Electrochemistry Communications 13 (2011) 10941097

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Electrochemistry Communications
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / e l e c o m

A combined redox-competition and negative-feedback SECM study of self-healing

anticorrosive coatings
Y. Gonzlez-Garca a,, S.J. Garca b, A.E. Hughes c, J.M.C. Mol a
a
b
c

Delft University of Technology, Department of Materials Science and Engineering, Mekelweg 2, 2628CD Delft, The Netherlands
Delft University of Technology, Novel Aerospace Materials, Kluyverweg 1, 2629HS Delft, The Netherlands
CSIRO Materials Science & Technology, Private Bag 33, Clayton South MDC, VIC 3169, Australia

a r t i c l e

i n f o

Article history:
Received 10 June 2011
Received in revised form 5 July 2011
Accepted 12 July 2011
Available online 23 July 2011
Keywords:
Self-healing coating
Silyl-ester
Encapsulation
Corrosion
Scanning electrochemical microscopy

a b s t r a c t
In this paper, the long-term anticorrosive efciency of a damaged self-healing coating is studied for the rst
time using scanning electrochemical microscopy (SECM). In the study an epoxy-coating with embeddedcapsules containing a silyl-ester is employed. The properties of the silyl-ester as a healing-agent for the
protection of AA2024-T3 were evaluated by complementary SECM experiments operating in negativefeedback and redox-competition modes. The experimental approach here presented allowed for monitoring
the early-stages of corrosion activity and subsequent healing mechanisms offered by the release of silyl-ester
into a relatively large coating defect. This result was observed by detecting the transition of the oxygen
reduction response from a redox-competition mode to a negative-feedback behavior. These measurements
demonstrated that the silyl-ester is released efciently after capsules break upon coating damage, covering
relatively large areas and gradually healing the damaged-site hindering the corrosion processes and providing
an effective protection for at least one month of immersion in chloride solution.
2011 Elsevier B.V. All rights reserved.

1. Introduction
Recently, increasing research efforts have been focused towards the
development of (anticorrosive) coatings based on self-healing concepts.
Self-healing materials are generally dened as materials exhibiting the
ability to repair themselves and to recover functionality using the
resources inherently available to them. In the eld of organic coatings,
several approaches have been successfully implemented so far [1], and a
critical overview of the actual and future perspectives within the eld can
be found elsewhere [2]. One of the most common self-healing approaches
is based on embedding discrete capsules lled with healing-agents in the
coating matrix [3]. Within this concept, the most common approach uses
two-healing agents (i.e. resin and cross-linker or catalyst) [39] with an
efficiency limited by the probability of having both species present at
the same time and in the required ratio at the damage site. More recently
an approach for organic coatings has been presented requiring a single
healing-agent that reacts with the environment upon fracture of the
containers [10,11]. In a previous paper, the authors presented a new
approach encompassing an encapsulated one-component healing-agent
based on a silyl-ester derivate [10]. In the case when the coating is
damaged, the capsules at the defect faces are ruptured and release the
silyl-ester. Once released, the agent wets both metal and polymer
surfaces within the defect, and reacts with ambient moisture and metallic
substrate, creating a protective hydrophobic barrier layer [10].

Corresponding author. Tel.: + 31 1527 88369.

E-mail address: y.gonzalezgarcia@tudelft.nl (Y. Gonzlez-Garca).
1388-2481/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.elecom.2011.07.009

