Surface characterization of polyether-ether-ketone by inverse gas chromatography and the application in the improvement of thermoplastic composites interlaminar performance
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摘要: 高性能热塑性聚醚醚酮树脂基复合材料具有高韧性、耐疲劳、原材料可长期贮存、成型速度快、可重复加工和回收再利用等独特优势，在航空航天等工业领域应用广泛。粉末悬浮法通过将聚醚醚酮细粉配制成水基悬浮液实现对纤维充分浸渍，现已成为制备连续纤维增强热塑性预浸料的重要方式。本文重点开展反气相色谱法研究聚醚醚酮表面性质，并结合微观形貌、粒径分布等方面对比国内外聚醚醚酮树脂的差异。研究表明：进口聚醚醚酮树脂色散表面能(19.2 mJ/m2)明显低于同级别国产树脂(41.1 mJ/m2)；极性探针分子吸附于聚醚醚酮表面的驱动力主要是酸碱作用力，表面总体表现为碱性。进口聚醚醚酮树脂相比于国产具有更高的极性，使其更容易分散在水中；而国产聚醚醚酮树脂微观形貌、表面性质则更加均匀。表面性质研究指导水基悬浮液配制，制备的连续纤维增强热塑性预浸料质量优异，孔隙率低于0.5%且纤维排布整齐，热塑性复合材料层压板层间剪切强度平均值达109 MPa，与传统热熔浸渍方法相比提升30%以上。Abstract: High performance polyether-ether-ketone (PEEK) thermoplastic composites have the advantages of good impact and fatigue resistance, unlimited ambient temperature storage life, short molding cycles, being recyclable and good reprocessing ability, which have been widely used in aerospace and other industry domains. Powder impregnation method can realize the infiltration of resin particles into fibers by water-based suspension, which has become an effective technical route for preparing continuous fiber reinforced thermoplastic prepregs. This paper focused on the surface characterization of PEEK produced in both domestic and overseas by inverse gas chromatography (IGC) as well as the comparison of microstructure and size distribution. The results show that the dispersion surface energy value of imported PEEK (19.2 mJ/m2) is obviously lower than the domestics (41.1 mJ/m2). The driving force of the adsorption between PEEK particles and polar probe molecules is acid-base interaction in nature, while the surface of PEEK particles is generally alkaline. With higher surface polarity, imported PEEK can more easily disperse into water through the dispersant. By preparing the water-based resin slurry based on the surface characterization results, the thermoplastic prepregs produced with powder impregnation method show excellent quality. The porosity of the powder impregnation prepregs is less than 0.5% and fibers are neatly arranged, with the short beam shear strength of 109 MPa, 30% higher comparing with prepregs produced by traditional hot melt impregnation method.
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图 1 悬浮浸渍工艺PEEK热塑性预浸料制备示意图
①—Fiber unwinding; ②—Suspension impregnation; ③—Melt impregnation; ④—Cooling
Figure 1. Diagram of powder impregnation PEEK thermoplastic prepreg preparation
图 2 PEEK树脂颗粒粒径分布图：(a) 进口树脂；(b) 国产树脂
Figure 2. Particle size distribution graphs of PEEK: (a) Imported resin; (b) Domestic resin
D10, D50, D90—Size below which 10%, 50%, 90% of all particles are found
图 3 PEEK树脂的SEM图像：((a), (c), (e)) 进口树脂；((b), (d), (f)) 国产树脂
Figure 3. SEM images of PEEK resin: ((a), (c), (e)) Imported resin; ((b), (d), (f)) Domestic resin
图 4 PEEK树脂的吸附自由能ΔGa和正烷烃探针的碳原子数的线性关系图
Figure 4. Linear relationship between adsorption free energy ΔGa and carbon number of n-alkane probes obtained on PEEK resins
图 5 PEEK树脂的支链烷烃和环烷烃数据与正烷烃拟合直线的比较
Figure 5. Branched and cyclic alkanes versus n-alkanes of PEEK resins
图 6 PEEK树脂的不同极性探针和正烷烃拟合直线的吸附自由能数据获得相应Isp值
THF—Tetrahydrofuran; MeAcet—Methyl acetate
