materials

Review
Self-Repairing Composites for Corrosion Protection:
A Review on Recent Strategies and
Evaluation Methods
Poornima Vijayan P 1 and Mariam Al-Maadeed 2,3, *
1 Department of Chemistry, Sree Narayana College for Women, Kollam, Kerala 691001, India
2 Center for Advanced Materials, Qatar University, Doha 2713, Qatar
3 Materials Science and Technology Program, Qatar University, Doha 2713, Qatar
* Correspondence: [email protected]




Received: 5 July 2019; Accepted: 29 July 2019; Published: 27 August 2019


Abstract: The use of self-healing coatings to protect metal substrates, such as aluminum alloys,
stainless steel, carbon steel, and Mg alloys from corrosion is an important aspect for protecting metals
and for the economy. During the past decade, extensive transformations on self-healing strategies
were introduced in protective coatings, including the use of green components. Scientists used
extracts of henna leaves, aloe vera, tobacco, etc. as corrosion inhibitors, and cellulose nanofibers,
hallyosite nanotubes, etc. as healing agent containers. This review gives a concise description
on the need for self-healing protective coatings for metal parts, the latest extrinsic self-healing
strategies, and the techniques used to follow-up the self-healing process to control the corrosion of
metal substrates. Common techniques, such as accelerated salt immersion test and electrochemical
impedance spectroscopy (EIS), for evaluating the self-healing process in protective coatings are
explained. We also show recent advancements procedures, such as scanning vibrating electrode
technique (SVET) and scanning electrochemical microscopy (SECM), as successful techniques in
evaluating the self-healing process in protective coatings.

Keywords: protective coating; self-healing; anticorrosion

1. Introduction
It is important to protect the surface of metals against corrosion. This protection is more important
when compared to the bulk protection, as the surface is more exposed to the environment and prone
to mechanical and solvent attacks. Corrosion can be expected in the metal if there are cracks or pits
on the surface. The estimated cost of corrosion is approximately 3.4% of the global GDP (2013) [1].
Most of this cost is related to the inspection processes, repairing techniques, and environment and
safety procedures. One of the most expensive corrosion cost is in oil and gas facilities. Protection
against corrosion is important for the modern world, as it will reduce the financial cost. It is important
to ensure the safety and reliability of industry, reduction of waste production, and energy consumption.
Cathodic protection, anodic protection, addition of inhibitors, protective coating, etc., are
commonly practiced corrosion protection methods. Among them, a widely accepted protection
method is the use of a suitable coating, which can protect the surface of the metal from the environment.
Chemical substances, called inhibitors, can be added into coating in small quantities to decrease the
corrosion rate. The basic idea of coating is to prevent the diffusion of oxygen and moisture to the metal.
In addition to that, organic coatings have excellent impact resistance, aesthetic properties, and substrate
adhesion [2]. Among protective coatings, organic coating is the oldest and most widely used protective
coating technology [3]. Inhibitors can be added to the coatings, which ensures that they will not be
leached and it is effective for the used metal [4].

Materials 2019, 12, 2754; doi:10.3390/ma12172754 www.mdpi.com/journal/materials

Materials 2019, 12, 2754 2 of 17

As a variant of organic coating, organic-inorganic hybrid coatings consist of both the organic
component and inorganic fillers (mostly silica), bonded together by the covalent bonds [5]. Hybrid
coatings with titania as the inorganic component have also been reported in sol-gel coating films and
nanocomposites coatings [6,7]. The combination of these two types of materials will ensure good
mechanical properties, flexibility, adhesion, and transparency. Though organic coatings are effective,
the needs for green anticorrosion techniques are high due to environmental issues such as greenhouse
gas emission and global warming. Moreover, the economic concerns of crude oil and manufacturing
prices encourage us to look to green alternatives for organic coating.
With the advancement in coatings research, many researchers have reported on smart coatings
that show stimuli responsive action. The smart coating can include different responses, such as
self-healing, self-cleaning, corrosion sensing, and anti-fouling. Among smart coating technologies,
the self-healing coating concept has been introduced as a novel approach for achieving the corrosion
protection function. The automatic response to corrosion can be tailored to different factors, such as
abrasions, change in pH, surface tension, and temperature. Self-repairing organic and inorganic coating
can increase the functional lifetime of the resulting coating structure. The self-healing functionality
can be imparted, due to the presence of nano/micro containers of polymer and inorganic origin in the
coating structure. The current review paper intended to detail these extrinsic strategies in designing
self-healing coating structures with greater focus on green approaches. Depending on the end use
applications, the follow-up methods that were adopted to evaluate the healing process are important
and those will also be discussed.

