目的 针对Ti-6Al-4V（TC4）合金作为人体骨修复材料时易受到体液腐蚀、目前单一CaSiO3涂层制备存在工艺复杂且应力大的问题,提出利用CaO、TiO2、SiO2的混合粉末在TC4表面激光原位制备CaTiO3/CaSiO3复合涂层。方法 采用扫描电子显微镜、X射线衍射仪分析涂层的微观形貌和组织成分;用维氏硬度计、电化学工作站测试涂层的显微硬度并模拟体液（SBF）中的耐蚀性能;通过SBF浸泡试验评价涂层的生物活性。结果 涂层与基体间呈冶金结合,无裂纹等缺陷,物相主要由CaTiO3、β-CaSiO3及少量CaO、SiO2组成。涂层硬度为718.4HV0.2,为基体的2.14倍,涂层在SBF中的腐蚀速率降低了49.7%,耐腐蚀性显著提升;经SBF浸泡14 d后,涂层表面生成大量的类骨磷灰石。结论 利用激光熔覆技术原位制备的CaTiO3/CaSiO3复合涂层具有高硬度、高耐蚀性以及优异的生物活性,有望提升含有害离子的钛合金植入材料的长期安全性和有效性。
Abstract
Ti-6Al-4V (TC4) alloy is widely utilized as an implantable material for human bone tissue repair due to its excellent biocompatibility, mechanical properties and processing characteristics. However, TC4 alloy is susceptible to corrosion in the physiological environment, leading to the release of harmful ions that degrades its long-term stability and safety. Wollastonite (CaSiO3) has been applied as a coating to enhance the bioactivity of TC4 alloy, owing to its superior chemical stability, corrosion resistance and bioactivity. In this study, CaTiO3/CaSiO3 composite coatings have been in-situ fabricated on the surface of TC4 alloy with a commercially available mixture of CaO, TiO2 and SiO2 powders (2∶1∶1, mol%) with particle sizes ranging from 53 µm to 105 µm as the laser cladding material. This work aims to provide a theoretical reference and experimental basis for the laser preparation of low-cost and high-performance composite coatings on titanium alloy surfaces.
The cladding powder was mixed with a 5 wt.% polyvinyl alcohol (PVA) binder solution to create a paste, which was uniformly preplaced to the TC4 substrate surface. The coated substrate was air-dried at room temperature for 24 h, and then placed in a vacuum drying oven at 40 ℃ for 2 h. Laser cladding was conducted with an XL-F500 fiber laser. The microstructure, surface morphology and micro-area composition of the specimens was examined by a MERLIN scanning electron microscope (SEM) equipped with energy-dispersive spectroscopy (EDS). The phase constituent of the coating was analyzed with an X-D6 X-ray diffractometer (XRD). Corrosion resistance testing was performed with a CS2350H electrochemical workstation, and in vitro bioactivity was assessed by immersing the specimens in simulated body fluid (SBF) at 36.5 ℃.
The in-situ laser-fabricated CaTiO3/CaSiO3 composite coating exhibited an excellent metallurgical bonding with the TC4 substrate, free from cracks and other defects. The coating primarily consisted of 50.4% CaTiO3 and 35.7% β-CaSiO3 without the presence of the substate phases, which reasonably inhibited the release of harmful elements such as Al and V from the substrate. The corrosion rate of the composite coating was measured at 0.0816 µm/a, which was approximately half that of the substrate (0.162 3 µm/a). Additionally, the composite coating exhibited significantly larger capacitive arc radius and phase angles compared to the substrate, with the coating resistance (Rt) reaching 1 021 Ω·cm2, nearly double that of the substrate (646 Ω·cm2). After 14 days of immersion in simulated body fluid (SBF), the composite coating surface developed spherical aggregates with a Ca/P ratio of 1.69, and the relative content of hydroxyapatite (HA) reached 48.41%, demonstrating outstanding bioactivity.
The CaTiO3/CaSiO3 composite coatings, prepared in-situ by laser cladding technique, are defect-free and exhibit a metallurgical bond with the TC4 substrate. This bond can significantly inhibit the release of hazardous elements from the substrate while simultaneously exhibiting excellent corrosion resistance, with a corrosion rate decrease of approximately twice compared to the substrate. After immersion in SBF, the specimen surface exhibits small spherical aggregates with a Ca/P ratio of 1.69 and a high hydroxyapatite (HA) content, indicating excellent bioactivity. The CaTiO3/CaSiO3 composite coating, fabricated in situ via laser cladding in this study, demonstrates high hardness, superior corrosion resistance, and excellent bioactivity. This combination of properties offers promising potential for enhancing the long-term safety and efficacy of titanium alloy implants that contain harmful ions.
关键词
激光熔覆 /
TC4合金 /
复合涂层 /
组织 /
性能
Key words
laser cladding /
TC4 alloy /
composite coating /
microstructure /
properties
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