Thin Solid Films 583 (2015) 151157

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Thin Solid Films

journal homepage: www.elsevier.com/locate/tsf

Interfacial structure of the rmly adhered TiO2 nanotube lms to

titanium fabricated by a modied anodization
Yanni Zhang, Yong Han , Lan Zhang
State Key Laboratory for Mechanical Behavior of Materials, Xi'an Jiaotong University, Xi'an 710049, China

a r t i c l e

i n f o

Article history:
Received 24 October 2014
Received in revised form 10 February 2015
Accepted 25 March 2015
Available online 1 April 2015
Keywords:
Anodization
TiO2 nanotube
Adhesion strength
Interfacial structure

a b s t r a c t
TiO2 nanotube lms rmly adhered to Ti substrate were fabricated by a modied anodization, which involved in a
traditional nanotubular structure formation stage in a uoride-containing electrolyte and an additional uoride
(F) ion sedimentation stage by addition of (CH3COO)2 Mg during the later period of anodization. The obtained
results showed that the adhesion strength of the modied anodization derived TiO2 nanotube lms, as characterized by critical load (Lc) using a scratch test, could be signicantly improved from 3.2 0.8 N for the traditional
anodization derived one to a maximum value of 17.5 1 N. There was no obvious change in surface morphologies of the amorphous TiO2 nanotube lms prepared by the traditional and modied anodization, respectively.
For the traditional anodization derived nanotube lm, there was an ultra-thin uoride-rich layer (about 15 nm in
thickness) existing between the nanotube bottoms and the Ti substrate, weakening the adhesion strength. However, the modied anodization derived TiO2 nanotube lm with the highest Lc value consisted of two layers: an
outer nanotube layer and an inner compact layer adjacent to the Ti substrate composed of amorphous titanium
oxide free of uoride ions. Such structure of TiO2/Ti interface led to a considerable improvement in the adhesion
strength between the nanotube lm and the Ti substrate.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Titanium and its alloys have been widely used in biomedical applications owing to their high specic strength, remarkable corrosion resistance and superior biocompatibility [13]. However, they are bio-inert
and cannot directly bond with the living bone at early stage after implantation [4,5]. Recently, self-organized TiO2 nanotube lms have
been demonstrated to be of enormous applications in orthopedic and
dental implants due to their excellent biocompatibility and unique
biological properties [69]. For example, compared with compact TiO2,
TiO2 nanotube lms can signicantly enhance the adhesion, proliferation, differentiation of cells (including osteoblast, mesenchymal stem
cell, endothelial cell and broblast) [1014], and TiO2 nanotubes with
controllable dimension and high surface-to-volume ratio have been
exploited as drug release platforms [1517].
Anodization is a commonly used method for the formation of nanotube lms on titanium [6,7,18]. However, the adhesion strengths of the
anodized nanotube lms are usually poor, signicantly limiting their
clinical applications [3,1921]. To overcome the drawback, many technologies have been explored. For example, micro- and nano-patterned
TiO2 nanotubes were anodized on laser-micromachined titanium substrate, but the improvement of adhesion was limited due to mechanical
anchoring [21]. Annealing treatment was also applied to improve the
Corresponding author. Tel.: +86 2982665580.
E-mail address: yonghan@mail.xjtu.edu.cn (Y. Han).

http://dx.doi.org/10.1016/j.tsf.2015.03.060
0040-6090/ 2015 Elsevier B.V. All rights reserved.

interfacial structure between the anodized nanotube lm and Ti

substrate, however, the adhesion strength was strongly dependent on
the lm thickness and appeared relatively weak when it was thicker
than 3.5 m [22]. Alternatively, although thermal treatment of the nanotube lm in acetylene atmosphere enhanced its mechanical strength,
the phase component of the lm changed to TiOxCy [23]. Therefore, it
is urgent to explore an effective alternative of anodization to fabricate
TiO2 nanotube lms with enhanced adhesion strengths.
It is known that the formation of TiO2 nanotube lms should be
attributed to the competition of the chemical dissolution and oxide
formation during the anodization [6,2426]. With regard to chemical
dissolution, uoride ions with small ionic radius are able to migrate
(twice rate of oxygen ions) into the growing oxide lattice and even to
the oxide/metal interface with the aid of the applied electric eld, and
accumulate at the nanotube/substrate interface in the form of a watersoluble uoride-rich layer which weakens the adhesion strength
[24,2729]. Therefore, the adhesion strengths of the nanotube lms
may be enhanced if the uoride-rich layer can be avoided. Our previous
work has reported a modied anodization with an additional F
sedimentated procedure, by which ZrO2 nanotube lms with signicantly enhanced adhesion strength to Zr substrate could be formed
[30]. However, whether or not the adhesion strength of TiO2 nanotube
can be improved by the modied anodization is unknown. The present
work focuses on the fabrication of TiO2 nanotube lms with enhanced
adhesion strengths by a modied anodization, which involved a traditional nanotubular structure formation stage in a uoride-containing

