Int. J. Corros. Scale Inhib., 2023, 12, no.

4, 1592–1609 1592

Uncovering intelligent self-healing coating: Synthesis strategies,

performance, and evaluation techniques – A review
Y. Albarqouni,1,2 E. Banius,1 N.H.A. Bakar3 and A. Abdullah1 *
1
Faculty of Chemical and Process Engineering Technology, Universiti Malaysia Pahang
Al-Sultan Abdullah, Gambang, 26300 Kuantan, Malaysia
2
Faculty of applied medical sciences, Clinical Nutrition Department, Al-Azhar University,
Gaza, 1277, Palestine
3
Faculty of Industrial Sciences and Technology, Universiti Malaysia Pahang Al-Sultan
Abdullah, Gambang, 26300 Kuantan, Malaysia
*E-mail: [email protected]

Abstract
Extrinsic intelligent-healing corrosion protective coatings have granted significant interest for
their sensitivity to environmental stimuli to prevent damage by releasing corrosion inhibitors
and polymerizable agents from micro/nanocarriers. Several micro/nanoencapsulation synthesis
technologies have been adopted to improve the loading capacity and regulate the releasing
behaviour of the healing agents. This context aims to review recent advances in intelligent-
healing corrosion protective coatings based on micro/nanocarriers. This review also provides
insights for synthesizing strategies and methods of such carriers. The study comprehends further
development of extrinsic self-healing coatings by evaluating the advantages and drawbacks of
different healing systems. Furthermore, the study includes other corrosion rate evaluation
techniques to understand better how to monitor such phenomena.

Keywords: physical barrier, corrosion resistance, coating, nanoencapsulation, inhibitors.

Received: July 25, 2023. Published: October 18, 2023 doi: 10.17675/2305-6894-2023-12-4-11

1. Corrosion Coating: from a physical barrier to intelligent protection

Metal corrosion, or as it is known as (Electro) chemical corrosion, is a common phenomenon
associated with the degradation of metallic structures. The phenomenon is considered a
significant threat to industries and the environment, causing gradual degradation and
continual damage to metallic facilities infrastructures [1], poisoning and reduction of shelf-
life in canned food industries [2], and other health and economical damages [3]. The
industrial operating loss due to corrosion worldwide had increased from 2012, out of which
34.7% were attributed to utility service providers, including gas, water, electricity and
telecommunications [4]. Furthermore, the number is increasing up to date. The concept of
corrosion is related to the chemical degradation of metallic materials that involve
heterogeneous redox reactions at the environment-metal interface [5]. In the environment,
the metal-air interface is coated with thin stable metal oxide layers; usually, this layer in the
 Int. J. Corros. Scale Inhib., 2023, 12, no. 4, 1592–1609 1593

disrupted areas, such as cracks and grain boundaries, begins to dissolve faster than that of
the homogenous areas. This layer, however, is easily dissolved when immersed in an
aqueous solution where an electrochemical reaction occurs represented as an oxidation
process, where the positively charged metal becomes metallic ion (Mn+), leaving out the
electrons on the metal (ne – ). Electrons in the metal interact with oxygen molecules that are
adsorbed on the metal surfaces and reduce synthesizing hydroxyl ions. In this circumstance,
the oxidation of metal is called an anodic reaction, while the reduction of oxygen (the non-
metal part of the reaction) is the cathodic one. Figure 1 illustrated the oxidation process of
iron (Fe) in an acid electrolyte. It is worth mentioning that the electrons are consumed at the
cathodic site once it is released by the anodic reaction [6].

Figure 1. Illustration of redox reactions for iron. Source: machinerylubrication.com (2012).

