Acta Biomaterialia xxx (2012) xxxxxx

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Acta Biomaterialia
journal homepage: www.elsevier.com/locate/actabiomat

Review

A review of the application of anodization for the fabrication of nanotubes

on metal implant surfaces
Sepideh Minagar a, Christopher C. Berndt a, James Wang a, Elena Ivanova b, Cuie Wen a,
a
IRIS, Faculty of Engineering and Industrial Sciences, Swinburne University of Technology, Hawthorn, Victoria 3122, Australia
b
Faculty of Life and Social Sciences, Swinburne University of Technology, Hawthorn, Victoria 3122, Australia

a r t i c l e i n f o a b s t r a c t

Article history: Metal implants are the best choice for the long-term replacement of hard tissue, such as hip and knee
Received 11 January 2012 joints, because of their excellent mechanical properties. Titanium and its alloys, due to their self-orga-
Received in revised form 31 March 2012 nized oxide layer, which protects the surface from corrosion and prevents ion release, are widely
Accepted 2 April 2012
accepted as biocompatible metal implants. Surface modication is essential for the promotion of the
Available online xxxx
osseointegration of these biomaterials. Nanotubes fabricated on the surface of metal implants by anod-
ization are receiving ever-increasing attention for surface modication. This paper provides an overview
Keywords:
of the employment of anodization for nanotubes fabricated on the surface of titanium, titanium alloys
Titanium
Niobium
and titanium alloying metals such as niobium, tantalum and zirconium metal implants. This work
Tantalum explains anodic oxidation and the manner by which nanotubes form on the surface of the metals. It then
Zirconium assesses this topical research to indicate how changes in anodizing conditions inuence nanotube char-
Anodized nanotubes acteristics such as tube diameters and nanotube-layer thickness.
Crown Copyright 2012 Published by Elsevier Ltd. on behalf of Acta Materialia Inc. All rights reserved.

1. Introduction elastic material due to these pores, which are lled with uid and
cells: osteoblasts, osteoclasts, osteocytes and bone-lining cells that
1.1. Bone: structure, composition and properties are regenerative. Bone, moreover, has values of compression
strength several times higher than, for example, concrete, but its
Like other parts of the body, bone becomes damaged or weak- low density is in the range of aluminium.
ened by age, accidents or disease. This damage, which includes
bone fractures, low back pain, osteoporosis, scoliosis and other
1.2. Bone implant materials
musculoskeletal problems, usually occurs in elderly people, though
not exclusively. Biomaterials such as implants are used to repair
Different materials are used for implants, including polymers,
injured bones, cartilage or ligaments and tendons [1].
ceramics, metals, composites and natural products. Metal implants
Weiner and Wagner [2] described basic bone composition as
can bear loads for several decades and are consequently used as
consisting of mostly brous protein collagen, carbonated apatite
endoprostheses. However, they need to be inserted into the human
(Ca5(PO4, CO3)3(OH)) and water. The crystal size and the propor-
architecture and become xed and stable in the surrounding natu-
tions of these components change over time. As a result, younger
ral tissue. Furthermore, these implants need to be bioinert within
bones replace older bones. Uddin et al. [3] emphasized that bones
the highly corrosive and demanding environment of the human
are tissues that are alive and growing. Bone-forming cells, such as
body. Polymers, in comparison to metals, give rise to inammation
osteoblasts, are responsible for generating the synthesis and depo-
because of monomers that are intrinsic to their structure or that
sition of the calcium phosphate crystals that are required to confer
become available through infection, thereby increasing the likeli-
hardness and strength in biomineralization. A schematic illustra-
hood of degradation. However, polymers demonstrate excellent
tion of the hierarchical structure of cortical bone is shown in
primary xation [1].
Fig. 1. It can be seen that cortical bone contains many different
Ceramics and bioglass exhibit lower fracture toughness and
structures, which exist on several levels of scale starting from
higher elastic modulus than bone, and also demonstrate property
sub-nanostructures. Mour et al. [4] described bone as a solid mate-
variations with respect to their formulation [5]. Their mechanical
rial that is highly porous on the micrometre scale. Bone is a visco-
and biological properties depend on many factors during synthesis,
such as maximum temperature, duration of the thermal steps, pur-
Corresponding author. Tel.: +61 3 9214 5651; fax: +61 3 9214 5050. ity of the powder, and size and distribution of the grains and poros-
E-mail address: cwen@swin.edu.au (C. Wen). ity, many of which cannot be accurately controlled [1].

1742-7061/$ - see front matter Crown Copyright 2012 Published by Elsevier Ltd. on behalf of Acta Materialia Inc. All rights reserved.
http://dx.doi.org/10.1016/j.actbio.2012.04.005

