Enhanced interfacial adhesion and osseointegration of anodic TiO₂ nanotube arrays on ultra-fine-grained titanium and underlying mechanisms

The poor adhesion of anodic TiO₂ nanotubes (TNTs) arrays on titanium (Ti) substrates adversely affects applications in many fields especially biomedical engineering. Herein, an efficient strategy is described to improve the adhesion strength of TNTs by performing grain refinement in the underlying Ti substrate via high-pressure torsion processing, as a larger number of grain boundaries can provide more interfacial mechanical anchorage. This process also improves the biocompatibility and osseointegration of TNTs by increasing the surface elastic modulus. The TNTs in length of 0.4 µm have significantly larger adhesion strength than the 2.0 µm long ones because the shorter TNTs experience less interfacial internal stress. However, post-anodization annealing reduces the fluorine concentration in TNTs and adhesion strength due to the formation of interfacial cavities during crystallization. The interfacial structure of TNTs/Ti system and the mechanism of adhesion failures are further investigated and discussed. Statement of Significance: Self-assembled TiO₂ nanotubes (TNTs) prepared by electrochemical anodization have a distinct morphology and superior properties, which are commonly used in photocatalytic systems, electronic devices, solar cells, sensors, as well as biomedical implants. However, the poor adhesion between the TNTs and Ti substrate has hampered wider applications. Here in this study, we describe an efficient strategy to improve the adhesion strength of TNTs by performing grain refinement in the underlying Ti substrate via high-pressure torsion (HPT) processing. The interfacial structure of TNTs/Ti system and the mechanism of adhesion failure are systematically studied and discussed. Our findings not only develop the knowledge of TNTs/Ti system, but also provide new insights into the design of Ti-based implants for orthopedic applications.