Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435

Contents lists available at ScienceDirect

Advanced Industrial and Engineering Polymer Research

journal homepage: http://www.keaipublishing.com/aiepr

Biodegradable synthetic polymers in sustainable corrosion protection:

Present and future scenarios
Chandrabhan Verma a, *, M.A. Quraishi b, Akram Alfantazi a, Kyong Yop Rhee c, **
a
Department of Chemical Engineering, Khalifa University of Science and Technology, P.O. Box 127788, Abu Dhabi, United Arab Emirates
b
Interdisciplinary Research Center for Advanced Materials, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia
c
Department of Mechanical Engineering, College of Engineering, Kyung Hee University, Yongin, 445-701, South Korea

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

Article history: Polymers have proven to be a successful alternative to conventional toxic corrosion inhibitors. Because
Received 9 February 2023 they have a lot of electron-rich donor sites, they can effectively adsorb on metallic surfaces, offering
Received in revised form excellent surface coverage and protection. They have a large number of applications in coating and anti-
26 April 2023
corrosion solution phases. Currently, corrosion science and engineering strongly encourage the invention
Accepted 27 April 2023
and utilization of biodegradable, nonbioaccumulative, and eco-friendly materials because of the
increasing demand for green chemistry and sustainable developments. This prompts the widespread use
Keywords:
of natural polymers. Unfortunately, they frequently experience physiochemical changes that negatively
Biodegradable polymers
Biodegradability
impact their performance, especially at high temperatures and electrolyte concentrations. The extraction,
Sustainable corrosion protection purification, characterization, and application of natural polymers are typically laborious, drawn-out and
Green synesthetic polymers not cost-effective approaches. Therefore, biodegradable synthetic polymers (BDSPs) have emerged as
Green corrosion inhibitors and corrosion ideal substitutes for sustainable corrosion protection. There are numerous studies that cover the various
prevention facets of corrosion inhibition, but they rarely discuss BDSPs' overall corrosion inhibition potential. The
current report discusses the potential of common BDSPs to inhibit corrosion. The obstacles and potential
of using biodegradable synthetic polymers in sustainable corrosion mitigation have also been discussed.
© 2023 Kingfa Scientific and Technological Co. Ltd. Publishing services by Elsevier B.V. on behalf of KeAi
Communications Co. Ltd. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction
1.1. Corrosion and corrosion protection: a journey from inorganic to
polymeric sustainable corrosion inhibitors
There are numerous manmade and natural chemicals present in
the environment that can interact with materials including wood,
paper, plastic, concrete, leather, glass, and metal and negatively
impact their properties and existence [1,2]. Corrosion is one of the
most common examples of metallic materials undergoing chemical
and/or electrochemical degradation by their reaction with chemical
species in the environment [3]. Except for a few noble metals and
alloys, most of the metallic structures are highly reactive and prone
to corrosive damage. Nowadays, corrosion is one of the biggest
* Corresponding author.
** Corresponding author.
E-mail addresses: chandraverma.rs.apc@itbhu.ac.in (C. Verma), rheeky@khu.ac.
kr (K.Y. Rhee).
challenges of the 21st century because of its association with huge
safety and socioeconomic influences [4]. As per the most updated
estimation of NACE, National Association of Corrosion Engineers,
the recent annual cost of corrosion is nearly US $2.5 trillion, which
is equivalent to about 3.4% of the world's GDP [5]. Corrosion is one
of the major concerns of the petrochemical industries where
metallic materials are employed in large quantities in the form of
storage tanks, distillation towers/units and transport pipelines [6].
Petrochemical fluids contain many dissolved gases including SO2,
H2S and CO2, organic acids and dissolved salts that initiate and
promote corrosion [7,8]. The rate of corrosion under these cir-
cumstances is significantly influenced by pH [9]. Numerous studies
have discovered that a drop in pH leads to a rise in corrosion rate
[10]. This rise is brought about by altering the electrochemical re-
action's mechanism and reducing the solubility of iron carbonate
protective layers (sweet corrosion) [10]. Notably, the pH rises cause
a decline in the cathodic reduction of Hþ (proton), which in turn
reduces the anodic dissolution of iron [10]. Corrosion is also a
promising challenge for many cleaning industries that utilize
extremely aggressive solutions for cleaning metallic surfaces that

https://doi.org/10.1016/j.aiepr.2023.04.005
2542-5048/© 2023 Kingfa Scientific and Technological Co. Ltd. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an open access article
under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
C. Verma, M.A. Quraishi, A. Alfantazi et al.
include oil-well acidification, acid pickling, scale removal (des-
caling) and acidization processes [11,12].
The metallic ores require special cleaning treatments to remove
the surface impurities of oxides, hydroxides, sulfides etc. The
cleaning treatments are not very selective and remove metallic
components, surface impurities, and solid contaminants. To avoid
the deterioration of metal components, some additives, called
corrosion inhibitors, are added to the aggressive electrolyte [6].
These additives build a protective film at the interface of metallic
structures and the atmosphere and their effectiveness depend
upon various internal and external parameters. The corrosion in-
hibition potential of these additives depends upon the electronic as
well as structural properties [13]. The use of additives along with
other controlling tactics helps in minimizing corrosion costs from
US $375 billion (15%) to US $875 billion (35%) annually [14,15]. Till
now many additives of organic or inorganic nature have been
developed and implemented [16].
Numerous series of organic compounds, primarily heterocyclic
ones, are used in corrosion control. These include imidazole, imida-
zoline, pyridine, quinoline and isoquinoline, pyrrole, azole, pyrazine,
morpholine, indole, thiophene, furan, naphthyridine, etc. [17]. Their
adsorption, which came after either physisorption, chemisorption, or
primarily physiochemisorption, enabled them to create the corrosion
protective film, which is how they became effective. The Gibb's free
energy of adsorption (DGads) value can be used to determine the type
and efficacy of adsorption. Physisorption is associated with a DGads
value of 20 kJmol‒1 or less negative, and chemisorption is associ-
ated with a DGads value of 40 kJmol‒1 or more negative. Physi-
ochemisorption is associated with a DGads value between 20
and 40 kJmol‒1. The majority of corrosion inhibitors, including
biodegradable polymers, are adsorbed primarily using a physi-
ochemisorption mechanism. Evidently, physisorption takes place via
the electrostatic force of attraction between a charged metal surface
and a charged inhibitor molecule, whereas chemisorption primarily
takes place through heteroatom charge sharing. The organic sub-
stitutes interact with the metallic surface and create shielding films
using the non-bonding electrons of the cyclic heteroatom(s) and
heteroatoms in the sidechain. Conjugation in the form of multiple
bonds (>C]C< and‒C^C‒) of aliphatic and aromatic moieties and
polar functional groups eOH, eCHO, eNH2, eOR, eNR2, ‒O‒, >C]O,
>C ¼ X (X ¼ O, N, S), eC^N, ‒COY (Y ¼ ‒X: ‒Cl, ‒Br, eI, eOC2H5 and
eNH2), eCOOH, eSO3H, etc. also facilitate their bonding capability
[13,18]. Organic inhibitors are widely used in solution phase and
anticorrosive coating formulations. The solution phase inhibitors
themselves can be divided into three classes varying on the nature of
the electrolyte i.e. aqueous/water-, oil- and solvent-based corrosion
inhibitors designated as WBCIs, OBCIs and SBCIs, respectively [19].
The WBCIs shared the largest revenues in the corrosion inhibitor
markets. The global market revenues of WBCIs, OBCIs and SBCIs were
US $4.61, $0.987 and $0.980 billion, respectively in 2015 and which
raised to $5.982, $1.379 and $1.309 billion in 2021. Due to industri-
alization and urbanization, the cost of corrosion as well as the rev-
enues of corrosion inhibitors are expected to rise.
1.2. Biodegradable polymers: sustainable replacement for
traditional polymers
Biodegradable polymers (BDPs) are those that are decomposed by
microorganisms [20]. BDPs can be classified as natural or synthetic
polymers based on their origin (Fig.1) [20]. Most natural polymers are
biodegradable however biodegradability of synthetic polymers is
restricted [21]. Natural polymers may be of plant, animal or micro-
organism origin. Natural biodegradable polymers are extensively
utilized for different industrial, biological and environmental uses
[22,23]. Nevertheless, synthetic polymers are more accessible for
408
Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435
tailoring, designing and chemical modification. In view of this,
extensive attention has been paid towards the synthesis, character-
ization, commercialization and use of biodegradable synthetic poly-
mers (BDSPs) [24,25]. Some of the common BDSPs include poly(lactic
acid) (PLA), poly (malic acid) (PMA), poly(caprolactone) (PCL), pol-
y(amino acids, polyphosphoesters, polyanhydrides, poly-
phosphazenes, Poly(ester urethane), poly(vinyl alcohol) (PVA) etc.
[24,26]. The BDSPs possess superior properties and are used as sus-
tainable replacements for natural and synthetic nonbiodegradable
polymers.
As one of the oldest and most reliable alternatives, inorganic in-
hibitors, in particular chromates, molybdates, nitrates, nitrites,
phosphates, and tungstates, were developed and put into use [27].
Typically, they form oxide layers on the metallic surface to passivate
it and prevent corrosion. Some of these inorganic species, which are
referred to as nonoxidizing anions, actually need oxygen present for
passivation. On the other hand, oxidizing anions refer to inorganic
species that do not require the presence of oxygen for the passiv-
ation. The inorganic species are currently not used at all because of
their significant toxicity and biomagnification potential, despite their
high protection effectiveness. By using organic corrosion inhibitors,
particularly heterocyclic compounds, they were completely replaced
[28,29]. However, the toxicity issues associated with the develop-
ment and use of organic corrosion inhibitors have not yet been fully
resolved as many of them, particularly heterocyclic compounds that
are highly toxic (such as pyridine and its derivative) and bio-
magnificent (e.g. benzotriazole).
Because of the rising popularity in green chemistry and sustain-
able developments, the use of biodegradable materials, particularly
natural polymers, in sustainable corrosion prevention has recently
received considerable attention. It is important to note that biode-
gradable polymers can be used to address a number of traditional
heterocyclic corrosion inhibitors' drawbacks [30,31]. Natural poly-
mers can be used to reduce the toxicity and non-environmental
problems associated with traditional corrosion inhibitors. These
species can be described as bio-tolerable, environmentally friendly
substitutes, non-bioaccumulative and bio-degradable [30,31]. Non-
biodegradable polymers (e.g. poly(ethene) and poly(propene), on
the other hand, do not disintegrate. They build up in the environment
and lead to biomagnification; as a result of this accumulation, they
contaminate soil and water and harm the environment. Such
polymer-based wastes pollute the air when they are burned. The
majority of chemicals, including polymers, are naturally broken down
by decomposers or microorganisms, though the process is very slow
and can take days, months, or even years [32,33]. A substance can be
deemed environment acceptable if it decays by 60% or more in just 28
days [33].
In contrast to organic compounds, they offer excellent surface
coverage and protection due to their large size. Polymers are
employed as corrosion inhibitors since they can form metal com-
plexes through their functional groups, and as these complexes
cover a large area on the surface of the metal, they shield the metal
from corrosive environment in the solution [34]. Polymeric corro-
sion inhibitors have a number of adsorption centers (such as eOH,
eCH2OH, ‒OMe, eNHCOCH3, ‒O‒, eNH2, eCOOH that can work
together and bind to the metallic surface successfully. These polar
functional groups also serve as sites for chemical modification for
enhanced solubility and better anticorrosive activities. The func-
tional groups typically serve three purposes in polymers that have
undergone chemical modification: (i) they can directly participate
in bonding with the metallic surface using non-bonding and p-
electrons, (ii) increases the hydrophilicity and solubility of poly-
mers by adding polar functional groups and, (ii) increases the
molecular size and thereby surface coverage. Many reviews
described the anticorrosive effect of natural pure and modified
C. Verma, M.A. Quraishi, A. Alfantazi et al.
Fig. 1. Classification of biodegradable (BDPs) and nonbiodegradable (NBDPs) polymers [20].
biodegradable polymers [35,36]. Despite the fact that there are
numerous and rapidly expanding reports on it, none of them
collectively describe the corrosion inhibition potential of biode-
gradable synthetic polymers (BDSPs), which is what inspired the
choice of the current topic. The present report describes the
corrosion inhibition potential of common BDSPs including poly(-
lactic acid) (PLA), poly (malic acid) (PMA), poly(caprolactone) (PCL),
poly(amino acids), polyphosphoesters, polyanhydrides, poly-
phosphazenes, poly(ester urethane) and poly(vinyl alcohol) (PVA).
2. Synthetic biodegradable polymers in sustainable corrosion
protection: literature survey
2.1. Poly(lactic acid) (PLA) in sustainable corrosion protection
Polylactide or poly(lactic acid) (PLA) is a thermoplastic polyester
(TPPE) having a backbone formula of [eC(CH3)HC(¼O)Oe]n or
409
Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435
(C3H4O2)n. PLA is synthesized by lactic acid (C(CH3)(OH)HCOOH;
PLA) condensation that proceeds by the loss of water. PLA can also
be synthesized by ring-opening polymerization of lactide
([eC(CH3)HC(¼O)Oe]2). The chemical structure of PLA and LA
polymerization are given in Fig. 2 [37]. The molecular weight of
polymerized PLA greatly depends upon the mode of polymeriza-
tion. Though the use of PLA is associated with many drawbacks
because of its numerous challenging physical and chemical prop-
erties, it is any applications [38]. The monomer, lactic acid is many
derived from fermented starch including from the pulp of sugar
beet or sugarcane, cassava and corn. As lactic acid is a chiral com-
pound, its polymerization deals with the formation of different
types of polymers e.g. polymerization of L-lactic acid, D-lactic acid
and D, L-lactic acid gives poly-L-lactic acid (PLLA), poly-D-lactic acid
(PDLA) and poly-D, L-lactic acid (PDLLA), respectively. The crystal-
linity, properties and applications of PLA greatly depend upon the
D- and L-enantiomers [39]. PLA polymers exist as semicrystalline
C. Verma, M.A. Quraishi, A. Alfantazi et al.
Fig. 2. Synthesis of poly(lactic acid) (PLA) from l- and d-lactic acids [37].
polymers having a melting point of 130e180  C and glass transition
temperature of 60e65  C [40]. PLA polymers have Young's modulus
of 2.7e16 GPa and they acquire the intermediate mechanical
strength of PET and polystyrene [40]. Both the melting point and
heat reflection capabilities of PLLA can be suitably enhanced by
40e50  C and 60e190  C y physically blending the polymer with
PDLA (poly-D-lactide). PLA manifests remarkable solubility in a
wide range of organic solvents including ethyl acetate.
The literature study suggests that the lactic acid (LA) solution
itself is highly corrosive due to the higher activity of hydrogen ions
[41]. LA-based formulations are employed for corrosion mitigation,
especially in aqueous electrolytes. PLA is neither soluble in water
nor in water-based electrolytes which limits its aqueous phase
anticorrosive application. However, PLA-based formulations are
widely used in anti-corrosive coatings, particularly for magnesium-
based alloys [42,43]. Abdal-hay et al. [40] developed a
hydroxyapatite-doped PLA (HAp) porous coating on an AZ31 Mg
alloy for improved anticorrosive and bioactivity. The coating was
employed using the spray method and the study was conducted by
soaking the coated samples in an SBF (simulated body fluid). The
outcomes of the study suggest that coated Mg samples showed
remarkable anti-corrosivity as well as improved bending strength
and cytocompatibility and reduced cytotoxicity. Zeng and co-
workers [44] reported the coating of AZ31 alloy by ZneAl layered
double hydroxide (ZnAl-LDH) followed by dealing with PLA for
improved corrosion resistance. The composite coating ZnAL-LDH
was characterized using EDX, XRD, SEM and FTIR techniques and
the anticorrosive property was assessed by EIS and SEM methods.
The authors reported that the inner compact layer of ZnAL-LDH
adheres strongly with the alloy surface and its outer porous sur-
face binds with the PLA and provides prolonged and efficient pro-
tection. The improved anticorrosive effect of the ZnAL-LDH/PLA is
410
Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435
attributed due to the combined effect of self-healing, ion-exchange
retardation and barrier protection. Coatings that have the internal
capacity to repair significant damage on their own or with external
stimulation are known as self-healing coatings. Automotive refinish
coatings, OEM clear-coat, and plastic clear-coat formulations all use
self-healing coatings. Polymers, metals, ceramics, and their com-
posites are examples of self-healing materials because they can
partially or completely restore their original set of properties after
being damaged during use.
Zhang et al. [45] reported the effect of a hydrophobic thin film of
stearic acid (SA) on PLA- and PCL (poly(ε-caprolactone))-coated Mg.
The coatings were characterized using FESEM, FTIR, XPS and con-
tact angle studies. The electrochemical (OCP, PDP and EIS) studies
were carried out in a phosphate buffer solution (PBS) having the
composition: KH2PO4 (0.48 g/L), KCl (0.24 g/L), NaCl (8.0 g/L) and
Na2HPO4$2H2O (3.81 g/L). OCP analysis shows that the Mg surface
manifests remarkable anodic dissolution in PBS. Whereas, the OCP
of SA coated sample i.e. Mg@SA was quickly settled and was stable
during the course of measurement (8 h). The SA coating not only
provided anticorrosive protection but also shifted the corrosion
potential in a more negative direction. The shifting of corrosion
potential in the negative direction is directly related to the pro-
tection performance of the coating. The potentiodynamic polari-
zation curves for Mg and coated-Mg surfaces in PBS at (37 ± 0.5  C)
are shown in Fig. 3. The authors observed that coated-Mg surfaces
manifest remarkable changes in the shape of anodic and cathodic
Tafel curves with remarkable shifts in the Ecorr values. They
observed the maximum current density for the corrosion of un-
treated Mg surface.
The SA-coated sample exhibit lower current density showing
an increase in corrosion protection. The PLA and PCL-coated
samples with and without SA exhibit the highest reduction in
C. Verma, M.A. Quraishi, A. Alfantazi et al. Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435

