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Journal of Magnesium and Alloys 6 (2018) 299–308

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Full Length Article
Evaluation of self-healing properties of inhibitor loaded nanoclay-based
anticorrosive coatings on magnesium alloy AZ91D
Swapnil H. Adsul a, c, K.R.C. Soma Raju a, B.V. Sarada b, Shirish H. Sonawane c, R. Subasri a, ∗
a
Centre for Sol–Gel Coatings, International Advanced Research Centre for Powder Metallurgy and New Materials (ARCI), Balapur, Hyderabad 500005,
Telangana, India
b
Centre for Solar Energy Materials, International Advanced Research Centre for Powder Metallurgy and New Materials (ARCI), Balapur, Hyderabad 500005,
Telangana, India
c
Department of Chemical Engineering, National Institute of Technology, Warangal 506004, Telangana, India
Received 14 February 2018; accepted 9 May 2018
Available online 14 June 2018

Abstract
This study emphasizes on the evaluation and comparison of the anticorrosive properties of sol–gel coatings with and without inhibitor loaded
nanocontainers. In this case, naturally available clay nanotubes (halloysite) were loaded with cationic corrosion inhibitors Ce 3 + /Zr 4 + . These
nanocontainers were dispersed in hybrid organic–inorganic sol–gel matrix sol. Coating was applied on magnesium alloy AZ91D using the sols
containing modified and unmodified nanocontainers employing the dip coating method and cured at 130 °C for 1 h in air. Corrosion resistance of
coated/uncoated substrates were analyzed using electrochemical impedance spectroscopy, potentiodynamic polarization and weight loss
measurements after exposure to 3.5 wt% NaCl solution for varying time durations between 24 h to 120 h. Self-healing ability of coatings was evaluated
by micro-Raman spectroscopy after 120 h exposure to 3.5 wt% NaCl solution. Coatings generated after dispersion of corrosion inhibitor loaded clay
in hybrid sol–gel matrix have shown more promising corrosion resistance when compared to just the sol–gel matrix coatings, after prolonged exposure
to corrosive environment.
© 2018 Published by Elsevier B.V. on behalf of Chongqing University.
This is an open access article under the CC BY-NC-ND license. ( http://creativecommons.org/licenses/by-nc-nd/4.0/ ) Peer
review under responsibility of Chongqing University

Keywords: Self-healing coating; Halloysite nanoclay; Cationic corrosion inhibitors; Magnesium alloy AZ91D; Micro-Raman spectroscopy; Corrosion protection.

