Progress in Organic Coatings 54 (2005) 317321

The effect of surface modification on the cathodic disbondment

rate of epoxy and alkyd coatings
M.K. Harun a , J. Marsh b , S.B. Lyon b,
a Faculty of Applied Sciences, MARA University of Technology, Malaysia
b Corrosion & Protection Centre, School of Materials, University of Manchester, UK

Received 3 May 2005; received in revised form 13 July 2005; accepted 14 July 2005

Abstract

Surface modification of carbon steel substrates using appropriate functionalised silanes was carried out to investigate their effect on the dry
and wet adhesion strength, and the cathodic disbondment rate, of coating binders based on epoxy and alkyd chemistries. Results show that
pre-treatment of the steel substrate with 3-glycidoxypropyltrimethoxy silane (3-GPS) enhanced the dry and wet adhesion of an epoxy-based
coating. Similarly, pre-treatment with 3-aminopropyltriethoxy silane (3-APS) enhanced the dry and wet adhesion of alkyd-based systems.
However, although pre-treatment with 3-GPS reduced the cathodic disbondment rate for epoxy by a factor of 3, no effect on the disbondment rate
for alkyd-based binders on substrates pre-treated with 3-APS was found. This strongly suggests that cathodic disbondment of epoxy proceeds
by disruption of interfacial bonds (i.e. at the binder/substrate interface) but that disbondment of alkyds proceeds by direct degradation of the
binder and that the interface plays little part in the process.
2005 Elsevier B.V. All rights reserved.

Keywords: Cathodic disbonding; Interfacial modification; Coatings performance

1. Introduction cathodic disbonding for an organic coating is not straightfor-

The relationship between the dry and wet adhesion and
the anti-corrosion performance of an organic coating is not
straightforward. Thus, although Funke [1] generalized the
claim that adhesion is performance, there are many systems
that demonstrate relatively poor adhesion but have excel-
lent anti-corrosion performance, e.g. coatings on phosphated
steel, Marsh et al. [2]. One primary mechanism for coating
failure derives from cathodic activity under an intact film. At
its most basic, such a disbonding process is derived from alka-
lisation at the cathode causing local destruction (hydrolysis)
of the chemical bonds between the coating and the air-formed
metal oxide/hydroxide present at the interface. Corrosion
inhibitors added to coatings that function to limit the kinetics
of the cathodic reaction are especially effective in prolonging
coating life [3]. Thus, the relationship between adhesion and
Corresponding author.
E-mail address: stuart.lyon@manchester.ac.uk (S.B. Lyon).
ward and most cathodic disbondment processes involve the
destruction of this region for example by chemical attack [4]
or other mechanisms [5].
This study was set up to model the effect of chemical modi-
fication of a steel substrate on coating adhesion and cathodic
disbonding rates. The premise here is that chemical func-
tionality is introduced onto the substrate by its reaction with
an appropriate functionalised silane. For a well-chosen sys-
tem, the coating chemistry should thus bond directly to the
substrate, enhancing local bond strength and resistance to
hydrolysis.
2. Experimental details
The substrates used in these experiments were carbon
steel panels, of dimension 15 cm 8 cm obtained from the
Q-Panel Co. The as-received panels were surface finished to
FEPA European P-Series #P150 or equivalent nominal grain
diameter of 90100 m. All samples were initially degreased

