Inhibition of Microbial Corrosion of 304 Stainless Steel in

Seawater by Some Novel Biocides

R S Dubey

Chemistry Research Laboratory, Dept. of Chemistry, R. J. College, University of Mumbai,

Ghatkopar (W), Mumbai-400 086, India.

Tel.: ® 022- 5599 1759, (o). 022-2515 2731Extn: 43 ; Fax: 022-25150957

Email: dubeyrsp@rediffmail.com

Abstract

Some heterocyclic organic compounds like Benzimidazole and its derivative i.e. 2-Methyl
benzimidazole; 2-Ethyl benzimidazole and 2-Benzylbenzimidazole has been synthesized and
used as corrosion inhibitors for protection of 304 Stainless Steel in Marine environment. The
inhibition effect of these compounds was investigated by using electrochemical polarization
techniques such as potentiodynamic and open circuit potential. The results obtained reveals
that these heterocyclic organic compounds are very good corrosion inhibitors and show their
best performance at a very low concentration of 10ppm. Potentiodynamic curves indicate that
these compounds are mixed type of inhibitors having heteroatoms in the ring of the
compounds.

Keywords: Microbial Corrosion, 304 Stainless Steel, Benzimidazole derivatives, inhibitors,

and Electrochemical techniques.

INTRODUCTION

Use of Coatings, paints and organic compounds are some way of corrosion mitigation. The
organic compounds especially, heterocyclic compounds containing heteroatoms like S, N, O,
Se with loosely bound lone pair of electrons and compounds with ð electrons, undergo
adsorption on the metal surface and protects the material from the aggressive environment.
Various workers have used organic compounds for corrosion inhibition of metals like Cu,
iron, mild steel, stainless steel, Al etc. at different concentrations in acidic, basic and salt
solutions [1-11]. Stainless steel, due to its high strength, workability and high corrosion
resistance property are used in various engineering applications like chemical and
pharmaceutical industry [12-13] food and beverage industry [14], petrochemical industry
[15-17], oil and water pipe lines [18], ship and Naval structures [19-20]; architectural
applications, water supply and desalination plants [13].
Inhibiting the corrosion of the structural parts of the various industries by organic compounds
as inhibitor is a great scientific and economic interest. The corrosion inhibition actions of the
organic compounds containing heteroatoms such as undecanoic acid hydrazide, 2-
mercaptobenzothiazole, and 2-hydrazinobenzothiazole on carbon steel in HCl solution [21],
morpholinium caprylate, morpholinium sebacate and laurate [22-23], morpholinium oleate
[24] and morpholinium stearate [25] have been investigated for steel. Al-Suhybani et al [26]
investigated the corrosion inhibition efficiency of azoles: 2-mercaptobenzoazole (CBA), and
its derivatives (2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercapto
benzothiazole); 2-methyl benzoazole and its derivatives (2-methyl benzoimidazole, 2-methyl
benzoxazole, 2-methyl benzothiazole and 2-methyl benzoselenazole) for 304 stainless steel
in acidic solution where some provides inhibition efficiency up to 90% at a concentration of
5x10-4 M and stated efficiency of the heteroatoms in the decreasing order as Se> S > N > O.
Dubey et al[27-28] investigated the corrosion inhibition efficiency of some heterocyclic
organic compounds like Ketoconazole, Fluconazole, Roxythromycin, Amoxycillin,
Ampicillin; and some benzimidazole derivatives like 2-methylbenzimidazole, 2-
ethylbenzimidazole, and 2-benzylbenzimidazole for 304 stainless steel in marine
environment. The aim of the present investigation was to find out the suitable inhibitor for
control of corrosion of 304 stainless steel in marine environment.

