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聚氨酯/纳米SiO2改性碳纤维增强环氧树脂复合材料界面性能

袁玉环 左进霞 彭聪 武湛君

袁玉环, 左进霞, 彭聪, 等. 聚氨酯/纳米SiO2改性碳纤维增强环氧树脂复合材料界面性能[J]. 复合材料学报, 2023, 40(11): 6073-6086. doi: 10.13801/j.cnki.fhclxb.20230117.005
引用本文: 袁玉环, 左进霞, 彭聪, 等. 聚氨酯/纳米SiO2改性碳纤维增强环氧树脂复合材料界面性能[J]. 复合材料学报, 2023, 40(11): 6073-6086. doi: 10.13801/j.cnki.fhclxb.20230117.005
YUAN Yuhuan, ZUO Jinxia, PENG Cong, et al. Interfacial properties of polyurethane/nano-SiO2 modified carbon fiber epoxy resin composites[J]. Acta Materiae Compositae Sinica, 2023, 40(11): 6073-6086. doi: 10.13801/j.cnki.fhclxb.20230117.005
Citation: YUAN Yuhuan, ZUO Jinxia, PENG Cong, et al. Interfacial properties of polyurethane/nano-SiO2 modified carbon fiber epoxy resin composites[J]. Acta Materiae Compositae Sinica, 2023, 40(11): 6073-6086. doi: 10.13801/j.cnki.fhclxb.20230117.005

聚氨酯/纳米SiO2改性碳纤维增强环氧树脂复合材料界面性能

doi: 10.13801/j.cnki.fhclxb.20230117.005
基金项目: 国家重点研发计划(2018YFA0702800);国家自然科学青年基金(12002074)
详细信息
    通讯作者:

    武湛君,博士,教授,博士生导师,研究方向为耐极端环境复合材料设计与表征,结构健康监测理论、方法与技术 E-mail: wuzhj@dlut.edu

  • 中图分类号: O631.2;O631.5;TB332

Interfacial properties of polyurethane/nano-SiO2 modified carbon fiber epoxy resin composites

Funds: National Natural Science Foundation of China (2018YFA0702800); National Natural Science Funds for Young Scholar (12002074)
  • 摘要: 聚合物与纤维之间的界面性能对提升复合材料力学性能尤为重要。本文采用异氰酸根(—NCO)封端的聚氨酯(PU)分子对纳米SiO2表面进行改性,同时采用KH550对碳纤维(CF)进行表面改性,利用—NH2与—NCO较高的反应活性,在CF和纳米SiO2粒子间通过PU分子链形成共价键连接。结果显示:PU极性分子链的引入,提高了CF的表面能,使其表面润湿性显著提高。相较于KH550直接接枝纳米粒子的碳纤维(CF-KH550-SiO2),通过PU分子链接枝纳米粒子的碳纤维(CF-KH550-PU-SiO2),其表面能提升23.0%,表面纳米SiO2粒子的接枝率和分散均匀性也明显提升。CF-KH550-PU-SiO2/环氧树脂(EP)的界面剪切强度(IFSS)和层间剪切强度(ILSS)相比未改性CF/EP分别提高72.9%和47.9%,相比CF-KH550-SiO2/EP分别提高17.3%和11.2%。

     

  • 图  1  (a)纳米SiO2表面接枝聚氨酯(PU)反应过程;(b)碳纤维(CF)表面多层结构制备示意图

    TEOS—Ethyl orthosilicate; HDI—Hexamethylene diisocyanate; PPG—Polypropylene glycol; DBTDL—Dibutyl tin dilaurate; KH550—3-aminopropyl triethoxysilane

    Figure  1.  (a) Reaction process of grafting polyurethane (PU) on nano-SiO2 surface; (b) Schematic illustration of multilayer structure grafted on carbon fiber (CF)

    图  2  微滴脱粘简图

    Figure  2.  Experimental setup for microbond testing

    图  3  未改性纳米SiO2 (a)及PU-SiO2 (b)的TEM图像、两种粒子的动态光散射(DLS)粒径曲线(c)及未改性纳米SiO2和PU-SiO2的分散液(d)

    $\overline{D} $—Average particle size of particles; PDI—Polydispersity index

    Figure  3.  TEM images of raw SiO2 (a) and PU-SiO2 (b), dynamic light scattering (DLS) curves of the synthesized SiO2 (c) and photograph of the particle disperdion (d)

    图  4  纳米SiO2改性前后的红外图谱及局部放大图:((a), (a1), (a2))未改性SiO2;((b), (b1), (b2))改性后的SiO2

    Figure  4.  Infrared spectra and local magnified images of nano SiO2 before and after modification: ((a), (a1), (a2)) Unmodified SiO2; ((b), (b1), (b2)) Modified SiO2

