Paper No.

14021

Electrochemical Corrosion Evaluation of a Novel

Doped Sol-gel Coating for Low Carbon Steel
Substrate in Saline Medium
Ubong M. Eduok
Department of Chemistry
King Fahd University of Petroleum & Minerals
Dhahran 31261, Saudi Arabia.
umeduok@kfupm.edu.sa

Rami Suleiman
Center of Research Excellence in Corrosion
King Fahd University of Petroleum & Minerals
Dhahran 31261, Saudi Arabia
ramismob@kfupm.edu.sa

Mazen Khaled
Department of Chemistry
King Fahd University of Petroleum & Minerals
Dhahran 31261, Saudi Arabia.
mkhled@kfupm.edu.sa

ABSTRACT
A novel effective, crack-free, hydrophobic, and fast-curing hybrid sol-gel coating was synthesized and
applied on mild steel panels in order to prevent them from corroding in aerated saline (3.5% NaCl)
solution. The performance of this functionalized coating, which was prepared via simple and well
known sol gel chemistry, was evaluated using Electrochemical Impedance Spectroscopy (EIS) and
Potentiodynamic Polarization (PDP) studies. The electrochemical results were complemented with a
Scanning Electron Microscopy (SEM) characterization. Results obtained showed excellent adhesion and
corrosion protection properties on steel surfaces against metal oxidation and other associated corrosion
reactions. The inhibition efficiency of the newly prepared sol-gel coating was dramatically improved
upon by encapsulating two corrosion inhibitors. This improvement was clear from observations of the
new impedance values, a surface analytical analysis and even visible inspections. This work is aimed at
contributing to the solutions of material degradation and failures in the Gulf region a view to reducing
the colossal economic cost and losses already incurred.
Keywords: Corrosion, sol-gel, steel, electrochemistry

1. INTRODUCTION
Sol-gel derived silicate films have been a major bridge between chemical science and material
protection application for the past decade. Various modifications in the reactants and variation of
reaction parameters have resulted in numerous hybrid coatings with different mechanical strengths and

chemical properties for various uses [1].Since these innovations focus on improving performance
properties such as interfacial adhesion, corrosion resistance, even thermal and optical characteristics [2]
are considered essential in the syntheses of these silica-based films.
Normal and functionalized organicinorganic hybrid, inorganic oxide, and other organically modified
silica (ORMOSILS) coatings have been reported to have some of these properties satisfied [3-5]. Sol-gel
coatings made from different processes, inhibitors and process conditions for numerous applications
have been used reliably for different metals. Since they are colloids on the metal surfaces, some are
susceptible to shrinking and could flake off from the metals over time if the interfacial chemistry is not
understood and effectively addressed. The pores in these inorganic-organic polymer hybrid films are
usually filled with several materials and to display different functionalities.
Several researchers have reported the effects of Titanium dioxide [6], Graphene [7], Nanoparticles [8],
Alumina [9], Carbon Nanotube [10] in coatings, yet some predominant defects still abound ranging from
irregular surface adhesion to surface in homogenity. In fact, having enhanced corrosion protection
properties and retaining surface adhesion, synthesizing promising coatings for metal structure and
industrial engineering materials is an issue. To address these channels of failed application properties in
synthesis, in this work, organically modified polydimethylsiloxane (PDMS) is linked to the network of
the sol-gel formed. By bonding the resulting Sol-gel network with a group similar to the side chain in
the polymer, a new Si-O-Si bond is formed; with properties, be far, different from those of the additives
listed above. Complete reactivity and hydrolytic stability over an extended stirring time bring about
material with enhanced properties.
The effect of film hydrophobicity and the curing period is considered to improve protection and surface
adhesion. Improvement of the microstructures of the film by encapsulation of some transition metalbased corrosion inhibitors into the coatings was done. The mechanism for corrosion inhibition by these
metals can be drawn from their ability to readily precipitate oxides and/or hydroxide complexes that can
further reduce the cathodic reaction at the metal-solution interface. The enhancement of the corrosion
resistance of the sol-gel system is then achieved and the passage of atmospheric oxygen, water, radical
and other corrosive ions is remarkably reduced without using the banned biocide Tributyltin (TBT) with
its obnoxious health and environmental concerns [11].
This study uses simple and available silane precursors for making doped sol-gel derived film for
corrosion protection of mild steel in saline (3.5% NaCl) solution. It explains the design of reliable flash
corrosion coating, encapsulated with commercially available zinc and molybdenum-based corrosion
inhibitors, for steel in marine and terrestrial applications.

