Progress in Organic Coatings 153 (2021) 106040

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Progress in Organic Coatings

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

Review

Research progress in organic zinc rich primer coatings for cathodic

protection of metals – A comprehensive review
Ahmed Khalid Hussain a, *, N. Seetharamaiah a, Moorthi Pichumani b, Ch. Shilpa Chakra c
a
Department of Mechanical Engineering, School of Technology, GITAM University, Hyderabad, India
b
Department of Nano Science and Technology, Sri Ramakrishna Engineering College, Coimbatore, India
c
Centre for Nano Science and Technology, Institute of Science and Technology, JNTU-H Hyderabad, India

A R T I C L E I N F O A B S T R A C T

Keywords: Zinc rich primer systems are one of the most utilized organic coating systems for corrosion protection of metals
Zinc rich epoxy coatings designed to operate at moderate to room temperature. Because of this reason, it remains the first choice of re­
Corrosion searchers for improvements by introducing different innovative functionalities. Nowadays a wide range of highly
Cathodic protection
efficient micro and nano materials have been explored that can be integrated within the organic coatings to
Graphene
enhance their performance. In this review article, we present a comprehensive literature gathered with a view
Carbon nanotubes
towards assessing the potentiality of zinc rich epoxy primer systems to protect the metal against corrosion. This
review is mainly focused on recent progress in zinc rich epoxy coatings embedded with different kinds of filler
materials to enhance their corrosion protection efficiency. Several new strategies and approaches have been used
by researchers to increase electrical percolation, barrier effect and galvanic longevity so that the coatings provide
extended service for a long period of time. Various topics covering fundamentals of protection mechanisms,
performance evaluation, challenges and future research directions pertaining to zinc rich epoxy composite
coatings are briefly discussed.

1. Introduction metal. The sacrificial metal acts as an anode with lower potential and
forms a galvanic couple with the base metal which makes the mixed
Sacrificial anticorrosion coatings based on cathodic protection potential of the system to be lower compared with the corrosion po­
property are one of the most recommended and extensively utilized tential of base metal thus protecting the base metal as cathode [6].
coatings to protect the metal surface against corrosion in a variety of Among the different types of sacrificial coatings, zinc rich primers
aggressive conditions including marine and industrial environments. (ZRPs) are the most widely used effective anti-corrosion coatings. Zinc
The reason for its popularity is its excellent property of shielding the rich primers are usually applied as the base coat above which the top
metal structures even after slight mechanical damage on the surface of coat of epoxy or polyurethane is applied forming a smooth glossy surface
the coating [1]. These coatings have reached a level of performance for durable and reliable heavy-duty protection [7] as shown in Fig. 2(a).
together with other latest coating systems where it can be regarded as a Depending upon the chemical nature of binder utilized, zinc-rich
viable solution to virtually any environment that demands long-term primers are basically divided into two broad categories i.e., organic
corrosion protection [2]. The anticorrosion coatings industry repre­ primers and inorganic primers. Commonly used binders for organic
sents only 10 % share by value of the total coatings market in 2018 and ZRPs are epoxy, urethane, polyamine-amide, chlorinated rubbers, vinyl
the demand is expected to increase at a rate of 3.5 % annually. Fig. 1(b) resins, unsaturated polymers, etc [8]. On the other hand, binders for
shows percentage distribution of world consumption of anticorrosion inorganic ZRPs are based on silicates or alkyl-silicates which either cures
coatings for the year 2018. Materials with low standard potentials are itself or by chemical reactions [9]. Zinc-rich primer provides cathodic
generally selected as filler materials in the sacrificial coatings such as protection to the steel substrate only when the zinc particles are in
zinc [3], magnesium [4] and various ferrite compounds [5]. Cathodic contact with each other and with the steel substrate. Zinc reacts with
protection of the base metal surface is achieved by inducing a galvanic water, oxygen and carbon dioxide to form corrosion products such as
couple between these sacrificial metals and electrochemically inert base zinc oxide, zinc hydroxide, hydrozincite and zinc carbonates [10]. These

* Corresponding author.
E-mail address: [email protected] (A.K. Hussain).

https://doi.org/10.1016/j.porgcoat.2020.106040
Received 29 September 2020; Received in revised form 27 October 2020; Accepted 8 November 2020
Available online 8 February 2021
0300-9440/© 2020 Elsevier B.V. All rights reserved.
A.K. Hussain et al. Progress in Organic Coatings 153 (2021) 106040

corrosion products cover the defects in primer film and form a stable of Science 2020 database, the number of scientific reports published
barrier which results in delaying water uptake. Typically, high per­ with keywords zinc rich coatings were approximately 713. Fig. 1(a)
centage of zinc dust (80− 90%) is required to obtain good electrical shows the number of publications each year since 1980 related to zinc
conductivity in a standard zinc rich primer. However, high zinc con­ rich coatings. The overarching goal of this paper is to review the
centration significantly influences the physico-mechanical properties research advancement in the area of zinc rich epoxy (ZRE) primer sys­
causing high viscosity, poor surface leveling, difficulties in spraying, and tems. The review includes a compilation of results extracted from the
separation of zinc dust during storage impairing shielding effect [11]. A published literature on anticorrosion properties of promising zinc rich
100 % pure zinc rich primer without any zinc oxide particles provides based epoxy coatings. Detailed information and understanding on
only cathodic protection during the initial stages of exposure to corro­ different corrosion protection mechanisms involved and the effects of
sive species whereas in case of other primers cathodic as well as barrier compositional changes on cathodic protection of different coating types
protection act simultaneously right from the beginning due to the are discussed briefly. In addition, the latest approaches and directions
oxidation of zinc particles during production [12]. used to enhance the corrosion performance of ZRE coatings are elabo­
Over the last 20 years, the increasing demand of protecting metals rated in separate sections.
against corrosion in industries led to the discovery of new varieties of
efficient zinc rich composite primer coatings and significant improve­ 2. Zinc rich epoxy coatings
ments in the performances of conventional zinc rich primers. After the
discovery of several novel 2D carbon materials such as carbon nanotubes Heavy duty ZRE coatings have been utilized widely since 1940′ s in a
(CNTs) and graphene, the collective worldwide efforts of scientists and variety of atmospheric environments to protect the metals against
engineers contributed to a significantly improved performance of ZRPs degradation and abrasion. A standard two part commercial zinc rich
which, in turn, led to the implementation of ZRPs in a variety of in­ epoxy primer is composed of zinc dust mixed with epoxy binder, sol­
dustrial environments [13]. Numerous scientific papers have been vents and additives as shown in Fig. 2(b). In ZRE primer, the epoxy
published on inorganic zinc rich based primers proving their superior forms a tough non-convertible film which acts as a barrier against cor­
anticorrosion performance [14]. However, only a few review papers rosive analytes, while the zinc dust filler provide cathodic protection
have been reported so far specifically reviewing the current status of against corrosion when the metal substrate is exposed to the corrosive
organic ZRPs for corrosion protection application. According to the Web environment [15]. It also effectively circumvents microbiologically

Fig. 1. (a) A bar graph representing number of published papers each since year 1981to 2020 (source: Web of Science, accessed on 09/08/2020). (b) A pie chart
showing percentage consumption of zinc rich primer coatings worldwide among different countries (source: https://ihsmarkit.com/products/chemical-high-perform
ance-anticorrosion-scup.html accessed on 09/08/2020).