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electrolyte and an additional uoride (F) ion sedimentation stage by

addition of (CH3COO)2 Mg during the later period of anodization, and
the interfaces between the TiO2 nanotube lms and Ti substrates were
also investigated.
2. Experimental materials
Prior to anodization, commercially pure grade titanium (99.9 wt.%
Ti) plates with a size of 16 mm 3 mm were mechanically polished
and ultrasonically washed successively in acetone, ethanol, deionized
water, and then dried in a vacuum. For the formation of the anodized
TiO2 nanotube lms, a direct current power source (WYK-602, Huatai,
China) was employed. A titanium plate was used as an anode, and a
graphite plate constructed cathode was kept at a distance of 5 cm
from the anode. The electrolyte was an ethylene glycol (EG) solution
containing 2 vol.% water and 0.08 M NH4F (98%, analytical reagent),
and was stirred continuously at 20 rps by a magnetic stirrer during
anodization. Under this condition, a part of Ti plates were treated by a
traditional procedure, e.g., anodized at an applied voltage of 60 V for
60 min; the other part of Ti plates were rstly subjected to the traditional procedure, and then continued to be anodized at 60, 80, 100, 120 and
140 V for 60 min and at 80 V for 30, 60, 70, 90 and 120 min, respectively.
During the additional anodization procedure, EG solutions containing
(CH3COO)2 Mg were added into the electrolyte at a speed of 0.5 ml/s,
with the electrolyte having Mg2+ concentrations of 0.04, 0.048, 0.06,
0.072, 0.088, 0.1 and 0.16 M, respectively. The (CH3COO)2 Mg derived
sedimentation of F in the electrolyte follows the reaction as:
Mg2+ + 2 F MgF2 (solid). The F concentrations in the anodizing
electrolytes with the sedimentation time were detected using ion chromatograph (WY IC6100, China) in triplicate for each test, which was
given in ppm and converted to mole concentration (M). After the anodization treatments, the obtained samples were immediately washed
ultrasonically with methanol and dried at room temperature.
An auto scratch coating tester (WS-2005, China) was applied to
characterize the adhesion strengths of the TiO2 nanotube lms. The
scratch test consisted of the generation of scratches using a spherical
stylus at a constant speed (3 mm/min) over the surface, and the normal
load that was increased linearly from 0 N to different loads. The critical
load (abbr. Lc), at which the recognizable failure occurred, was recognized as the smallest load and determined from the load versus acoustic
characteristics and SEM images of the scratches. The values of critical
loads were averaged by ve tests.
The phase components of the TiO2 nanotube lms were analyzed
using X-ray diffraction (XRD; D/MAX-2400, Rigaku, Japan) in 2
geometry. The morphologies of the samples were observed using a
eld emission scanning electron microscope (FESEM; JSM-6700F,
JEOL, Japan). The cross-sectional morphologies were directly conducted
on the mechanically fractured sections of the samples. Energy dispersive X-ray spectrometer (EDX; DX-4, Philips, Netherlands) equipped
in FESEM was used to examine the elements of the samples. The
cross-sectional structure of the TiO2 nanotube lms was further investigated using transmission electron microscopy (TEM, JEM-2100F, JEOL,
Japan). For the TEM observation, the cross-sectional slice was prepared
as details in previous work [30]. Analysis of the elemental composition
proles was conducted using EDX under STEM nano-probe condition
on the JEM-2100F eld emission microscope.
3. Results
3.1. Adhesion strengths of the TiO2 nanotube lms anodized without and
with F sedimentated procedure
During the modied anodization, the addition of Mg2+ could lead to
the sedimentation of F in the electrolyte, as shown in Fig. 1. It is obvious that the F concentration in the electrolyte decreased sharply with
increasing the Mg2+ concentration added in the electrolyte. For each

Fig. 1. F concentration in the anodizing electrolyte as a function of sedimentation time in

the case of each initial Mg2+ concentration.