In the present work, the anticorrosive protection efciency of the

silyl-ester for long-term immersion is evaluated for the rst time by
using the scanning electrochemical microscope (SECM). The SECM has
been introduced recently as an alternative local electrochemical method
to study healing processes upon coating damage with high spatial
resolution [12]. SECM provides the possibility to monitor the evolution
of the species involved in the corrosion onset selectively. SECM
operating in redox-competition mode can be used to monitor the
depletion of dissolved oxygen in solution as a consequence of the
cathodic processes taking place on a corroding metal [1218].
In this paper, we introduce a new approach of the use of SECM for
self-healing coating evaluation in which we combine oxygen-detection
experiments (redox-competition mode) with measurements using an
electrochemical mediator in solution (negative-feedback mode). This
allows distinguishing the transition of the oxygen behaviour from acting
as an active specie involved in cathodic processes to a mediator
behaviour. This transition was directly associated to the change of active
corrosion in the coating defect at the very early stages of exposure to
subsequent healing by the action of the released silyl-ester from the
capsules incorporated in the coating matrix. Furthermore, the developed approach also demonstrates the long-term protection provided by
the silyl-ester healing agent in a relatively aggressive chloride solution.
2. Experimental details
The synthesis and encapsulation of the silyl-ester (octyldimethylsilyloleate), preparation of the polymer coating and application on the

Y. Gonzlez-Garca et al. / Electrochemistry Communications 13 (2011) 10941097

1 day of immersion in NaCl solution. It is clearly observed in the

optical image (Fig. 1a) that the bare metal already showed evidence of
pitting corrosion while the area covered by the silyl-ester remained
unaltered. SECM-image operating at the oxygen-reduction potential
(Fig. 1b) showed a step in the current values across the transition
between bare and silylester-treated surfaces. Very low values are
detected at localized zones of the bare-metal surface. These zones can
be correlated to cathodic areas where consumption of oxygen occurs
and therefore less oxygen is available for the electroreduction at the
tip. While the high cathodic currents are attributed to anodic-areas
which are not detected by this SECM operating-mode. This result is in
accordance with the visual observations of localized attack of the
metal in Fig. 1a. On the silylester-area, the SECM-image presented an
averaged plateau of more negative currents suggesting no cathodic
activity. This result indicated that the silyl-ester is forming a
homogeneous protective layer on the metal hindering any corrosion
processes and consequently more oxygen is available in solution.
SECM-experiments were not inuenced by topology-effects since the
resolution of the tip is insufcient to detect the silylester-layer formed
onto the metal surface.
Approaching-curves in Fig. 1c with the oxygen-reduction as
reaction at the tip were performed in both areas of the sample to
conrm the protective effect of the silyl-ester. Firstly, it was observed
that curves showed negative-feedback behavior typical of a nonconductive surface. On the other hand, both curves presented

metallic substrate were carried out as described in literature [10].

Clear epoxy coating and epoxy coating containing silyl-ester doped
capsules were applied on AA2024-T3 substrate. The defects in the
coating were applied with a razor blade.
The SECM measurements were carried out with the Scanning
Electrochemical Workstation Model370 (Princeton Applied Research,
AMETEK Inc.). A Platinum-disk microelectrode of 5 m-radius was
used as the working electrode. An Ag/AgCl,KCl (sat) electrode as a
reference and a platinum plate as the counter-electrode completed
the electrochemical cell. SECM-scan measurements were carried out
at a tip-sample distance of 40 m. The size of the SECM-tip dened the
spatial resolution of the measurements. Experiments in negativefeedback mode were carried out using ferrocenemethanol in solution
as mediator and at + 0.6 V as tip-potential corresponding to the
oxidation of Fe(II) to Fe(III). Redox-competition measurements were
performed at tip-potential of 0.6 V which corresponds to reduction
of dissolved oxygen in solution. Samples were immersed in 0.05 M
NaCl solution containing 5 mM ferrocenemethanol in the case of
feedback-mode experiments.
3. Results and discussion
Firstly, the anticorrosive properties of the silyl-ester were studied
on a bare AA2024-T3 surface. Abraded AA2024-T3 specimen with the
half-part of the surface covered by silyl-ester was evaluated after

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Fig. 1. (a) Optical micrograph of AA2024-T3 sample with bare and silyl-treated surface after 1 day immersion in 0.05 M NaCl solution. (b) SECM image of the transition area on (a)
using the electroreduction of oxygen in solution as reaction at the tip. Scan rate: 40 ms 1.Scanned area: 1.25 1 mm2. (c) Approaching-curves performed on the bare metal (black
line) and on the silyl-covered area (red line). Currents corresponding to oxygen-reduction at the tip are plotted versus normalized sample-tip distance (L = distance/tip-radius).
(d) Overlapped approaching-curves corresponding to measurements using electrochemical mediator (red-dashed line) and oxygen reduction (black-solid line). On top curves
performed on bare sample, and on the bottom, curves on the silylester-treated surface.