Several methods for corrosion protection have been widely studied and applied,
including cathodic and anodic protection, barrier protection using coatings, and the
employment of corrosion inhibitors [7]. Cathodic protection involves applying DC current
to the metals, making them cathodic, and converting the active areas to become passive. Two
kinds of cathodic protections were reported: galvanic protection and impressed current
cathodic protection [8]. Although efficient, this method is considered unreliable for
corrosion protection due to its cost-effectiveness and maintenance. Meanwhile, anodic
protection involves synthesizing a passive layer like oxides on the metal interface by
elevating the metal potential. The passive layer acts as a shield to impede the corrosive ions
from metal surface invasion. The significant disadvantages of anodic protection are that its
lifespan is unknown. Moreover, monitoring and designing the protection method is difficult
[9]. In contrast, corrosion inhibitors are anticorrosive agents that work when metals are
subjected to an aggressive environment, decreasing the corrosion rate [10]. Anticorrosive
agents (Inhibitors) can be classified into two categories; the first group is the oxide film
boosters, where the protective agents arise due to the oxidizing effect nature of the inhibitor.
The second group of inhibitors can form a barrier layer of the aggressive ions by adsorbing
on the interface of the metal [11].
 Int. J. Corros. Scale Inhib., 2023, 12, no. 4, 1592–1609 1594

Compared to other methods, protective coating with anti-corrosive material is the most
convenient and effective method to protect metals against decomposition. The well-known
traditional coating method is the direct physical barrier approach. The approach relies on
creating a physical barrier to prevent the direct contact of metal substrates with the
environment such as corrosive ions and water [7]. This kind of physical barrier effect is
considered passive corrosion protection. It is worth mentioning that even though metal
substrates are physically coated, the coating structure still may be attacked by the corrosive
ions and stimulated by the external environment changes as the prolonged service time in
the aggressive environment. Many factors influence metal corrosion, including soil
resistivity, soil chemistry, temperature, pH, aeration, and microorganisms. All mentioned
factors can lead to the manifest of the nano/micro-pores and cracks along the coating surface.
The aggressive ions can easily invade and diffuse through these pores and reach out at the
metal surface, finally causing the deformation of the coating matrix and corrosion of the
underlying metals. Over time, the nano/micro-corrosion sites will be expanded, defeating
the protective coatings, and subsequently appear as severe deterioration of the metal
substrate. Therefore, in many cases, protecting metal substrates with only a physical barrier
effect is insufficient to prevent them from corrosion in the long term, especially when a harsh
environment is combined with mechanical impacts [12].
Several techniques have been applied to extend the coatings’ protective behavior,
service time, and corrosion protection efficiency. In recent days, the concept of ‘smart self-
healing coatings’ has become the gold era through research and widely investigated. The
self-healing concept is an emerging technique in the engineering field, where it can be
employed in several composites materials such as polymer matrix composites (PMCs),
ceramic matrix composites (CMCs), metal matrix composites (MMCs), and cementitious
composites. Apart from the specified areas, the self-healing concept is driven with a high
impact when applied to corrosion protection [13–15]. The concept of self-healing means
that coated material tends to heal itself when an aggressive factor is applied automatically.
The coated material is beneficial in automatic recovering properties as electrical,
mechanical, and aesthetic properties, which in turn plays a significant role in extending the
lifetime of the coating and the metal substrate’s lifetime.
Two well-known approaches can be used to achieve self-healing coating, either
intrinsic or extrinsic self-healing. The former self-healing coating approach mainly relies on
the breaking and reorganization of the chains. It, therefore, achieves independent self-
healing effects at the coating-molecular level, which is a deep-rooted characteristic of the
coating material itself. On the other hand, the latter self-healing approach can be achieved
by interfering with the active species as a healing agent and corrosion inhibitors to inhibit
corrosion activity or repair the coating structures. Such approaches can provide physical
barriers to coatings, which can resist the invasion of oxygen, water species, and aggressive
corrosive ions [1]. Even though a good insight into self-healing, several challenges need
more effort to be solved; among those challenges is the time-functioning limitation, where
the effect of self-healing is considered functioning until the protective agent is fully
 Int. J. Corros. Scale Inhib., 2023, 12, no. 4, 1592–1609 1595

