Effect of Various NaCl and Ammonium Molybdate

Concentrations on Pitting Corrosion Resistance of Duplex

Stainless Steel 410

Andi Rustandi1, Martina Yttria2, Andy Saputra3,Geraldo J.F. Sirait4

1,2
Metallurgy and Materials Department, Faculty of Engineering, University of Indonesia,
Depok, Indonesia

Email:1rustandia@gmail.com, 2yttria.martina@gmail.com, 3gatotandy@gmail.com,

4
siraitgeraldo@gmail.com

Abstract: An experiment to observe pitting corrosion resistance of 410 Martensitic Stainless

Steels was determined using Cyclic Polarization and Electrochemical Impedance Spectroscopy
at 1%wt, 2%wt, 3.5%wt, 4%wt, 5%wt of sodium chloride Solution and 100 ppm, 200 ppm of
ammonium molybdate at 3.5%wt of NaCl Solution had been conducted and investigated. The
result showed that at 3.5%wt NaCl solution, the martensitic alloy was most susceptible to
pitting corrosion, followed by 5%wt, 4%wt, 2%wt, 1%wt respectively. The 100 ppm and 200
ppm of ammonium molybdate has been added to 3.5%wt NaCl solution. The data showed that
the addition of ammonium molybdate can increase pitting potential and reduce susceptibility
on pitting of 410 martensitic stainless steel at 3.5%wt NaCl solution. This concludes that the
ammonium molybdate will also reduce the susceptibility of corrosion in the other
concentration variant of sodium chloride as well.

Keywords: Corrosion, 410 stainless steel, Pitting corrosion, Ammonium Molybdate

1. Introduction
The cost from the total maintenance caused by corrosion were about 25% at the gas sweetening
plant, 17% at the gas fractionation plant, 28% at the onshore production operation and 60 – 70% at the
offshore operation[1]. That’s why corrosion is such a harmful danger for the industry. Stainless steel
materials usually has a good resistance to corrosion at the atmospheric ambient but in the environment
that contain aggressive ion such as chloride ion, pitting corrosion can occurred on the stainless steel.
One of the effort that can be done to inhibit the corrosion is by adding the proper corrosion inhibitor.
Inhibitor solution that usually applicated to the steel to control the corrosion effect is the inorganic
inhibitor solution type such as chromate, nitrite, phosponate, silicate, zinc salt, cadmium salt, and the
arsenic salt are proven as an effective corrosion inhibitor for steel[2].
Based on the previous research, the electrochemistry behavior of 316L stainless steel in sodium
chloride solution that tested by using potentiodynamic, EDX and SEM method shows the effect of the
addition of 2-mecraptobenzimidazole (MBI). The result show the increasing of the inhibitor
concentration caused the pitting potential become more positive, means that the pitting resistance of
the stainless steel are increase as the increasing of the MBI concentration[3].
Another research show the corrosion resistance of 12Cr martensitic steel in different HCl solution
concentration. The corrosion inhibition of the sample in 1M HCL also evaluated with the addition of

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potassium dichromate as the inhibitor. The investigation were also using the polarization method, the
result show the higher the concentration of HCl, the lower the corrosion resistance of the steel [5]. The
research purpose is to investigate the effect of the sodium chloride solution concentration and the
effect of the addition of the ammonium molybdate and it’s concentration to the corrosion behavior of
410 stainless steel by using potentiodynamic. The corrosion resistance of each solution was
investigated by analyzing the plot by looking at the passive current. The greater the passive current,
the worse is the corrosion resistance of the materials because The higher passive current implies the
dissolution of the passive film in the former is faster than the dissolution of the passive film in the latter,
which leads to lower corrosion resistance of the former in the solution[7].The figure show the similar
result as the EIS plot and the table did. As can be seen the corrosion resistance of the sample which
influenced by the concentration of the NaCl solution from the greatest to the lowest were 1%, 2%,
5%, 4%, and 3.5% and the corrosion resistance of the samples which influenced by the inhibitor
concentration solution from the highest to the lowest were 200ppm, 100ppm, and 0ppm solution.

2. Details Experimental

2.1 Materials
A conventional 410 Stainless Steel with certificate was used in this research. Table 1 show the
specific chemical composition. The sample were cut into a plate with dimension of 35mm x 20mm x
6mm. It had demonstrated before, that different specimen geometry is very important in determining
whether or not pitting corrosion or crevice corrosion occur[6].The sample were abraded to 80, 120,
240, 400, 600, 800, 1200 grade of abrasive papers, then the samples were polished, etched and dried
before the microstructure examined by using optical microscope.. Kailing solution were used as the
etch reagent.The potentiodynamic test were doing in the condition of ambient temperature of 26oC.

