Chapter 1
Introduction
The most common loss an industry faces is loss of metal due to corrosion. In past few years,
inorganic-organic hybrid films have been used to improve the performance of anti-corrosive coating
on different metal substrates. Extensive study on silane chemistry is still being carried out to
improve performance of such coatings to protect metal substrate against corrosion. Organo
functional silanes are silane based chemicals bearing organic as well as inorganic moieties in a
single molecule. The general structure is given as (RO)3SiY, where OR is a hydrolysable alkoxy
group and Y is organo functional group, such as, peripheral epoxy group active amine group, thiol
group etc. One of the distinguishing features of silane compounds is that even a small amount of
silane can offer major enhancement of the adhesion between polymeric matrices and the metal
surface. In general, the silanes need to be hydrolyzed in dilute aqueous solution prior to application.
However these thin films of silanes are too brittle and cannot provide long term protection. Initially
they act as physical barrier towards permeation of water and corrosive ions[1].Epoxy resins are
widely used in protective coating, adhesive and encapsulating material due to their strong chemical
resistance adhesion and good processing characteristics. However, the epoxy resin cannot provide
satisfactory result in humid condition due to its hydrophilic nature. The high water uptake tendency
of epoxy resins restricts its application. Hence, to overcome the problems associated with silane film
and epoxy film, researchers have explored the improved performance of hydrolyzed silane modified
epoxy films in past decades. This kind of epoxy-silane hybrid leads to remarkable improvement of
adhesion as well as anti-corrosive characteristic due to the fact that higher Si-O bond energy
promotes strong adhesion and organic polymer backbone offers additional improvement of barrier
property of thin silane film and formation of crack free three-dimensional network.
The current work involved designing of epoxy-silane hybrid coatings to investigate their anti-
corrosion performance and adhesion on galvanized steel. Silanes with alkoxy group, epoxy group,
amine group and thiol group were used to modify epoxy polymer to explore the role of
functionalities in the performance of designed hybrid coatings. The silanes were added at three
different concentrations (1 wt%, 3 wt% and 5 wt%) into epoxy coating to assess the effect of
concentration on anti-corrosion and adhesion properties of the coating films.
It was found that due to the grafting of sol-gel coatings onto organic polymer backbone, the
adhesion property and anti-corrosive performance did improve remarkably as compared to non
1
grafted epoxy polymer alone. Also, silane concentration of1 wt% and 3 wt% in epoxy polymer
backbone led to improvement in both anti corrosive property and adhesion strength. Further increase
of silane concentration to 5 wt% led to deterioration of the protective property of the films. This
drop in performance can be attributed to excessive consumption of epoxide groups in epoxy resin
through crosslinking reaction with amino and thiol functionalities present in silane. Moreover, it was
observed that amino silane showed superior performance compared to thiol silane. The poor
performance of thiol silane grafted epoxy coating could be attributed to some chemical
incompatibility of hydrophobic and non-polar sulfur silane moiety and hydrophilic and polar water-
borne epoxy polymer backbone. Additionally, these coatings do have benefits of low VOC and are
free from toxic and carcinogenic elements which are the basic requirements of a coating for
compliance with safety, health and environmental regulations.
Table 1: Composition of epoxy-silane hybrid coating and their nomenclature[4]
FORMULATION NAME
Epoxy polymer + coating I(1wt%) Hybrid IA
Epoxy polymer + coating II(1wt%) Hybrid IIA
Epoxy polymer + coating III(1wt%) Hybrid IIIA
Epoxy polymer + coating I (3wt%) Hybrid IB
Epoxy polymer + coating II(3wt%) Hybrid IIB
Epoxy polymer + coating III(3wt%) Hybrid IIIB
Epoxy polymer + coating I(5wt%) Hybrid IC
Epoxy polymer + coating II(5wt%) Hybrid IIC
Epoxy polymer + coating III(5wt%) Hybrid IIIC
2
Chapter 2
Literature review
In this current study, epoxy-silane hybrid coatings were designed to investigate their anti-
corrosion performance and adhesion on galvanized steel. Silanes with alkoxy group, epoxy
group, amine groupand thiol group were chosen to understand the role of functionalities in the
performance of designed hybrid coatings. Moreover, the silanes were added at three different
concentrations into epoxy polymer to asses the effect of concentration on anti-corrosion and
adhesion properties of the coating films. From scanning electron microscopic (SEM) images, we
observed a uniform coating without any agglomeration of coating particles over galvanized steel
substrates. The corrosion performance of casted and cured films was evaluated by using
potentiodynamic polarization and AC impedance spectroscopy method .The physical properties,
such as, thermal behavior and thermo-mechanical behavior were studied using differential
scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) respectively
.The adhesion strength between coating films and galvanized steel substrate was checked by ‘pull
off adhesion test.
