Mechanical properties and in vitro bioactivity of surface-modified mesoporous bioglass-carbon fiber/polyetheretherketone ternary composites
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摘要: 碳纤维增强聚醚醚酮复合材料(CF/PEEK)因其稳定的化学性能、优异的物理和机械性能而被广泛应用于生物医学，并且CF/PEEK具有射线可透性，可作为骨科和牙科植入物。但是由于CF/PEEK的表面呈现出生物惰性，会导致骨整合不良。生物玻璃(BGs)具有良好的骨传导性能和一定的骨诱导性能。为了能够使CF/PEEK在保持优秀的力学性能的同时具有生物活性，在本文中选取了无孔BGs、介孔BGs(MBG，孔径5 - 7 nm)和通过氯化钙(CaCl2)进行改性后的介孔BGs(Ca-MBG)三种生物玻璃，分别制备得到BG-CF/PEEK、MBG-CF/PEEK和Ca-MBG-CF/PEEK三种三元复合材料。测试结果显示，BG-CF/PEEK、MBG-CF/PEEK和Ca-MBG-CF/PEEK的拉伸强度分别为114.85 MPa、111.34 MPa和92.45 MPa。制备的三元复合材料未使CF/PEEK的拉伸强度大幅下降。通过羟基磷灰石形成与骨髓间充质干细胞表面粘附进行的体外生物活性试验结果表明，加入通过CaCl2进行表面处理后的介孔BGs的样品类骨沉积量与表面粘附细胞数量最高，能明显增强CF/PEEK的生物活性。
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关键词:
- 碳纤维/聚醚醚酮复合材料 /
- 生物玻璃 /
- 力学性能 /
- 生物活性[1]
Abstract: Carbon fiber reinforced polyether ether ketone (CF/PEEK) are widely used in biomedical applications due to their stable chemical properties, excellent physical and mechanical properties, and the radiopacity of CF/PEEK for orthopedic and dental implants. However, CF/PEEK may lead to poor osseointegration due to the biologically inert surface it presents. Bioactive glasses (BGs) have good osteoconductive properties and weak osteoinductive properties, but due to their low mechanical strength and brittleness, they can easily cause stress shielding resulting in bone fixation failure. In this work, to make CF/PEEK bioactive while maintaining excellent mechanical properties, three bioactive glasses, namely, nonporous BGs, mesoporous BGs (MBG, pore size of 5 - 7 nm), and mesoporous BGs after surface treatment (Ca-MBG) by calcium chloride (CaCl2), were selected and prepared with CF/PEEK to form BG-CF/PEEK, MBG-CF/PEEK and Ca-MBG-CF/PEEK three composites. The test results showed that the tensile strengths of BG-CF/PEEK, MBG-CF/PEEK, and Ca-MBG-CF/PEEK were 114.85 MPa, 111.34 MPa, and 92.45 MPa, respectively. The mechanical strength of CF/PEEK was not decreased by the prepared composites. In vitro bioactivity assays were performed by formation of hydroxyapatite and surface adhesion of bone marrow mesenchymal stem cells (BMSCs). The results showed that the amount of bone deposition and the number of surface-adherent cells were highest in the composites with the addition of mesoporous BGs that were surface-treated via CaCl2, which could significantly enhance the bioactivity of CF/PEEK.-
Key words:
- CF/PEEK composites /
- Bioglass /
- Mechanical properties /
- Bioactivity
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图 1 三种生物玻璃(BGs)的微观形貌
Figure 1. Micro morphology by SEM of three Bioactive glasses (BGs)
图 4 生物玻璃-碳纤维/聚醚醚酮复合材料的表面微观形貌
Figure 4. Surface micro morphology by SEM of the bioglass-carbon fiber/polyetheretherketone composites
图 5 生物玻璃-碳纤维/聚醚醚酮复合材料的表面元素分布
Figure 5. Surface elements of the bioglass-carbon fiber/polyetheretherketone composites
图 6 力学性能：(a)拉伸强度；(b)拉伸模量；(c)拉伸应力应变曲线；(d)弯曲强度；(e)弯曲模量；(f)弯曲应力应变曲线；(g)冲击强度；(h)维氏硬度，**代表p < 0.01
Figure 6. Mechanical properties: (a) tensile strength; (b) tensile modulus; (c) tensile stress- strain curve; (d) bending strength; (e) bending modulus;(f) bending stress- strain curve; (g) impact strength; (h) Vickers-hardness, ** represents p < 0.01
图 7 生物玻璃-碳纤维/聚醚醚酮复合材料的弯曲断裂截面微观形貌
Figure 7. Bending fracture surface micro morphology by SEM of the bioglass-carbon fiber/polyetheretherketone composites
图 9 生物玻璃-碳纤维/聚醚醚酮复合材料在SBF中浸泡28天的羟基磷灰石形成
Figure 9. Formation of hydroxyapatite of the bioglass-carbon fiber/polyetheretherketone composites soaking in SBF for 28 days
图 10 BMSCs在生物玻璃-碳纤维/聚醚醚酮复合材料表面的24 h粘附状态，BMSCs用FITC-鬼笔环肽荧光染色
Figure 10. The 24 h adhesion state of BMSCs on the surface of the bioglass-carbon fiber/polyetheretherketone composites, BMSCs were fluorescent stained with FITC-phalloidin
图 11 BMSCs在生物玻璃-碳纤维/聚醚醚酮复合材料表面的24 h粘附数量，**代表p < 0.01
Figure 11. The 24 h adhesion number of BMSCs on the surface of the bioglass-carbon fiber/polyetheretherketone composites , ** represents p < 0.01
图 12 BMSCs在生物玻璃-碳纤维/聚醚醚酮复合材料表面的24 h、48 h、72 h的细胞增殖活性，**代表p < 0.01
Figure 12. The cell proliferation activity of BMSCs on the surface of the bioglass-carbon fiber/polyetheretherketone composites for 24 h, 48 h and 72 h, ** represents p < 0.01
表 1 三种生物玻璃的元素原子比
Table 1. Element atoms of three BGs
O Na Si P Ca Cl BG 55.15 0.26 44.12 0.38 0.09 MBG 41.15 0 56.38 2.36 0.11 Ca-MBG 30.14 0 24.85 1.08 17.15 26.78 Notes：BG, MBG and Ca-MBG are respectively non-porous bioglass, mesoporous bioglass and mesoporous bioglass modified by calcium chloride. 
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表 2 生物玻璃-碳纤维/聚醚醚酮复合材料的表面元素原子比
Table 2. Surface element atoms of the bioglass-carbon fiber/polyetheretherketone composites
C O Na Si P Ca BG-CF/PEEK 79.80 17.96 1.09 0.82 0.08 0.25 MBG-CF/PEEK 75.47 21.96 1.31 0.75 0.05 0.46 Ca-MBG-CF/PEEK 80.59 17.53 0.44 0.64 0.05 0.75
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