( )

, (7)740745

740

July

361005

0.5 molL-1 NaCl

. p
n Fe Cr .

. Cl-
.

O646

[13].
[4]

. [56]

1
20041111 20050120 .
cn).

(1Cr18Ni9Ti)
0.4 cm
1 cm
1 cm. 1200

(SCE) AUTOLAB
.
0.2 mVs -1.
10510-3 Hz
EQUIVCRT .
. 5
mVs-1 103 Hz
-0.7~0.25 V
-0.7~0.5 V. 0.5 molL-1 NaCl .

2.1
0.5 molL-1 NaCl
1 . 1ab
.

(Emailcjlin@xmu.edu.cn)(Emailrgdu@jingxian.xmu.edu.

* 59525112

741

). Nyquist

W(Warburg )

E / V (vs SCE)

1 0.5 molL-1 NaCl

Fig.1 Polarization curves the of stainless steel in
0.5 molL NaCl solution
-1

without (a) with (b) electrochemical treatment

0.5
molL-1 NaCl Icorr

Ecorr 0.28 V
1.29 V.

.
2.2
2 (a)(b)
(

. 3
Q1
[79] RL R1

R2
Q2
.

CPE
Cd. CPE ZQ
[10]
ZQ=(j)-n/Y0
(1)
Y0 n CPE . n 0<n<1
.
1 .
0.5 molL-1 NaCl

R1

2 0.5 molL-1 NaCl

Fig.2 Nyquist and Bode plot of the stainless steel in 0.5 molL-1 NaCl solution
without (a) or (b) with electrochemical treatment

742

Ac

(a)

(b)

3 0.5 molL-1 NaCl

Fig.3 Equivalent circuit for the stainless steel in 0.5 molL-1 NaCl solution
without (a) or with (b) electrochemical treatment

1 3
Table 1 The values of equivalent circuit description elements (Fig.3) of the stainless steel in 0.5 molL-1 NaCl solution

untreated
treated

RL

R1

Y01

cm2

kcm2

7.20

21.72

Fcm-2

6.75

4810

n1

R2

Y02

kcm2

Fcm-2

423.0

0.8795

36.0

259.9

0.9899

160.9

n2

20.39

0.8440

11.74

0.8895

Y0W
-1cm-2
0.0004

RL
solution resistance; R1film resistance; Y01film capacitance; n1power of Q1; R2
chargetransfer resistance;
Y02:double layer capacitance; n2power of Q2; Yowadmittance of Warburg impedance

R2 CPE n
1 4

. EIS

().

.
2.3 MottSchottky
.

.
MottSchottky .
n
1
2
KT
=
(E-Efb)
C2 0eND
e
(a)

p
1
2
KT
=
(E-Efb)
C2 -0eNA
e
0
15.6e ND NA
E Efb K
T .
1/C2 E

.
MottSchottky
1019 ~1022
cm-3[11].
5 0.5
molL-1 NaCl MottSchottky .

.
0.5 molL-1 NaCl MottSchottky
p
(b)

4
Fig.4

Micrographs of the stainless steel surface without (a) or with (b) electrochemical treatment

743

(a)

(b)

E / V (vs SCE)

(c)

E / V (vs SCE)

E / V (vs SCE)

5 0.5 molL-1 NaCl MottSchottky

Fig.5 The MottSchottky type plot of the stainless steel passivated by different potentials in 0.5 molL-1 NaCl solution
(a) without treatment, (b) 0.8 V, (c) with electrochemical treatment

MottSchottky

n . n
p
MottSchottky
.

6. 5 a 0.8 V
b-0.16 V
c
-0.20 V
40 mV .

p
n
Fe Cr .
[1214] n
p .

E / V (vs SCE)

6 0.5 molL-1 NaCl NA

ND
Fig.6 Influence of the formation potential on the
doping densities of the passive film formed on
the stainless steel in 0.5 molL-1 NaCl solution
NAacceptor density; NDdonator density

[1516].

MottSchottky .

Cr
Fe
n
.
Fe
Cr
p .

. [17]
(VMx )(VO..)
//
.
Cl-/
Cl - Mott
Schottky Pair /
/ Cl -
7.
.
/
.
.

.
5 MottSchottky

744

Ac
VMx +

x ..
V
2 O

Mottschottky
Pair reaction

.
2

..

..

VO+ Cl-nH2OClO +nH2O

vacancy condensation at the
metal/film interface

7 Cl-

p
n .