Fujian Tang, Yi Bao, Yizheng Chen, Yan Tang, Genda Chen have done a detailed analysis and
tests on the microstructure, impact resistance, pull-off adhesion strength, and corrosion
resistances of duplex epoxy/enamel coating applied on steel plates are investigated
experimentally. In comparison with those of individual epoxy and enamel coatings, the duplex
coating has lower adhesion strength, higher impact resistance, higher short-term and long-term
corrosion resistances both in 3.5 wt% NaCl solution and saturated Ca(OH)2 solution with various
chloride concentrations. This is because the outer epoxy fills the micro pores in the inner enamel.
Impact induced damage significantly reduces the corrosion resistances of epoxy and duplex
coatings but has little effect on the corrosion resistance of enamel coat.
M. Bahramia,b, Z. Ranjbarb,c,⁎, R.A. Khosroshahia, Sh. Ashharid in their research prepared
epoxy based thermal insulations three types of hollow glass microspheres with different particle
sizes 70, 115, and 170 μm. Thermal conductivity of coatings in the absence and presence of
hollow spheres were evaluated. Thermal conductivity of microsphere containing insulations was
found to be much less than epoxy coatings. Hollow spheres with 170μm diameter showed better
3
insulating properties. Epoxy thermal insulations were exposed to accelerated cyclic corrosion test
conditions, and then corrosion resistance reduction of coatings was evaluated by electrochemical
impedance spectroscopy. Results showed that microspheres can not only improve insulating
properties but also raising corrosion protection features of epoxy coating during 37 days of
exposure to cyclic corrosion conditions. Impedance modulus at low frequency (0.01 Hz) of 170
μm hollow sphere containing epoxy coatings were 1.10 and 530 ohm cm2 after 37 days,
respectively
4
Chapter 3
Results
3.1 FT-IR analysis
Fig. 1 a–d depicts the FTIR analysis of pure epoxy coating and solgel modified epoxy coatings.
For pure epoxy resin, the band at 3500 cm−1was assigned to OH stretching [1]. The bands
around 2790 and 1390 cm−1are ascribable for CH3asymmetricand symmetric stretching
vibrations respectively. Peaks appearing at 2877 cm−1and 1465 cm−1are due to asymmetric and
symmetric stretching mode of CH2groups. The characteristic band for epoxy group appeared at
910 cm−1. The sharp band at 1246 cm−1was due to the ether band in epoxide group. The bands
at 840,1510 and 1630 cm−1are assigned to substituted aromatic ring in epoxy ring. The FTIR
spectra of sol-gel modified epoxy resin are very much similar to that of pure epoxy resin [1].
However, some differences could be clearly identified. The peak intensity of secondary hydroxyl
groups decreased significantly after grafting with solgel polymer. This indicated that the
hydroxyl groups were consumed in modification reaction leading to decrease in intensity of the
absorption peak [1]. Additionally, in the modified epoxy resins, few intense peaks in the range of
1100–1200 cm−1couldbe observed, which can be assigned to the formation of Si-O-Si and Si-O-
C bond. These observations suggested that the solgel coating solutions were successfully grafted
to epoxy resin.
