Surface & Coatings Technology 203 (2009) 2017–2020

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Surface & Coatings Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s u r f c o a t

Corrosion protection of AZ31 magnesium alloy by a TiO2 coating prepared by

LPD method
Junhua Hu a,b, Guan Shaokang a,⁎, Caili Zhang c, Chenxing Ren a, Cuilian Wen a, Zhaoqin Zeng a, Li Peng a
a
Research Center for Materials, School of Materials Science and Engineering, Zhengzhou University, Zhengzhou, 450002, P.R. China
b
Graduate School of Science and Technology, Shizuoka University, 3-5-1 Johoku, Hamamatsu, Shizuoka 432-8011, Japan
c
Department of Civil and Architecture Engineering, Zhongyuan Institute of Technology, Zhengzhou, 450007, P.R. China

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

Article history: TiO2 layer was prepared as a protective coating for AZ31 magnesium alloy by the liquid phase deposition
Received 11 November 2008 (LPD) method followed by an annealing treatment. The structural evolution and crystallization of coating
Accepted in revised form 25 January 2009 brought by annealing were investigated by field emission scanning electron microscopy (FE-SEM) and X-ray
Available online 2 February 2009
diffraction (XRD), respectively. The corrosion protection performance was evaluated in a three-electrode
electrochemical examination system. The anatase TiO2 layer shows evident corrosion resistance. With the
PACS:
81.65.Kn
increase of the annealing temperature and prolongation of annealing time, the anticorrosion property was
81.15.-z improved. The improvements of the anticorrosion properties were related with the structural evolution of
the coating brought by the annealing treatment.
Keywords: © 2009 Elsevier B.V. All rights reserved.
AZ31 alloy
LPD
TiO2 layer
Polarization curves

1. Introduction
In recent years, magnesium alloys have been widely applied in the
fields of automotive, aerospace and electronic industry due to its low
density, high specific strength, good thermal conductivity, excellent
damping characteristics and well machinability [1]. Recently, magne-
sium alloy is also proposed as a promising biomaterial for the human
body implant because of its close mechanical property and good
compatibility with human bone [2,3]. However, magnesium and its
alloys have high chemical activity and low electrode potential (−2.37 V,
versus standard hydrogen electrode (SHE)) [4]. In addition, the oxide
layer on the surface of magnesium alloys is too loose to protect the
substrate from corrosion and oxidation effectively [5]. These dis-
advantages limit the expansion of application of magnesium alloys.
Although magnesium alloys are usually alloyed with aluminum,
manganese and zinc to improve corrosion resistance, further surface
treatment is also required to physically prevent contact with the
environment. The coating technologies, including the electrochemical
plating, conversion coatings, hydride coating, anodizing and thermal
spray coatings, were used to achieve the corrosion resistance [6–8].
Recently, TiO2 layers were used as protective layers on the substrate of
316 L stainless steel and other metals [9–11]. It should be pointed that it
is not easy to grow TiO2 layer on Mg alloy substrate because the corrosive
and oxidizing growth atmosphere in some preparation method of TiO2
⁎ Corresponding author.
E-mail address: skguan@zzu.edu.cn (S.K. Gaun).
always leads to poor adhesion and inhomogeneity of the layer. In our
previous work [12], a modified liquid phase deposition (LPD) method
was used to prepare the TiO2 layer on AZ31 magnesium alloy substrate.
Special emphases were put on the hydrolysis process and its influence
on the weight loss rate in sodium chloride solution. In present paper, the
structural evolution after annealing treatment is investigated. Further
measurement of corrosion resistance is carried out by electrochemical
method and an attempt is made to relate the anticorrosion property
with the structural evolution and compare with our former results.
1.1. Experiments
In this method, TiO2 layer was prepared by hydrolysis of
ammonium hexafluorotitanate [NH4]2TiF6. The chemically pure
[NH4]2TiF6 was dissolved in the deionized water with concentration
of 0.2 mol/L as the mother solution. At the same time, boric acid, as
F −scavenger, was dissolved in the solution with concentration of
0.075 mol/L and anatase TiO2 powder with the size of a few tens of
nanometers were added into the mother solution (2 g/l) and the
mixture was ultrasonically mixed for 30 min. The reaction and
hydrolysis process was described in detail in reference [12–14].
Wrought magnesium alloy AZ31 pieces (20 × 8 × 3 mm) were used
as the substrates. The substrates were ground by emery paper with
the No. from 100 to 1000 and polished by alumina powder of 0.05 µm
size; after that the substrate was washed ultrasonically in the acetone
(chemically pure) and ethanol (chemically pure) for 10 min, respec-
tively, and finally flushed with distilled water.

