Surface & Coatings Technology 258 (2014) 1737

Contents lists available at ScienceDirect

Surface & Coatings Technology

journal homepage: www.elsevier.com/locate/surfcoat

Functional and smart coatings for corrosion protection: A review of

recent advances
M.F. Montemor
Instituto Superior Tcnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal

a r t i c l e i n f o a b s t r a c t

Article history: Coatings tailored to corrosion protection of metallic substrates are of the utmost relevance to ensure reliability
Received 10 March 2014 and long-term performance of coated parts as well as the product value of the coated materials. Presently,
Accepted in revised form 17 June 2014 there is a strong emphasis on the development of advanced functional and smart coatings for corrosion protec-
Available online 24 June 2014
tion in different technological applications. On the one hand, there is a need for more advanced coatings for con-
ventional applications and, on the other hand, there is a need to answer the requirements of several new Hi-Tech
Keywords:
Functional coatings
applications. Thus, this review highlights the most recent trends in the eld of functional coatings for corrosion
Corrosion protection protection of metallic materials in a wide range of technical applications. Emphasis is given to self-healing coat-
Self-healing ings and smart coatings combining multiple functionalities for increased corrosion protection. Recent develop-
Smart coatings ments on the introduction of functionalities based on encapsulation of corrosion inhibitors, anti-fouling agents
Biocompatible coatings and superhydrophobic additives or modication of organic and hybrid matrices via chemical manipulation are
reviewed. Special attention is dedicated to functional coatings for corrosion protection of bioresorbable metallic
implants that have an important impact in biomedical applications.
2014 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2. Functional and smart coatings for corrosion protection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3. Functionalities based on carriers of active agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.1. Self-healing coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
3.2. Anti-fouling coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.3. Superhydrophobic coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
4. Functionalities based on modied matrices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
4.1. Siloxane-modied coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4.2. Polyaniline-modied coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
4.2.1. Coatings for controlled wettability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
5. Coatings for bioresorbable metallic implants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
6. Future trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35

Abbreviations: EIS, Electrochemical Impedance Spectroscopy; LEIS, Localised

Electrochemical Impedance Spectroscopy; SVET, Scanning Vibrating Electrode
1. Introduction
Technique; SIET, Selective Ion Electrode Technique; NMR, Nuclear Magnetic Resonance;
SIET, Selective Electrode Technique; SEM, Scanning Electron Microscopy; FIB, Focused
Ion Beam; XPS, X-Ray Photoelectron Spectroscopy; AFM, Atomic Force Microscopy; FTIR, Many conventional and advanced technological applications de-
Fourier-Transform Infrared Spectroscopy; LbL, Layer-by-Layer; LDH, Layered Double mand materials with well-dened surface properties, fullling specic
Hydroxides; HS, Halloysites; SRB, Sulfate-reducing bacteria; PANI, Polyaniline; CNT, requirements, which aim at both valorising the material and advancing
Carbon Nanotubes; DETA, Diethylenetriamine; PEI, Polyether Imide; HA, hydroxyapatite;
the related technology. For this purpose, surface functionalisation of
VOC, Volatile Organic Compounds; REACH, Registration, Evaluation, Authorisation And
Restriction Of Chemicals; HBSS, Hank's balanced salt solution. metallic materials has become one of the most active research areas in
E-mail address: mfmontemor@tecnico.ulisboa.pt. recent times. The denition of surface functionalisation has several

http://dx.doi.org/10.1016/j.surfcoat.2014.06.031
0257-8972/ 2014 Elsevier B.V. All rights reserved.
18 M.F. Montemor / Surface & Coatings Technology 258 (2014) 1737
variants, but can simply be considered a route employed to introduce
new properties to a certain material, aiming to full specic require-
ments. A functional surface comprises new and/or modied chemical
groups and/or morphological features that determine the interaction
with the surrounding environment and subsequent material behaviour.
Surface functionalisation has been known for many years and used
since ancient times, always aiming at improving specic responses of
a material when interacting with its environment. Nowadays, the ad-
vances in surface engineering, nanotechnology and nanomaterials
allow the manipulation of materials' composition down to the molecu-
lar scale, paving the way for new Hi-Tech functional materials.
The surfaces of many materials can be functionalised by applying
coatings. The origin of functional coatings is embedded in the heritage
of mankind and known examples are the protection of the rst metallic
tools and artefacts (iron, brass, silver) with animal fat, beeswax, gela-
tins, vegetable oils and various clay minerals. Water repellence, bright-
ness, corrosion protection, wear protection and lubrication are
examples of properties early man sought. The concept of a functional
coating has enjoyed a very long evolution and today many routes for
surface functionalisation are available. Nevertheless, some of those an-
cient surface modiers, after proper manipulation and engineering,
are still used today because of their outstanding properties.
Functional coatings (whether organic, inorganic or hybrid) are a
class of materials that can be tailored for many applications in which
they should be able to perform well-dened array of functions. There
are numerous functional coatings in many applications that are part of
our daily life. From home furniture, cars, laptops, mobile phones, solar
panels, or more advanced applications such as medical devices and or-
thopedic implants, invisible paints, radars or satellites; functional coat-
ings are present everywhere. The concept of a smart coating is more
recent and has been applied to functional coatings that can respond to
certain stimuli generated by intrinsic or extrinsic events. During recent
years, the boost of nanotechnology and nanomaterials has promoted an
explosion of new functional coatings and this trend will continue grow-
ing in the next years. Functional and smart coatings are undoubtedly a
class of materials with an enormous technological interest. Fig. 1 sum-
marises some of the most relevant properties of functional and smart
coatings, in which surface functionalisation plays a major role.
Functional and smart coatings have been regularly reviewed for var-
ious applications, including those requiring improved corrosion protec-
tion [111]. However, the continuous developments in this area require
a concise review on the latest trends. Thus, this paper aims at highlight-
ing the most recent developments on multifunctional and smart coat-
ings for technological applications in which innovative corrosion
protection strategies are considered.
2. Functional and smart coatings for corrosion protection
By denition, corrosion is the physic-chemical interaction between a
metal and its environment, which results in changes in the properties of
the metal and which may often lead to impairment of the function of the
metal, the environment, or the technical system of which these form a
part (ISO 8044-1986).
When the integrity of the material is affected by the external action
of the environment it may become necessary to protect it against this
detrimental action. Application of coatings is the most suitable route
to protect the metallic surfaces. Coatings designed for corrosion protec-
tion must offer an effective physical barrier, impeding the access of ag-
gressive species to the metallic interface. Examples of coatings in which
the barrier effects need to be extremely good are the ones used to pro-
tect hyper expensive assets in hostile environments such as offshore
structures. In addition to the barrier effect, the coating must have the
ability to inhibit the corrosion process if the protective barrier is
disrupted. Therefore, corrosion protection requires the use of anti-
corrosion pigments or corrosion inhibitors that protect the underlying
metal. The thickness of the coating system and the number of layers
Corrosion protecon
Thermal Barrier
Physico-Chemical
Hydrophilic or hydrophobic
Self cleaning
properes
An-fouling
An-microbrial
Fire-retardant
Wear
Abrasion
Mechanical properes
Hardness
Lubricaon
Photoluminiscence
Photocatalyc
Opcal Properes
An-reecon
Photo chromic
Conducve
Insulang
Electrical/magnec Dielectric
properes Shielding
Anstac
Electromagnec
Fig. 1. Overview of surface properties that can be developed or enhanced through func-
tionalisation by organic, inorganic or hybrid coatings.
depends on the nal application of the coated material and can range
from a few up to several hundreds of micrometers. Generally, each
layer is aimed for specic functionalities, that include adhesion to the
bare metal or adhesion between different layers, corrosion inhibition,
water repellence, anti-fouling and wear resistance, among others.
For many years the most effective corrosion protection systems
were based on the use of chromate-rich surface treatments and/or
primers and pigments based on chromates. However, the current legis-
lation imposed by REACH (Registration, Evaluation, Authorisation and
Restriction of Chemicals) prohibits the use of hexavalent chromium in
almost all sectors except the aerospace industry. It is anticipated that,
in the future, more pressure will be put on this sector too. REACH deci-
sions have instigated the search for more advanced and non-toxic coat-
ings for corrosion protection. Many alternatives have been explored so
far, including a wide range of green surface treatments and pre-
treatments, environmentally safe pigments and natural corrosion
inhibitors. The latest developments propose coatings with low volatile
organic compounds (VOCs), based on waterborne formulations and
isocyanate-free compositions, as well as smart and self-healing
polymers.
Application of functional and smart coatings is one of the most
promising routes to develop high performance anti-corrosion systems
for various sectors. Two main strategies have been pursued to introduce
the required functionalities into coatings: encapsulation/loading of
functional active species in host carriers or manipulation of the coating
matrix composition for inclusion of bulk and/or surface functional
groups. The most recent trends on corrosion protective coatings based
on these two strategies are reviewed below.
3. Functionalities based on carriers of active agents
Carriers of active agents can be loaded with functional species and
added to the coating formulation, to become dispersed in the coating
matrix. These carriers work as reservoirs, in which the functional
 M.F. Montemor / Surface & Coatings Technology 258 (2014) 1737 19

species are stored, until they are needed. Suitable carriers include poly-
meric capsules, porous and hollow particles, nanotubes, clays and a
wide array of mesoporous inorganic particles. When added to corrosion
protective coatings it is essential to ensure good compatibility between
the guest carrier and the host coating matrix. This is mandatory to main-
tain the expected barrier performance of the protective coating. More-
over, the guest carriers must be stable and able to store the functional
agent for long periods, releasing it only if required. Several functionali-
ties can be inserted in protective coatings using this approach. A well-
known example is the encapsulation of functional agents for the devel-
opment of self-healing coatings. This class of functional coatings has
been widely studied in the last 20 years [1229], but only few ap-
proaches show scale-up potential.
3.1. Self-healing coatings
Self-healing is required for the total or partial repair of coated areas
damaged by ageing or unexpected aggressive events. Concerning self-
healing coatings for corrosion protection, two main strategies have
been pursued: (i) mending of defects formed in the polymeric coating
matrix via addition of polymerisable agents and (ii) inhibition of corrod-
ing areas due to the presence of corrosion inhibitors. Table 1 summa-
rises some of the most important approaches recently reported in
literature [1229].
The encapsulation of polymerisable species into capsules or nanopar-
ticles sensitive to external stimuli can be considered one of the most vi-
able routes for introducing functionalities that heal the polymeric matrix.
The proof of concept has been demonstrated by combining various
electrochemical and physic-chemical characterisation techniques.
The incorporation of urea-formaldehyde microcapsules loaded with
polymerizing agents was one of the rst strategies proposed to develop
self-healing coatings with polymer repair functionalities. The work of
Sottos and White et al. [1214] is well-known in the eld, and represent
a breakthrough of this technology. The capsules were designed to be ac-
tivated by mechanical triggers, such as propagation of cracks through
the coating matrix. The crack propagation is expected to disrupt the
capsules, releasing the healing agents, which by themselves, or in the
presence of dispersed catalysts, can repair damaged volumes of the
polymeric matrix. Proof of concept was achieved using encapsulated
polysiloxanes as polymer mending agents. By incorporating a catalyst,
Si[OSn(n-C4H9)2OOCCH3]4, for polysiloxanes polymerisation, an auton-
omous corrosion protection is observed when scratched samples are
immersed for 120 h in NaCl solutions [15]. This approach constitutes
one of the most successfully reported so far, because corrosion protec-
tion was evaluated at longer-term by exposing the samples to aggres-
sive electrolytes. A similar route is proposed by Garcia et al. [1,16],
who encapsulated silyl ester in urea-formaldehyde microcapsules. The
smart concept makes use of properties changing with time that include
coating wettability, hydrophobicity, adhesion, water reactivity and den-
sication. The validation of the self-healing process was made by elec-
trochemical impedance spectroscopy and localised electrochemistry in
a short-term test. In this system the release of the polymerizing agent
is induced by the presence of moisture. This is very advantageous,
since moisture is always present in corrosion-induced damages. More-
over, encapsulated silyl ester does not require cross-linkers or catalysts
in the coating, which constitutes a competitive advantage in the coating
formulation.
Following the successful demonstrations reported for encapsulated
polymeric healing agents, the concept of self-healing based on the en-
capsulation of functional additives was extended to encapsulation of
corrosion inhibitors too. Recent literature [1229] is fertile in contribu-
tions addressing the encapsulation of functional additives for corrosion
protection claiming self-healing ability triggered by different extrinsic
or intrinsic stimuli (see Table 1). These include, for example, local pH
gradients, capsule rupture induced by mechanical stress, ion exchange
processes, water trapping, electrochemical potential changes, light irra-
diation, thermal variations and others; in some cases neither the kinet-
ics of healing nor the mechanisms are completely understood.
The concept of self-healing in corrosion protection has been studied
at different levels of the coating system: pre-treatment layers, primers
and topcoats, making use of different functionalities and incorporation
of different corrosion inhibiting species, either by direct addition to
the coating or by storage in containers sensitive to specic triggering
stimuli.
Concerning healing of thin pre-treatment layers, authors including
Montemor et al. [3033] have shown that thin functional silane coatings
directly modied with inhibiting species, such as cerium ions could pro-
vide effective healing of galvanised steel parts. It was demonstrated, for
the rst time, using scanning vibrating electrode technique (SVET), that
the presence of cerium ions directly added to silane thin lms can
provide self-healing effects [33]. This strategy successfully protects
galvanised steel, steel and aluminium alloys [31]. Although cerium
ions were found to be very compatible with some silane-based coatings,
other polymer chemistries and thin solgel layers reveal poor compati-
bility with cerium ions or other organic and inorganic inhibiting species.
The consequence is that the barrier properties can be signicantly

