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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-


ward and most cathodic disbondment processes involve the
The relationship between the dry and wet adhesion and destruction of this region for example by chemical attack [4]
the anti-corrosion performance of an organic coating is not or other mechanisms [5].
straightforward. Thus, although Funke [1] generalized the This study was set up to model the effect of chemical modi-
claim that adhesion is performance, there are many systems fication of a steel substrate on coating adhesion and cathodic
that demonstrate relatively poor adhesion but have excel- disbonding rates. The premise here is that chemical func-
lent anti-corrosion performance, e.g. coatings on phosphated tionality is introduced onto the substrate by its reaction with
steel, Marsh et al. [2]. One primary mechanism for coating an appropriate functionalised silane. For a well-chosen sys-
failure derives from cathodic activity under an intact film. At tem, the coating chemistry should thus bond directly to the
its most basic, such a disbonding process is derived from alka- substrate, enhancing local bond strength and resistance to
lisation at the cathode causing local destruction (hydrolysis) 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 2. Experimental details
of the cathodic reaction are especially effective in prolonging
coating life [3]. Thus, the relationship between adhesion and 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
Corresponding author. FEPA European P-Series #P150 or equivalent nominal grain
E-mail address: stuart.lyon@manchester.ac.uk (S.B. Lyon). 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 the disbonded area traced onto acetate film, which was then
with deionised water. They were then twice rinsed in acetone, cut and weighed. In order to accurately relate the weight to
with a final rinse in ethanol, prior to drying in a dust-free envi- an area of the film, a sample of thirty squares with an area of
ronment at room temperature overnight. Three commercial 1 cm2 each, were cut at random from six separate acetate films
non-pigmented lacquers (6070% solids) were used for this of the same type. Five squares were obtained from each film.
study: (a) a two-pack amine-cured epoxy, (b) a polyurethane Each of these squares was weighed and their mean value and
modified alkyd, and (c) a clear alkyd. All coatings were standard deviation was calculated. Finally, the mean value
obtained from H. Marcel Guest Ltd., Manchester, UK. obtained was used to calculate the actual area of delamina-
Pre-treatment was undertaken using functional silanes: tion of the coating. At the end of the experiment, the samples
3-aminopropyltriethoxysilane (3-APS) for reaction with were removed from solution and the coatings cut radially
binders based on polyurethane and alkyd chemistry, or 3- with a scalpel from the artificial defect in order to physi-
glycidoxypropyltrimethoxysilane (3-GPS), for reaction with cally remove the de-bonded area. By this way, the location
the binder based on epoxy chemistry. Both of these chemicals of the delamination front was confirmed to correspond with
were obtained from Lancaster Synthesis at 9698% purity. the visual difference in appearance [6,7].
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- 3. Results
treatment was carried out by rinsing each panel for 30 s with
3.1. Cathodic disbonding of epoxy-polyamide coating
the appropriate silane solution from a wash bottle. After treat-
system
ment, they were allowed to dry at room temperature for 2 h
then immediately coated by draw bar, with the relevant binder, Pre-treatment of mild steel with 3-GPS increases the wet
to 100 m wet-film thickness (resulting in a dry-film thick- adhesion strength of the epoxy system compared to the
ness of about 60 m). Coatings were allowed to cure for 24 h untreated system. This can be clearly seen from the adhe-
at room temperature (1822 C) then post cured for 46 h at sion pull-off values shown in Fig. 1. The overall increase
4050 C. in the wet adhesion strength was maintained throughout the
Wet and dry adhesion tests were performed using a stan- whole duration of experiment with a significant improvement
dard pull-off method: the hydraulic adhesion tester (HATE) (increase) in adhesion strength from initial immersion (5%
manufactured by Elcometer Ltd. Using this technique, small improvement) to 200 h of immersion (18% improvement).
dollies are attached to the coating surface using cyanoacry- The standard errors in the data (for ten determinations) were
late adhesive. After the glue has set, the dollies are then typically 0.15 MPa at each data point.
detached from the substrate with the maximum hydraulic The cathodic disbonding tests on these systems were
pressure registered being a direct measure of the adhesion conducted according to the method described earlier and the
strength of the coating. Care was taken to ensure that the results are shown in Fig. 2, where the standard errors in the
locus of failure was located at the coating-metal interface: data (six determinations) were approximately 0.15 cm2 .
thus, any results from samples that failed cohesively, or at the Although fresh new samples were prepared for this test, it
dolly-coating interface, were discarded. Ten replicate tests must be emphasized that in all the experiments, the thickness
are carried out for each sample and exposure time in order to of the coatings was kept constant to 5% of the overall
obtain an effective measure of the experimental variability. thickness.
