Studies of the Self Assembly of Linoleate on Stainless Steel: Application to Corrosion Inhibition Sasha Omanovic* and Sharon G.

Roscoe Department of Chemistry, Acadia University Wolfville, Nova Scotia, (B0P 1X0) CANADA

Many common corrosion inhibitors are health hazards. Therefore, there is an increased attention on the development of environmentally compatible, nonpolluting corrosion inhibitors. Hence, naturally occurring biological molecules are of considerable interest as possible corrosion inhibitors. The electrochemical behaviour of a high-purity austenitic low-carbon stainless steel (SS) surface in the presence of a sodium salt of linoleic acid, sodium linoleate (LA), has been studied in a phosphate buffer solution pH 7.0 at 299 K, using cyclic voltammetry (CV) (Fig.1) and electrochemical impedance spectroscopy (EIS) (Fig.2) techniques. The impedance spectra were interpreted in terms of an equivalent-electrical-circuit (EEC) based on a possible physical model with the circuit elements representing the electrochemical properties of the investigated system. The objective of the work is to understand better the inhibition mechanism of LA on the corrosion behaviour of stainless steel in neutral media and to give thermodynamic information on the adsorption of LA onto a metal surface
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the negatively charged carboxylate group to the stainless steel surface, (ii) self-assembly of LA molecules to form a dense ordered overlayer with the linear hydrocarbon hydrophobic tails oriented towards the solution which provides a hydrophobic core that blocks oxidation of the alloy by serving as a barrier to diffusion of ions and electrons, and (iii) sufficient solubility and rate of transport of LA molecules to the surface, implying that the self-assembled-layer can be formed in a time that is fast compared to corrosion.
-70 4 -60

-50

phase angle / degree

log (|Z| / cm )

-40

-30

-20 2 -10

phosphate buffer 20 M of LA 200 M of LA

1 -2 -1 0 1 2 3 4 5 0

log (f / Hz)

0.6
QA/QC / %

40 30 20 10

1 2 3 4 5
0 50 100 150 200

Fig. 2. Bode plots of the stainless steel electrode in 0.05 M phosphate buffer solution pH 7.0, recorded at the OCP (O) -0.637 V, () -0.616 V and ( ) -0.608 V. Symbols are experimentally measured values and lines are simulated values. The adsorption of LA onto the stainless steel surface was described with a Langmuir adsorption isotherm (inset in Fig.3). The calculated adsorption affinity constant (Bads = 6.52 106 dm3 mol-1) and Gibbs free energy of adsorption (Gads = -43.3 kJ mol-1) suggested a very strong irreversible adsorption of LA molecules through chemisorption.

0.4

j / mA cm

-2

0.2

c(LA) / M

0.0

-0.2 -0.8 -0.4 0.0 0.4 0.8 1.2

E / V vs. SCE

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Fig. 1. Cyclic voltammograms of the first cycle of the stainless steel electrode in (1) 0.05 M phosphate buffer solution pH 7.0 recorded with a scan rate of 100 mV/s and (2-5) the addition of various concentration of LA (10, 20, 30 and 160 M). Inset: Ratio of the normalized anodic and cathodic charge densities derived from voltammograms recorded with the anodic potential limit of: (O) +1.1 V; and () 0 V. The results (Figs.1 and 3) indicated that during the potentiodynamic anodic polarization of the electrode, an LA-layer self assembles on the electrode surface accompanied by chemisorption. At an open-circuitpotential the adsorption of LA onto the SS surface resulted in an almost saturated coverage (Fig.3) and high inhibition efficiency (94%) towards corrosion after a "threshold" LA concentration in the bulk solution (40 M) was reached. LA was found to act as a mixed-type inhibitor. The key elements of the model of corrosion inhibition by linoleate were postulated to be: (i) strong bonding by

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250

surface coverage / %

C / F cm

-2

200

c/ / M

30

60
150 100

20

40
50 0

10

50

100

150

200

20

c(LA) / M 0 0 50 100 150 200 0

c(LA) / M

Fig. 3. (O) Dependence of the double layer capacitance of the stainless steel electrode on the LA concentration obtained from the EIS measurements between -0.80 and -0.40 V. () Surface coverage of the stainless steel electrode with LA calculated from the capacitance values (bars represent the deviation from the mean values). Inset: Langmuir adsorption isotherm for adsorption of LA onto the stainless steel surface.