Materials and Design 84 (2015) 1–9

Contents lists available at ScienceDirect

Materials and Design

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

Effect of tin on the corrosion behavior of sea-water corrosion-resisting steel

Haixu Li a, Hao Yu a, Tao Zhou a, Baoliang Yin b, Shaojiang Yin b, Yanling Zhang a,⁎
a
School of Materials Science and Engineering, University of Science and Technology Beijing, No. 30 Xueyuan Road, Haidian District, Beijing 100083, PR China
b
Tangshan Iron and Steel Group Co., Ltd., Hebei Iron & Steel Group Co., Ltd., Wangtan, Laoting, Tangshan, Hebei 063610, PR China

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

Article history: This paper investigated the effect of tin on the corrosion resistance of tin-containing steel and tin-free steel using
Received 24 March 2015 electrochemical measurements in seawater. Results showed that tin-containing steel had lower corrosion
Received in revised form 18 June 2015 current and higher impedance than tin-free steel. Surface analyses of X-ray photoelectron spectroscopy (XPS)
Accepted 20 June 2015
and X-ray diffraction (XRD) indicated that tin could form SnO2 and SnO in rust layer, and both of them could
Available online 27 June 2015
improve impedance and corrosion resistance of rust layer. Besides, the coprecipitation process of tin oxides
Keywords:
with iron oxides could make the rust layer more uniform and compact, which could make the tin-containing
Low alloy steel steel have better corrosion resistance than tin-free steel. Secondary ion mass spectrometer (SIMS) showed that
Seawater there was no obvious segregation of tin on substrate steel when tin addition was 0.038 wt.%, and tin could
Tin improve the oxidation resistance of substrate steel evenly by lowering the steel's Fermi energy from
Electrochemical measurement −9.276 eV to −14.445 eV.
Secondary ion mass spectrometer © 2015 Elsevier Ltd. All rights reserved.
Corrosion

1. Introduction acting as a corrosion resistant element. Some researchers have pointed

Currently, the development of ocean energy has become a focus
point around the world, which provides a huge marketing demand for
the steel used in ocean engineering. Therefore, there would be a great
potential to develop steel with low cost and outstanding corrosion
resistance to seawater. Many countries have developed sea-water
corrosion-resisting steel, such as Mariner steel of America, Aps20A
steel of France and Mariloy steel of Japan, which belongs to Ni–Cu–P
series, Cr–Al series and Cu–Cr–Al series, respectively. Normally, chemi-
cal composition and microstructure are regarded as principal influence
factors of corrosion resistant property. Corrosion resistant properties of
frequently-used elements such as Copper, Aluminum, Chromium,
Molybdenum and Nickel have been investigated in lots of published lit-
erature [1–10], and their function on corrosion resistance has been
learnt by people. Nowadays,people started to pay more attention to
the effect of tin element on corrosion resistant property, especially
after the successful development of high-tensile corrosion resistant
steel containing tin in Japan in 2011.
The low melting point of tin will has a negative impact on billet
thermoplastic, which can adversely affect hot workability during
manufacturing process. But on the other hand, tin itself has excellent
corrosion resistance [11], and it was reported that a small content of
tin (about 0.05 wt.%) could improve the corrosion resistance of steel
[13], so the cost of steel would be reduced if tin was added into steel
⁎ Corresponding author.
E-mail address: zhangyanling@metall.ustb.edu.cn (Y. Zhang).
out the positive impact of tin on corrosion resistant property when tin is
added into steel [12–14]. Nguyen Dang Nam and A. Pardo [12,14] intro-
duced a conclusion that the corrosion rate decreased with the increas-
ing content of tin, and the addition of tin had a positive effect on
pitting corrosion resistance of steel as well. Particularly, A. Pardo and
M.C. Merino [13] reported that Cu could favor pit nucleation but inhibit
its growth, whereas Sn exerted an opposite effect, i.e. favoring pit
growth and inhibiting its nucleation. Wenjin Zhang [4] reported that
the corrosion resistance of Mg–Zr–Ca alloy was improved apparently
with the addition of Sr and Sn. However, these studies just referred
some phenomena. The impact of tin on corrosion resistant properties
in mechanism and essential aspects had not been discussed. Besides,
the previous investigations were mainly based on stainless steels or
steel under acid corrosive environment, and till now no research has
been made to investigate the effect of tin on corrosion resistant property
of low alloy steel in seawater environment.
This paper attempts to evaluate the effect of tin on corrosion
resistant properties in sea-water corrosion-resisting low alloy steel.
After the accelerated corrosion test, the corrosion resistant proper-
ties of the two steels were characterized by potentiodynamic polar-
ization tests and electrochemical impedance spectroscopy (EIS)
measurements. X-ray photoelectron spectroscopy (XPS) and X-ray
diffraction (XRD) were conducted to analyze the corrosion products.
Secondary Ion Mass Spectroscopy (SIMS) was also used to ascertain
the distribution of tin on substrate steel. Besides, the cross section
of corroded sample was observed using Scanning electron micro-
scope (SEM).

