37 2 Vol. 37 No.

2
2017 4 Journal of Chinese Society for Corrosion and Protection Apr. 2017

316L pH


113001

Mott-Schottky 316L pH 47 11
X 316L
pH
316L Mott-
Schottky n p
n p pH Cr Fe FeO(OH)
Fe3O4 Cr2O3
316L pH XPS
TG174 1005-4537(2017)02-0162-06

Electrochemical Behavior of 316L Stainless Steel in Borate

Buffer Solution with Different pH
WANG Yanliang, CHEN Xu, WANG Jidong, SONG Bo, FAN Dongsheng, HE Chuan
School of Petroleum Engineering, Liaoning Shihua University, Fushun 113001, China
Correspondent: CHEN Xu, E-mail: cx0402@sina.com
Supported by National Natural Science Foundation of China (51201009) and Natural Science Foundation of Liaon-
ing Province (2013020078)
Manuscript received 2015-12-23, in revised form 2016-08-03

ABSTRACT The electrochemical characteristics of the passivation film formed on 316L stainless steel
in borate buffer solutions with pH of 4, 7 and 11, respectively were characterized by means of potentiody-
namic polarization, electrochemical impedance spectroscopy and Mott-Schottky technology. The compo-
sition of passive film was analysized by X- ray photoelectron spectroscopy (XPS). The results showed
that the stable passivation film could form on the steel surface in all the three borate buffer solutions. The
passivation potential range decreased and the transpassive potential dropped significantly with the in-
creasing pH value. The transpassive current of 316L stainless steel in alkaline borate buffer solution in-
creased significantly. The integrity of the passive film was the best in the neutral solution, while it was the
worst in the acid solution. The Mott-Schottky results showed that the semiconductor type of the passive
film transferred from n-type to p-type with the increasing potential in acid solution. It was n-type and p-
type semiconductor in the neutral and alkaline solution, respectively. It was attributed to that the chromi-
um hydroxide dropped down and the formed iron compound was transformed from FeO(OH) to Fe3O4.
The content of Cr2O3 was decreased in alkaline solution, which resulted in lower corrosion resistance.
KEY WORDS 316L stainless steel, pH, passivation film, electrochemical behavior, XPS
(51201009) (2013020078)
2015-12-23 2016-08-03
1986
E-mailcx0402@sina.com
DOI 10.11902/1005.4537.2015.231
 2 316L pH 163

316L 1.2
PAR EG&G 2273
316L
(SCC) Pt (SCE)
SCC (OCP) EIS
SCC 105~10-2 Hz 10 mV
[1-3] ZSimpWin
SCC 0.667 mV/s-0.25~ 2 V (vs
[4,5] OCP) Mott-Schott-
ky 1 kHz
10 mV pH
SCE
pH [6] pH 1.3 XPS
[7,8] PHI 5400 ESCA System XPS 316L
Huang [9] pH
Mott-Schottky Fe Cr
690 pH 1.6 keV 2 mm
2 mm XPS Peak4.1
pH
Lu [6]690 300
Cr 2
Cr [10] 690 2.1
1 316L pH
Freire [11] 1 3
pH 316L

p





pH

(EIS)Mott-

Schottky X (XPS)

pH 316L

1


1.1

316L (
1 316L pH
%) Si 0.6Mn 0.8P 0.013Mo 2.28Cr 17.14
Fig.1 Potentiodynamic polarization curves of 316L stain-
Ni 12.58C 0.014S 0.0073Fe less steel in the solutions with different pH values
10 mm10 mm2 mm 316L
1
SiC Table 1 Fitting results of polarization curves
80# 1000#
Ecorr Passive potential range Ip
pH
V V Acm-2
H3BO3 LiOHH2O B3+
4 -0.527 -0.318~1.14 0.295
1100 mg/LLi + 2.5 mg/L 25 pH
7 -0.220 0.096~0.959 0.323
(70.5) CH3COOH NaOH H3BO3
pH 4 11 11 -0.378 -0.03~0.703 0.426
164 37

pH 11
(Ecorr) 2 pH 7 R2
316L R1 Q1 n1
pH 1 pH
pH 11 4 R2 Q1
0.733 V n1

316L 1.0 V 2.3 Mott-Schottky
Mott-Schottky
316L (C ) (E)
Mott-Schottky [12] 316L
2.2

2 316L pH

Nyquist Bode 3

C E Mott-Schottky [13]

n C E
3

EIS 2 1 = 2 E - E - KT
fb (2)
Rs R1 Q1 C 0 eN D
2 e
R2 Q2 p C E

CPE Cd
CPE (Y)
Y =( j)-n /Y 0 (1) 3

Y0 n CPE n 0n1 Fig.3 Equivalent circuit of EIS

2 316L pH EIS
Fig.2 Nyquist (a) and Bode (b) polts of 316L stainless steel in the solutions with different pH values
2 EIS
Table 2 Fitting results of EIS

pH Rs / cm2 Q1 / Fcm-2 n1 R1 / cm2 Q2 / Fcm-2 n2 R2 / cm2

4 0.34 1.0710-4 0.887 1.7310-5 4.2510-10 1.00 1156
7 0.01 3.2910 -10
1.000 1446 7.5010 -5
0.82 2.29105
11 189 7.6010-5 0.999 16.47 5.4810-5 0.89 1.38105
2 316L pH 165




1 = - 2 E - E - KT (3)
fb
C2 0 eN A e

0 (8.8541910 F/m)

-12

15.6[12]

ND NA Efb
K Boltzmann (1.3810-23 J/K)T

(K)e (1.610-19 C) KT/e

25 mV



M-S C

M-S

[14]

n p

n

n

p


[15]p
n [16]

