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 Effective corrosion inhibition performance of
La(NO3)3 doped sol-gel coating on galvanized
steel sheet
Akshya K. Guin, M. Bhadu and Mahua Sinhababu
Research and Development, Tata Steel Ltd, Jamshedpur, India
Ankita Mundhara
Department of Applied Chemistry, Indian School of Mines, Dhanbad, India
T.K. Rout
Research and Development, Tata Steel Ltd, Jamshedpur, India, and
G. Udayabhanu
Department of Applied Chemistry, Indian School of Mines, Dhanbad, India

Abstract
Purpose The aim of this work was to study the effect of La(NO3)3 on the corrosion behavior of sol-gel coating prepared by hydrolysis of
3-glycidoxypropyl)methyldiethoxysilane and 3-aminopropyltriethoxysilane. Generally, galvanized steel is subjected to a hexavalent chromium
passivation treatment. Hexavalent chromium passivation is not an environment friendly product and researchers are looking for a suitable alternative
for chromium passivation treatment. Some of the potential alternatives are silicate conversion coating or the use of silane-based coatings. In this
context, sol-gel coating was investigated as a potential replacement for hazardous hexavalent chromium passivation treatment.
Design/methodology/approach The sol-gel film was deposited on galvanized steel sheet by the dip coating method. The molecular vibration
and chemical properties of sol-gel solution and coated films were obtained by infrared spectroscopy. Images from a scanning electron microscope
were obtained to characterize the morphology of the film. The corrosion resistance of the coated samples was evaluated by electrochemical
impedance spectroscopy (EIS), potentiodynamic polarization curves and salt spray tests.
Findings The results indicated that La(NO3)3-doped coatings were more resistance to corrosion than undoped coating. The coating doped with
0.5 per cent La(NO3)3 offered improved corrosion protection due to the inhibitive action of the La3 ion.
Originality/value This result can provide a reference for the development of chromium-free passivation for galvanized sheeting.
Keywords Coatings and linings, Research
Paper type Research paper

1. Introduction associated with the same favors the use of cheap metallic
materials along with efficient corrosion prevention methods.
Metals such as iron, aluminum, copper and magnesium and
To reduce corrosion, two approaches can be utilized,
their alloys have wide applications in aircraft, marine
passive corrosion protection and active corrosion protection.
applications, etc. These metals are useful in industry because
Passive protection is normally provided by a barrier film that
of their stiffness and high strength to weight characteristics,
prevents contact of aggressive species with the metal surface
but they are highly susceptible to corrosion in aggressive
and therefore hinders the corrosion process. However, in the
environments. Corrosion is the major reason for energy and
case where a defect has formed in the barrier layer, the coating
material loss. Despite much advancement in the field of
cannot stop corrosion in that place. The second approach is
corrosion science and technology, the phenomenon of
active corrosion protection, which uses inhibitive species that
corrosion (mainly of Fe, Al, Cu, Zn, Mg and their alloys)
can decrease corrosion activity.
remains a major concern to industries around the world.
Industrial protection systems comprise different layers, such
Though the serious consequences of corrosion can be
as pre-treatment, primer and top coat. Pre-treatment plays an
controlled to a great extent by selection of corrosion-resistant
important role in providing an intermediate layer that
materials, in many industrial applications the cost factor
increases adhesion between the metal surface and organic
coating and also provides an additional barrier that eventually
The current issue and full text archive of this journal is available at may exhibit active corrosion prevention properties. Hexavalent
www.emeraldinsight.com/0003-5599.htm chromate conversion coatings are widely applied to metal posts
because of their high corrosion resistance and strong self-healing

Anti-Corrosion Methods and Materials

61/6 (2014) 370 379 The authors would like to thank the Senior Management of Tata Steel
Emerald Group Publishing Limited [ISSN 0003-5599] Limited for permission to publish and encouragement to carry out this
[DOI 10.1108/ACMM-08-2013-1292] work.