2. EXPERIMENTAL
2.1

Preparation of S-36 Q-panel sheets

The one-sided ground (0.03235) S-36 grade Q panel mild steel test substrate was effectively
sonicated (Vibra-Cell Sonics and Material INC., US) for 15 minutes in a solution of 70% acetone
(Sigma Aldrich, US) and 80% ethanol (Sigma-Aldrich, US), rinsed with doubly distilled water and
finally air-dried.

Paper No. 14021

15th Middle East Corrosion Conference & Exhibition

February 2-5, 2014
Manama, Kingdom of Bahrain

Page 2 of 11

2.2

RUS synthesis, modification and application

The siliconized sol-gel coating was synthesized by blending Tetraorthosiliate (TEOS) and
(Trimethoxymethyl siloxane) TMMS(10:6) in 0.05 N HNO3 (Sigma Aldrich, US) induced hydrolysiscondensation reactions with 5ml ethanol (Sigma Aldrich, US) as solvent at room temperature for 24 hrs.
The molecular structures of the two used silanes are depicted in Fig. 1. Docylmethylsiloxane(hydroxyl
alkyleneoxypropyl)methylsiloxane (DMHM) copolymer (Gelest, US) was added later (3 ml) in drop
wise manner with continuous stirring for one hour until a viscous gel resulted which formed a stable gel
phase network with the previously formed sol-gel. Stirring continued for 12 hours at room temperature,
the final colloid was indefinitely stable and labeled RUS.Moly-whiteS101-ED(MOLY) and
Hfucophos Zapp (ZAPP) were added (5%w/v), respectively, into 10 ml of the RUS coating and
sonicated for 15 min and labeled RUM and RUZ, respectively, being inhibitor-modified sol-gel (RUS)
mixtures. A neat 40 m thickness single-layer coating of each prepared sample matrices (both modified
and unmodified) was evenly applied on the previously pre-clean steel panels using a K101 Rod Coating
applicator (UK) and the panels were allowed to cure at 50C in oven then air-dried for 48 hours [12].
2.3

Scanning Electron Microscope (SEM) Analysis

Steel polishing was done with different grades of silicon carbide paper and diamond paste scrub prior to
SEM-EDX (JSM-5800LV Scanning Electron Microscope, JEON, Japan) analysis for the only the RUScoated steel before immersion in 3.5% NaCl test solution [13].
2.4

Electrochemical assay

A three-electrode conductivity cell of 100 ml capacity from Gamry was used with a Standard Calomel
Electrode (SCE) as reference electrode and graphite counter electrodes without mechanical stirring. The
cell was connected to a GAMRY 3000 (Gamry Instruments, US) corrosion measuring system.
2.4.1 Electrochemical Impedance Spectroscopy (EIS):
The electrochemical system response at a small amplitude voltage perturbation of 10 mV was
tested on a 1 cm2 area of the coated mild steel substrate over a frequency range of 10 kHz to 0.01
MHz at the end of 24-96 hr immersion periods in 3.5% NaCl solution and at corrosion potential
(Ecorr). EChem Analyst software was used to fit the experimental data and other simulations.
2.4.2 PotentiodynamicPolarization (PDP):
The linear Tafel fitting was done with GamryEChem Analyst software to extrapolate the necessary
polarization parameters for the potentiodynamic polarization at 0.25V versus Open Circuit
Potential (OCP) at 0.001V s-1 scan rate. Each experiment was carried out in triplicate for the sake
of reproducibility and the results presented here are average values of the measured
electrochemical parameters for 24-96hr immersion periods.

