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Self-Healing Polymer Coatings
By Soo Hyoun Cho, Scott R. White, and Paul V. Braun*

Autonomic healing materials respond without external interven- ane (HOPDMS) and polydiethoxysiloxane (PDES), which meets
tion to environmental stimuli in a nonlinear and productive this important requirement.[21] This healing chemistry is attractive
fashion, and have great potential for advanced engineering because it is air and water stable, and remains active even after
systems.[1–21] Self-healing coatings, which autonomically repair exposure to elevated temperatures (up to 150 8C), enabling its use
and prevent corrosion of the underlying substrate, are of particular in systems requiring a thermal cure. While the mechanical
interest. Notably, the worldwide cost of corrosion has been properties of the resultant cross-linked siloxane are not excep-
estimated to be nearly $300 billion per year.[22] Recent studies on tional, in a coating system the mechanical strength of the healed
self-healing polymers have demonstrated repair of bulk mechan- matrix is of secondary importance, compared to chemical stability
ical damage[1–21] as well as dramatic increases in the fatigue and passivating ability, two areas where siloxanes show exceptional
life.[23,24] Various approaches for achieving healing functionality performance. We explored two self-healing coating approaches,
have been demonstrated, including encapsulation,[1–7] reversible starting from this siloxane-based materials system. In the first, as
chemistry,[8–11] microvascular networks,[12] nanoparticle phase presented in Figure 1, the catalyst is microencapsulated, and the
separation,[13–15] polyionomers,[16–18] hollow fibres,[19,20] and siloxanes are present as phase-separated droplets. In the second
monomer phase separation.[21] The majority of these systems, approach, the siloxanes were also encapsulated and dispersed in
however, have serious chemical and mechanical limitations, the coating matrix. Encapsulation of both phases (the catalyst and
preventing their use as coatings. Modern engineered coatings the healing agent) is advantageous in cases where the matrix can
are highly optimized materials in which dramatic modifications of react with the healing agent.
the coating chemistry are unlikely to be acceptable. Here, we Our initial model system consists of an epoxy vinyl ester
describe a generalized approach to self-healing polymer-coating matrix, 12 wt% phase-separated healing agent, 3 wt%
systems, and demonstrate its effectiveness for both model and polyurethane (PU)-microencapsulated dimethyldineodecanoate
industrially important coating systems. tin (DMDNT) catalyst solution, and 3 wt% methylacryloxy propyl
Polymeric coatings protect a substrate from environmental triethoxy silane adhesion promoter. The percentages of each
exposure, and when they fail corrosion of the substrate is greatly component are selected based on our prior experiments on
accelerated. Because they are typically thin and in direct contact self-healing of bulk materials.[21] The PDMS-based healing agent
with the environment, some degree of environmental contamina- is a mixture of 96 vol% HOPDMS and 4 vol% PDES, and the
tion, by for example, O2 and H2O, is unavoidable. Thus, in catalyst solution consists of 5 wt% DMDNT in chlorobenzene.
contrast to bulk (thick) self-healing systems, where environmental The DMDNT/chlorobenzene-filled PU capsules average 90 mm in
contaminates can largely be avoided, a self-healing coating must
be highly stable to species present in the environment. We
previously demonstrated, in a bulk system, a self-healing
chemistry based on the di-n-butyltin dilaurate catalyzed poly-
condensation of hydroxyl end-functionalized polydimethylsilox-

[*] Prof. P. V. Braun

Beckman Institute
Department of Materials Science and Engineering
and Frederick Seitz Materials Research Laboratory
University of Illinois at Urbana-Champaign
Urbana, IL 61801, USA
E-mail: [email protected]
Dr. S. H. Cho
Beckman Institute
and Department of Materials Science and Engineering
University of Illinois at Urbana-Champaign
Urbana, IL 61801, USA
Prof. S. R. White
Beckman Institute Figure 1. Schematic of self-healing process. a) Self-healing coating con-
Department of Materials Science and Engineering taining microencapsulated catalyst (yellow) and phase-separated healing-
and Department of Aerospace Engineering agent droplets (blue) in a matrix (light orange) on a metallic substrate
University of Illinois at Urbana-Champaign (grey). b) Damage to the coating layer releases catalyst (green) and healing
Urbana, IL 61801, USA agent (blue). c) Mixing of healing agent and catalyst in the damaged region.
d) Damage healed by cross-linked PDMS, protecting the substrate from the
DOI: 10.1002/adma.200802008 environment.