Please cite this article in press as: Minagar S et al. A review of the application of anodization for the fabrication of nanotubes on metal implant surfaces.
Acta Biomater (2012), http://dx.doi.org/10.1016/j.actbio.2012.04.005
2 S. Minagar et al. / Acta Biomaterialia xxx (2012) xxxxxx
Fig. 1. Hierarchical structure of cortical bone (adapted from Ref. [102]).
Most of the metal implants used are stainless steels, cobalt
chromium alloy, and titanium and its alloys. SUS 316L stainless
steel, with a Youngs modulus of approximately 160 GPa, is the
only stainless steel that is biocompatible; however, its wear resis-
tance is poor in comparison with other metal implants. When a
stainless steel alloy contains nickel it may possibly be allergenic
[6], since the release of such metal ions can cause an adverse reac-
tion due to corrosion and the soluble corrosion products. Similar to
stainless steel, cobalt alloys generally contain nickel and chro-
mium; consequently, the fabrication of both nickel-free stainless
steels and nickel-free cobalt chromium alloys is under investiga-
tion since their corrosion resistance and mechanical properties
are superior, with the exception of the elastic modulus, which is
in the same range as stainless steel [6].
When a metal implant material is able to form a stable and
compact oxide layer that can rebuild itself, it can be described as
bioinert, since this surface can prevent the transmission of undesir-
able ions [7]. Other properties of a metal, which endow its mechan-
ical biocompatibility, are Youngs modulus, tensile strength,
ductility, fatigue life, fretting fatigue life and wear resistance [8].
As a result of the contact between the inserted implant and bone,
cyclic loading wear loss and fretting fatigue may occur, which can
cause the implant to become loose. Some oxide layers on metals
increase the wear resistance. A metal implant that has a lower
Youngs modulus can transfer stress homogeneously between itself
and bone. However, as the modulus approaches that of bone, the
strength of the implant will be lower than that of bone, and the
possibility of failure under large shear deformation will increase.
In vivo data show a smooth fracture callus for metals with a
lower Youngs modulus than that of bone. Fatigue testing implants
in vivo is difcult as it is difcult to replicate in vivo conditions ex-
actly [8]. A standardized in vitro fatigue test is therefore used. This
includes tension/compression, bending, torsion and rotating bend-
ing fatigue testing of the metal implant, which is then compared
with Ti6Al4V as a standard material [9]. Titanium and titanium al-
loys are more biocompatible than other implant metals for the
above-mentioned reasons, and these metals have demonstrated
an ability to integrate with bone. The microstructures, mechanical
properties and biological characteristics of commonly used metal-
lic implant materials are summarized in Table 1.
Researchers have paid more attention to titanium and its alloys
for load-bearing and long-term implants because of their good fa-
tigue strength, relatively low elastic modulus, low density, excel-
lent corrosion resistance and biocompatibility, the last property
being reected in the low release of ions [10,11]. Pure titanium
and Ti6Al4V ELI (Extra Low level of Interstitial content) are the
prime metals used for biomedical applications. However, alumin-
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Acta Biomater (2012), http://dx.doi.org/10.1016/j.actbio.2012.04.005
ium is classied as belonging to a group of materials that forms a
capsule, or scar tissue, and vanadium prevents cell division, and
both can display mutagenicity and cytotoxicity, and cause allergic
reactions. Research is active in developing biocompatible TiNb
TaZr alloys. Recently developed b-type titanium alloys have a
lower elastic modulus (Youngs modulus approximately 50 GPa)
than commercially pure titanium and Ti6Al4V (Youngs modulus
approximately 105 and 110 GPa, respectively), which are a and
a + b types. The stability of a b phase in titanium alloys depends
on the alloying element ratio and the b-transus temperature of
the alloy. It has been established that niobium and tantalum act
as b-stabilizers and the b phase exhibits a lower elastic modulus
in titanium alloys. In binary titanium alloys, it has been shown
that, when the b-stabilizer elements increase, the stability of the
b phase and the elastic modulus increase [6,1214].
1.3. Surface treatment for implant materials
The surface of an implant needs modication to optimize the
properties of the implant and to maximize its bioactivity when
interfacing with natural tissue. The biological characteristics of im-
plants can be enhanced by adding material with desired properties,
changing the composition or removing unwanted material from
the implant surface. These methods are known as surface treat-
ments or modications, and can be classied into four categories:
mechanical, physical, chemical and biochemical surface modica-
tions. Machining, grinding, polishing and blasting are mechanical
surface modications. Physical surface treatments include thermal
spraying, physical vapour deposition, ion implantation and deposi-
tion, and glow discharge plasma treatment. Chemical surface mod-
ications include chemical treatment (acid, hydrogen peroxide,
alkaline), anodic oxidation, the solgel process and chemical va-
pour deposition. A number of techniques have been specically
introduced for titanium and titanium alloys, such as silanized tita-
nia, photochemistry, self-assembled monolayers, protein resis-
tance and protein immobilization [7,15].
A thin 25 nm surface layer of titania (TiO2) forms when tita-
nium is exposed to air and protects the surface from corrosion
[16]. The layer that is in contact with the substrate consists of
TiO; the intermediate layer is composed of Ti2O3 and the outer
layer is TiO2. The titania outer layer is bioinert and cannot bond
to bone cells easily, subsequently it is encapsulated by brous tis-
sue that isolates it from the bone cells. Such implants, therefore,
tend to become loose and are not recommended for use over
lengthy periods [7]. On the other hand, ceramics, glass and several
other implant materials can bind to bone, which can form directly
through the layer of apatite that forms on their surfaces [17]. Thus,
 S. Minagar et al. / Acta Biomaterialia xxx (2012) xxxxxx 3

Table 1
Phases, mechanical properties and biological characteristics of metallic implant materials.

Alloy Phases Nominal composition (wt.%) Ultimate Elastic Yield Refs.

designation Log polarization resistance Distinct form strength modulus E strength
(MPa) (GPa) (MPa)
Al/Cr V/Ni Mn/Ta Zr/Nb Others
Stainless steel Austenite Cr = 1618 Ni = 10 Mn = 2 Mo = 23 465950 200 170750 [9,11]
316L 14
78/Sequestration
Co25Cr6Mo Austenite Cr = 2730/ Mo = 57 6001795 200230 2751585 [9,11]
(fcc)+hcp Al = 0.1
Titanium grade Unalloyed 345 102.7 275 [11,103]
2 (ASTM)
Ti6Al4V a/b Al = 6 4 Fe = 0.3 960970 110 850900 [9,11]
45/ 56/ 45/
Sequestration Toxicity sequestration
Ti6Al7Nb a/b Al = 6 Nb = 7 9001050 114 880950 [11,103]
4-5/ 67/Inertness
Sequestration
TiZr Cast /b Zr = 50 900 [9,11]
78/Inertness
00
Ti-30Ta a Ta = 29.6 587 69 [11,104]
68
Inertness
Ti30Nb x Nb = 30 >600 More than 530 [11,105]
67/Inertness 120
Ti29Nb Metastable b Ta = 13 Zr = 4.6Nb = 29 911 80 864 [11,103]
13Ta4.6Zr 68 78 and 68
Inertness inertness
Bone Viscoelastic 90140 1040 [7,11]
composite