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A.K. Hussain et al. Progress in Organic Coatings 153 (2021) 106040

induced attack in sulfate-reducing bacterial environments and protects volume concentration (CPVC). When PVC value becomes equal to CPVC
the external surface against corrosion [16]. Diglycidyl ether of bisphenol value cathodic protection of base metal starts and continues to increase
A epoxy resin is the most frequently used binder for zinc rich coatings until all the zinc particles in the coatings are oxidized. The CPVC value
due to their ease of processing, excellent chemical resistance, high also indicates the point where the primer coating changes from a 2-
cross-link density, remarkable adhesive strength and high compatibility phase system of binder and pigment to a 3-phase system via genera­
with different classes of topcoats [17]. Since epoxy resin doesn’t have tion of air bubbles in the matrix [20]. The CPVC value of the ZRE
good electrical conductivity, a high load of zinc particles (80− 90 wt.%) coatings can be computed according to the following equation [21]:
are needed to ensure electrical continuity between zinc particles and
93.2
metal substrate for galvanic action to occur [18]. In the later stages of CPVC = (2)
93.2 + (D × OA)
coating service life, the electrical contacts between the zinc pigments
and the steel substrate gradually weakens due to the production of zinc Where D and OA is the density of zinc dust and volumetric oil absorption
corrosion products diminishing cathodic protection property of the respectively. The sacrificial protection property of a ZRE primer depends
coatings. on the zinc content, pigment type and other additive materials like
Corrosion resistance and physicochemical properties of zinc-rich surface levelling agents, defoaming and anti-settling agents. In ZRPs zinc
primers strongly depend on size, shape, and pigment volume concen­ dust is usually introduced as spherical pigments with average diameter
tration (PVC) of zinc particles [19]. The PVC value for ZRE coatings has ranging from 5 microns to 40 microns due to its convenient
markedly effect on the mechanisms of corrosion protection. The PVC manufacturing process [22]. Recent findings show that when lamellar or
value can be determined for a zinc rich coating formulation using the flake shaped zinc particles are used, the value of zinc content can be
following Eq. (1) reduced to 40%–50% without affecting the cathodic property of the
Pigment Volume primer [23]. Zinc in the form of flakes provides large specific surface
PVC = (1) area and better distribution of the galvanic currents establishing good
Binder Volume + Pigment Volume
electrical contacts between them. The sacrificial potentiality of spherical
The barrier property dominates the protection mechanism of ZRECs shaped zinc pigments is very low, due to single point contact between
rather than cathodic protection with PVC lower than the critical pigment them and the secluded effect of the insulated epoxy binder [24]. Thus,

Fig. 2. (a) Components of a conventional three layer coating system to protect the carbon steel substrate against external atmospheric environment (b) Composition
of typical zinc rich epoxy paint.

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A.K. Hussain et al. Progress in Organic Coatings 153 (2021) 106040

the large percentage of zinc particles are not sacrificed during the metal substrate while the oxidation of zinc particles occurs at the
cathodic protection stage which results in pollution causing wastage and zinc-electrolyte junction. Finally after the exhaustion of the cathodic
adversely affect the coating properties [25]. The major advantages of protection period, the substrate is protected for a long period of time by
using ZRE primers include faster curing time, ease of forming thick film barrier action alone [30]. This is achieved by either sealing of the pores
without the risk of cracking and less surface preparation [26]. Albeit within the coating by zinc corrosion compounds or the inhibitive ac­
epoxy based zinc coatings are considerably less toxic than lead or tivity of zinc by-products formed during the electrochemical reactions,
chromate coatings, zinc corrosion compounds formed during cathodic thereby reducing the coating’s electrical conductivity as depicted in the
protection are classified as harmful to aquatic life. International safety Fig. 3.
standards (ISO 4618) with regard to the use of zinc rich paints are As the coating’s conductivity is suppressed, the electrochemical
becoming very strict, aiming to reduce the zinc contents of the paints. mechanism is transformed into the barrier effect which stops air and
One of the major drawbacks of using solvent based ZRE paint is the moisture reaching the substrate below [33]. The following two crite­
generation of toxic volatile organic compounds (VOC), which contrib­ rions must be satisfied by the ZRE coatings in order to provide effective
utes to environmental pollution [27]. The next issue, with zinc rich paint cathodic protection to the substrate. 1) There must be a continuous
is pigment settlement in the vehicle on account of high density of zinc electrical contact between zinc particles themselves and with the metal
dust particles. And since no aqueous system is stable for a long period of substrate. 2) There must be an uninterrupted electrolyte supply between
time with zinc, no water soluble paints with zinc can be formulated. The coating defects all along its film thickness. The extent of cathodic pro­
reasons mentioned above and some others factors too, stimulated in­ tection provided depends upon variables such as the presence of mois­
vestigators to develop highly efficient sacrificial paints with reduced ture, the purity of the zinc dust and the electrical conductivity between
zinc contents [28]. interconnected zinc particles and the substrate [34]. The electrical
contacts between the spherical zinc particles and steel substrate be­
3. Corrosion protections mechanisms in zinc rich epoxy coatings comes weak in a short period of time causing depreciation of sacrificial
property of the coating. Thus, high amount of zinc concentration (nor­
Zinc-rich epoxy coatings are unique in that they provide protection mally higher than 85 wt.%) is required to ensure continuous electrical
to the metal surface even after the appearance of defects such as conductivity by establishing particle-to-particle-to-substrate electrical
scratches, pinholes, voids, and other small defects in the coating system. contact percolation path. Investigation results proves that pore filling
The complex mechanism of corrosion protection in ZRE coating involves action forms a stable inorganic film by the zinc salts such as zinc car­
the formation of physical barrier by epoxy binder on the surface of metal bonates, zinc sulphate and zinc hydroxide with properties dependent on
that isolates it from the corrosive environment [29]. When the coating is particle size and content of zinc [35]. Some reports also suggest that
damaged by an external force, the electrolyte inevitably penetrates high galvanic activity between zinc particles within the coating en­
along the coating thickness and the zinc particles sacrifice themselves to courages the deposition of sturdy protective film of zinc compounds
provide cathodic protection to the underlying substrate, delaying the which results in high local pH (>9) values which protects the steel
onset of corrosion reactions. The reduction reactions take place at the substrate [36]. Generally, cathodic protection property becomes

Fig. 3. Schematic representing (a) electrochemical action of zinc on the artificial defect in the coating (b) electrochemical reactions taking place at the surface of zinc
pigment (c) corrosion protection mechanism in zinc rich epoxy coating (d) SEM image depicting the transformation of zinc to zinc corrosion products in the coating.
Reprinted from publications [22,31,32]with permission from Elsevier.