2. Self-healing Strategies in Protective Coatings

2.1. General Methods

With the introduction of self-healing concept, different self-healing strategies have been adopted
to repair the cracks and damages in the coating systems [8]. Intrinsic and extrinsic strategies have
both been applied to develop self-healing coatings. In intrinsic self-healing, the crack recovery can be
achieved with reversible chemistry [9]. In the extrinsic type, either a capsule or vascular network aided
healing method is used. In capsule aided self-healing, the healing agents are encapsulated in suitable
capsules for delivering the healing agent into the damaged area [10]. Alternatively, a coating consisted
of vascular network can be used to provide a uniform healing system throughout the surface [11].
Self-healing coatings that are based on micro/nano capsules are the most practiced systems.
The factors, such as controlled uptake and release of healing agent/corrosion inhibitor, high loading
capacity, multi-functionality, etc. can control the efficiency of such capsules. Microcapsules having a
shell of polymer origin, such as epoxy, urea–formaldehyde (UF), and polyurethane (PU) are commonly
used with either healing agents or corrosion inhibitors as the core materials [12–14]. Apart from
microcapsules, nanocapsules, such as silica nanocapsules [15], ceramic nanocontainers [16], TiO2
nanocontainers [17,18], etc. are reported to have efficient healing agent/inhibitor storing capability.
Mesoporous materials also showed excellent hosting ability [19–21].
Microencapsulation is an important step in the development of self-healing materials. The desired
properties of microcapsules could be tailored via proper control of the preparation parameters. Figure 1
shows the size variation in alkyd resin (derived from palm oil) encapsulated poly(urea-formaldehyde)
(PUF) microcapsules that were prepared at a different agitation rate [22]. Many authors [23–26]
mentioned the ability to tailor the required capsules with different thicknesses, morphologies, and sizes
before adding them to the paint or to the polymer matrix. Fayyad et al. [24] encapsulate tung oil in
a urea-formaldehyde shell. The group used in-situ polymerization to prepare microcapsules with
different sizes through changing the stirring rate. Smaller microcapsules had higher corrosion resistance
when compared to larger microcapsules [27].
Materials 2019, 12, 2754 3 of 17

Figure 1. Size distribution (left) and digital microscopic images of alkyd resin encapsulated
poly(urea-formaldehyde) (PUF) microcapsules (right), prepared at different agitation rates, (a) 500 rpm,
(b) 400 rpm, and (c) 300 rpm. Adapted from [22], with permission from © 2016 Elsevier.

When the capsules are broken due to the damage in coating, the content of these capsules get out
and a reaction is activated for self-healing procedure. For example, Figure 2 depicts the rupture of UF
microcapsules capsule and release of the reactive epoxy, which acts as a healing agent [12]. The similar
action can be arranged for color change or fluorescence light to be produced after the rupture as a
sign for the damage. Different parameters [28] should to be identified before tailoring the self-healing
coating such as concentrations of containers, concentration of inhibitors, kinetics of additives, diffusion
kinetics and environmental conditions.

Figure 2. Image of ruptured urea–formaldehyde (UF) microcapsules having both reactive epoxy resin
and solvent as the core material. The regions of deposited epoxy film are indicated. Adapted from [12],
with permission from © 2009 Elsevier.

The porous inorganic materials were also widely practiced as healing agent containers. The proper
functionalization of the orifice of mesoporous silica enabled them to act as pH sensitive self-healing
agent containers [29]. The organosilyl-functionalization of mesoporous silica containers was carried
out with ethylenediamine (en), en-4-oxobutanoic acid salt (en-COO–), and en-triacetate (en-(COO–)3 )
with different organic fillings. It was found that en-(COO–)3 -type functionalization with content of
0.23 mmol/g showed better pH stimuli self-healing anticorrosive performance, as the functionalized
Materials 2019, 12, 2754 4 of 17

