Effects of simulated acid rain on corrosion behaviour of Q235 steel in acidic soil

Y. H. Wu*1,2, T. M. Liu1, C. Sun2, J. Xu2 and C. K. Yu2

The effects of simulated acid rain (SAR) on corrosion behaviours of Q235 steel in acidic soil were studied using potentiodynamic polarisation, electrochemical impedance spectroscopy measurements, scanning electron microscopy and X-ray diffraction. The results indicated that the SAR heavily increased the corrosion rate of the steel in the acidic soil. The corrosion rate of the steel increased with decreasing SAR pH values. The corrosive characteristics of the soil obviously increased because of leaching of the acid rain. The corrosion products of Q235 steel surface were mainly composed of Fe2O3, Fe3O4 and some soil components such as SiO2.
Keywords: Q235 steel, Acid rain, Corrosion, Acidic soil

Introduction
Acid rain has been a problem of increasing ecological and environmental concerns worldwide, which causes environmental damage, such as soil acidication.14 In particular, acid rain exerts a signicant effect on the buried metals. Soil is the major recipient of acid rain, where a series of complicated changes occurs because of the leaching of the acid rain. When the amounts of acid rain exceed the buffer capacity of the soil, the soil will appear acidication. Studies show that because of some properties inherent in the acid red soils, such as low pH, high resistivity, low content of soluble salt and high content of moisture, the corrosion susceptibility of metals in the acidic soils is very high,5,6 which is obviously different from that of the alkaline and neutral soil. Most studies on soil corrosion in China have focused on the aspects of alkaline and neutral soils, in which some researchers have reported some achievements on the mechanism and inuencing factors of the corrosion.710 However, the corrosion mechanism and impacting factors of the acidic soil are not clearly understood. Studies on the corrosion behaviour of metals in acidic soils which are being acidied by acid rain have been seldom reported. In this study, a specic device was designed in order to simulate the leaching process of the acid rain. The effects of the simulated acid rain (SAR) on the corrosion behaviours of Q235 steel in acidic soil were investigated.

working surface area was 15615 mm. The unexposed edges were coated with a masking paint to prevent crevice corrosion between the epoxy mount and the electrode. The working surfaces were polished using a series of silicon carbide emery papers of grades 400, 800 and 1000, and then they were cleaned with ethanol, followed by rinsing with distilled water to remove the contamination on them.

Simulated acid rain

The leaching solution of soil was the SAR. Its composition was based on the typical characteristics of acid rain in Southern China. The SAR solution was prepared from distilled water and analytical grade reagents. Composition { of the SAR is listed as follows: 35?90 mg dm23 SO2 4 , 23 23 2 { 1?08 mg dm NO3 , 0?152 mg dm Cl , 3?37 mg dm23 23 NHz Ca2z, 0?063 mg dm23 Kz and 4 , 4?80 mg dm 0?103 mg dm23 Naz. The pH value of the solution ranged from 5?6 to 2?5 with the addition of sulphuric acid.

Experiment installation
The specic experiment installation designed by the authors was composed of a plastic column with a diameter of 100 mm and a height of 250 mm. There was a leaching device of SAR on the top of the column, and a beaker to collect the efuent samples at the bottom (Fig. 1). Before lling the column with soil sample, a piece of plastic lter and two pieces of paper lters were placed at the end of the column to prevent leakage of the soil. To reect the natural rainfall conditions, an intermittent inuent application method was employed. That is, a 250 mL inuent of the SAR was slowly sprayed at a rate of 5 cm3 min21 to the top of the column every 24 h with a total inuent application of 20 times and a total volume of 5000 mL SAR solution.

Experimental
Materials
The test material was Q235 steel with a composition of Fe0?22C0?01Si0?48Mn0?012P0?022S (wt-%). The
1

Soil sample
The soil used in the present study was collected from Yingtan Natural Environmental Test Station of Jiangxi Province in China which represented a typical site of red soil. The area is located in the latitude 28u159200N and
2010 Institute of Materials, Minerals and Mining

College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China 2 State Key Laboratory for Corrosion and Protection, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China *Corresponding author, email yuanhuil@126.com

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Published by Maney on behalf of the Institute Received 20 April 2009; accepted 10 October 2009 DOI 10.1179/147842209X12559428167643

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1 Experiment installation

longitude 116u559300E. The soil was derived from Quaternary red clay and classied as Udic Ferralsols. The soil sample was transferred to the laboratory immediately for analysis. Chemical compositions of the soil sample obtained from the experimental analysis are shown in Table 1. Soil sample was dried (105uC, 10 h), grinded, sieved with an average size of 1 cm in diameter and then hand packed into the experiment installation (see Fig. 1) with moderate compression before leaching the SAR, but the compression was not applied consistently during the experiment.