Fig. 3. Potentiodynamic polarization curves (PDP) of (a) Mg@PLA, Mg@SA@PLA, (b) Mg@PCL, Mg@SA@PCL in PBS solution at 37 ± 0.5  C as compared with Mg and Mg@SA (Upper)
and Electrochemical impedance spectroscopy (EIS) in PBS solution at 37 ± 0.5  C: Nyquist plots and the equivalent electrical circuit (EEC) of (a) Mg and Mg@SA, (b) Mg@PLA and
Mg@SA@PLA, (c) Mg@PCL and Mg@SA@PCL (with embedded equivalent electrical circuits), bode plots of |Z| vs. frequency and bode plots of phase angle vs. frequency of(e, f)
Mg@PLA, Mg@SA@PLA, (g, h) Mg@PCL, Mg@SA@PCL as compared with Mg and Mg@SA [45].

the corrosion current density. The current densities values
(snU1cm2) for Mg@SA@PLA and Mg@SA@PCL were 0.01 and
0.78, respectively. This observation also revealed that Mg@SA@-
PLA manifest better performance than Mg@SA@PCL. Even,
Mg@PLA demonstrates superior protection and lesser current
density (icorr: 0.08 snU1cm2) than Mg@PCL (icorr: 13.44
snU1cm2) and Mg@SA@PCL (icorr: 0.78 snU1cm2). The PDP
outcomes were supported by EIS studies. The Nyquist and Bode
curves for untreated and treated Mg surfaces are shown in Fig. 3. It
can be seen clearly that the Nyquist curve's diameters increased
for the coated sample and the Mg@SA@PLA and Mg@SA@PCL
manifest two times constant in the Bode curves. The increased
diameter of Nyquist curves suggests the higher corrosion resis-
tance for coated samples. The increase in the diameter of Nyquist
curves is consistent with the decrease in icorr values. The
maximum increase in the charge transfer resistance was derived
for the Mg@SA@PLA sample. The authors also performed the
immersion experiment and they observed that Mg@SA@PLA was
the most effective formulation for a long time immersion (up to 21
days). In another study, the anticorrosion potential of PLA/sodium
monofluorophosphate (MFP) microcapsules was prepared by
spray method [46]. The microcapsules manifested an excellent
release performance in an artificial concrete pore solution (CPS).
The anticorrosion potential of PLA-based coating for Mg alloys
has also been investigated elsewhere [47,48]. Li et al. [48] hypoth-
esized that 3-aminopropyltriethoxy (APTES) improves the CaP/PLA
composite coating's interfacial strength between the two materials.
In order to create an APTES-CaP/PLA composite coating, the CaP
coating was first chemically converted before having its surface
silanized with APTES. In comparison to the unaltered CaP/PLA
coating, the as-prepared APTES-CaP/PLA coating displayed a more
uniform and defect-free surface. The coupling of APTES with CaP
and PLA was successfully verified by the FTIR spectra. The corrosion
resistance of the composite coating was improved tremendously
after the addition of silane coupling agent, according to the results
of electrochemical tests and a 7-day immersion test in a simulated
body fluid (SBF) at 37  C. According to ASTM D3359-93, the inter-
facial adhesion was assessed using the Tape Test method, which
revealed that the composite coating's interfacial strength had been
significantly improved. Based on the findings, authors hypothe-
sized that the APTES-CaP/PLA coating, because of its outstanding
decomposition rigidity in body fluid environments, had a huge

411
C. Verma, M.A. Quraishi, A. Alfantazi et al.
potential to simplify the clinical application of Mg-based implant-
able devices.
Ren and coworkers [49] developed a nanostructured amorphous
magnesium phosphate (nAMP)/PLA composite coating AZ31 Mg
alloy for improved anticorrosive and bioactivity. SEM examination
shows that nAMP/PLA forms a highly smooth, and crack-free film in
which nAMP particles were uniformly and well-distributed. The EIS
and PDP studies were conducted to study the corrosion resistance
property of nAMP/PLA film in SBF. The electrochemical experi-
ments were carried out for AZ31 Mg, AZ31-PLA and AZ31 Mg-Mg-
PLA coated samples. The AZ31-PLA and AZ31 Mg-Mg-PLA coated
samples show a remarkable decrease in corrosion current density
and the corresponding increase in the charge transfer resistance.
Mousa et al. showed that the presence of 5 (PLAZ-1) and 10% (PLAZ-
h) of ZnO in PLA coating on the Mg surface provide excellent
resistance from degradation in the simulated body fluid [50].
Electrochemical EIS and PDP analysis showed that both PLAZ-1 and
PLAZ-h coated samples showed reasonably similar anticorrosive
protection. The effect of immersion time on the surface
morphology of coated and noncoated Mg specimens was assessed
by FESEM methods. The FESEM images for bare Mg, PLA, PLAZ-l and
PLAZ-h coated samples are shown in Fig. 4. It can be seen that the
noncoated Mg surface was highly damaged with huge surface im-
perfections and a mountain-like appearance and the imperfection
increases with increasing the immersion duration from 3 to 21
days. However, the surface morphologies of coated Mg samples
remain almost unchanged indicating the protectiveness of the
different coatings, especially PLAZ-l and PLAZ-h.
Fig. 4. FE-SEM images show the surface appearance of the samples after immersion in SBF solution for 3, 15, and 21 days [50].
412
Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435
The improvement in degradation resistance of Mg alloy by PLA
coating is also reported in another report [51,52]. Alrashed et al.
reported the encapsulation of 2-mercaptobenzothiazole (MBT) in
the PLA matrix followed by the use of encapsulated MBT in poly-
urethane coating [53]. Zhu et al. [54] developed PLLA coating
having a controlled hierarchical porous framework through the dip
coating method on the Mg surface for improved biocompatibility
and anticorrosion potential. The PLLA coating of different
morphology and pore size was constructed by adding a mixture of
hexane and ethanol. The corrosion resistance property of the PLLA
coatings was evaluated from electrochemical methods. The
outcome of the study suggests that PLLA coating shows remarkable
biocompatibility as compared to the untreated Mg surface. The
potentiodynamic study suggests that PLLA coatings demonstrate a
noteworthy decrease in the icorr.
Ji et al. [55] developed a composite formulation based on OL
(oleic acid)/MBT (2-mercaptobenzimidazole) corrosion inhibitors
in CS (chitosan)/PLA core-shell nanofillers in epoxy coatings. The
anti-corrosive effect of the coating formulations was tested by
electrochemical methods. The Nyquist and Bode curves for blank
and CS/PVA)@(OA þ MBI-based epoxy coatings demonstrate two or
more than two times constants indicating that corrosion in these
circumstances involve two or more charge transfer reactions.
Through EIS methods, the authors showed that after soaking the
coating in 3.5% NaCl for 35 days, the self-healing property of the
coating was lost. The OA and MBI showed 96.66% and 99.36% effi-
ciencies in alkaline and acidic electrolytes after 10 and 20 days of
immersion, respectively. The authors proposed that CS/PVA)
C. Verma, M.A. Quraishi, A. Alfantazi et al.
@(OA þ MBI provide self-healing protection in both acidic and basic
electrolytes as in Fig. 5.
2.2. Poly (malic acid) (PMA) in sustainable corrosion protection
A linear anionic homopolymer made of L-malic acid monomers
joined by ester bonds between their hydroxyl and carboxyl groups
is known as poly(-L-malate) (PMA) [56]. PMA and its derivatives
have potential uses in the food industry, in medicine, and in other
industrial fields due to their excellent water solubility, biocom-
patibility, and biodegradability [57]. High-molecular-mass PMA is
less water soluble, biocompatible, and biodegradable than low-
molecular-mass PMA [58,59]. The production of PMA has report-
edly used a variety of lignocellulosic feedstocks, including bagasse,
barley straw, soybean hull, corncob, corn fiber, and wheat straw
[60,61]. To release fermentable carbohydrates, these feedstocks
must first be hydrolyzed using acid treatment and heat. Addition-
ally, during the hydrolysis process, a number of toxic substances are
produced, including furfural and 5-hydroxymethyl furfural, etc.,
which could negatively impact cell growth and PMA synthesis. In
order to produce PMA, lignocellulose was thus replaced by starchy
feedstocks and molasses like Jerusalem artichoke tuber, soy
molasses, cane molasses, and sweet potato [62,63]. These feed-
stocks still need to be pretreated, though. The anticorrosion po-
tential of PMA is very scarily reported.
Recently, Chen et al. [64] synthesized poly(maleic acid-co-N-[3-
(dimethylamino)propyl]-methacrylamide) (PMD) and evaluated it
as a corrosion inhibitor for carbon steel in a neutral solution. PMD
manifests about 90% efficiency at 200 mg/L concentration. DFT
study indicates that HOMO was located over the tertiary amine
groups indicating that this moiety greatly participated in charge
transfer (Fig. 6). MD simulations suggest that PMD acquires the
negative value of Eads indicating that it had a spontaneous ability
to interact with the metallic surface. PMD also adsorb parallelly on
the metallic surface proving a high surface coverage and protection
(Fig. 6). Schematically these authors proposed that the hydrophilic
portion of PMD directs toward the metal side and avoids anodic
oxidation (Fig. 6).
Recently, Saleh et al. [65] synthesized an amine-grafted poly(-
acrylic-maleic) derivative (APAM) and evaluated it as a corrosion
inhibitor for 316 stainless steel in a 3.5% NaCl solution. The scheme
Fig. 5. Self-healing mechanisms of (a) the scratched crevice of nanofibers coating in (b) alkaline media and (c) acidic media [55].
413
Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435
for the synthesis of (APAM) is shown in Fig. 7. Weight loss study
indicates that APAM showed the best efficiency of 94.4% at 80 ppm
concentration at 25  C. The outcomes also suggest that increase in
the temperature causes a subsequent decrease. APAM manifests
85.71% and 74.60% efficiencies at 40  C and 60  C, respectively (at
80 ppm). Through the PDP study, it was assessed that APAM affects
both anodic dissolution and cathodic H2-evolution reactions and
behaves as a mixed-type inhibitor with slightly cathodic predom-
inance. The adsorption of APAM on the metallic surface followed
the Langmuir isotherm model. The adsorption mode of corrosion
prevention of APAM was also studied by AFM and SEM studies
(Fig. 7). The surface of the nonprotected metal surface was highly
corroded and damaged with an average surface roughness of
71.2 nm. However, in the presence of inhibitor molecules at 80 ppm
concentration, the average surface roughness reduced to 44.6 nm.
SEM analyses demonstrate the carbon steel surface was highly
corroded in the absence of APAM due to the free electrolytic at-
tacks. But in the presence of inhibitor molecules, the surface be-
comes smoother due to the formation of a protective film.
2.3. Poly(caprolactone) (PCL) in sustainable corrosion protection
Poly(caprolactone) (PCL) is a well-known biodegradable syn-
thetic polymer having a glass transition temperature of
about 60  C and a melting point of 60  C [66]. PCL is commonly
used as polyol component for polyurethanes (PUs) [67]. PCL pro-
vides excellent resistance to PU from oil, organic solvents, water
and chlorine attacks. Generally, PCL is used as an additive to
improve the properties and use of polymeric materials. The cost-
effectivity and biodegradability of PCL can be improved by mixing
it with starch. PCL is generally synthesized by the ring-opening
polymerization of ε-caprolactone using a suitable catalyst such as
stannous octoate. PCL is a water-insoluble polymer therefore PCL
itself and its derivatives especially its composites are widely used
anti-corrosion coating formulations, mostly for magnesium (Mg)
alloys [68,69].
Mousa et al. [70] proposed that PCL acts as a polydentate ligand
and possesses a strong ability to coordinate and bind with the
metallic surface. Recently, Zheng et al. [71] synthesized a folic acid
(FA) modified Cu-based MOF (HKUST-1) and PCL composite coating
(PCL-MOF) for enhanced biocompatibility and corrosion resistance
C. Verma, M.A. Quraishi, A. Alfantazi et al.
Fig. 6. Optimized configuration, frontier orbital density distributions and ESP of DMAPMA and PMD (Upper-left); top and side views of equilibrium configurations for corrosion
inhibitor PMD at 303 K on Fe (0 0 1) in neutral medium (Upper-right) and schematic diagram of a mechanism for corrosion inhibition of Q235 carbon steel by PMD molecules
(lower) [64].
for Mg alloy in phosphate buffer solution. The fabrication of PCL-
MOF and coating (Mg-PCL-MOF) are illustrated in Fig. 8. Electro-
chemical EIS and PDP studies suggest that PCL and PCL-MOF
coatings significantly improved the corrosion resistance of Mg
alloy a, which was more prominent in the presence of MOF. The
polarization resistance for bare Mg, PCL and PCL-MOF coated Mg
alloy was 7.80  105 Ucm2, 7.54  107 and 2.21  109 Ucm2,
respectively. The incorporation of MOF also enhances the biode-
gradability and biocompatibility of PCL chain and compactness of
the coating through H-bonding.
Many authors described the anticorrosive effect of PCL-based
formulations, mostly for Mg AZ31 Mg alloy in the simulated body
(Hank's solution and Kokubo solution) fluids. A summary of major
reports is presented in Table 1. The literature study suggests that
hydroxyapatite and/or cephalexin loading of PCL improves its
biocompatibility and corrosion resistance of AZ31 Mg alloy in
Hank's solution [72,73]. These coatings are 9e12 mm thick. The
414
Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435
additives enhance the adhesion (barrier or sealing) and blocking
property of the PCL-based coatings. Bakhsheshi-Rad et al. [74]
developed a fluorine-doped hydroxyapatite (nFHA)/PCL) coating
(nFHA/PCL) for Mge2Zne3Ce alloy in Kokubo solution. The thick-
nesses of nFHA and nFHA/PCL coatings were 8e10 and 70e80 mm,
respectively. Electrochemical and immersion experiments suggest
that nFHA coatings improve corrosion resistance and biocompati-
bility. The SEM images and EDS spectra of the coated and uncoated
samples immersed in SBF for 240 h are shown in Fig. 9. It can be
seen that the uncoated Mg alloy surface is highly corroded and
damaged displaying plentiful pits, dips and cracks. The formation of
cracks could be attributed due to water loss from corrosion prod-
ucts and surface shrinkage. EDS analysis proposed the existence of
O and Cl along with Mg in the corrosion product. Mg and Cl exist as
MgCl2. However, in the coated SEM images it can be seen that pints
and cracks become smaller, especially in PCL-based monolayer
coating. The corresponding EDX spectrum reveals the presence of C,
C. Verma, M.A. Quraishi, A. Alfantazi et al. Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435

Fig. 7. Schematic showing the synthesis of Amine grafted Poly-(Acrylic-Maleic) (upper left); AFM images of stainless steel surface coupon (a) in blank 3.5% NaCl (b) APAM inhibited
solutions (upper-right) and (a), (b) & (c) high, low magnification SEM micrographs & EDX spectrum of stainless steel coupon immersed in the blank (3.5% NaCl) solution (d), (e) & (f)
high, low magnification SEM micrographs & EDX spectrum of stainless steel coupon immersed in APAM inhibited solution [65].