mesoporous silica have high loading (26 wt %) and release (80%) capacities for the inhibitor and
stoppage of any possible leaking.
The amount of encapsulatable healing agent or anticorrosion agent in inorganic and polymeric
containers is comparatively low. The low amount of healing agent and high manufacturing cost can limit
the commercialization of self-healing technology based on such containers for vehicular applications
in automobiles and aircraft. To overcome this limitation, new anticorrosive layers that contain
core-shell nano- and micro-fibers as healing agent containers were introduced [30]. Electrospinning
can be employed to fabricate networks of core-shell nano- and microfibers that were filled with
sufficient amount of the healing agent. In such an attempt, Lee et al. [30] prepared core-shell nanofiber
coatings on steel substrate with dimethyl siloxane (DMS) as self-healing agent and dimethyl-methyl
hydrogen-siloxane (as curing agent) separately in the cores via the dual emulsion electrospinning
method. DMS and dimethyl-methyl hydrogen-siloxane were both encapsulated in polyacrylonitrile
(PAN) shells. These dual nanofibers were deposited onto a steel substrate. Finally, the nanofiber mats
were intercalated with poly(dimethyl siloxane) (PDMS) matrix. The corrosion experiments that were
conducted on the manually damaged nanofiber coating proved the self-healing efficiency and corrosion
resistance of these coatings. Apart from emulsion electrospinning method, co-electrospinning was also
proved to be an efficient method for fabricating encapsulated nanofiber mats [31]. Figure 3 shows a
schematic representation of co-axial electrospinning setup. In co-electrospinning, two syringes were
simultaneously used to electrospin the dimethylvinyl-terminated dimethyl siloxane (resin) encapsulated
PAN and methylhydrogen dimethyl siloxane (curing agent) encapsulated PAN nanofibers, which were
collected together by a drum to get intertwined nanofiber mat. This nanofiber mat embedded
transparent PDMS coating over steel surface efficiently acted as a corrosion barrier via the healing
process by the release of the resin monomer from the fiber cores to heal the corrosion.

Figure 3. Co-axial electrospinning setup for generating core-shell fibers.

Another extrinsic corrosion protection strategy is the layer-by-layer (LbL) deposition of

polyelectrolyte and inhibitor nanolayers over the metals surface. In this process, the release of inhibitor
is simulated by the change in pH [32]. Andreeva et al. [33] deposited nanolayers of poly(ethyleneimine)
(PEI), poly(styrene sulfonate), and an eco-friendly corrosion inhibitor (8-hydroxyquinoline) over
aluminum surface. They proposed a self-repairing mechanism, which involves three major steps:
(i) pH neutralization activity of the polyelectolytes, (ii) passivation of the cracked surface of the metal
by introducing the inhibitors to settle among the polyelectrolyte layers, and (iii) heal the damaged layer.

2.2. Green Concept in Self-Healing Coating

Common organic molecules that have heteroatoms are considered to be good inhibitors. These
include sulphur, phosphorus, and nitrogen [34]. However, these materials can have negative effects
on the environment. The use of natural materials as healing agents or corrosion inhibitors to fill
these capsules is considered to be a good green processing approach. The use of green inhibitors was
Materials 2019, 12, 2754 5 of 17