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A.K. Hussain et al. Progress in Organic Coatings 153 (2021) 106040

minimal after approximately 3 months and the consequent barrier approximately − 860 mV. Now the coating exhibits cathodic protection
protection extends up to 3–10 years with atmospheric exposure. The effect whenever the coating system potential is lower than this voltage
reactions involved in zinc dissolution can be expressed with the help of level and when the voltage level is higher than this point, the cathodic
following equations [37] protection effect depends on the zinc/steel active area ratio. Therefore,
the variation in corrosion potential indicates the size variation between
Anodic Reactions: Zn → Zn2+ +2e− (zinc dissolution) (3)
zinc-steel active areas and large sized zinc particles in the coating gives
−
Cathodic Reactions: O2 + 2H2O + 4e → 4OH- (Oxygen reduction on zinc) lower corrosion potential [39,40]. Hence, it can be noticed from the
(4) Fig. 4(a) that: (1) the corrosion potential primarily exhibits a U-shaped
shift, displaying a process in which the zinc/steel active area ratio in­
Zn + 2OH− → Zn (OH)2 + 2e− (5) creases necessarily due to continuous activation of zinc particles in the
coating, then reduces because of oxidation reaction of zinc (2) the time
Zinc hydroxide gets converted into zinc oxide (ZnO) and
duration of cathodic protection effect is directly proportional to the
Zn5(CO3)2(OH)6 after absorbing carbon dioxide from the atmosphere
percentage of zinc in the coating. Higher the zinc concentration in the
according to the following equation.
coating, lower the corrosion potential (under − 860 mV) in the graph
6Zn (OH)2 + 2CO2 → Zn5(CO3)2(OH)6 + ZnO + 3H2O (6) [41].
1. Activation stage: In this stage, there will be a continuous rapid
drop of corrosion potential to less negative values indicating decrease of
cathodic protection effect. During this stage, zinc-steel active area ratio
4. Stages in cathodic protection of zinc rich epoxy coatings increases constantly leading to continuous activation of zinc particles in
the coating. This shift in corrosion potential may be attributed to
The cathodic protection mechanism offered by ZRE coatings can be decrease in the electrolyte diffusion rate and coating porosity [44].
understood by studying electrochemical measurements recorded using 2. Cathodic protection stage: In this stage, large amounts of zinc
electrochemical noise (EN), open circuit potential (OCP), electro­ particles are activated and the zinc-steel active area ratio reaches a
chemical Impedance spectroscopy (EIS) techniques. These studies sug­ critical point which causes the corrosion potential to drop below
gest that cathodic protection property arises due to uniform activation/ − 860 mV. Depending upon the shifting behaviour of corrosion poten­
oxidation of the zinc anode particles in the coating matrix. Typically, the tial, the cathodic protection stage is further sub-divided into 3 stages. (II-
protection mechanism involves 4 stages namely activation stage, 1)Growth sub-stage: In this sub-stage, the activation rate of zinc parti­
cathodic protection stage, shielding stage and failure stage. The readings cles is much faster than its sacrificial dissolution rate and the corrosion
obtained in OCP measurements are used to plot a graph showing potential continues to drop while zinc/steel active area ratio continues
changes in corrosion current density with respect to immersion time of to increase. (II-2) Stabilization/Transition sub-stage: In this sub-stage,
the metallic substratum [38]. During the electrochemical analysis, the activation rate of zinc particles becomes approximately equal to its
critical potential of zinc for galvanic effect in the coating is sacrificial dissolution rate and the corrosion potential is maintained at

Fig. 4. (a) Open circuit potential curve representing four stages and variation of corrosion potential during cathodic protection of a ZRE coating. Adapted from
publication [42]. (b) Schematic exemplifying the dissolution of zinc particles at different protection stages in the presence of an electrolyte. Adapted from publi­
cation [43].

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A.K. Hussain et al. Progress in Organic Coatings 153 (2021) 106040

constant level. (II-3) Decline sub-stage: In this sub-stage, activation rate pigments and water uptake movement in the coatings. Hence, the
of zinc particles are slower than its corrosive consumption rate and corrosion resistance of CGC increased substantially due to resultant ef­
corrosion potential rises with decrease in zinc/steel active area ratio fect of improved barrier performance and low reactivity of modified zinc
[45]. particles. In a similar investigation Bastos et al. [50] pretreated the zinc
3. Shielding stage: The shielding stage corresponds to a long-term particles with different corrosion inhibitors such as 2- mercaptobenzo­
barrier protection period provided as a result of formation of zinc thiazole, 3-glycidoxypropyltrimethoxysilane and cerium nitrate in an
corrosion products inside the coating system as shown in Fig. 4(b). In effort to amend the corrosion protection efficiency of commercial
this stage, corrosive consumption of zinc particles continues but fails to weldable primers. In this work, the author employed electrochemical
generate sufficient galvanic effect. Zinc/steel active area ratio drops to a impedance spectroscopy (EIS) and scanning vibrating electrode tech­
critical point and the corrosion potential rises to above − 860 mV. Thus, nique (SVET) to assess the corrosion performance of the modified for­
the coating exerts only shielding protection effect, as cathodic protec­ mulations. However, no significant improvements were observed in
tion effect disappears completely [46]. slowing down the corrosion of zinc pigments. Organosilanes are well
4. Failure stage: In this stage, corrosion causing agents like water, known coupling agents that promote adhesion properties via formation
oxygen and chloride ions accumulates significantly at the coating/steel of chemical bonds between the organic coating and inorganic metal
interface leading to blistering or peeling of coating and considerable red substrate [51]. Because of superior pigment dispersion ability and hy­
rust appears on the coating surface. Finally the coating loses shielding drophobic properties of silanes, organosilanes can be used to maximize
protection due to rust formation and the corrosion potential of the the reaction stability of zinc particle to prolong the galvanic protection
coating-steel system fluctuates nearly equals to corrosion potential of period of ZRE coatings. Yun et al. [52] experimented with four different
steel i.e. − 650 mV [31]. organosilanes (OGS) to modify the surface of zinc dust particles chem­
ically in order to increase the anticorrosion capability of thin ZRE
5. Strategies and directions to enhance corrosion performance coatings on cold-rolled steel substrates. The chemical structures and the
of ZRECs weight percentage of four alkoxysilanes introduced in this study are
shown in Table 1 with their chemical formulas. Corrosion test results
High demand of zinc rich primers in various industries to protect from electrochemical polarization testing and accelerated salt spray
equipment from rusting led the academic and industrial laboratories to testing revealed that the coatings with zinc particles modified with
develop long lasting paints by modification of standard commercial ZRE organosilanes exhibited high degree of corrosion protection than coat­
paints. Numerous studies have been reported in the literature to develop ings comprising non-treated zinc particles. EIS spectra analysis showed
ZRE coatings with improved barrier performance and extended cathodic that the enhancement in corrosion resistance was directly correlated to
protection property by partial substitution of zinc particles with elec­ development of an OGS layer on the zinc particles and the subsequent
trically conductive and nonconductive fillers such as polyaniline, carbon reactions between the epoxy functional groups and OGS functional
black, carbon nanotubes, aluminium pigments, micaceous iron oxide, groups. P. Benda et al. [53] formulated a new anticorrosion pigment by
zinc nanoparticles, TiO2 nanoparticles, nano-clay. Some of the latest calcination of lamellar zinc dust along with iron oxide anticorrosion
strategies that are used to enhance the anticorrosion performance of ZRE pigment at a temperature of 400◦ c. During the heating process, zinc
coatings are discussed in the following sections. particles were partially oxidized forming zinc oxide on the surface which
acted as a core for the second layer of ferrite compounds. This developed
5.1. Surface modification of zinc particles pigment with superior corrosion resistance was later introduced in ZRE
coatings with a PVC ratio of 10 %. Corrosion and mechanical tests
In traditional zinc rich primers, the zinc dust may become too active proved that the synthesized coatings with double layer (core-shell)
as soon as it is subjected to an extremely aggressive environment and pigments provided the exceptional anticorrosion efficiency and accept­
can get consumed rather quickly. Additionally, the coatings may able mechanical strength. This enhanced performance was attributed to
develop blistering defects as a result of osmotic gradients associated a combination of barrier and cathodic protection exhibited by core-shell
with corrosion products due to strong galvanic interactions. Sacrificial pigments.
properties of a coating can be extended by surface modification of zinc
particles to slow down its dissolution rate, thus suppressing its electro­ 5.2. Partial substitution of zinc particles with micro pigments
chemical reactivity while maintaining the electrical percolation [47].
Therefore, the ZRE coating filled with surface treated zinc particles gives ZRE coatings loaded heavily with zinc particles provide good
service for a long period of time compared to a coating filled with un­ cathodic protection during the beginning stages of service life. But due
treated zinc particles. Surface modification method involves treating to the rapid consumption rate of zinc particles, the coating loses its
micro zinc particles (lamellar or spherical) with organic or inorganic sacrificial properties quickly. The galvanic contacts between zinc par­
chemicals possessing good corrosion inhibition ability. These chemicals ticles are lost after exposure to electrolyte for a long time as a result of
passivate the surface of zinc particles either partially or completely formation of stable and insoluble corrosion by-products (zinc oxides/
forming thin layers of complex compounds thereby reducing their hydroxides) providing extra barrier protection during the later stages
reactivity. Besides receding the reactivity of zinc particles, these layers [41,54]. Partial replacement of zinc is a productive approach to
of complex compounds also boosts the compatibility between the zinc
particles and coating binder [18]. It may also act as a reservoir of in­
Table 1
hibitors which can be activated whenever the electrolyte diffuses into
Chemical structure and percentage weight of Organosilanes added in ZRE
the coating film towards the metal substrate. It may be worth noting that coatings [52].
for very thin zinc rich coatings (below 10um), the least PVC value of zinc
S. Compound Chemical Structure Weight
pigments needed to activate cathodic protection property is 60 % and
No %
also does not provide any barrier protection [48].
1 Bis-trimethoxysilylpropyl amine (C2H5O)3Si (CH2)3NH 1.70 g
Xu et al. [49] attempted to improve the anticorrosion performance of
(BTSPA) (CH2)3Si(C2H5O)3
cold galvanizing coating (CGC) containing 96 % zinc particles by 2 Bis-1,2-triethoxysilyl ethane (C2H5O)3Si CH2CH2 Si 1.77 g
pre-treatment of zinc powder with phosphoric acid. After modification, (BTSE) (OC2H5)3
a layer of lamellar phosphate and flake phosphate Zn3(PO4)2⋅4H2O were 3 3-Aminopropyltriethoxysilane (C2H5O)3Si (CH2)3NH2 1.107 g
observed around the spherical zinc pigments. The generation of these (APS)
4 n-Propyltriethoxy silane (PES) (C2H5O)3Si (CH2)3H 1.03 g
two by-products causes reduction in electrochemical activity of zinc