3.2. DSC analysis
In the DSC curves of pure epoxy and hybrid coatings (see Fig. 1a–c), it could be observed that
the glass transition temperatures of hybrid A and Hybrid C series of coatings decreased slightly
as compared to pure epoxy coating. Only hybrid IIB system showed higher glass transition
temperature than pure epoxy coating by only 1◦C. 60.43◦C. However, such a small increase is
insignificant to impart better thermal stability of the hybrid network. The glass transition
temperatures of pure epoxy and all the hybrid coatings are tabulated in Table 2. This drop in
performance in case of thermal stability of the hybrid systems can be attributed to the
incorporation of additional organic groups in hybrid network.. A small increase of glass transition
temperature in case of hybrid IIB system can be ascribed to better crosslinking of amino group
5
with epoxy polymer backbone. It was clear from the values of glass transition temperatures that
among the three hybrid systems, Hybrid B series showed thermal stability superior to that of
other two systems. This indicates better crosslinking between the sol-gel network and polymer
backbone for grafting at 3 wt% concentration.
Table.2. Glass transition temperature of pure epoxy and different hybrid systems [4]
Coating Sample Glass transition temperature(◦C)
Pure Epoxy 59.63
Hybrid IA 53.67
Hybrid IB 58.89
Hybrid IC 53.29
Hybrid IA 52.55
Hybrid IB 60.43
Hybrid IC 57.08
Hybrid IA 53.00
Hybrid IB 57.08
Hybrid IC 54.94
6
Fig.1.(left) FTIR spectrum of pure epoxy and hybrid coatings.
(right) DSC overlay of pure epoxy and hybrid coatings.[4]
7
3.3 DMTA analysis++++
The DMTA curves of the hybrid systems have been depicted in Fig. 3a–c. Study of DMTA
curves again confirmed the best performance of Hybrid IIB system. Though the glass transition
temperature (Tg) of pure epoxy coating (86.63◦C, ) was higher than that of Hybrid IIB system
(81.16◦C) but due to grafting of sol-gel coating into epoxy polymer the storage modulus of
hybrid IIB system (1693.53 MPa) increased remarkably as compared to pure epoxy coating
(1345.89 MPa) at 35◦C. This can be ascribed to excellent crosslinking between amino group in
sol-gel network and epoxy polymer backbone. The lowest storage modulus was shown by Hybrid
IIIA system with a value of around 430.72 MPa at 35◦C.For all sol-gel coating systems, the best
performance was obtained from hybrid B series, whereas hybrid A series gave the worst
performance. Hybrid C series gave an intermediate performance. This trend can be explained in
the terms of the amount of sol-gel coating grafted into polymer backbone. In hybrid A series of
coatings, the sol-gel polymer was present at 1 wt% only, which could not result in complete
crosslinking with the organic polymer back-bone. On increasing the amount of sol-gel polymer
from 1 wt% to3 wt%, the extent of crosslinking significantly increased, which was established by
the higher values of storage moduli values of hybrid B series of coatings. On further increase of
the amount of silane grafting to 5 wt%, the crosslinking process was hampered and as a
consequence, a decrease in storage moduli value was observed for Hybrid C series of coatings.
The numerical values of glass transition temperature and storage moduli values at three different
temperatures for all the coating systems have been listed in Table 2. On raising the temperature
from 35◦C to 100◦C, a sharp fall in storage moduli values could be noticed for all coatings. This
is probably due to the breakage of inter-chain association in polymeric network and deterioration
of physical crosslinking.
3.4 Surface morphology study
The surface morphology of pure epoxy coated steel samples has been shown in Fig. 2a. It is clear
from the image that the coating particles were agglomerated on the metal surface and smooth
uniform coating film was not achieved with pure epoxy polymer. But on grafting with sol-gel
coatings into epoxy backbone, the smoothness of coating film improved remarkably. The most
uniform, smooth and defect free coating surface was obtained from coating II (Hybrid IIA,
Hybrid IIB and Hybrid IIC). Thorough crosslinking of amino group with epoxy group in organic
8
polymer backbone led to smooth film without any undesirable agglomeration of coating particles,
pores and cracks (see Fig. 2b & c). Coating I hybrid series (Hybrid IA, Hybrid IB and Hybrid IC)
films were not as smooth as coating II films. For Hybrid IA and Hybrid IB films, agglomeration
and some non uniformity could be noticed.