415
C. Verma, M.A. Quraishi, A. Alfantazi et al.
Fig. 8. Schematic illustration of the fabrication of the composite coating composed of folic acid (FA)-modified Cu-based MOF and poly(caprolactone) on AZ31 Mg alloy [71].
O, Ca, Mg and P. nFHA/PCL coating manifests large pore and cracks
size due to embedded nFHA nanoparticles.
The authors proposed that in the absence of coating, the
galvanic reaction occurs and the dissolution of Mg takes place
(Fig. 10a). The formation and accumulation of gas bubbles beneath
the coating also produced surface imperfections i.e. cracks and
pores that allow the diffusion of corrosive species even more easily
and quickly (Fig. 10b). CA-P (spherical shape) is formed by the re-
action of phosphate and Ca2þ ions (Fig. 10c). Obviously, under this
circumstance, the cracking and surface defects decrease however
some portion of the coating experience delamination and corrosive
attacks (Fig. 10d). Jia et al. [75] reported that the anticorrosive effect
of amorphous calcium carbonate (ACC) and PCL-based composite
coating is attributed due to the combined effect of physical barrier
formation for the charge transfer process and the formation of
insoluble Mg-phosphate. AlFalah and coworkers [76] showed that
the presence of ZnOeNiOeCuO in PCL-based anticorrosive coating
manifests better protection for mild steel in 1M HCl solution than
the individual presence of oxides.
The presence of Zn-doped HAzeolite [77], graphene oxide [78],
lawsone [79] and chitosan (CS)eZnO composite [79] improved the
anticorrosive as well as antibacterial activities of PCL-based coat-
ings. Using electrochemical EIS studies, Yang et al. [80] showed that
the presence of MIL-5 (MOF) with and without TA (tannic acid)
improves the charge transfer resistance of PCL coating. The prep-
aration of coating materials and coating are illustrated schemati-
cally in Fig. 11. The anti-corrosive effect of different coatings was
measured using PDP and EIS methods. The outcomes of the PDP
study suggest that a decrease in the corrosion current density fol-
lowed the sequence: PCL < MIL-53/PCL < MIL-53@TA/PCL which
was consistent with the order of corrosion protection. The order of
corrosion protection was also supported by EIS analyses where PCL
coatings with and without MIL-53 and TA manifest remarkable
improvement in the charge transfer resistance for the corrosion
process. The authors observed that MIL-53@TA/PCL composite
provides self-healing protection. The self-healing protection is
416
Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435
schematically presented in Fig. 11. The presence of ZnO [81] and
TiO2 [82] also improves the antibacterial, biocompatibility and
anticorrosive activities. Additives perform two functions, namely
sealing and blocking activities.
2.4. Poly(ethylene) glycol (PEG) in sustainable corrosion protection
Poly(ethylene glycol) (PEG) is a linear polyether which formed
by the polymerization of ethylene glycol. The PEG polymers having
different molecular weight are widely used for many industrial,
manufacturing, biological and pharmaceutical uses including as
corrosion protection [84]. In addition to being non-toxic, poly-
ethylene glycol is also non-corrosive. The use of PEG connected
with many advantages together with cost-effectivity, reduced
inflammation, toxicity and environmental risks [85]. PEG itself is a
nonbiodegradable polymer as its ‒C‒C‒ linkage shows reasonably
high resistance towards microbial degradation. Nevertheless, some
of the PEG derivatives, especially PEG functionalized with poly(-
lactic acid) (PLA), are susceptible for biodegradation [86]. More so,
PEG can undergoes biodegradation under some specific oxidative
environments [86]. Overall, PEG and its derivatives are well-
recognized ecofriendly derivatives with reduced cost, high
biocompatibility and nontoxicity [87]. The PEG exists in its various
molecular weight and most of them are approved by U. S. Food and
Drug Administration (US, FDA) for the internal use [88,89].
The molecular weight of PEG ranges from tens of thousands to
200 [85,90]. PEGs having molecular weight of 600, 600e800
and >800 are exists as viscus liquid, waxy solid and white solid
forms, respectively (at 25  C) [85,90]. The different molecular
weight PEGs are extensively used for different applications [91]. But
their anticorrosion use is relatively new and gaining significant
attention. Various oxygen atoms greatly involve in binding and
coordination with the metallic surface [92]. The one of the greatest
benefits in using PEG for corrosion mitigation is that they are
nonvolatile unlike to traditional organic inhibitors [93]. Therefore,
PEG and its derivatives having nonvolatility together with many
C. Verma, M.A. Quraishi, A. Alfantazi et al. Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435

Table 1
A summary of major reports on the anticorrosive effect of poly(caprolactone) and its composite coatings.

Nature of poly(caprolactone) Thickness of coating Metal/electrolyte Salient features Ref.

Poly(caprolactone) (PCL)
coating loaded with HA
(hydroxyapatite) and Ceph.
(cephalexin)
Bifunctional coatings based on
PCL and nanohydroxyapatite
(HA)
Fluorine-doped hydroxyapatite
(nFHA)/PCL) coating (nFHA/
PCL)
PCL (poly(caprolactone)) & ACC
(amorphous calcium
carbonate) composite (PCL/
ACC composite)
ZnOeNiOeCuO/PCL (PCL/ZnO
eNiOeCuO)
Zn-doped HAzeolite/PCL
composites coating
(ZnHAZeo/PCL)
Graphene oxide (GO) e
Poly(caprolactone) (PCL)
NCPs
Poly(caprolactone) (PCL) and
lawsone
Electro-grafted PCL coating
PCL/Chitosan (CS)/ZnO
composite coating
PCL-coating with MIL-53@TA
(MIL-53@TA/PCL)
Poly(caprolactone) (PCL)/ZnO
coating
Dicalcium phosphate
dihydrate(DCPD)/PCL-TiO2
(DCPD/PCL-TiO2)
9e11 mm Mg alloy of Al and Zn ❖ The barrier property of PCL coating was significantly enhanced in the [72]
(AZ31)/Hank's solution presence of HA and Ceph.
❖ The biocompatibility and effectivity of the coatings followed the
sequence: PCL, Ceph., HA > PCL-Ceph. > PCl.
z12 mm Mg AZ31 alloy/Hank's ❖ The coating is composed of the inner layer of polyetherimide (PEI) [73]
solution that promotes the adhesion property and the outer layer of HA-
PCL provide corrosion protection.
❖ PEI-10% PCL and 5% HA manifest excellent anticorrosive activity and
reduced cytotoxicity.
8e10 mm (nFHA) & Mge2Zne3Ce alloy/ ❖ nFHA/PCL coating was immersed for 10 days and showed 34% more [74]
70e80 mm (nFHA/PCL) Kokubo solution compression.
❖ nFHA/PCL-coated samples faced milder corrosion attacks.
❖ Authors proposed that a bilayer coating could be an even better
option.
3.51 mm (PCL) & Mg AZ31 alloy/ ❖ Electrochemical studies suggest that PCL/ACC provide excellent [75]
5.29 mm (PCL/ACC) simulated body fluid anticorrosive protection in two ways
(i) By creating a physical barrier for SBF attacks.
(ii) ACC releases phosphate that forms a protective film of Mg-
phosphate.
e Mild steel/1M HCl ❖ ZnO, NiO, and CuO were greatly distributed in the PCL matrix. [76]
❖ PCL/ZnOeNiOeCuO exhibits the best performance of 94.8%.
226260 mm Magnesium (Mg) ❖ The ZnHAZeo/PCL coatings improved the anticorrosive [77]
substrate/Kokubo performance and antibacterial activity.
solution
e Mild steel/3.5% NaCl ❖ GO was functionalized by 8-Bromo-[1,2,4]triazolo[1,5-a]pyridin-2- [78]
amine (BTP) (FGO).
❖ GO-PCL and FGO-PCL show similar protection for 1 day however for
10 days of immersion FGO-PCL exhibit the best performance.
18 mm PCL coating & AZ31 Mg alloy ❖ EIS and invitro tests showed a remarkable upsurge in corrosion [79]
4 mm oxide layer resistance.
❖ The coating exhibits excellent antibacterial activity for Escherichia
coli and Staphylococcus aureus
6.5 mm (PCL) MgeZneYeNd alloy/ ❖ The PCL coating was prepared by ring-opening polymerization. [83]
simulated body fluid ❖ The cytocompatibility was improved by adding arginine-glycine-
aspartic acid.
40e50 mm Mg alloy/simulated ❖ ZnO doping improves antibacterial activity and cytocompatibility. [83]
body fluid ❖ PCL/CS and PCL/CS/ZnO coated samples exhibit remarkable corrosion
resistance.
55 ± 5 mm Mg alloy/simulated ❖ The healing and anticorrosive properties were studied by EIS and [80]
body fluid photothermal tests.
❖ The anticorrosion potential of coatings followed the sequence: MIL-
53@TA/PCL < MIL-53@/PCL < PCL.
18 mm (MgO/MgCO3) & MgO/MgCO3 layered on ❖ The ZnO NPs loading of PCL improves the antibacterial, [81]
30 mm (PCL/ZnO) WE43 Mg alloy/Hank's biocompatibility and anticorrosive activities.
solution ❖ Electrochemical studies showed that PCL/ZnO coating exhibits
excellent corrosion resistance.
37 mm (DCPD/PCL-TiO2) Mg alloy/simulated ❖ In the composite coating, PCL shows a sealing effect and TiO2 [82]
body fluid manifests a blocking effect.
❖ Due to coating, the impedance increased 628 times and H2 evolution
decreased by 1/19 times for 14 days.

other advantages are ecofriendly substitutes for toxic corrosion
inhibitors [94,95]. PEG-based compounds possess extremely re-
sistivity in acidic and basic electrolytes offering them to be used for
a long term anticorrosive protection, especially at relatively high
temperature and drastic atmospheric conditions [96]. Another
advantage of PEG-based corrosion inhibitors is that they can be
recovered from the electrolyte and can be recycled many times
[97,98]. PEG-based polymers are widely used in different types of
electrolytes including H2SO4 [99e101], HCl [87,102], NaCl
[103e105] and metal hydroxide (MOH) [106].
2.5. Poly(amino acids) in sustainable corrosion protection
Amino acids (AAs) and their derivatives are well-known for their
anticorrosive application, especially in aqueous electrolytes [107].
They have been extensively employed as green and sustainable
corrosion inhibitors for different metals and alloys [107,108]. The
greenness of AAs is based on their natural and biological origin.
417
Pure amino acids manifest relatively less efficiency therefore
numerous attempts have been made to enhance their efficiency
[107,108]. One of the common attempts is the use of metal cations
or halide ions to improve their performance. These species are
called synergists and the phenomenon is known as synergism
[109]. Another important alternative method of enhancing the in-
hibition efficiency of AAs is their chemical functionalization or
modification using organic compounds. The outcomes of many
reports showed that AAs derivatives demonstrated better corrosion
protection than a corresponding amino acid [110]. Recently, the use
of polymerized amino acids (PAAs) is gaining particular attention
[111]. Because of their polymeric nature, PAAs provide excellent
surface coverage and protection. Among poly(acidic amino acids),
few studies describe the anticorrosive effect of poly(L-glutamic
acid) (PLG)-based formulations in coatings, mostly for magnesium
alloys [112]. Poly(aspartic acid) (PASP) is widely used in aqueous
phase corrosion and scale inhibition [113e116]. A summary of
major reports is presented in Table 2.
C. Verma, M.A. Quraishi, A. Alfantazi et al. Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435

Fig. 9. SEM micrograph of (a) uncoated MgeZneCe alloy; (b) PCL-coated; (c) nFHA/PCL-coated specimens after immersion into Kokubo for 240-h duration and EDS analysis of (d)
point A; (e) point B and (f) point C [74].

Fig. 10. Schematic illustration of the degradation mechanism of the coated specimens after immersion into Kokubo SBF solution [74].

The anti-corrosion and scale inhibition performances of PASP nearly 100% scale inhibition efficiency. PASP and its derivatives
are investigated in different electrolytes for different alloys mostly adsorb on the metallic surface and build corrosion-
(Table 2). Careful observation suggests that in most of the studies inhibitive film and their adsorption on metallic surfaces mostly
PASP manifest more than 90% corrosion inhibition efficiency and followed the Langmuir isotherm model, though other isotherm

418
C. Verma, M.A. Quraishi, A. Alfantazi et al.
Fig. 11. Schematic diagram for the preparation of MIL-53/PCL and MIL-53@TA/PCL coating (upper) and Schematic diagram of self-healing mechanism of MIL-53@TA/PCL coating
(lower) [80].
models have also been reported [117]. They retard both anodic and
cathodic Tafel reactions and behave as mixed-type corrosion in-
hibitors. In some studies, slight anodic or cathodic predominance
has also been pointed out. The PASP and its derivatives are effective
against most of the common scales including CaCO3, CaSO4 and
Ca3(PO4)2. Zeino et al. [116] studied the corrosion inhibition po-
tential of PASP for mild steel in 3% HCl using different techniques in
the absence and presence of Zn2þ ions. The authors observed that
the presence of PASP affects both the nature of anodic and cathodic
reactions. They also affect the charge transfer resistance for MS
corrosion in tested electrolytes. Through these outcomes, authors
concluded that PASP with and without zinc cations build a pro-
tective film that avoids the aggressive electrolytes. They also
observed the presence of a small amount of Zn ions (0.01 g/L)
causes a significant shift in the anodic and cathodic Tafel curves
(Fig. 12). The authors proposed that Zn2þ ions replace the Fe2þ due
to higher activity and build the phosphate complex of zinc which
precipitate over cathodic regions and passivate the metallic surface.
419
Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435
Because of this, PASP in the presence of Zn2þ behaves as predom-
inantly cathodic-type inhibitors. The PASP can bind with Zn2þ and
Fe2þ or metallic surfaces through its many electron-rich adsorption
sites (Fig. 12).
Wang and coworkers [118] developed an amine-terminated
PASP derivative (PASP/CD) by the reaction of poly(succinimide)
(PSI) and carbonothioic dihydrazide (CD) and then synthesized a
corresponding Schiff's base (PASP/SB) by the reaction of PASP/CS
with para-chlorobenzaldehyde (PACD) (Fig. 13). The developed
PASP and PASP/SB were evaluated for their anticorrosive effect on
carbon steel in 1M HCl using various methods. Weight loss and
electrochemical studies suggest that an increase in PASP and PASP/
SB concentration causes a corresponding increase in their corrosion
inhibition performance and maximum efficiency was derived at
80 ppm concentration. At all studied concentrations, PASP/SB ex-
hibits significantly high performance than PASP as PASP and PASP/
SB exhibit 39.39% and 90.39% efficiencies at 80 ppm, respectively.
EIS and PDP studies suggest that PASP and PASP/SB become
 Table 2

C. Verma, M.A. Quraishi, A. Alfantazi et al.

Summary of anticorrosive effect of polyaspartic acid (PASP).

Nature of amino acid Metal/electrolyte %IE/Conc. Adsorption mode Salient feature(s) Ref.