1. Introduction passive thin film of oxide are the main sources of localized
corrosion in magnesium alloys [3,4] . Hence, it is necessary to
Magnesium alloys are characterized by their low density (65% develop appropriate coating compositions/configurations for the
that of aluminum and 25% that of iron) and high specific strength corrosion protection of magnesium alloys. The con- ventional
which make them valuable materials for components in coating techniques such as electrochemical plating, conversion
automobile and aerospace applications [1,2] . However, when coatings, anodizing, chemical vapor deposition, laser cladding,
compared to other metals and alloys, cor- rosion resistance of gas phase deposition and flame/plasma spray- ing, etc. have their
magnesium alloys is inadequate due to their high-chemical own limitations such as poor adhesion, less wear resistance,
reactivities (standard electrode potential: −2.37 V) and this limits difficult to obtain uniform and pore-free layer and environmental
the range of applications for mag- nesium and its alloys. The concerns [2] .
galvanic couples formed between secondary phases and the Thin (0.1–10 μm) sol–gel coatings is an alternative, eco-
matrix, as well as the damage of the friendly, attractive approach that has the potential to over- come
the aforementioned limitations of other techniques. The
∗ Corresponding author. thickness of coatings varies depend on the coating composi-
E-mail address: subasri@arci.res.in (R. Subasri). tions. Sol–gel coatings exhibit a great potential to provide bar-
https://doi.org/10.1016/j.jma.2018.05.003
2213-9567/© 2018 Published by Elsevier B.V. on behalf of Chongqing University. This is an open access article under the CC BY-NC-ND license. (
http://creativecommons.org/licenses/by-nc-nd/4.0/ ) Peer review under responsibility of Chongqing University
300 S.H. Adsul et al. / Journal of Magnesium and Alloys 6 (2018) 299–308
Fig. 1. (a) FESEM image and (b) TEM image, of as-received HNTs.
rier for corrosive environment and a good adhesion between metal
substrate and organic top coat [5–7] . Hybrid organic– inorganic
sol–gel coatings come with two advantages; firstly their ability to
form crack-free thick coatings with low-curing temperature and
secondly their flexibility to include additives for improving
coating properties [8] . However, only hybrid coatings cannot give
prolonged corrosion protection in case of any mechanical damage
to the coated surface. Some re- searchers have used sol–gel method
along with other con- ventional methods such as anodizing,
conversion coatings, etc. and sol–gel coatings modified with
doping agents, have achieved better corrosion protection for
magnesium alloys [9– 11] . Hu et al. [12] observed that molybdate
conversion coat- ing followed by multilayered silica sol–gel
coating on AZ91D substrate gave better protection as compared to
single layered porous molybdate conversion coating. Ecofriendly
coatings of Mg(8-hydroxyquinoline) 2 synthesized by chemical
conver- sion treatment in 8-hydroxyquinoline sodium solution at
room temperature have shown prolonged corrosion protection to
AZ91D substrates [13] . Composite coatings comprising of micro-
arc oxidation (MAO) with titanium organic polymer as sealing
agent were generated on AZ91D alloy. It showed that composite
coating gave more effective corrosion resis- tance than only MAO
coating, because of the latter having a porous structure [14] .
Number of approaches have been implemented to attain
effective corrosion protection on magnesium alloys [15,16] .
However, prolonged corrosion protection requires sustained
release of corrosion inhibiting additive materials, which can be
achieved either by introducing corrosion inhibiting materials
directly into the coating matrix or by encapsulating them into
suitable micro/nanocontainers [17–20] . Previ- ous studies [21,22]
have shown that the use of rare earth elements like cerium as
cationic corrosion inhibitors has been effective in improving the
corrosion resistance. Use of micro/nanocontainers for
encapsulating corrosion inhibiting materials is considered to be an
effective way to provide sustained release of inhibitor to obtain
self-healing ability in the coating. Naturally occurring halloysite
nanoclay (HNT) has been considered as most promising way of
encapsulating corrosion inhibiting materials. It comes with the
advantages such as non-toxic, cheap, easily available and can
accom- modate large amount of inhibitors [23–26] . Previous
studies [27] reveal that only benzotriazole was used as corrosion
inhibitor loaded into halloysite nanotubes for corrosion protection
of magnesium alloys. Joshi et al. [28] confirmed that corrosion
inhibitor has got loaded inside the lumen of HNTs by applying
vacuum evacuation. However, there are no reports on magnesium
alloys with cationic corrosion inhibitors such as Ce 3 + and Zr 4 +
loaded into nanocontainers other than our earlier work [29] .
Hence, the main objective of present work was to study the
effect of addition of halloysite clay nanotubes loaded with
cationic corrosion inhibitors Ce 3 + and Zr 4 + into hybrid organic–
inorganic matrix sol upon exposure to 3.5 wt% NaCl solution.
2. Materials and methods
2.1. Substrate
Magnesium alloy, AZ91D coupons of dimensions
2.5 cm × 2 cm and with chemical composition in wt% Al- 9.14;
Zn-0.86; Mn-0.30; Cu-0.09; Si-0.08; Fe-0.01; Ni-0.01 and rest
Mg, were used as the substrates. All substrates were
mechanically ground successively to 1000 grit with silicon
carbide (SiC) papers followed by repeated degreasing with
acetone for 30 min and were finally dried in air.
2.2. Sol synthesis and coating deposition
Halloysite nanotubes (HNTs) with lumen diameter of ∼10 nm
were etched in 1 M H 2 SO 4 (SD Fine Chemicals, India, 98%) for
3 days at 60 °C, followed by washing with deionized water and
drying, in order to get enlarged lumen diameter [24] . Corrosion
inhibitors, cerium nitrate hexahydrate (Loba Chemie, India,
99.9%) and zirconium n-propoxide (Gelest Inc., USA, 70% in
propanol) were taken in molar ratio of 1:23, and added to the
etched HNTs. The mixture was then dried in vacuum desiccator.
The organic–inorganic
 S.H. Adsul et al. / Journal of Magnesium and Alloys 6 (2018) 299–308
Fig. 2. (a) EDS analysis of as-received HNTs, (b) EDS analysis of loaded HNTs
and (c) pore volume vs. pore diameter for as-received and loaded HNTs.
hybrid matrix (abbreviated hereafter as MAT) sol was pre- pared
by hydrolysis of 3-Glycidoxypropyltrimethoxysilane (GPTMS,
Gelest Inc., USA, 98%) with tetraethoxysilane in molar ratio of
3:5:1 with 0.1 N HCl as catalyst. The ends of HNTs were stoppered
301
with polymeric microcapsules of urea- formaldehyde that were
synthesized using the procedure as described elsewhere [29] . The
self-healing (abbreviated here- after as SH) sol was synthesized by
dispersing 2 wt% of inhibitors loaded HNTs stoppered with
polymeric microcap- sules into the hybrid matrix sol. For
evaluating the effect of HNTs, as-received HNTs (without
inhibitors’ loading) were also dispersed in the matrix sol to obtain
a modified sol, ab- breviated hereafter as clay matrix (CM) sol.
Coatings were generated on AZ91D substrates by dip coat- ing
technique at a withdrawal speed of 1 mm/s followed by curing at
130 °C for 1 h in hot air oven. The coating thick- ness was measured
using a non-destructive coating thickness gauge (PosiTector®
6000 supplied by DeFelsko Corporation, USA) and was found to
be in the range of 3–5 μm.
The adhesion of MAT sol, CM sol and SH sol coatings on
AZ91D substrates was investigated by cross-hatch cutter as per
ASTM D3359-17 test procedure. The surfaces were scribed in the
form of 1 mm 2 grid lines. A pressure sensitive adhesive tape was
applied over the grid and pulled off rapidly at an angle close to 180
°. The samples were inspected for any removal of the coating using
optical microscope (Olympus BX51M).
2.3. Transmission electron microscopy, scanning electron
microscopy and BET pore volume analysis
Transmission electron microscopy (TEM, Tecnai 200 G2 FEI,
Netherlands) was used to confirm the lumen diameter and length
of the nanotubes. The length of nanotubes was also ascertained
using scanning electron microscope, Hitachi model-S3400 N.
BET surface area and pore volume analysis was carried out using a
Micromeritics ASAP 2020 surface area and porosimetry analyzer.
2.4. Weight loss measurements
Weight loss measurements were carried out on un-
coated/coated AZ91D substrates as per ASTM G31 [30] .
Uncoated and coated substrates of AZ91D were exposed to 3.5
wt% NaCl solution for 24 h, 72 h and 120 h. Substrates were
washed with deionized water and ethanol followed by immersion
in chromic acid (200 g/l) for 2 min to remove cor- rosion products
from the surface. The substrates were again washed with water and
ethanol to remove traces of chromic acid. The substrates were
weighed before and after exposure to NaCl solution and corrosion
rate was obtained from the weight loss values. The consistency of
measurements was checked by measuring the weight loss for three
samples each for uncoated and coated substrates.
302 S.H. Adsul et al. / Journal of Magnesium and Alloys 6 (2018) 299–308