Table 1. Chemical compositions of duplex stainless steels 410.

Chemical C Ni Mn P S Cr Ni Cu N Mo Fe
Composition 0.052 0.390 0.730 0.021 0.004 11.790 0.13 - - - Balanced
(%)

Figure 3. AISI 410 microstructure

From the composition table above, PREN (Pitting Resistance Equivalent Number) can be calculated
according to the formula PREN = %Cr + 3.3 x (%Mo) + 16 x (%N) [7].

2.2 Electrolyte
NaCl solution were used as the electrolyte of the potentiodynamic test. NaCl solution was prepared
at various concentration of 1%, 2%, 3.5%, 4% and 5% wt. Ammonium Molybdate also added to the
3.5% wt NaCl solution to find out the effect of the inhibitor addition. The inhibitor solution were
prepared in various concentration of 100ppm and 200 ppm wt. All the solution pH was adjusted by

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using litmus paper to make sure all the solution have the same pH, to avoid the possibility of the
influence of the solution pH to the test result. The pH of all solution were 7.

2.3 Polarization Cell

Electrochemical test were performed using Gamry potentiostat in a chamber. The polarization cell
apparatus was refered to ASTM G61 – 86 Standard(2014)[8].Ag/AgCl was used as reference electrode,
Platinum was used as the counter electrode, and the sample was used as the working electrode. 2 types
of electrochemical tests were performed including cyclic polarization test and Electrochemical
Impedance Spectroscopy (EIS). Scan rate of 50 mVs-1 was used for the cyclic polarization test[9].EIS
measurements were carried out at open circuit condition. 10 mHz to 105 mV amplitude were used to
perform the measurement.The sample were immersed in every solution for 1 h before tested to
stabilize the surface at the open circuit potential also to obtain free corrosion potential.

3. Results and Discussion

Nyquist plot and cyclic polarization of AISI 410 were obtained at various NaCl concentrations of
1%, 2%, 3.5%, 4% and 5% w.t and also at various concentration of ammonium molybdate
concentration in 3.5% NaCl Solution. The concentrations of the ammonium molybdate were 100
ppm and 200 ppm. Ammonium molybdate was used as the corrosion inhibitor for the samples.
The test were done to deremine the current phenomenon in the metal or electrolyte
interface[10].The nyquist plot of each system fits will determine the most representative electrical
circuits of the system. Some electrical elements will be obtained by the equivalent circuit. Figure
xx and figure xx show the nyquist plot of the samples at various NaCl concentration and at
various ammonium molybdate concentrations. The nyquist plot form 45 degree angle, it represent
the influence of diffusion to the reaction occurred on the surface of the sample. It can concluded
then the reaction occurred was adsorption.[11].The impedance values were obtained from EIS plot,
the plot represent the corrosion resistance of the materials, figure 4a show the influence of NaCl
concentrations to the corrosion behaviour of the sample. It shows that 410 stainless steel corrosion
resistance from the highest to the lowest were at 1%, 2% , 5%, 4%, 3.5% w.t solution then figure
4b show the influence of inhibitor concentrations to the corrosion behaviour of the sample. It
show that the corrosion resistance from the highest to lowest were at 200ppm, 100ppm, 0ppm
solution.
5 5% NaCl
% 4% NaCl
n 3.5% NaCl
A
2% NaCl
c
L 1% NaCl

Figure 4a. Nyquist plot of AISI 410 in various NaCl concentrations

5 200ppm Inhibitor
% 100ppm Inhibitor
n 0ppm Inhibitor
A
c
L

Figure 4b. Nyquist plot of AISI 410 in various inhibitor concentrations in 3.5% NaCl

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Table 2a and table 2b show fitting result of figure 4a and figure 4b. The greater the Rpass, the
greater the corrosion resistance because the greater the Rpass, the lower current flow in the
sample’s surfaces, it’s according to the ohm law [12].The table’s show the similar result as the plot
showed that in the variation of NaCl concentrations 1% of NaCl solution has the greatest
corrosion resistance followed by 2%, 5%, 4% and 3.5%. Table xx also show the same result that
200 ppm has the greatest corrosion resistance followed by 100 ppm and 0ppm solution.

