Applied Surface Science 257 (2011) 8772–8777

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Applied Surface Science

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

In vitro degradation of AZ31 magnesium alloy coated with nano TiO2 film by
sol–gel method
Junhua Hu a,c,∗ , Caili Zhang b , Baohong Cui a , Kuifeng Bai a , Shaokang Guan a , Liguo Wang a , Shijie Zhu a
a
Research Center for Materials, School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450002, PR China
b
School of Civil and Architecture Engineering, Zhongyuan Institute of Technology, Zhengzhou 450007, PR China
c
Graduate School of Science and Technology, Shizuoka University, 3-5-1 Johoku, Hamamatsu, Shizuoka 432-8011, Japan

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

Article history: A nano TiO2 film was coated on AZ31 alloy substrate by sol–gel method. The TiO2 film was characterized
Received 6 October 2010 by X-ray diffractometry (XRD), differential scanning calorimetry-thermogravimetric analysis (DSC-TG),
Received in revised form 29 March 2011 field emission scanning electron microscopy (FE-SEM) and energy dispersion spectroscopy (EDS). The
Accepted 29 March 2011
degradation of the nano-TiO2 coated alloy was evaluated by immersion test and electrochemical mea-
Available online 5 May 2011
surement. An attempt was made to relate corrosion of coated alloys with the annealing treatment and
resultant structural evolution.
PACS:
© 2011 Elsevier B.V. All rights reserved.
81.65.Kn
81.15.−z
81.20.Fw

Keywords:
In vitro degradation
Sol–gel
Nano TiO2
Mg alloy

1. Introduction
Recently, Mg and its alloys have attracted great attention in
respect of biomedical applications because they possess significant
advantages, such as high specific strength, perfect biocompatibil-
ity and natural abundance [1–3]. Unfortunately, magnesium and
its alloys are highly susceptible to corrosion in chloride containing
environment of physiological systems, including human body fluid
or blood plasma, which has limited their biomedical applications
[3–5].
Although magnesium alloys are alloyed with manganese, alu-
minum and zinc to improve corrosion resistance, further surface
treatment is also required to physically diminish contact with
the environment. Different approaches, including electrochemical
deposition, sputtering process and micro-arc oxidation, were used
to achieve improved corrosion resistance for Mg alloys [6,7]. From
the viewpoint of the health safety, the inorganic films are attrac-
tive as coating materials because some metallic coatings always
contain elements that are less biocompatible. Some attempts have
∗ Corresponding author at: Research Center for Materials, School of Materials
Science and Engineering, Zhengzhou University, Zhengzhou 450002, PR China.
E-mail address: Hujh@zzu.edu.cn (J. Hu).
been made to use TiO2 films as protective layers on the steel sub-
strate [8] and some Mg alloys [9–12]. At the same time, TiO2 films
were also investigated as a surface coating to enhance the biocom-
patibility of biomaterials [13,14]. In this work, nano-TiO2 films were
fabricated on AZ31 alloys by sol–gel method. The degradation of the
nano-TiO2 coated alloy was evaluated by immersion test and elec-
trochemical measurement. The formation of defect structures on
the films was analyzed and related with the degradation of coated
alloys.
2. Experiment
2.1. Sample preparation
Precursor solutions for film coating were prepared using
tetra-n-butyl titanate, absolute ethanol, deionized water
and diethanolamine; the volume ratio is: Ti(OC4 H9 )4 :EtOH:
H2 O:NH(C2 H4 OH)2 = 14:112:2:3. All the chemicals are A.R. grade.
Tetra-n-butyl titanate was dissolved in the absolute ethanol
dropwise. After mixing vigorously at room temperature for 1 h,
deionized water and diethanolamine were added to the solution
in sequence and mixing continued. After 2 h stirring, a transparent
and light yellow collosol was obtained.