Fig. 3. Adhesion test micrographs of MAT sol coated (a) and (b), CM sol coated (c) and (d) and SH sol coated (e) and (f) substrates before putting on tape
and after removal of tape.
2.5. Micro-Raman spectroscopic analysis
Micro-Raman spectroscopic analysis was carried out for bare
and SH sol coated substrates in the scribed area before and after
120 h exposure to 3.5 wt% NaCl solution. The data were acquired
using Horiba Jobin Yvon-Lab Ram HR-800 Raman spectrometer
with Argon ion laser of 514 nm as the light source over the scan
range of 100–1000 cm −1 .
2.6. Electrochemical tests
Potentiodynamic polarization and electrochemical impedance
spectroscopy measurements were carried out using
Electrochemical Analyzer (CH instruments Model 600E series).
A three-electrode system comprising of sat- urated calomel
electrode (SCE) as reference electrode, platinum electrode as
counter electrode and the coated substrate as working electrode
with exposure area of 1 cm 2 was used. The electrochemical
impedance spectroscopy (EIS) was carried out over a frequency
range of 1 MHz to 0.01 Hz using AC signal of 10 mV amplitude.
The potentiodynamic polarization and open circuit potential
measurements were carried out on AZ91D substrates after
 S.H. Adsul et al. / Journal of Magnesium and Alloys 6 (2018) 299–308 303

different time exposures in 3.5 wt% NaCl solution. The
potentiodynamic polarization measurements were carried out at
scan rate of
0.8 mV/s. The surface morphology of uncoated and coated
area analysis. Pore volume as a function of pore diameter shown
in Fig. 2 (c) confirmed that in case of inhibitor loaded HNTs
pore volume has substantially reduced by 80%. Lit- erature
studies [23–28] have also revealed that the corrosion inhibitor
has got loaded in to the lumen of HNTs using vac- uum
evacuation.

