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FEATURE ARTICLE www.rsc.org/materials | Journal of Materials Chemistry

Sol–gel coatings for corrosion protection of metals

M. L. Zheludkevich,*a I. Miranda Salvadob and M. G. S. Ferreiraac
Received 21st December 2004, Accepted 21st July 2005
First published as an Advance Article on the web 18th August 2005
DOI: 10.1039/b419153f

Sol–gel derived films exhibit a high potential as substitutes for the environmentally unfriendly
chromate metal-surface pre-treatment methods. Inorganic sol–gel derived films offer good
adhesion between metals and organic paint. However, they cannot provide adequate corrosion
protection due to their high crack-forming potential. Introduction of an organic component to
Published on 18 August 2005 on http://pubs.rsc.org | doi:10.1039/B419153F

an inorganic sol–gel system leads to the formation of thicker, more flexible and functionalized
films with enhanced compatibility to different organic top coatings. Incorporation of
nanoparticles in the hybrid sol–gel systems increases the corrosion protection properties due to
lower porosity and lower cracking potential along with enhancement of the mechanical
properties. Furthermore, the incorporation of inorganic nanoparticles can be a way to insert
corrosion inhibitors, preparing inhibitor nanoreservoirs for ‘‘self-repairing’’ pre-treatments with
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controlled release properties.

Introduction with the metal surface forming a Cr2O3?nH2O solid hydrated

conversion coating. However, the inhibition mechanism of the
The huge economic impact of corrosion on metallic chromates for the corrosion protection of metals is still not
structures is very important issue. Most of the effective completely clear.
corrosion protection systems for metals contain chromates.1
Hexavalent chromium-containing compounds are a traditional
type of corrosion inhibitor which exhibit far better corrosion Isabel Miranda Salvado
resistance than any other inhibitors due to the strong oxidation received her PhD degree in
properties of Cr6+. When chromate coatings are applied, Materials Science from the
hexavalent chromium compounds, loosely bonded in the film, University of Aveiro in 1990
are slowly leached on exposure to aqueous media, healing and since 2003 has been an
Associate Professor at the
scratches and other defects. The chromate ions can interact
same University. Her research
covers synthesis by sol–gel pro-
a
University of Aveiro, ICEMS, Dep. Ceramics and Glass Eng.,
cessing of inorganic and hybrid
3810-193, Aveiro, Portugal. E-mail: mzheludkevich@cv.ua.pt; organic–inorganic materials
Fax: +351-234-425300; Tel: +351-234-378146 (bulk, fibers, films) with
b
University of Aveiro, CICECO, Dep. Ceramics and Glass Eng., different applications: ferro-
3810-193, Aveiro, Portugal electric, biomedical, corrosion
c
Instituto Superior Técnico, ICEMS, Dep. Chem. Eng., Av. Rovisco protection and encapsulation.
Pais 1049-001 Lisboa, Portugal
I. Miranda Salvado

Mikhail Zheludkevich is Mário G. S. Ferreira is Full

currently a post-doctoral
researcher in the Department
of Ceramics and Glass
Engineering at University of
Aveiro, Portugal. In 1998 he
graduated from the Belarusian
State University and in 2002
took his PhD degree in
Physical Chemistry at the
same University. His current
interests include investigation
of nanostructured sol–gel coat-
ings doped with nanoreservoirs
M. L. Zheludkevich of corrosion inhibitors for
‘‘intelligent’’ storage/release
properties.
Professor at the Department of
Ceramics and Glass Engineer-
ing, University of Aveiro, and
Adjunct Full Professor of the
Instituto Superior Técnico,
Portugal. He obtained his first
degree in Chemical Engineering
from the Instituto Superior
Técnico in 1971 and his PhD in
Corrosion Science and Engineer-
ing from UMIST, Manchester
in 1981. His main scientific
interests are focused on the study
M. G. S. Ferreira of materials degradation, the
development of advanced mate-
rials and ecological processes for
surface treatment.

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In spite of good corrosion protection, the leachability and
superior oxidation properties of the chromates make them
environmentally unfriendly. Skin contact, inhalation and
ingestion can cause penetration of the chromium waste into
the human organism. The hexavalent chromium species can
be responsible for DNA damage and cancer. However the
toxicological effects of chromates are not limited only to
cancer.2 Thus, strict environmental regulations will ban the
use of Cr6+-containing compounds in corrosion protection
systems. The need for the development of non-chromate
environmentally-friendly surface treatments is urgent.
One of the prospective candidates for substitution of the
chromate pretreatments are sol–gel derived thin films. Sol–gel
Published on 18 August 2005 on http://pubs.rsc.org | doi:10.1039/B419153F
films have a good adhesion to both metallic substrates
and organic top coats. Sol–gel technology can offer various
ways to prepare functional coatings with different properties.
Sol–gel coatings can be prepared using hydrolytic and
non-hydrolytic procedures in organic or aqueous media.3,4
The preparation of sol–gel materials can be controlled by
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variation of many parameters that influence the processes,
and in turn, the properties of the final coatings. The sol–gel
procedure is a method that allows deposition of a thin oxide
film at temperatures near to room temperature in contrast to
traditional ceramic processing technologies. The sol–gel
process has excellent potentiality to be used for preparation
of inorganic or organically modified protective coatings.
The sol–gel processes are mainly based on hydrolysis and
condensation reactions of metal alkoxides (M(OR)n). The
resulting oxide materials present structures varying in range
from nanoparticulate sols to continuous polymer gels depend-
ing on the rate of each of those reactions and subsequent
drying and processing steps. The close control of parameters of
the sol–gel reactions leads to the design of new advanced
materials with interesting properties for many applications.
Materials with different compositions can be easily obtained in
the form of glasses, fibers, ceramic powders and thin films.
