Corrosion Science 49 (2007) 10691080

www.elsevier.com/locate/corsci

Surface characteristics and corrosion behavior

of TiAlZr alloy implanted with Al and Nb
Y.Z. Liu
a

a,b

, X.T. Zu

a,

, C. Li b, S.Y. Qiu b, X.Q. Huang b,

L.M. Wang c

Department of Applied Physics, University of Electronic Science and Technology of China, Chengdu 610054,
PR China
b
National Key Laboratory for Nuclear Fuel and Materials, P.O. Box 436 (4), Chengdu 610041, PR China
c
Department of Nuclear Engineering and Radiological Sciences, University of Michigan, Ann Arbor,
MI 48109-2104, USA
Received 27 September 2005; accepted 6 June 2006
Available online 20 September 2006

Abstract
TiAlZr alloys were implanted with Al and Nb to doses ranging from 1 1017 to
1 1018 ions cm2. The valence states of element on the sample surfaces were analyzed by X-ray
photoelectron spectroscopy (XPS). Glancing angle X-ray diVraction (GAXRD) was employed on the
as-implanted specimens to understand phase formation. X-ray diVraction (XRD) measurement
revealed -Ti on Al-implanted samples and ( + )-Ti on Nb-implanted samples. The tendency was
observed in increasing corrosion resistance from - toward ( + )-phase. In deaerated 5 M HCl, the
ion-implanted TiAlZr surface containing Nb-stabilized -phase was spontaneously passive, while
Al-implanted surface displaying an active/passive behavior. In the aerated solution with pH D 10, all
the implanted surfaces are passive. Enhanced reoxidation was conWrmed on implanted surfaces by
Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) analysis. The corrosion in the solution with pH D 10 was governed by a predominantly TiO2 surface Wlm. The
cathodic kinetics was seen to aVect the corrosion behavior in 5 M HCl.
2006 Elsevier Ltd. All rights reserved.
Keywords: TiAlZr alloy; Al and Nb ion implantation; Phase formation; Corrosion

Corresponding author. Tel./fax: +86 28 8320 1939.

E-mail address: xiaotaozu@yahoo.com (X.T. Zu).

0010-938X/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2006.06.028

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Y.Z. Liu et al. / Corrosion Science 49 (2007) 10691080