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PDMS does not always remain in the scratch

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after healing, leading to corrosion of the

underlying substrate.
Scanning electron microscopy (SEM) ima-
ging of the scribe region in control and
self-healing coatings reveals the morphology
of the repaired coating (Fig. 3c and d). Flow of
healing agent and catalyst into the scribe and
recoating (passivation) of the substrate is
readily apparent. The damage is significantly
(40%) filled by polymerized healing agent in
the self-healing coating, while the scribe
extends about 15 mm into the metal substrate
in the control sample (Supporting Informa-
tion, Table S1). Profilometry measurements
and energy-dispersive spectroscopy of nickel-
coated cross-sectioned samples (post-healing)
confirmed these findings (Supporting Infor-
mation, Fig. S2).
Electrochemical testing provides further
evidence of passivation of the substrate by
self-healing coatings. In these experiments, the
coated metal substrate serves as one electrode
in an electrochemical cell (Fig. 3e). The
steady-state conduction between the coated
Figure 2. a,b) Optical microscopy images of a) DMDNT-containing PU microcapsules and metal substrate and a platinum electrode held
b) PDMS healing-agent-filled UF microcapsules. c) Size histogram for both microcapsules. at 3 V through an aqueous electrolyte (1 M
d) Thermogravimetric analysis of both microcapsules. NaCl) is measured (Fig. 3f). The current
passing through the control and self-healing
polymer coatings before scribing are nearly
diameter (Fig. 2a and c), and upon thermogravimetric analysis identical, 0.34 mA cm 2. After scribing, samples are allowed to
(TGA) exhibit a primary weight loss starting near the boiling point heal and are tested in the electrochemical cell. The current
of chlorobenzene (131 8C), and a secondary weight loss starting at passing through the scribed control samples is quite large
225 8C, corresponding to thermal decomposition of the poly- (26.6–58.6 mA cm 2, three samples), compared to the unda-
urethane shell (Fig. 2d). maged state, and we note rapid gas evolution from the scribed
The self-healing function of this coating system is evaluated region during the test. The self-healing samples show a
through corrosion testing of damaged and healed coated steel dramatically reduced current (12.9 mA cm 2–1.4 mA cm 2, four
samples compared to control samples (Fig. 3 and Supporting samples), and no gas evolution is observed from the self-healing
Information Fig. S1). Damage is induced by hand scribing sample.
through the 100 mm thick coating and into the substrate using a While this model coating system consisting of phase-separated
razor blade. Because the substrate is significantly harder than the PDMS healing agents and microencapsulated catalyst has
coating, the scribe depth is uniform to within 10 mm. Following impressive properties, some limitations are apparent. First, the
the scribing procedure, samples are allowed to heal at 50 8C for PDMS healing agents are in direct contact with the coating
24 h. Samples are then immersed in 5 wt% aqueous NaCl solution matrix, and are thus susceptible to matrix-initiated reactions. For
for a prescribed period of time. All control samples rapidly corrode example, amine curing agents found in many epoxies catalyze
within 24 h, and exhibit extensive rust formation, most prevalently PDMS healing-agent condensation. To overcome this limitation,
within the groove of the scribed regions, but also extending across and provide a more general approach, the PDMS healing agent
the substrate surface. In dramatic contrast, the self-healing phase is encapsulated within urea-formaldehyde (UF) micro-
samples show no visual evidence of corrosion, even 120 h after capsules, to produce a dual capsule self-healing coating system,
exposure (Fig. 3b); these experiments are highly reproducible. comprised of 12 wt% PDMS-filled UF microcapsules, 3 wt%
Separate control tests reveal that the presence of both the healing DMDNT catalyst-filled PU microcapsules, and 3 wt% adhesion
agent and catalyst are necessary for self-healing functionality. promoter dispersed in an epoxy-amine matrix. In this case, the
Removal of either phase results in a coating which corrodes healing agent is now protected by the UF shell wall from direct
rapidly, providing a clear indication that simple reflow of one of contract with the matrix polymer. The PDMS healing-agent
the phases into the crack is not sufficient to prevent corrosion capsules averaged 60 mm in diameter (Fig. 2b and c). TGA of
(Supporting Information, Fig. S1). The bifunctional adhesion these capsules shows a slow weight loss beginning at 150 8C
promoter, which served to enhance the bonding between the (Fig. 2d); the overall small weight loss of these capsules at even
siliane-based healing agent and the epoxy vinyl ester matrix, is not 500 8C is due to the high thermal stability of PDMS. In
necessary for self-healing. However, in its absence the cured preliminary corrosion testing of this epoxy-based coating,