370
 Effective corrosion inhibition performance
Akshya K. Guin et al.
ability. However, because of their toxicity and carcinogenicity,
use of hexavalent chromium passivation has been limited in
many countries. In recent years, chromium-free passivation has
become an area of active investigation.
To find a suitable alternative for chromate coating, researchers
are looking for improved organic coatings. The potential
alternatives include silicate conversion coatings or silane base
coatings; see Berger et al. (2007), Abdel-Rehman et al. (2012)
and Kim et al. (2004). Sodium silicate has been used as an
inhibitor for many years due to its effective inhibitory properties
and low cost. Yuan et al. (2011a, 2011b) and Dalbin et al. (2005)
prepared chromium free coatings for galvanized steel that were
composed mainly of zinc oxides/hydroxides, zinc silicate and
SiO2 on the galvanized steel surface. They found out that coating
formulated using sodium silicate solutions with high SiO2/Na2O
molar ratios (i.e. greater than 2.00) showed better corrosion
resistance performance.
Hamlaoui et al. (2009), Simes et al. (2011), Manchet et al.
(2010) and Fedel et al. (2010) also studied the silane-based
coatings as an alternative to chromium conversion coating. In
their work, they prepared films with synergistic blends of
siloxanes as tetraethyl-ortho-silane (TEOS), 3-methacryloxy-
propyl-trimethoxysilane (MPTS) and methyl methacrylate
(MMA). Coated surfaces were analysed using atomic force
microscopy and the coatings thicknesses were evaluated by
means of glow discharge optical emission spectroscopy
(GDOES). The results plainly showed the efficiency of the
anticorrosion properties of the film in a 3.5 wt% NaCl solution
and have clearly revealed the improvement of the protective
properties of the coating when the MPTS was added to the
formulations, pinpointing this component to be the main
component responsible for the coating anticorrosion action.
The addition of MMA to the formulation led to the formation
of coatings with long-term anticorrosion protection.
Sakai et al. (2011) tried a different type of conversion
coating; molybdatephosphatesilicate (MPS) coating on
industrial galvanized steel, which then was evaluated in different
concentrations of NaCl solution, for immersion times and at pH
values. As opposed to the chromate coatings and despite their
cracked morphology, the results showed that the MPS coatings
exhibited adequate corrosion behaviour even in concentrated
NaCl solutions.
Jalfarzdeh et al. (2005) studied the performance of
conducting polymers as an alternative to chromium
passivation. A conducting polymer, polyaniline (PANI), was
synthesized by chemical oxidative polymerization using
methane sulfonic acid (MeSA) as the dopant and ammonium
peroxodisulfate as the oxidizer. Coatings of PANIMeSA
dispersed in polyester acrylate resin were applied on
galvanized steel and were UV-cured.
Duarte et al. (2005) designed a chemical treatment
composed of fluoro-titanic acid, manganese phosphate,
phosphoric acid and an organic compound. The effects of the
two major constituents of the solution (i.e. the organic phase
and manganese phosphate) on the homogeneity, defects,
electrochemical behaviour and composition of the conversion
layer were investigated. For this purpose, electrochemical tests
were performed in a 3.5 per cent NaCl medium on hot-dipped
galvanized (HDG) samples treated with the standard version
of the Cr-free treatment or with derivative versions without
371
Anti-Corrosion Methods and Materials
Volume 61 Number 6 2014 370 379
either manganese phosphate or the organic compound. The
conversion coating obtained with the standard Cr-free
solution led to a significant decrease in the corrosion current
density (Icorr). On the basis of polarization curves and
electrochemical impedance spectroscopy (EIS) analyses, it
was shown that the coating also limited oxygen diffusion to the
HDG substrate. In the absence of either manganese
phosphate or the organic compound, the surface morphology
was noticeably different. Depth profiling analyses using
GDOES indicated the formation of thinner layers when
compared with the standard-treated sample. As a
consequence, the performance of the conversion layer was
affected significantly.
In other work on silane-based coatings done by Bexell
and Grehk (2007), an organofunctional silane,
-mercaptopropyltrimethoxysilane (-MPS), was deposited
on HDG cold rolled steel. The study was carried out for
different silane solution concentrations. Painted and
unpainted silane treated samples were corrosion tested and
painted samples were adhesion tested. The surface chemistry
of the unpainted silane treated samples was investigated with
AES, SIMS and EDS and the surface morphology was studied
with scanning electron microscope. The results showed that
the silane film thickness was dependent on the silane
concentration in the silane solution and a higher silane
concentration gave a thicker film.
Some previous studies by Motte et al. (2012), Tsai et al.
(2010) and Yang et al. (2010) showed that the barrier
properties of the silane layer could be improved by the
incorporation of clay or titania nanoparticles. Moreover,
inhibitive metallic cations can be incorporated in the
nanoclays by ion exchange, providing a way to prepare cheap
corrosion inhibitors nano-reservoirs offer self-healing
properties. Rare earth metal salts have been shown to be
effective corrosion inhibitors on a wide range of metals,
including HDG steel. For this study, montmorillonite clay was
modified to obtain a Ce(III) montmorillonite clay
(Ce-MMT).
In the present work, lanthanum nitrate (III) was used as the
inhibitor at different concentration levels and the corrosion
resistance properties of the lanthanum nitrate-doped sol-gel
coating were checked on galvanized iron (GI) sheet.
2. Experimental
2.1 Substrate preparation
GI sheets were cleaned in an alkaline solution containing 3 per
cent Ridoline at 60C. This enabled the removal of the oil
layer present on the as-received material and also increased
the number of hydroxyl groups. This helps in the formation of
hydrogen bonds between the substrate and sol-gel coating and
improves its adhesion. The sheets then were rinsed with water
and dried with hot air.
2.2 Preparation of silane solution
The typical sol-gel synthesis process adopted for this study
was as follows: 3-glycidoxypropyl)methyldiethoxysilane
(GPTMS) (0.10 mole) and 3-aminopropyltriethoxysilane
(0.04 mole) were added drop-wise simultaneously (but
separately through two necks of the round-bottomed flask) to
a dilute aqueous solution of acetic acid (0.2 mole) while
 Effective corrosion inhibition performance Anti-Corrosion Methods and Materials
Akshya K. Guin et al. Volume 61 Number 6 2014 370 379