Table 1
Examples of self-healing strategies implemented for the development of smart coatings based on the use of carriers of active species.

Metal Coating Reservoir Healing agent Trigger Ref.

n.a Epoxy polymer Urea-formaldehyde microcapsules Dicyclopentadiene Crack propagation [1214]

Steel Epoxy polymer Urea-formaldehyde microcapsules Polysiloxanes Crack propagation [15]
Aluminium Epoxy Urea formaldeyde capsules Silyl ester Moisture [16]
Aluminium Epoxy CaCO3 microbeads Cerium pH [17]
Aluminium Solgel Hydroxyapatite particles Cerium(III), Lanthanum(III), pH [18]
Salicylaldoxime, 8-hydroxyquinoline
Aluminium n.a Halloysites, hollow SiO2 particles and Benzotriazole pH [19]
poly-electrolyte capsules
Aluminium Sol gel Mesoporous TiO2 Benzotriazole Light [20]
Galvanised steel Silane CeO2 nanoparticles Cerium ions pH [21]
Aluminium Sol gel Mesoporous silica Benzotriazole pH [22]
Galvanised steel Epoxy Layered double hydroxides, cerium Mercaptobenzothiazole pH and Chloride [23]
molybdate
Glass Silane Sodium montmorillonite Sodium montmorillonite Moisture-induced expansion [24]
Aluminium Chitosan coating Chitosan Cerium ions pH [25]
n.a Epoxy Layered double hydroxides Nitrates Chloride ions [26]
Steel Polyurethane coating Polyurethane capsules Isosorbide derivatives n.d. [27]
Aluminium Epoxy TiO2 porous particles 8-Hydroxyquinoline n.d. [28]
Aluminium and Galvanneal Epoxy Polyelectrolyte nanocapsules Mercaptobenzothiazole pH [29]
Galvanised steel Epoxy Mixtures of Layered double Mercaptobenzothiazole pH and chloride [23]
hydroxides, cerium molybdate
20 M.F. Montemor / Surface & Coatings Technology 258 (2014) 1737
damaged and the corrosion protection of the host matrix is negatively
affected; early leaching of the inhibitor is likely to occur too. Therefore,
the use of inhibitor carriers for storage of corrosion inhibitors has been
pinpointed as a possible solution to overcome detrimental interactions
between corrosion inhibitors and the coating matrix. The strategy was
applied to epoxy [17] and solgel coatings modied with inorganic par-
ticles loaded with cerium as corrosion inhibitor [18,32] and results of
electrochemical and corrosion tests demonstrate improved corrosion
protection.
Effective corrosion inhibition and self-healing effects were observed
when CeO2 nanoparticles are used as carriers of cerium ions and added
to thin silane coatings [21,32]. The impact of these additives to the silane
layer was studied by electrochemical impedance spectroscopy and the
healing process was resolved using the scanning vibrating electrode
technique. Electrochemical impedance results reveal that CeO2 modi-
ed coatings develop increased barrier properties, due to good compat-
ibility of these nanoparticles with the SiO2-rich network of the silane
coating. Current density maps measured by SVET (Fig. 2) over articial
defects show that the anodic current density, in the coating modied
with CeO2 nanoparticles or CeO2 loaded with cerium (III) ions, is ap-
proximately one order of magnitude below the values measured in
blank coating. The SVET results evidence a continuous decrease of the
current density with time due to the formation of protective species
over the scratched areas. It was also shown that ceriumsilicate bonds
a actions. Depending on the nature of the bare metal and on the corrosion
b riers must be designed in such a way that they sense the pH variations
Fig. 2. Current density plots obtained from SVET measurements taken along a line crossing
an articial defect formed on a silane-treated surface exposed to 0.05 M NaCl. The zero
value on the X-axis corresponds to the centre of the defect. Plots were obtained on
galvanised steel substrates pre-treated in bis-1,2-[triethoxysilyilpropyl] tetrasulphide
silane solution containing: (a) CeO2 nanoparticles and (b) CeO2 nanoparticles activated
with cerium (III) ions. Scanned area = 0.2 cm 0.2 cm.
From Ref. [21].
are formed, trapping the ceria particles via SiOCe bonding within
the silica-rich coating formed. The resulting thin coating modied
with CeO2 shows decreased conductivity and improved barrier proper-
ties. When the ceria particles are loaded with Ce (III) ions there are
some changes in the chemistry of the silane solution, with the formation
of reactive silanol groups as demonstrated by nuclear magnetic reso-
nance (NMR). This process helps to form denser coatings with better
barrier properties [21,32] as reected in the electrochemical impedance
spectroscopy results. For the same coating, d.c. polarisation results show
that the presence of cerium-activated CeO2 nanoparticles shifts the cor-
rosion potential towards nobler values, decreases the anodic current
density and changes kinetics of the anodic processes. Cerium species
were found over the inhibited areas [21] and contribute to form more
stable protective species. It is concluded that CeO2 nanoparticles can
be effectively used to store cerium ions, leading to efcient corrosion in-
hibition and, simultaneously, improved barrier properties of silane
coatings.
The selection, design and fabrication of carriers for storage of corro-
sion inhibitors requires some considerations about its compatibility
with the host matrix, ability to store the corrosion inhibitor, the phe-
nomena triggering the release of the corrosion inhibitor and the kinetics
of release and inhibition. It is also necessary to ensure that a sufcient
amount of corrosion inhibitor is stored and released and that it reaches
the active corrosion spots, hindering the local redox activity.
One of the most successful triggers to control the delivery of corro-
sion inhibitors is the pH gradient, which results from the local redox re-
mechanism, acidic pH values can be observed at anodic areas and quite
high pH values can be obtained at the cathodic areas. For example, in
corroding galvanised steel, when iron starts to dissolve, the pH gradient
between anodic and cathodic areas can be as high as 6 units as evi-
denced in (Fig. 3). Fig. 3a, b depicts optical images, taken during immer-
sion, of an epoxy-coated galvanised steel surface containing a defect and
exposed to 0.05 M NaCl (Fig. 3a). The image shows the presence of a
greyish ring in the vicinity of the defect that is assigned to precipitates
of corrosion products. This ring denes the border between the acidic
(anodic) and alkaline (cathodic) zones. The local pH measurements
(Fig. 3c) reveal the near-neutral character of this border and shows po-
tential gradients close to 6 units between the defect and the outer ca-
thodic region. The current density map (Fig. 3d) reveals intense
anodic activity at the defect and a gradual decrease of the current inten-
sity over the ring area. The characterisation of the pH gradients occur-
ring at the active surface is essential to identify the chemical species
formed and to select and design pH sensitive carriers [34].
For self-healing of corrosion processes, pH-sensitive inhibitor car-
around the places to be healed. For example, CaCO3 microbeads [17]
and hydroxyapatite [18] particles sense pH acidication and start to dis-
solve at pH values around 4. Since these particles are very porous, they
can be used to store organic or inorganic corrosion inhibitors. Such acid-
ic pH values are very likely to occur in conned defects present in the al-
uminium alloy 2024 (AA2024) as demonstrated in Fig. 4. The local pH
variation measured by scanning ion selective electrode technique
(SIET), 20 m above an articial defect formed over an AlCu galvanic
couple, rapidly reaches 3.6 over the active anodic area. Therefore porous
CaCO3 microbeads or hydroxyapatite needles can be used as pH-
sensitive carriers in coated AA2024 because they sense the local acidi-
cation, releasing the inhibitor to the electrochemical active areas [17,
18].
The concept was proven by modifying a solgel matrix with hy-
droxyapatite microparticles loaded with different corrosion inhibitors
[18]. Fig. 5 depicts SEM images, including a focused ion beam (FIB)
image, showing the presence of uniformly dispersed hydroxyapatite
particles in the solgel coating. These particles were loaded with differ-
ent corrosion inhibitors (cerium (III), lanthanum (III), salicylaldoxime,
and 8-hydroxyquinoline). The inhibitor-loaded particles present
 M.F. Montemor / Surface & Coatings Technology 258 (2014) 1737
Fig. 3. Local electrochemical measurements obtained on a coated galvanised steel sample in which a FIB defect was initially formed. Results were taken after approximately one day of
immersion in 0.05 M NaCl. (a) optical image taken under immersion, (b) the corresponding SVET-SIET scans, (c) pH distribution maps and (d) current density maps.
From Ref. [34].
chemical stability, good compatibility with the solgel coating, ability to
store the inhibitor and sensitivity to corrosion onset (local acidication).
The nal corrosion protection mechanism is associated with two main
processes: (i) release of the corrosion inhibitor as consequence of pH
acidication and (ii) local pH buffering resulting from the dissolution
of the hydroxyapatite microparticles [8]. AFM measurements demon-
strate that in the pH range of 34 the particles can dissolve and re-
precipitate. During this process there is release of the corrosion
Fig. 4. Evolution of the local pH in a micro conned defect formed on an AlCu galvanic
couple. Values were measured by the Scanning Ion Selective Electrode Technique (SIET)
during immersion in 0.05 M NaCl.
From Ref [18].
21
inhibitor. Below pH 3, dissolution is irreversible and the particles dis-
solve completely.
Various families of pH-sensitive carriers can be loaded with corro-
sion inhibitors and added to different coating formulations. These in-
clude porous or hollow particles, single and multi-walled nanotubes,
layered and ion-exchange clays, capsules and particles layer-by-layer
(LbL) assembled with polyelectrolyte shells of pH-controlled perme-
ability, silica/polymer double-walled hybrid nanotubes, vesicular struc-
tures and nanovalves [19,22,23,3437]. Recent studies report the use of
mixtures of different inhibitor carriers for self-healing systems with dif-
ferent kinetics of inhibitor release [23].
The corrosion protection ability has been validated by different cor-
rosion experiments and advanced combinations of spatially resolved
electrochemical tools. The most powerful techniques to probe the self-
healing effect are the spatially-resolved ones. These include the scan-
ning vibrating electrode technique scanning ion selective electrode
technique (SIET) and localised impedance spectroscopy (LEIS). These
techniques provide complementary information on events occurring
at the micro-scale in defects made on coatings that contribute to the
understanding of self-healing mechanisms [23,29,34,37]. Montemor
et al. [23] applied these techniques to investigate the corrosion inhi-
bition ability of a new concept based on mixtures of containers, trig-
gered by different stimuli, loaded with corrosion inhibitor (2-
mercaptobenzothiazole) and its synergistic effect. The study was
performed on water-based epoxy coatings applied on galvanised steel.
Fig. 6 shows the evolution of the global current densities measured by
SVET over an area in which an articial defect was created. The results
show that LDH containers (NC1) are more effective at the early stages
of the corrosion process probably due to its fast ion exchange nature,
22 M.F. Montemor / Surface & Coatings Technology 258 (2014) 1737
a b
3 m
Fig. 5. SEM images of a solgel coating loaded with hydroxyapatite particles: a) top view of the thin solgel coating, showing dispersed microparticles and b) FIB section of the same coating
modied with hydroxyapatite particles loaded with an organic corrosion inhibitor.
From Ref. [18].
while the cerium molybdate (CeMo) containers (NC2) require pH trig-
gering and therefore some local redox activity prior to release of the in-
hibitor. The mixture of both (NC1 + NC2) clearly creates a synergistic
effect. The corrosion onset is delayed due to the early inhibitive anion-
exchange ability of LDH and the longer term corrosion activity is
inhibited due to the slower inhibition kinetics of CeMo. The results
depicted in Fig. 6 highlight both the ability of SVET to discriminate the
kinetics of corrosion healing and highlight, for the rst time, the syner-
gistic response of mixtures of containers loaded with the corrosion in-
hibitors that are triggered by different processes.
The synergistic combinations of smart carriers, with distinct healing
kinetics, can be an interesting approach to develop new smart coatings
with increased self-healing potential [23]. The approach can be extend-
ed to carriers, transporting different corrosion inhibitors with different
release rates and distinct inhibition kinetics and/or mechanisms (anod-
ic, cathodic, mixed) or to mixtures of carriers loaded with different
smart functional additives such as water traps, chloride traps, poly-
merizing agents and corrosion inhibitors as recently proposed by
Kartsonakis et al. [38]. In this work, cerium molybdate nanocontainers
were loaded with 8-hydroxyquinoline and added to an epoxy-silane
coating formulation together with polymer-based water traps and
silane-silica particles as chloride traps. The coating barrier properties
and ability to trap water were investigated by electrochemical imped-
ance spectroscopy and the self-healing process was determined by
localised impedance spectroscopy. The results show that the amount
Fig. 6. Global current densities measured by SVET over coated galvanised steel samples.
The coating was a water-based epoxy resin modied with layered double hydroxide
(NC1), cerium molybdate (NC2) loaded with 2-mercaptobenzothiazole and a mixture of
both (NC1 + NC2).
From Ref. [23].
2 m
of water retained in the coating increases in the presence of nanotraps
and that the presence of encapsulated corrosion inhibitor provides
self-healing of damaged areas. Such multifunctional coatings combine
increased barrier properties with efcient inhibition of the corrosion ac-
tivity in defects formed on epoxy-coated AA2024 coupons [38]. This
strategy is very promising because it allows development of a multilevel
corrosion protection strategy, based on additives that provide three
different functionalities: corrosion inhibition and water and chloride
trapping.
Cerium molybdate containers are reported as effective carriers for
organic corrosion inhibitors [23,38], but by themselves, they also con-
tribute to corrosion inhibition. The mechanism is still somewhat uncer-
tain, but is likely to involve dissolution of the containers and formation
of inhibiting species containing cerium and molybdates. Recently
Yasakau et al. [39] studied the inhibiting effect of cerium molybdate
nanowires on aluminium alloy (AA2024) coupons exposed to NaCl so-
lutions of different concentration. The work demonstrates the corrosion
inhibition ability and efciency of cerium molybdate in the presence of
increasing concentrations of chlorides in aqueous NaCl electrolytes. The
effect is explained assuming that a structural transformation of amor-
phous cerium molybdate nanowires into crystalline (NaCe)0.5MoO4 oc-
curs in concentrated NaCl solutions, thereby triggering the release of Ce
(III). XPS measurements demonstrate the formation of Ce (III) and Ce
(IV) species. It is shown that these species precipitate on corroding
areas, namely on the Cu and Mgcontaining intermetallics. These inter-
metallics, known as S-phase, are very sensitive to corrosion. In NaCl
solutions these intermetallics are initially more negative than the sur-
rounding matrix and dissolve preferentially. The corrosion process in-
volves de-alloying of the intermetallic and dissolution of aluminium,
copper and magnesium. However, the dissolution of the S-phase is sig-
nicantly inhibited in the presence of the cerium molybdate nanowires.
Molybdate, itself, also plays an important role in delaying dissolution of
Al and Mg from the S-phase [39].
Layered double hydroxides and other cation exchangers, such as
natural clays, zeolites and bentonites, have been used to store inorganic
corrosion inhibitors, releasing it by means of ion exchange mechanisms.
Well-known examples are the use of bentonites to store cerium ions as
demonstrated in pioneering work by McMurray et al. [40,41]. These
contributions investigate the ion exchange ability and release kinetics
of bentonites and their ability to delay cathodic delamination in
polyester-coated galvanised steel parts. The experimental data demon-
strates that clays modied with Ce(III) ions provide signicant corro-
sion inhibition and ability to delay cathodic delamination; the effect
being superior to that of strontium chromate and commercial
Shieldex [40,41]. However this system is not effective in mitigating
lliform corrosion on AA2024. This loss of efciency is related to the
 M.F. Montemor / Surface & Coatings Technology 258 (2014) 1737 23