studied by many authors [35–37], where corrosion protection can be achieved by the adsorption of
organic compounds on the metal surface through constituent polar function groups. Henna leaves
extract (HLE) has good protection ability over corrosion. It was reported that HLE with acrylic coating
(0.2 wt/vol%) achieved good protection due to the formation of a barrier, nevertheless the resin coating
fails with the increase in temperature due to the formation of ionic conducting paths. These conducting
routes are formed due to the thermal expansion [37].
Many researchers used different types of oils, such as tung oil [38,39], linseed oils [40–44], neem
oil [45], and sunflower oil [46], as greener corrosion inhibitors. These natural oils oxidase with
atmospheric oxygen and a film of polymerized dried oils are formed for further protection of the
coating surface. Among these natural oils, tung oil and linseed oil are the most practiced self-healing
agents due to their better drying performance and the ability of emulsification and cross-linking.
Similarly, green alternatives for nanocontainers have been investigated, such as chitosan [47]
and cellulose nanofibers [48,49] and different type of naturally occurring clay minerals, including
halloysite nanotubes [50], Attapulgite [51], etc. Zheludkevich et al. [47] successfully developed a
pre-layer of cerium-doped chitosan that acts as reservoir for corrosion inhibitor for the aluminum alloy
2024 substrate. A complex is formed between the cerium cations and the chitosan. This complex was
reported to be responsible for the immobilization and release of the corrosion inhibitor. The mechanism
of immobilization and release of self-healing agent in cellulose nanofiber was slightly different from
that of chitosan. Vijayan et al. [49] reported that epoxy monomer and amine curing agent were both
immobilized on cellulose nanofibers and incorporated to epoxy coating on carbon steel substrate. While
epoxy monomer adhered on the surface of cellulose nanofibers, the amine curing agent chemically
bonded with fibers. Up on the surface damage, the nanofibers made contact with the water and
deformed to release the epoxy monomer, which subsequently reacted with the active functional group
in curing agents to recover the damage. The coating based on cellulose nanofibers are proved to be
suitable for sea water applications, as these nanofibers become deformed upon contact with water,
thereby releasing the adhered corrosion inhibitors into the damaged area. Dong et al. [52] made use
the pH-dependent electrostatic interactions between L-valine and halloysite nanotubes to manufacture
smart anti-corrosive coating. The shuttling of charge in L-valine between acidic and basic pH has been
utilized for the pH based release of L-valine from HNT lumen.
Figure 4 shows the green components used in developing green coatings.

Figure 4. The green components of self-healing anticorrosive coatings.

2.3. Graphene as Potential Self-Healing Component

With the advancements in graphene research, scientists developed graphene based coatings with
good self-healing and anti-corrosive properties. Graphene based materials are commonly used in
waterborne coatings as anti-corrosive fillers, due to their excellent barrier properties. In addition to
that, various approaches were reported in utilizing the graphene family materials to enhance the
self-healing ability. Graphene oxide microcapsules can act as reinforcing healing capsules. They are
utilized because they have the following properties: mechanical stability, thin walls, and high loading
Materials 2019, 12, 2754 6 of 17

of healing materials [53], which are important parameters in defining good microcapsules within
the coating. Li et al. [53] reported the production of graphene oxide (GO) microcapsules with thin
shells thickness of nanometers. The healing material was linseed oil. There was a good compatibility
between GO and polyurethane (PU) matrix due to the presence of functional groups on the shell.
The production of these mechanically stable microcapsules is easy through th self-assembly of GO
sheets. 10 wt% of this microcapsules in waterborne PU coatings was found to heal a scratch with
20 µm in width on hot-dip galvanized steel surfaces. In another technique, graphene oxide/polysterene
(GO/PS) containers were produced with 8-HQ inhibitors [54]. The authors controlled the size of the
containers from 700 nm to 35 µm. The produced powders can be used in epoxy coatings over mild steel
as low cost self-healing anticorrosion materials. Alternatively, Fan et al. [55] used a multilayer structure
of GO with branched poly(ethylene mine) (PEI)/ poly(acrylic acid) (PAA) to protect magnesium
alloy. In this case, GO acted as both the barrier layer and the multilayers for self-healing. Very
recently, Wang et al. used graphene oxide based hybrid structures as healing agent containers [56].
They fabricated graphene oxide-mesoporous silicon dioxide layer–nanosphere structure full with
tannic acid healing agent (Figure 5). Such a coating was proven to be effective protection of metal
parts used in submarine vehicles from alternating hydrostatic pressure (AHP). Similarly, another
research group used graphene oxide@phosphate intercalated hydrotalcite to impart self-healing ability
to waterborne epoxy coating [57]. The self-healing ability of graphene oxide@phosphate intercalated
hydrotalcite came from the ion exchange between PO4 3− and Cl− on metal-coating interface.

Figure 5. (a). Schematic representation of synthesis procedure of graphene oxide-mesoporous silicon

dioxide layer-nanosphere; (b). Filed emission-scanning electron microscopic (FE-SEM) image of
graphene oxide-mesoporous silicon dioxide layer–nanosphere. Adapted from [56], with permission
from © 2019 Elsevier.

2.4. Other Latest Concepts

The generation of multi-shelled microcapsules boosted the research in self-healing coating.
The double shelled microcapsules showed better resistance to salt water, making them new promising
materials to be used with waterborne coatings [58]. The formations of double-layered polyurea
microcapsule are shown in Figure 6. The inner layer of polyurea microcapsule was formed via
interfacial polymerization, and then coated with an outer layer of PUF shell via in situ polymerization.

