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DOI 10.1002/mawe.201000578
1 Introduction
With the development of Chinese economy and society, more
and more pipelines for natural gas and oil transport and land
buried structures are constructed. They are often expected to
have a longer working life. The fundamental cause of the deterioration of land buried structures is soil corrosion. Soil corrosion is
an electrochemical interaction between underground structures
and the ambient soil environment. Actually, the concern with the
environment is of great importance and a better understanding
of the soil as a corrosive agent becomes necessary for the use of
adequate protection for buried structures, avoiding the occurrence of leakiness and, as a consequence, the contamination of
the soil [1]. An increasing awareness and understanding of the
soil corrosion concept has been noticed since the National Association of Corrosion Engineers (NACE) was founded in 1943.
Nowadays, in China, with the rapid development of petroleum
industries and constant increase in the numbers of steel pipelines buried underground, more and more attention needs to be
paid to this area of study [2].
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Mn
Si
Cu
Q235
0.176
0.023
0.019
0.057
0.233
0.033
1
2
3
4
5
6
7
0.01 M NaCl
0.01 M NaCl + 0.01 M CaCl2
0.01 M NaCl + 0.01 M MgCl2
0.01 M NaCl + 0.01 M KCl
0.01 M NaCl + 0.01 M Na2SO4
0.01 M NaCl + 0.01 M NaHCO3
0.01 M NaCl + 0.01 M NaNO3
2 Experimental
Specimens for electrochemical tests were made from Q235 carbon steel whose chemical composition was shown in Table 1.
Samples were cut into small squares of 10 mm 6 10 mm, and
then covered with epoxy resin except test surface, with a working
area of 1 cm2. Each sample was successively polished using silicon carbide emery papers from grit 150, 240, 400 to 600, then
rinsed with deionized water, and degreased with acetone.
The corrosion of buried structures is related to soil conditions
in which they are buried. The simulated soil solution was based
on the soil composition from Yingtan, China. 0.01 M NaCl solution was used as the matrix corrosion electrolyte, and other cations or anions were added into it in order to study the effect of
compositional ions on the corrosion behavior of carbon steel in
soil solution. The chemical compositions of the used corrosion
electrolytes were listed in Table 2.
Figure 1. Potentiodynamic polarization curves and EIS diagram about effect of Ca2+, Mg2+, K+ on Q235 carbon steel in NaCl solution.
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T. M. Liu et al.
Figure 2. Potentiodynamic polarization curves and EIS diagram about effect of SO42 on Q235 carbon steel in NaCl solution.
3 Results
Effect of Ca2+, Mg2+, K+ on electrochemical corrosion behavior of
Q235 carbon steel in simulated soil solution is shown in Figure 1.
Figure 1(a) stands for the potentiodynamic polarization curves.
Figure 1(b) and Figure 1(c) stand for the Nyquist diagram and
Bode plot for EIS, respectively. Effect of SO42 on electrochemical
corrosion behavior of Q235 carbon steel in simulated soil solution is shown in Figure 2. Effect of HCO3 on electrochemical corrosion behavior of Q235 carbon steel in simulated soil solution is
shown in Figure 3. Effect of NO3 on electrochemical corrosion
behavior of Q235 carbon steel in simulated soil solution is shown
in Figure 4.
In order to further understand the corrosion mechanisms, the
corresponding equivalent circuit for EIS tests is shown in Figure
5. The capacitance loop can be described with Rs, Rt and Q. Rt
was charge transfer resistance representing the resistance of
electron transfer during electrochemical reaction process. Q was
4 Discussion
4.1 Effect of Ca2+, Mg2+, K+ on electrochemical corrosion
behavior of carbon steel
In order to study the effect of Ca2+, Mg2+, and K+ on electrochemical corrosion behavior of carbon steel in simulated soil solution.
0.01 M CaCl2, 0.01 M MgCl2 and 0.01 M KCl were added into the
0.01 M NaCl solution, respectively. Clearly, for all the potentiodynamic polarization curves, the cathodic process are all controlled
by the reduction of dissolved oxygen, and the anodic process are
all controlled by the dissolution of carbon steel electrode. For the
addition of CaCl2, it reduces the cathodic current density a little,
and increases the anodic current density obviously. For the addition of MgCl2, it reduces the cathodic current slightly, but greatly
increases the anodic current density. For the addition of KCl, it
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Figure 3. Potentiodynamic polarization curves and EIS diagram about effect of HCO3 on Q235 carbon steel in NaCl solution.