surface treatments are needed for titanium alloys to achieve better
and more rapid bonding to bone, i.e. osteoinduction. The optimum
surface treatment would create a stable passive layer on the sur-
face of titanium implants with essential properties such as rough-
ness, wettability and electrostatic charges.
Titanium is the same as other transition metals that are able to
form an oxide layer on their surfaces, and can be the subject of
electrochemical surface modication. The method is an oxida-
tionreduction reaction which occurs through the cathode and an-
ode of an electrochemical set. By applying a potential that is
proportional to the electrolyte used, the desired oxide layer will
be formed on the surface; indeed, the ability and tendency of the
metal to tailor a self-protective oxide layer is used. In the compe-
tition between oxidation and dissolution in this process in the
presence of uorine ions, a patterned nanoporous cylindrical struc-
ture can be observed on the surface of oxide layer that has a conical
closed bottom. In addition to the ability to interlock with bone
cells, the chemical properties of this type of conguration change
along with other properties in comparison to the host metal. This
low-cost process can be used to achieve a specic nanotube diam-
eter, length and wall thickness by changing the electrochemical
conditions [18].
The current review initially describes the anodic oxidation of
titanium and titanium alloys using an electrochemical method,
with a view to their use in biomedical applications. It also de-
scribes how the method has been improved. It next examines the
anodic oxidation method with reference to titanium, a newly de-
signed titanium alloy, TiNbTaZr (TNTZ) and some binary alloys,
as well as titanium alloying metals.
2. Anodic oxidation as a metallic implant surface treatment
Electrochemical anodic oxidation has been used to grow a thick
and uniform oxide layer on metals for a decade or so. It has been
shown to play an excellent role in the biocompatibility of metal
implants [16]. A controllable and desired thickness is formed by
using the metals that demonstrate a spontaneous protective oxide
layer as the anode of an electrochemical cell. An ordered oxide
layer can be tailored when the type of electrolyte, applied current
density, electrolyte concentration, electrolyte temperature, agita-
tion speed and cathode-to-anode surface area ratios are controlled
[19]. It was initially demonstrated that a nanoporous oxide layer
could be formed on aluminium [20] in such conditions; thus, seed-
ing the fabrication of the same layer on titanium [21], niobium
[22], tantalum [23] and zirconium [24] has been undertaken. These
are known as the valve metals that are able to form dense, stable,
tightly adhering, electrically insulating oxides on their surface.
A nanotube titanium oxide layer with a controlled and uniform
diameter can be obtained by anodizing oxidation, which is a cost-
effective, versatile and simple technique. This nanotube titania
layer plays an important role in the enhancement of osseointegra-
tion through the improvement of the adhesion of the hydroxyapa-
tite (HAP) coating that is deposited onto TiO2. Oh et al. [25]
indicated that the cell adhesion could be improved by up to 400%
because of the mechanical interlocking between the HAP coating
and the nanotube titanium oxide layer.
Sibert [26] reported on the formation of a thick, adherent lm of
TiO2 on the surface of titanium when using anodic oxidation if the
nature and concentration of the electrolyte, forming voltage, cur-
rent density and temperature are properly adjusted [26]. Kokubo
[27] indicated the mechanism of apatite formation on a TiO2 sur-
face. Zwilling et al. [21] demonstrated the growth process of TiO2
nanotubes on pure titanium and Ti6Al4V using anodization in
chromic acid electrolytes, with or without the addition of a uorine
species. The diameter and thickness of the nanotubes were deter-
mined by the applied potential and time. Anodizing can form
TiO2 nanotubes that are open at the top and closed at the bottom,
and that are of different sizes, by changing the concentration and
type of electrolyte, the time and the voltage.
A standard two- or three-electrode set-up can be employed to
anodize the sample, mostly commercially pure titanium. There
are several combinations of electrolytes: (i) an aqueous acidic solu-
tion containing F; (ii) an aqueous buffered solution; or (iii) a non-

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4 S. Minagar et al. / Acta Biomaterialia xxx (2012) xxxxxx

aqueous electrolyte containing F ion with or without a trace
amount of H2O. Initially, compact titanium dioxide will be created
[28], as illustrated in Fig. 2.
Nanotubes then form as soluble uoride complexes through the
chemical dissolution of the oxide in the presence of the uoride an-
ion, and there will be an increase in current. A stage is then reached
where there is equilibrium between oxidation and dissolution, at
which point a nanostructured surface forms and the current ow
is constant [28,29]. A schematic currenttime curve is shown in
Fig. 3.
All chemical reactions respond to the in situ physical and chem-
ical conditions. The anodic oxidation mechanism is governed by
the type and concentration of the electrolyte, the applied potential
or the applied current density, the temperature, and the time of the
electrochemical reaction. By changing one of these conditions
when the others remain constant, different morphologies of TiO2
nanotubes can be obtained on commercially pure titanium. Nano-
tube formation under different electrolyte compositions (aqueous/
organic, different pH) and the different categories of nanotubes
have already been elaborated upon in an excellent review article
[18], therefore, this paper presents only a brief summary.
2.1. The inuence of the type and concentration of aqueous electrolyte
on TiO2 nanotubes
When the anodization of titanium takes place in an acidic con-
dition of pH, most of the composition of hydrouoric acid is in HF
form. The diameter of the TiO2 nanotube that grows in an HF-based
electrolyte was between 15 and 140 nm under conditions where
H3PO4 and H2SO4 were used and the applied potential was changed
from 1 to 25 V [28,30]. With an optimum voltage of 20 V, and an
optimum time of anodization, which had an inuence on the thick-
ness of the oxide layer, of 12 h, a maximum length of 500 nm of
TiO2 nanotube was obtained [31]. The amorphous structure of
nanotube arrays was changed to anatase at 450 C inside the tube
wall and was entirely changed to rutile at 600 C by annealing [32].
These phases exhibited different inuences on the apatite forma-
tion and/or cell fate [17,33]. Titanium-based layers are more
hydrophobic than other layers formed in a buffered electrolyte.
The hydrophilic value at the interface between the implant surface
and the tissue is a crucial factor in cell adhesion, and the best
hydrophilic value was reported to be 16 [34]. Fig. 4 shows scanning
electron microscopy (SEM) images of TiO2 nanotubes formed in

Fig. 2. Growth of regular TiO2 nanotubes: (a) cathodic reaction, (b) anodic reaction, (c) transition state of TiO2 layer, (d) starting of nanotube formation and (e) titania
nanotubes.

Fig. 3. Schematic currenttime curve (adapted from Ref. [29]).