Silicon–organic based sol–gel chemistry is more developed
nowadays when compared with other metal–organic based
precursors. The main aspects of the sol–gel chemistry and the
application of sol–gel derived materials are already described
in detail in a number of reviews and books.4–7
The first sol–gel processes were mainly based on simple
alkoxide precursors accessing to the ceramic or the glass-like
inorganic products.4 However, the low reaction temperature
also allows the introduction of organic groups in the inorganic
materials leading to a novel class of materials composed of
both inorganic and organic moieties.8–15 The inorganic
component confers enhanced mechanical properties while
the organic component leads to increased flexibility16 and
functional compatibility with organic paint systems. The
classical approach to join the properties of different materials
led to the development of composite materials, where two
different phases with complementary physical and chemical
properties are mixed. However, the properties of a hybrid
composite material depend not only on the properties of
the individual components, but also on the synergy between
them providing better properties than any of the two
constituents. The hybrid inorganic–organic sol–gel composites
can be prepared by two ways: the organic and inorganic
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groups can be linked by stable chemical bonds or the organic
component can be merely embedded into an inorganic
material, or vice-versa.17–20
Another important factor is the size of the organic–
inorganic domains in the final composite. The improved
physical properties can be achieved by reduction of the domain
size to the nanoscale, increasing the interfacial surface area.
Further reduction in domain size leads to formation of mole-
cular composites.20 This may be accomplished by incorporat-
ing the polymerizable inorganic group and an organic
constituent in the same molecule when the organic group is
bound to the oxide-forming element in a hydrolytically stable
way. Nanocomposites with a well defined structure can be
obtained using preformed nanobuilding blocks (NBB), such as
nanoclusters, nanoparticles or nanolayered materials. The use
of NBB strategy confers several benefits providing a mono-
dispersed well defined nanostructure of the final hybrid
material.17
Incorporation of an organic component into the inorganic
materials opens a wide range of possibilities for functionaliza-
tion and tailoring of the final material. The addition of
chromophore molecules or luminescent groups leads to
hybrids with advanced optical properties.21 Another key
property, which can be tuned using modification of the
organic functionality, is compatibility and adhesion of thin
protective hybrid sol–gel films to top organic paint systems.
Chemical bonding is possible between the sol–gel film and
the top coat conferring enhanced adhesion in comparison
to chromate pre-treatments where adhesion is based on
mechanical interlocking, dispersion forces and hydrogen
bonds.22 Fig. 1 depicts possible ways to obtain an enhanced
chemical compatibility of an epoxy-based or amino-containing
paint system to a sol–gel pretreatment by functionalizing
the organic component of the hybrid film with epoxy groups.
Other functional groups were used for pre-treatment func-
tionalization in the case of poly(urethane) and thioester paint
systems.22,23
The general objective of the present work is a critical review
of the recent publications in the area of the sol–gel coatings
for corrosion protection of metallic substrates. The influence
of various parameters on the sol–gel process and, in turn,
on the protection properties of the final systems is also
discussed. Prospective ways to develop new advanced nano-
structured sol–gel coatings with self-repair properties are
proposed.
Preparation of the sol–gel coatings
Synthesis of the sol–gel systems. The sol–gel route is based
on the evolution of a colloidal system through formation of an
inorganic or hybrid sol followed by its gelation to form a
continuous polymer network (gel). Alkoxides of silicon and of
some metals can be used as precursors for classical synthesis of
such sols. Alkoxysilanes, such as tetraethoxysilane (TEOS)
and tetramethoxysilane (TMOS), and alkoxides of zirconium,
titanium, cerium, tin and aluminium are commonly used in the
sol–gel route to prepare corrosion protective coatings. The
common reactions that take place during the sol–gel process
are shown in the following scheme:
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Replacement of the alkoxide groups (–OR) with hydroxyl
groups (–OH) occurs during the hydrolysis stage (1) due to
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the interaction of alkoxide molecules with water. The second
stage of the sol–gel route is the condensation of two –OH
groups (2b) or –OH group with –OR group (2a), which
produces M–O–M bonds and water or alcohol, respectively.4,7
Usually, the condensation process starts before the end of
the hydrolysis step. In this case the oligomeric or polymeric
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molecules are formed, depending on the rate of the hydrolysis
and condensation reactions. The rate of the hydrolysis reaction
is commonly higher than the rate of the condensation
processes.24–26 Moreover, an important factor that can
strongly influence the kinetics of the reactions in the sol–gel
system24 is the nature of the mutual solvent. Addition of a
mutual solvent, such as alcohol, is needed in order to achieve
homogenization of the reaction system, since the water and
metal alkoxides are immiscible liquids. The nature and
concentration of the solvent has also a significant influence
on the structure and thickness of the sol–gel derived protective
films. A high concentration of aprotic solvent enhances
corrosion resistance. However the effect is opposite when
small alcohols are used as a diluent due to solvent-induced
reesterification processes. The correct selection of solvent
allows tailoring of the sol–gel coating structure.27
The chemical reactivity of the various alkoxides is different
for similar alkoxy groups as shown for the following alkoxides:
Si(OR)4 ,,, Sn(OR)4 , Ti(OR)4 , Zr(OR)4 , Ce(OR)4.
Fig. 1 Schematic representation of enhanced compatibility of different paint systems with an epoxy-functional hybrid sol–gel coating.
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Therefore, different strategies can be used for the sol–gel
systems’ synthesis depending on the reactivity of the pre-
cursors. The hydrolysis and condensation reactions of the
metal alkoxides are very fast and must be controlled by the use
of inhibitors.17,18,28 b-Diketones,29 b-ketoesters,30 diethylene-
glycol,31 carboxylic acids32 or other complexing agents, which
inhibit the condensation reaction, are commonly used.33 The
complexing agents substitute the alkoxides groups by the
respective ligands generating a new precursor with a modified
structure and lower reactivity. The alkoxy groups are primarily
hydrolyzed upon addition of water and then the complex
bonds are slowly cleaved leading to decreased hydrolysis rate
of precursor.17,19 Changing the concentration of water and the
complexing agent leads to the modification of the sol–gel
system structure, and consequently, the coating properties.
In situ generation of water (through esterification or aldolisa-
tion reactions) can be a useful way to avoid nonuniform rate of
the hydrolysis processes which appear due to local increase of
water in different regions.17
Since the silicon alkoxides are not very reactive a catalyst
should be added. An acid or base type catalyst is commonly
used in order to accelerate these processes.4,34–37 Basic catalysis
leads to the formation of compact highly branched silica
networks in contrast to the acid-catalyzed hydrolysis–
condensation processes where primarily linear or randomly
branched polymers are formed.