http://dx.doi.org/10.1016/j.matdes.2015.06.121
0264-1275/© 2015 Elsevier Ltd. All rights reserved.
2 H. Li et al. / Materials and Design 84 (2015) 1–9

2. Experimental

2.1. Materials and test solution

All the specimens were cut from industrial plates with the thickness
of 20 mm, which were processed by thermo mechanical control process
(TMCP) technology. Table 1 shows the chemical compositions of the
two investigated steels. Results of optical microscopy observation of
the two steels are shown in Fig. 1, which indicate that the microstruc-
tures of both these two steels are ferrite–pearlite. Thus the effects of
different microstructures between the two steels on corrosion behavior
can be neglected.
The electrochemical test specimens had a dimension of 10 mm ×
10 mm × 3 mm, whereas those for the immersion tests had a dimension
of 60 mm × 30 mm × 5 mm. The solution used to simulate seawater was
prepared according to GB/T 19746-2005, with pH ranging from 8.2 to
8.4. Specifically, per liter of this solution contained 24.534 g NaCl,
4.094 g Na2SO4, 0.020 L standard solution A and 0.010 L standard
solution B. The chemical compositions of standard solution A and B
are listed in Table 2. The test temperature was controlled at 28 °C to
accelerate the corrosion process [15].

2.2. Weight loss test

The weight loss measurements were performed according to GB/T

16545-1996. The exposed surface area (60 mm × 30 mm × 5 mm) of
each specimen was polished with 1000-grit silicon paper, then cleaned
in an ultrasonic bath with ethanol for 5 min and dried in hot air.
After the initial mass was measured, the specimen was immersed in
the test solution for 1 day. After the test, each specimen was cleaned
with distilled water, then pickled in a solution of 500 ml HCl + 3.5 g
hexamethylene tetramine + balanced distilled water for 5 min to re-
move the products of the corrosion. These were then degreased in an ul-
trasonic cleaner with ethanol for 5 min, followed by a cleaning with
distilled water and drying in hot air. The final mass of the tested speci-
men was measured for the weight loss test. Besides, the processes of
specimen preparation and rust cleaning were also used to observe the
morphology after removing corrosion products.
2.3. Potentiodynamic polarization test
The exposed area of specimens was 10 mm × 10 mm with 100 mm2
area, and the other sides were embedded in epoxy resin. Before the po-
tentiodynamic polarization tests, all the specimens were grinded with
1000-grit silicon paper and then were polished to get a flat and glabrous
surface. Then the potentiodynamic polarization tests were conducted
on specimens after 1 day pre-corrosion in seawater.
During the electrochemical tests, all specimens were completely im-
mersed in 600 ml seawater at temperature of 28 °C. Electrochemical
measurements were carried out using a three-electrode system with
saturated calomel electrode as reference electrode, Platinum electrode
as auxiliary electrode and the sample as working electrode. The polari-
zation measurement started from a potential of + 250 mV (SCE) and
ended at a potential of −250 mV (SCE) versus the open circuit poten-
tial. The scanning rate was 0.2 mV/s during polarization curve
measurement.
Fig. 1. Microstructures of two steels. (a) Tin-containing steel, (b) Tin-free steel.
2.4. Electrochemical impedance test
The specimens used for electrochemical impedance tests were the
same as those used for potentiodynamic polarization tests. A three-
electrode system was used in EIS measurement. The test parameters
were as follows: 10 mV perturbation and five points per decade. Fre-
quency range was from 100 kHz to 10 mHz. Before EIS test proceeded,
the potential of specimens reached a stable state in the solution. The
experimental results were interpreted based on an equivalent electrical
circuit by using a suitable fitting procedure of ZSimpWin.
2.5. Corrosion products and elements test
The corrosion products obtained from different corrosion cycle were
examined by X-ray photoelectron spectroscopy (XPS) and X-ray diffrac-
tion (XRD), which could identify the relationship between corrosion
products and corrosion behavior. The specimens of XPS and XRD were
powder.
Besides, distribution of elements on the substrate steel was investi-
gated by Secondary Ion Mass Spectroscopy (SIMS). SIMS was performed
with a camera ION-TOF GmbH ion microscope. Direct-ion images with
size of 100 um × 100 um were acquired using a resistive anode encoder

Table 1
Chemical compositions of specimens (wt.%).