consumed. Another drawback is the lack of compatibility with the used polymeric matrix
and the protective agent, which can lead to the uncontrolled release of the protective agent
that will affect the overall performance of the employed coating. Furthermore, several
protective agents are considered toxic and carcinogenic, e.g., chromate-based coatings [1],
which can lead to serious environmental issues. Even worse, it can affect human health,
especially when used in food industries. Fortunately, the self-healing approach is currently
enhanced by applying an intelligent micro/nano container, which is the carrier of the
protective agent. The concept of such material relies on the control of releasing time of active
substrate using environmental stimulation (one or more). Typically, the protective agent is
pre-loaded to the intelligent container and then dispersed in the polymeric coating material.
Once environmental change happens, the intelligent container rapidly reacts to the corrosion,
and the encapsulated protective agent can inhibit or prevent corrosion [16]. Such an approach
is now in the gold rush era by research, where several intelligent carriers are designed.
Therefore, in this review, we included the recent research progress in designing the
micro/nanocontainers-based intelligent coatings, the established techniques for the self-
healing system, methods for fabricating micro-nanocontainers, and various corrosion stimuli
discussed.

2. Design Strategies
Different materials, such as polymers, epoxy coating, plastic, alloys or metals, and
cementitious alloys, have different systems for self-healing. In this review, various self-
healing methods are explored. Strategies have been established with specificity based on
different materials and their corresponding characteristics. The design prototype of self-
healing components is achieved by a) Release of the healing agent, b) Reversible crosslinks,
and c) Miscellaneous technologies such as electro-hydrodynamics, conductivity, shape
memory alloy, nanoparticle migration, co-deposition, etc.
2.1. Release of healing agent
Microencapsulation is by which micron-sized active solid agents or droplets of liquids are
trapped and encapsulated in an inert shell of the matrix to isolate them from outside
environments. The inertia of releasing is associated with the shell’s reactivity to the enfolded
material inside the capsule. Microcapsules with catalysts and healing agents are used to
design a release of self-healing polymer composites. The ideal microcapsule carries the
following characteristics; (i) it should be inactive with the healing agent, (ii) designed with
a long shelf-life, (iii) compatible with the polymeric dispersion region, (iv) have a thin
capsule wall for accessible agent’s Release, and (iv) matrix and envelope must be designed
with a high interfacial attraction [17–20]. The mechanism of fracture healing can be
profound during the development stage, where liquid ingredients such as hardeners, catalysts
dyes, and hollow channels are introduced into polymer-generated structures. This polymer-
like structure is ruptured when the fracture occurs, and the active healing ingredients are
 Int. J. Corros. Scale Inhib., 2023, 12, no. 4, 1592–1609 1596

leaked into the crevices by capillary force. A pre-dispersed catalyst is used to solidify the
leaked agent to heal the crack further.

2.2. Reversible cross-links

In the recent past, polymer science has reached an advanced point where it is possible to
fabricate “smart” polymers that can regenerate their original properties completely without
external interference. These polymers are considered one of the essential categories of self-
healing materials of recyclable healing polymers. The repairing mechanism is achieved
through the deep-rooted reversibility of bonding in the matrix phase, which acts as a healing
agent. The mechanism allows the healing agent to obtain excellent mechanical
characteristics such as solvent opposition, high modulus, and high break energy [21].
Recently, researchers reported a method for creating cross-linked reversible cross-
connections. In addition to recyclability, these polymers enable self-healing capabilities
which will not manifest their intrinsic self-mending abilities. Researchers reported different
stimuli as thermally reversible reactions-the Diels–Alder (DA) reactions [22], and light or
chemical triggering to evaluate the healing efficiency of the reversible bonding mechanism
[23, 24]. Ionomers [25] and Supramolecular Polymers (SP) [26, 27] are the most known
polymers that employed in the reversible cross-linked healing method.
2.3. Miscellaneous technologies
Advanced self-healing technologies have been reported recently. The following section
addresses the newly reported mechanisms of self-healing metals.
2.3.1. Electrohydrodynamic
Employing the electrohydrodynamic (EHD) flow theory generated self-healing materials.
The mechanism is ideally designed by employing a colloidal particle suspension fixed within
the two walls of a metal cylinder. The conductive coating is installed on the walls of the
metal cylinder, followed by a ceramic insulating layer. The electric field is applied to this
device where the current density at the affected spot is elevated when the isolated sheet is
damaged, aiding colloidal particles to be assembled at the issue spot due to EHD flow. Since
the gaps between colloidal particles prevent the assembly of a thick crust, the aggregation of
particles is considered inadequate to fix the flaws [28]. Self-healing is achieved by materials
such as thermo-reversible polymers [29], dietary fiber insulation, and electromagnetic cables
[30].
2.3.2. Conductivity
The fact that polymeric materials are considered isolative granted polymeric materials the
chance to be employed in several engineering applications as electronic devices by
transferring and tuning conductivity to the system, which can provide a systematic feedback
approach supporting the designed structural integrity. The obtained feedback can assist in
 Int. J. Corros. Scale Inhib., 2023, 12, no. 4, 1592–1609 1597

