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Ca2+辅助增强CNT/PEEK界面结合及其导电复合材料制备与性能

徐建蓉 梅启林 姜端洋 蔡永祺 刘备 丁国民

徐建蓉, 梅启林, 姜端洋, 等. Ca2+辅助增强CNT/PEEK界面结合及其导电复合材料制备与性能[J]. 复合材料学报, 2024, 42(0): 1-16.
引用本文: 徐建蓉, 梅启林, 姜端洋, 等. Ca2+辅助增强CNT/PEEK界面结合及其导电复合材料制备与性能[J]. 复合材料学报, 2024, 42(0): 1-16.
XU Jianrong, MEI Qilin, JIANG Duanyang, et al. Ca2+ assisted enhancement of CNT/PEEK interfacial bonding and its conductive composites preparation and performance study[J]. Acta Materiae Compositae Sinica.
Citation: XU Jianrong, MEI Qilin, JIANG Duanyang, et al. Ca2+ assisted enhancement of CNT/PEEK interfacial bonding and its conductive composites preparation and performance study[J]. Acta Materiae Compositae Sinica.

Ca2+辅助增强CNT/PEEK界面结合及其导电复合材料制备与性能

基金项目: 湖北省自然科学基金面上项目(2022 CFB384);国家自然科学基金 (52003120);武汉理工大学自主创新研究基金(2022 IVA004);江苏省“双创博士”人才计划
详细信息
    通讯作者:

    丁国民,博士,副教授,硕士生导师,研究方向为研究方向为纳米功能复合材料、特种工程热塑性复合材料 E-mail: sdscdgm@126.com

  • 中图分类号: TB332

Ca2+ assisted enhancement of CNT/PEEK interfacial bonding and its conductive composites preparation and performance study

Funds: Hubei Provincial Natural Science Foundation of China (2022 CFB384); National Natural Science Foundation of China (52003120); Fundamental Res-earch Funds for the Central Universities (2022 IVA004) and Shuangchuang Project of Jiangsu Province.
  • 摘要: 作为特种工程塑料,聚醚醚酮(PEEK)凭借高比强度、耐腐蚀、耐高温性能引起人们的研究兴趣。但PEEK的绝缘性限制了其在传感、防静电及电磁吸收等领域的应用。利用碳纳米管(CNT)作为增强体,同时提高PEEK的导电性能和力学性能已被公认为是一种行之有效的方法。然而由于CNT和PEEK表面均具有较强惰性,且两者适用的分散体系不同,从而严重影响了CNT/PEEK复合材料的性能。基于此,本研究通过乙醇-去离子水二元溶剂提高酸化CNT(aCNT)和PEEK粉体的分散性,并利用金属阳离子:钙离子(Ca2+)作为中间体桥联aCNT与PEEK,制备树脂未改性的aCNT-Ca2+/PEEK复合粉体,进而通过热压工艺得到了高导电、力学性能增强的aCNT-Ca2+/PEEK复合材料。通过FTIR、XPS、Zeta电位等测试深入探究了Ca2+桥联PEEK与aCNT的作用机制。结果表明:加入Ca2+后,aCNT能够均匀地吸附在PEEK表面,形成核壳结构的复合粉体,利用此复合粉体热压后可得到多通道三维导电网络。制得的复合材料导电渗流阈值为1.5 wt%,此时的电导率为9.9×10−4 S/cm,相较于纯PEEK树脂电导率提升了近12个数量级;aCNT含量为5 wt%时,电导率达到最大值3.5×10−2 S/cm。在填料含量为1 wt%时,复合材料拉伸强度达到最大,为92.87 MPa,相比于纯PEEK树脂提升了15.7%。此外,该导电复合材料具有良好的温敏特性,其温度-电导率在不同升温方式、多次升温过程中路径保持一致,表现出稳定的传感特性。因此,本文制备的aCNT-Ca2+/PEEK复合材料在导电、力学性能增强及温度感知等方面有巨大应用潜力。

     

  • 图  1  酸化碳纳米管(aCNT)-Ca2+/聚醚醚酮(PEEK)复合材料的制备示意图

    Figure  1.  Schematic preparation of acidified carbon nanotubes (aCNT)-Ca2+/Polyether ether ketone (PEEK) composites

    图  2  (a)、(b):相同含量的PEEK、aCNT在不同溶剂中的数码照片及紫外-可见光光谱图;(c)不同状态CNT在二元溶剂中的数码照片及紫外-可将光光谱图

    Figure  2.  (a), (b)Digital photos and UV-Vis spectra of the same content of PEEK and aCNT in different solvents; (c)Digital photos and UV-Vis spectra of CNT in different states in binary solvents

