Contents lists available at ScienceDirect
Corrosion Science
journal homepage: www.elsevier.com/locate/corsci
Anomalous enhancement of corrosion resistance and antibacterial property
of commercially pure Titanium (CP-Ti) with nanoscale rutile titania film
Nanda Gopala Krishna, R.P. George, John Philip*
Corrosion Science and Technology Division, Metallurgy and Materials Group, Indira Gandhi Centre for Atomic Research, Kalpakkam & Homi Bhabha National Institute,
Tamil Nadu, 603102, India
ARTICLE INFO
Keywords:
Titanium
Oxidation
Passive film
Polarization
XPS
ABSTRACT
We report an anomalous enhancement of corrosion resistance and antibacterial property of CP-Ti surface in the
presence of a uniform defect-free nanoscale (∼15 nm) rutile titania film. Selective absorption of blue light
(∼410 nm) due to matching photon energy with the film band gap, drastically enhanced the electron-hole pair
generation, recombination time and the photocatalytic activity. The corrosion resistance of the rutile phase
titania films is found to be better than the amorphous films and strongly dependent on the film thickness and
surface morphology. The impedance data accounts well for the dual layer structure with an outer barrier titania
and inner substochiometric oxide layer.
1. Introduction
Titanium (Ti) and its alloys exhibit exceptional corrosion resistance
in a wide range of environments and are known for their high specific
strength, biocompatibility and non toxicity [1]. The chemical inertness
of these materials is attributed to the continuous titania (TiO
2
) film
formed on the surface that acts as a barrier between the metal and the
electrolyte medium thus preventing corrosion. TiO
2
films formed by
thermal oxidation have a higher corrosion resistance and hardness (thus
better wear resistance) because of dense, uniform, compact and crys-
talline nature than the films formed by anodization, which are porous,
rough and amorphous [2,3]. Yet, anodization is a preferred choice due
to its simplicity and ability to fine-tune the surface morphology and
phase composition of oxide layers by process parameters. Even though
higher roughness and porosity of TiO
2
films are beneficial for os-
seointegration in bone implant applications, it suffers from lower wear
resistance against bone tissue, which limits their use in implant appli-
cations [4]. More often, thermal annealing treatment at tempera-
tures > 400 °C, is followed by anodization to improve the film prop-
erties to overcome some of the inherent limitations of the anodized
films [5]. Also, safer alloying elements have been attempted for over-
coming some of the drawbacks of CP-Ti [6,7].
For biomedical implants, especially for dental and orthopaedic, CP-
Ti and its alloys are preferred over stainless steel due to their superior
material properties. The corrosion resistance of an implanting material
is the prime factor that determines its service life in the host body. The
corrosion resistance of CP-Ti and its alloys is an order of magnitude
greater than that of stainless steel [8]. However, CP-Ti is not inherently
antibacterial and hence the risk of infection leading to the implant
failure gives rise to health complications. To improve the antibacterial
property of Ti based implants, other alternatives are being actively
considered, which include coating of the implant surfaces with anti-
microbial agents such as Ag, antibiotics and disinfectants [9,10].
Although there are studies on corrosion and antimicrobial proper-
ties of CP-Ti with titania film grown on their surface by anodization,
there are no systematic studies to understand the role of surface mor-
phology, crystallinity and thickness of the film, especially when the film
thickness is in nanoscale and grown by thermal oxidation. This study
was aimed at bridging the gap in the above aspects and at developing
CP-Ti metal with better antibacterial properties for biomedical implant
applications. We show here a facile and novel approach for enhancing
the antibacterial property of CP-Ti by using thermal air oxidation. We
exploit the thickness dependent selective absorption of TiO
2
film and
the resultant enhanced photocatalytic action. The corrosion perfor-
mance of the different oxidized CP-Ti is studied in simulated body fluid
and the underlying mechanism of improved corrosion and antibacterial
property are obtained.
https://doi.org/10.1016/j.corsci.2020.108678
Received 13 January 2020; Received in revised form 18 March 2020; Accepted 13 April 2020
⁎
Corresponding author.
E-mail address: philip@igcar.gov.in (J. Philip).
Corrosion Science 172 (2020) 108678
Available online 26 April 2020
0010-938X/ © 2020 Elsevier Ltd. All rights reserved.
T