Fig. 4. Comparison of corrosion rates of uncoated and coated substrates after

different time of exposure in h.

Fig. 5. Equivalent electric circuits used to fit EIS data for (a) bare and (b) coated
substrates.

substrates was observed using SEM after 120 h exposure to 3.5

wt% NaCl solution.

3. Results and discussion

3.1. Transmission electron microscopy, scanning electron

microscopy and BET pore volume analysis

The morphology of as-received HNTs observed through

FESEM and TEM is shown in Fig. 1 (a) and (b). As-received
HNTs have shown a tubular structure with lumen diameter of
∼10 nm, with lengths varying between 0.1 and 0.5 μm.
Elemental analysis of as-received HNTs confirmed the
composition to be alumino silicate as shown in Fig. 2 (a)
whereas elemental analysis of loaded HNTs shown in Fig. 2 (b)
confirmed the presence of corrosion inhibitors. The
confirmation of loading of corrosion inhibitors in the lumen of
HNTs was confirmed by using BET pore volume and sur- face
Fig. 6. Nyquist plots for bare and coated AZ91D substrates after (a) 24 h,
304 S.H. Adsul et al. / Journal of Magnesium and Alloys 6 (2018) 299–308

(b) 72 h and and (d)) had up to 35% of the removed coated area after the tape
(c) 120 h exposure to 3.5 wt% NaCl solution.
was removed and the adhesion of these coatings was ranked as 2B.
Table 1
Tafel fitting parameters after fitting of potentiodynamic polarization measure-
ments on bare and coated AZ91D substrates for different times of exposure in 3.5 3.3. Weight loss experiments
wt% NaCl solution.
Sl. no. Exposure time Substrate E corr (V) (vs. SCE) I corr (A/cm 2 Weight loss measurements provide more realistic informa- tion
(h) )
on the stability of coatings and corrosion resistance of test
01 24 Bare
MAT substrates. In this case, corrosion rate is calculated for bare and
CM coated AZ91D substrates in 3.5 wt% after 24 h, 72 h and 120 h. The
SH following formula was used for cal- culating corrosion rate in
02 72 Bare millimeter per year (mmpy) [30] :
MAT
CM
SH 8 . 76 × 10 4 × w
Corrosion rate = × × (1)
tAρ
where w is weight loss in grams (g), t is exposure time in hours
(h), A is exposed area in cm 2 and ρ is density of the alloy in g/cm
3
.
03 120 Bare Fig. 4 depicts the corrosion rate of bare, MAT sol coated, CM
MAT sol coated and SH sol coated substrates after 24 h, 72 h and 120 h
CM
of exposure to 3.5 wt% NaCl solution. It can be ob- served that,
SH
MAT sol and SH sol coated substrates shown least corrosion rate
up to 24 h of exposure indicating the barrier property of coating.
However, this barrier property gets de- pleted after further
exposure to corrosive medium and thereby showing increase in
corrosion rate. Whereas in case of bare substrates, formation of
thin oxide layer on the surface pre- vents the corrosive attack till
72 h of exposure. After 120 h, it can be discerned that corrosion
rate is least for SH sol coated substrates, clearly indicating that
there is an effect of the ad- dition of inhibitor loaded clay
nanotubes into the matrix sol unlike CM sol coated specimen
where very high-corrosion rate was observed.