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A.K. Hussain et al. Progress in Organic Coatings 153 (2021) 106040

formulate ZRE coatings with low content of zinc particles without by Marchebois et al. [58,59]. SEM, EIS, and micro-Raman spectroscopy
compromising its cathodic protection properties. Research aimed at techniques were used to evaluate the surface morphologies and elec­
substituting zinc with more suitable materials focuses mainly on amal­ trochemical parameters of the coatings. Addition of low content of
gamation of inorganic pigments and conducting polymers and zinc carbon black (≈2 wt%) restricted the modified coating to reach perco­
particles with different shapes. A reduction of 15%–19% of zinc contents lation threshold due to good wetting properties of the epoxy binder and
can be readily achieved by introducing conductive pigments while resulted in non uniform infiltration of electrolyte. Moreover, decrease in
increasing physico-mechanical properties and anticorrosion efficiency the pore resistance (Rp) value over time indicated high porosity with
of the coatings [55]. Micro sized conducting and non conducting pig­ traces of galvanic corrosion between zinc and carbon pigments [60].
ments of carbon black, graphite, zinc oxide, aluminium, micaceous iron Recently an attractive option of utilizing post-treated iron waste
oxide (MIO) can be added successfully to increase electrical percolation powder (IWP) with remarkable property of high electrical conductivity
within the ZRP coatings. Conductive pigments of aluminium and in polymer composites was discussed [62]. Diab et al. [63] attempted to
graphite are thermodynamically active and tend to behave like a bridge investigate the impact of partial replacement of zinc particles with IWP
between zinc particles and metal substrate increasing their electro­ particles on the corrosion protection efficiency of ZRE coatings. Surfaces
chemical reactivity with water and oxygen molecules. On contrary, of IWP particles were modified using a copolymer of poly
pigments of zinc oxide (ZnO) and micaceous iron oxide (MIO) are inert (aniline-co-anisidine) to generate compound action of ferrous oxide
in nature with limited or no electrochemical activity and acts as barrier and passivation film. Potentiodynamic polarization measurements
pigments because of their lamellar shape. According to a study, polari­ revealed that the replacement with 5 wt % IWP particles remarkably
zation test conducted on MIO loaded ZRP coatings showed high polar­ reduced icorr value to 0.69 μA/cm2 imparting 99.94 % protection effi­
ization resistance (Rp) and lower corrosion current density (icorr) during ciency. While replacing 40 % or 50 % of zinc particles resulted in
longer immersion times indicating superior cathodic behaviour reduced adhesion strength of the coating due to reduced binder content
compared to Al loaded coatings because of reduction in oxidation rate. and increased brittleness. However, plausible (underlying) mechanisms
Fig. 5 and 6 shows Tafel plots, salt spray results and noise resistances of of barrier and cathodic protection have not been extensively explored in
coated samples. It can be observed from the Fig. 5 that the addition of this work by the author.
MIO particles causes the polarization curves to shift towards more
positive potential with time whereas addition of Al particles does not
affect potential much [56]. 5.3. Partial substitution of zinc particles with carbon nanotubes
Nonetheless, Al particles provide barrier protection during initial
stages and cathodic protection in the subsequent stages of coating life. Carbon nanotubes (CNTs) are one-dimensional allotropes of carbon
Initial barrier property can also be induced by replacing certain per­ possessing excellent intrinsic electrical conductivity, high aspect ratio
centage (10%–20%) of zinc with zinc oxide particles in pristine ZRE and high stiffness which makes them one of the best reinforcing mate­
coating. Combination of zinc and zinc oxide particles provides dual rials for many metal-polymer anticorrosion coatings [64]. CNTs exhibit
protection (cathodic and barrier) and forms a p–n junction at their lower percolation threshold because of its high specific surface area
interphase causing an electron flow which in turn creates a positive when compared with other conductive fillers such as carbon fibers,
charge in ZnO pigments. This controlled flow of electrons lessens the carbon black or metallic pigments. Strategic combination of CNTs with
zinc electrochemical reactivity and provides better corrosion resistance polymers can give rise to hybrid composites with outstanding perfor­
properties compared to ZRP coatings with zinc pigments only. mances. Only few studies have been reported in the literature that fo­
Furthermore, ZnO acts as a corrosion inhibitor to chloride ions, im­ cuses on examining the interactions between micro-sized zinc particles
proves barrier properties and seal pores in the primer [57]. Carbon black and nano-sized CNTs in ZRE primers. The reason behind the dearth of
is a conductive powder produced by thermal decomposition of hydro­ studies construing the role of CNT application in ZRP is due to its
carbon materials and possesses high thermal stability, high negative results on corrosion resistance of metals [65]. Conventional
surface-area-to-volume ratio and low density. It is primarily used as ZRE coatings generally suffer by the problems of coating flexibility,
reinforcing filler in rubber and plastic products and often in paints as impact resistance and weak adhesion due to high loading of zinc parti­
color pigments. A few detailed studies on corrosion protection of ZRE cles. These demerits can be improved significantly by introducing a
coatings containing 0, 2 and 5 wt.% of carbon black have been published small percentage (0.1 to 0.5 wt%) of CNTs in the coating formulation
which results in strong interfacial interaction between the CNTs and

Fig. 5. Variation of current vs potential for zinc rich epoxy coatings loaded with Aluminium and Micaceous iron oxide particles immersed in 3.5 % NaCl solution at
different times. Adapted from publication [56].