Specimen C Si Mn P S Sn Cu Cr Al

Tin-free steel 0.060 0.300 1.100 0.017 0.003 – 0.490 0.500 0.035
Tin-containing steel 0.060 0.280 1.000 0.015 0.003 0.038 0.500 0.520 0.034
 H. Li et al. / Materials and Design 84 (2015) 1–9 3

Table 2
Chemical compositions of solutions (g/L).

Standard solution A Standard solution B

MgCl2·6H2O 555.57 KCl 69.46

CaCl2 57.94 NaHCO3 20.10
SrCl2·6H2O 2.12 KBr 10.06
H3BO3 2.72
NaF 0.30

digital imaging detector. Primary ion beam of Cs− (2 kV impact energy,

150 nA beam current) was used depending on the element to be ana-
lyzed. The primary beam was rastered over a 200 μm × 200 μm square
area to avoid crater edge effect.

3. Results and discussion

3.1. Distribution of elements on steel substrate Fig. 3. Calculation results of Fermi energy.

Fig. 2(a) shows the existence of tin in the steel. Fig. 2(b) and
(c) show the distribution of tin and Fe examined by SIMS, which can
be seen from spectral intensity. It can be identified that tin distributes
uniformly in the steel and there is no obvious segregation under the
condition of 0.038 wt.% addition. Gibbs function: ΔG = − nFΔE (n:
Electron transfer number, F: Faraday's constant) can judge the direction
of reaction. Electrochemical reaction could proceed when ΔG b 0, and
corrosion tendency will be enlarged when the value ofΔE increases
(ΔE = Eec − Eea,Eec: cathode potential, Eea: anode potential. The non
equilibrium electrode potential of Sn and Fe in 3.5 wt.% NaCl solution
is −0.25 V and −0.50 V, respectively. So the value of ΔE can be reduced
when tin is added into steel, which could reduce the corrosion
tendency.
Fermi energy is used to explain why it is beneficial when tin is added
into steel from the view of corrosion thermodynamic. From the
perspective of microscopic physics, electrons outside the nucleus are
fermions following the Fermi–Dirac statistical law. Eq. (1) is statistical

Fig. 2. Results of SIMS. (a) Mass Spectroscopy. (b) Surface scanning of tin. (c) Surface scanning of Fe.
4 H. Li et al. / Materials and Design 84 (2015) 1–9

structure. It can be seen from Fig. 3 that Fermi energy of tin-containing

atomic is lower than that of Fe–C atomic. The value reduced by tin is
higher than that reduced by Cr or Cu, which proves a tendency that
the tin addition can reduce Fermi energy of steel in some extent.
Fig. 2(b) shows that the distribution of tin is uniform, which indicates
that tin can increase tin-containing steel's oxidation resistance evenly.
This effect is conducive to improve the corrosion resistance of the tin-
containing steel.

3.2. Potentiodynamic polarization curves

Potentiodynamic polarization test for 1 day of immersion was

conducted to investigate the corrosion properties of the two steels, re-
spectively. Corrosion potential Ecorr obtained from the polarization
curve corresponds to zero current, where the sum of all anodic reactions
on the specimen surface is equal to the sum of all cathodic reactions. As
the curves in Fig. 4 show, the anodic current density increases continu-
Fig. 4. Potentiodynamic polarization curves corresponding to 1 day. ously with increasing potential, which indicates that both of the two
steels demonstrate active dissolution behavior in seawater. Besides,
Fig. 4 shows that tin-containing steel has lower anodic current density
Table 3 compared with tin-free steel. Ecorr of tin-containing steel has a higher
Electrochemical parameters in seawater from a curve-fitting approach. potential compared to tin-free steel, and this result is consistent with
Type Immersion Ecorr (mv) Icorr (uA/cm2) βa (mV/decade) the research by Wenjin Zhang [4] that element Sn could ennoble the
time (d) Ecorr value. The more positive potential indicates a negative reaction
Tin-containing steel 1 −676 13.329 0.0626 thermodynamic trend. All of these conclusions indicate that tin-
Tin-free steel 1 −717 18.621 0.0616 containing steel has better corrosion resistance than tin-free steel in
seawater.

