Advanced Materials Research Vols.

989-994 (2014) pp 420-424 Submitted: 2014-05-25

© (2014) Trans Tech Publications, Switzerland Accepted: 2014-05-30
doi:10.4028/www.scientific.net/AMR.989-994.420 Online: 2014-07-16

Effect of Ni on Corrosion Resistance of Weathering Steels in wet/dry

Environments
Rui Liu1,2,a, Xiaoping Chen2,b and Qingnan Shi1,c*
1
School of Material Science and Engineering, Kunming University of Science and Technology,
Kunming 650093, China;
2
Centeral Iron and Steel Research Institute, Beijing 100081, China
a
liurui6699@163.com, bchenxiaoping@cisiri.com, *Corresponding author: cshikust@vip.163.com

Keywords: Ni element, weathering steel, weight loss, rust, EIS

Abstract: Corrosion behavior of a low alloy steel A with 3% nickel content was studied by a
wet/dry cyclic test. A commercial weathering steel Q450NR1 was used for comparison. The
classical weight loss method was used to evaluate the weatherability of weathering steel, while the
iron rust layers formed on weathering steel were analyzed by using SEM, XRD and electrochemical
measurements. The results indicated that the corrosion resistance of steels A was better than that of
commercial weathering steel Q450NR1 in the wet/dry cyclic test. The addition of Ni promoted the
formation of α-FeOOH so as to improve the resistance of the rust. The EIS results indicated that the
charge transfer resistance of steel A was bigger than that of steel Q450NR1.

Introduction
Metal corrosion is a serious problem, which exists in various fields of national economy and
national defense construction[1]. So weathering steel has been widely used due to its excellent
atmospheric corrosion resistance performance in atmospheres which results from that the alloying
elements such as Cu, Cr, Ni, Si, P, etc. in the steel can promote to form a dense and adhesion
stability protective film[2]. Nowadays, Ni plays an important role in the corrosion process of
structural steel. The steel with Ni can make the selfcorrosion potential move to the positive
direction, which increases the stability. The atmospheric exposure research results showed that the
corrosion resistance in the sea side environment of the weathering steel with about 4 wt% Ni can be
significantly improved[3]. Japanese scholars[4] did the reaches on the corrosion resistance of
weathering steel with 3% wt% Ni in the coastal environment and they found that the grain was
refined and the density was increased because of the enrichment of Ni in the rust layer. It was
difficult for the chloride ion to get through the rust layer to the steel substrate resulting in the
reduction of the corrosion rate of the weathering steel. I. Diaz[5] found that weathering steel
containing Ni exposured in Marine atmospheric environment of medium chloride ion erosion after a
year showed better corrosion resistance, and the higher of the Ni content the better corrosion
resistance it had, It was because that the existing of Ni promoted the formation of the nano phase
and superparamagnetism α-FeOOH in the inner rust layer, and the particles size of α-FeOOH was
less than 15 nm, which can increase the density of the rust layer leading to the improvement of
marine atmospheric corrosion resistance.
In this paper, the characteristics of the steel with Ni and conventional weathering steel were
investigated in detail after wet/dry corrosion test. And the effect of Ni in improving the corrosion
resistance of weathering steel was explored.

Experimental
Composition of tested steels. The steel A with 3 wt% Ni and commercial weathering steel
Q450NR1 were used as tested steels and their chemical compositions are given in Table 1.

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 Advanced Materials Research Vols. 989-994 421

Table 1 Chemical composition of test materials (wt%)