added Mg2+ concentration, the F concentration dropped with

prolonging the sedimentation time and reached to a platform at 22
35 min depending on the Mg2+ concentration.
The critical loads of the TiO2 nanotube lms formed by the traditional anodization and modied anodization at different processing parameters are presented in Fig. 2. The average critical load of the traditionally
anodized TiO2 nanotube lms was 3.2 0.8 N (Fig. 2(a)). For the modied anodization derived TiO2 nanotube lms, the critical loads of the
lms generally increased rst and then decreased with increasing
Mg2+ concentration (Fig. 2(a)), sedimentation voltage (Fig. 2(b)) and
time (Fig. 2(c)). A maximum value of the critical load appeared at
17.5 1 N when F was sedimentated by the addition of 0.06 M
Mg2+ at 80 V for 70 min. Fig. 3 presents the curves of the acoustic output
versus the load and corresponding scratch morphologies of the TiO2
nanotube lms obtained by traditional anodization and modied anodization with F sedimentated procedure at 80 V in 0.06 M (CH3COO)2
Mg as examples. It is obviously observed that the traditionally anodized
TiO2 nanotube lm (abbr. TNT) was delaminated at the Lc of about 3 N
(Fig. 3(a)). However, the nanotube lm anodized with F sedimentated
procedure performed at 80 V for 70 min in the case of 0.06 M Mg2 +
(abbr. MNT) was peeled off from the Ti substrate at a much higher Lc
of about 18 N (Fig. 3(b)).
3.2. Microstructure characterization of TiO2 nanotube layers anodized
without and with F sedimentated procedure
In order to explain the reason why the adhesion strength of the TiO2
nanotube lms can be signicantly improved by the modied anodization, the microstructures of two typical TiO2 nanotube lms, TNT and
MNT, were analyzed as follows.
3.2.1. X-ray diffraction
The XRD patterns of the TNT and MNT lms are shown in Fig. 4. Ti
peaks were corresponding to the Ti substrates, indicating that the TNT
and MNT nanotubes were both amorphous.
3.2.2. SEM investigation
Figs. 5 and 6 show the surface morphologies and cross-sectional
images of TNT and MNT lms, respectively. The TNT lm exhibited
a highly ordered structure with an average tube diameter of about
100 nm (Fig. 5(a)) and length of about 6 m (Fig. 5(b)). Due to the
preparation process of cross-sectional SEM specimen of the TNT lm,
some nanotubes were peeled off from the substrate, indicating a poor
adhesion strength of the TNT lm (Fig. 5(b)). Some remnants in the
form of dimples were left on the exposed substrate surface (Fig. 5(b)).
EDX analysis of the remnants (inset in Fig. 5(b)) shows that besides O

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153

Fig. 2. Critical loads of the anodized TiO2 nanotube lms as a function of processing parameters: (a) the added (CH3COO)2 Mg concentration in the electrolyte at 60 V for 60 min; (b) the
sedimentation voltage for 60 min in the case of 0.06 M (CH3COO)2 Mg and (c) the sedimentation time at 80 V in the case of 0.06 M (CH3COO)2 Mg during the sedimentation procedure.

and Ti, the content of F was about 13.5 at.%, suggesting that the
remnants were uoride-rich.
Compared with the TNT lm (Fig. 5(a)), no obvious change in surface morphology is observed for the MNT lm, as shown in Fig. 6(a).
However, the thickness of the lm increased to about 8 m (inset in
Fig. 6(a)), and the lm consisted two layers (Fig. 6(b)). The outer
layer was nanotube layer (about 7.7 m); the inner layer (about
0.2 m) was compact. No apparent discontinuity between the compact
layer and the Ti substrate is observed, indicating that the layer could
tightly bond with the substrate. The EDX analysis (Fig. 6(b)) shows
that the MNT lm consisted of Ti, O and F, and magnesium could not

be detected. The content of F decreased gradually from the nanotube

layer to the zone adjacent to the inner compact layer/Ti interface.
3.2.3. TEM investigation
The cross-sectional TEM images of the TNT and MNT lms coated
Ti are shown in Figs. 7 and 8, respectively. Chemical compositions
(marked with green points in Figs. 7(a) and 8(a)) from the nanotubes
to the substrate are detected using EDX, where the F contents at marked
points are displayed in green numbers. In the case of the TNT lm
coated Ti (Fig. 7(a)), the F content increased with the distance near
the nanotube bottom boundary in the nanotube side, and reached to a

Fig. 3. Representative curves of the acoustic output versus the load and corresponding scratch morphologies (inserts) of the TiO2 nanotube lms: (a) TNT and (b) MNT lms.

