Ti45Al8.5Nb合金表面Zr-SiO2 复合涂层的制备及其抗高温氧化性能研究

doi:10.11902/1005.4537.2024.004

中国腐蚀与防护学报

2024, Vol. 44

Issue (6): 1423-1434 CSTR: 32134.14.1005.4537.2024.004 DOI: 10.11902/1005.4537.2024.004

研究报告

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Ti45Al8.5Nb合金表面Zr-SiO₂ 复合涂层的制备及其抗高温氧化性能研究

吴亮亮, 殷若展, 陈朝旭, 梁君岳, 孙擎擎, 伍廉奎(

), 曹发和

中山大学材料学院深圳 518107

Preparation and High Temperature Oxidation Resistance of Zr-SiO₂ Composite Coating on Ti45Al8.5Nb Alloy

WU Liangliang, YIN Ruozhan, CHEN Zhaoxu, LIANG Junyue, SUN Qingqing, WU Liankui(

), CAO Fahe

School of Materials, Sun Yat-sen University, Shenzhen 518107, China

引用本文:

吴亮亮, 殷若展, 陈朝旭, 梁君岳, 孙擎擎, 伍廉奎, 曹发和. Ti45Al8.5Nb合金表面Zr-SiO₂ 复合涂层的制备及其抗高温氧化性能研究[J]. 中国腐蚀与防护学报, 2024, 44(6): 1423-1434.
Liangliang WU, Ruozhan YIN, Zhaoxu CHEN, Junyue LIANG, Qingqing SUN, Liankui WU, Fahe CAO. Preparation and High Temperature Oxidation Resistance of Zr-SiO₂ Composite Coating on Ti45Al8.5Nb Alloy[J]. Journal of Chinese Society for Corrosion and protection, 2024, 44(6): 1423-1434.

全文: PDF(18270 KB) HTML

摘要:

针对电沉积SiO₂涂层在高温氧化过程中易产生裂纹的问题，在SiO₂涂层表面磁控溅射Zr沉积层来进行改善。研究表明，Zr沉积层氧化为ZrO₂填补了SiO₂涂层在烧结时产生的裂纹和孔洞等缺陷，并为SiO₂涂层与合金基体的热膨胀系数失配提供了缓冲。此外，氧化过程中形成的ZrO₂-SiO₂骨架结构提高了涂层结构的稳定性。总体上，Zr-SiO₂复合涂层在氧化初期显著抑制了氧向合金基体的扩散以及合金基体元素的外扩散，提高了合金的抗高温氧化性能，经氧化后复合涂层表面的氧化物颗粒明显减少，且氧化膜未出现明显生长。此外，在900℃下经过100 h的恒温氧化后，由于元素互扩散，涂层与基体界面形成了(Ti, Nb)O₂/Ti₅Si₃ + Al₂O₃ + Nb₃Al/TiN三层扩散层结构，提高了涂层与基体的结合力。

关键词 ： Zr-SiO₂复合涂层, 抑制缺陷, 抗高温氧化, 元素扩散

Abstract：

Addressing the issue of crack formation in SiO₂ coatings during high-temperature oxidation, a supplementary Zr layer was applied onto the SiO₂ coating surface through magnetic sputtering. This study revealed that the Zr layer, upon oxidation, transformed into ZrO₂, may effectively amend the cracks and voids that emerged during the sintering process of the SiO₂ coating. Furthermore, it mitigated the thermal expansion coefficient (TEC) disparity between TiAl and SiO₂ coatings. In addition, the ZrO₂-SiO₂ skeleton structure formed during the oxidation process may be able to improve the stability of the coating structure. The resultant Zr-SiO₂ composite coating significantly impeded oxygen inward diffusion from the ambient environment to the Ti45Al8.5Nb substrate, even the outward diffusion of alloy elements in the early stage of oxidation, which notably enhancing its resistance against high-temperature oxidation. Notably, limited growth of oxide particles was observed on the alloy, with a negligible increase in the thickness of oxide scale. Additionally, following a period of 100-hour oxidation at 900^oC, mutual element diffusion from both the substrate and coating led to the formation of a three-layered interdiffusion zone (Ti, Nb)O₂/Ti₅Si₃ + Al₂O₃ + Nb₃Al/TiN. This interdiffusion zone notably bolstered the bond strength between the composite coating and the Ti45Al8.5Nb substrate.

Key words： Zr-SiO₂ composite coating defect inhibition high-temperature oxidation resistance elemental diffusion

收稿日期: 2024-01-02 32134.14.1005.4537.2024.004

ZTFLH:

TG174

基金资助:国家自然科学基金(51971205);广东省基础与应用基础研究基金(2021B1515020056)

通讯作者: 伍廉奎，E-mail: wulk5@mail.sysu.edu.cn，研究方向为材料腐蚀与防护

Corresponding author: WU Liankui, E-mail: wulk5@mail.sysu.edu.cn

作者简介: 吴亮亮，男，1999年生，硕士生

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图1 制备态Zr-SiO2复合涂层表面SEM形貌及EDS谱

图2 制备态Zr-SiO2复合涂层表面XRD图谱

图3 制备态Zr-SiO2复合涂层截面SEM形貌，以及EDS元素分布分析

表1 图3a中各点的元素含量 (atomic fraction / %)

图4 未沉积和沉积SiO2，Zr-SiO2涂层的Ti45Al8.5Nb合金在900℃空气中的恒温氧化动力学曲线，以及Zr-SiO2复合涂层氧化100 h后的表面XRD图谱

图5 Ti45Al8.5Nb合金、SiO2涂层和Zr-SiO2复合涂层在900℃下恒温氧化100 h后的表面形貌

表2 图5中所标记各区域和各点处的元素含量 (atomic fraction / %)

图6 Zr-SiO2复合涂层在900℃下恒温氧化100 h后的截面形貌以及EDS元素分布分析

表3 图6a中标记的各点处元素含量 (atomic fraction / %)

图7 Zr-SiO2复合涂层在900℃下恒温氧化100 h后截面的EPMA元素分布图

图8 经900℃, 100 h氧化的SiO2涂层的表面Raman光谱, 以及相同条件氧化后的Zr-SiO2复合涂层的表面光学形貌与标记点1和2处的Raman光谱

表4 所测图8b中位置1和2处Raman谱峰位与文献中数据的对比(T表示四方相ZrO2)

图9 Zr-SiO2复合涂层在900℃下恒温氧化100 h后表面XPS分析结果：全谱及半定量元素含量分析及Zr、Si、Al、Ti、O和K的精细谱

图10 SiO2涂层和Zr-SiO2复合涂层在烧结制备和恒温氧化过程中结构和相变化示意图

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