the discovery of metal microcracks [31]. In polymeric materials, conversely, conductivity

could be exploited to produce capabilities that can be self-healing regarding their electrically
conductive characteristics. Graphene has been successfully incorporated with Zinc/thiol
composite as a self-healing composite [32]. The excellent barrier effect of the composite
coatings was expected earlier due to the insulative nature of the polymer and the
anticorrosion mechanism granted by graphene. The permeability nature of graphene and the
high surface area endows graphene with an excellent isolative ability against water, oxygen
species, and other corrosive agents. It is worth mentioning that graphene shows an
extraordinary metal/interface anodic corrosion by providing an alternative electrical pathway
for the electrons, so they cannot reach a cathodic site and complete the corrosion reaction
[33]. Furthermore, adding anodic materials, such as zinc, helps alleviate the galvanic
corrosion phenomenon. This characteristic can be helpful for extensive purposes, including
the evaluation of approaches for self-healing [32].

2.3.3. Shape Memory Effect (Self-healing based on shape memory materials (SMMs))
Shape memory materials are an emerging class of intelligent alloys/polymers that can restore
their original form from a temporarily fixed deformity by exposure to external stimuli such
as heat or light. Both polymers and alloys can demonstrate the shape memory effect. The
shape memory effects in shape memory alloys (SMAs) such as NiTi, Cu–Zn–Al, and Cu–
Al–Ni alloys are ruled by the phase transformation among twinned martensite, detwinned
martensite, and austenite [34]. In self-healing applications, SMA fibers have been employed
to heal the micro crack in composites encapsulated by microcapsules in parallel with
polymerizable healing agents [35]. For shape memory polymers (SMPs), the shape
reformation is brought by the mean of the viscoelastic transformation of polymer chains
when exposed to thermal transition temperatures (Ttrans), such as a glass transition
temperature (Tg) or a melting temperature (Tm) [36]. Compared with other classes of self-
healing coatings, the SMP-based self-healing agents can cure larger physical crakes due to
their excellent strain recovery ability. This characteristic endows SMPs with the ability to
reduce the consumption of healing agents such as corrosion inhibitors at the coating-defected
site, thereby ensuring better and long-lasting self-healing performance.

2.3.4. Migration of nanoparticles

In 2006, it was demonstrated that metal cracks could be cured by the segregation of
nanoparticles in the fluid where the depletion of the polymer is involved with the metal
surface and the particles [37]. The morphological analysis was employed to enhance the
efficiency of self-healing. It predicts the mechanical characteristic restoration of up to 75–
100%. It is worth mentioning that the migration of nanoparticles proved that it could increase
the system’s mechanical force and isolate the defect’s surface.
 Int. J. Corros. Scale Inhib., 2023, 12, no. 4, 1592–1609 1598

2.3.5. Co-Deposition
Self-healing anticorrosive coatings can be performed using an electrolytic-based co-
deposition system [38]. With this system, microcapsules loaded with anti-corrosion agents
interfered with composite plating. These capsules are coated with metal ions such as Zn+2
and Cu+2 to produce a metallic composite. In addition to the self-healing methods illustrated
above, various novel strategies are projected to synthesize self-healing materials [39].