distribution function which shows the distribution of electron in energy

level E.

f ðeÞ ¼ 1 E−E
 ð1Þ
exp f
þ1
KT

There are three criterions determining the state of electron in multi-

electron atoms. (1) Pauli exclusion principle, (2) Energy minimization
principle, and (3) Hund rules. Fermi energy is different due to the differ-
ence in species and structure of atom as well as numbers of primary and
secondary quantum. A system has higher Fermi energy are easier to lose
its electron outside, which means that metal will be easily corroded.
CASTEP module in Materials studio program was used to investigate
Fermi energy of the tin-containing steel (α-Fe standard cell, add C in
atomic structure and 2 × 2 × 2 supercell. C occupies only one set of
octahedral gap of the Fe sub lattice, and some Fe atoms of the α-Fe
cell are substituted by solid solution element tin). It was calculated
that how much the Fermi energy has changed after adding tin in atomic

Fig. 5. Comparison of corrosion rates between potentiodynamic polarization and weight Fig. 6. Nyquist plots of the two steels with different immersion time: (a) Tin-containing
loss measurements. steel; (b) Tin-free steel.
 H. Li et al. / Materials and Design 84 (2015) 1–9 5

Fig. 8. Equivalent electrical circuit used in ZSimpWin software.

containing steel is better than that of tin-free steel. The corrosion rates
of the two steels immersed for 1 day were calculated by Faraday's law
[11]:

Corrosion rate ðmm=yÞ ¼ 316  icorr  M=z  F  ρ ð2Þ

where icorr is the corrosion current density (uA/cm2), M is the molar

mass of the metal (g/mol), z is number of electrons transferred per
metal atom, F is the Faraday's constant, and ρ is the density of the
metal (g/cm3). The tin-containing steel has lower corrosion rate than
tin-free steel. Fig. 5 shows that the trend of the corrosion rate is also
in agreement with weight loss method. The corrosion rates of the
steel were determined using the following expression [12]:
.
Corrosion rate ðmm=yÞ ¼ 8:76  104  W ð3Þ
ATD

Fig. 7. Bode diagrams of the two steels for different immersion time: (a) Tin-containing where 8.76 × 104 is the metric and time conversion factor, W is the
steel; (b) Tin-free steel. weight loss (g), A is the area of exposure (cm2), T is the immersion
time (h) and D is the density (g/cm3). The results are shown in Fig. 5.

Table 3 lists the Tafel constants of the two steels, and these parame-
ters were got from curve-fitting by Tafel extrapolation method. Table 3
shows that tin-containing steel has lower Icorr than tin-free steel in
general. Normally, the value of Icorr stands for corrosion resistance
[16], so the lower Icorr indicates that the corrosion resistance of tin-
3.3. Electrochemical impedance spectroscopy
EIS was conducted on the specimens after they were immersed in
seawater for 0, 1, 2, 4, 8, 18, 26, 40 days. The typical Nyquist plots are
shown in Fig. 6. It shows that the magnitude of semicircle decreases

Table 4
Fitting results of equivalent electrical circuit conducted by ZSimpWin.

Type Immersion time (d) Rs (Ω cm2) Qdl (Ω−1 cm−2 sn) ndl Rct (Ω cm2) Qf (Ω−1 cm−2 sn) nf Rf (Ω cm2)