steel C S P Mn Si Cr Ni Cu Fe
A 0.075 0.0068 0.012 0.80 0.39 0.502 0.193 0.243 rest
Q450NR1 0.081 0.0058 0.0061 0.89 0.40 0.505 2.939 0.272 rest
Periodic immersion wet\dry cyclic corrosion test. The atmospheric corrosion resistance of
weathering steels was evaluated through a periodic immersion wet/dry cyclic corrosion test, which
was an accelerated corrosion test method under artificially simulated atmospheric environment.
There were three parallel samples and the dimension of the sample was 60mm×40mm×5mm. Each
cycle of wet/dry cyclic corrosion test lasted for 1 hour and included two stages: (1) immersing the
specimens into 2 wt% NaCl aqueous solution for 12±1.5 min (2) drying the specimens immediately
after immersion by heating lamps (the surface biggest temperature of the specimens was 70±10℃),
subsequently holding the specimens in the testing chamber with a constant humidity of RH 70±5%
at 45±2 ℃ totally for 48 min. The total corrosion test lasted for 96 cycles, i.e. 96 h. In this test, 2
wt% NaCl aqueous solutions were used to simulate a marine atmosphere, which is one of the
typical atmosphere environments encountered during the application of weathering steels.
A chemical dissolution method was adopted to remove the corrosion layer, i.e. immersing the as-
corroded specimen in a vigorously stirred specific diluted hydrochloricacid solution (500 ml
HCl+500 ml distilledwater+3.5 g hexamethylenetetramine) for at least 10 min at room
temperature[6,7].
Rust analysis. The powdered rust was scraped off from the rusted samples and the powdered
rust samples were characterized by means of X-ray diffraction (XRD) to determine its composition.
The XRD measurements were carried out using a Rigaku-D/max2000 diffractometer with a Cu Kα
target under 50 kV, 250 mA and with a scanning range of 5-40° at a scanning speed of 2° min-1.
The rusted samples for cross-sectional analysis were observed using scanning electron microscopy
(SEM). SEM observation was performed with a HITACHI_S-4300.
Electrochemical measurements. Polarization measurements were performed with a Model
273A-M398 Potentiostat/Galvanostat at a 0.332mV/s scan rate in 2 wt% NaCl solution while
keeping the solution in 30±2 ℃ by using a water bath pot. It used a saturated calomel electrode
(SCE) as reference and a Pt counter electrode. The scan range was -250 mV to 250 mV. The steel
samples were manually sectioned into coupons of dimensions 10 mm×10 mm×3 mm, which served
as the working electrode.
The electrochemical impedance spectroscopy (EIS) measurements were carried out over the
frequency rage 100 kHz to 10 mHz with a 5 mV amplitude signal at open circuit potential. Before
all the electrochemical experiments were performed, the specimens were kept in the solution for
half an hour in order to attain a stable open circuit potential. Electrochemical impedance
spectroscopy (EIS) measurements of the bare and rusted steel were carried out in 0.5 wt% NaCl
solution.

Results and discussion

Corrosion rate of weathering steel. The corrosion rate of the steels in the artificially simulated
marine corrosive atmosphere was determined by weighing the unaffected substrate part of each
specimen before and after the tests. The weight loss rate could be determined using the following
equation:
(1)
Where W is the weight loss rate (mg/(cm2·h)), G0 is the initial weight of the specimen before
corrosion test (mg), G1 is the weight of the as-corroded specimen after its surface corrosion product
was removed (mg), S is the initially total surface area of the specimen(cm2), t is the test time (h)[8].
Fig.1 presents the corrosion rate of the tested steels. It can be seen clearly that the weight loss of
the steel A with 3% wt% Ni is much lower than that of Q450NR1, indicating that the effectiveness
of Ni for using in salt-rich environment.
422 Materials Science, Computer and Information Technology

Figure 1.The corrosion rate of the tested Figure 2. XRD semiquantitative analysis of
steelswet/dry corrosionproducts formed on steel A and
cycles Q450NR1
Composition and structure of rust layer. It can be seen from the XRD that patterns of the rust
layers formed on the two steels after periodic immersion wet/dry cyclic corrosion for 72 h,
crystalline corrosion products were formed. The rust layers consist of maghemite (Fe2O3),
magnetite(Fe3O4), lepidocrocite(γ-FeOOH), goethite(α-FeOOH) and akaganeite(β-FeOOH). Fig.2
shows the constituents of steel A and Q450NR1 from a semiquantitative analysis. From this results
it can be concluded that the additions of Ni could greatly promote the transformation of
lepidocrocite(γ-FeOOH) to goethite(α-FeOOH). It has been reported that goethite (α-FeOOH) is
non active in the corrosion process, and the γ-FeOOH phase acts as the oxidation agent that
accelerates corrosion in a chloride-free environment[9,10]. Furthermore, the addition of Ni decrease
the content β-FeOOH which plays the primary role in accelerating the corrosion rate[11].