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 S. Minagar et al. / Acta Biomaterialia xxx (2012) xxxxxx
Fig. 4. SEM images of TiO2 nanotubes formed in 1 M H3PO4 + 0.3 wt.% HF at 10 V:
(a) top view and (b) cross-section. Reproduced from Bauer et al. [30].
1 M H3PO4 + 0.3 wt.% HF at 10 V, reproduced from the work of Bau-
er et al. [30].
Hydrouoric acid selectively etches the surface of some metals.
Therefore, the presence of uoride anions within the electrolyte
during the growth of titanium oxide allows the formation of a
nanotube oxide layer. A TiO2 nanotube of 70100 nm diameter
forms in less than 2 h when anodization occurs in an electrolyte
consisting of only HF at an applied potential of 20 V [34,35]. There
is a certain concentration range of F in which regular uniform
nanotubes can be formed and beyond which nanotubes cannot
be uniformly fabricated. The nanotube diameter increases with
increasing voltage. It has been reported that an oxide layer of
TiO2 nanotube with a thickness of 250 nm has been formed in
HF electrolyte [33,36]. A combination of an amorphous and crystal-
line structure for the TiO2 was observed; and the contact angle of
the TiO2 nanotube that grows in this type of electrolyte is still high-
er than the best proposed hydrophilic value. Fig. 5(a)(c) displays
SEM images of TiO2 nanotubes formed in 1 wt.% HF at 20 V for
15 and 30 min, and (d) a transmission electron microscopy (TEM)
image for 30 min, reproduced from Zhao et al. [35].
The bioactivity of the titanium oxide can be enhanced by
immersion in an NaOH solution, as sodium titanate nanostructures
will form on the top edge of the nanotube wall. Another process is
to heat the TiO2 nanotube so that anatase will form, onto which a
nanostructured HAP phase can be created by soaking in simulated
body uid. The presence of the nanostructured TiO2 accelerates the
formation of HAP [33]. The adhesion of MC3T3-E1 mouse osteo-
blast cells was signicantly promoted with the lopodia of grow-
ing cells actually going into the nanotube pores, producing an
interlocked cell structure [25].
One proposal for the prevention of bacterial infection following
orthopaedic implantation is local antibiotic therapy, such as using
bone cement or a polymer coating that is loaded with a therapeutic
agent [37]. It is possible to decrease the susceptibility of the implant
to the bacterial infection caused by limited chemical stability using
a controlled kinetic release of the therapeutic agent. It is proposed
that TiO2 nanotubes, following phase transformation to anatase by
annealing, can be loaded with antibiotics, e.g. 200, 400 and 600 lg
of gentamicin, to minimize the initial bacterial adhesion [37].
Macak et al. [38] observed the electrolyte dissolubility and
hydrolysis ability of a titanium oxide layer and indicated that
smooth and longer nanotubes can be formed in buffered electro-
lyte [((NH4)2SO4 + NH4F) or (Na2SO4 + NaF)]. The dissolution cur-
rent can be adjusted and, as the electrolyte is neutral, acid will
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5
be created at bottom of the pore. The pore thickness, regularity,
roughness, diameter and crystalline shape change with variations
in the concentration of F in the electrolyte, the sweep potential
rate and the potential applied. Under these conditions TiO2 nano-
tubes grow up to 4 lm in thickness and 100 nm in diameter,
based on a 20 V applied potential [3840]. The tube diameter is af-
fected by the voltage but it is not affected by time. However, the
time of anodization inuences the thickness of the nanotube layer.
Fig. 6 shows SEM images of TiO2 nanotubes formed in 1 M
(NH4)2SO4 + 0.5 wt.% NH4F at 20 V, reproduced from the work of
Macak et al. [38].
Apatite formation was evaluated on an annealed nanotube layer
with a diameter of 100 nm and a thickness of 2 lm [17]. In com-
parison to a at surface, such a nanotube surface encourages the
formation of apatite. The rate of apatite formation depends on
the thickness of the layer and the nanotube structure: apatite
forms more on thick, crystalline nanotubes [17]. A TiO2 nanotube
layer with a maximum layer thickness of 1 lm was formed in an
acidic electrolyte consisting of uoride salt at an applied potential
of 20 V [41]. When the length of the 3570 nm tubes was in-
creased, the Youngs modulus of TiO2, which was approximately
3643 GPa, decreased because of the substrate as well as the func-
tionality of the coating that inuences measured Youngs modulus
and hardness [42]. The modulus of elasticity of the nanotube oxide
layer is closest to that of the substrate near the interface; and the
thinner the layer, the more similar the moduli. An apatite coating
can be obtained on the TiO2 nanotube layer after immersing such
an annealed layer in a solution with a high calcium and phosphate
concentration. A carbonated apatite crystal with a column-like
shape of nanometer size was formed, and the bond strength be-
tween the HA coating and the nanotube layer was measured to
be higher than 15.3 2.5 MPa [41,42].
2.2. The inuence of the non-aqueous electrolyte on TiO2 nanotubes
An organic electrolyte has a small amount of oxygen in compar-
ison to an aqueous solution; therefore, the oxide chemical dissolu-
tion in an organic electrolyte depends on the water content [43]. As
a result, a thicker nanotube layer will form over a longer time in an
organic electrolyte, and the viscosity of the electrolyte, whether it is
stirred or not [44] and the H2O content all inuence the nanotube
formation. Nanotubes with a diameter of 20160 nm were obtained
at an applied potential ranging from 30 to 120 V using an organic
electrolyte [4347]. TiO2 nanotubes with a maximum height of
45 lm [43] or higher (>150 lm) [45] in electrolytes such as glycerol
[44,48], ethylene glycol [43,46] and acetic acid [47] were formed
after 115 h of anodization [43]. A smooth layer of TiO2 nanotubes
that were not connected by outside walls was formed when NH4F in
glycerol was used as the electrolyte [48]. Such an electrolyte exhib-
its a lower diffusion constant, which has an inuence on the pH va-
lue of the pore tip and consequently on the current transient and
the dissolution rate. The viscosity of the electrolyte is important
too because in highly viscose electrolyte the diffusion constant de-
creases. The diameter of these nanotubes was between 30 and
60 nm, with a up to 7 lm length and an aspect ratio of 233-117 [48].
The shape of the nanotubes is inuenced by the applied poten-
tial and the anodization time in a water-free electrolyte consisting
of acetic acid and NH4F. Under low potential conditions: (i) the
nanotube diameter is about 20 nm; (ii) the maximum length will
be 100 nm; and (iii) rings outside the walls connect the tubes
[47]. Nanotubes with a coral reef structures are formed and the
rings dissolve when the applied potential and anodization time
are increased. If the nonaqueous electrolyte consisting of glycerol
and NH4F is stirred, then the adhesion strength of the TiO2 nano-
tube (1.21.9 lm in thickness) to the substrate decreases, and
the contact angle with water ranges from 58 to 84 [44]. Fig. 7
6 S. Minagar et al. / Acta Biomaterialia xxx (2012) xxxxxx
Fig. 5. (a)(c) SEM images of TiO2 nanotubes formed in 1 wt.% HF at 20 V: (a) top view for 30 min; (b) cross-section for 15 min; (c) bottom view and cross-section for 15 min;
and (d) TEM image for 30 min. Reproduced from Zhao et al. [35].
shows SEM images of TiO2 nanotubes formed in ethylene gly-
col + 0.3 wt.% NH4F + 2 vol.% H2O, reproduced from the work of
Wan et al. [43].
One promising application of amphiphilic TiO2 nanotubes is the
fabrication of a drug release system. A hydrophobic cap using or-
ganic monolayer grafting was fabricated on a TiO2 nanotube, which
was treated using the anodizing method in the presence of the
uoride anion [49]. Another anodizing process was then under-
taken to fabricate a hydrophilic TiO2 nanotube underneath the ini-
tial layer; and the hydrophilic segment was loaded with
hydrophilic drugs. Detachment of the cap would be performed
using the ultraviolet-induced photocatalytic nature of TiO2, there-
by permitting controlled drug release [49].
2.3. The effect of pH value on the formation of TiO2 nanotubes
The pH value inuences the dissolubility of the electrolyte and
the hydrolysis ability of the titanium oxide layer. This behaviour
has been surveyed for titanium foils that were anodized in three
electrolytes of different pH values, and the mass loss of the anode
during the anodic oxidation was based on the currenttime curve
[50]. The time it takes for a nanotube to form increases with
increasing pH; consequently, the nanotubes have a longer length
compared to nanotubes formed in electrolytes with a lower pH
[50]. A length of 4.4 lm was achieved when the pH value was high
but still acidic (pH 4.5) [51]. As mentioned above, different tube
sizes can be expected when the conditions of the electrolyte, its
pH, the applied potential and the anodization time change.
The fabrication of TiO2 nanotubes can be divided into four cat-
egories, based on the anodizing electrolyte: acidic, buffered, polar
organic electrolytes and nonuoride-based electrolytes [52]. An
acidic electrolyte provides suitable conditions for an anodic oxida-
tion process. The dissolution rate, measured in nanometres per
second, can be determined by measuring the X-ray photoelectron
spectroscopy depth proles when an anodized oxide layer is
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etched at different pH values. The highest dissolution rate matched
the lowest pH value. The changes in pH values were observed dur-
ing electrochemical anodization [40].
To combine the benets of a nanostructure (e.g. nanotubes with
50 nm diameter), which enhances the biological interaction be-
tween bone cells and an implant surface, with a microscale struc-
ture (e.g. with a roughness of 120 lm), which encourages
biomechanical interlocking through bone tissue ingrowth, Craw-
ford et al. [5355] fabricated a dual porous hierarchical structure
on titanium using a simple anodic oxidation process. The hierarchi-
cal structure consisted of a dual porous structure of TiO2 nanotubes
(48 nm in diameter, 12 nm in wall thickness and 325 nm in length)
at the nanoscale and a random distribution of microscopic pores
with sizes ranging from the submicron range to 20 lm in diameter
[54]. They [55,56] reported that TiO2 nanotube growth could be af-
fected by the orientation of the titanium substrate. They also inves-
tigated the mechanical properties and deformation behaviour of
the TiO2 nanotubes in great detail, and measured the modulus of
the coating of nanotubes [55,57].
In the process of the fabrication of a TiO2 nanotube, it has been
shown that, when the pH value is slightly acidic, long smooth tubes
can be formed [51]. An irregular porous layer will be obtained if an
inappropriate applied potential is used. Increasing the anodization
time can increase the thickness of the nanotube oxide layer; how-
ever, there is a limit beyond which no further changes will be ob-
served or the oxide layer might possibly dissolve. The time limit for
a nonaqueous electrolyte is longer than for an aqueous one.
There are few studies on the effect of the nanotube length and
wall thickness on adhesion, wettability or surface energy, and con-
sequently on cell adhesion, proliferation and differentiation.
Although longer nanotubes have been obtained by improving the
method used and maximizing the conditions, the question of the
optimum length required to promote cell response has not been
addressed to date, except by Bauer et al. [58], who indicated that
the tube length does not affect the cell behaviour.
 S. Minagar et al. / Acta Biomaterialia xxx (2012) xxxxxx 7