EXPERIMENTAL

Materials

304 Stainless Steel of commercial grade in sheet form having composition as follows: C -
0.06%, Si - 0.53%, Mn - 0.10%, P - 0.032%, S - 0.016%, Ni - 8.16%, Cr - 18.17%; and Iron-
balance, were used in the present investigation. For electrochemical polarization, samples of
1cm x 3cm were sheared from the commercial grade sheets. The surface of these samples
was successively polished by using the Emery papers of grades 1 / 0, 2 / 0, 3 / 0, and 4 / 0
obtained from Sianor, Switzerland to obtain a scratch free mirror finish surface. The polished
samples were washed with detergent solution, rinsed with distilled water and finally
degreased with acetone. The specimens were dried and stored in a desiccators containing
silica gel as a dehydrating agent.

All chemicals used in the present investigation were of AR grade and procured from different
chemical companies. Some derivatives of the heterocyclic organic compound benzimidazole
i.e. 2-Methyl benzimidazole, 2-Ethyl benzimidazole, and 2Benzylbenzimidazole were
synthesized and their inhibition efficiency was determined with electrochemical techniques.
Molecular structures of the compounds are shown in Fig.1. Pure NaCl obtained from
S.D.Fine Chemicals was used to prepare its 3.5% solution with double distilled water. Their
performance was determined as a corrosion inhibitor.

Electrochemical Measurement System, DC 105,containing software of DC corrosion

techniques from M/S Gamry Instruments Inc., (No. 23-25) 734, Louis Drive, Warminster,
PA-18974, USA has been used for performing corrosion potential and polarization
experiments.
For electrochemical polarization studies (corrosion potential, and potentiodynamic
polarization) flag shaped specimens with sufficiently long tail were cut from the steel sheet.
These samples were polished as described earlier leaving a working area of 1cm2 on both
sides of the flag and a small portion at the tip for providing electrical contact. Rest of the
surface was isolated from the corroding solution by coating with enamel lacquer including
side edges. The test specimen was connected to the working electrode holder through the tip
of the tail. About 50ml of the corrosive medium was taken in a mini corrosion testing
electrochemical cell. This volume was appropriate to permit desired immersion of electrodes.
The electrochemical investigation was carried out using microprocessor based corrosion
measurement system (CMS-105, Gamry Instruments Inc., USA.). The three-electrodes i.e.
working electrode, reference electrode (calomel), and counter electrode (graphite rod) system
cell was used throughout the electrochemical measurements. Open circuit potential and
potentiodynamic polarization of the samples are studied in the concentration ranges 5, 10, 15,
20, 30, 40, and 50ppm of the inhibitors.

The value of inhibition efficiency in terms of corrosion current density

E = 100 (1– i / io ) ..................... ...................................................………………..1

Where io and i are the corrosion current density of uninhibited and inhibited 304 Stainless
Steel.

RESULTS AND DISCUSSION

Open circuit potential measurement (OCP)

Inherent reactivity of the metallic materials in a particular environment is determined from its
open circuit potential (corrosion potential). The influence of the corrosive and inhibitive
species present in the electrolyte may be predicted by analyzing the nature of the OCP curve.
The variation of open circuit potential of 304 Stainless Steel exposed to 3.5% NaCl solution
containing inhibitors i.e., Benzimidazole, 2-Benzyl Benzimidazole, 2-Ethyl Benzimidazole
and 2-Methyl Benzimidazole are shown in Fig. 2 to Fig. 5 respectively. The steady state
potential is obtained after few minutes of the exposure period. In the presence of different
concentration of inhibitors, OCP is shifted towards the positive potential direction and get
stabilized thus indicating the adsorption of the inhibitors on the metal surface. Maximum
shift of the corrosion potential in the positive direction is obtained in the presence of 30,5,10
and 15 of Benzimidazole, 2-Benzyl Benzimidazole, 2-Ethyl Benzimidazole and 2-Methyl
Benzimidazole respectively as shown in Fig.2 to Fig.5, which indicates the optimum
concentration of the compounds.