1. Introduction
There is a growing interest in the application of ion implantation as a versatile process
for surface modiWcation of materials. The process provides desired properties such as wear
resistance and corrosion resistance without aVecting the physical and mechanical stability
of the bulk [15].
The microstructure of Ti and its alloys plays an important role that controls the corrosion property. The dissolution of Ti15Mo in 40% H2SO4 is lowest for 100%  alloys and
increases for  +  and  +  alloys [5]. Solution heat-treated Ti15Mo3Nb3Al ( alloy)
becomes spontaneously passive in deaerated 5 M HCl, while the peak-aged alloy of the
same composition ( precipitates within the  titanium matrix) displays activepassive
behavior [6], indicating that the eVect of microstructure is dependent on the alloy composition. Previously works reported that the passive dissolution of -Ti is increased by additions of Al, V, Mo, Zr or Nb [6]. The microstructure-related corrosion also depends on the
medium: Ti-15-3 has a higher corrosion rate in boiling HCl [7,8], but becomes spontaneously passive in NaCl solutions [9,10]. Furthermore, it is well known that -Ti is more susceptible to corrosion cracking than -Ti [11]. These examples demonstrate the importance
of the microstructure in controlling corrosion. Generally, the microstructure is stabilized
by bulk material with a variety of solute elements. Typical  stabilizers are V, Mo and Nb,
while Al is  stabilizer. However, in order to make the Ti surface biocompatible, while preserving its beneWcial mechanical bulk properties, there is much interest in independently
adjusting surface and bulk properties.
The emphasis of present work is to examine whether the ion implantation is able to
form a model of the composition and microstructure of TiAlZr alloy. Such modiWed surfaces would provide a useful target for a systematic study of the correlation between
microstructure and corrosion. In the test, Al and Nb are chosen as phase stabilizers to produce  and  phases in TiAlZr alloy. The corrosion behavior, performed in a solution
with pH D 10 and 5 M HCl, are considered in relation to the phase and composition analysis by X-ray diVraction (XRD) and Auger electron spectroscopy/X-ray photoelectron spectroscopy (AES/XPS), respectively.
2. Experimental procedure
The material used in this study was an equiaxed h.c.p.  TiAlZr alloy that contained
2.2 wt% Al, 2.6 wt% Zr, 0.030.04 wt% Fe, 0.07 wt% O and 0.01 wt% N and had a basal
texture. The samples were cut from a 22-mm diameter rod, with one face polished to a mirror using corundum paste. The samples were implanted with 150 keV Al+ and 100 keV Nb+
respectively, at normal incidence. The nominal ion doses used are 1 1017, 5 1017, and
1 1018 Al+ cm2, and 1 1017, 6 1017 Nb+ cm2 with the target chamber at a vacuum of
approximately 5 106 mbar.
Corrosion measurements were performed with a potentiostat. The anodic polarization
was obtained at a scan rate of 1 mV/s following exposure to solution for 1 h to establish a
steady state open circuit potential. For experiments with deaerated solutions nitrogen
bubbling was made before measurement. A three-electrode corrosion cell, with Pt counter
electrode and saturated calomel reference electrode, was used. For evaluation, all potentials were given relative to the normal hydrogen electrode. The results are reported for corrosion tests made in the solutions (5.35 g/l NH4Cl + 70 ml/l ammonia, aerated pH 10) and

Y.Z. Liu et al. / Corrosion Science 49 (2007) 10691080

1071

5 M HCl (deaerated). XRD measurements were conducted with a step scan diVractometer
in grazing incidence geometry  D 0.3 with Cu K radiation. The counting time per step
and the step size were 1530 s and 0.1, respectively. The spectra were obtained by scanning
between 2 D 2080. The elemental composition of the implanted layer was determined by
Auger electron spectroscopy (AES). Sputter depth proWling was performed with a 3 keV Ar
ion gun and a current density of 2 A/mm2. The total sputtered depth was measured for
each sample by a proWlometer. Assuming an averaged sputter rate, the depth scale was
obtained for the depth proWling. The Auger transition energies used were Ti0LMM-418 eV,
AlKLL-1396 eV, NbMNN-163 eV, and OKLL-503 eV. The peak areas derived from direct
mode spectra were evaluated in order to analyze quantitatively. X-ray photoelectron spectroscopy were collected using Al K X-ray sources operated at 360 W. The X-ray angle of
incidence and electron exit angle were 45 relative to the sample surface. For qualitative
evaluation, high resolution spectra were measured for the core levels of Ti2p, Nb3d and
O1s, and C1s was used to account for specimen charging. The depth proWles were taken at
intervals of 2 min argon sputtering cycles (3.5 keV Ar+ at 1 A/mm2) corresponding to a
Wlm thickness removal of 9 nm.
3. Results and discussion
3.1. Depth dependence of the surface composition
Fig. 1 shows the AES spectra of TiAlZr alloy implanted with Al (b) and Nb (c). An
unimplanted control sample is presented (a) for comparison. The initial untreated state of
all the TiAlZr surfaces before ion implantation, as evidenced by Fig. 1a, is characterized
by an air-formed oxide Wlm, about 9 nm in thickness (taken as thickness at 1/2 of the oxygen surface concentration), and carbon contaminant with much less concentration and
extent (Fig. 2a).
The peak concentrations of Al (1 1018 cm2) and Nb (6 1017 cm2) are approximately 38 at.% and 42 at.% at the corresponding depths of 120 nm and 70 nm. The the
stopping and range of ions in solids (TRIM) calculated ion ranges [12] of 123 nm and
67 nm, are close to the experimental values.
Integrating the oxygen depth proWles shows that the oxygen content of the surface is
increased, compared to the control sample, by a factor of approximately 3.3 and 1.4 for
1 1018 Al+ cm2 and 6 1017 Nb+ cm2 implanted specimens, respectively (hereafter
called oxygen incorporation factor, OIF). This tendency is presumably originated from
two major processes: sputtering and reoxidation during and after implantation. The total
oxygen content observed reXects obviously the retained oxygen from the original surface
oxide plus the oxygen uptake due to reoxidation. During implantation, the surface oxide is
lost by sputtering and recoil implantation of oxygen takes place, being two competing
steps. The latter is evident from the greater penetration depths for oxygen observed with
the implanted samples. The sputtering eYciency increases in going from Al to Nb implantation. The sputtering yields (atoms/ion) calculated by TRIM are 0.31 for Al and 2.49 for
Nb at the implantation energies of 150 and 100 keV, respectively. Thus the retained oxygen
decreases. For the Nb implantation having the greatest sputtering yield, the retained oxygen is negligible and the measured oxygen comes almost completely from the reoxidation
after implantation, as conWrmed by an oxygen incorporation factor near one compared to
the unimplanted control sample. In contrast, Al has a signiWcantly smaller sputtering yield,