Tin-containing steel 0 3.06 0.000168 0.837 1310.0

1 2.74 0.000159 0.810 1278.0
2 3.85 0.000680 0.731 1055.2
4 3.84 0.005747 0.718 916.8
8 5.78 0.007570 0.609 884.6
18 5.05 0.004848 0.728 590.8
26 4.55 0.000481 0.757 552.8 0.007971 0.678 313.5
40 8.49 0.000403 0.614 582.0 0.006881 0.721 521.6
Tin-free steel 0 2.94 0.000182 0.871 750.1
1 2.16 0.000977 0.666 723.0
2 3.48 0.001240 0.509 734.5
4 1.95 0.001606 0.648 716.3
8 4.15 0.001492 0.845 642.3
18 3.02 0.000895 0.881 553.7
26 3.06 0.000868 0.860 511.4
40 3.94 0.000706 0.798 464.5 0.009280 0.789 258.3
6 H. Li et al. / Materials and Design 84 (2015) 1–9
Fig. 9. The surface morphology after removing corrosion products: (a),(c) and (e) are pho-
tographs of tin-free steel immersed for 18, 26 and 40 days; (b), (d) and (f) are photographs
of tin-containing steel immersed for 18, 26 and 40 days.
over time. Besides, the curves of the tin-free steel that immersed for 2
and 4 days include a long tail in the low-frequency region, which
indicates that the corrosion is controlled by Faraday impedance or the
diffusion of elements [6]. And it also implies an active corrosion
behavior. Moreover, the semicircle diameter of tin-containing steel
becomes larger after 18 days of immersion. The Nyquist plots of tin-
free steel have similar tendency with that of tin-containing steel, but
the semicircle diameter of tin-free steel increases after 26 days of
immersion.
Fig. 7 shows the Bode diagrams of the two steels. The Bode diagrams
of tin-containing steel indicate that the maximum magnitude of phase
angle arises at another frequency range when immersed for 8 days.
The reason could attribute to the formation of rust film on tin-
containing steel surface [17]. At the last period of corrosion cycle, the di-
verse diagrams of the two kinds of steels represent two time constants.
The Zsimpwin program was used to fit the EIS data, and the fitting
results are listed in Table 4 (percentage error within five percent). The
equivalent electrical circuit with one time constant, as shown in
Fig. 8(a), is proposed to simulate electrochemical process at the initial
stage of corrosion. An equivalent electrical circuit with two time
constants, as shown in Fig. 8(b), is proposed to simulate the electro-
chemical process at the last period of corrosion. Rs is the resistance of
solution, and Rct is the charge transfer resistance of the double-layer
capacitor. Qdl is the double-layer capacitance, and the impendence of
Qdl can be written as Z = [Qdl(jω)n]−1, where ω is the angular frequency,
j is the imaginary number and n is a parameter affected by the rough-
ness of surface. Besides, Rf is the resistance of rust layer and Qf has the
same form as Qdl. The equivalent impedance, shown in Fig. 8(a), can
be written as:


Z ¼ Rs þ 1 1


: ð4Þ
þ1
Z dl Rct
The equivalent impedance, shown in Fig. 8(b), can be written as:


Z ¼ Rs þ 1 1


: ð5Þ
Zf
þ1 1 1
Rf þ þ
Z dl Rct
The polarization resistance Rp = Rf + Rct (Rp = Rct at the early stage
of corrosion) has been widely used to account for the kinetics of electro-
chemical corrosion [16,18]. Table 4 shows the parameters of EIS. Rp
values obtained from tin-containing steel are higher than that of tin-
free steel. Furthermore, values of Rp decrease at the early stage of corro-
sion for both of the two steels, which could be ascribed to the increase of
corrosive area. These situations are corresponding to the increase of Qdl
values, which are associated with an increase of double-layer capaci-
tance. For the tin-containing steel, Rp values exhibit the lowest value
when specimen was immersed for 18 days, which may be due to
the relatively fast electrochemical corrosion rate between substrate
steel and steel covered by protective rust layer. For tin-free steel, Rp
values exhibit the lowest value when immersed for 26 days. In
general, tin-containing steel has higher impedance than tin-free
steel, and the Rp value of tin-containing steel is almost 34% higher
than that of tin-free steel when they have been immersed for
40 days.
Fig. 9 shows the surface morphology of corroded sample after
removing corrosion products. Tin-containing steel has lighter corrosion
degree than tin-free steel. Fig. 9(b) shows that some areas (Area A) of
the tin-containing steel exhibit a little more serious corrosion degree
than elsewhere, which may be because the rust layer can't cover the
whole corroded surface when the specimen was corroded for 18 days.
And the corrosion rate of the surface covered by rust layer is slower
than that of the surface without rust layer. The localized corrosion also
indicates that the rust layer formed on tin-containing steel is protective
[6]. Uniform corrosion is observed on the specimen immersed for
40 days, which could be attributed to that all corroded surface has
been covered by protective rust layer.
Fig. 10 shows the cross section of the rust layer. The thickness of the
rust layer of the tin-containing steel is thinner than that of tin-free steel.
Fig. 10(a) shows that the rust layers is porous. As time elapses, the rust
layers formed during immersion grow and become more compact,
which could attribute to the compaction and agglomeration of the rust
layer. The rust layer shown in Fig. 10(e) has some cracks and pores,
but the rust layer shown in Fig. 10(f) is dense and compact. This differ-
entia indicates that the tin-containing steel has a more protective rust
layer than tin-free steel.
In the analyses section of EIS, the comparison of tin-free steel and
tin-containing steel shows that the time for augment of tin-free steel's
Rp values is slightly later than that of tin-containing steel. The phenom-
enon can be explained consulting to corrosion morphology shown in
Fig. 10. Fig. 10(c) shows that the rust layer of tin-free steel is porous
and loosened. However, the rust layer shown in Fig. 10(d) is more
compact than the rust layer shown in Fig. 10(c), which indicates that
the rust layer shown in Fig. 10(d) is protective. This phenomenon indi-
cates that tin-containing steel has shorter time to form protective rust
layer than tin-free steel. Fig. 10(e) and (f) show that the rust layer of
the tin-containing steel is more compact than that of tin-free steel,
which is corresponding to EIS results for 40 days immersion that tin-
containing steel has higher Rp value than tin-free steel.
3.4. Results of XRD and XPS
Specimens immersed for 18 and 40 days were detected by X-ray
diffraction (XRD) to analyze the principal corrosion products.
Figs. 11 and 12 show the XRD graphs of the two steels. The composi-
tions of corrosion film measured by X-ray diffraction indicate
that corrosion products of the two steels are all principally composed
of the corrosion substance in seawater (containing plenty of Cl−).
 H. Li et al. / Materials and Design 84 (2015) 1–9 7