9
Fig.2. (a) Agglomerated coating particles on pure epoxy coated surface (left) and magnifying view of
agglomerated particles (right). (b) Cross sectional view of Hybrid IIA system (left) and uniform
surface morphology of Hybrid IIA system (right). (c) Cross sectional view of Hybrid IIB system
(left) and uniform surface morphology of Hybrid IIB system (right)[4]
10
Fig.3. (a) DMTA overlay image of Hybrid IA, Hybrid IB and Hybrid IC. (b) DMTA overlay image
of Hybrid IB, Hybrid IIB and Hybrid IIIB. (c) DMTA overlay image of Hybrid IC, Hybrid IIC [4]
11
3.5 Electrochemical analysis
3.5.1 Potentiodynamic polarization study
Potentiodynamic polarization study gives useful information on coating’s ability to resist
corrosion against a voltage gradient. Fig. 4 represents potentiodynamic polarization curves for
pure epoxy coated steel samples at different interval of time. The polarization resistance of pure
epoxy coated sample at initial immersion period was found to be 271.22 k_ with corrosion rate of
0.0017 mmpy. With prolonged reaction with electrolyte solution, the corrosion rate steadily
increased with time and was found to be 0.0142 at the end of 360 h. For hybrid IA series, the
initial corrosion rate was0.0010 mmpy and polarization resistance was equal to 409.080kΩ. At
initial immersion period, corrosion rates of Hybrid IB and IC were found to be 0.00085 mmpy
and 0.0015 mmpy respectively (see Fig. 8a–c). From the corrosion rate values, it was again con-
firmed that the best result was obtained from hybrid IB series. On comparing the values of
corrosion rate obtained from pure epoxy and sol-gel grafted epoxy coating, it was understood that
the corrosion rate decreased by ten times due to the incorporation of silane network in epoxy
polymer backbone at 3 wt% concentration .Hybrid IA and Hybrid IC coating gave almost similar
anti corrosion performance to that of pure epoxy coating at initial immersion period. However, at
the end of 360 h, performance of pure epoxy coating dropped drastically. This can be ascribed to
the formation of defects in coating matrix. Due to hydrophilic nature of organic polymer
backbone, it no longer provided strong resistance towards electrolytic solution. With longer
period of time, the electrolyte solution penetrated through coating matrix and reached the metal
surface to initiate the corrosion process. But surprisingly the sol-gel grafted epoxy coating
showed much better performance on prolonged contact with NaCl solution. The corrosion rates
were ten times lower at the end of 360 h than that of epoxy coating. This is ascribed to compact
coating network achieved from crosslinking between organic functionality in silane moiety and
epoxy polymer backbone and better adhesion to substrate surface through the reaction of
hydrolyzed OH group of silane and metal oxide/hydroxide group.
Now, if we come to the comparative aspect between three sol-gel modified epoxy coating
systems, a clear conclusion can be drawn about the superior performance of amino silane grafted
epoxy coatings as compared to the other two systems. At initial immersion period, the corrosion
rates of hybrid IIA, hybrid IIB and Hybrid IIC were 0.0006 mmpy, 0.0001 mmpy and 0.0003
12
mmpy respectively. The potentiodynamic polarization curves obtained from coating II hybrids at
different intervals of time have been depicted in Fig. 9a–c. It is evident that amino silane grafted
epoxy coating provided far better results than other coating systems. The amino group present in
the silane network took part in crosslinking reaction with the epoxy group present in both silane
moiety (inGPTS) as well as in epoxy polymer backbone. Due to polar nature of both amine group
and epoxy backbone, an additional stability was obtained from compatibility of two phases.
However, the performance deteriorated with time and at the end of 360 h, the corrosion rate
decreased from 1 × 10−4 mmpy to 1 × 10−3 mmpy in case of Hybrid IIB system. In coating III,
thiol group ( SH) is present as organic functional group. As thiols were not as reactive as amine
for crosslinking reaction with epoxy group, a compact network could not be achieved with MPTS
silane and epoxy polymer. Due to this incompatibility, much poorer anticorrosion performance
could be noticed in case of hybrid IIIA, hybrid IIIB and hybrid IIIC (See Fig. 10a–c). This trend
was clear from the polarization data listed in Table 3.