Figure 6. Schematic representation of double-layered polyurea microcapsule formation. Adapted

from [58], with permission from © 2016 Elsevier.
Materials 2019, 12, 2754 7 of 17

Similarly, multicore microcapsules were experimented. These materials provided the dual action
of self-healing and anticorrosion [59]. The authors showed that the microencapsulation of both
corrosion inhibitors and linseed oil in multicore phenol formaldehyde shells could provide successful
self-healing anticorrosive coating over polyurethane paint.
Over the last decade, polydopamine has emerged as a versatile material for functionalizing
surfaces [60]. Qian et al. [61] developed a new self-healing coating by using polydopamine
(PDA) as a pH-sensitive protector for inhibitor loaded in mesoporous silica nanoparticles (MSNs),
which overcame the limitation of spontaneous flow of inhibitors molecules from mesopores.
The designed PDA-decorated corrosion inhibitor loaded MSNs nanocontainers was used to prepare
self-healing water-borne alkyd coatings on mild steel. Benzotriazole, used as a corrosion inhibitor,
was loaded at neutral pH, and it facilitated fast release in acidic pH. PDA functioned to govern the
discharge of inhibitors and form protective complexes with corrosion products.
Smart containers tailored to specific actions can be used as self-healing materials. For example,
containers that respond to light stimulation function in a more controlled manner when compared
with those respond to other stimuli, such as pH or temperature, can be produced. Chen et al. [20]
developed a reversible light triggered self-healing water-born alkyd coating over aluminium alloy,
by incorporating azobenzene- modified hollow mesoporous silica nanocontainers. Upon ultraviolet
(UV) irradiation, azobenzene had reversible trans-cis isomerization associated with the decrease in
the size of trans to cis isomers, which resulted in expelling molecules out of the nanocontainers
to the corrosion site. Upon exposure to visible light, the trans isomer transformed to cis isomer,
which prevented the release of corrosion inhibitor. In this way, it is possible to avoid the extra discharge
of the inhibitors after healing the corroded area.

3. Techniques to Follow-up the Process of Self-Healing in Protective Coatings

In this section, we describe the common experimental techniques that are used to confirm the
self-healing process in proactive coating for metal structures. The working principle and application in
self-healing coatings of electrochemical impedance spectroscopy (EIS), scanning vibrating electrode
technique (SVET), and scanning electrochemical microscopy (SECM) are discussed in this section.

3.1. Accelerated Salt Immersion Test

Accelerated salt immersion test is a preliminary evaluation procedure for self-healing coatings.
This is the simplest procedure to follow-up with the self-healing process in protective coating.
The scribed coatings are immersed in 10 wt% salt solution, a concentration that is higher than that of
normal sea water concentration. The visible progression of corrosion is estimated on definite time
intervals. For instance, Huang et al. [62] used accelerated salt immersion test to evaluate the self-healing
ability of epoxy coating that contained 10 wt% of polyurethane microcapsules with hexamethylene
diisocyanate (HDI) as core material on steel substrate. It was observed that HDI microcapsule loaded
coating could resistant corrosion (Figure 7a), while the control coating was extensively corroded
(Figure 7b).
Materials 2019, 12, 2754 8 of 17

Figure 7. Photographs of steel panel coated with (a) 10 wt.% hexamethylene diisocyanate (HDI)
microcapsule incorporated coating and (b) pure coating after accelerated salt immersion test for two
days followed by storage at room temperature for six months. Adapted from [62], with permission
from © 2014 Elsevier.

3.2. Electrochemical Impedance Spectroscopy (EIS)

Electrochemical impedance spectroscopy (EIS) is a routine method for studying the self-healing
properties of protective coating for metal [63]. Traditionally, this technique has been used to evaluate
of the physicochemical processes that are associated with corrosion on coated substrates. With the
development of self-healing coating as an alternative route for anti-corrosion protection, EIS was
extended to follow the healing process. EIS was successfully applied to various self-healing coating
systems, such as polymers and their composites coatings, metal oxide coatings, coating based on
carbonaceous nanomaterials, such as carbon nanotubes (MWCNTs) and graphene etc.
Scribing on the coating surface manually forms defects. EIS consists of a three-electrode system in
which the scribed coating acts as the working electrode and normally the Ag/AgCl electrode acts as a
reference electrode. A counter electrode is aligned parallel to the coated material to complete the cell.
NaCl aqueous solution of desired concentration is used as the electrolyte. The used concentration of
NaCl solution depends on several factors, such as the type of coating, area of application, etc. The use
of low concentration NaCl helps to estimate the early stage corrosion process more accurately, as it
decreased rate of corrosion. The entire experimental setup is schematically shown in Figure 8.

