Synergistic Enhancement of Toughness and Viscosity of Carbon Nanotubes/Polyether Imide/Polyether Ether Ketone Nanocomposites
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摘要: 聚醚醚酮(PEEK)具有良好的力学性能，但其较高的熔体粘度导致其加工困难，因而限制了它的应用。本文采用湿粉法制备了碳纳米管(CNTs)和聚醚酰亚胺(PEI)修饰的PEEK纳米复合材料，纳米复合材料的熔体粘度降低了约50%。CNTs和PEI的加入使纳米复合材料的韧性得到协同提高，当PEI含量为4.95wt%，CNTs含量为0.05wt%时，纳米复合材料的断裂延伸率提高了129%，拉伸断裂能提高了97%。通过该方法制备的纳米复合材料熔体粘度较低，均匀分散的CNTs/PEI可以在不影响耐热性的前提下有效降低PEEK纳米复合材料的加工难度。这种粉末共混改性的方法有望应用于热塑性复合材料的粉末浸渍工艺或激光烧结技术。Abstract: Polyether ether ketone (PEEK) has favorable mechanical properties. However, its high melt viscosity limits its applications because it is hard to process. In this study, PEEK nanocomposites modified with carbon nanotubes (CNTs) and polyether imide (PEI) were prepared using a direct wet powder blending method. The melt viscosity of the nanocomposites decreased by approximately 50%. Under optimal conditions, the addition of CNTs and PEI resulted in a synergistic increase in the toughness of the nanocomposites. The elongation at break increased by 129%, and the fracture energy increased by 97%. The uniformly dispersed CNTs/PEI powder reduces the processing difficulty of PEEK nanocomposites without affecting the heat resistance. The nanocomposites prepared by this method have lower melt viscosity. This improvement of the properties of PEEK would facilitate its use in the preparation of thermoplastic composites by powder impregnation or laser sintering technology.
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Figure 1. Sample preparation, (a) The amination modification and in situ polymerization, and (b) CNT/PEI powder preparation and powder blending
Figure 2. Characterization of CNT-COOH and CNT-NH2, (a) Photographs of functionalized CNTs dispersed in anhydrous ethanol after different standing times. (b) FTIR spectra, (c) XPS survey spectra, (d) XPS spectra of CNT-COOH at C1s region, (e) XPS spectra of CNT-NH2 at C1s region, and (f) XPS spectra of CNT-NH2 at N1s region
Figure 3. Characterizations of CNTs/PEI, (a) FTIR spectra of CNTs/PEI, (b) TG curves of CNTs/PEI powder, (c) SEM image of PEI-0, (d) SEM image of PEI-1, and (e) SEM image of PEI-2
Figure 4. Rheological curves of PEEK nanocomposites, and (a) Viscosity vs. temperature at a shear rate of 0.016 Hz. (b) Viscosity vs. shear rate at a temperature of 390 °C
Figure 5. The tensile properties of the PEEK nanocomposites: (a) Tensile strength, modulus, and elongation at break (n = 6), (b) Tensile fracture toughness, and (c) Tensile stress–strain curve
Figure 6. (a) Flexural strength and flexural modulus (n = 6) and (b) Notched Izod impact strength (n = 6)
Figure 7. Cross-sectional SEM images of the tensile-fractured surfaces of the PEEK nanocomposites
Figure 8. Crystallization behavior of PEEK nanocomposites under POM: (a)–(d) P0, (e)–(h) P5, and (i)–(l) C5
Figure 10. Schematic illustration of the deformation behavior in PEEK nanocomposites: (a) The C1, C2, and C5 nanocomposites, (b) P0 nanocomposites. (c) P1 nanocomposites, and (d) P2 and P5 nanocomposites
Table 1. Compositions of the PEEK nanocomposite samples
Sample name PEEK (wt%) CNTs (wt%) Addition P0 100 0 0 P1 99.95 0.05 0 P2 99.9 0.1 0 P5 99.75 0.25 0 C0 95 0 5 wt% PEI-0 C1 95 0 5 wt% PEI-1 C2 95 0 5 wt% PEI-2 C5 95 0 5 wt% PEI-5 
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Table 2. Mechanical testing standards
Group/shape Testing Speed (mm/min) Standards Dumbbell Tensile test 1.0 GB/T 1040.1-2018/ISO 527-1:2012 Rectangular Flexural test 2.0 GB/T 9341-2008/ISO 178:2001 Notched sample Charpy impact test - GB/T 1043.1-2008/ISO 179-1:2000 Notched sample Single-edge notched bend test 10 ASTM D5045-14
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Table 3. Characteristic temperatures and crystallinity of PEEK nanocomposites
Sample name Ti (°C) Tmax (°C) Tg (°C) Tm (°C) ΔHm (J/g) Xm (%) P0 561 586 155.9 347.7 54.09 41.6 P1 566 590 154.6 346.9 58.09 44.7 P2 563 591 154.1 346.4 53.83 41.4 P5 566 589 157.4 346.1 53.49 41.2 C0 541 566 155.7 346.1 47.10 38.1 C1 546 584 159.9 348.2 48.95 39.6 C2 544 580 157.6 345.1 50.42 40.8 C5 542 576 153.6 345.9 47.72 38.6
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Table 4. Relevant studies on PEEK nanocomposites
Fillers Fabrication methods Content (wt%) Elongation at break (%) Increasement (%) Reference CNTs fused filament fabrication
additive manufacturing1 2.4 −22 [48] graphene nanoplatelets 3 3.5 12 CNTs compatibilized with polysulfones melt blending 0.1 (CNTs) 13.2 7 [45] graphene oxide melt blending 0.5 25 86.3 [19] TiO2 melt blending 3 42 20 [47] CNTs/PEI powder blending 0.05 (CNTs) 93 129 This study
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