1072

Y.Z. Liu et al. / Corrosion Science 49 (2007) 10691080

100
90

Concentration (at.%)

80
70
60

Ti
O

50
40
30
20
10
0
-10
0

50

100

150

200

Sputter Depth (nm)

90

Concentration (at.%)

80
70
60

Ti
Al
O

50
40
30
20
10
0
0

50

100

150

200

Sputter Depth (nm)

90

Concentration (at.%)

80
70
60
50

Ti
Nb
O

40
30
20
10
0
0

50

100

150

200

Sputter Depth (nm)

Fig. 1. AES depth proWles for various TiAlZr: (a) unimplanted, (b) 1 1018Al+ cm2 and (c) 6 1017Nb+ cm2.

Y.Z. Liu et al. / Corrosion Science 49 (2007) 10691080

50000

8000

7000

Intensity (cps)

40000

Intensity (cps)

1073

30000

20000

6000

5000

4000
1

10000

0
1000

800

600

400

200

1---1E17 ions /cm Nb

2
+
2---6E17 ions /cm Nb

3000

2000

215

210

B.E. (eV)

205

200

195

B. E. (eV)

d
8500

Intensity (cps)

8000
7500
7000

6500
6000

5500

1---1E17 ions /cm Nb

2
+
2---6E17 ions /cm Nb

5000
4500
470

465

460

455

450

B. E. (eV)

12000
2

Intensity (cps)

1---1E17 ions /cm Nb

2
+
2---6E17 ions /cm Nb

11000
10000
9000
8000
2
7000
1
6000
538

536

534

532

530

528

526

524

522

520

B.E. (eV)

Fig. 2. XPS survey spectrum from the unimplanted (a) TiAlZr and C1s (b), Nb3d (c), Ti2p (d) and O1s (e) XPS
spectra for the TiAlZr surface implanted with Nb.

producing more retained oxygen in addition to the reoxidation, and thus leading to the
greatest overall oxygen incorporation observed for the dose of 1 1018 cm2. Furthermore,
the OIF value for Al implanted samples is unexceptionally more than two times that of Nb
implanted samples. This suggests that the reoxidation after implantation occurs more
eYciently in the ion implanted samples than in the untreated TiAlZr surface, and this
was conWrmed further by determining the OIF at diVerent ion doses.