0300-9440/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2005.07.007
318 M.K. Harun et al. / Progress in Organic Coatings 54 (2005) 317321
with an anionic detergent solution before thoroughly rinsing
with deionised water. They were then twice rinsed in acetone,
with a final rinse in ethanol, prior to drying in a dust-free envi-
ronment at room temperature overnight. Three commercial
non-pigmented lacquers (6070% solids) were used for this
study: (a) a two-pack amine-cured epoxy, (b) a polyurethane
modified alkyd, and (c) a clear alkyd. All coatings were
obtained from H. Marcel Guest Ltd., Manchester, UK.
Pre-treatment was undertaken using functional silanes:
3-aminopropyltriethoxysilane (3-APS) for reaction with
binders based on polyurethane and alkyd chemistry, or 3-
glycidoxypropyltrimethoxysilane (3-GPS), for reaction with
the binder based on epoxy chemistry. Both of these chemicals
were obtained from Lancaster Synthesis at 9698% purity.
Prior to substrate pre-treatment, the silanes were dissolved
at 2% by volume in a 1:1 mixture ethanolwater mixture
and allowed to hydrolyse for 24 h prior to use. Substrate pre-
treatment was carried out by rinsing each panel for 30 s with
the appropriate silane solution from a wash bottle. After treat-
ment, they were allowed to dry at room temperature for 2 h
then immediately coated by draw bar, with the relevant binder,
to 100 m wet-film thickness (resulting in a dry-film thick-
ness of about 60 m). Coatings were allowed to cure for 24 h
at room temperature (1822 C) then post cured for 46 h at
4050 C.
Wet and dry adhesion tests were performed using a stan-
dard pull-off method: the hydraulic adhesion tester (HATE)
manufactured by Elcometer Ltd. Using this technique, small
dollies are attached to the coating surface using cyanoacry-
late adhesive. After the glue has set, the dollies are then
detached from the substrate with the maximum hydraulic
pressure registered being a direct measure of the adhesion
strength of the coating. Care was taken to ensure that the
locus of failure was located at the coating-metal interface:
thus, any results from samples that failed cohesively, or at the
dolly-coating interface, were discarded. Ten replicate tests
are carried out for each sample and exposure time in order to
obtain an effective measure of the experimental variability.
Cathodic disbonding tests were carried out conventionally
on coatings containing an artificially introduced defect. Thus,
a circular hole was mechanically milled in the coating down
to the substrate using a flat milling tool of diameter 1 mm.
Electrical connection was made to each panel using insulated
wire, and the panel was then masked at the edge and the rear
using wax, leaving the front coated surface with the defect
exposed. Six replicate panels for each coating/pre-treatment
system were polarized potentiostatically at 1000 mV versus
the standard calomel electrode (SCE) in 0.6 M NaCl solution.
Thus, the data obtained for each coating system presented
here is the arithmetic mean of these six readings.
In order to determine the area of coating disbonded, a
non-destructive test method was adopted. The difference in
appearance (shade) between the disbonded regions, com-
pared with the intact areas, was obvious and was used to
indicate the area of disbondment. The panels were removed
at set time intervals, were rinsed with deionised water, and
the disbonded area traced onto acetate film, which was then
cut and weighed. In order to accurately relate the weight to
an area of the film, a sample of thirty squares with an area of
1 cm2 each, were cut at random from six separate acetate films
of the same type. Five squares were obtained from each film.
Each of these squares was weighed and their mean value and
standard deviation was calculated. Finally, the mean value
obtained was used to calculate the actual area of delamina-
tion of the coating. At the end of the experiment, the samples
were removed from solution and the coatings cut radially
with a scalpel from the artificial defect in order to physi-
cally remove the de-bonded area. By this way, the location
of the delamination front was confirmed to correspond with
the visual difference in appearance [6,7].
3. Results
3.1. Cathodic disbonding of epoxy-polyamide coating
system
Pre-treatment of mild steel with 3-GPS increases the wet
adhesion strength of the epoxy system compared to the
untreated system. This can be clearly seen from the adhe-
sion pull-off values shown in Fig. 1. The overall increase
in the wet adhesion strength was maintained throughout the
whole duration of experiment with a significant improvement
(increase) in adhesion strength from initial immersion (5%
improvement) to 200 h of immersion (18% improvement).
The standard errors in the data (for ten determinations) were
typically 0.15 MPa at each data point.
The cathodic disbonding tests on these systems were
conducted according to the method described earlier and the
results are shown in Fig. 2, where the standard errors in the
data (six determinations) were approximately 0.15 cm2 .
Although fresh new samples were prepared for this test, it
must be emphasized that in all the experiments, the thickness
of the coatings was kept constant to 5% of the overall
thickness.
Fig. 1. The adhesion strength of an epoxy coating as a function of immersion
time in 0.6 M NaCl solution on untreated and 3-GPS pre-treated carbon steel
substrates.
 M.K. Harun et al. / Progress in Organic Coatings 54 (2005) 317321 319

Fig. 4. The variation of disbonded area of a polyurethane-modified alkyd

coating on a carbon steel substrate with and without pre-treatment using
Fig. 2. The variation of disbonded area of an epoxy coating on a carbon steel 3-APS.
substrate with and without pre-treatment using 3-GPS.