Potentiodynamic polarization

The anodic and cathodic polarization curves of 304 Stainless Steel exposed to 3.5% NaCl
solution containing Benzimidazole, 2-Benzyl Benzimidazole, 2-Ethyl Benzimidazole and 2-
Methyl Benzimidazole in concentrations ranges from 5-50 ppm are shown in the Fig. 6 to
Fig.9 respectively, which was carried out at a scan rate of 10mV / S. The effect of different
concentration of both compounds on various electrochemical parameters like corrosion
potential (Ecorr), corrosion current density (Icorr), anodic Tafel constant (âa), cathodic Tafel
constant (âc), corrosion rate and % inhibition efficiency etc. of 304 Stainless steel is shown in
Table-1. The action of an inhibitor in an aggressive chloride medium is probable due to
adsorption of the inhibitor on the metal / solution interface and acting as a barrier. Corrosion
inhibitors with heteroatoms having loosely bound lone pair of electrons and ð electrons
undergo adsorption (chemisorptions / physisorption), or complexation on the metal / metal
oxide surface preventing the access of cathodic reactant (O 2 , H+ etc.), and inhibits the
dissolution of metal. The inhibition efficiency (E) depends on the parameters of the system
(pH, temperature, exposure period, metal composition etc) as well as on the structure of the
inhibitor molecules [29-31]. Benzimidazole, 2-Benzyl Benzimidazole, 2-Ethyl
Benzimidazole and 2-Methyl Benzimidazole, all contain 2 nitrogen atoms and homo- and
heterocyclic rings with conjugated and isolated double bonds may get effectively adsorbed
on the surfaces of stainless steel and protects the surface from aggressive chloride ions. Here
the organic compound having heteroatoms with lone pair of electrons act as a Lewis base and
the Fe with vacant d-orbital acts as a Lewis acid. The affinity of the compounds towards
adsorption on the Fe surface is more than that of the H2 O and aggressive chloride ions. This
stability of inhibitor-Fe adsorption bond is based on the Pearson’s Hard and Soft Acid and
Base principle [32].

Fe Fe2+ + 2e- (Anodic reaction)

Fe2+ + O2 + 2e- + H2 O [Fe (H2 O) x ] 2+ / Fe (OH) 2 (Cathodic reaction)

Adsorption

Inhibitor (solution) + [Fe (H2 O) x ] 2+ [Fe(Inhibitor)x ]2+ + x H2 O solution

Complexation / Stabilized

The complex formed is stabilized on the surface assumed nonporous and insoluble in the
medium whereas the inhibitor is chemically inert and doesn’t decompose during service
condition. It is inferred since both compounds inhibit corrosion. The adsorbed layer
effectively protects the steel surface from the aggressive nature of chloride ions.

CONCLUSION

1. Benzimidazole, 2-Benzyl Benzimidazole, 2-Ethyl Benzimidazole and 2-Methyl

Benzimidazole are good inhibitors for 304 Stainless steel in sodium chloride solution.

2. The inhibition efficiency of these compounds are in the order:

Benzimidazole > 2-methylbenzimidazole > 2-benzylbenzimidazole > 2-ethyl

benzimidazole
3. All compounds act as mixed inhibitors.

ACKNOWLEDGEMENT

The author would like to thank the Department of Science and Technology (DST), Ministry
of Science and Technology, Government of India for sanctioning the research grant in the
form of research project no. 4146.
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Table-1. Electrochemical Parameters for Inhibition of Corrosion of 304 Stainless Steel
Exposed to 3.5% Sodium Chloride Solution with Different Concentration of
Benzimidazole and its derivatives.