Fig. 10. The cross section of corroded samples: (a),(c) and (e) are photographs of tin-free steel immersed for 18, 26 and 40 days; (b), (d) and (f) are photographs of tin-containing steel
immersed for 18, 26 and 40 days (a, b: 3000×; c, d, e, f: 1000×).

The corrosion products are mostly Fe2 O 3, Fe 3O 4 , γ-FeOOH and α-
FeOOH.
Fig. 11(a) and (b) show that the relative content of γ-FeOOH of the
corrosion compounds after 40 days of immersion is higher than
that of corrosion compounds after 18 days of immersion. XRD
graphs of tin-containing steel show the differentia that the relative
content of Fe3O4 in Fig. 12(b) is higher than that of Fig. 12(a). As is
well known, the corrosion resistant grade of iron oxide–hydroxide is
β-FeOOH b γ-FeOOH b α-FeOOH, and the metastable γ-FeOOH will
transform to steady Fe3O4 as corrosion period went. This shows that
the content of corrosion resistant substance of tin-containing steel's
rust layer is higher than that of tin-free steel's rust layer.
XPS was proceeded to analyze the corrosion products of the two
steels immersed for 40 days. Fig. 13 shows the XPS spectrum of the cor-
rosion products. Na− and Cl− are detected, which could be ascribed to
the diffusion of ion in the solution. Fig. 13(b) clearly indicates various
oxidation states of tin corresponding to the following binding energy:
Sn 3d5/2 peak at about 485 eV and Sn 3d3/2 peak at about 495 eV. Be-
sides, the Sn 3d5/2 peak is wide and asymmetrical, indicating the
existence of oxidation state of tin at different binding energy. The
peaks showed in Fig. 13(b) are related to binding energy of SnO at
485.60 eV and SnO2 at 488.60 and 495.60 eV according to the dates in
literature [12,19,20].
Anodic reaction includes the oxidization of metallic element. And
the rust layer is constructed by these reaction products. Corrosion resis-
tance of rust layer will be improved when beneficial elements are added
into steel. Beneficial elements can form corrosion resistant compounds
that modify the performance of rust layer. Some possible anodic
reactions of element tin under experimental condition are as follows
[19]:
Sn þ 2OH− − 2e− →SnðOHÞ2 ð6Þ
Sn þ 2OH− − 2e− →SnO þ H2 O ð7Þ
SnðOHÞ2 þ 2OH− −2e− →SnðOHÞ4 ð8Þ
8 H. Li et al. / Materials and Design 84 (2015) 1–9
Fig. 11. X-ray diffraction measurement of tin-free steel: (a) After 18 days of immersion.
(b) After 40 days of immersion.
SnO þ H2 O þ 2OH− −2e− →SnðOHÞ4 :
The compounds of Sn(OH)2 and Sn(OH)4 are not the final steady
state in rust layer, and most of them will transform into more stable
tin oxide (SnO and SnO2) as following reactions:
SnðOHÞ2 →SnO þ H2 O
SnðOHÞ4 →SnO2 þ 2H2 O:
As shown in Fig. 10(f), the corrosion scale of the tin-containing steel
is dense, which can restrict the contact between solution and substrate
steel efficiently. And the dense corrosion scale also can inhibit the anod-
ic reaction. The compounds of SnO and SnO2 are regarded as immune in
aqueous, and SnO2 can hardly dissolve in acid and alkali solutions.
Besides, SnO2 can remain stable in dilute acid and alkali solutions [21].
These can make the rust layer of tin-containing steel stable, protective
and have a better corrosion resistance. The results of XRD show the dif-
ference between the two steels at iron oxides and oxyhydroxides. The
differentia shows that there is a coprecipitation process of tin oxides