Polyaspartic acid (PASP) & sodium tungstate Cu30Ni alloy (B30)/ 94.52%/17.14 mg/PLASP1 2.86 mg/L Na2WO4 Anodic-type inhibitor  Both PASP and Na2WO4 inhibit B30 corrosion [124]
simulated cooling and PASP showed better anticorrosive
water solution activity.
 At 2o mg/L concentration, the ratio of
PASP:Na2WO4 was 6:1.
Poly(aspartic acid) (PASP) CS/0.5M H2SO4 80/4 g/L Anodic-type and Freundlich  PASP affects both anodic and cathodic [117]
isotherm reactions but is mainly anodic.
 SEM study reveals the formation of the
protective film of inhibitor molecules.
Polyaspartic acid (PASP) and imidazole (IM) Cu/in 3 wt% 95.4% at 1.0 g/L Cathodic-type  At 1.0 g/L PASP shows about 89.8% efficiency [125]
aminosulfonic acid and PASP þ IM it shows 95.4% efficiency.
 PASP behaves as a mixed- but predominantly
cathodic-type inhibitor.
PESA (Polyepoxysuccinic acid) & PASP Steel alloy/Salvetat z100%/0.25 (PESA) and 0.3 mg/L (PASP) e  At 0.25 (PESA) and 0.3 mg/L (PASP) [126]
water concentration almost complete scale
inhibition was observed in about 60 min.
 At lower concentrations, PESA manifests
better protection than PASP.
PASPemelamine grafted copolymer (PASPM) CS/simulated scaling 98.7%/10 mg/L e  PASPM exhibits good anti-scaling properties [127]
solution for CaCO3 and Ca3(PO4)2 scales.
 Scale inhibition and dispersibility of PASPM
for Fe2O3 was greatly depend upon
concentration.
PASP/3-amino-1H-1,2,4-triazole-5-carboxylic CS 20#/seawater 75%/16 mg/L e  PASP/3-A-1H-1,2,4-T-5-CA is a non- [128]
acid hydrate graft copolymer (PASP/3-A-1H- phosphorus-based scale and corrosion
1,2,4-T-5-CA) inhibitor.
420

 PASP/3-A-1H-1,2,4-T-5-CA is a biodegradable
composite.
 The scale crystals become regular on adding
graft copolymer.
Poly(aspartic acid) (PASP) MS/0.5 M H2SO4 87.9/2 g/L Mixed-type  Presence of 1 mM KI increases %IE from 88.0% [129]
to 98.8% (PDP).
 PASP with and without KI behaves as mixed-

Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435

and interface-type.
PASP/5-aminoorotic acid graft copolymer CS/seawater 60%/12 mg/L e  PASP/5-AOA exhibits 60% corrosion inhibi- [130]
(PASP/5-AOA) tion and 100% scale inhibition at 12 mg/L.
 Corrosion product (CaCO3 and Ca3(PO4)2)
show cascade and flower patterns
Poly(aspartic acid) (PASP) WE43Mg alloy/3.5% 94.4%/400 ppm Cathodic-type  Increase in APP concentration increased [131]
NaCl efficiency and the maximum value was
obtained at 400 ppm.
Polyaspartic acid derivative (PASP-SEA-ASP) CS/seawater 97%/14 mg/L Anodic-type  PASP-SEA-ASP exhibits chelating capability. [132]
 PASP-SEA-ASP show 97% corrosion inhibition
and 100% scale inhibition.
Serine-modified PASP (Ser-PASP) CS/seawater 100%/4 mg/L (for CaCO3)  Ser-PASP acts as scale inhibition and avoids [133]
the dispersibility of Fe2O3.
 Ser-PASP exhibits 100% scale inhibition at
4 mg/L and 22 mg/L for CaCO3 and
Ca3(PO4)2, respectively.
Polyaspartic acid-glycine adduct (Gly-PASP) CS/seawater 83.8%/250 ppm Mixed-type inhibitor  GLy-PASP exhibits 83.8% corrosion inhibition [134]
at 250 ppm and 90.2% scale inhibition at
125 ppm.
 SEM and EDX studies used to describe the
adsorption of GLy-PASP
 C. Verma, M.A. Quraishi, A. Alfantazi et al.
PASP/furfuryl amine graft copolymer (PASP/FA) N80 CS/simulated sea 30%l16 mg/L e  PASP/FA manifests 100% against CaCO3 at [135]
solution 1 mg/L, 100% efficiency against CaSO4 5 mg/
L and 96% efficiency against Ca3(PO4)2.
 The corrosion inhibition efficiency of about
30% was achieved at 16 mg/L concentration.
Valine-PASP (Val-PASP) and leucine-PASP (Leu- CS/seawater 88.62% (Leu-PASP)/250 ppm Mixed-type inhibitors  Val-PASP and Leu-PASP show 86.94 and [136]
PASP) 88.62% efficiency at 250 ppm, respectively.
 The scale inhibition potential reaches to
92.3% and 94.1% for Val-PASP and Leu-PASP,
respectively at 125 ppm.
Tyr-SA-PASP and Trp-SA-PASP CS/simulated scaling 98%/4 ppm (Tyr-SA-PASP) e  Tyr-SA-PASP and Trp-SA-PASP manifested [137]
solution nearly 98% scale inhibition at 4 mg/L and
5 mg/L concentration, respectively.
PASP/N-(3-aminopropyl)imidazole (PD-1) & MS/0.5M H2SO4 94.0%/100 ppm Mixed-type and Langmuir  SEM, EDX and XPS confirm the inhibition by [138]
PASP/N-(3-aminopropyl)-imidazole-co-n- isotherm adsorption.
dodecylamine (PD-2).  PDs exhibit better efficiency than PASP due to
a greater number of adsorption sites.
Threonine-modified PASP (PASP-Thr) CS/simulated cooling 95.02%/300 ppm Mixed-type and Langmuir  PASP and PASP-Thr exhibit 83.16% and [139]
water isotherm 95.02% efficiency, respectively at 300 ppm.
 PASP manifests 93.06% at 200 ppm
concentration.
PASP and CS Complex A3 CS/3.5% NaCl 87.56%/20 mg/L Anodic-type  PASP and PASP/CS exhibit 58.8% and 83.5% [140]
efficiencies, respectively at 8 mg/L.
 There is a competitive adsorption of PASP/CS
that occurs by chloride ions.
PASP/4-(2-aminoethyl) morpholine graft CS/0.5M H2SO4 93.1%/100 ppm Mixed-type and Langmuir  PASP/AEM exhibits around 100% scale [141]
copolymer (PASP/AEM) isotherm inhibition for CaCO3, CaSO4 and Ca3(PO4)2 at
1.25, 5 and 10 mg/L, respectively.
 88.4%, 90.3% and 93.1% %IE was derived using
EIS, WL and PDP studies, respectively.
421

Polyaspartic acid (PASP) MS in 3% NaCl 56%/2.0 g/L Mixed-type  PASP and PASPþ0.01 g/L Zn exhibit %IE of 56% [116]
and 100%, respectively (2 g/L).
 In 0.01 g/L Zn, 100% efficiency was obtained
at 1 g/L concentration.
Polyaspartic acid modified Schiff base (PASP/SB) CS/1 M HCl 90.39%/80 ppm Mixed-type and Langmuir  %IE of PASP/SB slightly depends upon the [118]
isotherm flow rate and temperature.

Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435

 %IE followed the order: PASP/SB > PASP.
Cysteamine-modified PASP (PASP-S) MS/0.5M H2SO4 93.9%/100 ppm Mixed-type and Langmuir  PASP and PASP-S exhibit 67.5% and 93.9% [142]
isotherm efficiencies at 100 ppm (at 298 K).
 The high %IE of PASP-S is due to the pendent
functional sulfhydryl group.
PASP grafted b-cyclodextrin N80 CS/simulated sea 68.4%/800 mg/L Mixed-type  The inhibition efficiencies and scale [143]
solution inhibition followed the order: PASP < PASP/
b-CD.
 Their viscosity also followed the same
sequence.
PASP/GO grafted copolymer (PASP/GO) CS/simulated cooling 100%/8 mg/L (CaCO3) e  The maximum performance was derived at [119]
water 10 mg/L concentration where 100% CaCO3
and CaSO4 inhibition occurs.
 PASP/GO demonstrate an excellent dispersity
in Fe2O3.
Poly(cysteaminoaspartamide (7) and 1018 steel/3.5% NaClþ 95%/100 ppm (7) Anodic-type  The 7 and 8 efforts the %IE of 95.0% and 93.8%, [144]
poly(methionenoaspartamide (8) CO2 respectively at 100 ppm.
 SEM and AFM studies validates that 7 and 8
become effective by adsorbing on the
metallic surface.
C. Verma, M.A. Quraishi, A. Alfantazi et al.
Fig. 12. Tafel plots at different concentrations of PASP (a) and PASP þ 0.01 g/L Zn (b) and The schematic illustration of different modes of interactions on metal/solution interface in
the presence of PASP and Zn inhibitors (lower) [116].
effective by creating a charge transfer barrier through their
adsorption. The adsorption mode of protection was also assessed by
SEM and AFM analyses where a significant smoothness in the
surface morphologies of protected specimens was derived (Fig. 13).
The non-protected metallic surface was highly corroded and
damaged but the PASP and PASP/SB protected surfaces were
smoothers and this smoothness was most pronounced in the
presence of PASP/SB.
Chen et al. [119] developed a polyaspartic acid/graphene oxide
grafted copolymer (PASP/GO) as per the scheme shown in Fig. 14
and utilized it for its scale-inhibiting property. PASP/GO serves as
a non-phosphorus green scale inhibitor. PASP/GO exhibits 95.6%
and 100% CaCO3 scale inhibition potential at 6 mg/L and 8 mg/L
concentration, respectively. The authors also observed that from
50  C to 80  C, the inhibitory efficacy for PASP/GO was kept con-
stant at 100%. At 80e100  C, the inhibitory efficiency falls from
100% to 85.23%. The protection efficiency of PASP/GO is adversely
affected by immersion time as after 18 h immersion its %IE falls to
65.37%. The scale inhibition potential of PASP/GO was also affected
by pH. The effectiveness of PASP/GO was 100% when the pH of the
solution is between 7 and 8. While its %IE was just 47.26% at pH 12.
PASP/GO also effectively inhibit CaSO4 scale formation. Based on
the outcomes of experimental studies, the authors proposed that
422
Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435
in the presence of PASP/GO the scale crystals (CaCO3 and CaSO4)
become irregular as their active sites can react with each other.
This results in the formation of irregular scale crystals. These polar
groups cause the scale crystals to have a slight negative charge, as
a result of which their surface possesses a weak negative charge
and repels each other, which is significant to dispersion.
Furthermore, eCOOH and eOH groups of PASP/GO can form
chelates with metal ions to create dissoluble chelates with
structural stability (Fig. 14).
Among poly(basic amino acids), poly(L-lysine) (PLL), poly-
arginine (PArg), poly (l-histidine) (PHis) are expected to have better
anticorrosive activities. The literature study reveals that PPL is very
rarely employed in corrosion mitigation. Recently, Raghavendra
et al. studied the PLL for aluminium in pickling solution (3M HCl)
using various methods [120]. PLL exhibits its best efficiency of
92.07 ± 0.005% at 4 mg/L concentration and it has major influence
on anodic dissolution of Al in acidic solution. The adsorption of PLL
followed the Langmuir isotherm model. The reports on anticorro-
sive effect of PArg is also very scares. Likewise, histidine is very
frequently used in corrosion protection [121,122], but the reports on
anticorrosive effect of poly (l-histidine) (PHis) is very less [121].
Similarly, poly(neutral amino acids) are less extensively studied for
their anticorrosive activities [123].
C. Verma, M.A. Quraishi, A. Alfantazi et al.
Fig. 13. Synthesis routes of PASP/CD and PASP/SB (upper), SEM (middle) and AFM (lower) images of carbon steel immersed in 1 M HCl for 6 h at 303 K: (a) polished carbon steel, (b)
without inhibitor, (c) with 80 ppm PASP, (d) with 80 ppm PASP/SB [118].
2.6. Poly(vinyl alcohol) in sustainable corrosion protection
Poly(vinyl alcohol) (PVA) is a well-recognized water-soluble
biodegradable synthetic polymer, having a chemical formula of
[CH2CH(OH)]n. Vinyl alcohol cannot polymerize because of their
greater stability of aldehydic tautomeric form over enolic form.
Therefore, PVA is generally synthesized by poly(vinyl acetate) or
poly(vinyl ester) hydrolysis (Fig. 15; Eqs. (1) and (2)) [145]. The
relative proportion of 1,2- and 1,3-diols depends upon the hydro-
lysis condition and nature of precursors. PVA manifests many po-
tential industrial and biological uses such as 3D printing, additive in
adhesive formulations, coating, emulsion stabilizer, papermaking,
vascular stents, textile warp sizing, biocompatible hydrogel, contact
lenses, thickener etc. The worldwide annual production of PVA is
more than one million metric tons. PVA is a linear polymer that can
be divided into two parts, hydrophilic and hydrophobic (Fig. 15)
[146,147]. Because of this property, PVA is expected to have good
anticorrosive activity as a proper combination of hydrophilicity and
hydrophobicity is essential for an effective performance [148,149].
The hydrophilic segment of PVA i.e. hydroxyl groups participates in
bonding with metallic surfaces whereas the linear hydrocarbon
chain provides a shelter for aggressive electrolyte attacks. The
nonbonding electrons of oxygen can be directly transferred in
metallic d-orbitals leading to coordination or chemical bonding.
423
Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435
Alternatively, in acidic electrolytes, electrostatic interactions may
occur between charged metallic surface and protonated hydroxyl
groups (Fig. 15).
½CH2 CHðOAcÞn þ C2 C5 OH / ½CH2 CHðOHÞn
þ C2 C5 OAc polyvinyl acetate (1)
½CH2 CHðOCORÞn þ C2 C5 OH / ½CH2 CHðOHÞn
þ C2 C5 OCOR polyvinyl ester (2)
PVA manifests an optimized anticorrosive activity that arises in
form of its optimized hydrophilic and hydrophobic character. PVA is
established as one of the most attractive alternatives of BDSPs
useful for many purposes including corrosion mitigation. As
compared to the traditional nondegradable organic corrosion in-
hibitors, the use of PVA in corrosion mitigation is a relatively newer
approach. Probably, the first document on anticorrosive effect of
PVA was documented in the first decade of the 21st century by
Rajendran et al. [150]. In this primary report, the authors investi-
gated corrosion protection of PVA for carbon steel in neutral NaCl
solution (60 ppm) in the absence and presence of zinc cations. PVA
displays only 29% efficiency at 100 ppm however in the presence of
75 ppm of Zn2þ cations its efficiency synergistically enhanced to
C. Verma, M.A. Quraishi, A. Alfantazi et al. Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435

Fig. 14. Synthesis of PASP, GO and PASP/GO [119].

Fig. 15. Schematic illustration of (a) hydrophobic and hydrophilic parts of PVA; (b) partial protonation of eOH groups; (c) complete protonation of eOH groups and (d) binding and
adsorption of PVA with the metal surface.