3. Micro/Nanocontainers fabrication methods

The process of self-healing corrosion protection works with the assistance of intelligent
containers. With the exploitation in research and the need for development in the self-healing
coating, several container synthesis methods were reported [40–42]. These containers can
be classified according to size i.e., subclassified as micro and nano containers, synthesis
method, and chemical composition. For the micro containers, the sphere size should be
around 50–200 mm. This size can easily encapsulate the active protective agent, which eases
the flow of the coating matrix on the cracks stimuli and assists in releasing the protective
agent.
On the other hand, nanocontainers possess a high surface area, which aids in loading
more active agents on them. The nanocontainers respond to external stimuli and give
feedback spontaneously to prevent corrosion along cracks in the exact mechanism as micro
containers [43]. These preventive actions can be categorized as self-healing and active
corrosion protection. Notably, the design of micro and nanocontainers can prevent direct
contact between the inhibitors and the coating matrix, thereby preserving the integrity of the
coating and ensuring long-term corrosion resistance. Micro/nanocontainers synthesize can
typically be achieved following a physical approach such as centrifugal extrusion [44],
solvent evaporation [45], spray drying [46], spinning disk method [47], and hydrothermal-
ion exchange hot pressing with silane method coating [48]. On the other hand, the chemical
preparation approach, as presented, can be classified based on the chemical composition of
the container into; organic containers, which can be prepared by one of the following
methods; in-situ polymerization [48], picker emulsion method [49], solvent evaporation
method [45] and shape memory polymerization (SMP) method [16]. In the meantime,
inorganic containers can be synthesized by sol-gel approach [50] and organic/inorganic
hybrid micro/nanocontainers can be synthesized by HF etching process [51]. In this section,
different organic synthesis methods for various kinds of micro/nanocontainers are discussed
in detail.

3.1. In-situ polymerization method

In situ polymerization is considered the standard method for organic anti-corrosion material
encapsulation. It is the most convenient and effective way among these physical-approaches
synthesis methods due to its simplicity, active material controllable capsule size and shell
thickness, cost-effectiveness, and commercial applicability for upscale production. The
 Int. J. Corros. Scale Inhib., 2023, 12, no. 4, 1592–1609 1599

typical process starts when in situ adding reactive monomers in parallel with the catalyst into
the continuous phase, called the core material. In-situ soluble monomer polarized on the
dispersed core material interface [43, 52]. Even with the significant advantages of in-situ
polymerization, it is considered time-consuming. Moreover, its performance is only
influenced by environmental stimuli, i.e., pH value, temperature, reaction time, etc. [53]. For
example, microcapsules containing acrylate boron nitride (BN) flakes were prepared using
in situ polymerization of 2-(perfluorohexyl)ethyl methacrylate to obtain BN-fluorinated poly
methacrylate (PFBP) composites product [54].

3.2. Pickering emulsion polymerization method

The Pickering emulsion method has risen by research since it provides a rigid and robust
film at the emulsion surface in overcoming in-situ polymerization. The process uses ultrafine
solid particles to stabilize an emulsion by decorating the oil/water interface. Pickering in
1907 was developed in 1996 by Velev et al., who clarified the potential of the Pickering
polymerization method as container polymerization-encapsulation [55]. Traditional
emulsion process typically uses surfactant, emulsifiers, and organic interface-active
substrate to stabilize the emulsion process. Nevertheless, these chemicals are driven with
high toxicity in contrast to the application of solid particles [56]. The Pickering emulsion
polymerization technique can be performed in either one emulsification step or two steps
method. The latter method is considered the most convenient and widely used to prepare
double Pickering containers on its excellent reproducibility. The first step in Pickering
begins with preparing puckering emulsion, where stabilizers are dispersed in the continuous
phase. The second step is encapsulating the core material where the single prepared emulsion
is homogenized with the continuous outer phase, and the mixture is emulsified into double
emulsions. In brief, the colloidal particles are first synthesized at the oil/water surface using
mechanical action to form a stable Pickering emulsion. After that, the colloidal particles are
cross-linked, utilizing a chemical reaction to produce a compact shell wall [57, 58]. Haiyan
reported a successful polymerization of Nano silica/Polystyrene (P.S./SiO2), and the
prepared capsules were further applied as self-lubricating coating material by incorporating
epoxy matrix. The self-lubricating microcapsules-incorporated epoxy were deposited onto
an aluminum plate. The microcapsules show an excellent dispersibility in the matrix and the
coatings exhibit high potential for antifriction and corrosion prevention [56]. Chen, with co-
workers, reported a modified poly-N-isopropyl acrylamide composite with Nile Red as a
Pickering emulsifier [59]. The reported particles work as a dual-stimuli responsive
emulsifier, where it is a pH and temperature-sensitive with a green fluorescent core.