Figure 3. The cross-sectional morphologies of rust layers: (a) Steel Q450NR1 (b) Steel A
The cross-sections of the steels after 72 cycles of accelerated tests were observed by SEM, as
shown in Fig.3 (a) and (b). It shows that the rust layers in these test steels all contain voids and /or
micro-cracks. Both of them are composed of two parts: the loose outer layer and the dense inner
layer. However, the inner rust layer of steel A is denser while the voids and micro-cracks are fewer.
Meanwhile, the thickness of the rust layer of steel A is about 200-300µm thinner than that of steel
Q450NR1 (400-500µm).
Electrochemical measurements. Fig.4 illustrates the polarization curves of the bare steel A and
Q450NR1 in NaCl solution. It can be seen clearly that the selfcorrosion potential of the steel A is
higher than steel Q450NR1. It indicates that the corrosion of steel A is harder to occur.
The Nyquist impedance plots of the two bare steels are shown in Fig.5, which show a well
defined semicircle. The semicircle diameter of steel A is larger than that of Q450NR1 which means
that the corrosion resistance of bare steel A is higher than that of bare Q450NR1.
 Advanced Materials Research Vols. 989-994 423

Figure 4. The polarisation of the bare steel of Figure 5. EIS for pre-corroded samples in a
steelA and steel Q450NR1 0.5 mass% NaCl aqueous solution

Figure 6. EIS of steel Q450NR1 and A that were subjected to a wet/dry cyclic test for 72cycles

Figure 7. Equivalent circuit for specimens immersed in a 0.5 mass% NaCl solution

Fig.6 shows the Nyquist diagrams of steel A and Q450NR1 that were subjected to a wet/dry
cyclic test for 72 cycles. The diagrams of the two steels are consisted of a depressed semicircle at
the high frequency region and a long tail at the low frequency region. As can be seen in Fig.6, the
impedance data can be well fit, marked by the rounded points, using the equivalent electrical circuit
(as shown in Fig.7). There is no obvious interface between the outer rust layer and the inner rust
layer. Besides, the inner rust layer can transform into the outer layer as the corrosion proceeds. So,
for EIS fitting, it is considered the two layers as a whole. In this case, Rr and CPEr represente the
resistance and capacitance represente the rust layer, respectively. Rct modeled the charge transfer
resistance, CPEdl describe the double layer capacity and W is used to model semi-infinite linear
diffusion. The Rct value of steel Q459NR1 is 125.2 Ω, while that of steel A is 186.4 Ω. The Rct value
of steel A increased to a certain degree, which implied that the charge transfer between the rust
layer and the solution became more difficult. This can attribute to the increasement of the chemical
activity stability α-FeOOH and the decreasement of the opposite effect γ-FeOOH, according to the
XRD analysis above.
424 Materials Science, Computer and Information Technology

Conclusion
The weatherability of two weathering steels in wet/dry environments was discussed and the effect
of Ni was clarified. The following conclusions can be drawn. The Ni can improve the corrosion
resistance of the weathering steel obviously. It can improve the selfcorrosion potential of the bare
steel. The addition of Ni can greatly promote the formation of chemical activity stability goethite
(α-FeOOH), which increases the transfer resistance of charge and promotes the formation of a
denser and adhesion rust layer, although there are the same crystalline corrosion products in the rust
layer of different test steels.

Acknowledgements
This work was supported by the National Key Basic Research and Development Programme of
China (No. 2014CB643300).

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Materials Science, Computer and Information Technology
10.4028/www.scientific.net/AMR.989-994

Effect of Ni on Corrosion Resistance of Weathering Steels in Wet/Dry Environments

10.4028/www.scientific.net/AMR.989-994.420

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