stirring at 300-400 rpm. The mixture was stirred for 18 h.
This solution was applied to the galvanized steel substrate
without any dilution and these samples were named as Blank.
To enhance the corrosion resistance property of the sol-gel
coating, 0.5, 0.75 and 1 per cent lanthanum nitrate La(NO3)3
was added separately to the above solution.
After 1 h of mixing LaNO3 in the sol-gel solution, the
coating was applied using a dipping process for 10 seconds at
room temperature on industrially produced GI sheet provided
by Tata Steel Limited, followed by drying at 90C for 30
seconds and the coated samples were labelled as Lan 2, Lan 3
and Lan 4, respectively.
2.3 Performance tests
Fourier transform infrared spectrometry (FT-IR) spectra of
the liquid coating and for the coated panels were recorded on
a Nicolet-6700 at a range of 400 cm1 to 4,000 cm1. In salt
spray tests (ASTM B117), the samples were placed in the salt
spray chamber at an angle of 45, exposed to 5 weight per cent
NaCl mist, at a temperature of 35C. EIS measurements were
made using an SR 810 frequency response analyzer and the
Versa Stat in 0.35 M NaCl electrolyte at room temperature,
with 1 cm2 contact area. The initial and final frequencies were
105 Hz and 102 Hz, respectively. The AC excitation
amplitude was 10 mV. A saturated calomel electrode (SCE)
was used as the reference electrode and a platinum rod was
used as the counter electrode. The panels were immersed in
0.35 M NaCl solution and readings were taken after 5, 24 and
48 h. Potentiostatic polarization tests were carried out in a
0.35 M NaCl solution. Tafel readings were taken using the
Versa Stat with density of iron 7.13 gm/cm3 and for a
molecular weight of 32.69. An open circuit reading was taken
for 600 seconds. After this initial Tafel polarization test was
done, the panels were immersed for 24 h in 3.5 per cent NaCl
solution. A reading was noted after 24 h. The reference and
counter electrodes were commercial SCE and a platinum rod,
respectively. A range of Ecorr 0.25 V potential was applied to
the panels. Optical laser spectroscopy (OLS) readings were
taken on a LEXTOLS 4,000 - laser confocal microscope. The
readings showed the roughness of the surface.
3. Results
3.1 FT-IR study
The FT-IR (spectroscopy) technique can be used to obtain an
infrared spectrum of absorption, emission, photoconductivity
or Raman scattering for a solid, liquid or gas. In the present
study, it was used to characterize the sol-gel hydrolysis,
condensation reactions and coating. Figure 1 shows the
FT-IR spectra of sol-gel coating solution for 30 minutes, 1, 2,
3, 4 and 24 h. A number of prominent peaks observed at 3,370
cm1, 3,000, 1,640 and 1,100-1,130 cm1 (Figure 2).
A sharp peak at 1,134 cm was observed on sol-gel coated
steel sample.

Figure 1 FT-IR spectra of silane solution

30 mins
1 Hr
160 2 Hrs
4 Hrs
1,640.9

5 Hrs
3,373.6

1,075.7
Silane sol 24hrs stirrring
150
3,774.1

1,549.2 1,529.7
1,639.3 1,658.2 1,640.9
3,371.5

140
1,075.1

402.7 417.5 410.6

438.3 480.0
603.2
130
538.3
1,077.4

491.4

430.3
602.9

440.9
3,372.8

467.4
451.3

428.8
410.6 407.5
120
%Reflectance

599.6 441.5
1,640.6

429.4
3,370.6

421.0 404.6

110
1,081.2
1,640.2

100
3,368.2

1,640.2

90
3,371.6

493.6
403.2
600.4

80
543.5534.8
421.8 490.5459.3
466.2
4091
598.7

4102

70
418.8
433.4

4162
447.8
436.2
426.7

60
3,500 3,000 2,500 2,000 1,500 1,000 500
Wavenumbers (cm-1)