3.3. Interfacial polymerization method

The interfacial polymerization method is favorable for the large-scale production of organic
containers. The ideal process typically occurs between two incompatible solutions at the
water-organic. Both water-organic solutions play a role in dissolving the core material and
the shell container. Subsequently, the formation of the capsules rapidly occurs, where the
 Int. J. Corros. Scale Inhib., 2023, 12, no. 4, 1592–1609 1600

core is formed at the surface [60]. The direct driven impacts of applying the interfacial
encapsulation method are saving time, the preparation process is considered mild, and
finally, the encapsulation efficiency is considered higher than other discussed methods
[61, 62]. Xiang, with co-workers, successfully loaded isocyanate pre-polymer in a
polyurethane microcapsule to serve as a core material for self-healing protection [63]. As
Figures 2(a and b) illustrate, the reported capsules show an ideal sphere shape. The
preparation process is more manageable than other methods since it can be achieved in one
step, as shown in Figure 2(c). It is crucial to consider the selection of both the preparation
method and the pre-polymer to reach the best performance of the capsule. In case of failure,
capsules may contain unpolymerized shell monomers that could chemically react with the
active material, which can impede the capsule’s performance [64].

Figure 2. SEM of polyurethane microcapsules (a and b). Preparation of polyurethane

microcapsule loaded with isocyanate prepolymer and Gum Arab following the interfacial
polymerization method (c). (Reproduced from Ref. [63] with permission from the mdpi).

4. Evaluation of coating effectiveness

Two types of corrosion-resistant tests are typically employed to evaluate the metal corrosion
type and rate which are salt spray test and electrochemical techniques. The latter technique
includes open circuit potential (OCP) study, potentiodynamic polarization study,
 Int. J. Corros. Scale Inhib., 2023, 12, no. 4, 1592–1609 1601

potentiostatic polarization study i.e., the current-time transient (CTT) study and double-log
plot, followed by electrochemical impedance spectroscopy (EIS) analysis including the
Nyquist plot, Bode impedance, and phase angle plots, and finally Mott-Schottky analysis
[65].

4.1. Salt spray test

Salt spray test (ASTM B117) is a standardized testing method carried out to monitor the
physical changes and evaluate the efficiency of the protective coating or corrosion resistance.
It can be defined as an accelerated aging testing method for evaluating the metal’s resistance
to corrosion when it is under extended exposure to saline or salty spray. The salinity stress
is applied using a 5% Sodium Chloride solution with a pH of 6.5 to 7.2 [66]. The test is
carried out in a time range starting from 8 hours to 3000 hours, depending on the response
and effectiveness of the coating.
4.2. Electrochemical testing techniques
Conventional electrochemical testing techniques are often employed to evaluate the rate of
metal corrosion. Such techniques can indicate the corrosion rate and the coating’s
effectiveness against corrosion. These polarization techniques are typically carried out using
an electrochemical workstation consisting of the traditional three-electrode cell;
(1) reference electrode (RE), whose material is either made of saturated calomel electrode
(SCE) or silver/silver chloride (Ag/AgCl), (2) counter electrode (CE), which is usually a
Platinum (Pt) wire, graphite, gold or carbon rod, and (3) working electrode (the desired
material for testing) [67]. Generally, the corrosion resistance of metallic substances can be
evaluated through electrochemical tests, which can be done in the following ways.
The open circuit potential (OCP) is a typical method to obtain the corrosion potential
of a material in bulk corrosion experiment and also employed to determine the conductivity
characteristics of the passive film. It is worth mentioning that the OCP technique indicates
the stability of samples in the electrolyte before performing polarization and EIS tests. Here,
it is known that the more stable the sample, the higher probability of corrosion resistance
[68–70]. For instance, Figure 3(a), shows the different OCP values of samples A, B, and C
regarding immersion time in the electrolyte. For sample A (the unburnished) illustrates that
the OCP needs more than half an hour to reach the OCP max value and remain stable
gradually. At the same time, OCP shows more positivity in potential values (higher OCP)
for burnished samples B and C. It was suggested that the OCP spends less time compared to
the A sample to reach stability. This phenomenon indicates the advantageous passivated
ability for B and C samples. Among these advantages, the work concluded that the passive
surface films on burnished samples are much denser and more protective than those on the
sample without being burnished [71]. Based on the OCP study, it is able to evaluate the
effectiveness of the coatings.
 Int. J. Corros. Scale Inhib., 2023, 12, no. 4, 1592–1609 1602