Paper No. 14021

15th Middle East Corrosion Conference & Exhibition

February 2-5, 2014
Manama, Kingdom of Bahrain

Page 3 of 11

3. RESULTS AND DISCUSSION

3.1

Surface analysis: Electron microscopy

The SEM image below (Figure 2) shows the surface of the well-bonded and crack-free RUS coating
alone (undoped) on mild steel (a) before and (b) after immersion in 3.5% NaCl for 2.5 weeks. No
prominent surface blisters or any other defects were observed for all the coatings before immersion,
though the surfaces were relatively uneven. The white spots are likely the uncross-linked molecules of
the gel which forms the bulk of the organic-inorganic polymer colloid. INCA software was used to
generate the Energy-dispersive X-Ray (EDX) elemental composition of the coated sample. Elemental
composition by X-Ray-assisted SEM mapping is an effective tool in accessing the composition of
surfaces without prior sampling and rigorous preparation steps. A large and prominent Si peak on the
EDX spectra along with peaks that correspond to C and O atoms prove that the hybrid RUS coating was
synthesized from the silane-based precursors. The molecules of the pre-cursors are made of Si, C,O and
H atoms (Figure 1). The surface began to degrade after the 2 weeks of immersion in the electrolyte
showing evidence of leaching at the interface (Figure 2b). The white patches of the image are crystals of
NaCl after immersion. Though RUS resisted corrosion of steel, this image shows a degradation of the
surface at extended immersion time (2.5 weeks) a possible solution being the addition of MOLY and
ZAPP. However, the dull colored coated metal substrate exhibited a charging effect on imaging, a factor
which is always avoided by immobilizing a fine and thin monolayer of Gold (Au) before analysis. This
is the reason why Au is appearing on the EDX spectrum.
3.2

Electrochemical evaluation results

Electrochemical evaluation results from AC and DC experiments were used to highlight the corrosion
protection effect of the various coatings on mild steel immersed in 3.5% NaCl solution.
3.2.1 Potentiodynamic polarization:
The kinetics of the mild steel electrodes coated with the doped and un-doped sol-gel derived
silicate films for the anodic and cathodic reactions in 3.5%NaClis shown as a currentpotential (iE) relation in Fig. 3a, b. The plots show that the presence of the immersed coatings at all
immersion periods led to a reduction in the corrosion rate and lowered the current densities. The
passage of corrosive ions to the metal surface through coating was greatly impeded due to an
improved interfacial barrier and the extra gained strength of the coated surfaces in the presence of
the corrosion inhibitors. For all of the studied immersion periods, and durations shown in the work,
these doped coatings by far performed better than in their undoped coating on steel with MOLY
being the best inhibitor. Values of Ecorr were higher and nobler for superior coating, and a marked
decrease in the corrosion current densities was observed. The values of the potentiodynamic
polarization constants extrapolated from the i-E curves of each system after 24 hr and 96hr
immersion are shown in Table 1.

Paper No. 14021

15th Middle East Corrosion Conference & Exhibition

February 2-5, 2014
Manama, Kingdom of Bahrain

Page 4 of 11

Table 1: Potentiodynamic polarization parameters for the inhibitor-doped hybrid sol-gel coating
on steel panels compared to the bare steel (uncoated) in 3.5%NaCl after 24 and 96 hours
immersion periods.
Coating
system

Ecorr (mV/SCE)

Icorr(A)