The data show that there is a delay time [8] where no

immediate disbonding for both systems occurred. Disbond-
ment was first observed after 29 h for the untreated system
and about 60 h for the treated system. The results also indi-
cated that the mean disbonded area for the untreated system
after 192 h immersion was 3.5 cm2 , while, the corresponding
area for the 3-GPS treated system was only 1.1 cm2 . Thus,
the rate of disbondment for the untreated system was in the
region of 0.018 cm2 h1 while that of the 3-GPS treated sys-
tem was 0.0059 cm2 h1 ; approximately three times slower
than that of the untreated substrate.
Fig. 5. The variation of disbonded area of an alkyd coating on a carbon steel
substrate with and without pre-treatment using 3-APS.
3.2. Cathodic disbondment of polyurethane modied
alkyd and alkyd
coatings, showing a 22% improvement in adhesion strength
A comparison of the wet adhesion strength for both alkyd, for the plain alkyd after about 200 h of immersion and an 8%
and polyurethane-modified alkyd, coatings on untreated and improvement for the polyurethane-modified alkyd.
3-APS treated carbon steel substrates are shown in Fig. 3. It is Despite this improvement in adhesion, however, it is evi-
clear that 3-APS enhanced the dry and wet adhesion of both dent from Figs. 4 and 5, indicate that the disbondment rate
was not affected by the 3-APS pre-treatment. In fact, since
the disbonding rate for both the coating systems on the con-
trol untreated panels is the same as that of the 3-APS treated
system, it is likely that the controlling factor determining the
cathodic disbonding of both systems is also the same. It is also
interesting to note that both alkyd-based binders show simi-
lar disbonding rates of about 0.27 cm2 h1 , which is about 15
times faster than the cathodic disbonding rate of the epoxy
binder on the untreated surface.