81%. The synergistic effect of halide ions on anticorrosive effect of
PVA is also reported by other group of [151,152]. The synergistic
effect of different halide followed the order: I > Br > Cl. Many au-
thors documented the anticorrosion effect of chemically modified
PVA [153e157].
Rahiman and Sethumanickam developed a cysteine-based PVA
derivative, a poly(vinyl alcohol-cysteine) composite (PVAC), as an
inhibitor for mild steel in 1M HCl [158]. The PVAC was
characterized using FT-IR, SEM-EDX and UVevis analyses. Electro-
chemical investigation revealed the interfacial and mixed-type
nature of PVAC. Thereby, PVAC molecules adsorb and block the
active sites accountable for corrosion. Their adsorption also asso-
ciated with rise in the charge transfer resistance. SEM study
revealed that the presence of PVAC in the corrosive electrolyte
improves the surface smoothness by avoiding the aggressive elec-
trolyte attacks. Similar observation was reported by Geethanjali1

424
C. Verma, M.A. Quraishi, A. Alfantazi et al.
Fig. 16. SEM image of Al-2219, PVA and GPVA coated Al-2219 before (a, c, e) and after (b, d, f) potentiodynamic polarization measurements [167].
and Subhashini [159] who reported the synthesis, characterization
and anticorrosion potential of poly(vinyl alcohol)-g-poly(vinyl
sulfonate-p-vinyl (benzene sulfonate) (PVA-VSA-PVBS), a
terpolymer, for mild steel/1 M HCl system. DSC, TGA, FTIR and NMR
techniques were used for the characterization. The studied
terpolymer behaves as an interface- and mixed-type inhibitor.
Presence of the terpolymer in the in 1 M HCl improves the surface
morphology as compared to nonprotected one. The presence of
additional peaks for O and S in protect EDX spectrum validate the
adsorption mode of corrosion mitigation by the terpolymer. Atomic
force microscope (AFM) study also suggests the similar observation
were a significant improvement in the surface morphology was
achieved in the presence of terpolymer. The anticorrosive effect of
another terpolymer, poly(vinyl alcohol)-g-poly(acrylic acid-vinyl
sulfonate) (PAPAAVS), was reported by Geethanjali et al. [160].
Al-Gorair and coworkers [161] recently reported the relative
anticorrosion potential of PEG (polyethylene glycol) and PVA for
iron corrosion in 1M NaCl solution. Both PEG and PVA manifest
good anticorrosive potential and their efficiencies get magnified on
increasing their concentration though they exhibit different opti-
mum concentration. PEG and PVA exhibit 92% and 79% efficiencies
at their respective optimum concentrations of 500 and 300 ppm,
respectively. PEG and PVA behave as mixed-type inhibitors and
their retard both Tafel reactions. Their presence diminishes the
magnitude of corrosion current densities validating the fact that
they block the metallic active sites. PDP study was reinforced by EIS
study were presence of PEG and PVA causes significant increase in
425
Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435
the diameter of Nyquist curves relative to black one. The single
semicircle indicates the single charge transfer mechanism of
corrosion with and without PEG and PVA. The increased diameter
of Nyquist curves with and without PEG and PVA indicated that
they adsorb at the interface of metal and electrolyte and increase
barrier for charge transfer process. The single charge transfer mode
was further assessed by single maxima in the Bode phase angle
plots with and without PEG and PVA. Abdallah et al. showed that
alginic acid showed better performance than PVA [162].
Not only solution phase, PVA is also used in formulation of
anticorrosive coating [163,164]. John et al. [165] developed PVA and
chitosan-based nanocomposites (CS-PVA) as coating formulations
for mild steel in 0.1M HCl. The authors measure the inhibition
potential of CS, one (CS-PVA layer) and two layers (CS-PVA layer)
CS-PVA coatings and they manifest the inhibition efficiencies of
59.10, 96.54 and 98.47%, respectively. Nowadays, the use of com-
posites of PVA and graphene oxide (GO) is acquiring attention in
corrosion mitigation [166,167]. Hikku and coworkers synthesized,
characterized and used PVA and graphene-based composite (GPVA)
as an anticorrosive coating formulation for Al-2219 alloy in 3.5%
NaCl [167]. The characterization of GPVA was achieved through
SEM, FTIR and XRD techniques and the inhibition potential of
coating was measured using EIS and PDP methods. The adsorption
mode of corrosion prevention was reinforced by EDX mapping and
SEM surface examination. Polarization study showed that GPVA
and PVA coatings exhibit 99.99% and 94.30% efficiency, respectively.
The SEM images of PVA, GPVA coated and bare Al-2219 specimens
C. Verma, M.A. Quraishi, A. Alfantazi et al.
Fig. 17. EDX mapping images of PVA coated Al-2219 before (aed) and after (eek) potentiodynamic polarization measurements, (l,m) corresponding EDX spectra [167].
are given in Fig. 16. Careful examination reveals that Al-2219 sur-
face was very smooth without any pitting before conducting the
PDP study however after the PDP study the surface is highly
corroded with the marked presence of pits. This observation sug-
gests that Al-2219 surface is greatly attacked by electrolytes during
the course of PDP measurement. However, in the PVP and GPVA-
coated samples the pit formation is greatly restricted. The authors
also performed the EDX mapping studies for three tested speci-
mens to further support the adsorption mode of corrosion
prevention.
The adsorption mode of corrosion protection was also supported
by EDX elemental mapping for all three samples. The EDX mapping
as well as EDX spectra for PVA coated Al-2219 surfaces are shown in
Figs. 17 and 18. The EDX analysis of pure Al-2219 sample before
performing the corrosion study reveals the availability of
91.5e93.8% Al, 5.8e6.8% Cu and with scattered and randomly
distributed Mg. The availability of oxygen in corroded Al-2219
426
Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435
sample is attributed due to the formation of different metal ox-
ides. Careful inspection of the EDX mapping graphs shows that
oxygen is present only on the corroded surface. The EDX mapping
of Al-2219 coated with PVA for the sample before performing the
potentiodynamic polarization manifests an enhanced intensity
peak for oxygen. This is attributed to the oxygen content of PVA. It is
important to mention that before performing the experiment, the
entire Al surface was covered by oxygen (O) and carbon (C) how-
ever after the experiment finished, it the chloride atoms that
dominated around the voids area. A similar observation was
derived in the EDX mapping study of the GPVA-coated Al-2219
surface. Other studies also suggest that PVA-based composite
coatings provide long-term protection [168,169].
Samide et al. [170] reported the anticorrosion potential of another
terpolymer, poly(vinyl butyral-co-vinyl alcohol-co-vinyl acetate)
(PVBA) for copper surface in 0.9% NaCl solution. The analysis was
performed using EIS, PDP and AFM methods. The coating was
C. Verma, M.A. Quraishi, A. Alfantazi et al.
Fig. 18. EDX mapping images of GPVA coated Al-2219 before (aed) and after (eeh) potentiodynamic polarization measurements, (i,j) corresponding EDX spectra [167].
implemented on the copper surface in methanol. The outcomes
suggest that PVBA exhibits greater than 80% efficiency. It was also
assessed that hydroxyl groups of PVBA bind with the metal surface.
AFM analysis support the EIS and PDP studies. Lin et al. [171] re-
ported the synthesis and characterization of a PVA-grated G (gra-
phene) and used as a container for cerium hydroxide. The
anticorrosion effect of rGPC was tested as an additive in the poly(-
vinyl butyral) (PVB) matrix for mild steel surface. rGPC/PVB com-
posite provide a long term and effective anticorrosive protection
solution at 4 and 7 pH. The developed composite was characterized
using FE-SEM, FTIR, XRD, TEM and XPS techniques. SEM, EDX and EIS
techniques were employed to test the anticorrosion effect of the
composite. Similarly, Ji and coworkers [55]industrialized a self-
healing EP composite anticorrosive coating material from oleic acid
(OA)/2-mercaptobenzimidazole (MBI) in chitosan (CS)/poly(vinyl
alcohol) (PVA) core-shell nanofibers (CS/PVA)@(OA þ MBI). The
anticorrosion potential was tested at two different pH, 4 and 11.8. The
outcomes of the EIS study revealed that CS/PVA)@(OA þ MBI dem-
onstrates an excellent self-healing tendency.
2.7. Poly(acrylic acid) (PAA) in sustainable corrosion protection
Poly(acrylic acid) (PAA) is a polymer of acrylic acid (CH2CHCO2H).
PAA is traditionally called a carbomer and it has a molecular formula
of (CH2eCHCO2H)n [172]. To increase the commercial value of PAA,
numerous crosslinked copolymers have been synthesized and used
for different purposes [173,174]. At neutral pH, in an aqueous solution,
427
Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435
PAA exists as an anionic polymer as many of the side chains of PAA
lose their proton and get converted into an anionic form. The
deprotonated (partially or fully) PAAs serve as polyelectrolytes and
acquire the ability to swell by absorbing and holding the water
[175,176]. The ability of PAA to absorb acid, bases and water makes it
an ideal material for many applications [177,178]. PAA can be syn-
thesized by free-radical polymerization of acrylic acid (AA) using
AIBN or potassium persulfate as initiators. The annual worldwide
production was 1.6  109 kg in 2008 [172]. PAAs are extensively used
for different applications including absorbents, cleaning detergents,
cosmetics and paints, metal quenching, drilling fluids, wound healing
and biocompatible materials [177,178]. PAA is a water-soluble and
biocompatible polymer which makes it a material of great choice.
Acrylic acid itself in its purified form does not attract much attention
however its derivatives are widely used in aqueous phase corrosion
mitigation.
The use of PAA in corrosion inhibition is not a recent approach
but it is long-recognized as Grchev et al. reported the corrosion
inhibition potential of polyacrylic acid (PAAC) and polyacrylamide
(PAA) in 1991 [179]. The anti-corrosive and scale inhibition appli-
cations of PAA in the aqueous phase have been greatly advanced
[180e183]. In the aqueous phase, PAA and its derivative become
effective by adsorbing on the metallic surface following mostly
through Langmuir adsorption isotherm. Through their adsorption,
they build charge transfer barriers restricting the attack of corro-
sion species i.e. ions and gases. The formation of the barrier also
increases the resistance to change transfer and decreases the
 C. Verma, M.A. Quraishi, A. Alfantazi et al.
Table 3
A summary of reports on poly(acrylic acid) as an aqueous phase corrosion inhibitor.

Nature of PAA Experimental Performance parameters Adsorption Ref.

Metal electrolyte Best %IE Opt. Conc chemical Electrochemical

Poly(acrylic acid) (PAAs) Aluminium Bicarbonate buffer solution (pH 97.91% 20  108/M e Mixed-type [189]
(PAA1 ¼ MW: 1800, 8 & 10)
PAA2 ¼ MW: 11,000 and
PAA3 ¼ MW: 14,000 g
mol1)
Poly(acrylic acid) þ iodide ions Pure Fe 0.5 M H2SO4 49% (PAA) & 91% (PAAþ 5 mM 1  103 M Temkin isotherm Mixed-type [190]
KI)
3
Poly(acrylic acid) þ iodide ions Bulk nanocrystalline ingot iron 0.1 M H2SO4 79% (PAA) & 85% (PAAþ 5 mM 1  10 M e Mixed-type [191]
(BNII) and Polycrystalline ingot KI)
iron (CPII)
Pectin-Grafted Mild Steel 3.5% NaCl 35.0% (Pec-g-PAAm) & 85.15% 300 ppm Langmuir isotherm Mixed-type [192]
Polyacrylamide (Pec-g-PAAm) (PAA-g-PAAm); EIS
& Pectin-Grafted Polyacrylic
Acid (PAA-g-PAAm)
Polyaniline(PANI)poly(acrylic 316 stainless steel (316SS) 0.5 M HCl 91.68% 200 ppm Langmuir isotherm Mixed-type [193]
acid) (PANIPAA)
Poly(acrylic acid) (PAA), SPT SPT (Potassium Sodium 60 ppm Cl- (NaCl) solution 96.32% 50 ppm Ni2þ þ 200 ppm Langmuir isotherm Cathodic-type [199]
(Potassium Sodium Tartrate, Tartrate) (PAA) þ 125 ppm SPT
428

and Zn2þ ions

Poly(acrylic acid) (PAA),
Sodium gluconate (SG), and
Zn2þ ions
Poly(acrylic acid) þ Nickel
ions þ SPT (Potassium
Sodium Tartrate)
Mild steel 60 ppm Cl- (NaCl) solution 97.79% 50 ppm Ni2þ þ 200 ppm e Cathodic-type [194]
(PAA) þ 100 ppm SG
Mild steel 60 ppm Cl- (NaCl) solution 92.64% 50 ppm Ni2þ þ 200 ppm Langmuir isotherm Cathodic-type [200]
(PAA) þ 600 ppm SPT

Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435

Poly(acrylic acid) þ Nickel Mild steel 60 ppm Cl- (NaCl) solution 88.97% 50 ppm Ni2þ þ 200 ppm Langmuir isotherm Cathodic-type, [195]
ions þ Sodium gluconate (PAA) þ 600 ppm SG
(SG)
Poly(Acrylic Acid-co-Sodium Carbon Steel AISI 1018 0.01 M NaCl 82.64% 100 ppm e e [196]
Styrene Sulfonate) (PAA-co-
NaSS)
Poly(acrylic acid) Mild steel 0.5 M HCl 94.6% 100 ppm Langmuir isotherm Mixed-type [201]
Poly(acrylic acid) þ potassium Mild steel 0.5 M HCl 86.6% (PAA) & 91.0% 10% e Mixed-type [202]
iodide (PAA þ 1 mM KI)
Poly(acrylic acid)/zinc colloidal Iron 3.5 wt% NaCl 82.3% 200 ppm e Mixed-type [203]
particles (PZCPs) doped
PAA
Poly(acrylic acid) (ACTP) Aluminium 1 M NaOH 57.85% (PAA) & 66.67% (ACTP) 0.07% conc. & 308 K Langmuir isotherm e [197]
bearing triazole pendant
Poly(sodium acrylate; PANa) & Mild steel 0.1 M HCl 93.5% (PANa) 7 97.1% (PAA) 5  10e5 M Langmuir isotherm Mixed-type [198]
Poly(acrylic acid sodium;
PAA)
C. Verma, M.A. Quraishi, A. Alfantazi et al.
Fig. 19. (Upper) Schematic presentation of PANIePAA composite formation, showing a proposed network-like structure in agreement with their TEM image and (Lower) Poten-
tiodynamic polarization curves of 316SS in the absence and presence of (a) 1.35% and (b) 2.25% PANIePAA composites [193].
corrosion current densities. They have also been employed as
anticorrosive composite coatings [184e188]. The PAA composite-
based coatings manifest self-healing behavior [185,187]. The use
of carbohydrate polymers grafted PAA has provided a new eco-
nomic and eco-friendly approach to scale inhibition. A summary of
some major reports on the anticorrosion potential of PAA in the
aqueous phase is illustrated in Table 3.
Amin et al. [189] investigated the effect of different molecular
weights of PAA ((PAA1 ¼ MW: 1800, PAA2 ¼ MW: 11,000 and
PAA3 ¼ MW: 14,000 gmol1)) on the aluminium corrosion in
weakly alkaline solution (pH 8 and 10) using chemical, electro-
chemical and surface studies. The authors observed that at constant
pH and concentration, an increase in molecular weight is associated
with a corresponding rise in the %IE. The weight loss studies sug-
gest that inhibition efficiencies of studied PAAs followed the
sequence: PAA1 (76.00%) < PAA2 (86.26%) < PAA3 (97.91%) at
20  108/M concentration. The electrochemical studies suggest that
the presence of PAAs in the corrosive medium increases the charge
transfer resistance by increasing the diameter of Nyquist curves for
aluminium corrosion. PAA1, PAA2 and PAA3 affect both anodic and
cathodic Tafel curves and retard anodic dissolution and cathodic
hydrogen evolution without shifting the Ecorr potentially. Based on
this observation, the authors conclude that PAA1, PAA2 and PAA3
429
Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435
behave as mixed-type corrosion inhibitors. Umoren et al. demon-
strated that the presence of iodide ions synergistically enhanced
the inhibition performance of PAA for pure iron, bulk nano-
crystalline ingot iron (BNII) and polycrystalline ingot iron (CPII)
corrosion in 0.5M H2SO4 solution [190,191]. The %IE of polyacrylic
acid at its 1  103 M concentration was synergistically enhanced
from 49% to 91% in the presence of 5 mM KI for pure iron. Whereas,
this increase was only from 79% to 85% polycrystalline ingot iron
(CPII). The adsorption of PAA in sulfuric acid solution at the pure
iron surface followed the Temkin adsorption isotherm. The poten-
tiodynamic polarization studies suggest that PAA behaves as a
mixed-type inhibitor and retard both anodic and cathodic Tafel
curves. They did not cause a marked change in Ecorr values.
A similar observation was reported for the corrosion protection
effectiveness of pectin-grafted PAA for mild steel corrosion in a 3.5%
NaCl solution [192]. The outcomes of the study suggest that Pectin-
Grafted polyacrylamide (Pec-g-PAAm) & Pectin-Grafted Polyacrylic
Acid (PAA-g-PAAm) manifest the best %IE of 35% and 85.15%,
respectively at 300 ppm concentration. Both PAA-g-PAAm and Pec-
g-PAAm behave as mixed-type inhibitors as they retard anodic and
cathodic Tafel reactions without any significant shift in the Ecorr
value. PAA-g-PAAm and Pec-g-PAAm adsorption on the metallic
surface followed the Langmuir isotherm model. Syed et al. [193]
C. Verma, M.A. Quraishi, A. Alfantazi et al.
prepared PANI-PAA globules in PAA networks (Fig. 19) and utilized
them as corrosion inhibitors for 316 stainless steel (316SS) in 0.5 M
HCl. The anti-corrosive effect of 1.35% and 2.25% PANIPAA was
tested using electrochemical methods. PDP study suggests that
1.35% and 2.25% PANIPAA affect the anodic and cathodic Tafel
curves and act as mixed-type inhibitors (Fig. 19). They retard both
anodic dissolution and cathodic hydrogen evaluation by blocking
the active sites. Both 1.35% and 2.25% PANIPAA manifest the best %
IEs of 91.04% and 93.88%, respectively at 200 ppm concentration.
The 2.25% PANIPAA provides the best anticorrosive activity
therefore the EIS study was conducted only in its presence. The
adsorption mode of corrosion inhibition was also supported by SEM
analysis. The adsorption of 1.35% and 2.25% PANIPAA on 316 SS
followed the Langmuir isotherm model.
Many studies reported the effect of Zn2þ and Ni2þ ions on the
corrosion inhibition potential of Poly(acrylic acid) and potassium
sodium tartrate (PST) and polyacrylic acid sodium gluconate (SG)
combinations in the weak alkaline solutions [194e196]. Their
adsorption mostly followed the Langmuir adsorption isotherm and
they most affect the hydrogen evolution reaction of polarization
studies. Thereby, they behave as predominantly cathodic-type in-
hibitors. These studies suggest that a proper combination of three
components is essential for optimized %IE as a too-high or too-low
concentration of any component adversely affects the inhibition
performance. Punitha et al. [197] observed that a triazole-modified
PAA exhibit better inhibition performance than pristine PAA. Ouass
et al. [198] describe the relative inhibition performance of sodium
polyacrylate (PANa) and PAA for mild steel in 0.1 M HCl using
experimental and computational methods. The results showed that
PANa and PAA showed the best %IEs of 93.5% and 7 97.1%, respec-
tively at 5  105 M. They act as mixed-type inhibitors and their
adsorption followed the Langmuir model. The adsorption of PANa
and PAA on the metallic surface was supported by SEM and EDX
studies where the presence of inhibitors causes a significant
smoothness in the surface morphology, especially by PAA and
surface elements.
3. Conclusion and future perspectives
The current debate suggests that polymeric corrosion inhibitors
can successfully replace the traditional organic corrosion inhibitors.
Due to their polymeric nature and the abundance of adsorption
sites, they effectively adsorb on the metal surface and offer superior
surface protection. Natural polymers occasionally have limitations
in long-term corrosion prevention due to their propensity to hy-
drolyze, degrade (decompose), or rearrange, particularly at high
electrolyte concentrations and high temperatures. Therefore, it is
now extremely demanding to use synthetic polymers to prevent
corrosion. Polymers that are not biodegradable, such as poly(-
ethene) and poly(propene), do not break down. They accumulate in
the environment and cause biomagnification, which contaminates
the soil and water and harms the environment. When burned,
these polymer-based wastes contaminate the air. In view of this,
the use of biodegradable synthetic polymers (BDSPs) such as pol-
y(lactic acid) (PLA), poly (malic acid) (PMA), poly(caprolactone)
(PCL), poly(amino acids), poly(vinyl alcohol) (PVA) and poly(-
ethylene glycol) (PEG) has received a lot of attention. They adhere
to the metallic surface and prevent corrosion. They typically
adhered through the Langmuir adsorption isotherm. These poly-
mers block the active sites on the metallic surface after being
absorbed, preventing corrosion. They slow down both cathodic and
anodic Tafel reactions in aqueous solution without significantly
changing the corrosion potential. They act as mixed-type corrosion
inhibitors. Additionally, the resistance to the charge transfer pro-
cess is increased by their adsorption. The BDSPs share several
430
Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435
benefits with natural polymers, including good surface coverage, a
large number of adsorption sites, and high efficiency at low con-
centrations. The BDSPs are thought to be more economical and
efficient than natural polymers, especially when applied to high
temperature applications.
The BDSPs contain many electron donor sites such as eOH,
eCOOH, ‒O‒, >C]O, eNH2, >C]C< etc. that enable them to
adsorb on metallic surfaces. Additionally, the polar functional
groups make polymers more soluble, which is important for ap-
plications in the aqueous phase. These polar functional groups are
used as locations for chemical functionalization or modification,
where appropriate functionalities can be added or removed to in-
crease their ability to provide protection. The chemically altered
BDSPs are more efficient than their unaltered counterparts.
Therefore, future research should focus on the utilization of
chemically modified materials, notably those derived from het-
erocyclic compounds. Further, the inhibition potential of PLA, PMA,
PCL, PAAs, PVA and PEG extensively studied however there are
many other BDSPs such as polyphosphoesters, polyanhydrides,
polyphosphazene and polyester urethane that are rarely used for
this purpose. Therefore, in future they can be explored as aqueous
and coating phase corrosion inhibitors in different metal/electro-
lyte systems.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
References
[1] M.F. Balandrin, J.A. Klocke, E.S. Wurtele, W.H. Bollinger, Natural plant
chemicals: sources of industrial and medicinal materials, Science 228 (1985)
1154e1160.
[2] S.O. Duke, F.E. Dayan, A.M. Rimando, K.K. Schrader, G. Aliotta, A. Oliva, et al.,
Chemicals from nature for weed management, Weed Sci. 50 (2002)
138e151.
[3] M.G. Fontana, N.D. Greene, Corrosion Engineering, McGraw-Hill, 2018.
[4] R.W. Revie, Corrosion and Corrosion Control: an Introduction to Corrosion
Science and Engineering, John Wiley & Sons, 2008.
[5] G. Koch, Cost of Corrosion. Trends in Oil and Gas Corrosion Research and
Technologies, 2017, pp. 3e30.
[6] M. Fin
sgar, J. Jackson, Application of corrosion inhibitors for steels in acidic
media for the oil and gas industry: a review, Corrosion Sci. 86 (2014) 17e41.
[7] D.S. Chauhan, M. Quraishi, A.A. Sorour, C. Verma, A review on corrosion in-
hibitors for high-pressure supercritical CO2 environment: challenges and
opportunities, J. Petrol. Sci. Eng. (2022), 110695.
[8] A.M. El-Shamy, S.M. Mouneir, Medicinal materials as eco-friendly corrosion
inhibitors for industrial applications: a review, J. Bio Tribo Corrosion 9 (2023)
3.
[9] M.H. Nazari, S. Allahkaram, M. Kermani, The effects of temperature and pH
on the characteristics of corrosion product in CO2 corrosion of grade X70
steel, Mater. Des. 31 (2010) 3559e3563.
[10] B.J. Usman, Z.M. Gasem, S.A. Umoren, M.M. Solomon, Eco-friendly 2-
Thiobarbituric acid as a corrosion inhibitor for API 5L X60 steel in simu-
lated sweet oilfield environment: electrochemical and surface analysis
studies, Sci. Rep. 9 (2019) 830.
[11] P. Rajeev, A. Surendranathan, C.S. Murthy, Corrosion mitigation of the oil
well steels using organic inhibitorsea review, J. Mater. Environ. Sci. 3 (2012)
856e869.
[12] A. Kadhim, A. Al-Amiery, R. Alazawi, M. Al-Ghezi, R. Abass, Corrosion in-
hibitors. A review, Int. J. Corrosion Scale Inhibition 10 (2021) 54e67.
[13] C. Verma, M. Quraishi, K.Y. Rhee, Electronic effect vs. Molecular size effect:
experimental and computational based designing of potential corrosion in-
hibitors, Chem. Eng. J. 430 (2022), 132645.
[14] A. Williamson, P. Eng, Building a corrosion management system via material
sustainability and stewardship, Mater. Perform. 7 (2020).
[15] M. Yeganeh, T.A. Nguyen, S. Rajendran, S. Kakooei, Y. Li, Corrosion Protection
at the Nanoscale: an Introduction. Corrosion Protection at the Nanoscale,
Elsevier, 2020, pp. 3e7.
[16] H.-S. Lee, V. Saraswathy, S.-J. Kwon, S. Karthick, Corrosion Inhibitors for
Reinforced Concrete: A Review. Corrosion Inhibitors, Principles and Recent
Applications, 2018, pp. 95e120.
C. Verma, M.A. Quraishi, A. Alfantazi et al.
[17] M.A. Quraishi, D.S. Chauhan, V.S. Saji, Heterocyclic biomolecules as green
corrosion inhibitors, J. Mol. Liq. 341 (2021), 117265.
[18] C. Verma, L.O. Olasunkanmi, E.E. Ebenso, M.A. Quraishi, I.B. Obot, Adsorption
behavior of glucosamine-based, pyrimidine-fused heterocycles as green
corrosion inhibitors for mild steel: experimental and theoretical studies,
J. Phys. Chem. C 120 (2016) 11598e11611.
[19] S. Ramachandran, C. Menendez, V. Jovancicevic, J. Long, Film persistency of
new high-temperature water-based batch corrosion inhibitors for oil and gas
wells, J. Pet. Explor. Prod. Technol. 2 (2012) 125e131.
[20] S.K. Prajapati, A. Jain, A. Jain, S. Jain, Biodegradable polymers and constructs:
a novel approach in drug delivery, Eur. Polym. J. 120 (2019), 109191.
[21] R.J. Bose, M. Kim, J.H. Chang, R. Paulmurugan, J.J. Moon, W.-G. Koh, et al.,
Biodegradable polymers for modern vaccine development, J. Ind. Eng. Chem.
77 (2019) 12e24.
[22] O. Olatunji, Natural Polymers: Industry Techniques and Applications,
Springer, 2015.
[23] A. Anwunobi, M. Emeje, Recent applications of natural polymers in nanodrug
delivery, J. Nanomed. Nanotechnol. S 4 (2011).
[24] H. Tian, Z. Tang, X. Zhuang, X. Chen, X. Jing, Biodegradable synthetic poly-
mers: preparation, functionalization and biomedical application, Prog.
Polym. Sci. 37 (2012) 237e280.
[25] L.S. Nair, C.T. Laurencin, Biodegradable polymers as biomaterials, Prog.
Polym. Sci. 32 (2007) 762e798.
[26] P.A. Gunatillake, R. Adhikari, N. Gadegaard, Biodegradable synthetic poly-
mers for tissue engineering, Eur. Cell. Mater. 5 (2003) 1e16.
[27] V.S. Sastri, Green Corrosion Inhibitors: Theory and Practice, John Wiley &
Sons, 2012.
[28] S.H. Zaferani, M. Sharifi, D. Zaarei, M.R. Shishesaz, Application of eco-friendly
products as corrosion inhibitors for metals in acid pickling processeseA re-
view, J. Environ. Chem. Eng. 1 (2013) 652e657.
[29] C. Verma, E.E. Ebenso, I. Bahadur, M. Quraishi, An overview on plant extracts
as environmental sustainable and green corrosion inhibitors for metals and
alloys in aggressive corrosive media, J. Mol. Liq. 266 (2018) 577e590.
[30] Y. Yu, M. Shen, Q. Song, J. Xie, Biological activities and pharmaceutical ap-
plications of polysaccharide from natural resources: a review, Carbohydr.
Polym. 183 (2018) 91e101.
[31] A. Rango, A. Laliberte, Impact of flight regulations on effective use of un-
manned aircraft systems for natural resources applications, J. Appl. Remote
Sens. 4 (2010), 043539.
[32] M. Chomel, C. Fernandez, A. Bousquet-Me lou, C. Gers, Y. Monnier,
M. Santonja, et al., Secondary metabolites of P inus halepensis alter
decomposer organisms and litter decomposition during afforestation of
abandoned agricultural zones, J. Ecol. 102 (2014) 411e424.
[33] C. Verma, E.E. Ebenso, M. Quraishi, C.M. Hussain, Recent developments in