Sols of inorganic oxides can be prepared also using a non-
hydrolytic sol–gel route. This process is based on the
condensation reaction between metal chlorides and oxygen
donors (alkoxides, ethers or aldehydes). Synthesis of the oxides
in this case is more controllable and occurs under milder
reaction conditions. The sols prepared are usually more
homogenous. For example, silica, alumina, titania and also
various binary oxide sols were prepared using non-hydrolytic
sol–gel procedure in several works.38,39
Synthesis of the sols commonly occurs with the active mix-
ing of components. The results of several works show that the
use of ultrasonic radiation during the hydrolysis–condensation
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process leads to the formation of more uniform sols with
higher stability.32,40–42
Another important factor from the point of view of coating
preparation is the stability of the synthesized sol. The aging of
sol leads to further condensation and crosslinking between
polymer molecules. Therefore, aging has a significant influence
on the corrosion protective properties of sol–gel derived
coatings. The aged sols lead to more porous structures during
coat drying due to formation of a stronger gel network, more
resistant to capillary-driven collapse.43 Fig. 2 shows DC
polarization plots for stainless steel coated with fresh and
aged sol gel systems. In the case of the aged sol–gel coating
both cathodic and anodic currents are one order of magnitude
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higher, exhibiting worse barrier properties than those obtained
with a fresh sol–gel film. Donley et al. found that dramatic
changes occur in the sol–gel solution in the first 24 h. After
this period, the condensation reaction becomes slower.26
However a FTIR study of the sol–gel system evolution shows
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that the condensation processes occur in gels even after very long
periods (t = 100tgelation).24 The rate of the aging processes can be
sufficiently increased by addition of metal alkoxides to silanol
sols. The condensation degree of the metal alkoxide-containing
sols is significantly higher in comparison with siloxane sols due
to the presence of metal alkoxides as a second condensable
component which reacts very fast with silanol groups.25
However addition of metal alkoxides to the sol–gel system
causes the formation of gels with lower porosity that can
improve the barrier properties of the coatings prepared from
such sol–gel systems.44 Another way to decrease the gel porosity
is by the increase of the strength of the catalytic acid.37
Deposition and curing of the sol–gel coatings. Corrosion
protective films can be deposited from sol–gel solutions
using different common methods, including spraying,45,46
dipping40,47 and spinning.48,49 Dipping and spinning techni-
ques can be used only for deposition of the coatings on a flat
surface. In the case of complex shapes it is difficult to achieve
uniform coating using these procedures. In several works it
was shown that the method of electrochemical deposition of a
sol–gel film is superior for structures with complex geometries
Fig. 2 Polarization curves of stainless steel substrates coated with
fresh and aged (for 15 d) MPS (3-methacryloxypropyltrimethoxy-
silane) sols. Reprinted from ref. 43, copyright 2001, with permission
from Elsevier.
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in comparison to dip or spin coating techniques.31,34,35,50–52
Electrodeposition techniques offer relatively thick crack-free
sol–gel derived coatings.31,34,35,50,53 For example Castro et al.
prepared crack-free silica coatings up to 20 mm after low
temperature drying and crack-free glass-like films of 12 mm
after heating till 500 uC.34,54 Corrosion testing of these
coatings showed superior barrier properties when compared
to coatings obtained by dipping or spinning. Fig. 3 shows the
impedance spectra for aluminium substrate coated by phenyl
trimethoxysilane (PTMOS) sol–gel coating using dipping and
electrodeposition techniques.50 In the case of the electrode-
posited sol–gel film the impedance is several orders higher than
the one conferred by coatings prepared by dipping. Such
difference in the impedance values reflects a sufficiently higher
thickness and a considerably lower porosity of the electro-
deposited sol–gel coating.
Another important stage after coating deposition is the
drying of the sol–gel film. Two different ways are commonly
used to dry the formulated coatings on stainless steel. The first
type of post-deposition treatment of the sol–gel derived films is
high temperature annealing. During this procedure the coated
substrate is heated to high temperatures (around 900 uC) in air.
Different processes occur during the heating of sol–gel coat-
ings: evaporation of solvent and continued polycondensation
occurs at 100–200 uC; oxidational decomposition of organics
and collapse of small pores takes place at 300–500 uC; collapse
of larger pores occurs after heating of sol–gel derived ceramic
films to temperatures around 700–900 uC. However, the
heating rate is also an important factor which can significantly
influence the structural and corrosion protective properties of
the final films. Thus, decrease of the heating rate leads to
formation of more compact coatings with better barrier pro-
perties.55 Gallardo et al. studied the evolution of the polariza-
tion resistance of silica-based sol–gel coatings on stainless steel
substrate during immersion (Fig. 4).56 An increase of the
drying temperature results in a lower corrosion resistance of
the silica-based sol–gel coatings due to cracks induced by
stresses that appear during sintering at high temperatures.
Similar behaviour was revealed for zirconia, alumina, silica
based and mixed sol–gel derived coatings.29,40,57–60 However,
Fig. 3 Bode plots of Al samples [(N) bare, (.) electrodeposited phenyl
trimethoxysilane and (¤) dip coated phenyl trimethoxysilane] obtained
at 20.74 V vs Hg–Hg2SO4. Reprinted from ref. 50, copyright 2003,
with permission from Elsevier.
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Fig. 4 Evolution of the polarization resistance with time of immer-
sion for silica coatings sintered at different temperatures. Reprinted
from ref. 56, copyright 2003.
the effect of the drying temperature is opposite from the point
of view of mechanical properties.56
High temperature sintering of sol–gel films in vacuum or in
a nitrogen atmosphere shows some improvement of the
anticorrosive properties, in comparison to the coatings fired
in air, due to the formation of less defective layers.32,47,61
Commonly, the fired sol–gel coatings do not provide adequate
corrosion protection42,58,62 and are used as wear-resistant
layers63–65 or barriers against high temperature oxidation of
metallic substrates.47,61 Especially, the mixed oxide coatings
are less resistant to wet corrosion due to the formation of
macropores during the sintering process.48,61,66
In the second case, the sol–gel derived film is dried at low
temperatures (less than 200 uC). Not only does evaporation of
solvent occur during this drying stage, but also gelation and
additional shrinkage of the formed gel. Compact crack-free
films, depending on the film composition and thickness, can be
formed on the top of metallic substrates using this procedure.67
Low temperature drying usually is applied for curing of hybrid
organically modified sol–gel derived coatings.68–70
A relatively new approach to densification of the sol–gel
coatings is using UV radiation. Sol–gel films treated by UV
radiation at room temperature show corrosion resistance
of about 2.5 times higher than conventional films dried at
300 uC.71 Increase of the corrosion resistance can be attributed
to formation of denser sol–gel coating layers.
