Process and performance control of 3D printed continuous carbon fiber/poly(ether ketone ketone) composites
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摘要: 以高热性能热塑性树脂—聚醚酮酮(PEKK)为基体与连续碳纤维(CCF)进行原位浸渍3D打印,制备连续碳纤维/聚醚酮酮复合材料(CCF/PEKK),并系统研究了3D打印工艺参数中分层厚度、流量比、打印温度及成型方向对复合材料内部结构、基体结晶、表面质量及力学性能等方面的影响。通过扫描电子显微镜观察3D打印CCF/PEKK的微观结构,采用X射线衍射分析复合材料中基体的结晶性能,使用超景深显微镜观察分析3D打印CCF/PEKK的表面形貌,同时对复合材料进行弯曲性能和层间剪切性能测试。结果显示:当分层厚度为0.2 mm、流量比为85%、打印温度为395℃,并使用水平成型方向时,3D打印CCF/PEKK复合材料的综合性能最优,其中弯曲强度达302.0 MPa,层间剪切强度达24.1 MPa。CCF/PEKK的弯曲强度较3D打印纯PEKK提升194%,层间剪切强度较工艺调控前提升113%。表明在未使用任何附加优化手段的情况下,3D打印CCF/PEKK具备制造复杂结构工程零部件的潜力。Abstract: High thermal performance thermoplastic, poly(ether ketone ketone) (PEKK), was used as the matrix for in-situ impregnation 3D printing with continuous carbon fiber (CCF) to prepare continuous carbon fiber/poly(ether ketone ketone) composites (CCF/PEKK). The effects of layer thickness, flow ratio, print temperature and build orientation in 3D printing process parameters on the internal structure, matrix crystallization, surface quality and mechanical properties of the composites were systematically investigated. The microstructure of 3D printed CCF/PEKK was observed by scanning electron microscopy, the crystallization properties of the matrix were analyzed by X-ray diffraction, the surface morphologies of 3D printed CCF/PEKK was observed and analyzed by ultra-deep field microscopy, and the flexural properties and interlaminar shear strength of CCF/PEKK were also tested. The results shows that with the layer thickness of 0.2 mm, the flow ratio of 85%, the printing temperature of 395°C, and the build orientation of flat, the performance of 3D printed CCF/PEKK is optimal, including the flexural strength of 302.0 MPa and the interlaminar shear strength of 24.1 MPa. The flexural strength of CCF/PEKK is improved by 194% compared with 3D printed pure PEKK, and the interlaminar shear strength is improved by 113% after process optimization. It indicates that 3D printed CCF/PEKK has the potential to manufacture complex structural engineering parts without using any additional optimization.
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图 5 低流量比 ((a1) F=65%、L=0.2 mm;(a2) F=75%、L=0.3 mm)、中流量比 ((b1) F=75%、L=0.2 mm;(b2) F=85%、L=0.3 mm) 和高流量比((b1) F=85%、L=0.2 mm;(b2) F=95%、L=0.3 mm) CCF/PEKK截面SEM图像对比
Figure 5. SEM images of cross-sections of CCF/PEKK with low flow ratio ((a1) F=65%, L=0.2 mm; (a2) F=75%, L=0.3 mm), middle flow ratio ((b1) F=85%, L=0.2 mm; (b2) F=95%, L=0.3 mm) and high flow ratio ((b1)F=85%, L=0.2 mm; (b2) F=95%, L=0.3 mm)
图 7 不同流量比CCF/PEKK表面三维形貌:(a1) L=0.3 mm、F=95%;(a2) L=0.3 mm、F=85%;(a3) L=0.3 mm、F=75%;(b1) L=0.2 mm、F=85%;(b2) L=0.2 mm、F=75%;(b3) L=0.2 mm、F=65%
Figure 7. 3D morphologies of CCF/PEKK surfaces with different flow ratio: (a1) L=0.3 mm, F=95%; (a2) L=0.3 mm, F=85%; (a3) L
=0.3 mm, F=75%; (b1) L=0.2 mm, F=85%; (b2) L=0.2 mm, F=75%; (b3) L=0.2 mm, F=65% 图 11 打印温度为395℃并采用85%流量比时CCF/PEKK弯曲性能 (a) 和层间剪切强度 (b) 随分层厚度的变化;打印温度为395℃并采用0.2 mm分层厚度时CCF/PEKK弯曲性能 (c) 和层间剪切强度 (d) 随流量比的变化
Figure 11. Flexural properties (a) and interlaminar shear strength (b) of CCF/PEKK preparing at 395℃ and flow ratio of 85% with different layer thickness; Flexural properties (c) and interlaminar shear strength (d) of CCF/PEKK preparing at 395℃ and layer thickness of 0.2 mm with different flow ratio
表 1 3D打印制备连续碳纤维/聚醚酮酮复合材料(CCF/PEKK)工艺参数设定
Table 1. Process parameters setting of 3D printed continuous carbon fiber/poly(ether ketone ketone) composites (CCF/PEKK)
Process parameters Set value Other values of paraments Layer thickness L/mm 0.5, 0.4, 0.3, 0.2 F=85%, T=375℃, B=Flat Flow ratio F/% 65, 75, 85, 95 L=0.2/0.3 mm, T=375℃, B=Flat Print temperature T/℃ 375, 385, 395, 405 L=0.2 mm, F=85%, B=Flat Build orientation B Flat, on-edge L=0.2 mm, F=85%, T=395℃ 表 2 不同分层厚度下CCF/PEKK样品的总层数、基体挤出速度(Er)、挤出量(Ea)及纤维含量(Wf)
Table 2. Number of layers, matrix extrusion rate (Er), extrusion amount (Ea) and fiber content (Wf) of CCF/PEKK with different layer thickness
L/mm Number of layer Er/(mg∙min−1) Ea/mg Wf/wt% 0.5 4 48.1 400.5 14.3 0.4 5 37.3 403.8 17.1 0.3 7 32.2 393.1 20.0 0.2 10 23.0 383.2 25.8 表 3 不同流量比CCF/PEKK的Er和Ea
Table 3. Er and Ea of CCF/PEKK with different flow ratios
F/% L/mm Er/(mg∙min−1) Ea/mg 65 0.2 17.9 297.7 75 0.2 20.7 345.5 0.3 27.5 335.7 85 0.2 23.0 383.3 0.3 32.2 393.1 95 0.3 34.2 416.9 表 4 不同打印温度CCF/PEKK的结晶性能
Table 4. Crystallization properties of CCF/PEKK with different print temperature
375℃ 385℃ 395℃ 405℃ Xs/nm 8.8 9.7 10.8 13.4 Xc/% 6.0 7.5 8.7 10.0 Notes: Xs—Grain size of PEKK matrix in CCF/PEKK; Xc—XRD crystallinity of PEKK matrix in CCF/PEKK. 表 5 本文与3D打印短切碳纤维(CF)/PEEK和常规工艺制备CCF/PEKK力学性能及纤维含量的比较
Table 5. Comparison of mechanical properties and fiber content between 3D printed short carbon fiber CF/PEEK and CCF/PEKK composites of common processes and this work
Fabrication method Flexural strength/MPa ILSS/MPa Fiber content/wt% Ref. Hot press molding with CCF/PEKK prepreg 687.6 78.2 65.0 [43] Vacuum molding with dry PEKK powder and CCF 849.0 59.0 60.0 [44] Vacuum molding with CCF/PEKK prepreg — 30.9 66.0 [45] 3D printed short CF/PEEK 147.2 — 15.0 [20] 3D printed CCF/PEKK 302.0 24.1 25.8 This work -
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