1096

Y. Gonzlez-Garca et al. / Electrochemistry Communications 13 (2011) 10941097

different trends. On bare metal, the curve showed an earlier and

gradual decay of the current (black solid-line) as compared to the
curve obtained from the silyl-area (red solid-line). This suggests
different availability of oxygen for its reduction at the tip depending
on the area on the sample. These curves were compared in Fig. 1d to
the same ones performed using an electrochemical mediator in the
solution. It is observed that oxygen on the silyl-zone showed the same
approach behavior as the one with mediator (Fig. 1dbottom).
Reduction at the microelectrode is only affected by the diffusion
blocking due to the proximity of the surface in the same way as for the
presence of an electrochemical mediator. However, on the bare metal,
approach-curves presented very different slopes (Fig. 1dtop). This
indicates an oxygen-reduction competition between corrosion processes on the metal and the electroreduction at the tip for the oxygen
approach-curve. For this reason, a signicant depletion was detected
at a distance still far away from the surface (180200 m). It is
possible to estimate the concentration of dissolved oxygen in solution

by application of Eq. (1) for the limiting-current at a microdisk [19].

Where n is the number of electrons transferred during the oxygenreduction reaction, F the Faraday constant, DO2 the dissolved oxygen
diffusion coefcient in water (2.01 10 9 ms 1[20]), CO2 the
dissolved oxygen concentration, and r the microdisk radius.
iO2 = 4nFDO2 CO2 r

It is well-known that during open-circuit corrosion of AA2024-T3

in near-neutral aqueous solutions, the dominant anodic reaction is the
aluminum dissolution and the cathodic process is the oxygen
reduction taking place preferentially on the cathodic intermetallics
[13]. From the limiting-currents measured at the curves in Fig. 1c and
an electron-transfer value of 4, the concentration of oxygen estimated
in the bulk solution at room temperature was ~0.22 mM which is in
good agreement with the 0.26 mM oxygen concentration proposed in
literature for a 0.05 M NaCl solution [21]. It is estimated from the

Fig. 2. Sequence of SECM line scans across the defect by using ferrocenemethanol as mediator which reects the topography (black solid line), and by electroreduction of oxygen at
the tip (red solid line) which reects the level of oxygen consumption in solution. Defective capsules-containing coating on AA2024-T3 metal after (a) 1, (b) 3, (c) 15 and (d) 30 days
of immersion in 0.05 M NaCl solution. Defect-size: ~ 240 m 1.9 mm. Coating-thickness: 240 20 m. Line scan-rate: 20ms 1. Damaged clear epoxy-coating on AA2024-T3 after
(e) 1 and (f) 3 days of immersion in chloride solution. Defect-size: ~ 200 m 1.5 mm. Coating-thickness:207 19 m. Line scan-rate: 20ms 1.