0169-4332/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2011.03.148
 J. Hu et al. / Applied Surface Science 257 (2011) 8772–8777
Since AZ31 Mg alloy has similar elastic modulus (∼45 GPa)
to that of natural human bone (40–57 GPa), it can help reduce
stress shielding effects compared with other metal when used as
bone plates. In this work, AZ31 pieces (20 × 8 × 4 mm) were used
as substrates. The substrates were ground by emery paper with
the No. from 100# to 1000# and polished by alumina powder of
0.05 ␮m size; after that the substrates were washed ultrasonically
in the acetone (chemically pure) and ethanol (chemically pure)
for 10 min, respectively. After pre-treatment, the substrates were
immersed into the collosol and withdrawn from it with a speed of
3–5 cm min−1 and dried at ambient temperature. Then annealing
processes were carried out at 200–400 ◦ C for 1–2 h in the vacuum
furnace (10−3 Pa) to avoid the oxidation of samples. The tempera-
ture was elevated gradually (5 ◦ C min−1 ). The thickness of the TiO2
coating was increased by repeating the coating cycle.
2.2. Microstructure characterization
The thermal analysis of condensed gel particles was carried out
by differential scanning calorimetry-thermogravimetric analysis
(DSC-TG, Netzsch, Germany) to specify the thermal stability and
crystallization of TiO2 coating. The measurement of DSC-TG was
carried out from room temperature to 600 ◦ C at a heating rate of
5 ◦ C min−1 in the Ar atmosphere. The crystallization of TiO2 film was
identified by X-ray diffraction (XRD, Philips, PW-1700X) with Cu K␣
( = 0.15406 nm) in the scanning angles from 20◦ to 80◦ . The surface
morphology was observed using field emission scanning electron
microscopy (FESEM, JEOL-6700F). Energy dispersive spectroscopy
(EDS) was employed to determine the elements distribution of the
layers.
2.3. In vitro degradation
In present stage, the degradation behaviors of metallic bio-
materials were assessed widely by the immersion test and
potentiodynamic polarization experiments in Hank’s SBF. The
immersion test was carried out to evaluate the corrosion rate of
samples. After different immersion periods in SBF, the specimens
were removed, rinsed gently with distilled water and dried. An
average of three measurements was used for evaluating the sample
mass variation.
A three-electrode cell was used for the electrochemical mea-
surements. The counter electrode was made of platinum and the
reference electrode was a saturated calomel electrode. The area of
the working electrode (bare and coated Mg alloy) exposed to the
solution was 1 cm2 . The measurements were carried out with a
scanning rate of 0.5 mV s−1 on an electrochemical station. Prior to
the beginning of the polarization tests, the samples were kept in
the solution for 1 h to establish the open circuit potential.
3. Result and discussion
The collosol was aged at room temperature to get gel particles.
Fig. 1 shows typical DSC and TG curves of the dried gel particles.
There are two endothermic peaks at 275 ◦ C (A) and 330 ◦ C (B) fol-
lowed by the only exothermic peak (C) in temperature range of
350–370 ◦ C. The significant exothermic peak C is because of the
crystallization of TiO2 from amorphous to anatase phase [15,16].
The TG curve shows a step-like decline. From room temperature to
200 ◦ C, the mass loss rate is about 17%. The weight loss in this stage
is because of the continuous evaporating of absorbed water. The
weight loss rates corresponding to the temperature ranges contain-
ing peak A and B are 9% and 11%, respectively. These weight losses
are attributed to evolution of organic residues. There is no other
detectable exothermic peak at investigated temperature, which
shows that other phase transition of TiO2 did not occur. Thus, 350 ◦ C
8773
Fig. 1. DSC (by dashed line) and TG (by solid line) curves of the gel particles. Two
endothermic peaks and only one exothermic peak were indicated by A, B and C,
respectively.
is the onset temperature of TiO2 transition from amorphous to
anatase.
The DSC-TG result provided us important information to deter-
mine the annealing parameters in order to evaporate the organic
residues and densify the film. Fig. 2 shows the XRD spectra of
TiO2 /AZ31 annealed at the temperature of 250 ◦ C (a), 300 ◦ C (b) and
400 ◦ C (c) for 1 h. The diffraction peaks corresponding to anatase
TiO2 and substrate were indicated by triangles and circles, respec-
tively. In Fig. 2(a) and (b), no diffraction peaks of anatase were
observed. In Fig. 2(c), the diffraction peaks corresponding to anatase
agree with the referenced stander PDF (powder diffraction profile,
Fig. 2d) pattern.
When the samples were annealed at 250–400 ◦ C for 1–2 h, TiO2
films with almost the identical morphology were obtained. Fig. 3
shows the typical surface FE-SEM image of the annealed TiO2 /AZ31
samples. Under such a magnification, the TiO2 layer is quite flat,
uniform and compact. Fig. 4 shows the annealing dependence of
surface morphology with the magnification of 100,000×. The sur-
faces consist of nearly spherical particles with the size of nano
scale. It is believed that morphology and phase type depends on
the preparation methods heavily [17–21]. The size of TiO2 particles
increased from several nanometers to thirty nanometers when the
annealing temperature increased from 250–400 ◦ C.
