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通过水热电沉积/水热处理制备的用于增强 HA 涂层在 C/C 复合材料上的粘附性能的聚乙烯醇/氧化石墨烯夹层。

Polyvinyl Alcohol/Graphene Oxide Interlayer for Enhancing Adhesive Performance of HA Coating on C/C Composites Prepared by Hydrothermal Electrodeposition/Hydrothermal Treatment.

机构信息

College of Materials, Shen Zhen Key Laboratory of Special Functional Materials, Shen Zhen University, Shen Zhen 518086, China.

Second People's Hospital of Changzhou, Nanjing Medical University, Changzhou 213003, China.

出版信息

ACS Appl Mater Interfaces. 2020 Dec 16;12(50):55710-55722. doi: 10.1021/acsami.0c17649. Epub 2020 Dec 2.

Abstract

Hydroxyapatite (HA) coatings directly deposited by hydrothermal electrochemical technology (HET) onto carbon/carbon (C/C) composites exhibited a catastrophic failure occurring at the interface of the HA and C/C. To overcome this problem, a polyvinyl alcohol (PVA)/graphene oxide (GO) interlayer (P/G interlayer) was applied on the (NH)SO-pretreated C/C substrate (named P/G-C/C) by using a dipping method. Subsequently, a calcium phosphate coating was deposited on P/G-C/C, shortened as M-P/G-C/C, by HET, and then converted into HA coating (abbreviated as HA-P/G-C/C) through posthydrothermal treatment. For comparison, HA coating was prepared onto C/C without a P/G interlayer through the same process, which was denoted as HA-C/C. The composition, microstructure, and morphology of the samples were characterized by X-ray diffractometry (XRD), energy-dispersive spectroscopy (EDS), scanning electron microscopy (SEM), Raman spectra, Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS). The adhesive performance of the coatings on C/C was measured by a scratch test. Finally, an in vitro bioactivity of the coatings was evaluated in a simulated body fluid solution at 37 °C. Results showed no apparent differences in the morphology and phase of the posttreated coatings, both of which are composed of a dense structure containing needle-like HA crystals. However, the HA-P/G-C/C sample possessed a higher Ca/P ratio and denser interface, thereby exhibiting higher adhesive performance and better bioactivity. The adhesive strength of the HA-P/G coating was observed at a critical load of 41.04 N, which increased by 29.3% relative to the HA coating. Moreover, the failure site was on the HA-P/G coating rather than at the interface. The enhanced adhesive performance was ascribed to the PVA/GO-repairing pits on C/C and PVA and GO toughening effects on the HA coating. In vitro and in vivo tests revealed no statistical significance for the two HA-coated C/C samples, although the HA-P/G coating exhibited better bioactivity, inducing the growth of bonelike apatite than the HA coating.

摘要

水热电化学技术(HET)直接沉积在碳/碳(C/C)复合材料上的羟基磷灰石(HA)涂层在 HA 和 C/C 的界面处发生灾难性失效。为了解决这个问题,通过浸渍法在(NH)SO 预处理的 C/C 基底(命名为 P/G-C/C)上施加了一层聚乙烯醇(PVA)/氧化石墨烯(GO)中间层(P/G 中间层)。随后,通过 HET 在 P/G-C/C 上沉积了磷酸钙涂层,简称 M-P/G-C/C,然后通过后水热处理将其转化为 HA 涂层(简称 HA-P/G-C/C)。为了比较,通过相同的工艺在没有 P/G 中间层的 C/C 上制备了 HA 涂层,标记为 HA-C/C。通过 X 射线衍射(XRD)、能谱(EDS)、扫描电子显微镜(SEM)、拉曼光谱、傅里叶变换红外(FTIR)和 X 射线光电子能谱(XPS)对样品的组成、微观结构和形貌进行了表征。通过划痕试验测量了涂层在 C/C 上的附着性能。最后,在 37°C 的模拟体液溶液中评价了涂层的体外生物活性。结果表明,后处理涂层的形貌和相没有明显差异,两者均由包含针状 HA 晶体的致密结构组成。然而,HA-P/G-C/C 样品具有更高的 Ca/P 比和更致密的界面,从而表现出更高的附着性能和更好的生物活性。在 41.04 N 的临界载荷下观察到 HA-P/G 涂层的附着强度,与 HA 涂层相比提高了 29.3%。此外,失效部位在 HA-P/G 涂层上,而不是在界面上。附着性能的提高归因于 C/C 上的 PVA/GO 修复凹坑以及 PVA 和 GO 对 HA 涂层的增韧作用。尽管 HA-P/G 涂层具有更好的生物活性,诱导了比 HA 涂层更多的骨样磷灰石生长,但体外和体内测试表明这两种 HA 涂层的 C/C 样品没有统计学意义。

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