Fig. 6. SEM images of TiO2 nanotubes formed in 1 M (NH4)2SO4 + 0.5 wt.% NH4F at 20 V: (a) top view; (b) bottom view; and (c) cross-section. Reproduced from Macak et al.
[38].

3. Nanotube oxide layer on titanium alloys and titanium
alloying metals
3.1. Anodization of biocompatible TiNbTaZr alloy
Some titanium alloying elements are beta (b)-stabilizers, e.g.
molybdenum, vanadium, niobium, tantalum (isomorphous; com-
pletely miscible elements in the phase), iron, tungsten, chromium,
silicon, cobalt, manganese (eutectoid; elements with eutectoid
temperature as 335 C below the unalloyed titanium transforma-
tion temperature) and zirconium (a neutral (continuous solid solu-
tion) alloying element). Beta titanium alloys exhibit a lower elastic
modulus compared to a and a + b titanium alloys [7,59]. TNTZ is
such an alloy, and is the alloy of choice for orthopaedic endopros-
theses [60]. Since TNTZ alloy cannot form apatite on its surface by
the usual chemical- and heat-treatment processes, another surface
modication method is required [6,60].
Nakada et al. [61] suggested using TNTZ for orthopaedic im-
plants because of its excellent mechanical properties, anticorrosion
ability, cytocompatibility and biocompatibility. An alloy of

Fig. 7. SEM images of TiO2 nanotubes formed in ethylene glycol + 0.3 wt.% NH4F + 2 vol.% H2O: (a) top view; (b, c) cross-section; and (d) bottom view. Reproduced from
Macak et al. [43].