Table.3. polarization data for bare steel surface at end of 360 hours
Sample Time Ecorr(V) Icorr βa(mV/dec) βc(mV/dec) Corrosion
(h) rate(mmpy)
Bare steel 360 -0.66 17.13 260.57 195.71 1.99E-1
Pure epoxy 360 -0.21 1.23 148.69 98.46 1.42E-2
Hybrid IA 360 -0.20 0.50 110.56 130.14 5.81E-3
Hybrid IIA 360 -0.13 0.20 67.05 79.44 2.31E-3
Hybrid IIIA 360 -0.27 1.87 178.49 377.54 2.18E-2
Hybrid IB 360 -0.19 0.78 160.60 111.02 9.0E-3
Hybrid IIB 360 -0.17 0.11 92.42 97.48 1.30E-3
Hybrid IIIB 360 -0.19 0.75 106.33 186.55 8.70E-3
13
Hybrid IC 360 -0.23 0.41 78.94 108.68 4.70E-3
Hybrid IIC 360 -0.23 0.44 47.50 67.02 5.11E-3
Hybrid IIIC 360 -0.21 0.70 73.81 142.41 8.11E-3
The coating properties such as corrosion potential(Ecorr) and corrosion current densities(Icorr)
were calculated by tafel method[2] . The polarization resistance was estimated by stern-Geary
equation(1)
𝐵
Icorr=𝑅𝑝 (1)
Fig.4. Potentiodynamic polarization curves of pure epoxy at different intervals of time.
Where Rp is the polarization resistance and B is the proportionality constant obtained from
anodic ( βa) and cathodic ( βc) region of Tafel plot as shown by Eq. (2).
14
𝛽𝑎.𝛽𝑐
𝐵 = 2.3(𝛽𝑎+𝛽𝑐) (2)
All the coated samples were immersed into electrolyte solution and investigated for 360 h. Of all
type of coatings, Hybrid B series gave the best performance as indicated by low corrosion current
and corrosion rate. However, as expected, the values of corrosion current and corrosion rate
increased with time. This is due to the fact that prolonged reaction between coated surface and
corrosive electrolyte solution led to the formation of defects in coating matrix. Water molecules
and chloride ions penetrated through defects formed in coating network and initiated corrosion
process on metal surface [16].
3.6. Salt spray test
The results obtained from salt spray test are completely in accordance with electrochemical
investigation. Of all the coating systems, the best performance was obtained from hybrid B
series. Images of test panels coated with pure epoxy, hybrid IB and hybrid IIB at the end of 1200
h salt spray exposure have been shown in Fig 5 a&b. Due to more hydrophilic nature of epoxy
polymer, formation of severe blisters could be noticed on pure epoxy coated surface (see Fig.5a.).
Hybrid IB and hybrid IIB systems were comparatively in better condition (see Fig.5a). Though in
case of hybrid B series coated panels, corrosion of zinc oxide/hydroxide surface could be clearly
understood from the formation of white rust on coated surface, but it was confirmed that the
corrosion process did not reach the underneath iron surface even after completion of 1200 h., as
we could not observe any red rust spot on the coated surface. On hybrid IIIB panels (not shown),
medium sized blister sand white rust spots could be observed at the end of 1200 h. Not only in
case of hybrid B series, but also in the case of hybrid A and hybrid C systems , no red rust was
observed at the end of 1200 h. But hybrid A and hybrid C coated panels were affected by blisters
and white rust to a greater extent as compared to hybrid B panels. An interesting fact was
observed in case of hybrid IIIC coating in salt spray test. After completion of 450 h, an adhesion
failure occurred and the coating film got peeled off the surface (see Fig.5b). This peeling off was
most probably due to poor wetting of substrate surface. With the increased vapor pressure of
NaCl solution in salt spray chamber and its aggressive corrosive action, the weak chemical
interaction between coating matrix and zinc surface as well as silane network and epoxy polymer
15
were destroyed and as a result, the coating film peeled off the surface. This also indirectly
confirms poor compatibility and crosslinking of thiol containing silane network and epoxy
backbone.