1074

Y.Z. Liu et al. / Corrosion Science 49 (2007) 10691080

The XPS spectra of the C1s, Nb3d, Al2p, Ti2p and O1s regions are shown in Figs. 2be.
The major amount of the carbon contaminant collecting in the outermost surface is
present as hydrocarbon with the characteristic C1s peak at 284.6 eV, Fig. 2b. Some CO or
CH bonds were also observed, as signiWed by the peak at about 286.0 eV [13]. The Ti2p
pattern in Fig. 2d indicates the compositional structure of the surface with Ti appearing in
two distinct oxidation states. The outmost surface is dominated by TiO2, which is evidenced by two peaks at 458.7 (2p3/2) and 464.5 (2p1/2) eV with a spin orbit splitting of
5.8 eV [14]. The extent of the TiO2 layer is 10 nm according to the AES results. The subsurface shows peaks at 454.2 (2p3/2) and 460.3 (2p1/2) eV corresponding to metallic Ti
with a spin orbit splitting of 6.2 eV [14]. However, we have to take into account that the
Ti2p peaks of Ti2O3 (456.1 eV), TiO (454.8 eV) [15] are close to that of metallic Ti.
The alloying component Nb is seen, like Ti, to exist mainly in oxidation state as oxide
on the surface and as metallic Nb in the subsurface, Fig. 2c. The Nb3d peaks at 203.6, 205.2
and 207.4 eV indicate the Nb oxide (NbO, NbO2 and Nb2O3), and that at 202 eV give evidence of metallic Nb. The relative amount of Nb oxide in relation to Ti oxide (comparing
Fig. 2d) conWrms, by taking into account their sensitivity factors, qualitatively the AES
depth proWle showing much more Ti at the surface than Nb.
The O1s spectrum, Fig. 2e, conWrms the compositional surface structure described
above. The outermost surface consists largely of TiO2, which is reXected by the major
peaks at 529.8 eV. The asymmetrically broadened line shape toward the higher binding
energy side of the spectra on the surface indicates the superposition of the oxygen-containing surface species occurring. The most probable surface species is Nb oxide. The broad
spectrum covering the energy range from 530.6 to 533.0 eV maybe indicative of oxygen
bound to lower valent. Ti and Nb species [16] are in consistence with the correlation in the
deep distribution of Nb and O, as evidenced from the AES depth proWle, Fig. 1c. The free
oxygen dissolved as solid solution in TiAlZr would exhibit the same binding energy
range, and thus, maybe also responsible for the spectrum behavior observed. The XPS
examination of the starting TiAlZr showed only negligible oxygen content indicating no
sign of free oxygen in the spectrum.
3.2. Phase composition of the implanted layer
All implanted samples were investigated by XRD in order to study the phase composition and the diVraction patterns are given in Fig. 3. The main peaks of all diVraction patterns correspond to the hexagonal -Ti. The samples have a texture in the bulk material
which results in intensity diVerences of the peaks compared to the tabulated powder data.
From the study of the alloying behavior of titanium, it is expected that Nb stabilize the
cubic -Ti phase, while Al is known for stabilizing the hexagonal -phase [6]. The Al
implanted samples have a diVraction pattern of purely hexagonal -Ti at Wrst glance.
There is some weak indication of the expected Ti3Al phase. The diVraction pattern of
Ti3Al phase is close to that of -Ti but all peaks are shifted to higher Bragg angles, and
this can be seen from the -Ti diVraction peaks which show a broadening at the right
wing. This can be explained by the existence of Ti3Al if one assumes that the lattice is
slightly expanded.
After niobium implantation in titanium, one observes the existence of some cubic peaks
in addition to the hexagonal bulk material of titanium. It is the expected cubic -Ti with a
lattice constant which agrees with the tabulated data. Niobium does not change the lattice

Y.Z. Liu et al. / Corrosion Science 49 (2007) 10691080

1075

1400
1200

+ --- NbTi4 $ --- Nb

Intensity (cps)

+$
1000
+
800

2
600
400

1---Al implanted
2---Nb implanted
#

200

# --- Ti3Al
#
#
#

1
0
20

30

40

50

60

70

80

Diffraction Angle (2-Theta)

Fig. 3. XRD patterns of unimplanted and implanted TiAlZr with 1 1018Al+ cm2 and 6 1017Nb+ cm2.