Y. Gonzlez-Garca et al. / Electrochemistry Communications 13 (2011) 10941097

approach-curve that consumption of oxygen on bare-metal occurred

at an approximate rate of 2.73 mMcm 1, reaching very low values
(~0.08 mM or 37% of cbulk) at a distance which is still considered bulk
solution from the approach-curve on the silylester-area. However, the
decay of current at the silylester-area took place at a very short
distance from the surface that is associated with the blocking of
oxygen diffusion.
The next step in this work was to study the long-term protective
efciency of the silyl-ester when is encapsulated and incorporated
into an epoxy coating. SECM measurements consisted of performing
scan-lines across the coating defect to monitor changes on oxygen
concentration at different immersion times in chloride solution.
Complementary scans in feedback-mode were carried out to establish
the effect of the topology. Fig. 2ab presents selected cross-sections of
the defect after 1 and 3 days of immersion, respectively. After 1 day of
immersion, the prole in Fig. 2a (bottomred) showed a signicant
depletion of oxygen in the area corresponding to the defect when it is
compared with the topology prole (Fig. 2a topblack). For this
immersion time, corrosion activity in the defect is evidently leading to
a massive consumption of oxygen. After 3 days of exposure, the
redox-competition mode prole in Fig. 2b (bottomred) still
presented evidence of corrosion from the low currents measured.
However, when it was compared with the prole in feedback-mode
(Fig. 2b topred) we observed that the line-scan slightly followed the
topology contour of the defect. This is a rst evidence of healing by the
action of silyl-ester. Demand of oxygen from cathodic areas is
decreasing and oxygen is able to act partially as a mediator in
feedback-mode. The activity of the silyl-ester was conrmed by
comparison with the experiment carried out for a capsule-free system
(clear coat). For this one, proles across the defect in Fig. 2ef showed
a gradually increasing depletion of oxygen with immersion time
without any evidence of a topology effect. This result is expected since
in absence of healing-agent the corrosion activity within the defect
can progress naturally. The proles of the defective encapsulated
system showed a progressive transition of the oxygen from redoxcompetition to negative-feedback mode with immersion time. After
15 days of experiment, no consumption of oxygen is detected within
the defect, and the prole (Fig. 2c) showed the topology solely, in
correspondence with the line-scan using the mediator (top-black). At
that moment, oxygen behaved purely as a mediator indicating a full
protection of the defect by the isolating silylester-layer. This result
corroborates the suggestion in our previous paper [8] of initial limited
protection (Fig. 2b) that increases in time due to a densication
process with subsequent increase of the barrier properties. The metal
underneath the initial defect remained protected by this layer during
the remainder of the experimental time. After one month of exposure,
the line-scan of oxygen-reduction (Fig. 2d bottom) presents the very
same behavior as the negative-feedback mediator-prole (top),
showing the topology across the defect exclusively indicating that
the defect area is still protected by the silyl ester.
4. Conclusions
The oxygen SECM-proles across a defect on the organic coating
containing encapsulated silyl-ester showed a transition from redoxcompetition at the tip (corrosion activity) to a negative-feedback
behavior (protected system) during immersion in chloride solution.

1097

While the healing agent was unable to cover or fully densify and
protect the damage completely as from a short exposure time, after
the silyl-ester formed a fully isolating layer, the coating defect
remained protected during the one-month experiment. These results
clearly demonstrate the long-term efciency of the encapsulated silylester incorporated in an organic coating for the corrosion protection
of aluminum alloys.
SECM measurements monitoring the changes of oxygen concentration in the proximity of an AA2024-T3 surface during immersion in
aggressive solution demonstrated that silyl-ester formed an isolating
and homogenous layer able to protect the surface against corrosion
effectively. Approach-curves established the different kinetics of the
oxygen-reduction in the absence and presence of the silyl-ester
healing-agent. In the presence of a protective layer of the silyl-ester,
oxygen behaved as a conventional electrochemical mediator. On bare
metal, oxygen redox-competition between corrosion processes at the
metal and at the tip was established indicating that the solution near
the metal surface had a depletion of available oxygen up to 60% with
respect to bulk concentration.
Acknowledgements
The authors gratefully acknowledge the nancial support from the
Innovative Research Program (IOP) in The Netherlands for this research
under project numbers IOP-SHM0633 and IOP-SHM08740C. S.J. Garca
also acknowledges the nancial support of The Netherlands Organization for Scientic Research (NWO-STW) for the Veni grant under
number 10690.
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