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A.K. Hussain et al. Progress in Organic Coatings 153 (2021) 106040

Fig. 6. (a) Photographic images showing corrosion performances of the ZRE coating containing aluminium and MIO particles exposed to neutral solution in salt
spray chamber (b) Variation of noise resistances of different compositions of ZRE coatings loaded with Al and MIO particles with respect to immersion times.
Reprinted from publication [61] with permission from Elsevier.

epoxy binder [66]. coatings. The CNT network threads also behave like a cluster of
In a typical ZRE-CNTs hybrid coating, CNTs reinforced in the epoxy conductive wires transporting electrons to the metal substrate through
matrix assemble themselves into thread-like structures forming an the zinc particles facilitating formation of more zinc compounds (oxide/
interconnecting circuitous network right through the coating. This CNT hydroxide compounds) [67,68]. Since CNTs are highly conductive in
complex network possessing high strength and stiffness enhances the nature, low percentage of zinc dust loading (approximately 35 wt% less
mechanical integrity and abrasion resistance of the coatings. The CNT compared to average PVC value of traditional zinc-rich primers) is suf­
network also mitigates crack development and propagation extending ficient to generate large electronic conduction by establishing stable
the durability of the coating system as a barrier coating. In case of electrical contacts between isolated zinc particles and metal substrate.
premature coating failure, the zinc particles sacrifice themselves by By decreasing the percentage loading of zinc dust in the primer, the solid
forming a solid layer of corrosion products covering the defects in the levels in the coatings are reformed and a good amount of binder adheres

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A.K. Hussain et al. Progress in Organic Coatings 153 (2021) 106040

to the substrate. Because of the optimized balance between the amount environment, it diminishes binding effect forming porosities between
of resin and the amount of pigment in the coating, the films integrity the epoxy binder and zinc particles for oxygen and moisture to permeate
enhances and aids in optimizing its barrier and physicomechanical along the coating thickness to the surface of the substrate [72]. Multi­
properties (such as coating flexibility and surface adhesion, impact and walled carbon nanotubes (MWCNTs) filled ZRE coatings have also
abrasion resistance, and fatigue and tensile strength) which conse­ proven to be effective in controlling or mitigating microbiologically
quently improves further with the addition of CNTs [69]. induced corrosion in the presence of bacterial consortiums or microor­
CNT based zinc primer exhibits reduced porosity and adequate ganisms. In this case, the ZRE coating forms a uniform biofilm layer on
adhesion strength even when it is applied on a surface without prepa­ the coating surface in addition to epoxy passive layer and solid corrosion
ration. Reduction in the content of zinc dust due to addition of CNTs in compounds. The contribution of this extra layer can be attributed to
the coating decreases the film thickness with fewer pathways for cor­ secretion of extracellular polymeric substances enhancing electro­
rosive ions to reach the coating/interface and reduces the overall weight chemical reactions and strengthening the barrier mechanisms within the
of the coating system [71]. However, when a ZRP coating is heavily coating (Fig. 7(a, b, c, d)). However, increase in CNT concentration
loaded with CNTs (>0.25 wt%) and exposed to the severe corrosive (>2 wt%) enhances the anodic reactions of the zinc particles which

Fig. 7. Nyquist plot and phase angle diagrams for ZRE coatings containing (a,b)1 wt% CNT (c,d) 2 wt% CNT and cross-section SEM images of ZRE coatings immersed
in an electrolyte solution with the SRM consortium with (e) 1 wt.% CNTs and (f) 2 wt.% CNTs. Reprinted from publication [70].

9
A.K. Hussain et al. Progress in Organic Coatings 153 (2021) 106040

severely impairs the growth of homogenous biolayer [70] as shown in mechanisms (i) by forming a passive and insoluble oxide layer through
Fig. 7 (e, f). continuous sacrifice of zinc pigments (ii) by providing extra shielding
protection via layered distribution of graphene sheets forming large
5.4. Graphene based zinc rich epoxy coatings number of barriers in epoxy matrix (iii) by forming a uniform and
smooth protective layer of epoxy phase on the substrate’s surface (iv) by
Graphene is a two-dimensional allotrope of carbon that has remained impeding permeation of corrosive species and redirecting them via
as a subject of focus in research community since its discovery vowing to tortuous routes along the coating thickness (v) by improving adhesion
its peculiar material properties such as high electrical conductivity, and reforming mechanical strength to resist cracks propagation on the
large specific surface area, high mechanical strength, chemical inert­ coating’s surface [81,85,86]. Graphene filled ZRE coating is a relatively
ness, and super hydrophobicity [73]. In addition, the flake-like structure new area of research where only a limited number of papers have been
of graphene nanosheets and its impermeable nature makes it one of the published showing the effectiveness of graphene as a barrier and
most suitable nanofiller to enhance both barrier and percolation prop­ conductor material and needs further improvements. The overall
erties of ZRE coatings [74]. Plentiful investigations have been conducted corrosion resistance of graphene-ZRE composite coatings depend on the
to understand the synergetic effects of graphene and its derivatives on type of graphene nanosheets added to the epoxy matrix. Studies have
the corrosion performance of protective organic coatings. The individual been conducted by employing graphene and its derivatives such as
two-dimensonal layer structure of graphene equips zinc rich coatings graphene oxide and reduced graphene oxide as nanofillers in zinc rich
with excellent impermeability against corrosive species and acts as a link epoxy matrix [43]. The amount of zinc content added to the coating also
between the zinc-zinc particles and zinc-metal substrate thereby decides the role of graphene in enhancing the coating performance. Zinc
increasing the galvanic protection performance [75] as shown in Fig. 8. content of at least 40 wt% is necessary to activate sacrificial protective
With the development of several advanced methods to produce gra­ effect on the steel substrate. Any amount below 40 wt% results in loss of
phene from a variety of economical sources like graphite [76] and bio electrical connection between zinc particles and the metal substrate
precursors [77–79], researchers around the world are exploring the [87].
possibility of using graphene in zinc rich primers [80]. Hayatdavoudi et al. [32] and Song et al. [84] reported a mechanistic
Graphene nanosheets incorporated in zinc rich epoxy matrix gives study on the influence of multilayered graphene on extension of sacri­
additional barrier protection to metals by forming numerous imperme­ ficial protection on ZRE coatings. A series of electrochemical measure­
able isolated layers and obstructs the ingression of water and oxygen ment results revealed that the inclusion of a small percentage (0.4 wt %
molecules through the pores within the coatings [81]. It should also be and 2.5 wt %) of graphene enhanced the percolation pathways of the
noted that the graphene possesses outstanding electrical conductivity, coatings compared to pristine ZRE coatings. This reformed corrosion
which can increase the conductivity of coatings when embedded with protection effect was attributed to excellent infiltration activity of gra­
optimum weight percentage. The electrical connections between zinc phene nanosheets with uniform activation of zinc particles. Moreover, a
pigments and metal substrate can be improved by introduction of gra­ precise equivalent circuit model was built to describe the influence of
phene layers which assists in preserving the galvanic effect with the coating structure and percolating particles. Apart from other electrical
metal surface, consequently extending the galvanic effect of the coating elements, Warburg impedance (W) was also included in the circuit
to some extent [82]. This electrical percolation process due to contin­ (Fig. 9(f)) to characterize the diffusion process and to demonstrate the
uous galvanic couple also reduces the amount of zinc pigments used in shielding effect of graphene nanosheets and zinc corrosion products in
the coating as compared with a traditional zinc rich coating [83]. terms of seepage effects and galvanic reactions. Fig. 9(e) shows Warburg
Graphene based zinc rich epoxy primers provides improved anti­ admittance of different graphene based ZRE coatings indicating the
corrosion performance mainly due to the following protection presence of a large number of active sacrificial particles inside the

Fig. 8. Schematic representation of corrosion protection mechanisms in graphene-based zinc rich epoxy coating. Reprinted from publication [84] with permission
from Wiley.