constant of -Ti [6]. The crystallite size of this phase is quite small since the peaks are signiWcantly broadened. In addition, none of the titanium oxides collected in the database [17]
could be identiWed by XRD although the AES data gave evidence for oxidation in all samples. The oxide layer is too thin for XRD. Table 1 summarizes the results of the XRD analysis.
Table 1
DiVraction angles (2) of the observed reXections and assignment to the crystallographic phases
Index

Unimplanted

Al-implanted

Nb-implanted

-Ti
(1 0 0)

35.08

35.27

(0 0 2)

38.10

38.13

(1 0 1)
(1 0 2)

40.04
41.75
52.80

40.23
43.85
53.16

(1 1 0)

60.80
63.08

34.89
36.80
38.13
38.52
40.04
42.71
52.80
55.53
61.75
62.72
68.43
69.57
70.52

(1 0 3)

(1 1 2)
(2 0 1)

70.14
72.61
74.15
75.86
77.35

63.10
63.85
70.52

76.24
77.38
78.72

76.06
77.58

Ti3Al
35.77(200)

40.84(201)
53.72(202)

63.23(2 1 2)
64.26(2 2 0)
70.61(3 1 1)

75.79(4 0 0)
77.60(2 2 2)
79.00(4 0 1)
-Ti
38.42(1 1 0)
55.46(2 0 0)
69.48(2 1 1)

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Y.Z. Liu et al. / Corrosion Science 49 (2007) 10691080

2.0

Potential (VSCE)

1.5

1---Unimplanted Ti-Al-Zr
2---Al-implanted
3---Nb-implanted

1.0
3
0.5
2
1

0.0

-0.5
-8.0

-7.5

-7.0

-6.5

-6.0

-5.5

-5.0

-4.5

-4.0

Log Current Density (A/cm2)

Fig. 4. Representative anodic polarization curves for unimplanted and implanted TiAlZr with 1 1018Al+ cm2
and 6 1017Nb+ cm2 in the solution with pH D 10.

3.3. Corrosion behavior measured in a solution with pH D 10

The open circuit potentials (OCP) for both implanted samples were similar, at about
0.16 0.05 V, compared to 0.35 V of the unimplanted sample. The ennoblement in OCP
by 0.2 V suggested that the modiWed surfaces promote the passivity because the active/
passive transition of TiAlZr occurred at more negative potentials. The positive values
observed were actually the steady-state OCP of surface Wlm in equilibrium with the solution. The similarity in OCP suggested that there was no signiWcant diVerence in the Wlm
composition despite of the surface alloying. This result was in agreement with those
obtained from AES and XPS analysis showing that the surface was dominated by TiO2.
The anodic polarization in the solution (5.35 g/l NH4Cl + 70 ml/l ammonia, aerated pH
10) was compared for all surfaces in Fig. 4 showing the average of six times scanning over a
potential region from 0.4 to 1.8 V. All surfaces were spontaneously passive, including the
unimplanted TiAlZr alloy. There are not any pitting behavior from the curves up to
1.8 V, as conWrmed by microscopic examination after polarization measurements. The passive current densities for implanted samples were lower than that for unimplanted one. The
lowest passive current density was supported by Nb implantation, followed by Al. Unlike
the unimplanted sample, no signiWcant increase in current density was observed at potentials higher than 1.8 V (not shown in Fig. 4) implying that the oxygen evolution was inhibited on the implanted surfaces [11]. This indicated a change in the electronic conductivity
and the larger thickness of the implantation induced surface coverage impeding the electron tunneling necessary for the oxygen evolution reaction [11]. The change in passivity,
from Al to Nb implantation, suggested diVerence in the protective oxide layer. The formation of the oxide layer began during the implantation. The corrosion test reXected roughly
the sum of these two processes, contributing to the total persistence of the surface Wlm. The
protective Wlm on Al-implanted surfaces was presumed to be more defective than that on
the Nb-implanted surface. The thickness of the oxide layer found for Al implantation and
reXected by their great OIF values, may be indicative of a more vigorous reoxidation