very acidic pH on the head of the laments. The pH in this acidic envi-
ronment is therefore insufcient, even at the cathodic places, to induce
the precipitation of protective rare-earth hydroxides. More recently,
LDH re-gained interest as anion exchangers, and attention has been
given to their composition, ability to store different functional species
and impact on the barrier properties of hybrid and organic coatings.
For example, it is shown that the nature of the interleaved anion af-
fects the barrier properties, which increase for CrO 24 or EDTA 4
entrapped anions, but decrease for species such as CO23 and Cl
[42]. Different ions such as vanadates and organic inhibitors were
intercalated in LDH, with effective healing ability studied in detail
[4345].
The inhibiting effect of LDH containers loaded with
mercaptobenzothiazole and added to epoxy coatings applied on
AA2024 was revealed by localised impedance spectroscopy. The corro-
sion inhibition efciency was tested in articial defects formed in the
coated AA204 and the results were compared with tubular halloysites
(HS) lled with 8-hydroxiquinoline and conventional chromate pig-
ments (Cr-reference). Data depicted in Fig. 7a and b reveals that LDH
containers provide effective early-stage corrosion inhibition, whereas

Fig. 7. a) LEIS maps of the AAA2024 coated with Chromate-reference coating (top row), coatings loaded with halloysites (HS) lled with 8-hydroxiquinoline (middle row) and layered
double hydroxides (LDH) lled with mercaptobenzothiazole (bottom row) over articial defects immersed in 0.001 M NaCl for 48 h. From Ref. [37]. b) Evolution of the maximum admit-
tance determined over the articial defect during immersion in 0.001 M NaCl. From Ref. [37].
24 M.F. Montemor / Surface & Coatings Technology 258 (2014) 1737
tubular halloysites lled with the inhibitor become effective after an ini-
tial step of corrosion activity [37].
An interesting property of ion exchanger clays, including layered
double hydroxides, is related to its ability to act as a chloride ion trap-
pers as proposed by Tedim et al. [26,45]. LDH modied with nitrates
are sensitive to the concentration of chlorides [26,4345] and based
on this, nitrates can be released from the LDH. This process is accompa-
nied by entrapment of chloride ions, being governed by an ion-
exchange equilibrium mechanism. Fig. 8 highlights the ability of
nitrate-containing LDH to trap chloride ions that diffuse through a coat-
ing, a process that can contribute to increased corrosion protection of
organic coatings [26].
LDH materials are of great interest due to their high lateral aspect
ratio that promotes better barrier properties when they are dispersed
in polymeric matrices and their ion-exchange smart ability. The LDH
structure has a high afnity for chloride ions resulting in them acting
as chloride scavengers. Upon entrapment of chlorides there is a release
of the interleaved anion, which can be a corrosion inhibitor. The LDH are
expected to deliver the corrosion inhibitor to the corroding areas when
the coating matrix is damaged. When present in the cathodic areas LDH
can trap either chlorides or hydroxyl anions, in an exchange process
with the interleaved inhibitor. At the anodic sites, LDH also trap chlo-
rides, releasing the corrosion inhibitor. However, since the anodic pro-
cess is accompanied by acidication, at sufciently low pH, the LDH
start to dissolve, buffering the electrolyte, while the inhibitor is released.
However, in very acidic conditions LDH are totally dissolved. LDH dis-
persions in polymeric matrices may result in better mechanical proper-
ties and stress dissipation ability. Another advantage of LDH is that they
do not damage the barrier properties of organic matrices as demonstrat-
ed in recent studies [43,44]. LDH loaded with effective corrosion inhib-
itors seem to be a powerful option to design new smart organic coatings
and present scale-up potential. For better compatibility with the organic
matrices the key parameters to observe include surface functionalisa-
tion of the LDH, its concentration and effective dispersion in the coating
formulation as well as long-term stability.
The inhibiting efciency of various healing systems has been
demonstrated by means of electrochemical and corrosion tests
complemented with physic-chemical characterisation. However, the
healing efciency and the time-response of smart carriers embedded
in protective coatings are difcult to predict and only few studies are
published regarding this specic issues. Recently Javierre et al. [46,47]
proposed some mathematical/analytical models, correlating the healing
kinetics with the coating composition. The authors conclude that the re-
lease kinetics can be explained and predicted whilst considering simul-
taneously the healing agent, its chemical nature and distribution within
Fig. 8. Results of permeability measurements depicting the concentration of chloride ions
through coatings, containing LDH pigments, as a function of the immerson time. Zn(2)
AlNO3 represents a form of empty chloride nanotrap, whereas and Zn(2)AlCl Is a
chloride lled nanotrap.
From Ref. [26].
the coating, the carrier properties and the chemical composition and
structure of the coating. For example, the mathematical model applied
to explain the healing process in the presence of expansible clays con-
siders the following parameters: the absorption and transport of mois-
ture through the clay, the relation between clay expansion and
moisture content and mechanical conditions of the coating. The healing
process depends on the thickness of the layers present in the coating,
elastic modulus of the coating and dimensions of the initial damaged
area. Interestingly, it is shown that expansible clays present in the
inner coating layers can heal defects, although the process may result
on undesirable displacement of the top layers [47].
The ingress of electrolyte through the defects present in organic
coatings is of utmost relevance for the onset of the corrosion processes.
Therefore, the understanding of this process is essential to properly de-
sign the self-healing strategies. The diffusion coefcient of water was
determined for composite coatings modied with nanospheres fabricat-
ed from cross-linked poly(methacrylic acid) sodium salts that can be
used as water traps (Fig. 9). The water trapping ability was studied by
combining quartz microbalance measurements and Fourier-transform
infra-red spectroscopy (FTIR) and the experimental proles were com-
pared with mathematical models. The work demonstrates the quantita-
tive benets of water traps in retarding water uptake through the
coating and also analyses the effect of the water traps concentration
and its distribution through the coating. The impact of water traps in
terms of coating adhesion and coating barrier properties is analysed as
well. When added to layers in contact with the metallic substrate,
water traps decrease adhesion and when added to outer layers there
is an increase of the coating porosity. However, if added to sandwich-
type coatings, in the middle layers, water traps reduce the water diffu-
sion coefcient to approximately one third of the value measured in
non-modied coatings [48].
The above discussion overviews the most recent approaches that
aim at introducing smart anti-corrosion functionalities in protective
coatings, using guest reservoirs as carriers of corrosion inhibitors. The
most promising concepts, closer to scale-up are the ones based on pH
sensitive carriers and ion-exchange clays. pH gradients are inherent to
the corrosion process and pH sensitive particles or capsules are easy to
fabricate, stable and robust and can be made compatible with various
coating formulations, including water-based epoxy coatings. LDH used
as chloride trappers and corrosion inhibitor exchangers provide effec-
tive corrosion inhibition, while contributing for good barrier effects. It
is worth noticing that addition of nanoparticles may contribute to en-
hancing other coating properties such as wear or abrasion resistance
as reported elsewhere [49,50]. However, it is essential to avoid the
Fig. 9. SEM picture of spherical particles fabricated from cross-linked poly(methacrylic
acid) sodium salts and used as water traps.
From Ref. [48].
 M.F. Montemor / Surface & Coatings Technology 258 (2014) 1737
formation of agglomerates that can damage the barrier properties of the
coatings and to ensure long-term stability of the modied formulations.
Recently, more advanced approaches are emerging, based on the use
of combinations of smart carriers triggered by different stimuli and
combining inhibitors with different kinetics and/or inhibition mecha-
nisms. Some pioneering work was reported [23,38], but the concept re-
quires further studies. This is undoubtedly an interesting area to explore
in order to design more effective anti-corrosion coatings, displaying
more efcient self-healing functionalities.
Another challenging problem related to storage of functional species
that display self-healing ability inside coatings for corrosion protection
deals with modelling and predicting the long-term stability and healing
efciency. This aspect is still an open issue and few works have been
published regarding it [4648]. In respect to corrosion protection, the
functional healing agents need to be stable and effective for several
years and should not be early-leached from the coating. Furthermore,
the size and geometry of the defects to be healed, the number of defects
and the area or volume to be protected as well the possibility of occur-
rence of multiple damaging events are still open questions for which
very few answers exist. Today there are no studies addressing these spe-
cic issues.
3.2. Anti-fouling coatings
Anti-fouling is essential for improved corrosion protection. For many
decades coatings designed to provide anti-fouling effect were dense or-
ganic matrices, containing biocides such as tributyltin and tributyltin
oxide. These species are broad-spectrum biocides and can be incorpo-
rated, for example, in marine paints, leading to protection of ship hulls
for up to ve years. However, accumulation of these chemicals in sea-
water has created a lot of environmental concerns and today these com-
pounds are no longer used. The same trend occurs with copper oxide
pigments. As a consequence of the environmental impact of those pol-
luting agents, there is growing interest in nding new and more benign
biocides as well as achieving a controlled release of the biocides from
coatings, as reviewed elsewhere [51]. In this sense, the use of carriers
lled with biocides is very attractive because a smart release can be
achieved. This ensures a well-controlled delivery of the functional
agent and more effective fouling protection, while minimizing environ-
mental impact.
Although anti-fouling coatings have been widely studied [5160],
the joint assessment of anti-fouling and corrosion protection has been
less explored. Table 2 depicts examples of encapsulated anti-fouling
agents that also result in coatings with increased corrosion protection.
Interesting approaches combining corrosion inhibitors and anti-
fouling species were recently reported [52]. For this purpose, mesopo-
rous silica nanoparticles with a pH/sulde ion-controlled release mech-
anism were used to encapsulate corrosion inhibitors (hydroxyquinoline
or triazoles) and benzalkonium chloride [52]. This last species renders
anti-fouling functionality to polyester coatings. The carriers are trig-
gered by pH gradients and by the presence of sulphide anions. This ap-
proach, which combines corrosion protection and anti-fouling, can be
interesting to protect steel parts exposed, for example, to S2-polluted
environments.
Table 2
Examples of encapsulated anti-fouling strategies implemented for the development of corrosion protective coatings.
Metal Coating Carrier
Steel Polyester coating Mesoporous silica
Steel Powder coating Gel particles
n.d n.a Polymeric capsules
n.d Commercial Silica particles
Steel primer Silica
Steel Acrylic paint Polymer microparticles
Stainless steel n.d LbL
25
Encapsulation of anti-fouling agents in gel particles is another prom-
ising route for introducing functionalities in corrosion protective coat-
ings. For example, encapsulation of zinc pyrithione provides effective