372
 Effective corrosion inhibition performance Anti-Corrosion Methods and Materials
Akshya K. Guin et al. Volume 61 Number 6 2014 370 379

Figure 2 FT-IR spectra of coated sheet

BLANK
120

110

2,882.9
3,318.8

1,573.5
100

1,409.0

689.2
90

766.3
921.1
%Reflectance

80

70

60

1,143.4
50

40

30

4,000 3,500 3,000 2,500 2,000 1,500 1,000 500

Wavenumbers (cm-1)

Table I Initial Tafel readings

Sample Ecorr Icorr Corrosion rate a c
2
Blank 1.018 V 0.43 A/cm 0.256 mpy 21.488 mV 179.283 mV
Lan 2 1.012 V 0.467 A/cm2 0.2760 mpy 11.597 mV 139.205 mV
Lan 3 1.005 V 1.557 A/cm2 0.9191 mpy 17.929 mV 187.533 mV
Lan 4 1.008 V 2.643 A/cm2 1.559 mpy 29.411 mV 106.421 mV

3.2 Linear polarization study

As can be seen from the Table I and Figure 3, Lan 2 and Blank
showed the lowest Icorr value where Icorr is directly
proportional to corrosion rate. Lan 3 also showed a low Icorr.
It can also be seen from the Tafel analysis that Lan 3 had a low
corrosion rate. Lan 4 showed the maximum Icorr and hence Figure 3 Comparison of initial Tafel data of blank and lanthanum
had the highest corrosion rate. a was lower in Lan 2 as nitrate
compared to the Blank sample.
Even after 24 h of immersion in a 3.5 per cent NaCl
solution, it is evident from Table II and Figure 4 that Lan 2
and Lan 3 overlap with the Blank sample values and show low
Icorr and consequently low corrosion rates. Lan 4 deviates
from the Blank curve and hence shows relatively high
corrosion rates.

3.3 Surface roughness

OLS was used to calculate the roughness of the sample sheet. An
average of line roughness gives surface roughness. OLS was done
on Blank, Lan 2, Lan 3 and Lan 4 samples. A comparison was
made of all the above and readings of surface roughness are
summarized in Table III below and Figures 58.

373
 Effective corrosion inhibition performance Anti-Corrosion Methods and Materials
Akshya K. Guin et al. Volume 61 Number 6 2014 370 379

Table II Tafel after 24 hr

Sample Ecorr Icorr Corrosion rate a c
2
Blank 1.02 V 9.64 A/cm 5.6884 mpy 61.373 mV 135.745 mV
Lan 2 1.019 V 7.343 A/cm2 4.333 mpy 60.105 mV 105.53 mV
Lan 3 1.024 V 16.741 A/cm2 9.8788 mpy 124.48 mV 139.92 mV
Lan 4 1.079 V 202.69 A/cm2 121.71 mpy 45.201 mV 61.624 mV

3.4 Salt spray test
Salt spray tests were carried out by exposing scribed samples
(3 3inch panels with a coating of 5-6 microns dry film
thickness) in a salt spray chamber, as per the ASTM B-117
test method. The panels were checked at regular intervals and
results were noted down in terms of blisters, creep and white
rust.
Salt spray tests on the coated samples were performed as per
the ASTM B-117 test standard. From the salt spray analysis
Figure 4 Tafel after 24 h
data (Table IV), it was observed that the samples coated with
Lan 3 and Lan 4 showed poor corrosion resistance. The onset
of corrosion took place within 24 h and samples became fully
corroded, whereas samples coated with Lan 3 and Lan 4
exhibited quite high corrosion resistance properties. Samples
coated with Lan 2 exhibited minimum corrosion damage and
only a small area was affected by localized corrosion, even
after 60 h of immersion in the salt spray unit.
3.5 Electrochemical impedance (EIS) study
EIS is an excellent tool to study the mechanism and kinetics of
the corrosion reaction. The change in impedance spectra due
to immersion in the corrosion environment of 3.5 per cent

Figure 6 OLS picture of LAN-2 coated sample

Table III Surface roughness readings

Sample Surface roughness (m)
Blank 0.962
LAN-2 0.888
LAN-3 0.927
LAN-4 0.981

Figure 7 OLS picture of LAN-3 coated sample

Figure 5 OLS picture of blank coated sample

374
 Effective corrosion inhibition performance Anti-Corrosion Methods and Materials
Akshya K. Guin et al. Volume 61 Number 6 2014 370 379