Electrochemical measurement
The electrochemical experiments were performed on each sample that buried in the soil during the whole test by 2273 electrochemical system driven by the software package Powrsuite. Three parallel experiments were carried out in order to check reproducibility. The classic three electrodes conguration was adopted, consisting of the Q235 steel as working electrode, graphite as auxiliary electrode and a copper/saturated copper sulphate electrode as reference. All potentials were referred to this electrode. The tests were performed at ambient temperature. The electrochemical impedance spectroscopy (EIS) measurements were carried out at the open circuit potential with an amplitude of 10 mV ac potential in the frequency range of 100 kHz to 5 mHz. The results were analysed using the t program ZSimpWin. Potentiodynamic polarisation curves were recorded by changing the electrode potential automatically from below 150 mV to 150 mV above the open circuit potential with the scanning rate of 0?16 mV s21.
2 Polarisation curves of Q235 steel in soil after a 1 day and b 60 days

applied for Q235 steel electrodes. The polarisation curves for Q235 steel in the soil leached with the SAR of different pH values after 1 and 60 days exposure are shown in Fig. 2.The corrosion current density are listed in Table 2. It is seen that, compared with distilled water, the corrosion rate of Q235 steel in the soil leached with the SAR was smaller, indicating that leaching the acid rain increased the corrosion rate of Q235 steel in the acidic soil. The red soil specimen used in the experiment is mainly composed of kaolinite clay mineral with small amount of negative charge, which weakens the capacity of cation exchange. Therefore, the buffer abilities of the soil against acid rain become weak. Hz ions in SAR were exchanged with cation in the soil, adsorbed on the surface of soil grains, and spontaneously reacted with
Table 2 Icorr variation of Q235 steel with pH value of SAR pH value Icorr, mA cm22 1 day 60 days 2.5 11 21 3.5 8.7 17 4.5 6.3 16 5.6 3.0 7.1 7.0 2.1 3.4

Results and discussion

Potentiodynamic polarisation curve measurements
In order to determine the changes in the corrosion current density Icorr with exposure time, the potentiodynamic polarisation curve measurements were

Table 1 Chemical compositions of soil sample from Yingtan (China), wt-% pH 4.6 Salt 0.0056 Cl2 0.0008
{ SO2 4

NO{ 3 0.0006

HCO{ 3 0.0010

Ca2z 0.0008

Mg2z 0.0005

Kz 0.0001

Naz 0.0002

0.0009

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3 Plot of EIS for Q235 steel in soil leached with different SAR pH values after one days exposure and equivalent circuit for EIS

aluminium ions which converted to exchangeable aluminium ions in the mineral crystal lattice. When the amount of the acid rain exceeded the buffer capacity of the soil, the soil was acidied. Table 3 shows the pH value of the soil leached with the SAR after 60 days. It is seen that the pH value of soil leached with the SAR was ,4?6 which was the pH value of soil untreated with the SAR. Therefore, soil acidication had occurred and corrosiveness of the soil obviously enhanced after leaching the SAR. It can be observed that with decreasing the SAR pH value from 5?6 to 2?5, Icorr increased from 3?0 to 11 mA cm22 after burying for one day and from 7?1 to 21 mA cm22 after burying for 60 days, which indicated that the corrosion rate for Q235 steel increased with decreasing the SAR pH value. As shown in Table 2 and Fig. 2, the corrosion rate of the steel in the acid soil treated with the SAR increased with increasing the time of burying. These results may due to the fact that the Hz ion concentration in the soil increased with increasing the leaching amounts of the SAR. Therefore, the corrosion current density of Q235 steel in the soil leached with the SAR increased with time.