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 Fig. 1. The adhesion strength of an epoxy coating as a function of immersion
indicate the area of disbondment. The panels were removed time in 0.6 M NaCl solution on untreated and 3-GPS pre-treated carbon steel
at set time intervals, were rinsed with deionised water, and 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- tion of the substrate with 3-GPS (for epoxies), or 3-APS (for
treatment the siloxyl molecular end of either functional silane alkyds), is effective in improving the adhesive strength of all
should bind to the hydroxy-terminated air-formed oxide film the coatings. Thus, although the functional silane treatments
on the carbon steel substrate. In fact, this is by no means are clearly present at the interface and affecting the adhe-
certain as it depends on the total system chemistry. Thus, sive strength of the coating, they do not necessarily affect the
Harun et al. [6] have shown, by angle-resolved XPS, that disbonding rate.
although 3-GPS binds conventionally (i.e. with a siloxane This dichotomy may be resolved by considering the pos-
linkage to the steel), 3-APS binds preferentially amine-side sible mechanisms for coating disbondment. Thus, for 3-GPS
to the steel. In this situation, both 3-GPS and 3-APS enhance and epoxy chemistry, the disbondment mechanism must
the dry adhesion of amine-cured epoxy, however, the wet involve interfacial degradation (since interfacial modifica-
adhesion on 3-APS treated steel rapidly falls to zero after tion affects the disbondment rate). Conversely, for 3-APS
2448 h immersion. It is therefore interesting that 3-APS pre- and alkyd chemistries, the disbondment mechanism must
treatment significantly enhances the dry and wet adhesion of involve direct degradation of the coating (polymer) binder
both the alkyd-based binders. (since interfacial modification has no effect on disbonding
For 3-GPS and epoxy chemistry, the formation of pri- rate).
mary bonds between the coating polymer and the glycidoxy- This is not perhaps unexpected, since epoxy chemistries
(epoxy) functional substrate surface is the obvious mech- are much more resistant to degradation under cathodic
anism for the observed improvements in adhesion (bond) conditions (i.e. in the presence of high pH and hydroxy-
strength. However, for 3-APS and alkyd chemistries, it is radicals produced during the reduction of oxygen) than alkyd
presumably acidbase interactions, ultimately resulting in chemistries which relatively easily undergo direct hydroly-
relatively stable amide formation, that is the likely mecha- sis (saponification) and chain scission. Nevertheless, the data
nism. presented in this paper provides the first direct supporting
evidence that, for some chemically resistant binders (e.g.
4.2. Cathodic disbondment epoxies), cathodic disbondment is controlled by interfacial
processes of hydrolysis and bond scission, while for less
The disbondment area from a defect in an organic coat- resistant binders (e.g. alkyds) cathodic disbondment is con-
ing is generally understood to increase as an approxi- trolled by hydrolysis and bond scission of the bulk polymer.
mate function of the square-root of time giving rise to Thus, Funkes maxim of adhesion is performance is not
parabolic disbonding kinetics [9,10]. This is understood always correct.
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- 5. Conclusions
tion of the diffusion distance, a diffusion-controlled dis-
bonding process will indeed be parabolic with time. How- 1. Surface modification of carbon steel substrates using
ever, for a circular or annular defect, where the disbonded appropriate functionalised silanes can significantly
area increases as a square of the diffusion distance, then improve both the dry and wet adhesion strength of coating
the expected kinetics for a diffusion-controlled process are binders based on epoxy and alkyd chemistries.
linear, which is the situation generally observed in this 2. Similar surface modification of carbon steel substrates
work. reduced the cathodic disbondment rate for an epoxy binder
The predominant reason for cathodic disbondment is by a factor of 3 (i.e. 3-GPS/epoxy) but had no effect for
due to alkalisation at the cathode (i.e. the substrate) where alkyd-based binders (i.e. 3-APS/alkyds).
the high pH developed over time results in several possi- 3. This evidence strongly suggests that cathodic disbond-
ble mechanisms of failure. Thus, either hydrolysis of the ment of epoxy proceeds by disruption of interfacial bonds
interfacial bonds that attach the coating to the substrate (i.e. at the binder/substrate interface) but that disbond-
resulting in direct delamination, or hydrolysis of the coat- ment of alkyds proceeds by direct degradation of the
ing itself resulting in de-polymerisation, may occur although binder and that the interface plays little part in the
there are other possible mechanisms including, for exam- process.
ple, local osmotic effects and direct chain scission as a
result of hydroxy radicals generated during oxygen reduction
[1113]. References
The disbonding data confirm that interfacial modification
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829.
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alkyd-based binder chemistries. It is important, therefore, (1988) 203.
to confirm, from the pull-off data, that interfacial modifica- [4] E.L. Koehler, Corrosion 40 (1984) 5.
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