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8 S. Minagar et al. / Acta Biomaterialia xxx (2012) xxxxxx
Ti15Nb4Ta4Zr was compared to conventional Ti6Al4V in terms of
new bone formation and bone mineral density (BMD) [62]. It was
demonstrated that the BMD around Ti15Nb4Ta4Zr was equivalent
to, or even higher than [61], that of Ti6Al4V.
Hard tissue replacements, especially knee and hip joints, are
eroded over time due to micromovement. As a result, microscopic
wear particles gather at the implanttissue interface and give rise
to inammation, osteolysis, infection and, potentially, implant
loosening. The wear resistance of Ti29Nb13Ta4.6Zr was measured
after different heat treatments and oxidation treatments [63].
Wear resistance was improved by increasing the niobium content,
especially by means of an oxidation treatment, since the Nb2O5
layer is hard and exhibits lubricity; however, no improvement
was observed following heat treatment [63].
Anodic oxidation of TNTZ alloy was shown to exhibit different
reaction rates because of the different electrochemical oxidation
rates of the elements in this alloy [64]. Consequently, dissolution
was more selective and a regular, self-organized pattern of anodic
tube layers grew to different sizes. Each tube with a large diameter
was surrounded by nearly eight tubes of a smaller diameter. The
process was initiated from two layers an outer nanoporous layer
and a nanotube layer when the sweep potential of a potentiom-
eter was employed. The top nanoporous layer dissolved when the
sample was held in the electrolyte, and additional time was also
necessary to grow nanotubes when the applied potential was
low [64,65].
Homogeneous oxide layers of 100 nm thickness were formed on
the a phase of Ti6Al4V due to electrochemical anodization of the
titanium alloy [66]. On the other hand, due to selective dissolution
of oxide layers during anodization, the b phase of Ti6Al4V exhib-
ited oxide layers that were inhomogeneous in terms of morphol-
ogy and diameter. An inhomogeneous oxide layer that was
nanoporous and a mixture of nanopores and nanoscratches were
observed for a complex of a + b phases. The element niobium
was observed in nanotubes formed on the surface of alloys consist-
ing of niobium [66,67]. An anodized nanotube oxide layer with
structures on two size scales was observed on Ti28Zr8Nb alloy
using buffered electrolyte [68]. In this study, two distinctly differ-
ent bottom tube diameters 175 nm large nanotubes surrounded
by several 98 nm small nanotubes were formed with a length of
8.5 lm. The thickness of this oxide layer depended on both the
anodization time and the applied potential: and it reached 22 lm
by extending the time to 8 h; and increased from 3.2 to 11.3 lm
by increasing the applied potential from 10 to 40 V for 1 h anodiza-
tion [68]. This study concluded that the nanotube length increased
almost linearly with anodization time for the rst 60 min, after
which the rate slowed, whilst the nanotube length increased line-
arly with applied potential up to 40 V. Further studies of the anodic
oxidation conditions required to tailor optimal nanotubes on tita-
nium alloys for orthopaedic applications using this new multi-
scale nanotubular geometry are needed, together with evaluations
of their effect on cell behaviour. Fig. 8(a)(c) shows SEM images,
and Fig. 8(d) a TEM image, of an anodic oxide nanotube layer
formed on a b titanium alloy after anodization at 20 V for 4000 s,
reproduced from the work of Tsuchiya et al. [66].
3.2. Anodization of binary titanium alloys for implant applications
There are studies [69,70] on binary titanium alloys such as Ti
xTa, TiyZr and TiAl, where researchers have investigated the ef-
fect of the alloy composition on the morphology of the anodic
oxide layers. Uniform nanotube arrays of oxide layers were formed
on a TiZr alloy, and the diameters of the tubes decreased and the
length increased with increasing zirconium content. Tube separa-
tion occurred when the titanium content of the TiAl alloy in-
creased [69]. In the case of Ti50Ta, the morphology and length
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Acta Biomater (2012), http://dx.doi.org/10.1016/j.actbio.2012.04.005
of the nanotubes depended on the phases of the alloy. It was re-
vealed that the nanoporous oxide layers that formed rst were dis-
solved after the growth of nanotubes beneath the substrate
surface. This dissolution arose because a local electrochemical con-
dition was established due to the different compositions of the
complex phases [70].
Titaniumzirconium alloys (Ti20Zr, Ti50Zr, Ti80Zr), which
had been fabricated by accumulative roll bonding (ARB), were trea-
ted electrochemically [71]. The ARB process did not inuence the
diameter, length or degree of arrangement of the tubes during
anodization. Tubular oxide layers were formed at all levels of zirco-
nium content without any transition from porous to tubular form.
The tube diameter also decreased, although the tube length in-
creased, when the zirconium content was increased. Two dissimi-
lar diameter tubes were observed on Ti50Zr and Ti80Zr. These
have also been observed previously as forming on Ti29Nb
13Ta4.6Zr and Ti50Ta [71]. Table 2 summarizes the anodization
conditions, characteristics and properties of TiO2 nanotubes on
titanium investigated by different research groups to date.
An equation was proposed to describe the linear relationship
between the outer diameter of a zirconium titanate nanotube
and the anodization potential from 1 to 100 V in a buffered electro-
lyte [72]. This study also indicated that the concentration of the
uoride ions inuenced the wall thickness and the composition
of the nanotube layer because the zirconium titanate nanotubes
grew as a result of competition between electrochemical oxide for-
mation and the chemical dissolution of oxide by uoride ions. The
wall thickness was smaller for high uoride ion concentrations due
to the accelerated dissolution rate of the oxide wall. The nanotube
length depended on the anodization charge until signicant etch-
ing of the nanotube top was observed [72]. Multiple nanotube lay-
ers that can be formed using multiple-step anodizing have
potential for such applications as ultraltration or drug release sys-
tems [73]. The lower layer of nanotubes started to form in the gaps
between the nanotubes of the upper layer created in the previous
anodizing step [73]. Zirconium titanate nanotubes that were
formed on Ti50Zr (wt.%) alloy surface were amorphous and were
converted to crystalline form after annealing, although TiO2 nano-
tubes on pure titanium were amorphous and ZrO2 nanotubes on
pure zirconium were crystalline [74]. The nanotube oxide layer
that grew on the Ti45Nb (wt.%) alloy was thicker and more regu-
lar in comparison to the layers formed on pure titanium and nio-
bium [75]. Under the same anodization conditions, the oxide
layer of TiO2 on pure titanium exhibited a thickness of 1.1 lm
and a tube diameter of 100 nm, and Nb2O5 nanotubes on pure nio-
bium exhibited a thickness of 0.6 lm with a 15 nm irregular pore
diameter, whilst a uniform oxide layer of nanotubes 60 nm in
diameter and 2.9 lm in length grew on the Ti45Nb alloy after
2 h anodization, and the length of the tubes increased to 6.3 lm
at 20 h anodization [75].
3.3. Anodization of tantalum as a b-stabilizer
Tantalum is more expensive and has a much higher density
(16.6 g cm3) [76] than titanium (4.5 g cm3) [77], and therefore
is not appropriate for implants. However, its chemical and physical
properties, such as biocompatibility [78], radiopacity, dielectric
properties [79] and high corrosion resistance to body uids, are
attractive [80]. Tantalum has applications for optical devices, stor-
age capacitors for very large-scale integrated circuits, and for elec-
tronic and sensor devices. Tantalum oxide has received a lot of
attention as a protective coating material due to its corrosion resis-
tance. In addition to aluminium, tantalum is one of several metals
onto which a porous oxide layer can be formed by anodizing
[23,81].
 S. Minagar et al. / Acta Biomaterialia xxx (2012) xxxxxx
Fig. 8. (a)(c) SEM images of an anodic oxide nanotube layer formed on a b titanium alloy after anodization at 20 V for 4000 s: (a) top view; (b) cross-section; (c) bottom
view; and (d) TEM image. Reproduced with permission from J. ECS Trans., 3, 365 (2007). Copyright 2003, The Electrochemical Society [66].
A porous oxide layer (Ta2O5) can be formed on tantalum metal
when it is electrochemically treated in acid that contains HF as the
electrolyte. Pore diameters are from 2 to 35 nm and the layer thick-
ness is 350400 nm. Similar to titanium, the structure and distri-
bution of the pores and the thickness of the porous layer can be
altered by changing the concentration of HF, the time allowed for
anodic oxidation and the anodization voltage. The equilibrium be-
tween porous oxide formation and its dissolution, as well as the
time scale, controls the lm thickness for the development of
porosity and ordering effects [23,79,82]. Before the reappearance
of a dimpled tantalum surface, anodized using a single H2SO4
and HF electrolyte without an organic additive, a high aspect ratio
tantalum oxide nanotubes (2.5 lm in length and 25 nm in inner
diameter) could be fabricated if the anodization time was longer
than 5 s and less than 2 min. The reason for the nanotube loss from
the surface was shown to be the formation of a thin, uoride-rich
(likely TaF5) layer built up at the Ta/Ta2O5 interface [83].
A tantalum oxide nanoporous layer was also fabricated in an or-
ganic electrolyte consisting of ethylene glycol and glycerol, with a
background salt such as (NH4)2SO4 plus a suitable amount of NH4F
to a maximum thickness of 11 lm, the pore diameters increasing
from 9 to 16 nm with increasing voltage from 10 to 40 V [84]. A
highly ordered Ta2O5 nanoporous layer grew on tantalum foils by
anodization using glycerol (1,2,3-propanetriol) and NH4F as elec-
trolyte. It was found that the average pore diameter and the thick-
ness of the porous layers were affected by the NH4F concentration.
The optimum conditions for forming a homogeneous nanoporous
oxide layer, with a high aspect ratio, a pore diameter of 17 nm
and a thickness of 16 lm, were a 0.2 M NH4F electrolyte and an ap-
plied potential of 20 V [85]. Fig. 9 shows SEM images of an anodic
oxide nanoporous layer formed on tantalum substrate using 1 M
H2SO4 + 2 wt.% HF electrolyte for 2 h with a sweep rate of
100 mV s1, reproduced from the work of Sieber and Schmuki [82].
Tantalum has been deposited on a titanium surface by electro-
deposition [86,87] and a solgel process [88] so that the good bulk
properties of titanium could be enhanced by the good surface
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Acta Biomater (2012), http://dx.doi.org/10.1016/j.actbio.2012.04.005
9
properties of tantalum oxide. The aim was to increase the corrosion
resistance as well as the bond strength between the bone tissue
and the titanium.
3.4. Anodization of niobium as a b-stabilizer
The functionality of niobium for its application in gas sensors,
catalysts, optical and electrochromic devices, and biocompatible
prostheses has been investigated with regard to increasing the lo-
cal surface area. Nanostructured niobium oxide has been fabricated
by reactive sputtering [89], solgel processes [90], templating
techniques [91] and anodic oxidation [92]. Sieber et al. [22] were
the rst group of researchers to fabricate self-organized porous
niobium oxide by anodizing oxidation in an electrolyte containing
F. Uniform layers of porous niobium oxide with 2030 nm pore
diameters were obtained. The HF concentration in the electrolyte
and the anodization time inuenced the thickness and microstruc-
ture of the porous layer. Steady-state porous lm formation and
lm dissolution limited the lm thickness to about 500 nm [22].
The effects of mixed electrolytes, applied potential and anodiza-
tion time were investigated to obtain a high aspect ratio of ordered
porous niobium oxide layers. It was revealed that ordered porous
niobium oxides with diameters of less than 10 nm were formed
by anodization of niobium foils at 2.5 V in a mixture of 1 wt.% HF
and 1 M H3PO4 for 1 h. Nanoporous niobium oxides could not
formed on niobium if a single HF electrolyte was used since the
pore wall dissolved as they formed [93].
Choi et al. [94] targeted a thickness of porous niobium oxide of
more than 500 nm by employing double anodizing and one-step
annealing. The annealing step was designed to form a protective
oxide layer that would delay the chemical dissolution as part of
the anodic oxidation in uorinated electrolytes. The thickness of
the outer layer formed in the rst step was around 90130 nm;
and the inner layer of around 300400 nm was grown underneath
the rst layer after annealing [94]. Fig. 10 shows SEM images of an
anodic oxide nanoporous layer formed on niobium substrate at an
 10
Acta Biomater (2012), http://dx.doi.org/10.1016/j.actbio.2012.04.005
Please cite this article in press as: Minagar S et al. A review of the application of anodization for the fabrication of nanotubes on metal implant surfaces.