    图  5  碳纤维的XPS图谱的C1s分峰拟合曲线

    Figure  5.  C1s fitting curves of XPS spectrum of carbon fiber

    图  6  CF表面的SEM和AFM图像:((a1)~(a4))未改性CF;((b1)~(b4)) CF-KH550;((c1)~(c4)) CF-KH550-SiO2;((d1)~(d4)) CF-KH550-PU-SiO2

    Figure  6.  SEM and AFM images of CF surfaces: ((a1)-(a4)) Untreated CF; ((b1)-(b4)) CF-KH550; ((c1)-(c4)) CF-KH550-SiO2; ((d1)-(d4)) CF-KH550-PU-SiO2

    图  7  碳纤维TEM图像及局部放大图:((a1), (a2)) CF;((b1), (b2)) CF-KH550;((c1)~(c3)) CF-KH550-SiO2;((d1), (d2)) CF-KH550-PU-SiO2

    Figure  7.  TEM microstructures of different CFs surfaces: ((a1), (a2)) CF; ((b1), (b2)) CF-KH550; ((c1)-(c3)) CF-KH550-SiO2; ((d1), (d2)) CF-KH550-PU-SiO2

    图  8  碳纤维表面的静态接触角(a)、动态接触角(b)及其表面能(c)

    Figure  8.  Static contact angle (a), dynamic contact angle (b) and surface energy (c) of CF

    图  9  碳纤维复合材料界面剪切强度(IFSS) (a)和层间剪切强度(ILSS) (b)

    Figure  9.  Interfacial shear strength (IFSS) (a) and interlaminar shear strength (ILSS) (b) of composites

    图  10  复合材料ILSS断口形貌:(a) CF/环氧树脂(EP);(b) CF-KH550/EP;(c) CF-KH550-SiO2/EP;(d) CF-KH550-PU-SiO2/EP

    Figure  10.  Cross-section morphology of composite: (a) CF/epoxy resin (EP); (b) CF-KH550/EP; (c) CF-KH550-SiO2/EP; (d) CF-KH550-PU-SiO2/EP

    图  11  复合材料ILSS断面形貌及局部放大图: ((a1), (a2)) CF/EP;((b1), (b2)) CF-KH550-SiO2/EP;((c1), (c2)) CF-KH550-PU-SiO2/EP

    Figure  11.  Cross-section of morphology of CF/EP composite: ((a1), (a2)) CF/EP; ((b1), (b2)) CF-KH550-SiO2/EP; ((c1), (c2)) CF-KH550-PU-SiO2/EP

    图  12  拔脱前的CF/EP微滴及放大图((a), (b))、拔脱后的CF/EP (c)及CF-KH550-PU-SiO2/EP (d)的SEM图像

    Figure  12.  SEM images of before (a) and partial enlarged view (b) removal of desized CF/EP composite, CF/EP (c) and CF-KH550-PU-SiO2/EP (d) composite after removal

    图  13  不同碳纤维的界面增强机制示意图

    Figure  13.  Schematic diagram of the interface enhancement mechanism of different CFs

    表  1  测试液的极性分量$ {\gamma }_{{\rm{l}}}^{{\rm{p}}} $、色散分量$ {\gamma }_{{\rm{l}}}^{{\rm{d}}} $及表面能$ {\gamma }_{\rm{{l}}} $

    Table  1.   Polar component$ {\gamma }_{{\rm{l}}}^{{\rm{p}}} $, dispersive component $ {\gamma }_{{\rm{l}}}^{{\rm{d}}} $ and surface free energy $ {\gamma }_{{\rm{l}}} $ of the testing liquids (mJ·m−2)

    Testing liquid$ {\gamma }_{{\rm{l}}}^{{\rm{p}}} $$ {\gamma }_{{\rm{l}}}^{{\rm{d}}} $$ {\gamma }_{{\rm{l}}} $
    Water5121.872.8
    CH₂I₂ 050.850.8
    下载: 导出CSV

    表  2  CF表面元素含量变化

    Table  2.   Changes in surface element content of CF

    SampleElement/wt%
    C1sO1sN1sSi2p
    CF 81.33 16.01 2.33 0.33
    CF-KH550 70.53 22.64 4.74 2.09
    CF-KH550-SiO2 51.36 30.42 3.48 15.74
    CF-KH550-PU-SiO2 29.09 42.80 6.43 21.68
    下载: 导出CSV
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出版历程
  • 收稿日期:  2022-11-21
  • 修回日期:  2022-12-29
  • 录用日期:  2023-01-08
  • 网络出版日期:  2023-01-18
  • 刊出日期:  2023-11-01

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