Types of protective sol–gel coatings
Inorganic sol–gel coatings for corrosion protection.
Historically, the first type of sol–gel pre-treatments are
inorganic oxide sol–gel derived films. Inorganic sol–gel coat-
ings for corrosion protection of different metallic substrates
were developed and investigated in several works.29,67,72 The
corrosion protection of zirconia sol–gel films is at least as good
as the tricationic phosphate pretreatment for a steel sub-
strate.29 Khobaib et al. showed that a sol–gel pretreated
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AA2024 substrate coated with poly(urethane) layer provided
an acceptable corrosion protection level close to that of
conventional chromate system. However, results of corrosion
tests for scribed panels clearly demonstrate the superior
performance of the chromate pretreatment over the sol–gel
based coating systems.72 Preparation of thick sol–gel coatings
induces the formation of cracks during the drying procedure.
Local breakdown of sol–gel coatings at isolated sites causes
pitting corrosion of aluminium and stainless steel51 after
contact with corrosive species. Sol–gel derived inorganic
coatings prepared using low temperature drying can offer
better barrier properties against wet corrosion than fired sol–
gel films as shown above. However, the barrier properties of
these coatings are also not enough to achieve a good
protection against corrosive species due to the formation of
non compact coatings with high amount of micropores.
The crack-free films usually are very thin (about 100 nm) or
incompact. These films can be cracked during the coatings
drying due to the different thermal expansion coefficients of
the sol–gel derived films and the metallic substrates. The
thermal expansion coefficient of aluminium is twice as higher
than that of steel. Therefore the critical coating thickness
(without formation of cracks) is much lower for aluminium
than for steel substrates.35
On other hand inorganic sol–gel coatings provide a good
adhesion layer between metallic substrate and organic
coatings.29,62,65,73 The advantage of sol–gel coatings is the
formation of strong van der Waals bonds between polymer
molecules and the metallic surface. These bonds can be
transformed to stable covalent Me–O–Si or Me1–O–Me2
bonds during the film drying stage30 as shown in Fig. 5.
Schmidt et al. estimated the thermodynamic possibility of
Si–O–Al bonds formation in sol–gel film/aluminium
substrate systems. Thermodynamical calculations show that
the alumina–silica mixed compounds altogether have a lower
Gibbs energy than the boehmite, which is produced on the first
stage of oxidation of aluminium in the presence of moisture.74
The enthalpy of interaction between two Al–OH groups:
–Al–OH + HO–Al– A –Al–O–Al– + H2O, DH = 248 kJ mol21
is sufficiently higher than:
–Al–OH + HO–Si– A –Al–O–Si– + H2O, DH = 2462 kJ mol21
Fig. 5 Schematic representation of formation of covalent bonds
between a metallic substrate and a silica based sol–gel film.
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leading to the formation of a stable alumina/sol–gel film
interface.60,75 This interface is not only stable but also has some
renewal ability. The hydrolyzed Me–O–Al bonds can be formed
again, according to the law of mass action and thermodynamical
equilibrium, reducing the propagation of corrosion.74 For
example, the zirconium oxide coating on anodized aluminium
shows high alkaline corrosion resistance due to the self-repairing
action caused by repetition of formation and cleavage of oxane
bonds during the penetration of the base solution into the sol–gel
film.71 Yang et al. revealed that pitting corrosion occurred on the
Al alloy surface coated with SiO2 : ZrO2 sol–gel coating in the
initial immersion period. However further corrosion was inhibited
even after long immersion time.76 The authors explain this
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behavior in terms of the formation of a mixed (aluminium–silicon)
oxide insoluble layer, which blocks pores and defects in the sol–gel
coating as shown in Fig. 6. Zheludkevich et al. found a similar
effect in the case of nanostructured sol–gel coatings on 2024
aluminium alloy.30 The EIS (electrochemical impedance spectro-
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scopy) measurements revealed an increase of the pores resistance
after 40–60 h of immersion in 3% NaCl solution. However
these ‘‘self-repair’’ effects are much lower than in the case of
chromium pretreatments.
Fig. 6 Schematic diagram showing that pits are stopped due to
formation of a mixed aluminium–silicon oxide layer. Reprinted from
ref. 76, copyright 2001, with permission from Elsevier.
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Hybrid sol–gel derived coatings. Hybrid films are very
interesting because they combine properties of the organic
polymeric material and properties of the ceramic. Hybrid
coatings can be prepared over a continuous compositional
range from almost organic to almost inorganic.77 The
properties of these coatings can be changed continuously to
form an optimum coating.78 The inorganic components
contribute to the increase of scratch resistance, durability
and adhesion to the metal substrate. The organic component
increases density, flexibility, and functional compatibility with
organic paint systems. An advantage of the organically
modified sol–gel systems is the possibility to prepare thick,
crack-free coatings.79,80 As an example it is shown in Fig. 7
that the addition of the poly(vinyl butyral) component to
the silica-based sol–gel coating prevents formation of cracks.
It was also found that the hybrid films have a good bio-
compatibility for bio-medical applications.43 The use of
organofunctional silanes can improve the mechanical pro-
perties and adhesion to specific organic paint systems (Fig. 1)
in comparison to sol–gel materials based on non-functional
organosilanes.81,82 Different chromophore molecules can be
introduced to improve aesthetic properties21 when the sol–gel
film is used as a top coat.
