Ca2+ assisted enhancement of CNT/PEEK interfacial bonding and its conductive composites preparation and performance study
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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。Abstract: Polyether ether ketone (PEEK) is a high-performance engineering polymer that has garnered attention from researchers because of its remarkable specific strength, good corrosion resistance, and high temperature resistance. However, its insulating qualities restrict its use in applications like electromagnetic absorption, anti-static, and sensing applications. CNT reinforcement has been acknowledged as a successful technique for concurrently enhancing the mechanical properties and electrical conductivity of PEEK. Nevertheless, because of the high inertness of the PEEK and CNT surfaces as well as the different dispersing systems, it is difficult to disperse CNT in the PEEK matrix. This has a significant negative effect on the performance of CNT/PEEK composites. Based on this, in this study, ethanol-deionized water binary solvent was used to improve the dispersion of acidified CNT (aCNT) and PEEK powders. Calcium ion (Ca2+) was then used as an intermediate to bridge aCNT and PEEK to prepare aCNT-Ca2+/PEEK composite powders, which were then hot-pressed to produce highly conductive, mechanically enhanced aCNT/PEEK composites. FTIR, XPS, and Zeta potential experiments were used to thoroughly analyze the mechanism of Ca2+ bridging PEEK with aCNT. The findings demonstrate that, with the addition of Ca2+, aCNT can uniformly adsorb on the surface of PEEK, which produces a composite powder with a core-shell structure. By hot pressing this composite powder, a multi-channel three-dimensional conductive network may be produced. The obtained composite exhibits a conductivity of 9.9×10−4 S/cm at the conductive percolation threshold of 1.5 wt%, which is over 12 orders of magnitude higher than the conductivity of pure PEEK resin; the conductivity increased to 3.5 × 10−2 S/cm at a 5 wt% aCNT concentration. The composites reached their maximum tensile strength of 92.87 MPa at a 1 wt% filler, a 15.7% increase over the pure PEEK resin. Furthermore, the conductive composite exhibits good temperature-sensitivity qualities, and its temperature-conductivity paths remain consistent across different heating methods and multiple heating processes, demonstrating stable sensing characteristics. Therefore, the aCNT-Ca2+/PEEK composites show great promise in temperature sensing, mechanical enhancement, and electrical conductivity.
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Key words:
- CNT /
- Ca2+ /
- PEEK /
- dispersion /
- interface bonding /
- conductive composite materials /
- mechanical properties
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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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