with iron oxides, which can fill the crack in the rust layer effectively as
shown in Fig. 10(f). These results are corresponding to the research
results of Nam N D [12] that interaction of Sn with other elements can
improve the formation of the continuous rust layer. The existence of
SnO, SnO2 and the coprecipitation process are the reason why more
uniform and compact rust layer was formed. Meanwhile, the interaction
of Sn with Cu may also has a positive effect on it [12]. Furthermore, it is
Fig. 12. X-ray diffraction measurement of tin-containing steel: (a) After 18 days of immer-
sion. (b) After 40 days of immersion.
ð9Þ
obvious that the coprecipitation process also make the tin-containing
steel have shorter immerse period than tin-free steel to form a protec-
tive rust layer.
Besides, the EIS has showed that tin-containing steel has higher rust
layer impedance than tin-free steel, and the results of XPS have
ð10Þ confirmed the existence of tin oxides in the rust layer. SnO2 is a p-type
semiconductor [22], which has low electronic conductivity and
high corrosion resistance. The better corrosion resistance of tin
ð11Þ
oxides could increase the impedance of rust layer of the tin-containing
steel.
4. Conclusions
(1) The distribution of tin showed there is no obvious segregation on
substrate steel when tin addition was 0.038 wt.%, and the
addition of tin in the steel could improve the corrosion resistance
of steel by decreasing Fermi energy from − 9.276 eV to
−14.445 eV.
(2) Tin-containing steel had lower corrosion current and higher
impedance than tin-free steel. EIS and corrosion morphology
results showed that tin-containing steel could form a more
uniform and compact rust layer with higher Rp. The formation
of protective rust layer needed a shorter immersed period com-
pared to tin-free steel. All the results showed that corrosion
resistance of tin-containing steel was higher than that of tin-
free steel.
 H. Li et al. / Materials and Design 84 (2015) 1–9
Fig. 13. XPS analysis for the corrosion products of two steels immersed for 40 days: (a) Wide scan spectra, (b) Narrow scan spectra of tin, (c), (d) Narrow scan spectra of Fe.
(3) Tin-containing steel exhibited more obvious localized corrosion
than tin-free steel at the early corrosion stage. After long time
immersion, XPS results indicated that tin could form SnO2 and
SnO in the corrosion scale, which had outstanding corrosion
resistant property and they could increase the impedance of
rust layer. Besides, the coprecipitation process of tin oxides
with iron oxides made the rust layer more uniform, compact
and adherent, which inhibited the dissolution of steel and
increased the impedance of rust layer. All of these contributed a
better corrosion resistance to the tin-containing steel.
References
[1] T.K. Kandavel, R. Chandramouli, P. Karthikeyan, Influence of alloying elements and
density on aqueous corrosion behaviour of some sintered low alloy steels, Mater.
Des. 40 (2012) 336–342.
[2] Su Hang, Xiaobing Luo, Caifu Yang, et al., Effects of Cu on corrosion resistance of low
alloyed steels in acid chloride media, J. Iron Steel Res. Int. 21 (6) (2014) 619–624.
[3] K. Hashimoto, K. Asami, A. Kawashima, H. Habazaki, E. Akiyama, The role of corro-
sion resistant alloying elements in passivity, Corros. Sci. 49 (1) (2007) 42–52.