The sol–gel derived hybrids can be classified in two different
classes, depending on the nature of interfaces between organic
and inorganic phases, as schematically depicted in Fig. 8. No
chemical bonds usually exist between inorganic and organic
phases in the hybrids from first class (Fig. 8a). Only weak
dispersion forces and van der Waals interactions are present in
these hybrids. The synthesis of the first class of hybrids can be
performed by mixing an inorganic sol with an organic phase
and carrying out the sol hydrolysis and condensation reactions
Fig. 7 SEM images of silica and silica-polymer hybrid films; (a) silica,
(b) silica + 0.5 wt% poly(vinyl butyral). Reprinted from ref. 80,
copyright 2004.
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Fig. 8 Structural models of different classes of hybrid materials
formed by the sol–gel process;96 (a) no chemical bonds usually exist
between inorganic and organic phases; (b) polymerizable organic
groups are bounded to the inorganic nanoparticles; (c) non-
polymerizable organic groups are bounded to the inorganic phase.
in the presence of a preformed organic polymer.17,18,80,83,84
Such composites usually can not provide effective long term
stability during weathering. The precursors with already
covalent or complex bonded organic groups are used for
synthesis of the hybrid sol–gel systems in the second class of
hybrids. Strong chemical bonds form between organic and
inorganic parts in the final hybrid materials (Fig. 8b,c). The
commonly used sol–gel precursors are commercially available
as organoalkoxysilanes and metal alkoxides.
Organically modified sol–gel coatings can be classified into
two groups based on the type of the organoalkoxysilane
organic part: non-functional organoalkoxysilanes; organo-
functional alkoxysilanes.82,84 Methyl groups are commonly
used as the organic part for preparation of the hybrids with non-
functional component.44,50,60,79,85–88 Organofunctional pre-
cursors are epoxy,25,45,46,81,85,89–92 methacrylic,36,41,43,80,93–95
acrylic,93 allyl,81 alkyd,96–98 phenyl,50,52 pyridine,99 amino100
or vinyl-functional organosilanes.81,89,101
Some of the used organofunctional groups (epoxy, vinyl,
methacrylic, etc.) are open to additional polymerization
(Fig. 8b). Sol–gel derived coatings with such groups have a
higher crosslink density and better mechanical properties due
to the additional cross-linking of the organic groups16,82,93 in
comparison to sol–gel materials based on non-functional
organosilanes. The different organic groups are used to achieve
a tailored compatibility of the sol–gel pre-treatments to the
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organic paint systems (as shown in Fig. 1) and to alter the
hydrophobicity of coatings.50,73,81,99 The amino groups are
especially capable to react with the epoxy polymer coatings
and provide an excellent binding of the polymer top layer to
the sol–gel pre-treatment.73,81 However the amino-containing
sol–gel pretreatments can not provide an adequate barrier
against water after curing at room temperature, due to the low
hydrolytic stability.81 In several works the hybrid materials
were prepared using alkyds as the organic phase.96–98
Naturally-occurring oils were used as raw materials that
lead to higher environmentally compatibility of the resultant
coatings. Linseed, sunflower and soybean oils were used for
preparation of the alkyds.
The simplest hybrid coating is the methyl modified silica,
which shows better protection against corrosion for steel
substrates than inorganic sol–gel coatings.61,102–104 However
hybrid sol–gel films prepared on aluminium using phenyl
trimethoxysilane as precursor have even higher corrosion
resistance in comparison to methyl modified silica coatings
due to higher hydrophobicity of phenyl groups.50 The barrier
properties of methyl modified silica coatings can also be
improved by addition of TiO2 precursor during the sol
synthesis due to decreased volume of macro and mesopores.44
Bescher and Mackenzie found that the methyl–epoxy hybrid
coatings exhibited a good resistance to UV and effectively
protect brass and bronze substrates from corrosion.105 High
UV stability was revealed also for the hybrid coatings prepared
from polyfunctional silanols.70 These coatings exhibit very
good anti-adhesive surface properties that can be interesting
from the point of view of automotive clear-coats.
Epoxy–silica sol–gel films on 2024-T3 aluminium alloys
prepared with a thickness of 2.2 mm showed excellent barrier
properties and enhanced corrosion protection under acceler-
ated corrosion tests in comparison to the standard Alodine-
1200 type surface pre-treatment.45 Epoxy–zirconia hybrid
coatings also present good barrier properties for the alumi-
nium alloy.33 Addition of the epoxy or vinyl components to
silica sols can decrease the rate of pitting corrosion of the AA
2024-T3 alloy due to the elimination of cracks and enhanced
flexibility of the coating.89 Good barrier properties of such
coatings can be explained by additional polymerization of
the epoxy component during preparation of the coating. The
epoxy rings in the case of the epoxy-containing sol–gel systems
can be opened due to interaction with water25,46,90 according
to the following equation:
ð1Þ
The decrease in pH and the increase of water content in sol–
gel systems tend to accelerate the ring-opening processes.46
The ring-opening reaction can also be accelerated by the
addition of metal alkoxides during sol synthesis.25 The diol
groups significantly increase the hydrophilicity, and in turn,
decrease the barrier properties of the sol–gel films.46 Therefore,
it is very important from the point of view of the corrosion
protection to achieve polymerization of the epoxy groups
during or after the ring-opening processes. Metroke et al.
studied the polymerization of epoxy groups in sol–gel systems
using different curing agents.90 Two kinds of curing agents
J. Mater. Chem., 2005, 15, 5099–5111 | 5105

were studied: the primary aliphatic amines and the superacids.
Primary aliphatic amines participate in the ring-opening
reaction and can be chemically bonded to the organosiloxane.
Superacids promote the homopolymerization of the epoxy
groups to form poly(ester)s. Results of this work demonstrated
that amine curing leads to formation of highly crosslinked,
dense films with good corrosion resistance. Superacid
curing produces films with oligomeric structure, and in turn,
with poor barrier properties and adhesion to the metal
substrate. Khramov et al. used mono-, di-, and tri-functional
amino-silanes as crosslinking agents.69 The sol–gel films
prepared using amino-silanes exhibited improved corrosion
protection over primary aliphatic amines used in the work of
Published on 18 August 2005 on http://pubs.rsc.org | doi:10.1039/B419153F
Metroke et al.90
The methacrylate-containing hybrid sol–gel coatings on
stainless steel also provide enhanced corrosion protection by
forming uniform, defect-free and relatively dense physical
barrier against corrosion species.36 Ono et al. prepared hybrid
silica–PMMA [poly(methylmethacrylate)] and silica–PVB
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[poly(vinyl butyral)] films on steel and aluminium alloy
substrates.80 They clearly demonstrated that introducing the
polymer solution during the sol–gel system synthesis leads to
the formation of crack-free coatings. The increase of the
polymeric component concentration tends to promote the
formation of thicker films.43,80 However, a too high concen-
tration of organic polymer impairs the corrosion protection
and adhesion of the sol–gel coatings to the metallic substrate.