Y.Z. Liu et al. / Corrosion Science 49 (2007) 10691080

1077

Potential (VSCE)

1.5

1---Unimplanted Ti-Al-Zr
2---Al-implanted
3---Nb-implanted

1.0

0.5

0.0

-0.5
-9

-8

-7

-6

-5

-4

-3

-2

Log Current Density (A/cm2)

Fig. 5. Polarization behavior in deaerated 5 M HCl for TiAlZr alloy exposed to the same implantation conditions as in Fig. 3.

process leading to imperfections such as non-stoichiometric oxides TiOx and low-valent

oxides TiO and Ti2O3 [1821]. A more perfect oxide, at least the stoichiometric TiO2, was
assumed for Nb implantation due to a less vigorous reoxidation, as conWrmed by the low
OIF value.
3.4. Corrosion behavior measured in 5 M HCl
The test measurements were conducted in 5 M HCl in order to conWrm further the eVect
of the ion implantation-produced microstructure on the corrosion behavior, Fig. 5 shows
the polarization curves on samples exposed to 5 M HCl. The solution was deaerated earlier
with N2. The unimplanted sample displayed a distinctly active/passive behavior with a critical current density of 0.057 mA/cm2 at 0.22 V, Nb-implanted sample was seen to be spontaneously passive. However, a strongly weakened and hardly visible active/passive
transition emerges at 0.03 V for the Al-implanted sample, which was quite diVerent from
that known in the literature about the relation between microstructure and passivity for
titanium alloys. An active/passive transition behavior on commercial  and ( + ) titanium alloys (peak-aged Ti alloys: Ti5Al2.5Sn, Ti15Mo3Nb3Al, Ti15 V3Cr3Al
3Sn, Ti15Zr4Nb4Ta0.2Pd, Ti15Sn4Nb2Ta0.2 Pa) has been observed in previous
research [6,7,18,19]. The -Ti phase has been reported to be deleterious to the formation of
a protective passive Wlm on peak-aged -21 S Ti alloy in 5 M HCl [6], while Mo/Nb-stabilized -Ti alloy is passive [6,7,19].
In addition, a marked increase in current was observed for the Al-implanted sample at
1.4 V, indicating the occurrence of pitting as conWrmed by microscopic inspection of the
surface after anodization while with the Nb-implanted sample the passive surface persisted
over the entire anodic potential range examined. The corrosion of the implanted surface
appeared clearly to be reduced compared to the unimplanted sample surface, as evidenced
by the corrosion current densities determined from the polarization curves, Table 2. The
reduction in corrosion, reaching its maximum level for the Nb-implantation, in 5 M HCl is

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Y.Z. Liu et al. / Corrosion Science 49 (2007) 10691080

Table 2
Comparison of corrosion data for unimplanted and implanted samples exposed to 5 M HCl
Sample

Ecor

Icor

TiAlZr
Al-implanted
Nb-implanted

509
190
180

21
3.2
2.1

Ecor: corrosion potential (mv); Icor: corrosion current density (A/cm2).