Figure 8 OLS picture of LAN-4 coated sample
The typical impendence spectra of the samples coated with
sol-gel coating with and without La(NO3)3 are presented in
Figures 10-25.
From the above EIS results, it was observed that the corrosion
resistance of coated samples was enhanced by the incorporation
of La(NO3)3. Results from the initial EIS study shows that the
impedance value of the coating containing La(NO3)3 was higher
than sample coated without La(NO3)3. The coated sample
prepared with Lan 2 provided better corrosion protection
compared to coating prepared with the Lan 3 and Lan 4
formulations. Samples coated without any La(NO3)3, i.e. Bare,
Lan 3 and Lan 4, showed poor corrosion protection and after 24

Figure 10 EIS curve fitting of blank-initial reading

1,000
24

22

20

18

|Z| (ohm)
16
NaCl solution in static condition helps in the development of 100
14
an understanding of the protective capability of the developed
12
coatings. The resistance obtained at low-frequency
10
perturbations is crucial to explain the corrosion resistance
8
performance and intactness of the coatings. In the present
6
study, EIS measurements on the coated samples were carried 10
out between 100 kHz and 0.01 Hz at the Ecorr. The physical 0.01 0.1 1 10 100 1,000 10,000 1,00,000
Frequency (Hz)
values were modelled with the VERSATEC software as an
equivalent circuit. The system can be assumed to consist of
Figure 11 EIS curve fitting of blank after 5 h
three interfaces with different resistance and capacitance
characteristics, as shown in Figure 9. The first interface is 1,000 36
34
between sol-gel coating and NaCl electrolyte. The second is 32
between the coating and the metal substrate and the third is at 30
28
the metal surface where corrosion activity takes place. The 26
24
spectra revealed three time constants Rcoat-Qcoat, Rox-Qox and
|Z| (ohm)

22
Rct-Qdl corresponding to the resistance and capacitance values 100 20
18
of the sol-gel film, intermediate oxide layer and double layer, 16
14
respectively. Gradual reduction in the Rcoat value with time 12
was an indication of attack at the metal surface by chloride 10
8
ions due to degradation of the coating. 6
10
0.01 0.1 1 10 100 1,000 10,000 1,00,000
Frequency (Hz)
Table IV SST observation
Sample 24 h 48 h 60 h Figure 12 EIS curve fitting of blank after 24 h
Blank OK OK 20% white rust 1,000
Lan 2 OK OK 5-10% white rust 32
Lan 3 5% white rust 20% white rust 60-70% white rust 30
28
Lan 4 10-20% white rust 30-40% white rust 100% white rust
26
24
22
|Z| (ohm )

Figure 9 Curve fitting circuit of EIS diagram 20

100
18
Q 16
14
12
10
8
6
10
0.01 0.1 1 10 100 1,000 10,000 100,000
Frequency (Hz)

375
 Effective corrosion inhibition performance Anti-Corrosion Methods and Materials
Akshya K. Guin et al. Volume 61 Number 6 2014 370 379

Figure 13 EIS curve fitting of blank after 48 h Figure 16 EIS curve fitting of Lan 2 after 24 h
1,000 100
30
28
28
26 26
24 24
22 22
20
20
18
|Z| (ohm)

|Z| (ohm)
18 16
100 16 14
12
14
10
12 8
10 6
8 4
2
6 0
4 2
10 10
0.01 0.1 1 10 100 1,000 10,000 100,000 0.01 0.1 1 10 100 1,000 10,000 100,000
Frequency (Hz) Frequency (Hz)

Figure 14 EIS curve fitting of Lan 2 initial reading Figure 17 EIS curve fitting of Lan 2 after 48 h
1,000 1,000 32
30
40 28
26
35 24
22
30
20

|Z| (ohm)
|Z| (ohm)

25 18
100 16
100
20 14
12
15 10
8
10 6
4
5
2
0 0
10 10
0.01 0.1 1 10 100 1,000 10,000 100,000
0.01 0.1 1 10 100 1,000 10,000 100,000
Frequency (Hz)
Frequency (Hz)

Figure 15 EIS curve fitting of Lan 2 after 5 h Figure 18 EIS curve fitting of Lan 3 initial reading
10,000
1,000
55
45
50
45 40
40
35
35
|Z| (ohm)

30 30
|Z| (ohm)

