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碳纤维增强含酯键环氧树脂基复合材料的化学降解与回收

张洋 张隽爽 马崇攀 孙忠霄 王宇

张洋, 张隽爽, 马崇攀, 等. 碳纤维增强含酯键环氧树脂基复合材料的化学降解与回收[J]. 复合材料学报, 2023, 40(9): 5026-5034. doi: 10.13801/j.cnki.fhclxb.20221111.001
引用本文: 张洋, 张隽爽, 马崇攀, 等. 碳纤维增强含酯键环氧树脂基复合材料的化学降解与回收[J]. 复合材料学报, 2023, 40(9): 5026-5034. doi: 10.13801/j.cnki.fhclxb.20221111.001
ZHANG Yang, ZHANG Junshuang, MA Chongpan, et al. Chemical degradation and recovery of carbon fiber reinforced epoxy resin matrix composites containing ester bond[J]. Acta Materiae Compositae Sinica, 2023, 40(9): 5026-5034. doi: 10.13801/j.cnki.fhclxb.20221111.001
Citation: ZHANG Yang, ZHANG Junshuang, MA Chongpan, et al. Chemical degradation and recovery of carbon fiber reinforced epoxy resin matrix composites containing ester bond[J]. Acta Materiae Compositae Sinica, 2023, 40(9): 5026-5034. doi: 10.13801/j.cnki.fhclxb.20221111.001

碳纤维增强含酯键环氧树脂基复合材料的化学降解与回收

doi: 10.13801/j.cnki.fhclxb.20221111.001
基金项目: 国家自然科学基金(52102033);装备预研教育部联合基金(6141 A02033231)National Natural Science Foundation of China (52102033); Joint Fund of Ministry of Education for Equipment Research (6141 A02033231)
详细信息
    通讯作者:

    王宇,博士,副教授,硕士生导师,研究方向为聚丙烯腈基碳纤维及其复合材料 E-mail:wangy@mail.buct.edu.cn

  • 中图分类号: TQ342.31;TB332

Chemical degradation and recovery of carbon fiber reinforced epoxy resin matrix composites containing ester bond

  • 摘要: 随着环氧树脂基碳纤维复合材料的广泛应用,其废旧产品的回收成为低碳发展的重要问题。采用GC-MS、FTIR、XPS、SEM等表征方法研究了含酯键的环氧树脂基碳纤维复合材料的树脂降解机制及降解过程对回收碳纤维结构和性能的影响。研究结果表明:在苯甲醇用量120 mL、质量比W(NaOH)∶W(ZnCl2)=1∶1和降解温度190℃的前提下,最佳降解时间为1 h,较优的降解配方为NaOH和树脂均为1 g。降解得到的产物静置分层,上层清液的苯甲醇含量达99%;环氧树脂的降解机制为苯甲醇在碱性环境下电离生成苄氧基,苄氧基进攻环氧树脂中的酯键,发生酯交换反应,使酯键断裂实现降解,生成苯甲醇酯及醇阴离子,苯甲醇酯在碱性环境下发生皂化反应重新生成苯甲醇,酯交换反应和皂化反应重复进行,直至最终降解完成;回收碳纤维与原始碳纤维的表面O/C、表面光洁程度均在一个水平,回收碳纤维的强度保留率达97%。

     

  • 图  1  降解时间对环氧树脂基体降解率的影响

    Figure  1.  Effect of degradation time on degradation rate of epoxy resin matrix

    Benzyl alcohol 120 mL, mass ratio W(NaOH)∶ W(ZnCl2)=1∶1, NaOH 1 g, ZnCl2 1 g, composite materials 2 g

    图  2  NaOH加入量对环氧树脂基体降解率的影响

    Figure  2.  Effect of NaOH dosage on degradation rate of epoxy resin matrix

    图  3  回收所得上清液与纯苯甲醇的FTIR图谱

    Figure  3.  FTIR spectra of recovered supernatant and pure benzyl alcohol

    图  4  降解后溶液下层的胶状产物的液质联用测试结果: (a) 正离子;(b) 负离子

    Figure  4.  Results of LC-MS of degraded and recovered colloid: (a) Positive ion; (b) Negative ion

    m/z—Mass-to-charge ratio

    图  5  降解回收胶体与纯环氧树脂的FTIR图谱

    Figure  5.  FTIR spectra of degraded and recovered colloid and pure epoxy resin

    图  6  环氧树脂基体降解过程机制图

    Figure  6.  Schematic diagram of degradation process of epoxy resin matrix

    图  7  原始碳纤维和降解回收碳纤维的表面形貌对比图

    Figure  7.  Comparison diagram of surface morphology of original carbon fiber and degraded carbon fiber

    表  1  碳纤维复合材料环氧树脂降解后所得碳纤维力学性能和表面理化结构与原始碳纤维对比表

    SampleTensile strength of monofilament/GPaElement contentsurface morphology
    C/%O/%C/O
    Initial carbon fibers3.44±0.0884.6513.260.157
    Recycled carbon fibers3.34±0.1084.5113.360.158
    下载: 导出CSV

    表  1  碳纤维复合材料降解1 h后上清液的GC-MS结果

    Table  1.   GC-MS results of supernatant after 1 h degradation of carbon fiber composite

    Sequence numberRetention time/minComponents’ nameMolecular structureContent mol/%
    18.460Benzaldehyde0.101
    29.842Benzyl alcohol99.878
    Others0.021
    下载: 导出CSV

    表  2  降解前后碳纤维表面的元素含量

    Table  2.   Element content of carbon fiber surface before and after degradation

    SampleDegradation rate/%C/%O/%C/O
    Initial carbon fibers84.6513.260.157
    Recycled carbon fibers (W(NaOH):W(Resin)=1∶1)10084.5113.360.158
    Recycled carbon fibers (W(NaOH):W(Resin)=0.1∶1) 75.780.4017.340.216
    下载: 导出CSV

    表  3  原始碳纤维和降解回收碳纤维的单丝拉伸强度对比

    Table  3.   Comparison of tensile strength of carbon fiber monofilament before and after degradation

    SampleDegradation rate/%Tensile strength of monofilament/GPa
    Initial carbon fibers3.44±0.08
    Recycled carbon fibers
    (W(NaOH)∶W(Resin)=1∶1)
    1003.34±0.10
    下载: 导出CSV
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  • 收稿日期:  2022-10-05
  • 修回日期:  2022-10-29
  • 录用日期:  2022-11-06
  • 网络出版日期:  2022-11-14
  • 刊出日期:  2023-09-15

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