Figure 3. (a) Variation of open circuit potential (OCP) values, EOCP, with time for A, B and C
samples in borate buffer solution. (b) Potentiodynamic polarization (Tefal plot).

The second electrochemical corrosion testing technique is the potentiodynamic

polarization, which discusses the corrosion aggression in terms of the variation of corrosion
current density (icorr) and corrosion potential (Ecorr), which can be determined from the
corrosion graph using the Tafel extrapolation method (Figure 3(b)). It is generally believed
that the lower the corrosion current density (icorr) and higher (more positive) the corrosion
potential (Ecorr), the better tendency toward the formation of the passive film, hence
improving the corrosion resistance [72]. As shown in Figure 3(b), the Tafel plot can be
categorized into two regions: anodic in the positive potential region and cathodic in the
negative potential region. From the anodic polarization region, there are four categories
which are activation zone (A region), where the icorr gradually increases with Ecorr, (B region)
is the activation-passivation transition zone, where the (icorr) decreases gradually and starts
showing passivation film, (C region) is the passivation zone, which involves a further
decrease in (icorr) indicating the formation of more passivation film, and (D region) or called
the trans-passive zone, showing the degradation of the passive film with a rapid increase in
(icorr).
In the electrochemical impedance spectroscopy (EIS) analysis, the samples with better
charge-transfer impedance and phase angle are believed to have a stabilized and more
protective passive film, hence obtaining better corrosion resistance [73]. Furthermore, the
Nyquist plots and their equivalent circuit can be obtained from EIS analysis. The fitted
equivalent circuit parameters evaluate the electrolyte resistance (Rs), pore resistance, (Rpore),
charge transfer resistance (Rct), constant phase element for coating (CPEc) and constant phase
element for electric double layer (CPEdl). In this regard, higher Rpore and Rct values indicates
the higher corrosion resistance behavior while higher Rct value denotes that the coating
successfully reduces the anodic reaction in the corrosion process, thereby protecting the
metal underneath [74]. On the other hand, Bode plot deduce the high breakpoint frequency
(fh) which indicates the capacitive and resistive transition boundary of the coating and it is
independent of the substrate. When the fh values shift towards higher frequency, it signifies
 Int. J. Corros. Scale Inhib., 2023, 12, no. 4, 1592–1609 1603

the corrosion activity increases. Besides, the water permeation in the coatings could be
evaluated by measuring the changes in the electrical capacitance of the coating. Since
capacitance is directly proportional to the dielectric constant, the increment of water
permeation into the coatings would affect the dielectric constant of the coating.

5. Challenges and future perspectives

Several limitations associated with smart coating technologies can be recorded for further
study. For example, developing a cost-effective active anticorrosion or self-healing coating
is considered a subject of discussion. Often, in trying to reduce cost, the functionality of the
coating could be improved. Moreover, incorporating innovative additives into coatings often
compromises the integrity of the coating. For instance, these additives may create a pathway
for easy water uptake, delamination of coating, etc.

Acknowledgments
The authors would like to thank the Ministry of Higher Education Malaysia for providing
financial support under Fundamental Research Grant Scheme No.
FRGS/1/2021/TKO/UMP/02/75 (RDU210141) and Universiti Malaysia Pahang Al-Sultan
Abdullah for additional financial support under Internal Research Grant RDU210350.

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