BARE

24hr
-788.0

96hr
-777.0

24hr
5.320

96hr
5.340

24hr
-

96hr
-

RUS

-544.0

-577.0

1.320

1.490

74.19

72.10

RUZ

-519.0

-536.0

0.822

1.340

84.46

74.91

RUM

-497.0

-527.0

0.476

0.900

90.86

83.15

The corrosion protection behavior of these coating systems in 3.5% NaCl solution increased in this
order: RUM>RUZ>RUS compared to the bare steel that enormously corroded after the immersion
period. An improved inhibiting behavior has been observed for the coating containing Moly-based
corrosion inhibitor compared to Zinc and the undoped inorganic-organic (RUS) sol-gel. Molybased inhibitors draw this ability from the basis that molybdenum ions readily precipitate stable
oxides and hydroxides that prevent cathodic reduction reactions [14] at the working electrode
surface in the electrolytic solution [15], and the charge transfer instituting behavior of this metal is
more than Zinc. The ability of the molybdenum ions to remain inside the coating substrate for
extended immersion periods in any electrolyte is another key factor in solution-based oxidation
impedance compared to Zinc and Cesium (Cs) which readily leach out from the coating surfaces.
Wang and Akid [14] have reported the effect of compounds of this metal compared to
molybdenum.
3.2.2 Electrochemical impedance analysis:
The behavior of the electrochemical system at a minute AC amplitude perturbation and scan rate in
the solution of the electrolyte shows the degree of solution impedance in the matrix. With this, EIS
was employed to further demonstrate the corrosion protection performance of the newly prepared
of the sol-gel on the metal. The degree of protection of each coating is marked by a remarkably
large Zmodule values compared to the bare steel. By far the best coating with the highest corrosion
resistance, being MOLY-doped, had a 40M and 0.4M values, respective for 24 hr and 96 hr
immersion period more than other hybrid silicate films. The electrochemical impedance-frequency
plots of inhibitor-doped coatings on Q panel steel compared to a bare steel (uncoated) in
3.5%NaCl after (a) 24hr and (b) 96hr immersion periods is shown in Fig.4. EIS confirms the
corrosion protection order previously shown in the DC evaluation with the undoped coating being
the least of the coating: RUM>RUZ>RUS. Enhanced photo-digital images of these coated systems
in the solution of the electrolyte show a similar trend of results as in the electrochemical
techniques (Fig. 5). However, since there is no physical appearance of corrosion on these coated
steel samples, collection of electrochemical data will continue with a view to understanding the
system. Similar comparison has been done by Suleiman et al. [12]. Future studies will attempt to
explain the interfacial electrochemistry of highly passivating metals relation to the microstructures
of these silicate films which can demonstrate surface adhesion, corrosion protection and
hydrophobicity in the presence of other corrosive molecules in aqueous solutions [16].
RUZ

Paper No. 14021

RUM

15th Middle East Corrosion Conference & Exhibition

February 2-5, 2014
Manama, Kingdom of Bahrain

Page 5 of 11

4. CONCLUSIONS
The following conclusions were drawn from this study; that:
(1) The synthesized hydrid inorganic-organic sol-gel derived silicate films in this study showed an
excellent corrosion inhibition for steel based on the electrochemical and surface analytical results,
and these coatings demonstrated good surface hydrophobicity.
(2) The modified sol-gel derived silicate films demonstrated superior corrosion protecting ability
compared to the unmodified film, possibility from the oxide, hydroxide or complex precipitate
formation by molybdenum and zinc metal ions which prevented cathodic reduction reaction at the
steel working electrode.
(3) The MOLY-doped coating demonstrated the highest corrosion protection property at all conditions,
compared to the ZAPP-doped and unmodified coating. This improved property of MOLY-doped
coating could be determined from its hydrophobic and blister-free surface, and possibly, from the
ability of zinc to leach readily from the coatings. This studyis a contribution to the various solutions
to the problem of material degradation and failures with a view to reduce the colossal economic
cost and losses already incurred.