Impedance measurements
The impedance plots for the corrosion of Q235 steel in the soil leached with different SAR pH values after burying for one day are shown in Fig. 3. It is seen that there is a single non-standard semicircle caused by dispersion in all cases, which had been attributed to the roughness and inhomogeneity of the surface for Q235 steel, and the radius of the loops increases with increasing the SAR pH values. The results indicated that the control step of corrosion was the charge transfer process, and the corrosion tendency of the steel was enhanced with leaching the SAR.1113 The impedance graphs were tted via the equivalent circuit model (Fig. 3) to single layer circuit R(QR), where Rs is representative of soil electrolyte resistance, Rt is the charge transfer resistance and Q is a constant
Table 3 pH value of soil leached with SAR after 60 days After leaching the SAR Before leaching pH 2.5 pH 3.5 pH 4.5 pH 5.6 pH 7.0 4.6 3.5 3.8 4.1 4.2 4.5

phase element (CPE) related to the dispersion of a capacitance around a mean value.14 The impedance of Q is expressed as ZQ ~Y0 {1 (j v){n , where v is angular frequency (rad s21), Y0 is the admittance magnitude of CPE which can be approximately converted into a capacitance, and n is the exponential term. For n50, {1 , for n51 a ZCPE presents a resistance with R~Y0 capacitance with C5Y0, for n50?5, a Warburg element {1 15 . and for n521, an inductance with L~Y0 The electrochemical parameters can be obtained by tting the EIS based on the equivalent circuit of Fig. 3, and are listed in Table 4. The above results show that the charge transfer resistance decreased with decreasing the SAR pH values. The impedance plots of the steel in the soil leached with different pH SAR values after 60 days exposure are shown in Fig. 4. It can be seen that great changes have taken place in EIS plots of Q235 steel with time. For leaching the distilled water, the Nyquist plot after 60 days exposure in soils was composed of a capacitive arc at the high frequency part and a line with a 45u slope at the low frequency part that is typical of features of a diffusion controlled Warburg impedance (Fig. 4a), indicating the corrosion process of the steel was controlled by concentration polarisation. For leaching with the SAR of pH 5?6 and pH 4?5, the Nyquist plot are characterised with double capacitance arcs after burying for 60 days (Fig. 4b), showing two time constants, which might be caused by the adsorption of the intermediate products on the surface of the steel.16,17 Many anions in the SAR might be adsorbed on the surface of Q235 steel and form complex compounds. In this stage, the reaction process of the electrode was controlled by two state variables, i.e. electrode potential and covering density of the interim products,18 which caused the formation of a new capacitive loop in the low frequency region. For the SAR with pH 2?5 and pH 3?5, the EIS plots consist of a capacitive loop at the high frequency part and an inductive loop at the low frequency part after burying for 60 days (Fig. 4c). The capacitance arc at higher frequency was related to the charge transfer resistance, representing the corrosion rate of the Q235 steel. The other inductive loop at the low frequency was related to the active dissolution of anode,19 indicating the corrosion rate of local reaction for the Q235 steel was high. In this stage, the control step for the corrosion of steel is charge transfer process.

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a pH 7?0; b pH 5?6, pH 4?5; c pH 3?5, pH 2?5 4 Plots of EIS for Q235 steel in soil leached with different SAR pH values after 60 days exposure and equivalent circuit for EIS

The impedance graphs obtained for the Q235 steel exposed to various experimental conditions were tted via different equivalent circuits (Fig. 4) to: (i) a single layer Warburg circuit R[Q(RW)] used for the SAR with pH 7?0 (Fig. 4a) (ii) a double layer equivalent circuit R{Q[R(QR)]} for the SAR with pH 5?6 and 4?5 (Fig. 4b) (iii) an equivalent circuit R[QR(LR)] for the SAR with pH 3?5 and 2?5 (Fig. 4c). The electrochemical impedance for the circuit of Fig. 4ac can be expressed by the following

equations (1)(3) respectively Z ~R s z 1 : 1= Rt zYW (j v){0 5 zY0 (j v)n (1)

Z ~R s z

1 n h io (2) 1 1=SR1 z 1= R Y01 (j v)n1 z Y02 (j v)n2 Tz t 1 f1=R1 zj vLgz1=Rt zY0 (j v)n (3)

