大长径比TiO2纳米管与基体界面结合强度提升机制

蓝剑锋; 张贤慧; 常江凡; 吴波; 陈柏屹; 吴建华

doi:10.16490/j.cnki.issn.1001-3660.2025.18.014

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表面技术 ›› 2025, Vol. 54 ›› Issue (18) : 142-155. DOI: 10.16490/j.cnki.issn.1001-3660.2025.18.014

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大长径比TiO₂纳米管与基体界面结合强度提升机制

蓝剑锋, 张贤慧, 常江凡, 吴波, 陈柏屹, 吴建华^*

作者信息 +

Mechanisms for Enhancing Interface Bonding Strength between High-aspect-ratio TiO₂ Nanotube Arrays and Substrate

LAN Jianfeng, ZHANG Xianhui, CHANG Jiangfan, WU Bo, CHEN Baiyi, WU Jianhua^*

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摘要

目的研究大长径比TiO₂纳米管与基体界面结合强度的影响因素和提升机制。方法对大长径比TiO₂纳米管进行两次阳极氧化后处理和热处理,采用立柱拉拔法和微米划痕法测定不同处理工艺下的TiO₂纳米管与基体的界面结合强度。结果大长径比TiO₂纳米管与基体的界面结合强度的影响因素是底部可溶性含F层和残余应力层,前者对界面结合强度的影响高于后者。TiO₂纳米管在400 ℃保温1 h的热处理可完全消除可溶性含F层,在含F电解液中进行10 V和5 min的一次阳极氧化后处理可减小残余应力层,在无F电解液中进行60 V和5 min的二次阳极氧化后处理可在底部构建厚度约140 nm的连接层。采用单一的热处理或阳极氧化后处理均可小幅度提高TiO₂纳米管与基体的界面结合强度。结论大长径比TiO₂纳米管与基体的界面结合强度的提升机制为消除底部可溶性含F层和残余应力层。采用上述的两次阳极氧化后处理和热处理相结合的手段,可大幅度提高TiO₂纳米管与基体的界面结合强度,其拉拔结合强度和临界载荷分别提高5.87倍和7.06倍。

Abstract

This study aims to explore the factors that influence the interface bonding strength between the high-aspect-ratio TiO₂ nanotube arrays and the substrate, so as to provide a comprehensive understanding of the mechanisms responsible for enhancing this interface bonding strength. TiO₂ nanotube arrays with an aspect ratio of 130 were subjected to a two-step post-anodization treatment followed by a heat treatment. The interface bonding strength between the high-aspect-ratio TiO₂ nanotube arrays and the substrate was measured by column pulling tests and micro-scratch tests, which allowed for the evaluation of the effects of different treatment processes on the interface bonding strength.
The results showed that the interface bonding strength between the TiO₂ nanotube arrays and the substrate was significantly influenced by two main factors: the presence of a soluble F^--containing layer and the residual stress layer at the TiO₂ nanotube arrays bottom. Among these influencing factors, the soluble F^--containing layer had a more pronounced effect on the interface bonding strength than the residual stress layer. The interaction between these layers and the substrate was found to play a crucial role in determining the overall interface bonding strength. One important finding of the study was that the heat treatment at 400 ℃ for 1 h was highly effective in eliminating the soluble F^--containing layer at the bottom of the TiO₂ nanotube arrays. This step significantly improved the interface bonding strength, as the F^- ions, which could potentially weaken the interface bonding strength between the TiO₂ nanotube arrays and the substrate, were removed. In parallel, a post-anodization treatment at 10 V for 5 min in an electrolyte consisting of 99vol% C₂H₆O₂, 1vol% H₂O, and 0.5wt.% NH₄F was applied. This treatment reduced the residual stress layer at the bottom of the TiO₂ nanotube arrays. Additionally, a post-anodization treatment at 60 V for 5 min in an electrolyte consisting of 95wt.% C₂H₆O₂ and 5wt.% H₃PO₄ resulted in the formation of a connecting layer with a thickness of 140 nm at the bottom of the TiO₂ nanotube arrays. This connecting layer was found to further enhance the interface bonding strength by providing a more stable and robust attachment to the substrate. Both the heat treatment and post-anodization treatments slightly enhanced the interface bonding strength between the TiO₂ nanotube arrays and the substrate, with the heat treatment providing a more substantial improvement.
The underlying mechanism for enhancing interface bonding strength was found to involve the elimination of the soluble F^--containing layer and the reduction of the residual stress layer at the bottom of the TiO₂ nanotube arrays. Furthermore, the combined approach of the two-step post-anodization treatment followed by heat treatment was found to have a significant synergistic effect on the interface bonding strength. Specifically, this combined processes led to a dramatic increase in the tensile bonding strength, which was enhanced by 5.87 times, and the critical load, which showed an improvement of 7.06 times. These results highlight the effectiveness of combining post-treatment techniques to achieve a significant enhancement in the interface bonding strength between the TiO₂ nanotube arrays and the substrate, which is crucial for the performance and stability of devices incorporating high-aspect-ratio TiO₂ nanotube arrays.

导出引用

蓝剑锋, 张贤慧, 常江凡, 吴波, 陈柏屹, 吴建华. 大长径比TiO₂纳米管与基体界面结合强度提升机制[J]. 表面技术. 2025, 54(18): 142-155 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.18.014

LAN Jianfeng, ZHANG Xianhui, CHANG Jiangfan, WU Bo, CHEN Baiyi, WU Jianhua. Mechanisms for Enhancing Interface Bonding Strength between High-aspect-ratio TiO₂ Nanotube Arrays and Substrate[J]. Surface Technology. 2025, 54(18): 142-155 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.18.014

中图分类号： TB34

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