25 1,000
100
20 25

15
20
10
5 15
0
10
5
10 100
10
0.01 0.1 1 10 100 1,000 10,000 100,000
0.01 0.1 1 10 100 1,000 10,000 100,000
Frequency (Hz)
Frequency (Hz)

h of immersion in a 3.5 per cent NaCl solution in static condition
in a closed container, and coating resistance decreased drastically
from the original value. This is indicative of high water
permeability and the porous nature of the coating. However,
samples coated with the Lan 2 formulation exhibited higher
charge transfer resistance values even after 48 h of immersion in
the NaCl solution.
4. Discussion
4.1 FT-IR study
Figure 1 shows the FT-IR spectra of sol-gel coating solution
for 30 minutes, 1, 2, 3, 4 and 24 h. The peak at 3,370 cm1
relates to O-H stretching mode. Small peaks observed at
around 3,000 cm1 correspond to the C-H stretching
mode. The peak at 1,640 cm1 relates to O-H bending
mode. Strong bands observed at 1,100-1,130 cm1 indicate
the presence of Si-O-Si moieties. As the stirring time (1, 2,
4, 5 and 24 h) was increased, the peak region started to
diminish, indicating that the OH group had been
decreasing. This can be explained as hydrolysis and
condensation processes take place at the same time, so as
soon as the OH group was formed through hydrolysis it was
converted into Si-O-Si due to condensation. The results of
the peak ID are shown in Table V.

376
 Effective corrosion inhibition performance Anti-Corrosion Methods and Materials
Akshya K. Guin et al. Volume 61 Number 6 2014 370 379

Figure 19 EIS curve fitting of Lan 3 after 5 h Figure 22 EIS curve fitting of Lan 4 initial reading
10,000 40 100,000 45
38
36 40
34
32 10,000 35

1,000 30
28 30

|Z| (ohm)
|Z| (ohm)

26
24 1,000 25
22
20 20
100 18
16 100 15
14
12 10
10
8 5
10 10
0.01 0.1 1 10 100 1,000 10,000 100,000 0.01 0.1 1 10 100 1,000 10,000 100,000
Frequency (Hz) Frequency (Hz)

Figure 20 EIS curve fitting of Lan 3 after 24 h Figure 23 EIS curve fitting of Lan 4 after 5 h
1,000 10,000 45
18
40
16
35
14
1,000
12 30
|Z| (ohm)
|Z| (ohm)

10 25
100
8
20
100
6
15
4
10
2

10 5
10 0
0.01 0.1 1 10 100 1,000 10,000 100,000
0.01 0.1 1 10 100 1,000 10,000 100,000
Frequency (Hz)
Frequency (Hz)

Figure 21 EIS curve fitting of Lan 3 after 48 h Figure 24 EIS curve fitting of Lan 4 after 24 h
1,000
10,000
30 35
28
26 30
24
22 25
1,000
20
|Z| (ohm)
|Z| (ohm)

18 20
100
16
14 15
100 12
10 10
8
6 5
4
10
10 2
0.01 0.1 1 10 100 1,000 10,000 100,000
0.01 0.1 1 10 100 1,000 10,000 100,000
Frequency (Hz)
Frequency (Hz)

It can be seen from the results in Table V that coated sheets
also showed the same peaks as those of the liquid sample. This
indicated that sol-gel coating was efficiently coated on the
sample sheets.
4.2 Linear polarization study
It can also be seen from the Tafel analysis that Lan 3 showed low
corrosion rates. Lan 4 showed the maximum Icorr and hence had
a high corrosion rate. This is possibly because of an increase in
the porosity of the coating. a was decreasing in Lan 2 compared
to the Blank sample. This may be attributed to the action of the
La3 ions. La3 has an affinity for oxygen and hence when
oxygen reduction occurs at the cathode during corrosion of the
metal, hydroxyl ions are produced and the rise in local pH
encourages the precipitation of La(OH)3 at the cathodic areas. c
also decreased for Lan 2 samples, which indicates that cathodic
reaction was decreasing. This confirmed that lanthanum nitrate
behaves as a cathodic inhibitor.
Even after 24 h of immersion in the 3.5 per cent NaCl
solution, it can be seen from Table I and Figure 4 that Lan 2
and Lan 3 data overlapped with that from the Blank sample
and exhibited low Icorr and low corrosion rates. Lan 4 deviates
from the curve for the Blank sample and hence showed
relatively high corrosion rates.