Z ~R s z

Table 4 Fitted results for EIS of Q235 steel after one days exposure pH 2.5 3.5 4.5 5.6 7.0 Equivalent circuits R(QR) R(QR) R(QR) R(QR) R(QR) Rs, V cm2 2.76102 2.86102 2.66102 2.36102 2.56102 Y0, Sn V cm22 5.761025 5.761025 6.261024 6.061025 6.161025 n 0.86 0.84 0.86 0.83 0.84 Rt, kV cm2 10 16 29 48 65

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a pH 2?5; b pH 3?5; c pH 4?5; d pH 5?6; e pH 7?0 5 Morphologies (SEM) of Q235 steel in soil leached with SAR of different pH values after 60 days exposure (A: SiO2; B: Fe2O3; C: Fe3O4)

where Yw is the modulus of the Warburg, v the angular frequency (rad s21), Y0 the admittance magnitude of CPE, n the exponential term, Rs the soil resistance, Rt the charge transfer resistance, R1 the corrosion resistance of the rust and L the inductance. The electrochemical parameters in equations (1)(3) could be obtained by tting the EIS based on the equivalent circuits of Fig. 4, and are listed in Table 5. These respective ts were based on a minimum systematic deviation between the data measured and the t results. Based on the equivalent circuits, the EIS data were tted well (Fig. 4). From Tables 4 and 5, it can be seen that the charge transfer resistance, which is inverse correlation with the corrosion rate, decreased with decreasing the pH value and decreased with time. The above results of EIS measurements were in well agreement with those of the polarisation curves.

Surface analysis
Figure 5 shows the corresponding SEM images of Q235 steel in the acid soils leached with the SAR of different pH values after 60 days exposure. It can be seen that the uniform corrosion occurred on the surface the steel. The steel surface was strongly damaged for the soil leached with the pH 2?5 SAR, and the roughness of the corroded surfaces decreased with increasing the pH values of the SAR, indicating that the SAR heavily increased the corrosion rate of Q235 steel in the acidic soil, which was in agreement with the results of the electrochemical studies. Figure 6 is the XRD spectra of the powered rusts of Q235 steel in the soil leached with the SAR of different pH values. It can be seen that the corrosion products of the steel surface were mainly composed of Fe2O3, Fe3O4 and some soil components such as SiO2

Table 5 Fitted results for EIS of Q235 steel after 60 days exposure pH 2.5 3.5 4.5 5.6 7.0 Equivalent circuits R[QR(LR)] R[QR(LR)] R{Q[R(QR)]} R{Q[R(QR)]} R[Q(RW)] Rs, V cm2 1.16102 1.26102 1.76102 1.96102 3.56102 Y01, Sn V cm22 4.861024 3.761024 2.561024 3.061024 1.761025 n1 0.76 0.81 0.76 0.77 0.82 Rt, kV cm2 1.5 2.2 3.0 4.9 11 L, H cm22 4.16104 5.86104 R1, V cm2 5.96103 5.36103 7.06102 7.36102 Y02, Sn V cm22 0.9861024 4.661024 n2 0.61 0.65 YW, S20?5 V cm22 5.861024

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a pH 2?5; b pH 3?5; c pH 4?5; d pH 5?6; e pH 7?0 6 X-ray diffraction spectra of powered rusts of Q235 steel in soil leached with SAR of different pH values

Conclusions
1. The SAR heavily increased the corrosion rate of Q235 steel in the acidic soil. 2. The corrosion rate of Q235 steel increased with decreasing the SAR pH value. 3. The corrosion tendency of the soil obviously increased with the leaching time of the SAR. 4. For leaching the SAR, a capacitive loop was observed in EIS plot after burying for one day. There were two capacitive semicircles for the acid rain with high pH values, and a capacitive loop in the high frequency region and an inductive loop in the low frequency region for the low pH value after burying for 60 days. The control step for the corrosion of Q235 steel is the charge transfer process. 5. For leaching the distilled water, a capacitive semicircle in the high frequency region and a Warburg resistance in the low frequency region were present, and the process was controlled by concentration polarisation process. 6. The corrosion products of the steel surface were mainly composed of Fe2O3, Fe3O4 and some soil components such as SiO2.

Research Programme of the Ministry of Science and Technology of China (grant no. 2005DKA10400-CT-2-02).

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Acknowledgements
This work was supported by National Natural Science Foundation of China (grant no. 50671112) and Basic

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