3.4. Electrochemical impedance spectroscopy (EIS) and

potentiodynamic polarization

EIS studies were carried out on bare and coated AZ91D

substrates after 24 h, 72 h and 120 h exposure to 3.5 wt% NaCl
Fig. 7. Comparison of charge transfer resistance of uncoated and coated substrates
solution. Suitable electrical equivalent circuit was se- lected for
obtained from EIS fitted data. measuring and analyzing impedance of uncoated and coated
substrates as shown in Fig. 5 .
Here, the charge transfer resistance ( R ct ) is in parallel with
3.2. Adhesion test
electrical double layer capacitance (CPE edl ) that is in series with
coating resistance ( R coat ). C coat corresponds to coating
Fig. 3 shows images obtained using optical microscope for
capacitance. Here, constant phase element is preferred over pure
coated substrates after carrying out adhesion test using cross-
capacitor as the Nyquist plots are deviating from ideal behavior.
hatch cutter. The MAT sol coatings on AZ91 ( Fig. 3 (a) and (b))
The value of pseudo capacitance is calculated from following
have shown very smooth edges of cut after the tape was peeled off.
expression:
The adhesion of the coatings was adjudged as rank 5B, which
represented best adhesion property according to ASTM D3359 C = ( Q 0 × R) (1 ÷n) (1 ÷ R) (2)
[32] . Similar case was observed with SH sol coatings ( Fig. 3 (e)
and ( f)), where none of the edges of coating were detached and
adhesion was ranked as 5B. How- ever, CM sol coatings ( Fig. 3 (c)
 S.H. Adsul et al. / Journal of Magnesium and Alloys 6 (2018) 299–308 305

where C is pseudo capacitance in F/cm 2 ; Q 0 is constant phase
element in S-sec n /cm 2 ; n is frequency factor and R is resis- tance
in Ω .
The Nyquist plots for bare and coated AZ91D after differ- ent
exposure times to 3.5 wt% NaCl solution are shown in Fig. 6 .
After 24 h of exposure, SH sol coated substrates ex- hibited
highest impedance values in low-frequency region, in- dicating
higher corrosion resistance for SH coated substrates. However,
the corrosion resistance of SH sol coated substrates reduced after
72 h of exposure which may have occurred due to loss of barrier
property of coatings. Further exposure of SH coated substrates
depicted higher impedance values due to formation of passive
layer of cerium and zirconium oxides after release of corrosion
inhibitors from HNTs. This can be ascertained from Fig. 7
showing the charge transfer resistance
306 S.H. Adsul et al. / Journal of Magnesium and Alloys 6 (2018) 299–308
 S.H. Adsul et al. / Journal of Magnesium and Alloys 6 (2018) 299–308 307

Fig. 8. SEM images of bare (a) and (b), MAT sol coated (c) and (d), CM sol coated (e) and (f) and SH sol coated (g) and (h) AZ91D substrates before and after 120 h of
exposure to 3.5 wt% NaCl solution.
of uncoated and coated substrates as a function of different broad peaks at 254 cm −1 and 446 cm −1 before exposure to 3.5 wt%
exposure times obtained from EIS fitting data. NaCl solution. These peaks cor- respond to MgO and Mg(OH) 2 on
MAT sol coated substrates exhibited some resistance to scribed area. The spectrum also shows peaks at 633 cm −1 ; 752 cm
corrosion similar to SH sol coated substrates, but it lasts only until −1
due to Al 2 O 3 and
the barrier properties of coatings remains intact. Among the coated
substrates, CM coatings exhibit the least corrosion resistance. The
reason for this can be attributed to the fact that the HNTs do not
have the favorable aspect ratio for dis- persion in the matrix sol. A
similar investigation by Huttunen- Saarivirta et al. who dispersed
HNTs in an epoxy matrix and studied the corrosion resistance of
coatings generated from the modified epoxy formulation observed
that HNTs were distributed randomly on the coating surface and
hence, not completely embedded in the coating matrix. This
resulted in a less homogeneous coating morphology [31] . Thus,
CM sol coated substrates have shown the least impedance values
due to porous nature of coatings and coatings were also seen to
have a tendency to crack, as seen from the SEM images shown in
Fig. 8 (f), which allows corrosive medium to diffuse through. The
poor adhesion strength of coatings is another factor that affected
the corrosion resistance of CM sol coat- ings as specified earlier in
Section 3.2 . Though according to the SEM analysis, the SH
coatings also exhibit cracks due to the presence of clay particles,
the corrosion resistance is not affected due to release of corrosion
inhibitors from the clay nanotubes in the vicinity of the cracks.
The results of potentiodynamic polarization analysis for
uncoated and coated substrates after immersion in 3.5 wt% NaCl
for 24 h, 72 h and 120 h, shown in Fig. 9 showed simi- lar behavior
as seen from results of EIS studies. The corrosion currents and
corrosion potentials for different exposure times in 3.5 wt% NaCl
solution are shown in Table 1 . The corrosion potentials were
calculated using Tafel extrapolation method. However, corrosion
potential tends to reduce after 72 h of exposure in case of SH sol
coated substrates because of loss of barrier property of coatings
and bare substrates found to be showing more positive corrosion
potential because of for- mation of thin film of oxides as shown in
Fig. 9 (b). Fig. 9 (c) shows polarization data after 120 h of exposure
to 3.5 wt% NaCl solution. The corrosion current for SH sol-based
coat- ings is least after 120 h of exposure, due to self-healing prop-
erties obtained from inhibitor loaded nanotubes. This confirms
that inhibitor loaded nanoclay-based coatings are capable to
provide prolonged corrosion protection. These results are fur- ther
corroborated with micro-Raman spectroscopic analysis.