Figure 6. Adsorption free energy data of polar and n-alkane probes straight lines used for the Isp values determination of PEEK resins
图 7 Gutmann法计算PEEK样品酸性常数Ka和碱性常数Kb
AN—Acceptor number; DN—Donor number
Figure 7. Gutmann method used to achieve the acidity constant Ka and basic constant Kb of PEEK resins
图 8 PEEK树脂正辛烷探针的吸脱附等温曲线
Qads—Reversibly adsorbed amounts
Figure 8. Reversible n-octane desorption isotherms of PEEK resin
图 9 PEEK树脂吸附能量分布函数曲线(绝对位点数量)
Figure 9. Adsorption energy distribution functions curve of PEEK resins (Absolute adsorption site number)
图 10 PEEK树脂吸附能量分布函数曲线(标准化为1 μmol位点)
Figure 10. Adsorption energy distribution functions curve of PEEK resins (Normalized to 1 μmol adsorption site)
图 11 (a) 所制备热塑性预浸料实物；粉末悬浮浸渍工艺 (b) 和传统挤出热熔浸渍工艺 (c)下的纤维树脂分布金相显微镜图像
Figure 11. (a) Photograph of as-prepared thermoplastic prepreg; Metallographic microscope of fiber resin distribution of prepregs using powder impregnation method (b) and traditional hot melt impregnation method (c)
图 12 热塑性复合材料层压板无损检测评价：(a) 三维CT扫描；(b) 超声扫描
Figure 12. Nondestructive testing evaluation of thermoplastic composite laminates: (a) Three-dimensional computed tomography scanning; (b) Ultrasonic scanning
图 13 热塑性复合材料层间剪切性能：(a) 室温干态；(b) 高温湿态
Figure 13. Interlaminar shear performance of thermoplastic composites: (a) Room temperature and dry; (b) High temperature and humidity
图 14 热塑性复合材料层间剪切断面的SEM图像：(a)室温干态；(b)高温湿态
Figure 14. Interlaminar shear section SEM images of thermoplastic composites: (a) Room temperature and dry; (b) High temperature and humidity
表 1 聚醚醚酮(PEEK)悬浮液配制比例表
Table 1. Compound of polyether ether ketone (PEEK) resin suspension system
Sample PEEK/kg AOT/kg H2O/kg Brand 1 10 2 200 VESTAKEEP® 2 10 6 200 PFLUON® Note: AOT—Docusate sodium. 
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表 2 PEEK树脂的色散表面能数据
Table 2. Dispersion surface energy data of PEEK resins
∆Ga/(kJ·mol–1) $\gamma _{\rm{s}}^{\rm{D}}/{\rm{(mJ \cdot m^{-2})}}$ R2 Imported resin 1.794±0.021 19.2±0.4 0.9997 Domestic resin 2.626±0.012 41.1±0.4 1.0000 Notes: ∆Ga—Free energy of adsorption; $\gamma _{\rm{s}}^{\rm{D}}$—Dispersive component of surface energy; R2—Coefficient of determination.
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表 3 PEEK树脂的形态学指数(IM)
Table 3. Results of morphology index (IM) of PEEK resins
IM (Isooctane) IM (Cyclooctane) Imported resin 0.261±0.001 0.595±0.012 Domestic resin 0.340±0.007 0.801±0.016
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表 4 PEEK树脂在极性探针下Isp数据
Table 4. Results of specific interaction Isp using polar probes of PEEK resins
Imported resin Domestic resin Acetonitrile 13.5±0.1 12.2±0.1 Chloroform 12.6±0.1 11.1±0.1 Acetone 10.9±0.1 8.9±0.1 Me-Acetate 9.8±0.2 7.2±0.2 Ether 5.4±0.2 3.2±0.2 THF 10.4±0.2 7.0±0.2 Benzene 11.1±0.2 8.2±0.2 ΣIsp 73.7±1.1 57.8±1.1
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表 5 计算所得PEEK树脂的酸碱常数值
Table 5. Results of the Ka and Kb constants of PEEK resins
Ka Kb Imported resin 11.0 83.4 Domestic resin 2.6 70.1
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表 6 PEEK树脂比表面积数据
Table 6. Specific surface area data of PEEK resins
Q0/(μmol·g-1) SBET/(m2·g-1) Imported resin 26.5±0.3 10.1±0.1 Domestic resin 111.9±10.4 42.4±3.9 Notes: Q0—Amount of adsorbed n-octane; SBET—specific surface area.
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