Messaddeq et al. found that 17 vol% of poly(methylmetha-
crylate) is an optimal concentration in the case of the zirconia
based sol–gel coatings from the point of view of corrosion
protection.94
Zirconocene-modified poly(siloxane)-2-pyridine sol–gel
derived coatings were found to confer high corrosion protec-
tion properties for aluminium substrate. EIS measurements
revealed that low frequency impedance of such coatings is
higher than 1 MV even after 40 d of immersion in 0.5 M NaCl
solution. The chemical state of the interface between the
polymer and the aluminium surface can play an important role
in this good behaviour due to the formation of –NAO–Al
bonds between the nitrogen atom of the pyridine ring and
oxygen on the substrate surface.99
Conducting polymer based hybrid sol–gel coatings were
produced by electropolymerization of anchored pyrrole rings in
a hybrid xerogel providing reasonable protection properties.53
Recently another type of hybrid coating based on bis-
functional silanes was described in the several works, exhibit-
ing very promising results for corrosion protection of
aluminium alloys and galvanized steel.106–111 The results show
that the bis-sulfur silane film on AA2024 performs even better
than traditional chromate reference treatment at least for short
periods.107 Water-based bis-aminosilane–vinyltriacetoxysilane
mixtures also provide the corrosion protection comparable
with that of chromates.108 These pre-treatments demonstrate
results so promising that they are the subject of several
patents.112,113
Nanostructured sol–gel coatings. Organic components in sol–
gel films lead to improved corrosion protection properties due
to formation of thicker crack-free films as discussed above.
5106 | J. Mater. Chem., 2005, 15, 5099–5111
View Online
Fig. 9 Photos of bare and coated AA2024-T3 substrate after 1 week
immersion in 3% NaCl solution; (Al) bare alloy; (A) alloy coated with
zirconia nanoparticle-containing hybrid film; (B) alloy coated with
particle-free hybrid film.
However, the organic constituent leads to the simultaneous
decrease of wear resistance and mechanical properties of the
sol–gel coatings.16 Recent work shows that the polymer sol–gel
network can be reinforced by dispersing inorganic particles in
the hybrid matrix.49,56,85,114 Particles with a diameter in the
nano-range are commonly used as reinforcements for hybrid
sol–gel coatings, since the suspensions that contain particles of
diameter higher than 500 nm are not stable, the preparation of
uniform sol–gel films is in this case impeded.56 Incorporation
of nanoparticles into the hybrid sols leads to an additional
improvement of the barrier properties due to enhanced
thickness and low crack ability of such composites.30,114
Fig. 9 shows the photos of Al 2024 samples immersed in 3%
NaCl solution during 1 week. The alloy coated with the hybrid
sol–gel film doped with zirconia nanoparticles shows almost
no signs of corrosion attack contrasting to the sample coated
with the same sol–gel film without nanoparticles. However, the
corrosion resistance strongly depends on the concentration
and size of the particles.
Different strategies for nanoparticle introduction can be
used, such as addition of nanopowders into the sol–gel
system49,56,85,114 and design of functional nano-structured
materials through the use of controlled hybrid organic–
inorganic interfaces.26,28,30,35,69,115–128
The first strategy was used in several works for the prepara-
tion of protective films on metallic substrates. Chen et al.
found that flexible, crack-free coatings with a thickness of
about 7 mm on aluminium substrates can be prepared by
spinning of hybrid sol–gel system with Al2O3 particles.49 The
coatings showed good corrosion protection properties. The
incorporation of 10% glass particles into the sol greatly
increases the corrosion resistance of the hybrid sol–gel coatings
as well.56 Increase of the glass particle content from 5 to 10%
was found to enhance the average and maximal thickness of
the sol–gel coatings. However, high diameter (3 mm) of the
used reinforcements leads to the formation of some cracks in
the ‘‘neck’’ areas around the particles. Conde et al. noticed
significant improvement of the corrosion protective properties
due to addition of 25% nanosilica to epoxy–silane sol–gel
coatings.85 EIS results showed that low frequency impedance
of coatings without nanoparticles is one order of magnitude
lower than in the case of the same films with nanosilica. It
means that the non-particulated coating has much higher
degree of porosity, and is thus less protective. The bis-
functional silanes were also doped with silica microparticles
exhibiting enhanced corrosion protection to the aluminium
alloys and the galvanized steel.129,130 The addition of silica
This journal is ß The Royal Society of Chemistry 2005

particles leads to the formation of thicker films enhancing
barrier properties. However overload of the silane films
causes the opposite effect as in the case of epoxy–silane sol–gel
coatings.
Reinforcement of the sol–gel coatings by mechanical
addition of nanopowders to hybrid sols leads to the increase
of corrosion protection as it was shown above. However, this
strategy can not provide chemical bonds between a hybrid
matrix and nanoparticles. Therefore direct synthesis of oxide
nanoparticles during the sol–gel process is a preferable
technology. Hydrolysis and condensation of most metal
alkoxides can lead to the formation of particulated sols
depending on preparation conditions. The prepared sols can be
Published on 18 August 2005 on http://pubs.rsc.org | doi:10.1039/B419153F
stabilized by changing the pH due to electrostatic repulsion
forces. Additional stabilization can be achieved by using
complexing agents,125–127,131 which influence the structure and
zeta-potential of the synthesized sols. The complexing agents
establish chemical bonds with metallic atoms located on the
oxide particle surface acting as a surface stabilizer and allow
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the formation of nanoparticles by more controllable way.
