Professional Documents
Culture Documents
a r t i c l e
i n f o
Article history:
Received 26 October 2007
Received in revised form 15 August 2008
Accepted 12 September 2008
Keywords:
Self-repairing coating
Cagelike smart particles
Self-assembly latex particles
Metallic corrosion
Aluminum alloy
a b s t r a c t
The development of effective anticorrosion pre-treatments for metallic substrates is an issue of great
importance for durability of metal structures and components. In this work, we proposed and demonstrated the concept of self-repairing coating for corrosion protection of aluminum alloys, using cagelike
oil core/silica gel shell particles. These micron-scale, cagelike smart microspheres with opened and closed
pores were successfully fabricated, and at the same time encapsulated repairing agent (methyl methacrylate) and catalysts (potassium persulfate and sodium thiosulfate) into the microspheres, respectively. Such
smart particle composites (SPCs) were prepared based on an interfacial self-assembly process and solgel
reaction. They were then self-assembled on the AA2024 aluminum alloy surface, followed by the application of a solgel lm. The hybrid lm worked as a primer coating featuring the self-repairing property.
Both the EIS and SEM/EDS data demonstrated that the encapsulated repairing agent was released as a
response to external stimulus (scratches) and polymerized to repair the coating defects. By comparing
the corrosion rate of AA2024 in three coating systems, the self-repairing effect is quantied to be 22%
after 2 h immersion in deoxidized 3% NaCl solution.
2008 Elsevier B.V. All rights reserved.
1. Introduction
The development of effective anticorrosion pre-treatments for
metallic substrates is an issue of great importance for durability
of metal structures and components. Conventional chromate conversion coatings (CCC) work well for iron and aluminum alloys
in terms of their corrosion protection performance. However, the
strong oxidation properties of chromates make them a potential
lung carcinogen responsible for the DNA damage [1]. Due to the
toxicity of hexavalent chromium (Cr6+ ), numerous efforts have been
spent to develop environmentally benign alternatives to CCC; and
the most promising ones identied thus far have been rare-earth
corrosion inhibitors (e.g., cerium oxide conversion coatings) [2]
and hybrid organicinorganic materials (e.g., organically modied
silicates) [3].
Currently there is an urgent need to establish innovative design
of protective coating systems that feature both excellent performance and environmental stewardship. To this end, one promising
technology for primer coating is solgel derived thin lms. Solgel
lms have good adhesion to both metallic substrates and organic
top coats. Good adhesion of solgel lms to metals derives from the
Corresponding author. Tel.: +1 406 994 6486; fax: +1 406 994 1697.
E-mail address: xianming s@coe.montana.edu (X. Shi).
0300-9440/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2008.09.003
38
exceptional corrosion resistance and long-term coating performance. Nonetheless, such SNAP primer coating serves simply as
a physical barrier for corrosion resistance, lacking the ability to
launch corrosion inhibitors upon the coating defects or to minimize corrosion of the unprotected substrate areas as in the case of
chromates.
One way to improve the repairing properties of such nanocomposite primer coating is the addition of corrosion inhibitor, which
can suppress corrosion initiated at the coating defects [14]. However, the inhibitors can also have a negative effect on the properties
of the solgel lm, decreasing its stability and consequently its
barrier properties [15]. Additionally, the release of inhibitors from
coatings is relatively fast and not controllable.
A more novel strategy is that of self-repairing, where a damaged structure is repaired by materials already contained within
it. A liquid repairing system can be encapsulated within brittlewalled containers. These containers are fractured during impact,
and allow the liquid repairing agent to ow into the areas of damage
where it subsequently cures. The technique was rst proposed by
Dry [16], who identied hollow glass tubes as a potential container
for a repair system. The system was initially studied for the repair
of cracks in concrete and a restoration of strength and exibility
was demonstrated for concrete specimens using the self-repairing
technique [17].
It has been reported that the corrosion protection properties
of SNAP coatings on aluminum substrates can be signicantly
improved by -cyclodextrin encapsulating of corrosion inhibitors
within the coating matrix [18]. The slow release of the inhibitor
from the cyclodextrin/inhibitor complexes provides an effective
long-term self-healing effect that protects the metallic substrates
from corrosion. The corrosion protection performance was examined using a potentiodynamic scan method and a scanning
vibrating electrode technique.
Inorganic nanoparticles can also be a way to incorporate corrosion inhibitors into coating, preparing inhibitor nanoreservoirs for
self-repairing lms with controlled release properties. The particles (nanoreservoirs) store and slowly release inhibitors when a
defect is formed in the solgel lm. As such, it reduces the negative
effect of inhibitors on the stability of the solgel matrix.
Fig. 1. Schematic illustration of the preparation procedure of cagelike silica gel microspheres.