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A.K. Hussain et al. Progress in Organic Coatings 153 (2021) 106040

Fig. 9. Nyquist and Bode plots of ZRE coated sample (a,b) without graphene (c,d) with 0.6 wt% graphene immersed in 3 wt% NaCl solution [88] (e) Comparison of
Warburg admittance as a function of immersion time for various zinc rich coating systems. (f) Equivalent electrical circuit model with Warburg resistance for sample
coated with graphene based ZRE coating. Reprinted from publication [32] with permission from Elsevier.

coatings.The fitting data indicated that high amount of graphene leads longer immersion times, due to the combined effects of cathodic pro­
to lower coating resistance (Rc) and lower charge transfer resistance tection and barrier protection. Fig. 9a and 9b shows Nyquist and Bode
(Rct) due to better interconnectivity and uniform activation zinc plots for the coated samples in this study at different immersion times in
particles. 3 wt. % NaCl solution. EIS impedance results after fitting into equivalent
A similar investigation was conducted by Liu et al. [88] to analyse circuit indicated that coating resistance (Rc) of sample without graphene
the effects of single layer graphene nanosheets (Gr) on corrosion per­ decreased to a value of 3345 Ω⋅cm2 while sample with graphene almost
formance of ZRE coatings. In this study, in addition to OCP measure­ doubled to a value of 11,200 Ω⋅cm2 after immersion for 25days. This
ments and EIS analysis, the author employed localized electrochemical behaviour of increase in coating resistance might be attributed to the
impedance spectroscopy (LEIS) for the first time to evaluate the barrier formation of ZnO and Zn5(CO3)2(OH)6 and increased galvanic activity
performance and cathodic protection of graphene loaded ZRE coatings. due to graphene nanosheets.
The output results demonstrated that 0.6 wt% of single layer graphene Ding et al. [31,42] prepared graphene low-zinc protective coatings
can considerably enhance cathodic properties of ZRE coatings even after for the first time and applied microstructure impedance analysis

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A.K. Hussain et al. Progress in Organic Coatings 153 (2021) 106040

approach and water permeation dynamics to analyse the performance of the active surface of graphene nanoplatelets. However, this technique
coating system and the role of graphene in the coating. The author yielded negative results. Detailed EIS studies showed that the electrical
explained the detailed mechanism of cathodic protection during conductivity of the coatings drastically reduced as graphene was ori­
long-term testing and how corrosive mediums can penetrate during four ented along the magnetic field (Fig. 10(a) and 10(b)). This reduction in
different stages. In this study, graphene provided longer corrosion pro­ conductivity was due to size increase and flocculation of graphene
tection by forming large impervious dispersed layers in the coating and nanosheets in the coatings which subsequently provided extra active
maintaining the continuous galvanic couple with the substrate sacri­ interfacial zinc and reduced the effective electron transport pathways.
ficing more zinc particles. Moreover, the obtained results were validated However, self alignment of magnetized graphene in the presence of
by micro-Raman spectroscopy and the process of water permeation into magnetic fields significantly enhanced the barrier effect. This enhance­
the coating takes place according to Fick’s diffusion law represented by ment of shielding property was attributed to double potential barriers i.
the equation e., graphene-metal barrier & graphene-graphene barrier (Fig. 10(c) and
/ 10(d)) which must be overcome by an electron lost by zinc towards
∑+∞
φ(z, t) = 1 + 4 π n=1 [( − 1)n /(2n − 1) ]cos[(z/L)(n metal during the mitigation process. The breakdown and tunneling of
electrons (Fig. 10(e)) across the two barriers were described by the
following mathematical equations
− 1/2)π ]e(− (Dt/L )(n− 1/2)2 π2 )
(7)
2

/ →
To further extend the barrier performance of graphene based ZRE η = 3Mzn 2qeNAρznπR3 f − 1 ( E )|E| = Eb (8)
coatings, Ding and his team magnetized graphene by treating it with
and
triton tetroxide. The idea behind this approach is to self align the
magnetized graphene by subjecting it to a magnetic field to maximize

Fig. 10. Schematic diagram representing (a) Nyquist plot (b) bode plot (c) simplified ball-wafer model of metal-graphene potential barrier (d) simplified model of
Graphene-Graphene potential barrier (e) probability equation of electrons tunneling graphene-graphene potential barrier. Reprinted from publication [89] with
permission from Elsevier.

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A.K. Hussain et al. Progress in Organic Coatings 153 (2021) 106040

Fig. 11. (a) Schematic representing in-situ synthesis process of GO-PANI composite (b,c) High resolution FESEM images showing the effect of GO-PANI composite
after 1000 h salt spray test (d) Schematic showing protection mechanism of ZRE coatings containing GO-PANI composite. Reprinted from publication [91] with
permission from Elsevier.

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A.K. Hussain et al. Progress in Organic Coatings 153 (2021) 106040

∫π/2 / Table 2
Dg(ϕ) = cos ϕ 2
{1 Comparison of electrochemical parameters obtained from the Tafel plots [92].
− π /2 Coating Type Ecorr icorr (μA. βa (mV. βc (mV. Rp (kΩ.
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
/ (mV) cm− 2) dec− 1) dec− 1) cm2)
+ sin2 ϕcos2 {a [(E − Ue)/ℏυF]2 − E2 tan2 ϕ υ2 F(1 + tan2 ϕ}}dϕ ZRE − 631 0.246 69 327 119
GO/ZRE − 579 0.102 104 76 31.1
(9) Graphene/ − 560 0.0817 103 61 11.1
ZRE
Graphene sheets tend to agglomerate in epoxy matrix which can
Zn-rGO/ZRE − 540 0.0633 107 229 700
severely undermine the electrical conductivity of zinc particles isolating
them each other. Several pioneering strategies have been proposed in
the literature to avoid re-agglomeration of individual graphene layers. mentioned above showed improvements in both cathodic protection and
One of these strategies is to covalently functionalize the graphene with barrier property but neglected the cathodic delamination strength of the
conductive polymers to enhance the interfacial interactions between the coatings. This adhesion property is one of the main characteristics of
graphene and epoxy. protective coatings and plays a dominant role in determining the effi­
Yanhua Lei et al. [90] reported an effective strategy of passivating cacy of coatings. Mohammadi et al. [93] employed electrically
graphene nanosheets with PANI to synthesize highly crystalline conductive functionalized multilayer graphene (FMLG) nanosheets
conductive G/PANI composite and analysed its synergetic effects on the prepared by rapid thermal expansion of graphite intercalated compound
corrosion performance of ZRPs. LEIS and EIS measurements indicated (GIC). Electrochemical test results revealed that the addition of 0.75 wt
that the presence of 0.6 wt% G/PANI, facilitated electron charge % of FMLG, cathodic protection and long-term barrier performances of
transfer by forming a bridge between zinc particles and the metal sub­ ZRE coating were improved in the presence of FMLG layers due to su­
strate resulting in enhanced sacrificial efficiency. Furthermore, perior percolation effect. Furthermore, there was a significant
SEM-EDS mapping images of coated steel panels also showed spatial improvement in adhesion strength and reduction in cathodic delami­
dispersion of G/PANI composite particles in the epoxy matrix. Thus, nation due to the limitation of OH− ions enhancement at the metal/­
G/PANI composite noticeably enhanced coating resistance and sacrifi­ coating interface. Table 2 shows the electrochemical parameters of ZRE
cial behaviour of zinc by prolonging its active period. The following coatings with and without nano-fillers in the presence of electrolyte.
anodic and cathodic reactions were involved during the interaction of
G/PANI and zinc in the presence of electrolytic molecules.
5.5. Partial substitution of zinc particles with other nanoparticles
Zn ↔ Zn2+ + 2e− (10)