646 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2009, 21, 645–649
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room-temperature activity, unlike DMDNT
this catalyst does not require moisture for
activation,[25–27] potentially enabling self-
healing coatings for moisture-free environ-
ments, such as found in aerospace applications
or at buried interfaces. The corrosion perfor-
mance of the dual-capsule room-temperature
system is demonstrated by the incorporation of
self-healing components into both a general
epoxy-based coating system and a commercial
marine (epoxy) coating system (Fig. 4). For
both systems, 3 wt% TKAS catalyst-filled PU
microcapsules, 14 wt% PDMS healin-
g-agent-containing UF capsules, and 3 wt%
adhesion promoter are added to the appro-
priate matrix. A coating 100 mm thick is placed
onto the primed steel substrate and cured. For
the marine coating, a second layer 100 mm
thick (without self-healing components) is
applied, to provide a smooth surface texture.
Corrosion-test results after scribing and heal-
ing for 24 h at room temperature show the
efficacy of the room-temperature activity for
both these systems (Fig. 4).
Our dual-capsule PDMS healing system
provides a general approach to self-healing
coatings that place rigorous demands on
chemical compatibility and stability. By incor-
porating TKAS catalyst, we show that auto-
nomic corrosion protection can be obtained by
Figure 3. Corrosion, morphological, and electrochemical evaluation of self-healing coatings. self-healing under ambient environmental
a,b) Optical images after 120 h immersion in salt water of a) control sample, consisting of the conditions. Multilayered coatings can also be
epoxy vinyl ester matrix and adhesion promoter, and b) self-healing coating, consisting of matrix, formulated to provide self-healing functional-
adhesion promoter, microencapsulated catalyst, and phase-separated PDMS healing agent. ity while maintaining extreme tolerances on
c,d) SEM images of the scribed region of the control coating c) and the self-healing coating after surface finish, specific requirements for
healing d). e) Schematic diagram of electrochemical test. f) Current versus time for scribed
control and self-healed sample.
engineered primers, or unique surface che-
mistries (e.g., self-cleaning). We believe the
microcapsule motif also provides a delivery
adhesion to the substrate was found to be inadequate, and thus a mechanism for multifunctional chemical agents, which provide
50 mm thick epoxy-based primer layer is applied to the substrate, healing as well as corrosion inhibitors,[28] antimicrobial agents,[29]
and cured prior to coating application. Corrosion-test results for or other functional chemicals.
100 mm thick control and dual capsule self-healing coating
samples are virtually identical to our observations on the
phase-separated system (Fig. 3). All control samples show
extensive corrosion following 120 h of salt water exposure, while Experimental
self-healed samples (healed for 24 h at 50 8C) show no evidence of Microcapsules containing 5% DMDNT (Gelest) in chlorobenzene, and
rust formation (Supporting Information, Fig. S3) 2% TKAS in chlorobenzene, were microencapsulated within polyurethane
True self-healing requires no external intervention, including capsules, as previously described [21]. PDMS healing-agent-filled urea-
heating to temperatures greater than ambient, a requirement formaldehyde microcapsules were formed following our published pro-
cedure [1] with the following modifications. 250 mL of reaction mixture was
we note for our model coating system using DMDNT as the
heated to 55 8C and stirred at 700 rpm. 60 mL of a mixture of the PDMS
catalyst phase. This catalyst has reduced activity at room healing agent, HOPDMS (48 mL), PDES (2 mL), and n-heptane (10 mL)
temperature, and although corrosion tests demonstrated some was added. After 4 h, the reaction mixture was cooled to room temperature,
level of self-healing at room temperature, healing performance and the microcapsules were separated.
for this system is not ideal. Room temperature (20 8C) TKAS, Si[OSn(n-C4H9)2OOCCH3]4, was synthesized following US
self-healing is achieved through the synthesis and encapsulation patent 4,137,249 [27]. 0.1 mol of di-n-butyltin diacetate and 0.025 mol
of tetraethylsilicate were first mixed in a round flask. The solution was
of Si[OSn(n-C4H9)2OOCCH3]4, (TKAS), a highly effective catalyst
heated to 150 8C while stirring under anhydrous conditions. The reaction
for curing PDMS. The diameter and morphology (Supporting by-product, ethyl acetate, was distilled off at atmospheric pressure. The
Information, Fig. S4) of these capsules is very similar to those of ethyl acetate started to condense at 130 8C, and most of it was removed
DMDNT-filled capsules presented in Figure 2. Along with after 15 min at 150 8C. The crude TKAS reaction product has the form of

Adv. Mater. 2009, 21, 645–649 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 647
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A 100 mm layer of Intergard 264 was subsequently

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applied over the self-healing layer, and similarly

cured.

Acknowledgements
This work has been principally sponsored by North-
rop Grumman Ship Systems (SRA 04-307), as well as
the Air Force Office of Scientific Research and by
the Beckman Institute for Advanced Science and
Technology at the University of Illinois at Urbana-
Champaign. The authors gratefully acknowledge
A. Jackson for assistance with TGA and optical
microscopy, and helpful discussions with Prof.
N. Sottos, Prof. J. Moore, X. Yu, and R. Shimmin.
Supporting Information is available online from Wiley
InterScience or from the author.

Received: July 15, 2008

Figure 4. Salt-immersion corrosion testing of control and of room-temperature self-healing Revised: October 17, 2008
epoxy coatings. All images were obtained after healing at 20 8C for 24 h and 120 h immersion Published online: December 2, 2008
in salt water. a) Control coating, consisting of the epoxy-amine matrix containing adhesion
promoter coated on a primed substrate. b) The self-healing coating prepared as a), with
the addition of PDMS healing-agent capsules and TKAS-catalyst capsules. c) Two-layer com-
mercial marine coating, containing adhesion promoter (control sample). d) Self-healing
coating prepared as c), with the addition of PDMS healing-agent capsules and TKAS-catalyst
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M. R. Kessler, S. R. Sriram, E. N. Brown, S. Viswa-
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648 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2009, 21, 645–649
 15214095, 2009, 6, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.200802008 by Anadolu University, Wiley Online Library on [13/12/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
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Adv. Mater. 2009, 21, 645–649 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 649