Table 2
Anodization conditions and the characteristics and properties of TiO2 nanotubes on titanium and titanium alloys.

Anodization condition Characteristics of TiO2 nanotubes Properties Refs.

Electrolyte Applied Time Others Nanotube Wall Nanotube Phase Other treatment Hardness / Wetting angle (water) Roughness
potential diameter thickness layer structure bonding
(V) (nm) (nm) thickness strength
H2SO4/HF 20 2h 50100 Amorphous HT to anatase & [32]
rutile
H3PO4/NaF 20 28 min 30 C 100 Amorphous HT to anatase- Bonding [106]
Stirred deposition; Ca to strength ;
P = 1.67, pH 4.5 7.41 MPa
H2SO4/HF 20 3h 100 500 nm Amorphous HT to anatase & Enhanced Rsm = 25 nm [17]
rutile apatite
formation
H3PO4/HF 20 2h 400 77.45 Ra = 14 nm [34]

S. Minagar et al. / Acta Biomaterialia xxx (2012) xxxxxx

H2SO4/NaF/Citric acid 20 15 min pH 4.5 3570 1018 230 Youngs [42]
4h 670 nm modulus = 36
43 GPa
HF/NH4H2PO4 20 1h 20 C 100 19 1 lm HT to anatase-HA Bonding [41]
Stirred deposition by strength;
immersing 15.3 2.5 MPa
HF 20 2h 100 83.39 Ra = 19 nm [34]
HF/NH4F 20 2h 60 55.45 Ra = 16 nm [34]
HF 20 20 min 80 10 250 nm Amorphous HT to anatase & [36]
rutile
Na2SO4/NaF 20 3h 100 2 lm Amorphous HT to anatase & Signicantly Rsm = 77 nm [17]
rutile enhanced
apatite
formation
(NH4)2SO4/NaF 20 2h 120 16 Ra = 23 nm [34]
Glycerol/NH4F 30 30 min 30 C 5065 Ripple 1.20 lm Amorphous 3.5 0.2 MPa 58 2 Ra = 0.32 0.2 lm [44]
Stirred
Glycerol/NH4F 30 60 min 30 C 6075 Ripple 1.45 lm Amorphous 4.1 0.2 MPa 73 2 Ra = 0.49 0.3 lm [44]
Stirred
Glycerol/NH4F 30 120 min 30 C 7585 Ripple 1.7 lm Amorphous 3.7 0.3 MPa 78 2 Ra 0.17 0.2 lm [44]
Stirred
Glycerol/NH4F 30 240 min 30 C 110130 Ripple 1.9 lm Amorphous 3.6 0.2 MPa 84 1 Ra = 0.13 0.2 lm [44]
Stirred
NH4F and H2O in Ethylene glycol 60 18 h 100 25 45 lm Amorphous HT to anatase & [43]
rutile
Ethylene glycol/HF 120 15 h 70 45 261 lm [46]
CH3COOH-0.2% H2O/NH4F 30 1h 10 200 nm [47]
KF/NaHSO4/citri acid 25 20 h pH 4.5 110120 4.4 lm Amorphous HT to anatase & [51]
rutile
H2SO4/NaF/citric acid 20 4h pH 4.5 51.1 50.58 600 nm Amorphous HT to anatase & 1.51.7 GPa Water = 7.5 3 Cell Rms = 51.83 7.77 [107]
rutile (3643 GPa) media = 2 1 (surface
energy of 332.6 mJ/m2)
Acetic acid/HF 520 30100 Amorphous HT to anatase 11,9,7,4 Ra = 13.0,12.7,13.5,13.2 nm [108]
HT = Heat treatment
 S. Minagar et al. / Acta Biomaterialia xxx (2012) xxxxxx 11

Fig. 9. SEM images of an anodic oxide nanoporous layer formed on tantalum substrate using 1 M H2SO4 + 2 wt.% HF electrolyte for 2 h with a sweep rate of 100 mV s1: (a) top
view and (b) cross-section. Reproduced with permission from J. Electrochem. Soc., 152, C639 (2005). Copyright 2003, The Electrochemical Society [82].