3.7 Pull off adhesion test
The pull-off adhesion data were nicely supported by electrochemical investigation study and salt
spray test results. The adhesion test results are listed in Table 4. The hybrid B series panels gave
much better results than other two hybrid series. Among the hybrid B series, hybrid IIB has
showed outstanding result. The pull-off adhesion strength of hybrid IIB was 8.95 MPa, whereas
the same for hybrid IB and hybrid IIIB were 6.89 MPa and 4.32 MPa respectively. This trend can
be explained in terms of superior interaction of amino silane network with both the metal
oxide/hydroxide layer and epoxy polymer backbone. Severe delamination was observed after
testing pure epoxy coated samples, hybrid IIIA and hybrid IIIC.
The failure observed in case of pure epoxy coated panel was found to be cohesive in nature.
But, hybrid IIIA and hybrid IIIC panels showed partial adhesive as well as partial cohesive
failure. The occurrence of both adhesive failure and cohesive failure can be attributed to poor
compatibility of thiol network and organic back-bone. The epoxy polymer was not bridged
with the metal surface through underlying silane network and hence, on applying a very little
force it peeled off the surface. Similarly due to poor crosslinking of silane network and
organic polymer network, the molecular attraction by which the particles are united
throughout the mass were affected and as a result, cohesive failure was observed in coating
matrix. For rest of the coating systems, occurrence of cohesive failure could be noticed. This
is because, on applying large amount of force, the intermolecular attraction and inter-chain
association in polymeric matrix was destroyed leading to the formation of cracks in coating
films.
16
Table.4. Pull off adhesion test and nature of failure observed on coated panels. [4]
Sample Adhesion strength (MPa) Nature of failure
Pure epoxy 4.12 Total cohesive
Hybrid IA 4.89 Total adhesion
Hybrid IIA 7.03 Total cohesive
Hybrid IIIA 3.29 partial cohesive & adhesion
Hybrid IB 6.89 Total cohesive
Hybrid IIB 8.95 Total cohesive
Hybrid IIIB 4.32 partial cohesive & adhesion
Hybrid IC 5.23 Total cohesive
Hybrid IIC 7.88 Total cohesive
Hybrid IIIC 3.58 partial cohesive & adhesion
17
Fig. 5. (a) Salt spray images of pure epoxy (left), Hybrid IB (middle) and Hybrid IIB (right) after
1200 h. (b) Salt spray images of pure epoxy (left) and adhesion failure of Hybrid IIIC coating film at
the end of 450 h. (right).
18
Chapter 4
Mechanism of corrosion protection and adhesion promotion.
Strong adhesion between two phases can be achieved from the provision of multiple, strong
linkages across the interface between two materials. This can be most readily achieved with the
help of bi functional molecules where, one functionality can bond with one phase and the second
functionality with other phase. If such a molecule is placed at the interface or capable of
migrating to that interface, then it can effectively ‘couple’ the two phases and is accordingly
known as ‘coupling agent’. Silane molecules were found to be promising coupling agent for
epoxy and polyurethane organic coating. The mechanism of this coupling activity of variety of
silane molecules is well documented in several available literatures [5]. All the silane molecules
can be considered as bi-functional molecule and composed of silane end and organic end. On the
silane end, generally alkoxy groups are attached and organic end contains reactive organic group
that can readily react with the organic polymer. Groups that are very much reactive towards
organic polymer and directly attached with silicon atom generally render the silane too unstable.
As a consequence, a bridging group R, often (CH2)n, where n is two or three is necessary. The
alkoxy groups that are directly substituted on silicon atom can be readily hydrolyzed under mild
condition to form silanol groups. These silanol groups can condense with other silanol groups to
form extended Si-O-Si network and hydroxylated inorganic surface to form M-O-Si linkages.