    图  3  PEEK、aCNT及混合粉末的溶液在加入不同金属阳离子后的沉降效果数码照片

    Figure  3.  Digital photos of the sedimentation effects of PEEK, aCNT and mixed powder solutions after adding different metal cations

    图  4  (a)、(b):Ca2+/PEEK的FTIR图谱及C=О、C—O—C特征伸缩振动峰放大图;(c) PEEK、Ca2+/PEEK的拉曼光谱中C=О、C—O—C特征峰;(d) CaCl2、Ca2+/PEEK中Ca2+的XPS图谱;(e) PEEK中C1 s的XPS图谱、(f) Ca2+/PEEK中C1 s的XPS图谱;(g) Ca2+/PEEK配合物的形成示意图

    Figure  4.  (a), (b): FTIR spectra of Ca2+/PEEK and characteristic stretching vibrational peaks of C=О、C—O—C; (c) Raman spectra of PEEK, Ca2+/PEEK characteristic peaks of C=О, C—O—C; (d) XPS patterns of Ca2+ in CaCl2, Ca2+/PEEK; (e) XPS patterns of C1 s in PEEK; (f) XPS patterns of C1 s in Ca2+/PEEK; (g) Formation process of Ca2+/PEEK complexes

    图  5  不同Ca2+含量下PEEK的DSC、DTG图

    Figure  5.  DSC and DTG diagrams of PEEK with different Ca2+ contents

    图  6  (a)不同Ca2+浓度下aCNT的Zeta电位;(b) aCNT-Ca2+的形成示意图;(c) aCNT-Ca2+/PEEK的形成示意图

    Figure  6.  (a) Zeta potential diagram of aCNT at different Ca2+ concentrations; (b) Formation process of aCNT-Ca2+; (c) Schematic representation of the formation of aCNT-Ca2+/PEEK

    图  7  不同Ca2+含量下:(a)混合粉体沉降状态数码照片;(b)混合粉体溶液在沉降前的紫外-可见光谱图;(c) 混合粉体干燥后的SEM图;(d)复合材料的电导率;(e)~(f) Ca2+加入前后aCNT的分散状况TEM图

    Figure  7.  Different Ca2+ contents:(a) Digital photographs of the settling state of the mixed powders; (b) UV spectra of the mixed powder solution before settling; (c) SEM images of the mixed powders after drying; (d) electrical conductivity of the composites; (e)~(f) TEM images of the dispersion state of aCNT before and after Ca2+ addition

    图  8  (a)室温下不同aCNT含量的aCNT-Ca2+/PEEK复合材料的导电率; (b)质量分数的双对数曲线

    Figure  8.  (a) Electrical conductivity of aCNT-Ca2+/PEEK composites with different aCNT contents at room temperature; (b) Double logarithmic curves of the mass fraction

    φc: The percolation threshold; t: The critical index; R2: Goodness of Fit

    图  9  不同aCNT含量下:(a)温敏曲线;(b)持续升温和间隔升温时的温度-电导率变化;(c)经历多次持续升温后的温度-电导率变化

    Figure  9.  Different CNT contents of (a) Temperature sensitivity curve; (b) Temperature-conductivity changes during continuous heating and interval heating; (c) Temperature-conductivity changes after multiple continuous heating

    图  10  (a)、(b) 不同CNT含量的aCNT-Ca2+/PEEK复合材料的应力-应变曲线及拉伸强度;(c)~(f) 不同CNT含量的aCNT-Ca2+/PEEK复合材料断裂面SEM图

    Figure  10.  (a), (b) Stress-strain curves and tensile strength of aCNT-Ca2+/PEEK composites with different CNT contents; (b)~(e) Fracture surface SEM image with different CNT contents

    表  1  不同CNT/PEEK复合材料的导电性能

    Table  1.   Conductive properties of different CNT/PEEK composite materials

    Name Experimental Methods φc/wt% Maximum filler content/wt%) Maximum conductivity/(S·cm−1)
    PEEK/MWCNT[39] Melt blending 3.6 10 10−5
    PEEK/CNT[6] Solution mixing 3 5 2.0× 10−5
    AgGNT/PEEK[40] Molecular mixing - 6 10−3
    PEEK/Wh-CNT[7] Melt blending - 10 9.12×10−2
    This work Solution mixing 1.5 5 3.5×10−2
    Notes: MWCNT is multi-walled carbon nanotubes; AgGNT is the Ag nanoparticles decorated GO-CNT (GNT) nanostructures; Wh‐CNTs is whisker CNTs
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  • 文章访问数:  103
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出版历程
  • 收稿日期:  2024-02-29
  • 修回日期:  2024-04-25
  • 录用日期:  2024-04-25
  • 网络出版日期:  2024-05-14

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