Fig. 10. SEM images of an anodic oxide nanoporous layer formed on niobium substrate at an anodization temperature of 15 C: (a) top view and (b) cross-section. Reproduced
from Choi et al. [94].

anodization temperature of 15 C, reproduced from the work of cal etching behaviour of the electrolyte and the porous to tubular
Choi et al. [94]. morphology, which is important in different applications [99].
Pretreatments such as dip etching [98], electropolishing [100]
and two-step anodizing [98] were used in the investigations of
the effect of pretreatment of the zirconium surface on anodized
3.5. Anodization of zirconium as a neutral titanium alloying element
nanotubes. The regular nanotubes that formed on the dip-etched
surface indicated that the mechanical deformation layer and/or zir-
Zirconium is one of the valve metals reported to form porous
conium surface impurities were the reason(s) for the irregular, pat-
oxide layers on their surface. Zirconium oxides have noteworthy
chy (coherent) oxides. Needle-like structures (nanopillars) on the
properties, such as chemical and thermal stability, mechanical
top of the tube walls were also observed due to thinning and par-
strength, wear resistance, good ion exchange and excellent bio-
tial etching-out [98]. Highly regularly hexagonal ordered dimples
compatibility. Zirconium is used as a catalyst, so an increase in
of the right spacing were formed on the zirconium surface after re-
its surface area improves its functionality. Other applications in-
moval of the layer that resulted from the rst anodization step. The
clude magnetic recording media, optical devices, functional elec-
nanotubular oxide layer exhibited a thickness of 3 lm and a diam-
trodes and waveguides [95].
eter of 60 nm, with highly ordered hexagonally pores that could be
Tsuchiya and Schmuki [24] were among the rst researchers to
removed [98]. The roughness of the zirconium surface decreased
report on the fabrication of sponge-like porous zirconium oxide
from 18.6 nm for the bare surface to 1.1 nm upon electropolish-
layers manufactured by electrochemical anodization in an acidic
ing. This reduction had an inuence on the homogeneous electric
electrolyte containing F. An applied potential between 20 and
eld distribution over the entire metal surface during the anodiza-
40 V was needed, and the pore diameter was several tens on nano-
tion step, thus nanotubes grew regularly on the entire surface
metres, with a thickness of several tens on micrometres.
[100]. Fluorine can be removed from the ZrO2 nanotubes by heat
The formation mechanism of a self-organized nanotube oxide
treatment at 300 C for 6 h, and it has been shown that, although
layer has been described in detail [96] with regard to the effect
800 C heating will lead to crystallization, collapse of the nano-
of changing (i) the concentration of uoride ions and pH, (ii) the
tubes will be observed [101]. Fig. 11(a)(c) shows SEM images,
composition of the electrolyte and (iii) the potential sweep rate
and (d) a TEM image, of an anodic oxide nanotube layer formed
and holding potential on the morphology and geometry of the por-
on a Zr substrate using a 1 M (NH4)2SO4 + 0.5 wt.% NH4F electro-
ous oxide structures. By improving the method, smooth, high-as-
lyte, reproduced from the work of Tsuchiya et al. [97].
pect-ratio zirconia nanotubes, with a diameter of 50 nm and a
length of 17 lm, were obtained using a buffering electrolyte, in-
stead of the wavy, irregular wall morphology of pore arrays 4. Summary
[96,97]. Organic electrolytes were also used to grow signicantly
thicker, continuous and smoother ZrO2 nanotubular layers up to As bone is alive, an implant has to be accepted by the bone cells,
40 lm on zirconium substrates [98100]. It has been shown that and must be able to bond to and grow on it, in order to prevent
the water content of the organic electrolyte inuenced the chemi- loosening and inammation when it is inserted close to the bone.

Please cite this article in press as: Minagar S et al. A review of the application of anodization for the fabrication of nanotubes on metal implant surfaces.
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12 S. Minagar et al. / Acta Biomaterialia xxx (2012) xxxxxx
Fig. 11. (a)(c) the SEM images of an anodic oxide nanotube layer formed on Zr substrate using 1 M (NH4)2SO4 + 0.5 wt.% NH4F electrolyte: (a) top view; (b) cross-section;
(c) bottom view; and (d) TEM image. Reproduced with permission from J. ECS Trans., 1, 351 (2006). Copyright 2003, The Electrochemical Society [97].
It is well known that titanium and its alloys are more biocompat-
ible than other metal implants, and that the TiNbTaZr alloys
have the lowest Youngs modulus and highest biocompatibility. If
there is a uoride anion in an electrolyte, controllable metal oxide
nanotubes can be fabricated by anodization on titanium, titanium
alloying metals (niobium, tantalum and zirconium) and biocom-
patible titanium alloys, that is, TiNbTaZr alloys and binary Ti
Nb, TiTa and TiZr alloys. The nanotubes on titanium promote
bonding to bone due to their high surface area and the ability for
cell interlocking.
The tube diameter and the length of TiO2 nanotubes depend on
the conditions of electrochemical oxidation, such as the type, con-
centration and pH of the electrolyte, the applied potential and the
anodization time. The tube diameter can be increased by increas-
ing the applied potential if the pH value remains constant; and
the tube diameter is pH independent if the applied potential re-
mains constant. In comparison to using an aqueous electrolyte, a
higher applied potential is required to obtain the same diameter
nanotubes if an organic electrolyte is used. The tube length or
the thickness of the nanotube layer increases with the time of
anodization, but there is always a point at which the thickness re-
mains constant with any further increase in time. It is worth noting
that in an acidic electrolyte with a pH value less than 1, although
nanotubes form, their length will not increase with increasing time
of anodization. In an organic electrolyte, although the process re-
quires a longer time, considerably longer nanotubes can be tailored
beyond a certain water content.
Nanotubes fabricated on implant material surfaces provide
great potential in promoting cell adhesion, proliferation and differ-
entiation. Nanotubes also offer the possibility of bacterial infection
control by loading the tubes with antibacterial agents. However,
there is still insufcient data to establish the optimum nanotopog-
raphy for favourable cell response. Further studies are needed to
nd the optimum sizes for the length and diameter of nanotubes
in order for recognition and adherence by the sensing element of
a bone cell.
Please cite this article in press as: Minagar S et al. A review of the application of anodization for the fabrication of nanotubes on metal implant surfaces.
Acta Biomater (2012), http://dx.doi.org/10.1016/j.actbio.2012.04.005
Acknowledgements
S.M. would like to acknowledge the State Government of Victo-
ria in Australia for supporting and funding this research project
through the Victorian International Research Scholarship. C.W. is
also supported by the Australian Research Council (ARC) through
the ARC Discovery Project DP110101974.
Appendix A. Figures with essential colour discrimination
Certain gures in this article, particularly Figs. 13, are difcult
to interpret in black and white. The full colour images can be found
in the on-line version, at http://dx.doi.org/10.1016/
j.actbio.2012.04.005.
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