Fe ↔ Fe2+ + 2e− (11) Pigments in the form of nanoparticles are increasingly being intro­
duced in the coating composition in order to improve their anticorrosive
PANI m+(m/ n) n−
A + xe− ↔ PANI(m− x)+{(m − x)/n}
An− + (x / n) An− (12) properties. One of the latest promising techniques to improve the
cathodic performance of ZRE coatings is to replace zinc particles with
O2 + 2H2O + 4e ↔ 4OH − −
(13)
other particles of different shapes and dimensions. A ZRE paint loaded
Ramezanzadeh et al. [91] reported a new strategy of using GO/PANI with 92 wt.% of zinc dust contains only 52 % zinc dust, 28.6 % epoxy
composite in ZRE coatings to connect zinc particles with steel substrate binder and 19.4 % air of paint volume indicating large empty spaces
and compared the performance with coatings containing pristine GO between the zinc particles. These free spaces can be filled with
sheets. The in-situ polymerisation process for grafting PANI nanofibers conductive nanoparticulates such as zinc and aluminium nanoparticles
on GO surface is explained in the Fig. 11(a). After the introduction of to enhance the duration of cathodic protection of the coatings [94].
GO/PANI composite, GO acted a physical barrier and PANI nanofibers Substituting relatively small percentages of micro zinc particles with
acted as bridge between zinc particles resulting in extended cathodic conductive nanoparticles increases the number of contact points be­
protection. Moreover, microscopic images of coatings confirmed the tween zinc particles ensuring good electrical network among zinc par­
reduction in agglomeration of GO nanosheets due to the presence of ticles and the steel substrate. Moreover the tendency of nanoparticles to
nanofibers. Electrochemical tests revealed extended corrosion protec­ agglomerate assists in increasing the conduction paths between zinc
tion performance with the inclusion of 0.1 wt% GO/PANI composite to particles. Addition of zinc and aluminium nano pigments in ZRE paint
ZRE coating. Fig. 11(b,c) and 11(d) shows the high magnification im­ generally does not affect much its formulation as well as its electro­
ages of oxidized zinc particles and protection mechanism in GO/PANI chemical and mechanical properties. However, replacement of zinc
ZRE coatings. Higher coating impedance values even after 50 days of particles with high percentage of nano pigments (more than 10 %) can
immersion indicated the active role of conductive PANI and imperme­ cause total separation of micro particles negatively effecting electrical
able behaviour of GO nanosheets. A new approach of simultaneous contacts between them [95].
reduction of graphene oxide with zinc micro-powder and dispersion of The evolution of self healing anticorrosion coatings designed with
resulting reduced graphene oxide in ZRE coatings was proposed by Teng addition of nano-inhibitor particles began in the early 2000′ s. Layered
et al. [92] to enhance their anticorrosion performance. In this strategy, double hydroxide (LDH) represents another variety of 2D layered
zinc micro powder was reacted with GO nanoparticles and compounded nanoparticles capable of providing the effective barrier against diffusion
together in ZRE coating and reduces GO to rGO with homogenous of corrosive ions and partially blocking the microscale defects in the
dispersion. Coating submicron images, salt spray test and electro­ coatings. LDH anion-exchange nano containers impregnated with 2-
chemical measurements demonstrated that the highly dispersed Zn-rGO mercaptobenzothiazole (MBT) as corrosion inhibitor have shown
nanolayers provided effective protection for zinc particles and decreased encouraging results in controlling corrosion with epoxy primers [96].
the coating porosity compared to ZRE coating loaded with pristine GO Hayatdavoudi et al. [97] evaluated the synergistic effects of LDH nano
and graphene. Table 2 shows the electrochemical parameters obtained containers filled with MBT inhibitors in ZRE primer in 3.5 % NaCl so­
from Tafel extrapolation of polarization curves. It can be clearly seen lution for long term protection of metal substrate via amalgamation of
from the table that corrosion current density (icorr) is minimum while sacrificial cathodic protection, barrier protection and smart inhibition
polarization resistance (Rp) is maximum for ZRE coatings containing action. Intercalated LDH nano containers in the coating not only trap
Zn-rGO when compared to GO and graphene loading. penetrating chloride anions but also provide MBT corrosion inhibitor
All of the aforementioned studies on graphene based ZRE coatings species according to the requirement at defective areas.
This combined action causes uniform consumption of the zinc

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A.K. Hussain et al. Progress in Organic Coatings 153 (2021) 106040