316L pH

Mott-Schottky 4 pH

M-S

n p
pH 7 M-S n pH










11 M-S p


Freire [11]
4 316L pH Mott-Schottky
p
Fig.4 Mott-Schottky plots of passive films of 316L stain-
2.4 XPS less steel in the solutions with pH=4 (a), pH=7 (b)
and pH=11 (c)
316L n
p Cr2O3FeCr2O4 NiO
n p M-S p Fe2O3 FeO(OH)
[17] n
Fe Cr Ning- [19]Fe n Cr
shen [18] p
316L pH XPS
5 5ac e Fe 2p
Fe pH 4 Fe0
p n Fe3O4 FeO(OH) pH 7 4
166 37

5 316L pH XPS
Fig.5 Detailed XPS spectra of Fe (a, c, e) and Cr (b, d, f) of passive films formed on 316L stainless steel in the solu-
tions with pH=4 (a, b), pH=7 (c, d) and pH=11 (e, f)

Fe3O4 pH 11 Fe0 Cr2O3 Cr

FeO(OH) Fe3O4 Fe
pH Fe Fe 0
Cr
FeO(OH) Fe3O4M-S Lu Huang Cr
pH n FeOOH p [6,9]
Fe3O4 5bd f pH
3
Cr 2p XPS Cr 3
pH Cr2O3 pH (1) 316L
Cr pH
 2 316L pH 167

chemical behavior of passivation film on alloy 690 [J]. Mater. Pro-

tect., 2010, 43(12): 4

(, , . pH 690
(2) 316
[J]. , 2010, 43(12): 4)
[11] Freire L, Carmezim M J, Ferreira M G S, et al. The passive behav-
(3) 316L iour of AISI 316 in alkaline media and the effect of pH: A com-
n p pH bined electrochemical and analytical study [J]. Electrochim. Acta,

n 2010, 55: 6174

p
(4) pH Cr [13] Sikora J, Sikora E, Macdonald D D. The electronic structure of the
Fe FeOOH Fe3O4 passive film on tungsten [J]. Electrochim. Acta, 2000, 45: 1875
Cr2O3
[14] Zhao J M, Gu F, Zhao X H, et al. Semiconductor properties of an-
[1] Ford F, Andresen P. Corrosion in nuclear systems [A]. Corrosion
Mechanisms in Theory and Practice [M]. 2nd ed. Boca Raton:
CRC Press, 2002
[2] Sato Y, Atsumi T, Shoji T. Continuous monitoring of back wall
stress corrosion cracking growth in sensitized type 304 stainless
steel weldment by means of potential drop techniques [J]. Int. J.
Pres.Ves. Pip., 2007, 84: 274
[3] Almubarak A, Belkharchouche M, Hussain A. Stress corrosion
cracking of sensitized austenitic stainless steels in Kuwait petro-
leum refineries [J]. Anti-Corros. Methods Mater., 2010, 57: 58
[4] Lu B T, Luo J L, Lu Y C. Correlation between film rupture ductility
and PbSCC of Alloy 800 [J]. Electrochim. Acta, 2008, 53: 4122
[5] Lu B T, Luo J L, Peng B, et al. Condition for lead- induced corro-
sion of Alloy 690 in an alkaline steam generator crevice solution
[J]. Corrosion, 2009, 65: 601
[6] Lu B T, Luo J L, Lu Y C. Effects of pH on lead-induced passivity
degradation of nuclear steam generator tubing alloy in high temper-
ature crevice chemistries [J]. Electrochim. Acta, 2013, 87: 824
[7] Maurice V, Yang W P, Marcus P. XPS and STM study of passive
films formed on Fe-22Cr(110) single-crystal surfaces [J]. J. Electro-
chem. Soc., 1996, 143: 1182
[8] Hashimoto K. 2002 W.R. Whitney award lecture: In pursuit of new
corrosion-resistant alloys [J]. Corrosion, 2002, 58: 715
[9] Huang J B, Wu X Q, Han E-H. Influence of pH on electrochemical
properties of passive films formed on Alloy 690 in high tempera-
ture aqueous environments [J]. Corros. Sci., 2009, 51: 2976
[10] Li C T, Cheng X Q, Dong C F, et al. Effect of pH value on electro-
[12] Paola A D. Semiconducting properties of passive films on stainless
steels [J]. Electrochim. Acta, 1989, 34: 203
odic oxide film formed on aluminum [J]. Acta Phys.- Chim. Sin.,
2008, 24: 147
(, , . [J].
, 2008, 24: 147)
[15] Zhuang P Q, Xiao Z W, Zhu X D, et al. Study on semiconductor
properties of anodic oxide films on tantalum [J]. Electr. Compon.
Mater., 2011, 30(8): 35
(, , . [J].
, 2011, 30(8): 35)
[16] Cheng X Q, Li X G, Du C W. Electrochemical behavior of 316L
stainless steel in Cl- containing acetic acid solution under high
temperature [J]. Acta Metall. Sin., 2006, 42: 299
(, , . 316L Cl-
[J]. , 2006, 42: 299)
[17] Chen C F, Jiang R J, Zhang G A, et al. Analysis of the space
charge capacitance of bipolar semiconductor passive films [J]. Ac-
ta Phys.-Chim. Sin., 2009, 25: 463
(, , .
[J]. , 2009, 25: 463)
[18] Ningshen S, KamachiMudali U, Mittal V K, et al. Semiconducting
and passive film properties of nitrogen- containing type 316LN
stainless steels [J]. Corros. Sci., 2007, 49: 481
[19] Lin Y H, Du R G, Hu R G, et al. A correlation study of corrosion
resistance and semiconductor properties for the electrochemically
modified passive film of stainless steel [J]. Acta Phys.-Chim. Sin.,
2005, 21: 740
(, , .
[J]. , 2005, 21: 740)