[4] W. Zhang, M. Li, Q. Chen, et al., Effects of Sr and Sn on microstructure and corrosion
resistance of Mg–Zr–Ca magnesium alloy for biomedical applications, Mater. Des. 39
(2012) 379–383.
[5] S. Ningshen, M. Sakairi, K. Suzuki, S. Ukai, The corrosion resistance and passive film
compositions of 12% Cr and 15% Cr oxide dispersion strengthened steels in nitric
acid media, Corros. Sci. 78 (1) (2014) 322–334.
[6] R. Wang, S. Luo, M. Liu, Y. Xue, Electrochemical corrosion performance of Cr and Al
alloy steels using a J55 carbon steel as base alloy, Corros. Sci. 85 (1) (2014) 270–279.
[7] N.D. Greene, C.R. Bishop, M. Stern, Corrosion and electrochemical behavior of chro-
mium‐noble metal alloys, J. Electrochem. Soc. 108 (9) (1961) 836–841.
[8] H. Cano, D. Neff, M. Morcillo, P. Dillmann, I. Diaz, D. Fuente, Characterization of cor-
rosion products formed on Ni 2.4 wt.%–Cu 0.5 wt.%–Cr 0.5 wt.% weathering steel ex-
posed in marine atmospheres, Corros. Sci. 87 (5) (2014) 438–451.
9
[9] J.H. Hong, S.H. Lee, J.G. Kim, J.B. Yoon, Corrosion behaviour of copper containing low
alloy steels in sulphuric acid, Corros. Sci. 54 (1) (2012) 174–182.
[10] S. Khireche, D. Boughrara, A. Kadri, L. Hamadou, N. Benbrahim, Corrosion mecha-
nism of Al, Al–Zn and Al–Zn–Sn alloys in 3 wt.% NaCl solution, Corros. Sci. 87 (5)
(2014) 504–516.
[11] I. De Ryck, E. Van Biezen, K. Leyssens, A. Adriaens, P. Storme, F. Adams, Study of tin
corrosion: the influence of alloying elements, J. Cult. Herit. 5 (2) (2004) 189–195.
[12] N.D. Nam, M.J. Kim, Y.W. Jang, J.G. Kim, Effect of tin on the corrosion behavior of
low-alloy steel in an acid chloride solution, Corros. Sci. 52 (1) (2010) 14–20.
[13] A. Pardo, M.C. Merino, M. Carboneras, A.E. Coy, R. Arrabal, Pitting corrosion behav-
iour of austenitic stainless steels with Cu and Sn additions, Corros. Sci. 49 (2)
(2007) 510–525.
[14] A. Pardo, M.C. Merino, M. Carboneras, F. Viejo, R. Arrabal, J. Munoz, Influence of Cu
and Sn content in the corrosion of AISI 304 and 316 stainless steels in H2SO4, Corros.
Sci. 48 (5) (2006) 1075–1092.
[15] M. Esmaily, M. Shahabi-Navid, J.E. Svensson, Influence of temperature on the atmo-
spheric corrosion of the Mg–Al alloy AM50, Corros. Sci. 90 (2015) 420–433.
[16] Y. Kayali, B. Anaturk, Investigation of electrochemical corrosion behavior in a
3.5 wt.% NaCl solution of boronized dual-phase steel, Mater. Des. 46 (4) (2013)
776–783.
[17] W. Liu, H. Zhang, Z. Qu, Y. Zhang, Corrosion behavior of the steel used as a huge stor-
age tank in seawater, J. Solid State Electrochem. 14 (6) (2010) 965–973.
[18] D.P. Le, W.S. Ji, J.G. Kim, K.J. Jeong, S.H. Lee, Effect of antimony on the corrosion be-
havior of low-alloy steel for flue gas desulfurization system, Corros. Sci. 50 (4)
(2008) 1195–1204.
[19] X. Zhong, G. Zhang, Y. Qiu, Z. Chen, X. Guo, C. Fu, The corrosion of tin under thin elec-
trolyte layers containing chloride, Corros. Sci. 66 (2013) 14–25.
[20] M. Kwoka, L. Ottaviano, M. Passacantando, S. Santucci, G. Czempik, J. Szuber, XPS
study of the surface chemistry of L-CVD SnO2 thin films after oxidation, Thin Solid
Films 490 (1) (2005) 36–42.
[21] D. Li, P.P. Conway, C. Liu, Corrosion characterization of tin–lead and lead free solders
in 3.5 wt.% NaCl solution, Corros. Sci. 50 (4) (2008) 995–1004.
[22] C.H. Lee, B. Nam, W.K. Choi, Mn: SnO2 ceramics as p-type oxide semiconductor,
Mater. Lett. 65 (4) (2011) 722–725.