0257-8972/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2009.01.036
2018 J. Hu et al. / Surface & Coatings Technology 203 (2009) 2017–2020

Fig. 1. (a) XRD patterns of TiO2/AZ31 prepared at the annealing temperature of (A)250 °C,
(B)300 °C, (C)350 °C and (D)380 °C. The diffraction peaks of anatase TiO2 and AZ31 were
shown by the mark of triangle and circle, respectively. (b) a standard powder diffraction
profile (PDF) of anatase TiO2 [15].

After pre-treatment, the substrates were immersed into the

mother solution and suspended therein vertically for 20 h at the
room temperature. Then, the substrates were withdrawn from the
solution, sufficiently rinsed in the deionized water and dried at ambient
temperature. After deposition, the annealing process was carried out
in the vacuum furnace with the vacuum degree of 2 × 10− 4 Pa. The
annealing temperature was from 250 °C to 380 °C and the annealing
time was 1.5 h. At the temperature of 250 °C, the annealing time were
prolonged to 3 h.
The crystal structure of the resultant layer was investigated by X-ray
diffraction (XRD) instrument (Philips, PW-1700X) with Cu Kα
(λ = 0.15406 nm) in the scanning angles from 20° to 80°. The surface
and cross-section morphology were observed using field emission
scanning microscopy (FE-SEM, JEOL-6700F). Energy dispersive spectro-
scopy (EDS) was employed to determine the elements composition of
the layers. Electrochemical measurements were carried out in a three-
electrode cell using a computer-controlled EG&G (M352) electrochemi-
cal corrosion system, employing a carbon auxiliary electrode and a
saturated calomel reference electrode (SCE). The working electrode is
testing materials and the testing solution is 3.5 wt.% NaCl solution at the
temperature of 25 ± 1 °C.

2. Result and discussion

Fig. 1(a) shows the XRD patterns of TiO2/AZ31 prepared at different

annealing temperatures for 1.5 h. As comparison, a standard powder
diffraction profile (PDF) of anatase TiO2 is shown in Fig. 1(b) [15]. In
Fig. 1(a), diffraction peaks corresponding to anatase TiO2 are observed,
and the spectra agree with that of PDF file. It should be noted that one
peak of the anatase, at position of 2θ = 48.0°, is coincident with that of
substrate. The peak intensity of anatase TiO2 increases with the
annealing temperature, which proves that crystallization of anatase
can be improved by the increase of annealing temperature.
The influence of annealing temperature on the morphology of the
TiO2 layers is shown by some FE-SEM images in the Fig. 2. These layers
Fig. 2. FE-SEM images of surface morphology of TiO2 layer. Here, the layers were
were deposited for 20 h and annealed at different temperatures deposited for 20 h and annealed at different temperatures for 1.5 h in vacuum furnace.
for 1.5 h in vacuum furnace. From Fig. 2(a), which shows the image of (a) as-deposited TiO2 layer; (b) annealed at 250 °C; (c) annealed at 350 °C; (d) enlarged
an as-deposited TiO2 layer, the loosely deposited particles on the image of the particles on the surface shown in Fig. 2 (c).
 J. Hu et al. / Surface & Coatings Technology 203 (2009) 2017–2020 2019

Table 1
Electrochemical parameters obtained from Tafel polarization curves

Sample Ecorr Icorr Rp

V A.cm− 2 Ω.cm2
−6
380 °C −1.111 6.19568 × 10 28448.29 ± 451
300 °C −1.448 1.31383 × 10− 5 20876.3 ± 650
250 °C −1.468 1.38381 × 10− 4 1914.28 ± 116
As-deposited −1.518 2.73441 × 10− 4 1220.33 ± 142
Blank AZ31 −1.524 2.91413 × 10− 4
3.0 h −1.377 1.83167 × 10− 5 13780.24 ± 742
2.0 h −1.450 2.33769 × 10− 5 11101.36 ± 580
1.5 h −1.468 1.38381 × 10− 4 1914.28 ± 116