Figure 8. Schematic diagram of the electrochemical impedance spectroscopy (EIS) measurement.

Adapted from [62], with permission from © 2014 Elsevier.

One of the popular representation methods of EIS result is the Bode plot, where log frequency is
plotted against both the absolute values of the impedance (|Z| = Z0 ) and the phase-shift. Bode plot
for the coated metal surface with a defect is primarily used to probe the self-healing phenomena.
Materials 2019, 12, 2754 9 of 17

Upon creating an artificial defect on the coating surface, the impedance at low frequencies gets suddenly
dropped due to the failure of the oxide film and the start of the corrosion process. Once the healing
of the defect starts, the impedance recovers its initial values. For instance, Zheludkevich et al. [64]
analyzed the Bode plot to follow the self-healing performance of a corrosion inhibitor doped hybrid
so-gel coating on aluminium alloy (Figure 9). 8-hydroxyquinoline is used as a corrosion inhibitor in
this coating. The authors found that the initially dropped impedance values retrieved the initial value
after a short period of 20 min. (Figure 9a). However, continuously decreased low frequency impedance
values of undoped single-layer sol–gel coating indicated coating failure without recovery (Figure 9b).

Figure 9. EIS plots of (a) inhibitor doped double-layer sol-gel film and (b) undoped single-layer sol–gel
film during immersion in 0.5 NaCl. Adapted from [64], with permission from © 2007 Elsevier.

The time that is required to initialize the healing process is an important parameter in judging
a self-healing coating. EIS gives evidence of this self-recovery time. The EIS investigation on epoxy
coating with epoxy microcapsules applied on carbon steel revealed that the coating was able to heal
within 4 h (Figure 10) [14]. This confirmed the microcapsules that were immediately released the
healing agent as the cracks propagated through the coating.
An alternative method for quantifying the self-healing process is to fit the EIS data with an
equivalent circuit while using data analysis. This method provides some more knowledge regarding
the self-healing performance of the coated layers by assigning the impedance spectra to the components
of the circuit [62]. The change of components of the equivalent circuits, such as healing resistance
(Rhealing ) and healing capacitance (Chealing ) with immersion time, gives direct information about the
self-healing process. Hexamethylene diisocyanate (HDI) filled polyurethane microcapsules containing
epoxy coating on steel substrate was evaluated for its self-healing performance by fitting the EIS plots
with equivalent circuit [62] (Figure 11a). The equivalent circuit of the scratched HDI filled microcapsule
containing self-healing coating in EIS measurement is shown in Figure 11b. The value of Rhealing
increases with the immersion time (Figure 11c), which reflects the self-repairing of coating surface.
Materials 2019, 12, 2754 10 of 17

Figure 10. EIS Bode plots of epoxy coatings containing 20% microcapsule during immersion in 12 wt.%
NaCl solution at different time intervals. Adapted from [14], with permission from © 2012 Elsevier.

Figure 11. (a) Bode plots and fitted curves (solid line) of scratched epoxy coating with HDI filled PU
after 8 h of immersion in 1 M NaCl solution, corresponding (b) equivalent circuit in EIS measurement
and (c) healing resistances (Rhealing ) versus immersion time plot. Adapted from [62], with permission
from © 2014 Elsevier.