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Y. Zhang et al. / Thin Solid Films 583 (2015) 151157

shows that the lattice stripes gradually disappeared from the substrate
to the inner compact layer, indicating that the interfacial structure
was continuous. Additionally, the white particles in the inner compact
layer were also observed by HRTEM. Fig. 8(d) shows the particle marked
with a green square in Fig. 8(b) as an example. The particle was titanium
oxide (EDX result in Fig. 8(d)) with an amorphous structure, although
some short lattice stripes were visible.
4. Discussion
It is well known that the anodic growth of TiO2 nanotubes is
primarily governed by a competition between eld-assisted oxidation
of TiO2 at the nanotube bottom (reaction (1)) and the F etchings
(eld-assisted etching and chemical etching) to the formed TiO2
(reactions (2) and (3)), as follows [6,24].

Fieldassisted oxidation : Ti 2H2 OTiO2 4H 4e

Fig. 4. XRD patterns of (a) TNT and (b) MNT lms.

Fieldassisted etching : TiO2 6F 4H Ti F6 

maximum value of about 14.16 at.% at the boundary. Then it decreased
when the detected point was far away from the nanotube bottom
boundary into the substrate side. Such uorine element distribution
indicated that a uoride-rich layer less than 15 nm in thickness
(Fig. 7(a)) existed between the TiO2 nanotube bottom and the Ti
substrate, which was in accordance with the SEM results in Fig. 5(b).
Fig. 7(b) shows a magnied HRTEM image of the region around the
nanotube bottom boundary. The uoride-rich layer was almost amorphous, and it was further conrmed by the corresponding SAED pattern
(inset in Fig. 7(b)), in which only halation is observed.
The MNT lm, as shown in Fig. 8(a) and (b), was composed of an
outer nanotube layer and an inner compact layer adjacent to the Ti
substrate. F content gradually decreased with closing to the Ti substrate,
and there was almost free F at the interface of the inner compact layer/Ti
substrate. Such structure and F element distribution obtained by TEM
were consistent with those by SEM in Fig. 6(b). Fig. 8(b) shows a magnied image of the area marked with a square in Fig. 8(a). Some white
particles are observed in the inner compact layer, and nanotubular
characteristics gradually disappeared with closing to the Ti substrate.
The corresponding SAED pattern (inset in Fig. 8(b)) shows that the
halation is observed besides a few of diffraction spots ascribed to the
Ti substrate, indicating that the inner compact layer which tightly bonded with the Ti substrate was amorphous. Fig. 8(c) shows an HRTEM
image of the interface of the inner compact layer/substrate (marked
with a white square in Fig. 8(b)). Lattice stripes were ascribed to the
Ti substrate. The area surrounded by the red-dotted line (in Fig. 8(c))

Chemical etching : TiO2 6HFTi F6 

Fieldassisted migration : Ti

2H2 O

2H2 O 2H

6F Ti F6 

1
2
3
4

It is extremely important for the nanotube formation that the eldassisted etching and chemical etching of F to TiO2 (reactions (2) and
(3)) could proceed successfully during the anodization [25]. However,
the uoride ions with small ionic radius can migrate into the growing
oxide lattice at twice the speed of oxygen ions, and accumulate at the
oxide/metal interface with the aid of the applied eld [28], leading to
the formation of a water-soluble uoride-rich layer at the nanotube/
substrate interface (according to reactions (2) and (4)). Such watersoluble uoride-rich layer weakens the adhesion strength of the nanotubes to the substrate [24,27]. In our results, an amorphous and
uoride-rich layer is observed between the TiO2 nanotube bottoms
and the Ti substrate (shown in Figs. 5 and 7), and it weakens the adhesion strength of the TNT lm to the Ti substrate, resulting in a low critical load of just about 3 N (Fig. 3(a)). During the modied anodization,
the F concentration decreases rapidly due to the addition of Mg2 +
into the electrolyte (Fig. 1), and the formation of insoluble MgF2 species
results in the reduction of eld-assisted etching and chemical etching to
TiO2 (reactions (2) and (3)). As a result, a paucity of F at the nanotube
bottom leads to the formation of a relative compact oxide layer with a
lower density which consists of titanium oxide particles (Fig. 8(b)).
Since the conversion of the Ti metal to amorphous anodic TiO2 results

Fig. 5. (a) Surface SEM image of the TNT lm; (b) cross-sectional SEM images of the TNT lm and EDX spectrum taken at the square region inset in (b).