377
 Effective corrosion inhibition performance
Akshya K. Guin et al.
Figure 25 EIS curve fitting of Lan 4 after 48 h
1,000
|Z| (ohm)
100
10
0.01 0.1 1 10 100
Frequency (Hz)
Table V Peak assignments for coating systems
Peaks Assignments
3,373 O-H
3,000 C-H
1,640 O-H
1,100-1,130 Si-O-Si and Si-O-C
476, 870 SiO2, disiloxane Si-O-Si
4.3 Surface roughness
A comparison was done on all of the above and readings of
surface roughness are summarized in Table II and Figures
58.
As can be seen from Figures 58 and Table II, Lan 2 and
Lan 3 had less surface roughness than the Blank sample. A low
surface roughness variation will provide more uniform
coating, less possibility for surface potential variation and
lower the probability of corrosion compared to higher surface
roughness values. With this logic it can be assumed that Lan
2 and Lan 3 provided low corrosion rates and this assumption
is supported by Tafel polarization reading.
4.4 Salt spray tests
From the salt spray analysis data (Table IV) it was observed
that the samples coated with Lan 3 and Lan 4 showed poor
corrosion resistance. Onset of corrosion was evident within 24
h and samples became fully corroded. In contrast, the sample
coated with Lan 2 exhibited quite high corrosion resistance
and only a small area was affected by localized corrosion, even
after 60 h of exposure in the salt spray cabinet.
4.5 Electrochemical impedance (EIS) study
The typical impedance spectra of the samples coated with
sol-gel coating with and without La(NO3)3 are presented in
Figures 1025. It was observed from the above EIS results that
the corrosion resistance of coated samples was enhanced by
the incorporation of La(NO3)3. Initial EIS results indicated
that the impedance value of coatings containing La(NO3)3
was higher than was the case without La(NO3)3. The coated
sample prepared with Lan 2 provided better corrosion
protection compared to coatings prepared with the Lan 3 and
Lan 4 formulations. Samples coated without La(NO3)3, i.e.
Bare, Lan 3 and Lan 4, showed poor corrosion resistance and
Anti-Corrosion Methods and Materials
Volume 61 Number 6 2014 370 379
after 24 h of immersion in 3.5 per cent NaCl solution coating
resistances had decreased drastically from the original value.
35
This was indicative of high water permeability and the porous
30 nature of the coatings. However, samples coated with the
25
Lan-2 formulation provide higher corrosion resistance even
after 48 h of immersion in NaCl solution. This may be due to
20
the high inhibition efficiency of La(NO3)3. At concentrations
15 greater than 0.5 per cent of La(NO3)3 (as in Lan 2), the
efficiency of inhibition decreased, which may be due to the
10
non-uniform dispersion or agglomeration of La(NO3)3
5 particles. OLS results also indicated non-uniform coverage.
Thus, samples coated with Lan 3 and Lan 4 do not provide
0
any corrosion inhibition properties, whereas the sample coated
1,000 10,000 100,000 with Lan 2 exhibited greater corrosion resistance. After 48 h of
immersion, the coating resistance of Lan 2 was higher than
was that of the Blank, Lan 3 and Lan 4 samples. Furthermore,
no additional time constant was observed after 48 h
Comments immersion in 3.5 per cent NaCl solution and this indicated
that the sample coated with Lan 2 provided good barrier
Broad O-H stretching protection and improved corrosion protection for the steel
Symmetric C-H stretching
substrate.
O-H bending
Si-O stretching
Symmetric stretching and 5. Conclusions
bending
Sol-gel coatings can be used on galvanized iron sheets to
improve its corrosion resistance. Different additives can be
incorporated in sol-gel formulations to increase the corrosion
protection properties of the coated sheet. La(NO3)3 was used
as the corrosion inhibitor. Tafel and salt spray cabinet studies
showed that the Lan 2 formulation, i.e. 0.50 per cent
lanthanum nitrate in silane solution, can be used in a sol-gel
solution to improve corrosion protection of coated substrates.
The reason for this above observation is that La3 has an
affinity for oxygen and hence when oxygen reduction occurs at
the cathode during corrosion of the metal substrate, hydroxyl
ions are produced and the rise in pH encourages the
precipitation of La(OH)3 at the cathodic areas. This reduces
the cathodic reaction and therefore decreases the corrosion