5. ACKNOWLEDGEMENTS
Authors would like to appreciate CORE-C and KFUPM for providing the necessary support for this
work.

6. REFERENCES
[1]

Cohen, T, Starosvetsky, J., Cheruti, U. and Armon, R. (2010).Whole Cell Imprinting in Sol-Gel
Thin Films for Bacterial Recognition in Liquids: Macromolecular Fingerprinting, Int. J. Mol.
Sci., 11, 1236-1252

[2]

Ivanoua D.K., Starykevich, M., Lisenkov, A.D., Zheludkevich, M.L., Xue, H.B., Lamaka, S.V.,
Ferreira, M.G.S. (2013). Plasma anodized ZE41 magnesium alloy sealed with hybrid epoxysilane coating. Corrosion Science, 73: 300308

[3]

Elshad Abdullayev and Yuri Lvov (2010).Clay nanotubes for corrosion inhibitor encapsulation:
release control with end stoppers. J. Mater. Chem., 20, 66816687

[4]

Abdel Salam Hamdy, D.P. Butt, A.A. Ismail (2007). Electrochemical impedance studies of sol
gel based ceramic coatings systems in 3.5% NaCl solution. Electrochimica Acta, 52: 33103316

[5]

Andres Pepe, Pablo Galliano, Mario Aparicio, Alicia Duran, Silvia Cere (2006).Sol-gel coatings
on carbon steel: Electrochemical evaluation, Surface & Coatings Technology, 200, 3486 3491

[6]

Zaharescua, M., Predoanaa, L., Baraua, A.Raps, D., Gammel, F., Rosero-Navarroc, N.C.,
Castroc, Y., Durnc, A., Aparicio, M.(2009). SiO2 based hybrid inorganicorganic lms doped
with TiO2CeO2 nanoparticles for corrosion protection of AA2024 and Mg-AZ31B alloys.
Corrosion Science, 51: 19982005

[7]

Kousalya, AS., Kumar, A., Paul, R., Zemlyanov, D., Fishe, T.S. (2013). Graphene: An effective
oxidation barrier coating for liquid and two-phase cooling systems, Corrosion Science, 69: 510

Paper No. 14021

15th Middle East Corrosion Conference & Exhibition

February 2-5, 2014
Manama, Kingdom of Bahrain

Page 6 of 11

[8]

Sharmila, R., Selvakumar .N.,Jeyasubramanian, K. (2013). Evaluation of corrosion inhibition in

mild steel using cerium oxide nanoparticles. Materials Letters, 91: 7880

[9]

Gergelya,A., Pfeifer, E., Bertti, I., Trk, T., Klmn, E. (2011). Corrosion protection of coldrolled steel by zinc-rich epoxy paint coatings loaded with nano-size alumina supported
polypyrrole, Corrosion Science, 53: 34863499

[10]

Jeon, H.R., Park, J.H., Shon, M.Y. (2013). Corrosion protection by epoxy coating containing
multi-walled carbon nanotubes. Journal of Industrial and Engineering Chemistry, 19: 849853

[11]

Heming Wang, Robert Akid (2007). A room temperature cured solgel anticorrosion pretreatment for Al 2024-T3 alloys. Corrosion Science, 49: 44914503

[12]

Suleiman, R., Mizanurrahman, M., Alfaifi, N., El Ali, B., Akid, R.(2013). Corrosion resistance
properties of hybrid organicinorganic epoxyamino functionalized polysiloxane based coatings
on mild steel in 3.5%NaCl solution. Corrosion Engineering, Science and Technology, DOI
10.1179/1743278213Y.0000000093

[13]

moren, S.A., Li, Y., Wang, F.H. (2010). Electrochemical study of corrosion inhibition and
adsorption behavior for pure iron by polyacryl amide in H2SO4: Synergistic effect of iodide ions,
Corrosion Science, 52: 17771786

[14]

Heming Wang, Robert Akid (2007). A room temperature cured solgel anticorrosion pretreatment for Al 2024-T3 alloys. Corrosion Science, 49: 44914503

[15]

S.A. Umoren, U.M. Eduok, M.M. Solomon, A.P. Udoh (2011). Corrosion inhibition by leaves
and stem extracts of Sidaacuta for mild steel in 1 M H2SO4 solutions investigated by chemical
and spectroscopic techniques. Arabian Journal of Chemistry, doi:10.1016/j.arabjc.2011.03.008

[16]

Ubong Eduok, E. Inam, S. A. Umoren & I. A. Akpan (2013). Chemical and spectrophotometric
studies of naphthol dye as an inhibitor for aluminum alloy corrosion in binary alkaline medium.
Geosystem Engineering,16, 2: 146-155.