3.5. Micro-Raman spectroscopic analysis

Micro-Raman spectroscopic analysis was carried out on bare

and SH sol coated AZ91D substrates before and after 120 h
exposure to 3.5 wt% NaCl solution in the scribed area. The spectra
of uncoated and coated substrates before and after exposure are as
shown in Fig. 10 . In case of bare substrates, the spectrum shows
308 S.H. Adsul et al. / Journal of Magnesium and Alloys 6 (2018) 299–308

Fig. 9. Potentiodynamic polarization data for uncoated and coated substrates after
24 h, (b) 72 h and (c) 120 h exposure to 3.5 wt% NaCl solution.
 S.H. Adsul et al. / Journal of Magnesium and Alloys 6 (2018) 299–308 309

Fig. 10. Micro-Raman spectroscopic analysis of bare AZ91D (a) before exposure; (b) after exposure and coated AZ91D (c) before exposure; (d) after exposure
to 3.5 wt% NaCl solution for 120 h. erties of the HNT-based self-healing coating [29] . For the first
time, micro-Raman spectroscopic studies have been car- ried
out on self-healing sol coated substrates, after scribing and
380 cm −1 due to ZnO on the scribed area ( Fig. 10 (a)). Broad
exposing to corrosive medium. The phase composition on the
nature of peak indicated that very thin layer of oxides has
scribe after exposure to NaCl solution could be unequiv- ocally
formed on the substrates. However, after 120 h exposure to 3.5
confirmed by micro-Raman spectroscopy to be CeO 2 and ZrO 2
wt% NaCl solution, sharp and high-intensity peak was observed
. It could be concluded that in addition to using scan- ning
at 254 cm −1 on scribed area which indicated that the crystalline
electrochemical techniques, micro-Raman spectroscopy can
phase of oxides has formed ( Fig. 10 (b)) [33] .
also be employed to confirm the self-healing properties of the
SH coated substrates in scribed area ( Fig. 10 (c)) have shown
coatings.
the appearance of MgO, Mg(OH) 2 at 254 cm −1 and ZnO at 393
cm −1 before exposure to NaCl solution. After 120 h of exposure
4. Conclusion
( Fig. 10 (d)), sharp peaks at 233 cm −1 and 560 cm −1 correspond
to ZrO 2 ; peak at 277 cm −1 corresponds to MgO, whereas peak
Halloysite nanotubes loaded with cationic inhibitors Ce 3 + /Zr 4
at 449 cm −1 corresponds to CeO 2 in scribed area [34,35] . This +
dispersed in hybrid matrix sol provide prolonged corrosion
indicates that inhibitor has got re- leased into the scribed area
protection due to the controlled release of inhibitors, when
further confirming the self-healing action.
exposed to corrosive environment. Hybrid matrix sol coatings
In our earlier investigations, scanning vibrating electrode
were also found to be effective to provide barrier properties and
technique (SVET) was used to confirm the self-healing prop-
310 S.H. Adsul et al. / Journal of Magnesium and Alloys 6 (2018) 299–308

retained this property until the coatings remain unblemished for
certain duration of exposure, as confirmed from electrochemical
measurements. HNTs without loading of any corrosion inhibitors
were found to be affecting the barrier properties of hybrid matrix
sol, thereby deteriorating the corrosion resistance. The
anticorrosive and self-healing properties of SH sol coated
substrates could be confirmed with EDS analysis after weight loss
measurements and micro- Raman spectroscopic analysis. The use
of cationic corrosion inhibitors loaded into naturally occurring
halloysite clays can be used as a self-healing material as an
additive to any hybrid sol–gel matrix as well as to paints to improve
their corrosion protection properties.
Acknowledgements
The authors would like to thank Director, ARCI, Hyder- abad
for the constant encouragement and support throughout the entire
duration of work. The authors would like to thank G.V.R. Reddy
for the SEM-EDS analysis. Swapnil H. Adsul and R. Subasri
would like to acknowledge the financial sup- port from SERB,
DST for the funding provided through grant number
SB/S3/ME/007/2014 .
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