particles and decreases the local corrosion of zinc particles subsequently drawback of low electrical conductivity which can be possibly altered by
enhancing the corrosion resistance of the coating (Table 3). combining with nanoclay or graphite nanoparticles to form nano­
In a similar research finding, Anandhi et al. [98] recently reported a composites. These nanocomposites can act as active corrosion inhibitors
conceptual study on the impact of mesoporous titanium dioxide and barrier pigments, and decreases the ion permeability of the coating
(M-TiO2) nanocontainers filled with propargyl alcohol (PA) on corrosion [107,108]. Akbarinezhad et al. [109] developed and characterized a
resistance and adhesion properties of ZRE primer. Electrochemical and novel method to fabricate exfoliated polyaniline-graphite (PAG) nano­
pull off adhesion testing results revealed that the introduction of 4 wt% composites and exfoliated polyaniline-clay (PAC) nanocomposites [99]
of PA filled M-TiO2 nanoparticles resulted in superior adhesion and via in-situ polymerization in supercritical carbon dioxide (ScCO2) me­
improved anticorrosion performance compared to neat ZRE primer. The dium with high electrical conductivity and high barrier performance. He
enhanced adhesion properties were associated to the establishment of later partially replaced zinc particles with synthesized PAG and PAC
strong metal-inhibitor chemisorptions bonds on the steel surface. conductive pigments in commercial ZRE primer to modify its barrier and
Exceptional corrosion protection efficiency was confirmed by the cathodic protection period by enhancing the electronic conduction
reduced charge transfer resistance (Rct) and lower percolation resistance pathways between zinc particles themselves and the steel substrate. OCP
of the coatings due to formation of zinc corrosion compounds. and EIS analysis of modified primer coated specimen immersed in 3.5 %
Conventional ZRE coatings render long-lasting cathodic protection NaCl solution showed more negative potential Ecorr values (less than
to metal substrates but due to their shorter barrier properties it allows -0.88 V/SCE) and coating resistance of at least one order of magnitude
moderate anticorrosive performance. Incomplete blockage of defects higher than non modified primers at the beginning of immersion indi­
can be improved by using intrinsically conducting polymers (ICPs) such cating extended cathodic protection properties on account of low
as polypyrrole (ppy) which reduces electrolytic conductivity while porosity in modified coatings and delay in inhibition of zinc powder
retaining galvanic function. However, the compatibility and dis­ consumption [110]. Thus, the fully exfoliated PAG and PAC nano­
persibility of ppy particles in epoxy binder remained an issue for many composites acted as initial barriers against water vapors and corrosive
investigators until nano-sized particles came into existence. To achieve ions and delayed formation of zinc corrosion products which was
optimal balance of suppressed galvanic function and inhibition of confirmed by electrochemical noise measurements and salt spray testing
sacrificial action Gergely et al. [102] and his team explored ppy coated [100].
nano-size alumina particles forming a highly dispersible composite with
increased conductivity to amend the corrosion properties of ZRE coat­ 6. Summary and future trends
ings. They found the active zinc content in the coatings can be reduced
from 90 % to 70 % with addition of 3.2 wt.% ppy coated alumina Zinc-rich primers are considered to be the best alternative to haz­
nanoparticles causing slow degradation of epoxy binder, moderate ardous chromate (Cr (VI)) based primers commercially available in the
galvanic reaction with enhanced electrolytic barrier behaviour resulting market to mitigate corrosion on metal surfaces. During the past decade,
in durable protection performance. The hybrid coating also exhibited a lot of research progress has been achieved with regard to performance
strong adhesion strength by preventing self-corrosion of zinc pigments in zinc-rich primer technology mainly due to development of new types
and scavenging incoming oxidative radicals [103].Recent studies prove of materials and characterization techniques. Novel ideas and concep­
that addition of montmorillonite clay nano-layers as barrier pigments tions have been designed to attain better anticorrosion properties by
improves the long term protective performance of zinc rich organic tailoring the composition and controlling the electron flow processes. In
coatings by resisting ingress of H2O molecules through the defects this comprehensive review, the fundamentals concepts related to
[104]. Presence of clay reduces the electronic conduction between the corrosion protection mechanisms and the expedient strategies used to
zinc particles without deteriorating its sacrificing properties [105]. simultaneously improve the sacrificial and barrier properties of ZRE
However, high concentration of clay nanoparticles causes detrimental coatings are discussed. Review of literature shows that ZRE composite
effects on intercalation of clay and severe stacking of nano-layers lead­ paints provide higher corrosion protection with extended durability
ing to high porosity in coatings [101]. Fig. 12(a,b,c,d) and 12(e,f,g,h) compared to standard commercial ZRE paints. However, in most of these
shows EDX and salt spray results of coated panels containing clay studies only few authors have worked on improvement of coating’s
nanoparticles suggesting oxidation of zinc particles and degeneration of adhesion strength and extension of cathodic protection period. Since the
coatings. coating’s service life also depends on how quickly the coating layer
Application of polyaniline (PANI) as a corrosion inhibitor in delaminates, it is extremely important to develop new methods to
conjunction with zinc rich primers is of great interest to investigators enhance adhesion strength between the coating and the metal surface.
during the last decade [106]. Addition of PANI in zinc rich primer helps Corrosion behaviour of ZRE composite coatings were evaluated under
to reduce zinc dust content by increasing the electronic conduction laboratory conditions using artificial electrolyte and for a shorter im­
paths between zinc particles [15]. Unfortunately, PANI suffers from the mersion time. But in a real-time environment, the failure mechanisms of

Table 3
Optimal electrochemical impedance parameters of ZRE coatings tested with and without nanofillers immersed in 3.5 wt% sodium chloride solution.
Without nano-filler With nano-filler Ref
Nano-filler Zinc wt% Filler wt% Immersion time in days
Rc (Ω. cm2) Rct (Ω. cm2) Rc (Ω. cm2) Rct (Ω. cm2)

Mesoporous TiO2 80 % 4% 30 – 4.403 × 103 – 2.79 × 105 [98]

Layered double hydroxide 80 % 1% 25 6.24 915 789 3528 [97]
Carbon nanotubes 70 % 1% 29 – 2.7 × 103 – 3.9 × 103 [70]
PANI-clay 80 % 1% 365 8.77 × 104 2.11 × 104 4.09 × 103 5.29 × 104 [99]
Pani-graphite 80 % 1% 120 1.28 × 104 3.24 × 105 1.29 × 103 4.08 × 103 [100]
Single layer graphene 80 % 0.6 % 25 3030 220 11,200 983 [88]
Graphene-tripolyphosphate 75 % 1% 30 1.72 × 105 4.85 × 105 3.45 × 105 1.75 × 105 [43]
Graphene 70 % 0.5 % 60 4.57 × 105 1.59 × 105 9.03 × 104 9.11 × 103 [31]
Graphene-PANI 40 % 0.3 % 100 9.36 × 109 2.41 × 1010 2.49 × 106 8.44 × 105 [82]
Graphene-PANI 80 % 0.6 % 30 653 7790 79,200 2280 [83]
Reduced graphene oxide 60 % 0.5 % 57 1.50 × 105 2.79 × 105 2.85 × 108 3.01 × 107 [85]
Reduced graphene oxide 40 % 1% 30 – 52.5 × 103 10.5 × 103 424 × 103 [92]

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A.K. Hussain et al. Progress in Organic Coatings 153 (2021) 106040

Fig. 12. Energy dispersive X-ray analysis and surface images of scribed area of ZRE coated samples containing (a,e) 0 wt% (b,f) 1 wt% (c,g) 2 wt% (d,h) 3 wt%
montmorillonite clay nanoparticles after immersion test for 1400 h in 5 wt% NaCl solution. Reprinted from publication [101] with permission from Elsevier.

these coatings in the long run are still unclear. Researchers are putting forming a composite with other materials. More research is needed for
their strenuous efforts to explore different varieties of micro and nano better understanding of interactions between the epoxy binder and the
materials to partially replace zinc in order to improve overall perfor­ filler nanoparticles to obtain advanced nanostructured coatings with
mance of ZRE coatings. The interest in employing graphene as partial exceptional corrosion inhibition capabilities. Additionally, by selecting
nanofiller in ZRE coatings has been increased drastically in the last 5 the appropriate filler materials, optimizing their content and improving
years. This could be partially attributed to availability of high quality of their dispersion in epoxy matrix, may conceivably lead to evolution of
graphene at reduced prices. In many studies addition CNTs in ZRE high performing new generation ZRE coatings. Future research in ZRE
coatings failed to provide adequate protection to coated surfaces when coatings should be directed towards reducing the final cost of coatings
exposed to erosion and corrosion phenomenon. The biggest challenge in using low cost nanofillers, loading with eco- friendly corrosion in­
embedding nano materials as fillers in ZRE coatings is their severe hibitors, employing surface pretreatment methods and developing novel
agglomeration in epoxy matrix. Several investigators have phased out strategies to enhance the cathodic performance period.
this limitation by modifying nanofillers either by chemical method or by

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A.K. Hussain et al. Progress in Organic Coatings 153 (2021) 106040

Acknowledgements [31] R. Ding, Y. Zheng, H. Yu, W. Li, X. Wang, T. Gui, Study of water permeation
dynamics and anti-corrosion mechanism of graphene/zinc coatings, J. Alloys.
Compd. 748 (2018) 481–495.
Moorthi Pichumani would like to thank The Management, Sri Ram­ [32] H. Hayatdavoudi, M. Rahsepar, A mechanistic study of the enhanced cathodic
akrishna Engineering College, Coimbatore, Tamil Nadu, India. protection performance of graphene-reinforced zinc rich nanocomposite coating
for corrosion protection of carbon steel substrate, J. Alloys. Compd. 727 (2017)
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