1:2. Because of the out diffusion of Mg from substrate, in the interface

Fig. 3. (a) Cross section morphology of the TiO2 layer with the thickness of about 10 µm.
EDS scanning direction across the TiO2 layer was shown by dashed line. (b) Distribution
profiles of Ti and O elements through cross section. The solid line shows the distribution
of Ti element and the doted line show that of O element.
substrate can be found. As shown by the XRD results in Fig. 1(a), after
annealing, the crystallization of anatase is improved, which can also
be proved by the morphology evolvement revealed in the Fig. 2(b) and
(c). In the Fig. 2(b), pinholes can be found on the surface of TiO2 layer
annealed at 250 °C. And they get eliminated by the annealing at 350 °C
as shown in the Fig. 2(c). In Fig. 2(c), the surface of the layer, consisting
of fine particles, is finished, uniform and compact. Fig. 2(d) shows the
enlarged image of one of the particles on the surface of Fig. 2(c). The
partials on the surface, with the size of several hundreds nanometers,
have the characteristically octahedral shape of anatase TiO2. According
to Wuff construction and surface energy calculation of anatase [16,17],
the surfaces of the octahedral particle were limited by (101) natural
surface [18].
Fig. 3(a) shows the cross-section image of the sample shown in the
Fig. 2(c). The thickness of the layer is less than 10 µm. Distribution of Ti
and O elements along cross section was also detected and shown in
the Fig. 3(b). In the region of layer, the atom ration of Ti and O along
the scanning direction (shown in the Fig. 3a by dashed line) is around
region of TiO2/AZ31, the relative content of Ti and/or O is not as much
as that in other region. It was concluded that the wider distribution of
O than that of Ti was because of the easy oxidation of sample.
Fig. 4 shows the Tafel polarization curves of samples prepared at
different annealing temperatures. The samples were deposited in the
same condition for 20 h and then annealed at the temperature of
250 °C, 300 °C and 380 °C, respectively, for 1.5 h. The polarization
curve of a specimen without annealing is also presented as the Fig. 4
(d). It is visible when the potential reach a certain stage, curve of the
as-deposited specimen became zigzag.
The corrosion protection can be evaluated by their corrosion
potentials (Ecorr) and corrosion current densities (Icorr) obtained from
their polarization curves. The polarization resistance (Rp) is calculated
as the inverse of the slope of I versus E graph at the corrosion potential
Ecorr. The electrochemical parameters obtained by auto-analytical
EG&G software are shown in the Table 1. From Table 1, with the
increase of annealing temperature from 250 °C to 380 °C, it is shown
that the Icorr decreases by several tens of times of magnitude and the
Rp increases by almost the same order of magnitudes. The Ecorr is
shifted positively 0.357 V (vs. SCE). The corrosion protection of the as-
deposited specimen is not improved much compared with that of the
bare AZ31 alloy [19–21].
Fig. 5 shows the influence of annealing time on the polarization
curves at the annealing temperature of 250 °C, which shows sim-
ilar tendency with that of annealing temperature. The analyzed
results were listed in the bottom row of Table 1. It can be found the
corrosion resistance increases with the prolongation of annealing
time. When the annealing time increases from 1.5 h to 3 h, the
corrosion potential increases by 0.091 V; Icorr decreases by several
times and Rp increases by almost same times. It also can be found
that increase of annealing time has a mild influence compare with
that of annealing temperature.
After coated by the TiO2 layer and annealing treatment, the corrosion
protection of AZ31 alloy was improved evidently. It can be found the as-
deposited layers are not compact and cannot prevent contact with the
corrosive environment (Fig. 2a). In the Fig. 4, it also can be found that

Fig. 4. Tafel polarization curves of samples prepared at different annealing temperature of

380 °C (a), 300 °C (b) and 250 °C (c) for 1.5 h. The polarization curve of an as-deposited Fig. 5. Tafel polarization curves of samples prepared at the annealing time of 3 h (a), 2 h
specimen is presented as (d). (b) and 1.5(c) at the annealing temperature of 250 °C.
2020 J. Hu et al. / Surface & Coatings Technology 203 (2009) 2017–2020

corrosion potential of as-deposited samples is only −1.518 V, which is by 0.091 V; Icorr decreases by several times and Rp increases by the
just a little above that of bare AZ31 substrate. During the procedure of same times. The enhancements of the anticorrosion property were
thermal treatment, improvement of crystallization of anatase TiO2 related with the structural evolvement.
occurred (Figs. 1 and 2), accompanied by the elimination of some
structure defects in the layer, e.g. pinholes, pores, and the compactness
Acknowledgement
of TiO2 layer was therefore increased. As a result, the corrosion
resistance will be enhanced by annealing treatment. However, the
This work is financially supported by the National Basic Research
annealing parameters are limited by the thermal stability of the sub-
Program of China. (Grant NO. 2008CB617509).
strate. The influence of annealing temperature and time on the anti-
corrosion property also agrees well with that measured in the weight
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