EDS analysis in the area of TiO2 /AZ31 interface in cross section
demonstrated the inter-diffusion of Mg and O between the TiO2
layer and AZ31 substrate, which is the same as the findings in the
previous study [22] (data not shown). The inter-diffusion of Mg and
O indicated the formation of metallurgic bonding on the TiO2 /AZ31
interface due to ready formation of oxo bridges (Ti–O–Mg). Gener-
ally speaking, a well adhered interface, namely metallurgic bonding
interface is expected, which will improve their stress resistance and
avoid the peeling-off of the coating during service term. From ele-
mental distribution, it was concluded that TiO2 coating analyzed is
with a thickness of 450 nm.
Fig. 5 shows the relationship of degradation rate with the
annealing parameters. In Fig. 5(a), the degradation rate increases
with the annealing temperature. At the temperature higher than
350 ◦ C, the degradation rate increases with a weaker slope. How-
ever, as shown in Fig. 5(b), the weight loss rate was decreased by
the prolongation of annealing time gradually at the temperature of
300 ◦ C.
TiO2 layers acting as barrier layers are responsible for the differ-
ent degradation rates. The formation of defect structures, including
aggregation and pores, always resulted in the exposure of part of the
substrate to the SBF and deteriorated inhibition effect. The defect
density was calculated as the relation of the defects area to the total
8774 J. Hu et al. / Applied Surface Science 257 (2011) 8772–8777
Fig. 2. XRD spectra of TiO2 /AZ31 annealed at the temperature of 250 ◦ C (a), 300 ◦ C (b)
and 400 ◦ C(c) for 1 h. The diffraction peaks corresponding to anatase TiO2 were indi-
cated by triangle and the peaks originated from substrate were indicated by circles.
A standard anatase TiO2 powder diffraction pattern was shown as comparison (d).
Fig. 3. Typical FE-SEM image of the surface of TiO2 /AZ31 after annealing.
Fig. 4. Surface morphology of TiO2 layers annealed at 250 ◦ C (a), 300 ◦ C (b), 350 ◦ C
(c) for 1 h with the magnification of 100000×.
area analyzed. It should be pointed out that other approaches of
defects quantification have been also proposed and this one shows
some advantages [23]. In Fig. 6, the relationship of the defect den-
sity with annealing temperature was illustrated. Clearly, the defect
density increases with the annealing temperature in both cases. The
annealing temperature dependence of defect density can be divided
into two stages. At the stage of temperature higher than 350 ◦ C, the
increasing rate of defect density is with a weak slope compared
with that at the stage of temperature lower than 350 ◦ C. This phe-
nomenon can be explained by evolution of stress and crystallization
of anatase in the TiO2 coating.
 J. Hu et al. / Applied Surface Science 257 (2011) 8772–8777
Fig. 5. (a) Dependence of the degradation rate on the annealing temperature with
the same annealing time of 1 h. (b) Dependence of the degradation rate on the
annealing time at the annealing temperature of 300 ◦ C.
The stress in films is undoubtedly the main origin of defect for-
mation, which develops in gel films on annealing as discussed by
Scherer and co-workers [24,25] and Brinker et al. [26]. The stress
formation is related to both the chemical precursors and the heat-
treatment. In the initial state of wet-film, the coating solution is still
a viscous liquid and thus able to undergo isotropic condensation in
consequence of drying and annealing. As the solvent evaporates,
the viscosity of the colloidal solution will increase and water will
enrich in the wet film. Successively, further hydrolysis and con-
Fig. 6. Relationship of defect density (%) with annealing temperature. The dip-
coating times were 8 and 10 times as shown, respectively. The annealing time was
1 h.
8775
densation reactions between sol particles occur [27]. As soon as
a rigid particulate network is formed by sol–gel transition, the so-
called xerogel film can only shrink perpendicularly to the substrate,
which may result in a considerable tensile stress [28,29]. Upon ther-
mal treatment the tensile stress is further increased until factors
such as (thermal) network relaxation or viscous flow provide some
release [30]. If the tensile stress during film heating and cooling
exceeds the stability of the network, defects are formed [31,32].
The increase in stress with heating temperature could also have
two causes. One is the increase in the intrinsic stress due to densi-
fication of the films under constraint, and the other is the increase
in thermal stress on cooling due to mismatch of thermal expansion
coefficients between AZ31 substrate (2.6 × 10−5 K−1 ) [33] and TiO2
coating (2.1–2.8 × 10−6 K−1 ) [34]. Thermal stress is proportional
to Young’s modulus of the film, difference in thermal expansion
coefficient and temperature drop. Therefore, densification, which
increases Young’s modulus of the film, can also increase the thermal
stress as well as the intrinsic stress [31].
As revealed by XRD and DSC-TG analysis (Figs. 1 and 2), at
the temperature higher than 350 ◦ C, the crystallization of anatase
occurred. It is believed that the crystallization of anatase will induce
some release of stress in the coating. The stresses can also be accom-
modated by viscous flow or diffusive creep because the sintering