Table 2a. Fiting result of Nyquist plot of AISI 410 in various NaCl concentrations.
NaCl
Ru (Ω) Rp (Ω)
Concentration
1 14.60 13.85e9

2 61.63 8.236e9

3,5 17.20 4.196e3

4 20.67 166.2e3

5 26.92 1.913e9

Table 2b. Fiting result of Nyquist plot of AISI 410 in various Inhibitor concentrations.
Inhibitor
Ru (Ω) Rp (Ω)
Concentration
0 ppm 17.20 4.196e3

100 ppm 12.69 42.10e3

200 ppm 15.85 5.683e6

The cyclic polarization plots were also show the identical result. Figure 5a show the influence of
NaCl solution concentrations to the corrosion resistance of the sample, then figure 5b show the
influence of inhibitor concentration to the corrosion resistance of the sample. As can be seen on
the figure, pitting were occurred in the sample. It showed by the greater current occurred after the
turning point of the plot which leads to the more anodic current.
5 5% NaCl
% 4% NaCl
n 3.5% NaCl
A
c 2% NaCl
L 1% NaCl

Figure 5a. Cyclic polarization of AISI 410 in various NaCl concentrations

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 5 200ppm Inhibitor
% 100ppm Inhibitor
n 0ppm Inhibitor
A
c
L

Figure 5b. Cyclic polarization of AISI 410 in various inhibitor concentrations in 3.5% NaCl

4. Conclusions
Based on the results of this study, the conclusions are as follows:
1. Nyquist plot and the cyclic polarization show the similar result.
2. The corrosion resistance of AISI 410 in various concentrations of NaCl solution from the
greatest to the lowest was 1% followed by 2%, 5%, 4%, 3.5%.
3. The corrosion resistance of AISI 410 in various concentrations of ammonium molybdate
inhibitor from the greatest to the lowest was 200ppm followed by 100ppm and 0ppm

5. Acknowledgments
The authors wish to thank Direktorat Riset dan Pengabdian Masyarakat Universitas Indonesia (DRPM
UI) for financial support in this experiment.

6. References

1. M. Al-Zahrani, “Cost of Corrosionin Oil Production & Refining,” Saudi Aramco J. Technol.,
2006.
2. A. Rustandi, J. W. Soedarsono, and B. Suharno, “The Use of Mixture of Piper Betle and Green
Tea as a Green Corrosion Inhibitor for API X-52 Steel in Aerated 3.5 % NaCl Solution at Various
Rotation Rates,” Adv. Mater. Res., vol. 383–390, pp. 5418–5425, 2011.
3. S.A.M. Rafey, F. Taha, and A.M. Abd El-Malak. "Corrosion and Inhibition of 316L stainless steel
in neutral medium by 2-Mercaptobenzimidazole." Int. J. Electrochem. Sci 1 (2006): 80-91.
4. Y. Ait Albrimi, A. Ait Addi, J. Douch, and R.M. Souto. "Inhibition of the pitting corrosion of 304
stainless steel in 0.5 M hydrochloric acid solution by heptamolybdate ions." Corrosion Science 90
(2015): 522-28
5. C.A. Loto, O.S.I. Fayomi, and R.T. Loto. "Electrochemical corrosion resistance and inhibition
behaviour of martensitic stainless steel in hydrochloric acid." Der Pharma Chemica (2015): 102-
11.
6. X. Li, H. Cong, F. Gui, C.S. Brossia, G.S. Frankel, Development of liquid-Air-Interface corrosion
of steel in nitrate solutions, corrosion 70 (2014) 230-246.
7. Z. Brytan., J. Niagaj., L. Reiman., (2016), Corrosion Studies using potentiodynamic and EIS
electrochemical techniques of welded lean duplex stainless steel UNS S82441, Applied Surface
Science, 388(2016) 160-168.
8. ASTM G61 – 86(2014), Standard Test Method for Conducting Cyclic Potentiodynamic
Polarization Measurements for Localized Corrosion Susceptibility of Iron-, Nickel-, or Cobalt-
Based Alloys
9. Kocijan. Aleksandra, Conradi.Marjetka, The Corrosion Behaviour of Austenitic and Duplex
Stainless Steels in Artificial Body Fluids, MTAEC, 2010.
10. N. Ebrahimi., et al., (2012), A Comparative study of critical pitting temperature (CPT) of stainless
steels by Electrochemical Impedance Spectroscopy (EIS), Potentiodynamic and potentiostatic
Techniques, Corrosion Science, 59(2012) 96-102.
11. Zaya, piere. (1984). Evaluation theories for the initial stages of pitting corrosion, McMaster
University: Ontario.

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12. Revie R.R., Uhlig H.H.,(2008), Corrosion and Corrosion Control : An Introduction to corrosion
Science and Engineering, CANMET & MIT : Canada & Massachusetts.