one order of magnitude. The OCP revealed distinct diVerences. The OCP for the control
sample is 509 mV, while the values for implanted samples are more noble, 180 mV
and 190 mV for Nb and Al implantation, respectively. Table 2 summarizes the corrosion
data obtained for samples exposed to 5 M HCl in relation to the implantation-produced
microstructures. All the formed phases displayed behavior corresponding to an improved
corrosion resistance. Pure -phase is inferior to mixed ( + )-phase, suggesting that pure
-phase should be most favorable. Nb support the spontaneity in the passivity of TiAl
Zr, the mechanism of which was seen to partially relate to the kinetics of the hydrogen evolution reaction aVected by the implantation-modiWed surface [11].
On the other hand, the modiWcation of the protective Wlm may be attributed to radiation damage and ion beam heating that would change the in situ as well as subsequent
metal oxidation. The implantation of the inert gases or substrate metal ions [2224] can
validate the eVect. Improved corrosion resistance due to the thickening of the oxide layer
after Ar implantation has been reported [7,25,26]. However, the mismatch of the implanted
atom and its reactivity to the dynamically developing surrounding were also aVecting factors that were diYcult to test adequately by inert gas implantation. Pham et al. [11]
reported the polarization curves for Ar-implanted Ti exposed to 5 M HCl. The same active/
passive behavior, like unimplanted TiAlZr, was observed even with enhanced critical
and passive current densities. Although being beyond the focus of the present work, this
result did conWrm the chemical reactivity of the implants under study. The chemical role of
alloying additives to render titanium passive in aqueous electrolyte solutions has been
hypothesized in relation to Ti2O3, an intermediate product of the Ti oxidation [6,2729]. A
non-protective Ti2O3 Wlm formed in the active/passive transition on Ti has been reported
[3032]. Alloyed Mo, for instance, was believed either to lower the oxidation rate of the
metal substrate beneath the Ti2O3 Wlm, or to directly modify Ti2O3.
4. Conclusions
TiAlZr alloy implanted with Al and Nb ions was tested for corrosion in the two
diVerent solutions. The implanted surfaces were analyzed in terms of Ti phase composition, surface depth distribution of implanted additives, and chemical composition.
1. The implanted additives reached up to 40 at.% at the proWle corresponding to depths of
70 nm for Nb and 120 nm for Al underneath the surface. -Ti was detected after Al
implantation, while a mixture of - and -Ti was formed following Nb implantation.
2. Enhanced incorporation of oxygen was characteristic of all implanted surfaces examined, with decreasing tendency from Al to Nb, which was attributable to a balance
between gain and loss of oxygen due to reoxidation and sputtering.