Concentration βa βc Icorr Ecorr Corr. Rate Inhibition

-2
(PPM) (V/dec.) (V/dec.) ( µA/cm ) (mV) (mpy) Efficiency

Control 1.893 203.4e-3 1.470 µA -303.0 670.4e-3 ---

Benzimidazole
50 470.3e-3 110.3e-3 0.323 -282.0 147.8e-3 78.03
40 1.054 217.2e-3 2.570 -355.0 1.176 ----
30 209.2e-3 132.2e-3 0.021 -90.00 9.591e-3 98.57
20 211.2e-3 132.5e-3 0.0213 -90.20 9.745e-3 98.55
15 234.7e-3 95.40e-3 0.0457 -189.0 20.89e-3 96.89
10 368.6e-3 174.0e-3 0.302 -161.0 137.8e-3 79.45
5 375.4e-3 179.4e-3 0.289 -123.0 131.9e-3 80.34

2-Methyl Benzimidazole
50 437.5e-3 114.0e-3 0.205 -252.0 93.66e-3 95.69
40 1.092 300.9e-3 5.480 -354.0 2.503 -------
30 558.0e-3 173.3e-3 1.920 -343.0 878.8e-3 59.66
20 680.3e-3 257.3e-3 0.347 -113.0 158.6e-3 92.71
15 517.2e-3 256.2e-3 0.287 -50.60 131.1e-3 93.97
10 397.4e-3 168.9e-3 0.214 -137.0 97.71e-3 95.50
5 468.0e-3 126.9e-3 0.398 -258.0 182.0e-3 91.63
2-Benzyl Benzimidazole
50 661.2e-3 202.7e-3 2.130 -313.0 974.5e-3 55.25
40 583.6e-3 191.0e-3 1.340 -301.0 612.8e-3 71.84
30 802.3e-3 196.2e-3 1.850 -325.0 844.9e-3 61.13
20 753.9e-3 223.6e-3 2.640 -337.0 1.207 44.53
15 1.254 230.0e-3 3.210 -363.0 1.465 31.15
10 592.1e-3 189.9e-3 1.460 -309.0 667.4e-3 69.32
5 250.4e-3 133.0e-3 0.316 -239.0 144.2e-3 93.36

2-Ethyl Benzimidazole
50 241.3e-3 120.0e-3 0.152 -200.0 69.30e-3 89.66
40 249.3e-3 162.8e-3 0.241 -133.0 110.1e-3 83.60
30 434.7e-3 147.4e-3 0.650 -245.0 296.8e-3 55.78
20 504.9e-3 137.9e-3 0.584 -267.0 267.0e-3 60.27
15 749.6e-3 168.4e-3 1.640 -307.0 749.9e-3 -----
10 256.2e-3 180.0e-3 0.290 -68.70 132.6e-3 80.27
5 551.4e-3 140.1e-3 0.606 -268.0 276.8e-3 58.77
________________________________________________________________
Fig. 1. Molecular Structure of the Compounds (a) Benzimidazole, (b) 2-Methyl
Benzimidazole, (c) 2-Ethyl Benzimidazole, and (d) 2- Benzyl Benzimidazole.

Fig. 2. Corrosion potential of 304 Stainless steel exposed to 3.5% NaCl with different
concentrations of Benzimidazole.
Fig. 3. Corrosion potential of 304 Stainless steel exposed to 3.5% NaCl with different
concentrations of 2-Benzyl benzimidazole.

Fig. 4. Corrosion potential of 304 Stainless steel exposed to 3.5% NaCl with different
concentrations of 2-Ethyl benzimidazole.
Fig. 5. Corrosion potential of 304 Stainless steel exposed to 3.5% NaCl with different
concentrations of 2-Methyl benzimidazole.

Fig. 6. Potentiodynamic polarization of 304 Stainless steel exposed to 3.5% NaCl with
different concentrations of Benzimidazole.
Fig. 7. Potentiodynamic polarization of 304 Stainless steel exposed to 3.5% NaCl with
different concentrations of 2- Benzyl benzimidazole

Fig. 8. Potentiodynamic polarization of 304 Stainless steel exposed to 3.5% NaCl with
different concentrations of 2- Ethyl benzimidazole
Fig. 9. Potentiodynamic polarization of 304 Stainless steel exposed to 3.5% NaCl with
different concentrations of 2- Methyl benzimidazole