rate. Lanthanum nitrate acts as a cathodic inhibitor.
References
Abdel-Rehman, E-S., Harm, U., Mangold, K-M. and
Furbeth, W. (2012), Protection of galvanized steel from
corrosion in NaCl solution by coverage with phytic acid
SAM modified with some cations and thiols, Corrosion
Science, Vol. 55, pp. 339-350.
Berger, R., Bexell, U., Grehk, T.M. and Hrnstrm, S.
(2007), A comparative study of the corrosion protective
properties of chromium and chromium free passivation
methods, Surface and Coatings Technology, Vol. 202,
pp. 391-397.
Bexell, T. and Grehk, M. (2007), A corrosion study of
hot-dip galvanized steel sheet pre-treated with -
mercaptopropyltrimethoxysilane, Surface & Coatings
Technology, Vol. 201 No. 8, pp. 4734-4742.
Dalbin, S., Maurin, G., Nogueira, R.P., Persello, J. and
Pommier, N. (2005), Silica based coating for corrosion
protection of electro galvanized steel, Surface & Coatings
Technology, Vol. 194, pp. 363-371.
378
 Effective corrosion inhibition performance
Akshya K. Guin et al.
Duarte, R.G., Bastos, A.C., Castela, A.S. and
Ferreira, M.G.S. (2005), A comparative study between Cr
(VI)-containing and Cr-free films for coil coating systems,
Progress in Organic Coatings, Vol. 52 No. 4, pp. 320-327.
Fedel, M., Druart, M.-E., Olivier, M., Poelman, M.,
Deflorian, F. and Rossi, S. (2010), Compatibility between
cataphoretic electro-coating and silane surface layer for
corrosion protection of galvanized steel, Progress in Organic
Coatings, Vol. 69 No. 2, pp. 118-125.
Hamlaoui, Y., Tifouti, L. and Pedraza, F. (2009), Corrosion
behaviour of molybdate-phosphate-silicate coatings on
galvanized steel, Corrosion Science, Vol. 51 No. 10,
pp. 2455-2462.
Kim, H.J., Zhang, J., Yoon, R.-H., and Gandour, R. (2004),
Development of environmentally friendly nonchromium
conversion coating for electrogalvanized steel, Surface &
Coatings Technology, Vols 188/189, pp. 762-767.
Manchet, S., Le, L.J., Richard, C. and Verchre, D. (2010),
Study of a chromium-free treatment on hot-dip galvanized
steel: electrochemical behaviour and performance in a saline
medium, Surface & Coatings Technology, Vol. 205 No. 2,
pp. 475-482.
Motte, C., Poelman, M., Roobroeck, A., Fedel, M.,
Deflorian, F. and Olivier, M.-G. (2012), Improvement of
corrosion protection offered to galvanized steel by
incorporation of lanthanide modified nanoclays in silane
layer, Progress in Organic Coatings, Vol. 74 No. 2,
pp. 326-333.
Sakai, R.T., Cruz, F.M., Melo, H.G., Benedetti, A.V.,
Santilli, C.V. and Suegama, P.H. (2012), Electrochemical
study of TEOS, TEOS/MPTS, MPTS/MMA and TEOS/
MPTS/MMA films on tin coated steel in 3.5% NaCl
Solution, Progress in Organic Coating, Vol. 74 No. 2,
pp. 288-301.
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Anti-Corrosion Methods and Materials
Volume 61 Number 6 2014 370 379
Simes, A.M.P., Carbonari, R.O., Sarli, A.R., Amo, B. and
Romagnoli, R. (2011), An environmentally acceptable
primer for galvanized steel: formulation and evaluation by
SVET, Corrosion Science, Vol. 53 No. 1, pp. 464-472.
Tsai, C.-Y., Liu, J.-S., Chen, P.-L. and Lin, C.-S. (2010), A
two-step roll coating phosphate/molybdate passivation
treatment for hot-dip galvanized steel sheet, Corrosion
Science, Vol. 52 No. 10, pp. 3385-3393.
Yang, H., Kong, X., Lu, W., Liu, Y., Guo, J. and Liu, S.
(2010), High anticorrosion chromate free passive films
made by titanate and waterborne polyurethane on
galvanized steel sheet, Progress in Organic Coatings, Vol. 67
No. 4, pp. 375-380.
Yuan, M.-R., Lu, J.-T., Kong, G. and Che, C.-S. (2011a),
Self-healing ability of silicate conversion coatings on hot
dip galvanized steels, Surface & Coatings Technology,
Vol. 205 No. 19, pp. 4507-4513.
Yuan, M.-R., Lu, J.-T., Kong, G. and Che, C.-S. (2011b),
Effect of silicate anion distribution in sodium silicate
solution on silicate conversion coatings of hot-dip
galvanized steels, Surface & Coatings Technology, Vol. 205
No. 19, pp. 4466-4470.
Further reading
Shadi, J., Adhikari, A., Sundall, P.-E. and Pan, J. (2011),
Study of PANI-MeSA conducting polymer dispersed in
UV- curing polyester acrylate on galvanized steel as
corrosion protection coating, Progress in Organic Coatings,
Vol. 70 No. 2, pp. 108-115.
Corresponding author
Akshya K. Guin can be contacted at: akshya.guin@
tatasteel.com