sustainable corrosion inhibitors: design, performance and industrial scale
applications, Mater. Adv. 2 (2021) 3806e3850.
[34] S.A. Umoren, U.M. Eduok, Application of carbohydrate polymers as corrosion
inhibitors for metal substrates in different media: a review, Carbohydr.
Polym. 140 (2016) 314e341.
[35] C. Verma, M. Quraishi, Chelation capability of chitosan and chitosan de-
rivatives: recent developments in sustainable corrosion inhibition and metal
decontamination applications, Curr. Res. Green Sustain. Chem. 4 (2021),
100184.
[36] P. Je˛ drzejczak, M.N. Collins, T. Jesionowski, Ł. Klapiszewski, The role of lignin
and lignin-based materials in sustainable constructionea comprehensive
review, Int. J. Biol. Macromol. 187 (2021) 624e650.
[37] R. Auras, B. Harte, S. Selke, An overview of polylactides as packaging mate-
rials, Macromol. Biosci. 4 (2004) 835e864.
[38] A. Jime nez, M. Peltzer, R. Ruseckaite, Poly (Lactic Acid) Science and Tech-
nology: Processing, Properties, Additives and Applications, Royal Society of
Chemistry, 2014.
[39] H.R. Kricheldorf, J.M. Jonte , New polymer syntheses, Polym. Bull. 9 (1983)
276e283.
[40] A. So € dergård, M. Stolt, Properties of lactic acid based polymers and their
correlation with composition, Prog. Polym. Sci. 27 (2002) 1123e1163.
[41] X. Zhang, Y. Zhang, Y. Su, X. Wang, R. Lv, Synthesis and corrosion inhibition
performance of mannich bases on mild steel in lactic acid media, ACS Omega
7 (2022) 32208e32224.
[42] P. Sikder, Y. Ren, S.B. Bhaduri, Synthesis and evaluation of protective poly
(lactic acid) and fluorine-doped hydroxyapatiteebased composite coatings
on AZ31 magnesium alloy, J. Mater. Res. 34 (2019) 3766e3776.
[43] N. Rahimi Roshan, H. Hassannejad, A. Nouri, Corrosion and mechanical
behaviour of biodegradable PLA-cellulose nanocomposite coating on AZ31
magnesium alloy, Surf. Eng. 37 (2021) 236e245.
[44] R.-C. Zeng, X.-T. Li, Z.-G. Liu, F. Zhang, S.-Q. Li, H.-Z. Cui, Corrosion resistance
of ZneAl layered double hydroxide/poly (lactic acid) composite coating on
magnesium alloy AZ31, Front. Mater. Sci. 9 (2015) 355e365.
[45] W. Zhang, Y. Chen, M. Chen, S. Zhao, J. Mao, A. Qu, et al., Strengthened
corrosion control of poly (lactic acid)(PLA) and poly (ε-caprolactone)(PCL)
polymer-coated magnesium by imbedded hydrophobic stearic acid (SA) thin
layer, Corrosion Sci. 112 (2016) 327e337.
[46] J. Zuo, J. Zhan, C. Luo, B. Dong, F. Xing, D. Chen, Characteristics and release
property of polylactic acid/sodium monofluorophosphate
microcapsules prepared by spray drying, Adv. Powder Technol. 28 (2017)
2805e2811.
431
Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435
[47] A.W. Nafi, A. Afifi, N.I.Z. Abidin, H. Aziz, N. Kalantari, Effect of the poly l-lactic
acid coating on the corrosion of magnesium in hank's solution, Sains Malays.
47 (2018) 169e179.
[48] B. Li, J. Niu, H. Liu, G. Li, Fabrication and corrosion property of novel 3-
aminopropyltriethoxy-modified calcium phosphate/poly (lactic acid) com-
posite coating on AZ60 Mg alloy, Appl. Phys. A 124 (2018) 1e13.
[49] Y. Ren, E. Babaie, S.B. Bhaduri, Nanostructured amorphous magnesium
phosphate/poly (lactic acid) composite coating for enhanced corrosion
resistance and bioactivity of biodegradable AZ31 magnesium alloy, Prog. Org.
Coating 118 (2018) 1e8.
[50] H.M. Mousa, A. Abdal-Hay, M. Bartnikowski, I.M. Mohamed, A.S. Yasin,
Ivanovski So, et al., A multifunctional zinc oxide/poly (lactic acid) nano-
composite layer coated on magnesium alloys for controlled degradation and
antibacterial function, ACS Biomater. Sci. Eng. 4 (2018) 2169e2180.
[51] H. Cai, J. Meng, X. Li, F. Xue, C. Chu, C. Guo, et al., In vitro degradation
behavior of Mg wire/poly (lactic acid) composite rods prepared by hot
pressing and hot drawing, Acta Biomater. 98 (2019) 125e141.
[52] H. Cai, X. Li, F. Xue, C. Chu, C. Guo, J. Bai, et al., In vitro study on cyto-
compatibility of Mg wire/poly (lactic acid) composite rods, J. Mater. Eng.
Perform. 30 (2021) 7214e7222.
[53] M.M. Alrashed, S. Jana, M.D. Soucek, Corrosion performance of polyurethane
hybrid coatings with encapsulated inhibitor, Prog. Org. Coating 130 (2019)
235e243.
[54] Y. Zhu, Y. Sheng, L. Zheng, L. Qin, T. Ngai, Poly (l-lactic acid)(PLLA) coatings
with controllable hierarchical porous structures on magnesium substrate: an
evaluation of corrosion behavior and cytocompatibility, ACS Appl. Bio Mater.
2 (2019) 3843e3853.
[55] X. Ji, W. Wang, J. Duan, X. Zhao, L. Wang, Y. Wang, et al., Developing wide
pH-responsive, self-healing, and anti-corrosion epoxy composite coatings
based on encapsulating oleic acid/2-mercaptobenzimidazole corrosion in-
hibitors in chitosan/poly (vinyl alcohol) core-shell nanofibers, Prog. Org.
Coating 161 (2021), 106454.
[56] Z. Chi, G.-L. Liu, C.-G. Liu, Z.-M. Chi, Poly (b-l-malic acid)(PMLA) from Aur-
eobasidium spp. and its current proceedings, Appl. Microbiol. Biotechnol.
100 (2016) 3841e3851.
[57] J.A. Portilla-Arias, M. García-Alvarez, A.M. de Ilarduya, E. Holler, J.A. Galbis,
S. Mun ~ oz-Guerra, Synthesis, degradability, and drug releasing properties of
methyl esters of fungal poly (b, l-malic acid), Macromol. Biosci. 8 (2008)
540e550.
[58] W. Cao, X. Chen, J. Luo, J. Yin, C. Qiao, Y. Wan, High molecular weight b-poly
(l-malic acid) produced by A. pullulans with Ca2þ added repeated batch
culture, Int. J. Biol. Macromol. 85 (2016) 192e199.
[59] Y. Li, Z. Chi, G.-Y. Wang, Z.-P. Wang, G.-L. Liu, C.-F. Lee, et al., Taxonomy of
Aureobasidium spp. and biosynthesis and regulation of their extracellular
polymers, Crit. Rev. Microbiol. 41 (2015) 228e237.
[60] S. Yegin, B.C. Saha, G.J. Kennedy, T.D. Leathers, Valorization of egg shell as a
detoxifying and buffering agent for efficient polymalic acid production by
Aureobasidium pullulans NRRL Y-2311-1 from barley straw hydrolysate,
Bioresour. Technol. 278 (2019) 130e137.
[61] W. Cao, W. Cao, F. Shen, J. Luo, J. Yin, C. Qiao, et al., Membrane-assisted b-
poly (L-malic acid) production from bagasse hydrolysates by Aureobasidium
pullulans ipe-1, Bioresour. Technol. 295 (2020), 122260.
[62] W. Cao, Y. Wang, F. Shen, J. Luo, J. Yin, C. Qiao, et al., Efficient b-poly (L-malic
acid) production from Jerusalem artichoke by Aureobasidium pullulans ipe-1
immobilized in luffa sponge matrices, Bioresour. Technol. 288 (2019),
121497.
[63] C. Cheng, Y. Zhou, M. Lin, P. Wei, S.-T. Yang, Polymalic acid fermentation by
Aureobasidium pullulans for malic acid production from soybean hull and
soy molasses: fermentation kinetics and economic analysis, Bioresour.
Technol. 223 (2017) 166e174.
[64] T. Chen, Z. Chen, M. Chen, C. Fu, Evaluation of anti-corrosion performance of
poly (maleic acid-co-N-[3-(dimethylamino) propyl]-methacrylamide) as
novel copolymer inhibitor for carbon steel in neutral medium, J. Mol. Liq. 338
(2021), 116638.
[65] T.A. Saleh, K. Haruna, M.M. Nur, B. Alharbi, Synthesis of Amine Grafted Poly
(Acrylic-Maleic) as an efficient inhibitor against stainless steel corrosion in a
highly saline medium, Prog. Org. Coating 170 (2022), 106974.
[66] G. El Fawal, H. Hong, X. Mo, H. Wang, Fabrication of scaffold based on gelatin
and polycaprolactone (PCL) for wound dressing application, J. Drug Deliv. Sci.
Technol. 63 (2021), 102501.
[67] F. Hajiali, S. Tajbakhsh, A. Shojaei, Fabrication and properties of poly-
caprolactone composites containing calcium phosphate-based ceramics and
bioactive glasses in bone tissue engineering: a review, Polym. Rev. 58 (2018)
164e207.
[68] A. Alcudia, B. Begines, P. Rodriguez-Lejarraga, V. Greyer, V.C.F. Godinho,
E. Pajuelo, et al., Development of porous silver nanoparticle/poly-
caprolactone/polyvinyl alcohol coatings for prophylaxis in titanium inter-
connected samples for dental implants, Colloid Interface Sci. Commun. 48
(2022), 100621.
[69] P. Thiangpak, A. Rodchanarowan, Self-healing abilities of shape-memory
epoxy-contained polycaprolactone microspheres filled with cerium (III) ni-
trate coated on aluminum 2024-T3, ACS Omega 5 (2020) 25647e25654.
[70] H.M. Mousa, M.A. Mahmoud, A.S. Yasin, I. Mohamed, Polycaprolactone tri-
dentate ligand corrosion inhibitors coated on biodegradable Mg implant,
J. Coating Technol. Res. 18 (2021) 1191e1197.
C. Verma, M.A. Quraishi, A. Alfantazi et al.
[71] Q. Zheng, J. Li, W. Yuan, X. Liu, L. Tan, Y. Zheng, et al., Metaleorganic
frameworks incorporated polycaprolactone film for enhanced corrosion
resistance and biocompatibility of Mg Alloy, ACS Sustain. Chem. Eng. 7
(2019) 18114e18124.
[72] A. Zomorodian, C. Santos, M. Carmezim, T.M. e Silva, J. Fernandes,
MdF. Montemor, In-vitro” corrosion behaviour of the magnesium alloy with
Al and Zn (AZ31) protected with a biodegradable polycaprolactone coating
loaded with hydroxyapatite and cephalexin, Electrochim. Acta 179 (2015)
431e440.
[73] A. Zomorodian, M. Garcia, T.M. e Silva, J. Fernandes, M.H. Fernandes,
MdF. Montemor, Biofunctional composite coating architectures based on
polycaprolactone and nanohydroxyapatite for controlled corrosion activity
and enhanced biocompatibility of magnesium AZ31 alloy, Mater. Sci. Eng. C
48 (2015) 434e443.
[74] H. Bakhsheshi-Rad, E. Hamzah, M. Kasiri-Asgarani, S. Jabbarzare, N. Iqbal,
M.A. Kadir, Deposition of nanostructured fluorine-doped
hydroxyapatiteepolycaprolactone duplex coating to enhance the mechani-
cal properties and corrosion resistance of Mg alloy for biomedical applica-
tions, Mater. Sci. Eng. C 60 (2016) 526e537.
[75] S. Jia, Y. Guo, W. Zai, Y. Su, S. Yuan, X. Yu, et al., Preparation and character-
ization of a composite coating composed of polycaprolactone (PCL) and
amorphous calcium carbonate (ACC) particles for enhancing corrosion
resistance of magnesium implants, Prog. Org. Coating 136 (2019), 105225.
[76] M.G.K. AlFalah, E. Kamberli, A.H. Abbar, F. Kandemirli, M. Saracoglu, Corro-
sion performance of electrospinning nanofiber ZnO-NiO-CuO/
polycaprolactone coated on mild steel in acid solution, Surface. Interfac. 21
(2020), 100760.
[77] N. Iqbal, S. Iqbal, T. Iqbal, H. Bakhsheshi-Rad, A. Alsakkaf, A. Kamil, et al.,
Zinc-doped hydroxyapatitedzeolite/polycaprolactone composites coating
on magnesium substrate for enhancing in-vitro corrosion and antibacterial
performance, Trans. Nonferrous Metals Soc. China 30 (2020) 123e133.
[78] K. Rajitha, K.N. Mohana, Application of modified graphene
oxideepolycaprolactone nanocomposite coating for corrosion control of
mild steel in saline medium, Mater. Chem. Phys. 241 (2020), 122050.
[79] H. Asadi, B. Suganthan, S. Ghalei, H. Handa, R.P. Ramasamy, A multifunctional
polymeric coating incorporating lawsone with corrosion resistance and
antibacterial activity for biomedical Mg alloys, Prog. Org. Coating 153 (2021),
106157.
[80] J. Yang, D. Wang, J. Wang, W. Hu, Corrosion resistance and near-infrared light
induced self-healing behavior of polycaprolactone coating with MIL-53@ TA
on magnesium alloy, Appl. Surf. Sci. 585 (2022), 152729.
[81] K. Xing, Q. Chen, J. Lin, Z. Hu, Z. Li, J. Chen, et al., Polycaprolactone/ZnO
coating on WE43 magnesium alloy combined with a MgO/MgCO3 transition
layer for promoting anticorrosion and interfacial adhesion, Prog. Org. Coating
171 (2022), 107029.
[82] Y. Xu, T. Wang, X. Qu, Z. Liu, Y. Guo, G. Li, et al., Preparation of anticorrosion,
biocompatible and antibacterial dicalcium phosphate dihydrate/
polycaprolactone-titania composite coating on Mg alloy, Prog. Org. Coating
172 (2022), 107133.
[83] W. Huang, D. Mei, J. Zhang, D. Chen, J. Li, L. Wang, et al., Improved corrosion
resistance and cytocompatibility of MgeZneYeNd alloy by the electro-
grafted polycaprolactone coating, Colloids Surf. A Physicochem. Eng. Asp.
629 (2021), 127471.
[84] M. Kidwai, D. Bhatnagar, N.K. Mishra, Polyethylene glycol (PEG) mediated
green synthesis of 2, 5-disubstituted 1, 3, 4-oxadiazoles catalyzed by ceric
ammonium nitrate (CAN), Green Chem. Lett. Rev. 3 (2010) 55e59.
[85] J. Chen, S.K. Spear, J.G. Huddleston, R.D. Rogers, Polyethylene glycol and
solutions of polyethylene glycol as green reaction media, Green Chem. 7
(2005) 64e82.
[86] Y. Wang, S. Zhang, D.S. Benoit, Degradable poly (ethylene glycol)(PEG)-based
hydrogels for spatiotemporal control of siRNA/nanoparticle delivery, J. Contr.
Release 287 (2018) 58e66.
[87] V. Srivastava, D.S. Chauhan, P.G. Joshi, V. Maruthapandian, A.A. Sorour,
M.A. Quraishi, PEG-functionalized chitosan: a biological macromolecule as a
novel corrosion inhibitor, ChemistrySelect 3 (2018) 1990e1998.
[88] N. Akiya, P.E. Savage, Roles of water for chemical reactions in high-
temperature water, Chem. Rev. 102 (2002) 2725e2750.
[89] U.M. Lindstro €m, Stereoselective organic reactions in water, Chem. Rev. 102
(2002) 2751e2772.
[90] F. Bailey Jr., J. Koleske, Poly (Ethylene Oxide), Academic Press, New York, NY,
USA, 1976.
[91] A.A. D’souza, R. Shegokar, Polyethylene glycol (PEG): a versatile polymer for
pharmaceutical applications, Expet Opin. Drug Deliv. 13 (2016) 1257e1275.
[92] G. Totten, N. Clinton, Poly (Ethylene Glycol) and Derivatives as Phase
Transfer Catalysts, 1998.
[93] F.M. Kerton, R. Marriott, Alternative Solvents for Green Chemistry, Royal
Society of chemistry, 2013.
[94] P. Wang, D. Zhang, Y. Zhou, Y. Li, H. Fang, H. Wei, et al., A well-defined
biodegradable 1, 2, 3-triazolium-functionalized PEG-b-PCL block copolymer:
facile synthesis and its compatibilization for PLA/PCL blends, Ionics 24 (2018)
787e795.
[95] H.F. Naguib, M.S.A. Aziz, S.M. Sherif, G.R. Saad, Thermal properties of
biodegradable poly (PHB/PCL-PEG-PCL) urethanes nanocomposites using
clay/poly (ε-caprolactone) nanohybrid based masterbatch, Appl. Clay Sci. 57
(2012) 55e63.
432
Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435
[96] Y. Li, H. Zhang, Y. Yao, T. Gong, R. Dong, D. Li, et al., Promoted off-on
recognition of H2O2 based on the fluorescence of silicon quantum dots
assembled two-dimensional PEG-MnO2 nanosheets hybrid nanoprobe,
Microchim. Acta 187 (2020) 347.
[97] E. Rytting, K.A. Lentz, X.-Q. Chen, F. Qian, S. Venkatesh, A quantitative
structure-property relationship for predicting drug solubility in PEG 400/
water cosolvent systems, Pharmaceut. Res. 21 (2004) 237e244.
[98] H. Yang, J.J. Morris, S.T. Lopina, Polyethylene glycolepolyamidoamine den-
dritic micelle as solubility enhancer and the effect of the length of poly-
ethylene glycol arms on the solubility of pyrene in water, J. Colloid Interface
Sci. 273 (2004) 148e154.
[99] S. John, M. Kuruvilla, A. Joseph, Surface morphological and impedance
spectroscopic studies on the interaction of polyethylene glycol (PEG) and
polyvinyl pyrrolidone (PVP) with mild steel in acid solutions, Res. Chem.
Intermed. 39 (2013) 1169e1182.
[100] M. Mobin, M.A. Khan, Adsorption and corrosion inhibition behavior of
polyethylene glycol and surfactants additives on mild steel in H 2 SO 4,
J. Mater. Eng. Perform. 23 (2014) 222e229.
[101] A. Algaber, E.M. El-Nemma, M.M. Saleh, Effect of octylphenol polyethylene
oxide on the corrosion inhibition of steel in 0.5 M H2SO4, Mater. Chem. Phys.
86 (2004) 26e32.
[102] M. Awad, M. Metwally, S. Soliman, A. El-Zomrawy, Experimental and
quantum chemical studies of the effect of poly ethylene glycol as corrosion
inhibitors of aluminum surface, J. Ind. Eng. Chem. 20 (2014) 796e808.
[103] H. Boudellioua, Y. Hamlaoui, L. Tifouti, F. Pedraza, Effects of polyethylene
glycol (PEG) on the corrosion inhibition of mild steel by cerium nitrate in