or crystallization processes require high atomic mobility [35].
As discussed above, the annealing temperature plays an impor-
tant role in the defects formation and degradation of TiO2 coated
alloys. However, the dependence of degradation on annealing tem-
perature is quite different with that in [22]. The great difference
arose from the different microstructure, phase type and stress evo-
lution. For TiO2 /AZ31 prepared by liquid phase deposition (LPD),
the as deposited film is nano porous. At the same time, the anatase
crystallization occurred at the low temperature of 200–250 ◦ C. And
the crystallization and growth of anatase into pyramid-like par-
ticle (several hundred nanometers) resulted in the formation of
dense films and improved corrosion resistance, which dominated
in the annealing treatment. On the other hand, for TiO2 /AZ31 pre-
pared by sol–gel method, before annealing, it is a flat, homogenous,
nonporous film. The crystallization of anatase occurred at the high
temperature (350–370 ◦ C.). So when the temperature increased,
only the stress evolvement dominated in the annealing treatment.
Another important difference is that there were no organic residues
in reference [22]. So the related stress evolution as discussed in
present work would not occur for TiO2 /AZ31 prepared by LPD
method.
The annealing time dependence of degradation rate (Fig. 5b) is
considered as fellows. Fig. 7 (a) and (b) shows the morphology of
the TiO2 films annealed at 300 ◦ C for 1 h and 2 h, respectively. In
Fig. 7(a), a typical incompletely densified region, containing some
pores with the size less than/about 10 nm, was found on the surface,
which was accompanied by the formation of aggregation of TiO2
particles [36,37]. The aggregation of TiO2 particles may be respon-
sible for the formation of the un-densified region. In Fig. 7(b), these
defect structures, i.e. pinholes, were eliminated by the prolongation
of annealing time, although the existence of TiO2 particles aggre-
gation also can be found as pointed by arrows. After elimination of
the defect structures on the TiO2 coating, the degradation rate will
be decreased.
From the DSC curve (Fig. 1), it also can be found that the organic
residues began to largely evaporate/decompose at the tempera-
ture of about 243 ◦ C (onset of peak A). Prolongation of annealing
time can help the elimination of dissoluble organic residues, which
will also suppress the degradation of the coated alloys in corrosive
solution.
By taking into account of the dependence of protection effect on
annealing (Fig. 5a and b), the as-coated TiO2 /AZ31 was annealed at
250 ◦ C for 3 h for electrochemical measurement. It is expected that
8776 J. Hu et al. / Applied Surface Science 257 (2011) 8772–8777
Fig. 7. Comparison of morphology of the TiO2 films annealed at 300 ◦ C for 1 h (a)
and 2 h (b).
organic substance will be evaporated and the defected structure
will remain at a low level. Fig. 8 shows the polarization curves of the
annealed TiO2 /AZ31 and uncoated samples. It is evident that cor-
rosion potential (E) increases by 0.16 V positively; Icorr decrease by
more than 2 orders of magnitudes, compared with uncoated sam-
ple. The electrochemical parameters were summarized in Table 1.
Up to now, both TiO2 and Ca–P [6,22,38] coating have been
fabricated for surface modification of Mg alloys. The typical nano-
flake, nano-fiber or nano-plate morphology of Ca–P coating always
resulted in the formation of porous surface [6,38]. In such a case, the
Fig. 8. Polarization curves of annealed TiO2 /AZ31 and uncoated samples.
Table 1
Electrochemical parameters obtained from the polarization curves.
Sample Corrosion Corrosion current
potential, E (V) density, Icorr (A cm−2 )
AZ31 −1.596 3.163 × 10−5
TiO2 /AZ31 −1.419 1.26 × 10−7
TiO2 coating showed superior ability to get nano-structured surface
and improved corrosion resistance. The increase in corrosion resis-
tance is important for maintaining the mechanical integrity of the
alloy.
4. Conclusion
Nano-TiO2 coating was prepared on AZ31 alloy by sol–gel
method. The coatings, consisting of nanoscale particles with a size
of several tens of nanometer on the surface, were quite finished,
uniform and flat. The interdiffusion of Mg and O was observed by
EDS measurement, which is helpful for the formation of metallur-
gic bonding interface and avoiding peeling-off of the coating. The
annealing dependence of degradation rate of the coated Mg alloys in
SBF was analyzed. Low temperature annealing treatment resulted
in the decreased corrosion rate of the samples even through the
occurrence of anatase crystallization induced some relaxation of
stress at the high temperature. Prolongation of annealing time
can eliminate some defect structures and organic residues in the
films, which help to enhance the corrosion resistance. The evident
improvement in electrochemical performance was obtained when
samples were annealed at 250 ◦ C for 3 h. The corrosion potential (E)
increased by 0.16 V positively; Icorr decreased by almost 3 orders of
magnitudes, compared with uncoated sample.
Acknowledgements
This work is financially supported by the National Basic Research
Program (no. 2008CB617509) and the National Natural Science
Foundation of China (nos. 30870634, 51001091).
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