Paper No. 14021

15th Middle East Corrosion Conference & Exhibition

February 2-5, 2014
Manama, Kingdom of Bahrain

Page 7 of 11

7. LIST OF FIGURES

(a)

(b)

Fig. 1: Molecular structures of the two silanols used in the synthesis of the base sol-gel (a)
Tetraethyloxysilicate (TEOS) and (b) Trimethoxymethylsilane (TMMS).

(a)

Spectrum 1

(b)

Si

O
Fe
Cl Fe

Cl Cl

1
2
3
Full Scale 5769 cts Cursor: 4.271 (27 cts)

Fe
4

Fe
7

10
keV

Fig. 2: A 100m SEM image and EDX spectrum of the RUS-coated sample coated onto the mild steel
substrate (a) before and (b) after 2.5 weeks immersion in 3.5%NaCl showing morphology and elemental
composition, respectively.

Paper No. 14021

15th Middle East Corrosion Conference & Exhibition

February 2-5, 2014
Manama, Kingdom of Bahrain

Page 8 of 11

BARE_24HR

RUS_24HR

RUZ_24HR

RUM_24HR (a)

-0.20
-0.30

E (V vs SCE)

-0.40
-0.50
-0.60
-0.70
-0.80
-0.90
-1.00
1E-10

1E-09

1E-08 0.00000010.000001 0.00001 0.0001

0.001

0.01

i (A)
BARE_96HR

RUS_96HR

RUZ_96HR

RUM_96HR

(b)

-0.20
-0.30
-0.40

E (V vs SCE)

-0.50
-0.60
-0.70
-0.80
-0.90

-1.00
-1.10
1E-10

1E-09

1E-08 0.00000010.000001 0.00001 0.0001

0.001

0.01

i (A)
Fig. 3: Potentiodynamic polarization plots of the inhibitor-doped coatings on Q panel steel compared to
a bare steel (uncoated) in 3.5%NaCl after (a) 24 hr and (b) 96 hr immersion periods

Paper No. 14021

15th Middle East Corrosion Conference & Exhibition

February 2-5, 2014
Manama, Kingdom of Bahrain

Page 9 of 11

BARE_24HR

RUS_24HR

RUZ_24HR

RUM_24HR

100,000,000
10,000,000
1,000,000

Zmod

100,000
10,000
1,000
100
10
1
0

100

10,000

1,000,000

Freq. (Hz)

BARE_96HR

RUS_96HR

RUZ_96HR

RUM_96HR

1,000,000
100,000

Zmod

10,000
1,000
100
10
1
0

100

10,000

1,000,000

Freq. (Hz)
Fig.4: Electrochemical impedance plots of the inhibitor-doped coating systems on Q panels steel
compared to bare steel (uncoated) in 3.5%NaCl after (a) 24 hr and (b) 96 hr immersion periods.

Paper No. 14021

15th Middle East Corrosion Conference & Exhibition

February 2-5, 2014
Manama, Kingdom of Bahrain

Page 10 of 11

BARE

RUS

RUZ

RUM

Fig. 5: Photo-digital images of the bare and coated steel substrates with different doped sol gel systems
submerged in 3.5%NaCl at room temperature after (a) 24 hour (b) 96 hour immersion .

Paper No. 14021

15th Middle East Corrosion Conference & Exhibition

February 2-5, 2014
Manama, Kingdom of Bahrain

Page 11 of 11