Y.Z. Liu et al. / Corrosion Science 49 (2007) 10691080

1079

3. Testing in 5 M HCl conWrmed the tendency of increasing corrosion resistance from

-toward ( + )-phase. The protective Wlm formed in 5 M HCl was diVerent from
that in the solution with pH D 10, as evidenced by the enhanced cathodic process and
the well-resolved OCP values.
Acknowledgements
This work is conducted under the support of the Youth Science and Technology Foundation of Nuclear Power Institute of China and of Program for New Century Excellent
Talents in University. The authors are grateful to Prof. Z.Q. Sheng for his useful comments
and encouragement of this work and criticism of the manuscript. The work of Dr. L.H.
Guo (Sichuan University) in performing the GAXRD and Prof. C. Xin in performing the
XPS are gratefully acknowledged.
References
[1] Xuanyong Liu, Paul K. Chu, Chuanxian Ding, Mater. Sci. Eng. R 47 (2004) 49.
[2] F.A. Bonilla, P. Skeldon, T.G.E. Thompson, J. Piekoszewski, A.G. Chmielewski, B. Sartowsk, J. Stanislawski,
P. Bailey, T.C.Q. Noakes, Surf. Coat. Technol. 200 (2006) 4674.
[3] C. Blanco-Pinzon, Z. Liu, K. Voisey, F.A. Bonilla, P. Skeldon, G.E. Thompson, J. Piekoszewski, A.G. Chmielewski, Corros. Sci. 47 (2005) 1251.
[4] F.A. Bonilla, T.S. Ong, P. Skeldon, G.E. Thompson, J. Piekoszewski, A. Chmielewski, B. Sartowska, J. Stanislawski, Corros. Sci 45 (2003) 403.
[5] N.D. Tomashov, G.P. Chernova, Y.S. Ruscol, G.A. Ayuyan, Electrochim. Acta 19 (1974) 159.
[6] D.G. Kolman, J.R. Scully, J. Electrochem. Soc 140 (1993) 2771.
[7] R.W. Schutz, J.S. Grauman, C.S. Young, J.C. Durham (Eds.), Industrial applications of titanium and zirconium, vol. 917, ASTM STP, 1986, p. 130.
[8] I. Tsyganov, E. Wieser, W. Matz, H. Reuther, E. Richter, Surf. Coat. Technol. 158159 (2002) 318.
[9] D.G. Kolman, J.R. Scully, J. Electrochem. Soc. 141 (1994) 2633.
[10] D. Krupa, J. Baszkiewicz, E. Jeziersk, J. Mizera, T. Wierzchon, A. Barcz, R. Fillit, Surf. Coat. Technol. 111
(1999) 86.
[11] M.T. Pham, I. Zyganow, W. Matz, H. Reuther, S. Oswald, E. Richter, E. Wieser, Thin Solid Films 310 (1997)
251.
[12] J.F. Ziegiler, J.P. Biersack, U. Littmark, The Stopping and Range of Ions in Solids, 1, Pergamon, New York, 1985.
[13] I. Bertoti, M. Mohai, J.L. Sullivan, S.O. Saied, Appl. Surf. Sci. 84 (1995) 357.
[14] M. Scrocco, Chem. Phys. Lett. 61 (1979) 453.
[15] M. Wolf, J.W. Schultze, H.H. Strehblow, Surf. Interface Anal 17 (1991) 726.
[16] P.A. Lee, K.F. Stork, B.L. MaschhoV, K.W. Nebesny, N.R. Armstrong, Surf. Interface Anal. 17 (1991) 48.
[17] PDF-2 database, sets 1-44, ICCD, 1995.
[18] M.C. Burrell, N.R. Armstrong, J. Vac. Sci. Technol. A1 (1983) 1831.
[19] Yoshimitsu Okazaki, Sethumadhvan Rao, Yoshimasa Ito, Tetsuya Tateishi, Biomaterials 19 (1998) 1197.
[20] Y. Sugizaki, T. Yasunaga, H. Tomari, Surf. Coat. Technol. 83 (1996) 167.
[21] D. Krupa, J. Baszkiewicz, J.A. Kozubowski, A. Barcz, J.W. Sobczak, A. Bilijski, M. Lewandowska-Szumie,
B. Rajchel, Biomaterials 23 (2002) 3329.
[22] M. Levy, G.N. Sklover, J. Electrochem. Soc. 116 (1969) 323.
[23] A. Caprani, J.P. Frayret, Electrochim. Acta 24 (1979) 835.
[24] D. Krupa, J. Baszkiewicz, E. Jezierska, J. Mizera, T. Wierzchon, A. Barcz, R. Fillit, Surf. Coat. Technol. 111
(1999) 86.
[25] C.R. Clayton, Nucl. Instr. Meth. B 182183 (1981) 865.
[26] G. Dearnaley, P.D. Good, Nucl. Instr. Meth. B 189 (1981) 117.
[27] V. Ashworth, W.A. Grant, R.P.M. Procter, T.C. Wellington, Corros. Sci. 16 (1976) 393.
[28] I. Tsyganov, E. Wieser, U.W. Matz, A. Mcklich, H. Reuther, M.T. Pham, E. Richter, Thin Solid Films 376
(2000) 188.

1080

Y.Z. Liu et al. / Corrosion Science 49 (2007) 10691080

[29] L. Thair, U. Kamachi Mudali, N. Bhuvaneswaran, K.G.M. Nair, R. Asokamani, B. Raj, Corros. Sci. 44 (2002)
2439.
[30] J. He, X. Bai, C. Ma, H. Chen, Nucl. Instr. Meth. B 100 (1995) 59.
[31] J. De Damborenea, A. Conde, C. Palacio, R. Rodriguez, Surf. Coat. Technol. 91 (1997) 1.
[32] I. Tsyganov, E. Wieser, W. Matz, A. Mucklich, H. Reuther, Nucl. Instr. Meth. B 161163 (2000) 1069.