Moreover, hydrolysis with a water solution of p-toluene-
sulfonic (a weak complexing acid) facilitates the redistribution
of the M–O–M bonds leading to crystallization of the
nanoparticles.125–127,132 Variation of the pH and the complex-
ing agent concentration can be used for preparation of the sols
with targeted particle size. The shape and size of nanoparticles
can be also controlled by use of colloidal assemblies as
templates.133 The organosiloxane component is commonly
added to prepared particulated sols to form a hybrid matrix
around oxide particles. The surface of the prepared nano-
particles can be chemically modified before mixing, by
introduction of components which form chemical bonds with
oxides. Functional organosiloxanes are mainly used in the case
of silica particles and functionalized complexing ligands in the
case of other oxide nanoparticles.17,19,125 This can sufficiently
improve the compatibility of the inorganic nanoparticles
with the hybrid matrix, and in turn, lead to the formation of
compact crack-free coatings.28,115–117
Zheludkevich et al. prepared epoxysilane hybrid coatings
with incorporated zirconia nanoparticles by using the sol–gel
procedure.30 Increase of the TPOZ (zirconium tetrapropoxide)
hydrolysis time and temperature lead to the formation of
sol–gel films with larger content of incorporated ZrO2
nanoparticles. EIS results showed that the incorporation of
the nanoparticles enhances the corrosion protection conferred
by the sol–gel hybrid films. In another work124 poly(acryl-
amide)–silica nanocomposites with particle–matrix structure
were prepared by the sol–gel route in acidic aqueous solution.
The relatively new approach for the preparation of nano-
structured hybrid sol–gel coatings using NBB strategy is the
self-assembled nanophase particle (SNAP) process. The SNAP
sols are prepared by drop-wise addition of tetramethoxysilane
(TMOS) and glycidooxypropyltrimethoxysilane (GPTMS) in
the ratio 3 : 1 to a solution of acetic acid followed by
aging.26,68,69,119–123,134 Particle-like nanosized siloxane oligo-
meric molecules with epoxy functionalities in the sol are
formed. Crosslinking agents are added to the SNAP solution
directly before coating deposition. During the drying stage the
crosslinking agent forms chemical bonds with the epoxy
This journal is ß The Royal Society of Chemistry 2005
View Online
Fig. 10 AFM image of SNAP coating. Reprinted from ref. 26,
copyright 2003, with permission from Elsevier.
groups of the nanoparticles producing uniform nanostructured
compact crack-free coatings as depicted in Fig. 10. The low
corrosion current densities and high values of the impedance at
low frequencies (in the order of 107 V cm2) show that the
SNAP surface treatment provide a fully dense protective
barrier with excellent corrosion protection to metallic sub-
strates.68,69,119–121 Choice of the crosslinking agent used in the
SNAP process is very important from the point of view of
corrosion protection properties. Commonly, the amines are
used as curing agents and can link nanoparticles.121 However
the amino-silanes were found to be a good alternative for
aliphatic amines.69 Khramov et al. showed that SNAP
coatings cross-linked with amino-silanes confer significant
better coating performance than the films with aliphatic amine
cross-linkers69 as presented in Table 1. Additionally the SNAP
process is water based and the use of this technology can
achieve significant reduction of VOCs release during the
pretreatment process.
Furthermore, the incorporation of inorganic nanoparticles
can be a way to insert corrosion inhibitors, forming an
inhibitor reservoir for ‘‘self-repair’’ with controlled release
properties.135 Khramov et al. reported that the corrosion
protection properties of hybrid nanostructured sol–gel coat-
ings on aluminum substrates can be significantly improved by
means of the encapsulation of corrosion inhibitors within
the coating matrix.68 SNAP films show also high potentialities
to be a reservoir for the ‘‘intelligent’’ release of organic
inhibitors.68,119 This is discussed in the following section.
Hybrid sol–gel films with corrosion inhibitors. Sol–gel coat-
ings especially the hybrid films provide dense barrier for
Table 1 Values of impedance modulus at low-frequency (1022 Hz)
for different samples69
Immersion
Coating time |Z|/V cm2
SNAP with 3-aminopropyltrimethoxysilane Initial 7.9 6 105
14 d 2.8 6 105
SNAP with 3-(2-aminoethyl)aminopropyl- Initial 2.9 6 105
trimethoxysilane 14 d 5.6 6 105
SNAP with 3-(trimethoxysilyl)propyldiethyl- Initial 1.4 6 106
enetriamine 14 d 2.5 6 105
SNAP with diethylenetriamine 14 d 1.3 6 104
Bare AA 2024-T3 Initial 1.2 6 104
J. Mater. Chem., 2005, 15, 5099–5111 | 5107

corrosive agents. However the coating alone is not sufficient to
protect a metal substrate from corrosion. Since a coating
contains micropores, cracks, and areas of low cross-link
density they provide a path for diffusion of corrosive species
such as water, oxygen and chloride ions to the coating/metal
interface. Some sol–gel coatings present a ‘‘self-healing’’ effect;
however this effect is lower than in the case of the chromate
pretreatments. Therefore, sol–gel coatings can provide an
adequate protection to the substrate only when they don’t have
mechanical defects. Incorporation of inorganic or organic
inhibitors into the sol–gel films can significantly improve
corrosion protection. Phosphates, vanadates, borates, cerium
and molybdenum compounds were found to have an inhibiting
Published on 18 August 2005 on http://pubs.rsc.org | doi:10.1039/B419153F
action on corrosion processes of different metallic substrates.