anti-fouling and slows down the release rate of the active species, com-
pared to coatings in which the same agents are freely dispersed in the
coating [53]. The silica gel particles lled with the biocide are dispersed
in the coating matrix and can be opened by wear-related effects.
Moisture-degradable polymer capsules, such as poly(L-lactide) and
poly(caprolactone) were proposed for long-term delivery of anti-
fouling agents. This approach was demonstrated by encapsulation of
the anti-bacterial molecule (chlorhexidine) encapsulated in poly(L-
lactide) microspheres through the emulsionevaporation route [54].
The release rate attains 39% in the rst 24 h but little is known about
the longer-term release and compatibility with corrosion-protective or-
ganic matrices.
The encapsulation of enzymes that produce hydrogen peroxide in
polyethylenimine-templated silica particles by co-precipitation
methods was recently reported [55]. The activity of the enzymes is
pH-dependent, with a maximum in the near neutral- to slightly acidic
range. The release of the active agent from coatings lled with enzymes
stored in capsules was measured for more than four months. The data
evidences that the release rate of the active agent shows a continuous
decreasing trend. Enzymatic systems, consisting of hexose oxidase,
glucoamylase and starch, able to produce hydrogen peroxide, were en-
capsulated in silica particles and added to a marine coating. The anti-
fouling activity of this bio-inspired coating could be followed for more
than three months [55,56] with positive effects. The effectiveness of
the approach is dependent on the type of microorganisms that are
present in the environment.
Microspheres or polymer particles (Fig. 10) loaded with silver that
works as anti-fouling agent, were added to corrosion protective coat-
ings. The active agent affects the outer membrane of living organisms
and inhibits the enzymes that are responsible for the cell activity. The
modied-coatings provide inhibition of the fouling activity on steel sub-
strates, while showing a slow release prole of the active species. This
provides longer-term anti-fouling compared to a situation in which
the active agent is freely dispersed in the coating [57]. Szab, et al.
[59] also reported a one-pot synthesis of gelatine based, slow-release
polymer microparticles, containing silver nanoparticles, and their appli-
cation in solvent-based acrylic paints, which produced effective results
in a seven months exposure test in seawater. The anti-fouling activity
of silver is attributed to its catalytic oxidative reactivity, disruption of
electron transfer and detrimental effects over the DNA of biological spe-
cies. The anti-fouling effect was studied for Ag/SiO2 coreshell nanopar-
ticles that show corrosion activity much reduced compared to for
identical coatings containing 40 wt.% of Cu2O particles [57,58].
Thin coatings displaying anti-corrosion properties can be prepared
based on layer-by-layer assembly of laponites (natural clays) and
polycationic copolymers containing catechol groups and alkyl quaterna-
ry ammonium salts [60]. This route can also be used to introduce the
anti-fouling functionality. For this purpose, silver-containing micelles
were prepared. Effective corrosion inhibition and anti-fouling ability
were demonstrated for galvanised steel and stainless steel substrates,
respectively, as reported by Faure et al. [61] and Daudr et al. [62]. The
anti-bacterial activity of alkanethiol self-assembled monolayers with
Active agent Trigger Ref.
Benzalkonium chloride pH; S2 ions [52]
Zinc pyrithione n.d [53]
Chlorhexidine Moisture [54]
Enzymes pH [55,56]
Silver Mechanical damage [57,58]
Silver Moisture [59]
Silver n.d [60]
26 M.F. Montemor / Surface & Coatings Technology 258 (2014) 1737
Fig. 10. SEM image of microspheres loaded with silver as anti-fouling agent.
From Ref. [57].
uorinated terminations was tested on copper plates by using a combi-
nation of analytical techniques. The anti-bacterial effect shows an im-
portant dependence on the amphiphilic thiol groups present of the
surface [63].
Encapsulation of natural and environmentally friendly species with
anti-fouling properties in coatings used for corrosion protection is time-
liness, but also a challenging task because it demands the proper selec-
tion and manipulation of the anti-fouling agents and its successful
encapsulation and controlled release to the coating surface. Encapsula-
tion opens the route to immobilise anti-fouling agents for prolonged ac-
tivity and stability, while providing enhanced corrosion protection
[6466]. Various release stimuli can be applied, including breakage, dis-
solution and slow degradation of the carriers, or diffusion across capsule
walls. Although many strategies have been published and many routes
proposed [5263], there is still a lack of long-term solutions based on
encapsulated anti-fouling species in corrosion protective coatings and
clear denition of the trigger process. Strong links are required between
different elds such as biology, polymers chemistry, and materials sci-
ence. Successful ideas for encapsulation of anti-fouling species have
been transferred from the medical and biological elds, in which several
concepts are already proven at laboratory scale. However, the large-
scale application is still in its infancy and scale-up is still not convincingly
addressed. Nevertheless, some approaches promising industrialisation
potential are based on the introduction of biological and natural species
with anti-fouling activity into solgel coatings or capsules added to
organic coatings. The release due to wear seems a promising strategy
in applications in which this effect is relevant.
3.3. Superhydrophobic coatings
Hydrophobicity and superhydrophobicity are key surface properties
for corrosion protection because they result in water and aqueous elec-
trolytes repellence, anti-icing, bio-corrosion and also anti-fouling. These
functionalities can be achieved by encapsulating functional species [67]
or by changing the composition, structure or morphology of the
Table 3
Examples of encapsulated strategies implemented for the development of corrosion protective coatings with superhydrophobic properties.
Metal Coating
n.d n.d
n.d Styrene and methacrylates
Al alloys Epoxy
Steel Polyurethane
n.d Acrylate
n.d. Solgel
n.d Solgel
outermost surface layers of the coating system. Although several
encapsulation-based strategies appear to be successful, there are only
few contributions validating them concerning corrosion protection
such as the ones described elsewhere [6785]. Table 3 depicts some en-
capsulation routes employed for the development of corrosion protec-
tive coatings displaying superhydrophobic properties.
The lotus leaf effect, one of the most effective routes to create
superhydrophobic surfaces, can be simulated by different encapsulation
routes. For example, storage of calcium hydroxide inside microcapsules
reveals good superhydrophobic performance, including regenerative
ability. The process involves treatment of the capsules with potassium
stearate and further diffusion of calcium hydroxide, leading to the for-
mation of a nanostructured calcium stearate layer through the porous
structure of the capsules shell. Advantages of this approach are that it
is inexpensive and shows potential for scale-up and application over dif-
ferent substrates [67]. For identical purposes, porous silica capsules
were tested and the results conrm that they are very effective in devel-
oping superhydrophobic surfaces for various applications [6769].
Recently, Huang et al. [70] reported the fabrication of a
superhydrophobic composite coating made of styrene copolymers,
methyl methacrylate and silica nanoparticles, the surface of which
was previously modied with hexamethyldisilazane. The work demon-
strates that the presence of silica particles in the composite coating al-
lows obtaining superhydrophobic surfaces, displaying contact angle
above 160, with reduced hysteresis. The method is considered very
promising for large scale fabrication of superhydrophobic coatings for
metallic parts.
An approach combining different functionalities, including the for-
mation of a hydrophobic protective layer was proposed by Garcia
et al. [16], who synthetised poly(urea-formaldehyde) capsules and en-
capsulated (octyldimethylsilyloleate), a silyl ester, for modication of
epoxy coatings. The active agent reacts with moisture, forming a hydro-
phobic layer that increases the corrosion protection ability.
Polyurea capsules functionalised with amino silanes were used to
encapsulate hydrophobic linseed oil. The capsules were embedded in
a polyurethane coating applied on steel and tested in 5% NaCl solution.
The nal system showed improved corrosion resistance due to release
of linseed oil into micro cracks [71]. Linseed oil forms a protective sur-
face lm on the metallic surface due to oxidative polymerisation and
shows self-healing behaviour, thus being effective as corrosion inhibitor
too [72]. Linseed oil can also be used as direct additive to modify poly-
meric matrices to increase the protective performance [7174]. Linseed
oil is abundant and, being a natural product, is free of environmental
concerns.
Polyaniline (PANI) capsules can work as redox responsive carriers.
This property was explored in a recent research work [75]. A hydropho-
bic agent, poly-dimethylsiloxane, was encapsulated in PANI capsules
and its redox-responsive release was monitored by nuclear magnetic
resonance spectroscopy. It was found that the release of silane is stimu-
lated upon reduction and delayed upon oxidation. The capsules reveal
good stability when added to acrylate coatings. Therefore, this combina-
tion is an interesting approach for self-healing and hydrophobic anti-
corrosion coatings.
The solgel route is a versatile method to produce superhydrophobic
surfaces. Recently, Liang et al. [76] reported the formation of
Carrier Active agent Ref.
Mesoporous silica Calcium hydroxide [6769]
Silica particles Hexamethyldisilazane [70]
Polymeric capsules Silyl ester [16]
Polyurea capsules Linseed oil [71]
Polyaniline Dimethylsiloxane [75]
Silica particles Silanes [77,78]
Solgel particles Fluor-polymers [80]
 M.F. Montemor / Surface & Coatings Technology 258 (2014) 1737
superhydrophobic layers on aluminium substrates using successive hy-
drolysis and condensation polymerisation reactions of organosilanes as
co-precursors and ammonia as catalyst. The employed route results in
the formation of spherical silica-based particles with strawberry-like hi-
erarchical microstructure that can establish covalent bonds between the
vinyl groups and the native aluminium surface. The surface displays
contact angles close to 150 C and the coating provides good corrosion
protection (Fig. 11).
Siliica particles successfully work as carriers of hydrophobic agents.
Transparent solgel coatings were modied with hollow silica nanopar-
ticle sols lled with 3-aminopropytriethoxysilane and after heat treat-
ment the coatings showed high transparency and superhydrophobic
behaviour [77]. Using the same route, silica particles functionalised
with vinyl groups were also fabricated. The coating showed increased
contact angle and resistance to acid attack [78].
Fluorinated coating surfaces is considered a well-established route
to develop superhydrophobic coatings. Capsules or particles modied
with uoro-containing additives have been reported in literature [79,
80]. For example, Brassard et al. [79] reports the fabrication of uorinat-
ed silica particles that can induce high contact angle when added to
coating formulations. Modication of nanoparticles existing in the
structure of solgel coatings with uoro-polymer emulsions as co-
precursors was proposed recently and the produced coatings show in-
creased surface angles and water repellent properties in addition to cor-
rosion resistance and good adhesion [80]. In the same line, mesoporous
silica particles were proposed as reservoir for octadecylamine, a
superhydrophobic molecule. In order to better control the release prop-
erties, the surface of silica was covered with poly-dopamine. This mole-
cule allows chemical reactivity in a wider pH range, reversible healing-
etching cycles and helps to disperse the silica particles in organic matri-
ces. The effect is more effective in wet environments comparatively to
