Effect of high-temperature gas-phase oxidation of carbon fiber on tensile and interlaminar shear properties of PEEK composites
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摘要: 聚醚醚酮(PEEK)复合材料具有优异的抗冲击性能，在航空领域具有重要的应用价值。然而，聚醚醚酮复合材料成型温度高，成型过程中可能存在环氧上浆剂分解残留，导致界面强度降低、载荷传递变差等问题，影响其使用性能。系统地研究了碳纤维(CF)高温气相氧化对CF/PEEK复合材料拉伸和层间剪切性能的影响。首先采用不同氧化工艺处理碳纤维，采用XPS、IGC、复丝拉伸等方法表征了碳纤维表面活性、表面能以及拉伸性能。结果表明，合适的氧化条件有利于改善纤维表面活性和表面能，但同时会降低纤维拉伸强度。采用熔体法制备了CF/PEEK预浸料，研究了高温气相氧化对CF/PEEK复合材料拉伸和层间剪切性能的影响。结果表明，纤维高温氧化后CF/PEEK复合材料0°拉伸强度下降超过20%，表明高温氧化会导致纤维严重损伤；90°拉伸强度变化不超过10%，层间剪切强度变化小于5%，表明碳纤维高温氧化未能实现复合材料界面性能改善。上述结果表明，在预浸料制备工艺中增加碳纤维高温氧化工序，不利于改善复合材料性能。Abstract: Polyetheretherketone (PEEK) composites have excellent impact resistance and thus have important potential application value in aviation field. However, the molding temperature of PEEK composites is too high for carbon fiber (CF) with epoxy sizing agent, which will result in the decomposition of sizing agent and further cause the reduction of interface strength and deterioration of load transfer. It will affect the application of PEEK composites. The effect of high-temperature gas-phase oxidation of CFs on the tensile and interlaminar shear properties of PEEK composites was systematically studied. CFs oxidized under different conditions were firstly prepared and characterized by XPS, IGC, bundle tensile testing to study the effect of oxidation on surface activity, surface energy and mechanical properties of CFs. The results show that appropriate oxidation conditions are beneficial to improving surface activity and surface energy of the CFs, while oxidation will decrease the tensile strength of CFs. CF/PEEK prepregs were prepared using the melt method, and the tensile properties and interlaminar shear properties of the composites were compared between untreated fibers and oxidized fibers. The results show that after oxidation, the 0° tensile strength decreases by more than 20%, indicating that high-temperature oxidation of CFs will cause fiber damage; the difference in 90° tensile strength does not exceed 10%, and the difference in interlaminar shear strength is less than 5%, indicating that the high-temperature oxidation of CFs failed to improve the interface properties of the composites. The above results show that adding the high-temperature oxidation process of CFs to the prepreg preparation process is not conducive to improve composite properties.
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图 6 预浸料截面抛光形貌(a)纤维未处理(b)纤维高温处理
Figure 6. Sectional polished morphology of prepregs (a) CF untreated,(b) CF oxidized at high-temperature
图 8 聚醚醚酮复合材料0°拉伸断口宏观形貌(a)碳纤维未处理，(b)碳纤维高温处理
Figure 8. Fracture macro-morphology of 0° tensile samples of PEEK composites (a) CF untreated, (b) CF oxidized at high-temperature
图 9 聚醚醚酮复合材料0°拉伸试样截面抛光形貌(a)碳纤维未处理，(b)碳纤维高温处理
Figure 9. Sectional polished morphology of 0° tensile specimens of PEEK composites (a) CF untreated, (b) CF oxidized at high-temperature
图 10 试验件断口侧面形貌(a)碳纤维未处理，(b)碳纤维高温处理
Figure 10. Fracture side face morphology of specimens (a) CF untreated, (b) CF oxidized at high-temperature
图 11 试验件断口端面形貌(a)碳纤维未处理，(b)碳纤维高温处理
Figure 11. Fracture end face morphology of specimens (a) CF untreated, (b) CF oxidized at high-temperature
图 13 聚醚醚酮复合材料90°拉伸断口形貌(a)碳纤维未处理，(b)碳纤维高温氧化处理
Figure 13. fracture morphology of 90° tensile specimens of PEEK composites (a) CF untreated, (b) CF oxidized at high-temperature
表 1 碳纤维(CF)表面处理方法
Table 1. Surface treatment method of carbon fiber (CF)
Sample Method Temperature Time 1# Untreated — — 2# Oxidized 300℃ 60 s 3# Oxidized 300℃ 120 s 4# Oxidized 300℃ 600 s 5# Oxidized 350℃ 60 s 6# Acetone dissolved — — 
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表 2 碳纤维表面元素含量
Table 2. Surface element content of CFs
Sample Conditions Element content /mol % O/C C O Si N 1# Untreated 92.01 6.91 0.00 1.08 0.08 2# 300℃，60 s 93.65 6.35 0.00 0.00 0.07 3# 300℃，120 s 91.87 7.27 0.86 0.00 0.08 4# 300℃，600 s 88.49 8.54 0.97 1.20 0.10 5# 350℃，60 s 91.91 7.08 0.00 0.99 0.08 6# Acetone dissolved 94.39 5.61 0.00 0.00 0.06
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表 3 不同处理条件碳纤维表面官能团含量
Table 3. Content of CF surface functional groups under different conditions
sample conditions functional group content(mol%) —C—C—
or —C—H—C—OH
or —C—OR—COOH
or —COORratio of active functional
groups (mol%)1# untreated 83.08 16.13 0.79 16.92 2# 300℃，60 s 74.93 20.26 4.81 25.07 3# 300℃，120 s 65.34 26.67 7.99 34.66 4# 300℃，600 s 69.4 25.44 6.05 30.6 5# 350℃，60 s 64.95 30.21 4.84 35.05 6# acetone dissolved 82.37 9.84 7.80 17.64
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表 4 不同处理条件下碳纤维表面能
Table 4. Surface energy of CFs under different conditions
Sample Conditions γd/(mJ·m−2) γp/(mJ·m−2) γ/(mJ·m−2) 1# Untreated 38.33 7.33 45.66 2# 300℃，60 s 41.68 6.47 48.15 3# 300℃，120 s 42.58 6.34 48.92 4# 300℃，600 s 44.87 8.92 53.79 5# 350℃，60 s 42.68 6.86 49.54 6# Acetone dissolved 46.12 5.60 51.72 Note: γd: dispersion component，γp: polar component，γ: total surface energy
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