4. Discussion

4.1. Adhesion enhancement

Pre-treatment of the carbon steel substrates with the appro-

Fig. 3. The adhesion strength of both alkyd and polyurethane-modified alkyd priate functionalised silane resulted in significant increases in
coatings as a function of immersion time in 0.6 M NaCl solution on untreated adhesion strength for all coatings under both dry (i.e. immer-
and 3-APS pre-treated carbon steel. sion for 0 h) and after extended immersion (i.e. up to 200 h)
320 M.K. Harun et al. / Progress in Organic Coatings 54 (2005) 317321
in 0.6 M NaCl solution. Thus, during the initial wash/dip pre-
treatment the siloxyl molecular end of either functional silane
should bind to the hydroxy-terminated air-formed oxide film
on the carbon steel substrate. In fact, this is by no means
certain as it depends on the total system chemistry. Thus,
Harun et al. [6] have shown, by angle-resolved XPS, that
although 3-GPS binds conventionally (i.e. with a siloxane
linkage to the steel), 3-APS binds preferentially amine-side
to the steel. In this situation, both 3-GPS and 3-APS enhance
the dry adhesion of amine-cured epoxy, however, the wet
adhesion on 3-APS treated steel rapidly falls to zero after
2448 h immersion. It is therefore interesting that 3-APS pre-
treatment significantly enhances the dry and wet adhesion of
both the alkyd-based binders.
For 3-GPS and epoxy chemistry, the formation of pri-
mary bonds between the coating polymer and the glycidoxy-
(epoxy) functional substrate surface is the obvious mech-
anism for the observed improvements in adhesion (bond)
strength. However, for 3-APS and alkyd chemistries, it is
presumably acidbase interactions, ultimately resulting in
relatively stable amide formation, that is the likely mecha-
nism.
4.2. Cathodic disbondment
The disbondment area from a defect in an organic coat-
ing is generally understood to increase as an approxi-
mate function of the square-root of time giving rise to
parabolic disbonding kinetics [9,10]. This is understood
to be driven by ionic diffusion from the defect, under-
neath the coating, to the disbonding front. Thus, for a line
defect or scratch, where the disbonded area is a linear func-
tion of the diffusion distance, a diffusion-controlled dis-
bonding process will indeed be parabolic with time. How-
ever, for a circular or annular defect, where the disbonded
area increases as a square of the diffusion distance, then
the expected kinetics for a diffusion-controlled process are
linear, which is the situation generally observed in this
work.
The predominant reason for cathodic disbondment is
due to alkalisation at the cathode (i.e. the substrate) where
the high pH developed over time results in several possi-
ble mechanisms of failure. Thus, either hydrolysis of the
interfacial bonds that attach the coating to the substrate
resulting in direct delamination, or hydrolysis of the coat-
ing itself resulting in de-polymerisation, may occur although
there are other possible mechanisms including, for exam-
ple, local osmotic effects and direct chain scission as a
result of hydroxy radicals generated during oxygen reduction
[1113].
The disbonding data confirm that interfacial modification
by 3-GPS is effective in reducing the cathodic disbonding
rate of an epoxy-based binder chemistry, but that modifi-
cation with 3-APS does not affect the disbonding rate for
alkyd-based binder chemistries. It is important, therefore,
to confirm, from the pull-off data, that interfacial modifica-
tion of the substrate with 3-GPS (for epoxies), or 3-APS (for
alkyds), is effective in improving the adhesive strength of all
the coatings. Thus, although the functional silane treatments
are clearly present at the interface and affecting the adhe-
sive strength of the coating, they do not necessarily affect the
disbonding rate.
This dichotomy may be resolved by considering the pos-
sible mechanisms for coating disbondment. Thus, for 3-GPS
and epoxy chemistry, the disbondment mechanism must
involve interfacial degradation (since interfacial modifica-
tion affects the disbondment rate). Conversely, for 3-APS
and alkyd chemistries, the disbondment mechanism must
involve direct degradation of the coating (polymer) binder
(since interfacial modification has no effect on disbonding
rate).
This is not perhaps unexpected, since epoxy chemistries
are much more resistant to degradation under cathodic
conditions (i.e. in the presence of high pH and hydroxy-
radicals produced during the reduction of oxygen) than alkyd
chemistries which relatively easily undergo direct hydroly-
sis (saponification) and chain scission. Nevertheless, the data
presented in this paper provides the first direct supporting
evidence that, for some chemically resistant binders (e.g.
epoxies), cathodic disbondment is controlled by interfacial
processes of hydrolysis and bond scission, while for less
resistant binders (e.g. alkyds) cathodic disbondment is con-
trolled by hydrolysis and bond scission of the bulk polymer.
Thus, Funkes maxim of adhesion is performance is not
always correct.
5. Conclusions
1. Surface modification of carbon steel substrates using
appropriate functionalised silanes can significantly
improve both the dry and wet adhesion strength of coating
binders based on epoxy and alkyd chemistries.
2. Similar surface modification of carbon steel substrates
reduced the cathodic disbondment rate for an epoxy binder
by a factor of 3 (i.e. 3-GPS/epoxy) but had no effect for
alkyd-based binders (i.e. 3-APS/alkyds).
3. This evidence strongly suggests that cathodic disbond-
ment of epoxy proceeds by disruption of interfacial bonds
(i.e. at the binder/substrate interface) but that disbond-
ment of alkyds proceeds by direct degradation of the
binder and that the interface plays little part in the
process.
References
[1] W. Funke, J. Oil Colour Chem. Assoc. 68 (1985) 229.
[2] J. Marsh, J.D. Scantlebury, S.B. Lyon, Corrosion Sci. 43 (2001)
829.
[3] I.M. Zin, R.L. Howard, S.J. Badger, S.B. Lyon, Prog. Org. Coat. 33
(1988) 203.
[4] E.L. Koehler, Corrosion 40 (1984) 5.
 M.K. Harun et al. / Progress in Organic Coatings 54 (2005) 317321 321

[5] W.J. van Ooij, A. Sabata, J. Adhes. Sci. Technol. 5 (1991) 843.
[6] M.K. Harun, S.B. Lyon, J. Marsh, Prog. Org. Coat. 46 (2003) 21.
[7] H. Leidheiser Jr., J. Adhes. Sci. Technol. 1 (1987) 79.
[8] M. Kendig, R. Addison, S. Jeanjaquet, J. Electrochem. Soc. 137
(1990) 2690.
[9] J.D.B. Sharman, J.M. Sykes, T. Handyside, Corrosion Sci. 35 (1993)
1375.
[10] H. Leidheiser Jr., W. Wang, L. Igetoft, Prog. Org. Coat. 11 (1983)
19.
[11] E.L. Koehler, Corrosion 40 (1984) 5.
[12] M. Kendig, R. Addison, S. Jeanjaquet, J. Electrochem. Soc. 137
(1990) 2690.
[13] W. Funke, in: H. Leidheiser Jr. (Ed.), Corrosion Control by Organic
Coatings, NACE, Houston, 1981, p. 97.