dry ones [81].
Modication of paint systems with carbon nanotubes and nanobers
allows the obtainment of nanostructured surfaces, while increasing the
mechanical properties. These additives can be additionally functionalised
with uorosilanes to increase the surface hydrophobicity. Such a strategy
can be applied to the functionalisation of corrosion protective coatings to
prevent fouling of painted structures exposed to seawater [82].
In addition to superhydrophobicity, coatings that are used for pro-
tection of metallic parts such as marine vehicles, off shore platforms
and wind turbines also require additional functionalities to improve
other relevant properties. Among these, drag reduction, anti-fouling,
anti-icing and stain resistance are of utmost importance for the lifetime
of those systems. Superhydrophobic polyurethane coatings modied
with waterborne peruoroalkyl methacrylic co-polymers and montmo-
rillonite clays were applied on aluminium parts that can be used in
Fig. 11. Cross section of a silane-based solgel coating applied on aluminium (left) and the coating after 30 min of immersion in 3.5 wt.% NaCl.
From Ref. [76].
27
extreme environments. It is demonstrated that after thermosetting the
contact angle is above 160, showing hysteresis values below 8. These
surfaces display effective anti-wetting and self-cleaning properties too.
These properties were also evaluated under mechanical load and the re-
sults show that they are not signicantly affected [83]. Steel parts coated
with a superhydrophobic coating modied with carbon nanotubes
(CNT), with a mesh type structure were submitted to different tests, in-
cluding variations of temperature. The results demonstrate that the ad-
dition of the CNT enhances the thermal and electrical properties of the
coated parts. This behaviour promises interesting results in naval appli-
cations [84,85].
Superhydrophobicity enhances anti-fouling protection. Surface
nishing and encapsulation of active agents can deliver these combined
properties. The solgel route and the use of silica particles (porous,
mesoporous, hollow, functionalised or not) are the simpler and most ef-
fective routes to achieve these objectives. The possibility of hosting dif-
ferent functionalities widens the range of organic matrices that can be
modied with carriers loaded with functional agents.
4. Functionalities based on modied matrices
Coatings for corrosion protection require a combination of prop-
erties that include good barrier effect, the presence of pigments pro-
viding efcient inhibition of the corrosion processes, good adhesion
to the substrate, as well as compatibility with additional layers
such as top coats. As discussed above, some of these requirements
can be developed through the use of carriers loaded with functional
agents that are added to the coating. Another route that has been ex-
plored consists of functionalisation of the coating surface, or bulk
matrix, by manipulating its molecular structure and/or chemical
composition [8699].
During the last years, attention has been given to advanced function-
al coating chemistries, with low volatile organic (VOCs) and isocyanate
free compounds. Cyclic carbonates, amines and siloxanes-modied
chemistries are considered greener routes, of simple scale-up, and
are attracting a lot of attention for developing functional barrier coat-
ings for multi-substrate application [8691]. The manipulation of
cross-linking and molecular structure of polymeric matrices such as
polyurethanes, acrylics or epoxies, by adding different additives (si-
lanes, amines, polyaniline) allows producing thinner, but denser func-
tional coatings, with signicantly better barrier properties that result
in increased corrosion protection, durability, and cost effectiveness.
Thus, this section aims at highlighting the most recent advances related
to introduction of various functionalities, by changing the composition
of conventional anti-corrosion coatings.
28 M.F. Montemor / Surface & Coatings Technology 258 (2014) 1737
4.1. Siloxane-modied coatings
Siloxane compounds are largely inorganic in nature and very resis-
tant to most common ageing processes, like oxidation, corrosion, UV
degradation, thermal gradients and mechanical stresses. The SiO
bond has higher bond strength compared to CC bonds and the barrier
protection effect of matrices modied with SiO is strongly enhanced. In
addition, siloxanes have low viscosities, contribute to decreased VOCs
contents and are good adhesion promoters, resulting in coatings that
are less prone to delamination. Siloxane-based formulations eliminate
the need for isocyanates and the modied coatings can be cured at
lower (including room) temperatures, even in the presence of moisture.
This facilitates in-situ painting (or re-painting) of structural parts.
The most successfully used siloxane-based paints are epoxy and
acrylics, in which the siloxane concentration vary in a wide range, de-
pending on the nature of the siloxane, the polymeric matrix and the re-
quired coating properties [9399]. Table 4 depicts some examples of
conventional organic matrices that were modied with different silanes
in order to design coatings with increased corrosion performance.
Siloxane-based coatings are very resistant to weathering effects
even at reduced coating thickness, a competitive factor when weight re-
duction of the painted components is considered. Furthermore, the per-
formance of these coatings offers the possibility to reduce the number of
coats in the corrosion protection system. This promises more competi-
tive technologies with signicant reduction of costs. Siloxanes can be
used to modify different polymeric matrices such as epoxy, acrylates
and polyurethanes. Advantages of acrylic-siloxanes include: high
weathering resistance, good barrier properties, corrosion resistance,
and low content of organics. Improved corrosion protection was ob-
served for hybrid siloxane coatings containing a functional SiO2 network
and functional acrylates. The positive results are mainly attributed to
improved barrier properties of the resulting layer. Moreover, the coat-
ing performance could be increased by functionalizing the SiO2 particles
with -methacryloxy-propyltrimethoxysilane [92]
Silane-modied epoxy coatings are attracting a lot of attention be-
cause water-based epoxy paints are currently widely used and repre-
sent a large market share. Although its good corrosion protection,
conventional epoxy coatings are prone to ageing, colours fade and
gloss degradation, requiring additional topcoats. However, when modi-
ed with siloxanes these properties are signicantly improved and ad-
ditional coats may be not needed. Hybrid epoxy-siloxane coatings
present reduced water and oxygen permeability, lower capacitances
and increased ionic resistances and can provide superior corrosion pro-
tection of various metallic substrates, including steel substrates,
outperforming conventional thicker epoxy-polyurethane coatings in ac-
celerated corrosion tests as reported by Diaz et al. [93]. The multi-
substrate compatibility of siloxane-modied paints is a great advantage
compared to non-modied matrices. This is of relevance for example for
magnesium alloys. These alloys are strategic materials for the transpor-
tation sector, because they offer an attractive combination of properties
that include mechanical resistance and low weight. Magnesium alloys
are very susceptible to corrosion and require very effective corrosion
protection strategies and, normally, thick coatings need to be applied
to ensure long-term durability. However, epoxies are not very protec-
tive when applied on magnesium alloys. The corrosion process of
Table 4
Examples of anti-corrosion coatings based on siloxane-modied organic polymers.
Metal Coating Active agent
Steel Epoxy/polyurethanes Various silanes
AZ31 Epoxy Various silanes aminosilanes (Fig. 12)
Steel Silicone-epoxy Various silanes
Al alloys Polyester Various silane
Tin Poly(methyl methacrylate) Mixture of silanes
magnesium alloys is accompanied by strong alkalinisation at the inter-
face that reduces the chemical stability of epoxy matrices, making the
coated parts susceptible to delamination and fast corrosion-induced
degradation. Recently, model epoxy-based coatings were modied
with silanes and amines, as cross linkers, to develop high performance
hybrid epoxy-silane coatings for corrosion protection of magnesium al-
loys used in the aeronautical industry [94]. Fig. 12 depicts the chemical
composition of silanes used to design an epoxy-based corrosion protec-
tive coating.
Brusciotti et al. [94] demonstrated that the protective performance of
silane-modied epoxy coatings was affected by the chemical nature of
the functional silane. The best corrosion protection was achieved by
adding silanes containing the amine functional group (Fig. 12). The pres-
ence of this group helps to form a denser and more cross-linked hybrid
matrix, due to the bonding of the amine groups in diethylenetriamine
(DETA) with the glycidyl group in the epoxy component [94]. Electro-
chemical impedance spectroscopy measurements revealed that silane-
modied epoxy coatings, showing thicknesses around 30 m, can resist
up to various months of immersion in 0.5 M NaCl, without signicant
loss of the protective performance. This can be clearly observed in the
EIS Bode plots where total impedance values above 200 M cm2 were
measured for 2.5 months of immersion (Fig. 13) in an aggressive
solution.
The slow decay of the impedance of the protective coating during
the immersion test in 0.5 M NaCl (Fig. 13) indicates electrolyte uptake
through the coating and therefore a slight decrease of the barrier prop-
erties. However, corrosion was not observed up to a period of approxi-
mately three months of immersion. Standard salt spray corrosion tests
reveal that these samples can survive more than 1500 h in the test,
without corrosion damage. It is noteworthy that these coatings possess
thicknesses around 30 m and a classication of zero in the adhesion
test according to the ISO 2409.
Siloxane-modied epoxy coatings are compatible with various me-
tallic substrates such as magnesium [94], steel [93,95,96], aluminium al-
loys [97,98] and tin [99], and offer improved corrosion protection due to
improved barrier effects. Siloxane-modied epoxy and polyamide coat-
ings present improved colour and gloss retention, anti-dust properties
as well as enhanced mechanical and thermal resistance. These coatings
applied on steel, are resistant to organic solvents and acid attack, and
are stable under exposure to alkaline environments [95]. Epoxy-
siloxane coatings applied on carbon steel exhibit good corrosion resis-
tance under exposure in alkaline, acidic and saline conditions. Electro-
chemical tests show that coated samples remain protected for more
than one month. However, the mechanical properties determined by
the pencil hardness are somewhat reduced and adhesion requires im-
provements [96].
Water-based organosilane-polyester coatings obtained by the sol
gel route were applied on aluminium alloys. Increased concentrations
of silane improve corrosion resistance, hydrophobicity, hardness and
weathering stability. Moreover, the coatings also display good perfor-
mance in wear tests [97].
Siloxane-modied coatings can also be electrodeposited on the me-
tallic surfaces. The work of Xue et al. [98] reports improved corrosion
protection, which is attributed to higher contents of electrodeposited si-
lane and epoxy compared to coatings deposited by dipping. FTIR and
AFM measurements suggest good adhesion to the substrate, more
cross-linked networks and more uniform coatings. It is shown that de-
position of thicker coatings requires the existence of epoxy particles in
the deposited lm that further cross-link under the action of curing
agents [98].
Ref. Siloxane-poly(methyl methacrylate) coatings applied on tin re-
[93] vealed good barrier properties; however, the protection performance
[94] is dependent upon the silane content and silane chemistry. The addition
[96] of tetraethosysilane increases the lm thickness, but results in brittle
[97] coatings that are porous and non-uniform, being more prone to corro-
[99]
sion attack. These lms are more hydrophilic compared to lms without
 M.F. Montemor / Surface & Coatings Technology 258 (2014) 1737 29