Y. Zhang et al. / Thin Solid Films 583 (2015) 151157

155

Fig. 6. (a) Surface SEM image of the MNT lm and cross-sectional SEM image of the MNT lm inset in (a); (b) magnied view of the region around the lm/substrate interface and EDXdetected F, O and Ti proles.

in the volume expansion which causes the generation of stress [6], this
particle-dispersed layer may, to some extent, alleviate the adverse effect
of the stress on the adhesion strength of the nanotubes to the substrate.
When F in the electrolyte are almost sedimentated, a compact titanium
oxide layer (according to reaction (1)) forms at the TiO2/Ti interface
(Fig. 8(b) and (c)). Such interfacial structure leads to a considerable improvement in the adhesion strength of the nanotubes to the Ti substrate.
In addition, the adhesion strength is affected by the (CH3COO)2
Mg concentration, sedimentation voltage and time during the F
sedimentated procedure, respectively (Fig. 2). It might be explained as
follows. When (CH3COO)2 Mg is added into the electrolyte, the formation of a buffer solution system (CH3COOH/CH3COONH4) and the slow
mobility of the ions in the high viscous electrolyte cause the anodic
current to gradually drop off. In the case of Mg2+ concentration lower
than 0.06 M in the electrolyte, the adhesion strength can be promoted
more effectively with the increase of Mg2 + concentration. However,
when Mg2 + concentration is higher than 0.06 M, the buffer solution
system of CH3COOH/CH3COONH4 is formed too soon. As a result, anodic
current rapidly drops to zero, which is unfavorable for the formation of
the compact titanium oxide layer, and the adhesion strength decreases
with the increase of Mg2 + concentration. On the other hand, the
increased voltage accelerates the ionic mobility in the electrolyte,
which is benecial for the formation of oxide. However, when the sedimentation voltage is higher, such as 80 V, a large number of

discharges are observed on the anode surface. The oxide layer can be
broken by the discharges [31], and the adhesion strength of the TiO2
to the Ti substrate decreases with increasing the voltage. The length of
the nanotube layer increases from about 6 m to about 7.7 m after
the additional procedure, indicating that the nanotubular formation is
still proceeding at the initial stage of (CH3COO)2 Mg addition. In that
way, properly extending the sedimentation time is probably helpful
for the formation of the inner compact layer, but the side effect of the
voltage emerges after too long sedimentation.

5. Conclusion
The TiO2 nanotube lms with signicantly improved adhesion
strengths to the Ti substrates are successfully fabricated by a modied
anodization process with an additional F sedimentated procedure.
There is no obvious change in surface morphologies of the amorphous
TiO2 nanotube lms prepared by the traditional and modied anodization. As for the nanotube lm formed by the traditional anodization, an
amorphous and water-soluble uoride-rich layer is proved to be existent between the nanotube bottoms and the Ti substrate, weakening
the adhesion strength of the TiO2 nanotubes to the Ti substrate. For
the modied anodization derived TiO2 nanotube lm, a compact layer
containing amorphous titanium oxide is formed between the nanotubes

Fig. 7. (a) Cross-sectional TEM image of the TNT lm coated Ti; (b) HRTEM image of the region around the nanotube bottom boundary (marked by red line). (For interpretation of the
references to color in this gure legend, the reader is referred to the web version of this article.)

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Y. Zhang et al. / Thin Solid Films 583 (2015) 151157

Fig. 8. (a) Cross-sectional TEM image of the MNT lm coated Ti, in which the green numbers are F contents detected at the marked points by EDX; (b) magnied view and corresponding
SEAD pattern taken at the square region inset in (a); (c) and (d) HRTEM image taken at the region around the inner compact layer/substrate interface (marked by a white square) and at
the middle portion of the compact layer (marked by a green square) in (b), respectively; the inset view in (d) shows the corresponding EDX spectrum of the white particle (marked by a
green square in (b)). (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

and the Ti substrate. Such interfacial structure leads to a considerable

improvement in the adhesion strength of the TiO2 nanotube lms.
Acknowledgments
We appreciate the National Program on Key Basic Research Project
(973 Program) of China (Grant number 2012CB619103), the National
Natural Science Foundation of China (Grant numbers 51201129,
51371137), the Research Fund for the Doctoral Program of Higher
Education of China (Grant number 20110201120001), and the Fundamental Research Funds for the Central Universities for nancially
supporting this work.
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