3.3. Scanning Vibrating Electrode Technique (SVET)

Corrosion and self-healing process in coated metal substrates are initiated over the micro
area. This process is usually associated with changes in the electrochemical potential and current
density. SVET can probe corrosion initiation by measuring the local corrosion current densities in
micro-confined defects. SVET maps the electric field produced above the electrochemically active
surface level, and graphically show it as a contour map. This technique provides real time mapping
and quantifying of local electrochemical and corrosion events. The use of vibrating reference electrode
to measure the electric field improves the resolution and lower minimum measurable signal when
compared with a static reference electrode.
The electrochemical cell setup of SVET involves a microelectrode, which is the main part of the
SVET. It is immersed in an electrolyte, in which the coated material is fixed with a holder. Figure 12
shows electrochemical cell setup for SVET. A computer program mechanically managed the scanning
probe of the microelectrode. The observer can vertically oscillate the probe over the coated material.
The results can be recorded as a current density map.
Materials 2019, 12, 2754 11 of 17

Figure 12. Electrochemical cell setup for scanning vibrating electrode technique (SVET) experiments.
Adapted from [65], with permission from © 2017 Electrochemical Society, Inc.

SVET was used to follow the self-repairing in epoxy coating containing corrosion inhibitor doped
microgel on aluminum substrate by Latnikova et al. [66]. A maximum increase in current density
recorded after 12 h of immersion in SVET current density map confirmed an intense corrosion on
control epoxy coating, as shown in Figure 13a–c. At the same time, the epoxy coating containing 5 wt%
of corrosion inhibitor doped microgel particles showed no signs of corrosion, indicating the continuous
release of 2-methylbenzothiazole (MeBT) from microgel in to the damaged area (Figure 13d–f).

Figure 13. The current density distribution above scratched aluminium substrates covered with (a–c)
control epoxy coating and (d–f) epoxy coating modified with 5 wt% of MeBT doped microgel particles:
a,d—0 h of immersion, b,e—6 h of immersion, c,f—12 h of immersion in 0.1MNaCl solution. Adapted
from [66], with permission from © 2012 Royal Society of Chemistry.

SVET has been successfully used to follow the self-healing process in polyelectrolyte multilayer
coating containing an inhibitor on aluminum plates [33]. The current density maps of this polyelectrolyte
based coating were compared with that of the SiOx /ZrOx sol-gel coating. The current density map of Al
surface coated with sol-gel film showed increasing anodic activity with the immersion time ultimately
ending up in total failure of metal surface. However, an extremely different behavior was shown by
inhibitor loaded polyelectrolyte coated Al alloy surface as neither anodic activity nor corrosion product
was observed until 16 h of immersion.

3.4. Scanning Electrochemical Microscopy (SECM)

Similar to SVET, scanning electrochemical microscope (SECM) is also an important local
electrochemical method for following self-healing with high spatial resolution [67]. The microelectrode
probe is the main component in SECM. This probe laterally scans across the coating surface and it is used
to monitor processes locally in solutions, and map the corresponding surface reactivity [68]. The size of
the probe tip is critical, as it controls the spatial resolution of SECM measurements. SECM facilitates the
Materials 2019, 12, 2754 12 of 17

chemical changes by detecting the ionic species involved in the corrosion process, which is unable to be
provided with SVET. Latest literatures report the use of both redox competition mode and a combined
redox-competition and negative-feedback mode to monitor healing process. González-García et al. [69]
monitored the self-healing phenomena in epoxy coating embedded with capsules containing silyl-ester
on aluminum alloys with the help of SECM. They opted a combined mode in SECM that was clearly
able to distinguish the oxygen behavior as an active component in the cathodic processes and as
a mediator. Figure 14 shows SECM profile of the transition area on aluminum alloy surface with
control coating and silyl-treated coating upon immersion in salt solution. The average plateau of
more negative current that was observed on silylester-area indicates the absence of cathodic activity.
The silyl-ester that was released from capsules regenerates the uniform surface layer to protect the
metal from corrosion and consequently more oxygen is available in immersion medium.

Figure 14. Scanning electrochemical microscopy (SECM) profile of the transition area on aluminium
Alloy with control and silyl-treated coatings immersed in 0.05 M NaCl solution for 1 day. Adapted
from [69], with permission from © 2011 Elsevier.