Fig. 12. Chemical structure of the coating components.

From Ref. [94].

addition of tetraethosysilane. The coating displays hydrophobic behav-
iour and electrochemical experiments demonstrate that the coating
hinders diffusion of aggressive species [99].
Literature [9299] demonstrates that modication of corrosion pro-
tective organic chemistries with siloxanes present several advantages
that include: high barrier properties and therefore improved corrosion
resistance, without signicant contents of volatile organic solvents,
low (and room) temperature curing, resistance against weathering,
longer-term retention of surface properties, chemical stability under a
wide range of pH and increased mechanical resistance. Siloxane chem-
istries are very exible and they can be combined with different poly-
meric matrices such as epoxy, acrylic, vinyl, urethane, uoro-polymers
and phenolic resins to design coatings, adhesives and composites tai-
lored for superior corrosion protection performance. Siloxane-
modied chemistries offer the possibility to decrease the number of
layers, or the thickness of the layers, and the application time can be
shorter. The long-term stability is enhanced, resulting in reduced
repainting frequency, and consequently important cost savings in
large scale application. Moreover, their exible chemistry allows the de-
velopment of various surface and bulk functionalities that can be ex-
plored to design and tailor coatings that display good anti-grafti, self-
cleaning, hydrophobic/superhydrophobic, anti-dusting, anti-fogging
and ice-repellent properties compatible with a wide range of substrates.
4.2. Polyaniline-modied coatings
Modications of corrosion protective coatings with conductive
llers such as graphite, carbon black, carbon nanotubes, graphene, ful-
lerenes or metallic particles are common routes to functionalise coat-
ings in terms of electroactivity. For example, addition of up to 10% of
carbon black additives to the corrosion protective matrix referred to in
Fig. 13, increased the conductivity by approximately seven orders of
magnitude with little impact on the overall barrier properties.
Conductive polymers such as polyaniline (PANI), polypyrrol and
thiophenes can be used to modify the conductivity of corrosion protec-
tive barrier coatings. Among these, one of the most successful has been
PANI (and its various forms) [100120]. Table 5 displays some PANI-
modied chemistries that have been used to modify conventional
anti-corrosion coatings.
Addition of polyaniline salts to organic coatings has been investigat-
ed by Williams et al. [100102]. The work highlights relevant ndings
that include the role of the polyaniline salt, the nature of the bare

1011 -90
10 1h
10
1 week
Phase angle / degree

2.5 month
109
-65
|Z| / ohm cm 2

108 1h
1 week
107 2.5 month
-40
106

105
-15
104

103
10-2 10-1 100 101 102 103 104 105 10-2 10-1 100 101 102 103 104 105
Frequency / Hz Frequency / Hz