Fig.7 Schematic diagram of reaction process

between Cl and
-

..
VO )

..
VO

oxygen vacancy ; VOx) metal vacancy

1.84
1021 cm-3 4.141021 cm -3
9.381020 cm -3
2.781021 cm-3

.
Nerstian [18]
EFB=-EF0 /q+H
EF0 /q H
qs Helmholtz .
E0F/q

Helmholtz [19].

H .
40 mV
3

CrO
NO [56]
2CrO4 /
Cr(OH)3+5OH- CrO42-+4H2O+3e

24

CrO
NO

Cl-
.

.
24

3
-

. CrO42-
NO3

Cl-

.
References
1

Monnartz, P. Metallurgie, 1911, 8161

2 Belo, M. D.; Hakiki, N. E.; Ferreira, M. G. S. Electrochim. Acta,

1999, 442473
3

Schultze, J. W.; Lohrengel, M. M. Electrochim. Acta, 2000, 45

2499

Strehblow, H. H. Surf. Interf. Anal., 1988, 12363

Lin, C. J.; Mao, Y.; Tian, Z. W. China Corrosion and Protection

Transaction, 1992, 12(3): 205 [ .
(Zhongguo Fushi Yu Fanghu Xuebao), 1992, 12(3):
205]

Hu, R. G.; Lin, C. J. China Corrosion and Protection Transaction,

2000, 20(3): 149 [.
(Zhongguo Fushi Yu Fanghu Xuebao), 2000, 20(3):149]

Alves, V.A. Brett, C.M.A. Brett. Electrochimica Acta, 2002, 47

2081

Li, W. S.; Luo, J. L. Corr. Sci., 2002, 441695

MetikoHukovic, M.; Omanovic, S.; Jukic, A. Electrochim. Acta.,

1999, 45977

10 Zen, J. M.; Nangovan, G.; Jou, J. J. Anal. Chem., 1997, 712797

11 Schultze, J. W.; Lohrengel, M. M. Electrochim. Acta, 2000, 45
2499
12 Li, W. S.; Luo, J. L. Electrochemistry Communication, 1999, 1
349
13 Paola, A. P.; Shukla, D.; Stimming, U. Electrochim. Acta, 1991,
36345

1EIS

14 Sunseri, C.; Piazza, S.; Di Quarto, F. J. Electrochem. Soc., 1990,

1372411

7
15
16

Hakiki, N. E.; Boudin, S.; Rondot, B.; Belo, M. D. Corr. Sci.,

18 Bockris, J. OM.; Khan, S. U. M. Surface electrochemistryA

1995, 371809

molecular level approach. New YorkPlenum Press, 1993170,

Hiroaki, T.; Shinji, F.; Osamu, C.; Toshio, S. Electrochim. Acta,

179, 486
19 Stimming, U.; Schultze , J. W. Electrochim. Acta, 1979, 24859

2002, 474357
17

745

Macdonald, D. D. J. Electrochem. Soc., 1992, 1393434

A Correlation Study of Corrosion Resistance and Semiconductor Properties for the

Electrochemically Modified Passive Film of Stainless Steel*
LIN, YuHua

DU, RongGui

HU, RongGang

LIN, ChangJian

(State Key Laboratory for Physical Chemistry of Solid Surfaces, Department of Chemistry, Xiamen University, Xiamen

361005)

Abstract Using polarization scan, electrochemical impedance spectroscopy and capacitance measurement, the
correlation of corrosion resistance and semiconductor properties for electrochemically modified passive film
formed on stainless steel in 0.5 molL -1 NaCl solution was investigated, and the mechanism of the corrosion
resistance of the electrochemically modified passive film was further studied. The result reveals that the films
behave as ntype and ptype semiconductors in the potential range above and below the flat band potential,
respectively. This behavior is assumed to be the consequence of the semiconducting properties of the iron oxide
and chromium oxide regions which compose the passive film. Compared with natural passive film,
electrochemically modified passive film has lower donor and acceptor density. The change of EFB was discussed as
a function of anions adsorption on surface of passive film. With low donor and acceptor density and anion
adsorption on surface of passive film, effectively preventing the adsorption of Cl - in passive film, the resistance
to localize corrosion of passive film was greatly improved.
Keywords Stainless steel, Passive film, Corrosion resistance, EIS, Semiconductor property

November 11 January 20 5 LIN, ChangJiancjlin@xmu.edu.cn; DU, RongGui

(Emailrgdu@jingxian.xmu.edu.cn) * 59525112