The formation of three-dimensional extended Si-O-Si network can effectively act as a physical
barrier towards corrosive agent and thereby offering protective performance towards metal
surface. On the other hand, through the formation M-O-Si linkages, improved adhesion property
can be easily obtained (see Fig. 16a & d).In order to act as a good ‘coupling agent’, on the
organic side strong chemical bonds must be formed between the organofunctional group of silane
and the reactive species in the polymer matrix. In many literatures, it has been reported that
amino andepoxy functional silanes are very much suitable for use with epoxy resin. Though some
researchers have reported the use of mercaptosilane as a coupling agent for epoxy resin but
satisfactory results were not obtained. Controlled compatibility of silane phase and organic phase
is crucial and the reactivity rate of silane organic functionality is also critically important. The
reaction rate must be identical to that of occurring within the polymer matrix (e.g. between
polyamide and epoxy; see Fig. 16b & c) so that the silane gets bonded to the epoxy polymer
19
before the latter’s reactive groups are consumed or immobilized. The superior performance of
amino silane as compared to mercapto silane can be easily justified by the above mentioned
reasons. Good compatibility of amino and epoxy backbone originated from polar nature of the
two phases. The amino group can easily participate in ring opening reaction of epoxy group to
form secondary alcohol. Due to moderate reaction rate, this ring opening reaction can take place
very easily leading to enhancement in crosslinking within polymer matrix. Many authors have
comprehensively reviewed addition reaction of epoxy resin with mercaptans. It has been reported
that thiols are not as reactive as amines. Specially, the curing reaction is not at all feasible in
absence of proper catalysis and at room temperature. Moreover, non-polar and hydrophobic
mercapto silane is not compatible with polar and hydrophilic epoxy polymer. Compatibility
afforded by the organo functional group allows the advantageous penetration of that group into
the organic polymer leading to the formation of crosslinked, three-dimensional compact coating
network. Such a compact coating matrix can act as a strong physical barrier towards corrosive
agents. Another important parameter that has to be optimized to achieve efficient coupling
activity is the amount of prehydrolyzed silane that has to be incorporated into organic matrix.
Degree of curing has got a marked effect on the stability of coating network. Over cured layers
will be too rigid and incompatible, while under-cured layers may dissolve in the resin and not be
available for bonding at the interface. This is why on increasing the silane con-centration from 1
wt% to 3 wt%, a remarkable improvement was noticed in both anti corrosion performance and
adhesion. But further increase of the concentration to 5 wt% led to formation of a rigid over
cured layer and hence the performance deteriorated.
20
Fig.6 (a) Probable reaction mechanisms of hydrolysis, condensation and surface coverage of Coating
(b) Condensation reaction between the dimeric fatty acid and polyamine to form polyamide cross
linker. (c) Curing reaction of epoxy resin with polyamide cross linker. (d) Reaction of amino group
with epoxy group and interaction of hydrolyzed silanol group with metal surface; silane acting as
bridging agent between metal surface and organic polymer matrix.[5]
21
Chapter 5
Conclusion
In the present study, water based epoxy coating has been grafted with three types of sol-gel
coating with different organic functionality. Pre-hydroyzed silane solutions were added in three
different concentrations into epoxy coating. It was found that the amino containing sol-gel
grafted epoxy coating offered the best result when added at 3 wt% concentration. The
performance of mercapto silane grafted epoxy coating was inferior to that of other two systems.
This can be clearly explained in terms of compatibility of silane network with epoxy backbone.
From both electrochemical study and salt spray test, it was found that amino containing sol-gel
grafted epoxy coating gave much better anticorrosion performance than thiol containing coatings.
The similar trend was observed in adhesion test too. The pull off adhesion strength in case of
amino containing coatings was also much higher than that of other systems. Superior
performance of amino-grafted sol-gel coating was also confirmed by uniform and defect free
surface morphology and higher storage modulus values obtained in DMTA analysis. We also
found that with increase of the amount of sol-gel coating from 1 wt% to 3 wt%,the corrosion
behavior and adhesion were improved, but on further increasing the silane content from 3 wt% to
5 wt%, drop in performance was noted. This can be ascribed to over curing of coating films and
formation of rigid and incompatible coating network.
22
References
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inhibition of corrosion of aluminum alloys.
[3] S. Bera, T.K. Rout, G. Udayabhanu, R. Narayan, Comparative study of corrosion protection
of sol–gel coatings with different organic functionality on Al-2024 substrate.
[4] Saheli Bera, T K Rout, G Udayabhanu, Water and epoxy-silane hybrid coatings for enhanced
corrosion and adhesion on galvanized steel
[5] M. Chaudhury, A.V. Pocius, Adhesion Science & Engineering -2 Surface Chemistry &
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23