Fig. 13. Electrochemical impedance results obtained for silane-modied epoxy coatings applied on AZ31 and immersed in 0.5 M NaCl solutions for 2.5 months of immersion.
30 M.F. Montemor / Surface & Coatings Technology 258 (2014) 1737
Table 5
Examples of anti-corrosion coatings based on PANI-modied organic polymers.
Metal Coating
Zinc and AA2024 Polyvynilbutyral
AA2024 Epoxy
Steel Epoxy-ester
AZ31 Solgel
Steel Epoxy
Steel Epoxy
Steel Polyurethane
Steel Epoxy or Polyimide
metal and the interfacial pH that might have a relevant buffering
effect, inhibiting the corrosion activity. Addition of polyaniline to
polyvinylbutyral coatings hinders cathodic delamination on galvanised
steel. The process is related to a delay of the alkaline dissolution of
the zinc oxide barrier layer [100]. Polyaniline emeraldine salts of
paratoluene sulphonic acid were tested to evaluate cathodic delamina-
tion of coated AA2024 [101,102]. Based on the use of the scanning
Kelvin probe technique it is shown that those coatings effectively inhibit
liform corrosion of coated AA2024 coupons. The protective mecha-
nism is associated with more stable and protective oxide lms formed
at the metal-coating interface. Similar coatings were used to evaluate
the resistance against cathodic delamination of coated cold-rolled
steel substrates and it was found that the protective effect is dependent
upon the nature of the acid used in the PANI-modied coating formula-
tion [102].
The addition of inhibiting species such as lignosulfonate as
polyaniline dopant results in improved corrosion protection of alumin-
ium substrates due to formation of thick and stable oxide lms and sta-
ble aluminiumsulfonate complexes [103]. The coatings reveal uniform
dispersion of doped PANI and display increased pore resistance, which
hinders water and oxygen diffusion compared to non-modied coat-
ings. An epoxy-ester coating, containing dodecylbenzenesulfonicacid-
doped polyaniline nanoparticles also reveals improved corrosion pro-
tection of steel substrates, the mechanism of which likely involves the
formation of stable interfacial species that contain Fe3+ cations as dem-
onstrated by XPS analysis [104].
Wang et al. [105] modied a solgel matrix with powders of
emeraldine salt. The coating performance was studied by electrochem-
ical impedance spectroscopy and by salt spray tests. The results show
that the anti-corrosion effect is dependent upon the ratio between the
solgel matrix and the conductive polymer. Neither liform corrosion
nor creepage around the scratched edges were observed after 500 h of
salt spray. Moreover, the authors propose a protective mechanism
that is assigned to the formation of a passive layer at the surface leading
to a self-repair process [105].
Epoxy coatings modied with nanocomposites of polyaniline have
been investigated as anti-corrosion coatings for protection of cold-
rolled steel. Steel panels coated with a PANI-montmorillonite composite
coating reveal superior corrosion resistance as ascertained by weight
loss and impedance measurements [106]. The corrosion rate decreases
to half of the value determined in a non-modied epoxy coating. Mont-
morillonite contributes to increased tortuosity that hinders the diffusion
of aggressive agents through the coating. Since organo-modied mont-
morillonite is more hydrophobic, it contributes for increased corrosion
resistance.
Epoxy coatings modied with polyaniline bers and epoxy llers
were applied on mild steel and tested in NaCl 12%. The coatings display
corrosion resistance for more than three months of immersion in the ag-
gressive electrolyte. The improved corrosion protection is related to the
controlled release of the epoxy llers and to the passivating properties
of the polyaniline nanobers. Furthermore, the intertwined PANI bers
can swell, enhancing the protection of damaged areas [107].
Polyaniline coatings displaying superhydrophobic behaviour were
also proposed for corrosion protection of steel. Potentiodynamic
Active agent Ref.
PANI-emeraldine salt of paratoluene sulphonic acid [100102]
PANI-lignosulfonate [103]
dodecylbenzenesulfonicacid polyaniline [104]
PANI-emeraldine salt [105]
PANI and montmorillonite [106]
PANI Fibers [107]
Aniline trimmers [109,110]
Aniline trimmers without and with SiO2 [111113]
polarisation and electrochemical impedance spectroscopy measure-
ments reveal a shift of the corrosion potential of cold-rolled steel
towards more positive values and increased polarisation resistances.
The corrosion protection mechanism is explained by the formation of
protective surface lms composed of iron oxides covered with a
superhydrophobic PANI layer [108].
Polyurethane coatings can be modied with amino-capped aniline
trimmers, which are electroactive aniline-based compounds [109,110].
The electroactive polyurethane coating provides better corrosion pro-
tection on cold-rolled steel compared to non-electroactive coatings
used as reference. The protective effect can be related to the formation
of a passive and more protective layer of metal oxide layer as evidenced
by SEM and XPS measurements. An identical strategy was reported by
Huang et al. [111,112] for the functionalisation of epoxy and polyimide
coatings. Thus, the organic matrices were modied with an amine-
capped aniline trimmer, which confers electroactivity. The addition of
siloxanes allows preparing a polyurethane composite coating, contain-
ing dispersed SiO2 nanoparticles. The redox properties of the aniline
units promote the formation of stable and protective interfacial oxides,
while the silica nanoparticles enhance the barrier properties [113].
Polyaniline-modied coatings are reported as effective anti-
corrosion systems for various metallic substrates, which include zinc,
steel, aluminium and magnesium. PANI, as an electroactive additive,
modies the conductivity of the coating and promotes the formation
of stable and nobler interfacial protective layers that delay delamination
and corrosion propagation [100115]. The dispersion of ne PANI parti-
cles or PANI nanobers [107,116] in the host polymeric matrix can cre-
ate nanostructured networks that enhance the corrosion protection,
while contributing to modications in the material conductivity. The
effect can be enhanced by addition of dopants [103,104,117] or
fabrication of nanocomposites with other particles that result in more
dense, stable and increased barrier properties [106,113,118]. PANI-
containing nanocomposites can bring additional functionalities such as
superhydrophobicity or re-retardant properties [119,120], offering a
exible route to design functional corrosion protective coatings.
4.2.1. Coatings for controlled wettability
The functional groups present at the coating surface can control the
hydrophobic or hydrophilic response of the coating and, therefore, the
corrosion protection ability. There are numerous approaches to change
the surface wettability. Silicones are well-known due to their
superhydrophobic properties because polydimethilsiloxane displays
low surface energy and it is easily deformable. However, there are sev-
eral organic matrices, such as polystyrene, polycarbonates and silox-
anes, among others, that can be modied for controlled wettability
and corrosion protection [121132]. The most relevant examples are
summarised in Table 6.
A study performed by Bierwagen et al. [121], correlates the structur-
al and compositional variations of polymeric lms based on the glycidyl
carbamate chemistry with their barrier properties. The coating compo-
sition was tailored to include a wide range of wettability: polar hydro-
philic groups, non-polar hydrophobic groups, and reactive epoxy
groups. Moreover, the study discusses water and aqueous electrolytes
repellence and corrosion performance. The capacitance of the lm,
 M.F. Montemor / Surface & Coatings Technology 258 (2014) 1737
Table 6
Examples of anti-corrosion coatings displaying different surface wettability.
Metal Coating Active agent
Steel panels Commercial resins Glycidyl carbamate
Steel Silicone rubber Inorganic nanoparticles
Steel Acrylics Inorganic llers
Copper Isocyanate Graphene oxide
Mg alloy n.d Ferric myristate
and its ability to uptake electrolyte, was related to the presence of hy-
drophilic or hydrophobic groups. A surface richer in hydrophobic
groups shows much lower uptake and therefore improved corrosion re-
sistance compared to a hydrophilic surface [121].
Arianpour et al. [122] reports that insulating corrosion protective
coatings can also display hydrophobic or superhydrophobic properties,
depending on surface chemistry. Thus, different wetting behaviours can
be prepared, using silicone rubber chemistries modied with powders
of titania, ceria and carbon black. While carbon black increases surface
conductivity [123], ceria and titania improve the electrical eld distribu-
tion along the insulator because these materials possess higher dielec-
tric permittivity compared to the matrix. In addition to the required
insulating properties, and improved ashover performance under pol-
lution and icing conditions, the coatings also delay ice formation [122],
thus behaving as ice repellents. Improved corrosion resistance under
salt spray tests is observed for acrylic and epoxy waterborne coatings
modied with inorganic pigments and applied on steel substrates. The
polymer particles adsorb onto the pigments surface and act as spacers,
hindering particle agglomeration and allowing a more uniform distribu-
tion of inorganic additives in the coating matrix [124].
Surface functionalisation for wettability control is extremely rele-
vant for protection against fouling and subsequent bio-corrosion. A
coating based on the deposition of polysilsesquioxanes and quaternary
poly(2-(dimethyamino)ethyl methacrylate) outer blocks on stainless
steel plates demonstrates good anti-corrosion properties and, in addi-
tion, anti-bacterial effects. These coatings can prevent bio-corrosion ac-
tivity induced for example by the presence of sulfate-reducing bacteria
(SRB) [125].
Coatings containing functionalities based on solutions employed by
nature are attracting a lot of interest. These coatings can display a
wide range of surface properties, from hydrophilic to superhydrophobic
and can be tailored to display anti-fouling activity as well. The water
repellence of coatings and its anti-fouling performance can be con-
trolled by a strategy that consists on the development of self-polishing
paints. The concept replicates the behaviour of whale skin or some
plant leaves and is based on keeping a low energy surface to avoid the
adhesion and growth of living organisms found in a maritime environ-
ment. Therefore, the coatings may contain functional polymers with
groups that can enter cycles of consecutive hydrolysis and dissolution,
in a way that a permanently renewed surface is obtained as addressed
by Rahul et al. [126]. Moreover, the functional groups can also respond
to changes of pH or salinity in the environment that are induced by
the bioactivity. The outermost layers are able to dissolve and with
them the rst bioactive species.
The surface features of plant leaves were used as a template for an
epoxy-graphene composite coating applied on cold rolled steel. The
coating reveals improved corrosion protection due to improved barrier
effect and displays hydrophobic behaviour [127]. Identical trend is ob-
served for graphene oxide and isocyanate composite coatings applied
on copper substrates [128]. The work of Zhao et al. [129] reports the cor-
rosion protection effect of coatings displaying hydrophobic behaviour
based on the lotus effect. The contact angle is approximately 165 and
XPS analysis revealed that the surface is protected by a layer composed
of ferric myristate. These coatings also display anti-fouling activity
against some bacteria when applied on magnesium alloys.
31
Wettability control is essential to control hydrophobicity, anti-
fogging, water condensation, anti-dusting, anti-icing and oleophobicity.
Ref. Today the challenge is to produce corrosion protective water-borne
superhydrophobic coatings, with these additional functionalities at com-
[121]
[122] petitive prices. The siloxane technology appears very promising to tailor
[124] corrosion protective coatings displaying different wettability, ranging
[128] from hydrophilic to superhydrophobic and even to superamphiphobic
[129]
with good adhesion to a wide range of substrates [130133]. The pres-
ence of nanoadditives can enhance this behaviour [132] and silanes or
polyaniline can be used to fabricate hybrid composites compatible with
several corrosion protective matrices.
5. Coatings for bioresorbable metallic implants
Functional coatings for corrosion protection of metallic implants, es-
pecially bioresorbable metallic components, constitute a very specic
corrosion protective system that is reviewed in this section. In addition
to corrosion protection, these coatings must be biocompatible and free
of cytotoxic and genotoxic effects. These constraints make the selection
of corrosion protective coatings for biomedical applications a very chal-
lenging task. There is a wide range of coating chemistries that have been
developed in order to increase biocompatibility of metallic biomaterials
and its corrosion resistance [4]. The functionalisation of the surface of
metallic implants with hydroxyapatite coatings has been widely report-
ed [134142] because hydroxyapatite composition is similar to that of
the bone and promotes bone formation around the implants. Hydroxy-
apatite coatings, of different composition and morphologies, can be de-
posited by various routes such as thermally sprayed calcium phosphate
[134], electrophoretic deposition [135,136], composites of hydroxyapa-
tite with TiO2, Ti powders, chitosan and alginates, silica, zinc or other
metallic particles [137141] and composites with graphene [142].
These coatings can be applied on different substrates such as Ti alloys,
steel and CoCr alloys for increased biocompatibility.
Functionalisation of metallic implants with bioactive glass or com-
posites of bioactive glass and polymers such as poly(methyl methacry-
late) have also been tested [143]. TiCN coatings can also be applied,
for example, on Ti6Al4V alloy to increase biocompatibility and wear re-
sistance [144]. Tantalum oxide nanotubes grown on Ta metallic plates
by anodisation and annealing were studied in terms of corrosion protec-
tion, protein adsorption and biological compatibility with stem cells and
the results revealed that this material can be used as corrosion resistant
implant [145].
The design of corrosion protective coatings for metallic implants, of-
fering a wider range of surface functionalities has gained signicant rel-
evance in the last years. New coating functionalities include cellular
adhesion, prevention/reduction of infections and drug delivery as
reviewed recently by Lyndon et al. [146].
For many years, metallic implants made of stainless steel, titanium
alloys or chromium and cobalt alloys were used as load-bearing im-
plants, with and without application of coatings. These are bare mate-
rials suitable for permanent or long-term implants, which must be
stable in vivo. They are also used as temporary implants and, in this sit-
uation its removal requires a second surgery, which is a disadvantage.
Today there is an increasing interest in biodegradable implants that
work temporarily and slowly dissolve in the physiological media, thus
avoiding the need of a second surgery for implant removal. These biode-
gradable (or bioresorbable) metallic implants are breaking the para-
digm that all metallic biomaterials need to be stable and corrosion-
resistant. Materials classied as bioresorbable include magnesium al-
loys, zinc alloys and iron alloys [147149]. Zinc, for example, is consid-
ered very promising for bioresorbable stents because zinc is necessary
in biological processes, exhibits anti-atherogenic and anti-bacterial
properties and possesses the required mechanical properties and the
necessary ductility [147]. Zinc degrades slowly and can be continuously
released without reaching concentrations that may cause adverse
effects.
32 M.F. Montemor / Surface & Coatings Technology 258 (2014) 1737
Amongst the bioresorbable metallic materials, pure magnesium and
magnesium alloys are attracting a lot of attention. The reason relies on
the fact that Mg ions are essential to several biological mechanisms
and excess of these ions is easily excreted. The mechanical properties
of these materials are also very interesting because magnesium and
magnesium alloys have density, compressive yield strength and elastic
modulus close to that of the human bones. However, when exposed to
the physiological media magnesium corrodes very fast. This can be a
drawback, because there is maximum corrosion levels imposed for cer-
tain applications, such as stents (b 20 m/year) [150]. The corrosion ac-
tivity depends on the alloy composition and the presence of certain
alloying elements decreases the corrosion rate as reported in recent
works [151156]. These studies are focused on the behaviour of alloys,
containing different alloying elements and address various properties
such as corrosion resistance, mechanical behaviour, cellular adhesion
and in-vitro and in-vivo biocompatibility. In most of the cases positive
results were observed, without relevant toxicity effects reported. How-
ever, the release of alloying elements such as aluminium, zirconium or
rare-earths, may require further studies to fully assess genotoxicity
