPs by electrochemical technology; (b) Infrared imaging by post-treatment process; (c) Diagram of the process conditions of super/subcritical fluid method with different material energy consumption distribution; (d) Overview of supercritical fluids; (e) Diagram of recovery of CFRPs by supercritical fluid
图 4 (a) 基于可降解CFRP设计[55];(b) 解离型共价适应网络(CANs)和结合型CANs[60];(c) Vitrimer合成及优异的耐溶剂性、抗蠕变性和可焊接性[62];(d) 基于脂肪酸的可回收CFRP[63];(e) 基于芳族二硫交联键的可回收CFRP[64];(f) 生物基可回收CFRP[65]
Figure 4. (a) Design based on degradable CFRPs[55]; (b) Dissociated covalent adaptation networks (CANs) and bound CANs [60]; (c) Vitrimer synthesis and excellent solvent resistance, creep resistance and weldability[62]; (d) Recoverable CFRPs based on fatty acid[63]; (e) Recoverable CFRPs based on aromatic disulfide cross-linking bond[64]; (f) Bio-based recoverable CFRPs[65]
PMMA—Polymethyl methacrylate; HDPE—high-density polyethylene; EG—Ethylene glycol; BGPDS—Bis(4-glycidyloxyphenyl)disulfide; AFD—4-aminophenyl disulfide;DTT—Dithiothreitol; HDMO—2-(4-hydroxy-3-methoxyphenyl)-1,3-dioxan-5-ol; σ—Stress
图 5 (a) 高性能不连续纤维法(HiPerDiF)纤维取向法[71];(b) 机械与工程学院开发的工艺(I2M)取向法制备碳纤维带[72];(c) ELG碳纤维公司、德国纺织纤维研究所(DITF)、德国凯撒斯劳滕的复合材料研究所(IVW)和本田欧洲研发公司合作开发的长纤维取向回收再利用工艺
Figure 5. (a) High performance discontinuous fiber method (HiPerDiF) fiber orientation method[72]; (b) Preparation of carbon fiber tape by institut de mécanique et d’ingénierie (I2M) orientation method[72]; (c) ELG carbon fibers company, German Institute for Textile Fibers (DITF), Institute for Composite Materials (IVW), Kaiserslautern, Germany and long fiber orientation recovery and recycling process developed in collaboration with Honda Europe R&D
ADFRC—Aligned discontinuous fibre composite
表 1 现有主要机械法回收技术公司及产品应用
Table 1. Major existing companies in mechanical recovery technology and product applications
Company Country Products Characteristics Eco-Wolf, Inc. American Short fiber(<3 cm) Fiber damaged greatly; short fiber obtained; Generally suitable for recycling low-cost raw materials: glass fiber Reprocover Belgium Hatches, Street facilities, Double track train tracks, etc Hambleside Danelow England Packing, Injection molding, etc Filon Products Ltd. England Trash cans, Concrete, etc MCR-group Plactic Omnium France Asphalt, concrete, composite materials, etc 表 2 热处理回收法优缺点及现有主要热处理法回收技术公司
Table 2. Advantages and disadvantages of heat treatment recovery method and existing major companies on technology of heat treatment recovery method
Method Company Scale/(kg·year−1) Products Characteristic Pyrolysis Carbon Conversions
(USA)2 000 000 Nonwoven mat Commercial production, harmful gases, properties decrease (10%-20%) ELG Carbon Fibre (UK) 2 000 000 Short fiber, nonwoven, milled fibre Nantong Fuyuan New Material Technology Co. Ltd 1 500 000 Nonwoven, non-bearing components CFK Valley Stade Recycling GmbH & Co. KG (Germany) 1 000 000 Chopped and grinded fiber Fluidized bed pyrolysis University of Nottingham (UK) 1 000 000 – Cleaner fiber surface, short fiber, properties decreased greatly Milled Carbon Ltd. Lab Milled fibre Sicomp Lab – Microwave pyrolysis Taiwan Yonghong Advanced Materials Co. Ltd (80-100) ×103 Car seat, tailplane, automobile and leisure products Recovery rate >90%, cleaner fiber surface, strength retention rate >90%, non-toxic, low cost Firebird Advanced Materisls Inc. Lab – University of Nottingham (UK) Lab – 表 3 化学回收法特点及用途
Table 3. Characteristics and applications of chemical recovery method
Method Advantage Disadvantage Products Company Solvolysis Strength basically maintained; Process simple Degradation mechanism is complex, Operation is difficult, Environmental pollution, Laboratory stage Lightweight components, SMC products, etc Adesso, Adherent Technologies, Siemens, Hitachi Chemical Electrochemical recycling Recycling larger size CFRPs, Simple procedure, Green and friendly High voltage, High energy consumption, Fiber property decreases greatly Construction, carbon fiber mats, etc – Supercritical/
Sub-critical solventLittle fiber damage, Controllable fiber size Incomplete degradation, High cost, Harsh conditions, Laboratory stage Additive and filler University of Nottingham, CMBC Laboratory, Panasonic Electric Works Co. Note: SMC—Sheet molding compound. -
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