39
Fig. 2. SEM images of cagelike silicon microspheres with closed (a) and opened (b) pores and TEM image of cagelike silicon microspheres (c).
40
Fig. 3. Schematic illustration of the self-assembling of SPCs and self-repairing of primer coating on aluminum alloy.
2.6. Characterizations
The localized surface morphology and chemistry of the primer
coatings were assessed by means of SEM coupled with EDS, which
were implemented on a Hitachi S-4100 system with beam energy
of 25.0 keV.
Fig. 4. SEM images of the scratched coating samples before (a) and after (b) immersion in deoxidized 3% NaCl solution at 45 C for 2 h.
41
Table 1
EDS data of the coating surface and of the agglomeration in scratch, compared with the calculated composition of PMMA.
Element content (wt.%)
Coating surface
Agglomeration in scratch
PMMA
Na
Al
Si
Ca
21.57
55.09
67.61
14.97
20.61
22.54
8.39
6.90
1.05
0.40
31.67
9.36
14.52
5.32
3.21
1.01
4.61
1.31
of MMA. This served the purpose of demonstrating the feasibility of the self-repairing coating concept. For practical application,
however, we plan to encapsulate repairing agents other than MMA
(most likely siloxanes) to obtain better corrosion resistance of the
polymerized repairing agent layer; and to encapsulate catalysts that
do not entail an oxygen-free environment to polymerize.
3.2.2. Electrochemical analyses
EIS provides information on interfaces and thus sheds light on
the properties of the primer coating layer on the surface of AA2024.
The complex impedance of the coated alloy depends on the frequency of the externally applied AC polarization signal, allowing
the representation of the system using an equivalent circuit with
typically resistors and capacitors to characterize different interfaces. As such, EIS was also used to evaluate the level of corrosion
protection offered by various primer coatings on AA2024.
Fig. 5 depicts the EIS data in the form of Bode plots, for the primitive coating (A), for the scratched coating (B), and for the scratched
coating after immersion in deoxidized 3% NaCl solution at 45 C for
2 h (C). Two well-dened time constants can be observed for all
three systems. The time constant at high frequencies (105 Hz) can
be ascribed to the capacitance of the coating layer, Ccoat . The time
constant around 101 Hz can be associated with the presence of
an intermediate layer (Coxide ), which is due to interaction of AlOH
groups with SiOH forming AlOSi covalent bonds as described
elsewhere [22]. A plateau on the impedance curve between the
two time constants reveals a resistive response (Rcoat ), as a function of the pore structure of the coating layer. At lower frequencies,
another resistive response (Roxide ) was detected, as a function of
cracks potentially formed in the intermediate oxide layer.
In the low frequency range, the impedance values for coating A were more than one order of magnitude higher than the
impedance values measured for coating B, evidencing the corrosion protection properties of the primitive coating. The coating C
had impedance values between coating A and coating B, signifying
the self-repairing property of the coating.
Fig. 5. Bode plots obtained for the primitive coating (A), for the scratched coating
(B), and for the scratched coating after immersion in deoxidized 3% NaCl solution at
45 C for 2 h (C).
42
Table 2
Parameters of the coating/substrate systems obtained by tting the experimental
EIS data with three different equivalent circuits.
Coating A
2
Rsolut ( cm )
Rcoat ( cm2 )
Qcoat (S cm2 )
ncoat
Roxide ( cm2 )
Qoxide (S cm2 )
noxide
Rpolar ( cm2 )
Qdl (mS cm2 )
ndl
W (mS cm2 )
9.27
2387
22.6
0.80
437.8
11.9
0.86
260.2
11.4
0.20
12.9
0.39
20
0.6
0.01
64.3
0.9
0.01
37.1
0.29
0.02
1.4
Coating B
8.07
9.15
183.8
0.78
43.1
204.5
0.75
2.27
55.9
0.33
124.0
0.41
2.93
27.6
0.03
3.1
31.3
0.03
0.51
9.9
0.09
26.8
Coating C
6.85
155.3
37.6
0.87
83.0
155.7
0.90
10.2
36.6
0.39
435.4
0.16
3.1
2.3
0.01
10.8
25.2
0.04
1.7
4.4
0.04
244.1
43
[22] G.P. Thim, M.A.S. Oliveira, E.D.A. Oliveira, F.C.L. Melo, J. Non-Cryst. Solids 273
(2000) 124128.
[23] M.L. Zheludkevich, R. Serra, M.F. Montemor, K.A. Yasakau, I.M.M. Salvado, M.G.S.
Ferreira, Electrochem. Acta 51 (2005) 208217.
[24] S. Feliu, J.A. Gonzalez, J. Appl. Electrochem. 26 (1996) 305309.