and detrimental accumulation in the human body. Today there is a
wide variety of magnesium alloys have been proposed as suitable tem-
porary bioresorbable implants and those containing elements such as
calcium or zinc or very low contents of aluminium are the most studied
and considered the most suitable. Nevertheless, unprotected magne-
sium alloys show high corrosion rate in physiological media. This pro-
cess releases H2 gas and induces large pH gradients at the implant
surface. The local alkalinisation induces toxicity and inammatory
events on the tissues surrounding the implant. Without proper surface
protection, the use of magnesium alloys is seriously limited by these
detrimental effects that may kill the cells during the initial adhesion
step as depicted in Fig. 14a. Application of functional coatings is the
most promising route to overcome the drawbacks related to early corro-
sion events and further toxicity consequences. If properly designed, bio-
compatible coatings, on the one hand can slow down corrosion rate, and
on the other hand can be functionalised to promote cell adhesion,
osteointegration and drug delivery. Fig. 14b depicts a schematic view
of a functional coating loaded with nano hydroxyapatite particles and
drugs for osteointegration and early-inammatory events, respectively.
This coating is expected to slow-down the corrosion process, mitigating
Physiological media + cells
a
Non-protected Bare Mg alloy
t=0
Physiological media + cells
b
Composite coang + HA + Drug
Bare Mg alloy protected with a
funconal coang
t=0
Fig. 14. Schematic view of a the corrosion process and cell growth on non-protected Mg alloy (a) and Mg alloy protected with a functional coating (b).
H2 release and local pH uctuations, thus creating a proper environment
for healthy cells adhesion and proliferation (Fig. 14b).
The design of such coatings is a complex task and although many
strategies have been reported, there are still several problems to be
solved [157162] because the corrosion rate is not properly controlled.
For example, biomimetic coatings composed of peptides or proteins are
reported to enhance corrosion resistance and to promote calcium phos-
phate precipitation for enhanced osteointegration and bone formation
[157]. However, hydrogen evolution is not totally suppressed because
these coatings do not provide sufcient corrosion protection.
Ceramic coatings [158162] have been widely studied too. H2 re-
lease is reduced but they still show some drawbacks such as high risk
of cracking and failure due to poor bonding between the bio-ceramic
layer and the magnesium substrate as reported by Oosteerbeek et al.
[162]. These events may release debris that can damage seriously the
surrounding tissues.
One of the most promising alternatives to overcome the drawbacks
referred above relies on the use of biocompatible polymeric or compos-
ite coatings designed to decrease the corrosion resistance to acceptable
levels. These coatings present high application potential because they
can be tailored for corrosion protection, drug delivery, anti-bacterial ac-
tivity and osteointegration, while being totally biodegradable.
Biocompatible thin silane coatings (Fig. 15) composed of an outer
porous layer and an inner protective and dense barrier were proposed
for corrosion protection of AZ31 Mg alloys used as bioresorbable im-
plants. The inner layer provides the required protection, while the po-
rous outer layer enhances cellular growth. These coatings signicantly
reduce the corrosion activity compared to non-coated parts and, fur-
thermore, they are compatible with various surface pre-treatments.
Electrochemical studies reveal an increase of one to two orders of mag-
nitude in the corrosion resistance of the silane coatings compared to the
uncoated alloy, depending on the surface pre-treatment [163].
Zomorodian et al. [164] propose the use PEI (polyether imide) coat-
ings modied with nano-hydroxyapatite for corrosion protection and
for stimulation of cell growth. PEI coatings are characterised by high
barrier properties and can be easily modied with inorganic llers,
like hydroxyapatite (HA) nanoparticles, to fabricate composites that en-
hance osteoblastic cytocompatibility, cell adhesion and proliferation.
Fig. 16 shows electrochemical impedance plots that reect the evolution
Physiological media + cells
H2 H2
Mg precipitates and increased pH
Corroding Bare Mg alloy
t = few days
Physiological media + cells
Composite coang +
HA
Slowly Corroding Bare Mg alloy
t = few days
 M.F. Montemor / Surface & Coatings Technology 258 (2014) 1737
Fig. 15. SEM image revealing a thin silane lm applied on AZ31 Mg alloys to decrease the
corrosion rate in electrolytes simulating physiological uids.
of the corrosion protection ability of PEI coatings modied with 2% and
5% of hydroxyapatite applied on AZ31 Mg alloys in Hank's balanced salt
solution. It is clear that the barrier effect (high frequency domain resis-
tance) is more effective for the coatings containing the lowest content of
nano-hydroxyapatite. During exposure to Hanks' solutions, the global
Fig. 16. Evolution of the Bode plots obtained by electrochemical Impedance spectroscopy measurements in Hank's balanced salt solution (HBSS) for PEI coatings modied with 2% (left)
and 5% (right) of hydroxyapatite after 1 h, 3 h and 24 h immersion.
From Ref. [164].
33
impedance decreases from values above 1E9 cm2 to values around
1E6 cm2. The increased content of hydroxyapatite reduces the imped-
ance of the system coating-alloy, but keeps it within a narrower
window.
PEI and HA composite coatings provide corrosion protection ability
and enhance MG63-like osteoblastic cell adhesion and growth as
shown in Fig. 17 [164]. Confocal laser scanning microscopy images
(Fig. 17a and b) show that after one day of cell culture, the cells are
well-spread, with prominent nucleus and cell-to-cell contact, suggest-
ing healthy cellular growth. The cells also display a well-organised F-
actin cytoskeleton (which stained intensively at the cell limits). When
the cells are cultured on the 5% HA-containing coating (the one that
shows lower corrosion resistance at initial stages) they evidence some
toxicity signs. The cells show cytoplasm shrinkage, with reduced vol-
ume. There are also an increased number of cells that display aberrant
cytoskeleton organisation and morphology. This behaviour contrasts
with that observed on the coating modied with 2% HA (the more pro-
tective coating at early stages), in which healthier cells were observed
for the test period. The changes in the cytoskeleton structure seem to
be induced by early-stage toxicity events that may be related to slightly
more intense corrosion activity on the coating modied with 5% HA
compared to the one containing 2% of HA (Fig. 16). This behaviour sup-
ports the schematic view proposed in Fig. 14. These effects were not ob-
served in control specimens (coating deposited over glass). In this case,
healthy cellular growth was observed for the testing period, thus reveal-
ing that the coating provides a compatible biointerface. The presence of
34 M.F. Montemor / Surface & Coatings Technology 258 (2014) 1737
Fig. 17. Confocal laser scanning microscopy (a, b) and scanning electron microscopy (c) images of representative coating compositions made of Polyether imide (PEI) and
Diethylenetriamine (DETA) with different contents of hydroxipatite (HA) applied over AZ31 Mg alloy and seeded with MG63 osteoblas-like cells, at day 1 (a, b) and day 4 (c). Bar:
80 m (a), 20 m (b) and 50 m (c).
From Ref. [164].
HA induces morphological alterations, such as the formation of agglom-
erates that are expected to promote cell adhesion. High-magnication
SEM images (Fig. 17cday 4) reveals that the cells are well-adapted to
the coating topography, in both the coatings modied with HA applied
over glass or the bare magnesium alloy [164].
PEI coatings can be prepared at different thicknesses by controlling
the addition of cross linkers (amines) and solvent. They can be used as
pre-layer for the deposition of other biocompatible coatings, including
porous layers or scaffolds targeted for osteointegration, drug delivery
or anti-bacterial effects, which by themselves do not provide sufcient
corrosion protection. However, the porosity effect is controversial. By
one hand, it seems to promote cells adhesion but, on the other hand, lit-
erature also reports that dense and non-porous coatings show better
cell proliferation and differentiation compared to porous coatings
[165]. Most probably the negative effects are related to early corrosion
events that affect the cellular response.
Other functional coatings that show potential to protect Mg alloys
are biodegradable polymers based on polycaprolactone (PCL) or poly
(L-lactic acid). These coatings can be fabricated with various functional
additives [166]. PCL coatings are compatible with hydroxyapatite (HA)
particles creating a porous and high surface area or polymeric reticu-
lates that can be used for controlled drug delivery of antibiotics. The in-
crease of the HA/PCL ratio increases surface roughness, compressive
strength and the elastic modulus. Moreover such composite coatings
suppress large pH variations and decrease the amount of Mg2+ ions re-
leased [167]. These coatings can be used to fabricate composites with
biocompatible inorganic llers and can be used to create complex archi-
tectures in which different functionalities can be inserted. The concen-
tration of PCL can be easily controlled and the barrier effect of these
coatings can be very high, thus providing the required corrosion protec-
tion. By changing the ratio PCL to solvent and by controlling the curing
temperature it is also possible to tune the porosity and the thickness.
Polysiloxanes functionalised with phosphorylcholine or sulfobetaine
macromolecules were used to decrease the corrosion activity and to in-
crease the resistance against thrombotic events around Mg implants.
These molecules are expected to reduce protein adsorption and cell ad-
hesion, thus reducing the early risk of thrombo events [168]. The charge
transfer resistances determined by EIS and by d.c. polarisation increased
in the presence of functionalised siloxane molecules and the system re-
vealed a slow degradation rate as required for a bioresorbable implant
[169].
Electrochemically polymerised pyrrole lms with cauliower mor-
phology were deposited on Mg alloys and it was found that the conduc-
tive coating decreases the corrosion current density [170]. However, the
cytotoxicity of pyrrole was not assessed. This can be a drawback for bio-
medical applications, since this compound is not recognised as totally
biocompatible. Coatings for bioresorbable Mg alloys can be further proc-
essed to introduce functional groups, to modify surface roughness or to
fabricate scaffolds for enhanced osteointegration and delivery of specic
molecules [171,172].
The design of functional coatings that full the specic requirements
of bioresorbable metallic implants can enhance the biocompatibility of
 M.F. Montemor / Surface & Coatings Technology 258 (2014) 1737
the material and its short and long-term behaviour under physiological
media. Biodegradable polymers (or their composites) are the most
promising for this application due to the possibility of tailoring different
architectural biointerfaces that overcome drawbacks observed in inor-
ganic coatings. Despite many advances in this eld, there are several
challenges to overcome in order to develop highly effective functional
coatings with controlled corrosion activity for bioresorbable metallic or-
thopedic implants. The condence provided by In-vivo tests is still lack-
ing for solutions based on polymer-coated bioresorbable Mg alloys. This
is, undoubtedly, a very dynamic area, in which many challenges will be
imposed before acceptance fully acceptance by the health authorities
[172,173]. The various strategies described above were focused on cor-
rosion protection of bioresorbable Mg implants, but can be extended to
other bioresorbable metallic materials too. Polymeric or polymer-
composite functional coatings pave the way for more advanced bioma-
terials in which corrosion is a required process, rather than a limitation.
6. Future trends
This contribution reviews the most recent advances related to func-
tional coatings applied for corrosion protection of metallic substrates.
Encapsulation of functional agents in stimuli-responsive polymeric
or inorganic carriers provides the opportunity to introduce a wide vari-
ety of functionalities into coatings, creating a new generation of smart
responsive materials. The combination of carriers sensitive to different
stimuli and loaded with healing or functional species with different ki-
netics of release paves the way for combinatorial healing abilities and
multifunctional properties.
Self-healing coatings based on the use of carriers of healing species
are attracting a lot of attention. Various solutions have been proposed,
which include the use of capsules, hollow particles, mesoporous parti-
cles, layered clays or tubular reservoirs. For release of corrosion inhibi-
tors, pH is the most suitable stimuli because pH gradients are
intrinsically associated with the redox electrochemical processes. Sever-
al concepts have been proven at laboratory scale, but only a few have
passed standard corrosion tests required for industrial acceptance.
Open questions, and scientic challenges, include the design of systems
incorporating various healing functionalities, prediction of the lifetime
of the encapsulated or dispersed healing agents, understanding the ki-
netics of healing at different ages and preventing early-uncontrolled
leaching of the carriers. Today, there is a need to model, predict and val-
idate the ability to heal multiple damage events and to dene the
thresholds concerning geometry and dimensions of the defects to be
healed.
The encapsulation of anti-fouling species inside smart carriers is an
acknowledged need, especially if combined with species that provide
corrosion inhibition. The combination of these functionalities is essen-
tial to mitigate corrosion problems in assets exposed to marine
environments.
Coatings that include functionalities targeted for water repellence, in-
cluding hydrophobicity, superhydrophobicity and ice-repellence are of
utmost importance and there is a fast growth of new products, with sev-
eral solutions and routes being proposed. In this domain, the challenge is
to nd new autonomic solutions combining multi-functionalities such as
superhydrophobicity, ice-repellence, bio-fouling, decreased wear, drag
reduction and corrosion protection.
The versatility and exibility of polysiloxane chemistry allows devel-
opment of high performance corrosion protective coatings that comply
with the latest requirements for environmental friendliness. The advan-
tages include the possibility to apply thinner layers and to reduce the
number of coats compared to conventional coating systems. The exible
chemistry of siloxanes also allows building surface properties contain-
ing additional functionalities such as superhydrophobicity, self-
cleaning and ice-repellence. There are also other interesting surface
functionalities being researched such as waterborne soft touch coatings,
which are very attractive for the portable electronics market or interior
35
of cars and aircrafts. These coatings must also provide increased resis-
tance to abrasion and scratches. The fabrication of these systems requires
manipulation of the water based coating chemistries (polyurethanes are
the most common) at the molecular levels, while inserting the required
functional additives.
Superhydrophobic (or highly hydrophilic), self-cleaning and anti-
dusting surfaces for architectural parts and for the transportation sector
also open several challenges when these functionalities must comply
with improved corrosion protection. TiO2 or uoro-polymers are
state-of-art, but recent advances pursue advanced solutions that repli-
cate those employed by nature.
The biomedical sector imposes specic requirements and consti-
tutes a great challenge to the development of advanced functional coat-
ings for bioresorbable implants. To date, most of the coatings proposed
for bioresorbable implants are thick inorganic barrier layers that delay
corrosion propagation. Polymeric coatings more exible solutions
since they provide compatible biointerfaces that can be tailored for dif-
ferent functionalities. However, the whole range of functionalities that
can be introduced in these coatings has not been fully explored simulta-
neously. Biodegradable organic coatings can incorporate nanoparticles
to stimulate cell adhesion, bone growth and anti-bacterial activity.
These coatings can be used for controlled drug delivery of molecules
such as antibiotics or anti-inammatories, while providing controlled
corrosion protection. Such advanced functional coatings will disrupt
the application of bioresorbable metallic implants.
Acknowledgements
The author acknowledges the valuable contribution of all the re-
searchers working under her scientic supervision and also the nancial
support of various research projects such as: MUST (NMP3-LA-2008-
214261- under the FP7 program), ERA MNT/0001/2009, PTDC/CTM/
66041/2006, PTDC/CTM/65632/2006 and teams and institutions (Uni-
versity of Aveiro, University of Paderborn, Faculdade de Medicina
Dentria da Universidade do Porto, Demokritos and Max-Planck Insti-
tute) involved in these projects.
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