Some of the most effective and environmentally friendly
inhibitors are derived from cerium salts.2,136–140 Deposition of
the hydrated cerium oxide in the case of aluminium alloys
occurs onto cathodic intermetallic particles and the cathodic
reaction is suppressed.137,141 The results of several works
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showed that the incorporation of cerium dopants into sol–gel
coatings can be an alternative to chromate pretreatments in
the case of aluminium alloys and galvanized steel.135,142,143
N. Voevodin et al. investigated the corrosion protection
properties of the epoxy–zirconia sol–gel coatings with incor-
porated non-chromate inhibitors of Ce(NO3)3, NaVO3, and
Na2MoO4.143 Fig. 11 depicted the DC polarization curves for
AA2024 alloy coated with epoxy–zirconia sol–gel coatings
doped with the above mentioned inhibitors and with undoped
one. Sol–gel films with NaVO3 and Na2MoO4 did not provide
adequate corrosion protection due to decrease of the sol–gel
network stability. However the sol–gel coatings with cerium
dopants perform at least as good as the undoped epoxy–
zirconia films.143 The critical concentration of the cerium
inhibitor is in the 0.2–0.6 range (wt%). Higher concentrations
could lead to the formation of defects in the network of the
sol–gel film.142 In order to decrease the negative effect of
inhibitor on the stability of the hybrid matrix the cerium ions
Fig. 11 Potentiodynamic polarization curves obtained in 3.5% NaCl
solution for Al 2024-T3 coated with: (1) standard Zr–epoxy sol–gel; (2)
Zr–epoxy sol–gel with Ce(NO3)3 (5 wt%); (3) Zr–epoxy sol–gel with
Na2MoO4 (5 wt%)and (4) Zr-epoxy sol–gel with NaVO3 (4 wt%).
Reprinted from ref. 143, copyright 2001, with permission from
Elsevier.
5108 | J. Mater. Chem., 2005, 15, 5099–5111
View Online
Fig. 12 Schematic representation of self-healing in a defect by the
inhibitor slowly released from the nanoreservoirs in the sol–gel
coating.
can be introduced into oxide nanoparticles. The particles play
the role of nanoreservoirs storing and slowly releasing cerium
ions when a defect is formed in the sol–gel film.144,145 Fig. 12
presents the possible mechanism of the self-healing effect
when inhibitor-doped nanoreservoirs are incorporated into the
hybrid matrix. The released inhibitor can act when the coating
is partially damaged providing an effective long term self-
healing effect that protects the metallic substrates from
corrosion.
Organic inhibitors can also be incorporated into the sol–gel
matrix in order to improve corrosion protection of metallic
substrates. An additional inhibition effect was revealed when
the phenylphosphonic acid is introduced in the hybrid sol–gel
matrix containing phenyl groups.52 The entrapment of
phenylphosphonate into the sol–gel matrix occurs due to p-p
interactions. In several cases, the release of organic molecular
species from the hybrid sol–gel matrix can be described by
the pH dependent triggered release mechanism.146 Triggering
the desorption processes can provide an ‘‘intelligent’’ release of
corrosion inhibitor only in the places of local pH changes
originated from localized corrosion processes. However,
ionisable inhibitors show a far weaker effect than that of the
non ionisable ones since the first are too strongly attached to
the sol–gel matrix to be released during corrosion.147 Khramov
et al. studied the corrosion protection properties of the
SNAP films with incorporated mercaptobenzothiazole and
mercaptobenzimidazole as corrosion inhibitors.68 Fig. 13
exhibits current density distribution maps for Al/Cu artificial
defects on AA 2024 coated with undoped SNAP and doped
with mercaptobenzimidazole. After 3 h of immersion the
current peak in the case of the SNAP film with inhibitor is
almost 25 times lower than that for the undoped one, showing
the inhibition of the corrosion processes by the mercapto-
benzimidazole molecules. b-Cyclodextrin was included in some
of the coatings mentioned. The corrosion protection of the
sol–gel derived coatings was sufficiently improved due to
encapsulation of the organic inhibitor in the presence or
absence of b-cyclodextrin. This fact can be explained by the
prolonged release of inhibitor from the cyclodextrin–inhibitor
complexes.
Yang et al. encapsulated the triazole inhibitor using plasma
polymerization to produce PP-perfluorohexane and PP-
pyrrole layers.59 The plasma-treated triazole was used as a
pigment in a water-based epoxy coating slowly releasing the
inhibitor and providing a long-term corrosion protection.
This journal is ß The Royal Society of Chemistry 2005

Published on 18 August 2005 on http://pubs.rsc.org | doi:10.1039/B419153F
Fig. 13 Current density distribution maps for Al/Cu artificial defects on AA 2024 coated with (a) SNAP film and (b) SNAP film doped with
mercaptobenzimidazole. Reprinted from ref. 68, Copyright 2004, with permission from Elsevier.
Downloaded by Duke University on 30 June 2012
Conclusions
Sol–gel films have been reviewed as potential candidates to
substitute environmentally unfriendly chromate surface treat-
ments for metallic substrates. The final coating properties are
dependent on the different parameters of the processes of
synthesis and deposition of sol–gel films. In this way it is
possible to tailor the preparation of films in order to obtain
specific properties.
Inorganic sol–gel pre-treatments show good coupling
between the metallic substrate and organic coatings. High
adhesion of sol–gel films to metals is due to the formation of
strong covalent Si–O–Me bonds. This originates corrosion
stable metal/sol–gel film interfaces with noticeable renewal
ability. However, inorganic sol–gel derived films cannot
provide adequate barrier properties for corrosion species due
to pores and cracks that are present in the film after the drying
procedure.
Addition of an organic component to the sol–gel systems
leads to the formation of thicker and more flexible films with
better compatibility with organic top coatings. The hybrid
films show interest because they combine the properties of
organic polymer materials and ceramics. Hybrid coatings can
be prepared over a continuous compositional range from
almost organic to almost inorganic. An advantage of the
organically modified composites is the possibility to prepare
thick, crack-free coatings that can provide an effective barrier
to corrosive agents. Moreover, the hybrid films can be
reinforced by doping with nanoparticles that improve corro-
sion protection properties. This improvement results from the
reduced porosity and cracking potential of such films.
Incorporation of inorganic nanoparticles can also be a way
to insert corrosion inhibitors, creating an inhibitor reservoir
for ‘‘self-repairing’’ coatings that slowly release the inhibitor.
The presence of nanoparticles also reduces the negative effect
of inhibitors on the stability of the sol–gel matrix. Another
way to obtain intelligent storage/release properties is the nano-
encapsulation of active inhibiting species in polyelectrolyte
capsules or other polymer layers.
This journal is ß The Royal Society of Chemistry 2005
View Online
The dense hybrid sol–gel coatings with intelligent ‘‘self-
repairing’’ systems are promising environmentally-friendly
candidates for replacement of the chromate-based pre-
treatments due to a synergistic effect of good barrier properties
and effective ‘‘self-healing’’ action.
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