4. Applications of Self-Healing Coatings

When considering the various technologies available, the development of self-healing coatings
depends on the end use applications. Most of the above-discussed self-healing coatings are currently
in the product development stage. The introduction of such smart coatings in many modern industries
would protect the metal parts from the corrosive environment, improve the performance and ensure
safety. The applications include automotive, electronics, aerospace, oil and gas, medical materials,
and marine industries. The existing self-healing technologies in the market can repair scratches on
paints and coatings in automobiles [70]. Coatings with self-healing ability triggered by sunlight on
concrete have been reported [71] and a similar coating over metal substrate would have potential use
in outdoor applications. Coatings that use corrosion inhibitors as healing agents would produce cost
effective anti-corrosion coatings for infrastructure and oil and gas pipelines. Thin self-healing coatings
that were obtained with sol-gel technique are potentially useful for aluminum alloys in aerospace
applications. Self-healing coatings are feature smart materials, which can impart aesthetic function in
addition to protective functions to automobiles and infrastructure.
Advanced research in this area focuses on integrating multi functionalities on self-healing coatings.
Most importantly, properties, such as anti-fouling, super hydrophobic, and anti-friction, can be
integrated along with self-healing [72,73]. In this process, different functional materials are used,
depending on the required applications. The long time release of healing agents is important for
different applications, especially the one that is related to aging protection. In this system, the required
treatment is released when needed. For example, in [74], two techniques can be used at the same time:
the first technique is the fast release of inhibitors by nanocontainers under the required environment
conditions, the other technique is the long time, slow release of inhibitors. Ecofriendly vegetable
oils and clay minerals are potential candidates as healing agents and nanocontainers, respectively,
for scalable industrial application.
Table 1 summarizes different types of self-healing coatings, their key characteristics, and
potential applications.
Materials 2019, 12, 2754 13 of 17

Table 1. Different type of self-healing coating, key characteristics, and potential application.

Sl No. Type of Self-Healing Coating Characteristics Potential Applications

Popular self-healing coatings.
Micro/nano polymer capsules to An anticorrosive coating to enhance the durability of
1 Preparation of capsules can be
load the healing agent. metallic structures.
tedious. Challenges in stability.
Multi-shelled microcapsules to
2 Good resistance to salt water. Waterborne self-healing coatings for automobiles.
load the healing agent.
Commercially available porous
Porous inorganic materials with
inorganic materials can be used
3 functionalized orifices to load the pH sensitive self-healing coating for metals.
directly. Controlled release of
healing agent.
healing agent.
Sufficiently large amount of
Core−shell nano- and micro-fibers Anticorrosive coating for large scale
4 healing agent could be loaded in
as healing agent containers industrial applications.
core-shell fibers.
Layer-by-layer coating to
Thin coating offers long term To protect aluminum alloys used for
5 immobilize healing
corrosion protection. aerospace applications
agent/corrosion inhibitor
Cellulose nanofibers to immobilize
6 Ecofriendly coating technology. For submarine applications.
healing agent/corrosion inhibitor
Economic and green coatings.
Halloysite nanotube as healing
7 Halloysite nanotubes act as Anticorrosive paint for commercial applications.
agent containers
reinforcing agent for the coating.
Anti-corrosive metal coatings for scalable industrial
8 Natural oils as healing agents Green and economic.
applications.
Henna leaves extract as Suitable to protect variety of metals exposed to a
9 Eco-friendly corrosion inhibitor.
corrosion inhibitor wide range of electrolytes.
Graphene oxide (GO) based
Mechanical stability and high Protect metal parts used in submarine vehicles from
10 microcapsules as healing
loading capacity. alternating hydrostatic pressure (AHP).
agent container

5. Conclusions
New generation of self-healing protective coatings confirmed their candidature as alternative
anti-corrosion coatings. The current review gave a concise discussion on the latest self-healing strategies
that were adopted in protective coating technology. Greener coatings avoid the use of solvents and
volatile organic coating. The emerging green synthetic approach, role of graphene family members and
polydopamine in self-healing coating technology were discussed. We explained both the conventional
and advanced techniques that were used to follow the self-healing process in coatings. We also
discussed the use of specific new techniques, such as SVET and SECM, in detecting and following
the self-healing phenomenon in protective coatings need to be explored more in future. As intensive
research is progressing in this field, multifunctional self-healing coatings will be the future of coating
technology in marine, aeronautical, and oil and gas industries. The new modified surfaces can offer
reduced production cost and prolonged service life.

Author Contributions: Conceptualization, P.V.P and M.A.-M.; Writing—Original Draft Preparation, P.V.P and
M.A.-M.; Editing, P.V.P and M.A.-M.; Supervision, M.A.-M.; Funding Acquisition, M.A.-M.
Funding: The continuous support from Qatar University is appreciated.
Conflicts of Interest: The authors declare no conflict of interest.

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