Table 3. EIS fitting results of Q235 carbon steel in all the simulated soil solutions
Solutions
0.01 M NaCl
0.01 M NaCl + 0.01 M CaCl2
0.01 M NaCl + 0.01 MgCl2
0.01 M NaCl + 0.01 KCl
0.01 M NaCl + 0.01 Na2SO4
0.01 M NaCl + 0.01NaHCO3
0.01 M NaCl + 0.01NaNO3
Equivalent
circuit
R(QR)
R(QR)
R(QR)
R(QR)
R(QR)
R(QR)
R(QR)
Rs
(ohm/cm2)
118.1
40.08
36.61
57.82
44.50
61.12
44.66
Capacitance Q
Rt
(ohm/cm2)
Q-Yo (ohm/cm2/s)
Q-n
0.001084
0.0008365
0.000976
0.001126
0.001532
0.0004054
0.001.070
0.7925
0.8278
0.8579
0.8011
0.8179
0.7229
0.8058
1522
1684
1586
1496
1296
1374
1459
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T. M. Liu et al.
Figure 4. Potentiodynamic polarization curves and EIS diagram about effect of NO3 on Q235 carbon steel in NaCl solution.
Figure 5. Equivalent circuit for EIS plots of Q235 carbon steel in all
the test solutions. Rs is the resistance of corrosive electrolyte; Q is
constant phase element parameter; Rt is the charge transfer resistance.
added into 0.01 M NaCl solution, respectively. For all the cases,
the cathodic processes are characterized by reduction process of
dissolved oxygen, and the anodic processes are dissolution of carbon steel electrode. For Figure 2, the addition of Na2SO4 can
increase the cathodic and anodic current density of carbon steel
in NaCl solution (Figure 2(a)), decrease the size of capacitive
semicircle (Figure 2(b)), and can decrease the charger transfer
resistance in low frequency and solution resistance in high frequency (Figure 2(c)).
For the results of addition of NaHCO3 in Figure 3, it can
increase both the cathodic and anodic current density of carbon
steel in NaCl solution as seen in Figure 3(a). The diffusive impedance in low frequency range in Figure 3(b) indicates that the diffusion process is the step control process. Figure 3(c) also indicates that the addition of NaHCO3 can decrease the solution
resistance. Higher corrosion current density and lower charge
transfer resistance indicate the corrosivity of NaHCO3 on the cor-
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5 Conclusions
(1)
O2 + 2H2O + 4e 4OH
(2)
Effect of cations, Ca2+, Mg2+, K+, and anions, SO42 , HCO3 , NO3 ,
on electrochemical corrosion behavior of carbon steel in simulated soil solution was investigated via potentiodynamic polarization curves and electrochemical impedance spectroscopy. The
obtained conclusions are as follows:
1. In simulated soil solution, the aggressiveness of the compositional cations is order of K+ A Mg2+ A Ca2+, and that of anions is
in order of SO42 A HCO3 A NO3 .
2. Addition of Ca2+ and Mg2+ can increase the charge transfer
resistance and K+ can decrease it. All the anions, SO42 ,
HCO3 , and NO3 can decrease the charge transfer resistance.
But, both the cations and anions can reduce the solution
resistivity in 0.01 M NaCl solution.
3. For soil solution, the corrosivity of cations is more aggressive
than that of anions. This may due to their difference in
radius.
As soil is a very complex mixture, it is quite difficult to understand the real corrosion mechanism and the effect of different
ions, and we studied this in simulated soil solutions. This may
provide information for the forecast of resistance of certain soil,
and can guide the engineers to select more suitable construction
materials.
Acknowledgement
This work was supported by Science and Technology Foundation
of Guizhou Province of China (No. 20082008) and Science and
Technology Foundation of Zunyi City of China (No. 200724).
6 References
The dissolution of carbon steel from the steel matrix to corrosive electrolyte stands for the anodic reaction, and oxygen dissolving and diffusion through the soil solution towards the steel electrode surface stands for the cathodic reaction. The corrosion rate
is often expressed by corrosion current density. The corrosion
current density has relation to the resistance of electrolyte
besides the anodic dissolution rate and cathodic dissolved oxygen
reduction rate. Both the cations and anions can decrease the solution resistance in simulated soil solution as can be seen in Figure 1(c), Figure 2(c), Figure 3(c), Figure 4(c), and Table 3. The difference of the ions on the aggressiveness of corrosion electrolyte
may lies in their radii and adsorption energy. Ion with shorter
radius and high adsorption energy can preferentially adsorb at
the special sites of carbon steel electrode surface, leading to
T 578
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