chloride solution, Appl. Surf. Sci. 473 (2019) 449e460.
[104] S. Bo
zovic, S. Martinez, V. Grudi c, A novel environmentally friendly syner-
gistic mixture for steel corrosion inhibition in 0.51 M NaCl, Acta Chim. Slov.
66 (2019) 112.
[105] S. Yahya, N. Othman, M. Ismail, Corrosion inhibition of steel in multiple flow
loop under 3.5% NaCl in the presence of rice straw extracts, lignin and
ethylene glycol, Eng. Fail. Anal. 100 (2019) 365e380.
[106] D. Gelman, I. Lasman, S. Elfimchev, D. Starosvetsky, Y. Ein-Eli, Aluminum
corrosion mitigation in alkaline electrolytes containing hybrid inorganic/
organic inhibitor system for power sources applications, J. Power Sources
285 (2015) 100e108.
[107] J. Haque, V. Srivastava, M.A. Quraishi, D.S. Chauhan, H. Lgaz, I.-M. Chung,
Polar group substituted imidazolium zwitterions as eco-friendly corrosion
inhibitors for mild steel in acid solution, Corrosion Sci. 172 (2020), 108665.
[108] B. El Ibrahimi, A. Jmiai, L. Bazzi, S. El Issami, Amino acids and their derivatives
as corrosion inhibitors for metals and alloys, Arab. J. Chem. 13 (2020)
740e771.
[109] Q. Zhang, Y. Li, Y. Lei, X. Wang, H. Liu, G. Zhang, Comparison of the synergistic
inhibition mechanism of two eco-friendly amino acids combined corrosion
inhibitors for carbon steel pipelines in oil and gas production, Appl. Surf. Sci.
583 (2022), 152559.
[110] K. Zhang, W. Yang, X. Yin, Y. Chen, Y. Liu, J. Le, et al., Amino acids modified
konjac glucomannan as green corrosion inhibitors for mild steel in HCl so-
lution, Carbohydr. Polym. 181 (2018) 191e199.
[111] B. El Ibrahimi, N.K. Sebbar, Poly (amino acid) corrosion inhibitors, Polymeric
Corrosion Inhibitors for Greening the Chemical and Petrochemical Industry,
2022, pp. 79e96.
[112] P. Roy, S.K. Saha, P. Banerjee, S. Dey, D. Sukul, Experimental and theoretical
investigation towards anti-corrosive property of glutamic acid and poly-g-
glutamic acid for mild steel in 1 M HCl: intramolecular synergism due to
copolymerization, Res. Chem. Intermed. 43 (2017) 4423e4444.
[113] B. Zhang, J. Li, X. Lv, Y. Cui, Y. Xu, Synthesis of polyaspartic acid/2-amino-2-
methyl-1, 3-propanediol graft copolymer and evaluation of its scale inhibi-
tion and corrosion inhibition performance, Desalination Water Treat. 54
(2015) 1998e2004.
[114] J. Feng, L. Gao, R. Wen, Y. Deng, X. Wu, S. Deng, Fluorescent polyaspartic acid
with an enhanced inhibition performance against calcium phosphate,
Desalination 345 (2014) 72e76.
[115] D. Wang, J. Xu, J. Wang, W. Hu, Preparation and corrosion resistance of
polyaspartic acid-zinc self-assembled film on carbon steel surface, Colloids
Surf. A Physicochem. Eng. Asp. 608 (2021), 125615.
[116] A. Zeino, I. Abdulazeez, M. Khaled, M.W. Jawich, I.B. Obot, Mechanistic study
of polyaspartic acid (PASP) as eco-friendly corrosion inhibitor on mild steel
in 3% NaCl aerated solution, J. Mol. Liq. 250 (2018) 50e62.
[117] R. Cui, N. Gu, C. Li, Polyaspartic acid as a green corrosion inhibitor for carbon
steel, Mater. Corros. 62 (2011) 362e369.
[118] C. Wang, J. Chen, J. Han, C. Wang, B. Hu, Enhanced corrosion inhibition
performance of novel modified polyaspartic acid on carbon steel in HCl so-
lution, J. Alloys Compd. 771 (2019) 736e746.
[119] Y. Chen, X. Chen, Y. Liang, Synthesis of polyaspartic acid/graphene oxide
grafted copolymer and evaluation of scale inhibition and dispersion per-
formance, Diam. Relat. Mater. 108 (2020), 107949.
[120] N. Raghavendra, S.R. Chitnis, D.S. Sheelimath, Anti-corrosion investigation of
polylysine (amino acid polymer) as efficacious corrosion inhibitor for Al in
industrial acidic pickling environment, J. Bio Tribo Corrosion 7 (2021) 1e17.
[121] M. Tsoeunyane, M. Makhatha, O. Arotiba, Corrosion inhibition of mild steel
by poly (butylene succinate)-L-histidine extended with 1, 6-
diisocynatohexane polymer composite in 1 M HCl, Int. J Corrosion 2019
(2019).
C. Verma, M.A. Quraishi, A. Alfantazi et al.
[122] A. Dehghani, G. Bahlakeh, B. Ramezanzadeh, A.H.J. Mofidabadi, Improvement
of the anti-corrosion ability of a silane film with b-cyclodextrin-based
nanocontainer loaded with L-histidine: coupled experimental and simula-
tions studies, Prog. Org. Coating 157 (2021), 106288.
[123] R.S. El-Kamel, A.A. Ghoneim, A.M. Fekry, Electrochemical, biodegradation
and cytotoxicity of graphene oxide nanoparticles/polythreonine as a novel
nano-coating on AZ91E Mg alloy staple in gastrectomy surgery, Mater. Sci.
Eng. C 103 (2019), 109780.
[124] Q.J. Xu, G.D. Zhou, H.F. Wang, W.B. Cai, Electrochemical studies of poly-
aspartic acid and sodium tungstate as corrosion inhibitors for brass and
Cu30Ni alloy in simulated cooled water solutions, Anti-Corrosion Methods
Mater 53 (2006) 207e211.
[125] H. Wang, Q. Wu, C. Li, N. Gu, Copper corrosion inhibition by polyaspartic acid
and imidazole, Mater. Corros. 64 (2013) 347e352.
[126] D. Liu, W. Dong, F. Li, F. Hui, J. Le dion, Comparative performance of poly-
epoxysuccinic acid and polyaspartic acid on scaling inhibition by static and
rapid controlled precipitation methods, Desalination 304 (2012) 1e10.
[127] Y. Xu, L. Zhao, L. Wang, S. Xu, Y. Cui, Synthesis of polyaspartic
acidemelamine grafted copolymer and evaluation of its scale inhibition
performance and dispersion capacity for ferric oxide, Desalination 286
(2012) 285e289.
[128] B. Zhang, D. Zhou, X. Lv, Y. Xu, Y. Cui, Synthesis of polyaspartic acid/3-amino-
1H-1, 2, 4-triazole-5-carboxylic acid hydrate graft copolymer and evaluation
of its corrosion inhibition and scale inhibition performance, Desalination 327
(2013) 32e38.
[129] B. Qian, J. Wang, M. Zheng, B. Hou, Synergistic effect of polyaspartic acid and
iodide ion on corrosion inhibition of mild steel in H2SO4, Corrosion Sci. 75
(2013) 184e192.
[130] Y. Xu, B. Zhang, L. Zhao, Y. Cui, Synthesis of polyaspartic acid/5-aminoorotic
acid graft copolymer and evaluation of its scale inhibition and corrosion
inhibition performance, Desalination 311 (2013) 156e161.
[131] L. Yang, Y. Li, B. Qian, B. Hou, Polyaspartic acid as a corrosion inhibitor for
WE43 magnesium alloy, J. Magnesium Alloys 3 (2015) 47e51.
[132] Y. Gao, L. Fan, L. Ward, Z. Liu, Synthesis of polyaspartic acid derivative and
evaluation of its corrosion and scale inhibition performance in seawater
utilization, Desalination 365 (2015) 220e226.
[133] J. Chen, L. Xu, J. Han, M. Su, Q. Wu, Synthesis of modified polyaspartic acid
and evaluation of its scale inhibition and dispersion capacity, Desalination
358 (2015) 42e48.
[134] M. Migahed, S. Rashwan, M. Kamel, R. Habib, Synthesis, characterization of
polyaspartic acid-glycine adduct and evaluation of their performance as
scale and corrosion inhibitor in desalination water plants, J. Mol. Liq. 224
(2016) 849e858.
[135] S. Shi, X. Zhao, Q. Wang, H. Shan, Y. Xu, Synthesis and evaluation of poly-
aspartic acid/furfurylamine graft copolymer as scale and corrosion inhibitor,
RSC Adv. 6 (2016) 102406e102412.
[136] M. Migahed, S. Rashwan, M. Kamel, R. Habib, Synthesized polyaspartic acid
derivatives as corrosion and scale inhibitors in desalination operations,
Cogent Eng. 4 (2017), 1366255.
[137] S. Zhang, H. Qu, Z. Yang, C-e Fu, Z. Tian, W. Yang, Scale inhibition perfor-
mance and mechanism of sulfamic/amino acids modified polyaspartic acid
against calcium sulfate, Desalination 419 (2017) 152e159.
[138] C. Chai, Y. Xu, S. Shi, X. Zhao, Y. Wu, Y. Xu, et al., Functional polyaspartic acid
derivatives as eco-friendly corrosion inhibitors for mild steel in 0.5 MH 2 SO
4 solution, RSC Adv. 8 (2018) 24970e24981.
[139] J. Chen, C. Wang, J. Han, B. Hu, C. Wang, Y. Zhong, et al., Corrosion inhibition
performance of threonine-modified polyaspartic acid for carbon steel in
simulated cooling water, J. Appl. Polym. Sci. 136 (2019), 47242.
[140] T. Chen, D. Zeng, S. Zhou, Study of polyaspartic acid and chitosan complex
corrosion inhibition and mechanisms, Pol. J. Environ. Stud. 27 (2018).
[141] S. Shi, D. Li, C. Chai, Y. Wu, Y. Xu, Synthesis of a polyaspartic acid/4-(2-
aminoethyl) morpholine graft copolymer and evaluation of its scale and
corrosion inhibition performance, Polym. Adv. Technol. 29 (2018)
2838e2847.
[142] C. Chai, Y. Xu, D. Li, X. Zhao, Y. Xu, L. Zhang, et al., Cysteamine modified
polyaspartic acid as a new class of green corrosion inhibitor for mild steel in
sulfuric acid medium: synthesis, electrochemical, surface study and theo-
retical calculation, Prog. Org. Coating 129 (2019) 159e170.
[143] L. Fu, J. Lv, L. Zhou, Z. Li, M. Tang, J. Li, Study on corrosion and scale inhibition
mechanism of polyaspartic acid grafted b-cyclodextrin, Mater. Lett. 264
(2020), 127276.
[144] I.B. Obot, M.I. Ul-Haq, A. Sorour, N.M. Alanazi, T.M. Al-Abeedi, S.A. Ali, et al.,
Modified-polyaspartic acid derivatives as effective corrosion inhibitor for
C1018 steel in 3.5% NaCl saturated CO2 brine solution, J. Taiwan Inst. Chem.
Eng. 135 (2022), 104393.
[145] M.L. Hallensleben, Polyvinyl Compounds, Others, Ullmann's Encyclopedia of
Industrial Chemistry, 2000.
[146] M. Ahmed, M. Abo-Ellil, Effect of dopant concentration on the electrical
properties of polyvinyl alcohol (PVA), J. Mater. Sci. Mater. Electron. 9 (1998)
391e395.
[147] J.F. Lopes, C. Simoneau, Solubility of polyvinyl alcohol in ethanol, EFSA
Supporting Publications, 2014, p. 660E.
[148] C. Verma, M. Quraishi, Polyvinyl alcohol (PVA) as a biodegradable polymeric
anticorrosive material: a review on present advancements and future di-
rections, Corrosion Eng. Sci. Technol. (2022) 1e17.
433
Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435
[149] S. Umoren, I. Obot, A. Madhankumar, Z. Gasem, Effect of degree of hydrolysis
of polyvinyl alcohol on the corrosion inhibition of steel: theoretical and
experimental studies, J. Adhes. Sci. Technol. 29 (2015) 271e295.
[150] S. Rajendran, S. Sridevi, N. Anthony, A.J. Amalraj, M. Sundaravadivelu,
Corrosion behaviour of carbon steel in polyvinyl alcohol, Anti-corrosion
Methods Mater 52 (2005) 102e107.
[151] S. Umoren, E. Ebenso, P. Okafor, U. Ekpe, O. Ogbobe, Effect of halide ions on
the corrosion inhibition of aluminium in alkaline medium using polyvinyl
alcohol, J. Appl. Polym. Sci. 103 (2007) 2810e2816.
[152] A.A.F. Sabirneeza, S. Subhashini, R. Rajalakshmi, Water soluble conducting
polymer composite of polyvinyl alcohol and leucine: an effective acid
corrosion inhibitor for mild steel, Mater. Corros. 64 (2013) 74e82.
[153] A. Ali Fathima Sabirneeza, S. Subhashini, A novel water-soluble, conducting
polymer composite for mild steel acid corrosion inhibition, J. Appl. Polym.
Sci. 127 (2013) 3084e3092.
[154] A. Ali Fathima Sabirneeza, S. Subhashini, Study of synergistic influence of l-
cysteine on polyvinyl alcoholeTaguchi method: continuous electrochemical
monitoring of corrosion inhibition of mild steel by poly (vinyl alcohol-
cysteine), J. Adhes. Sci. Technol. 29 (2015) 1268e1294.
[155] S. Nwanonenyi, O. Ogbobe, I. Madufor, E. Oguzie, Influence of polyvinyl ac-
etate on the corrosion inhibition of mild steel in sulphuric acidic environ-
ment, Eur. J. Adv. Eng. Technol. 3 (2016) 52e61.
[156] K. Alaoui, Y. El Kacimi, M. Galai, R. Touir, K. Dahmani, A. Harfi, et al., Anti-
corrosive properties of polyvinyl-alcohol for carbon steel in hydrochloric
acid media: electrochemical and thermodynamic investigation, J. Mater.
Environ. Sci. 7 (2016) 2389e2403.
[157] M.I. Abdulwahab, A.B. Ahmed, A.S. Yaro, Corrosion inhibition of low carbon
steel in sulfuric acid using polyvinyl alcohol, Iraqi J. Chem. Petroleum Eng. 17
(2016) 21e36.
[158] A.F.S.A. Rahiman, S. Sethumanickam, Corrosion inhibition, adsorption and
thermodynamic properties of poly (vinyl alcohol-cysteine) in molar HCl,
Arab. J. Chem. 10 (2017) S3358eS3366.
[159] R. Geethanjali, S. Subhashini, Synthesis and kinetics of corrosion inhibition of
water-soluble terpolymer of polyvinyl alcohol functionalized with vinyl
sulfonate and p-vinyl benzene sulfonate, in molar HCl, J. Bio Tribo Corrosion
4 (2018) 1e13.
[160] R. Geethanjali, R. Menaka, S. Subhashini, Gravimetric and electrochemical
study of temperature effect of PVA grafted terpolymer on corrosion inhibi-
tion of mild steel in hydrochloric acid, Mater. Today: Proc. 5 (2018)
16246e16257.
[161] A.S. Al-Gorair, H. Hawsawi, A. Fawzy, M. Sobhi, A. Alharbi, R.A. Hameed, et al.,
Evaluation of the anticorrosion and adsorption properties of polyethylene
glycol and polyvinyl alcohol for corrosion of iron in 1.0 M NaCl solution, Int.
J. Electrochem. Sci. 16 (2021) 2.
[162] M. Abdallah, A.S. Al-Gorair, A. Fawzy, H. Hawsawi, R. Abdel Hameed,
Enhancement of adsorption and anticorrosion performance of two polymeric
compounds for the corrosion of SABIC carbon steel in hydrochloric acid,
J. Adhes. Sci. Technol. 36 (2022) 35e53.
[163] H. Liu, B. Fan, Z. Liu, X. Zhao, B. Yang, X. Zheng, et al., Electronic effects on
protective mechanism of electropolymerized coatings based on N-
substituted aniline derivatives for mild steel in saline solution, J. Ind. Eng.
Chem. 106 (2022) 297e310.
[164] B. Fan, Z. Liu, X. Zhao, H. Liu, G. Fan, H. Hao, Fabrication, characterization and
efficient surface protection mechanism of poly (trans-cinnamaldehyde)
electropolymerized coatings for EH36 steel in simulated seawater, Colloids
Surf. A Physicochem. Eng. Asp. 629 (2021), 127434.
[165] S. John, A. Joseph, M. Kuruvilla, Inhibition of mild steel corrosion using
ChitosanePolyvinyl Alcohol nanocomposite films by SoleGel method: an
environmentally friendly approach, Journal of Bio-and Tribo-Corrosion 3
(2017) 1e9.
[166] S. De, J.L. Lutkenhaus, Corrosion behaviour of eco-friendly airbrushed
reduced graphene oxide-poly (vinyl alcohol) coatings, Green Chem. 20
(2018) 506e514.
[167] G. Hikku, K. Jeyasubramanian, A. Venugopal, R. Ghosh, Corrosion resistance
behaviour of graphene/polyvinyl alcohol nanocomposite coating for
aluminium-2219 alloy, J. Alloys Compd. 716 (2017) 259e269.
[168] J. Zhang, Y. Huang, H. Wu, S. Geng, F. Wang, Corrosion protection properties
of an environmentally friendly polyvinyl alcohol coating reinforced by a
heating treatment and lignin nanocellulose, Prog. Org. Coating 155 (2021),
106224.
[169] M. Kaseem, T. Hussain, S.H. Baek, Y.G. Ko, Formation of stable coral reef-like
structures via self-assembly of functionalized polyvinyl alcohol for superior
corrosion performance of AZ31 Mg alloy, Mater. Des. 193 (2020), 108823.
[170] A. Samide, C. Merisanu, B. Tutunaru, G.E. Iacobescu, Poly (vinyl butyral-Co-
vinyl alcohol-Co-vinyl acetate) coating performance on copper corrosion in
saline environment, Molecules 25 (2020) 439.
[171] Y. Lin, R. Chen, Y. Zhang, Z. Lin, Q. Liu, J. Liu, et al., Sandwich-like polyvinyl
alcohol (PVA) grafted graphene: a solid-inhibitors container for long term
self-healing coatings, Chem. Eng. J. 383 (2020), 123203.
[172] T. Ohara, T. Sato, N. Shimizu, G. Prescher, H. Schwind, O. Weiberg, et al.,
Acrylic acid and derivatives, Ullmann’s Encyclopedia of Industrial Chemistry
(2000). https://doi.org/10.1002/14356007.a01_161.pub4.
[173] K. Kumeta, I. Nagashima, S. Matsui, K. Mizoguchi, Crosslinking reaction of
poly (vinyl alcohol) with poly (acrylic acid)(PAA) by heat treatment: effect of
neutralization of PAA, J. Appl. Polym. Sci. 90 (2003) 2420e2427.
C. Verma, M.A. Quraishi, A. Alfantazi et al. Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435

[174] E. Jabbari, S. Nozari, Swelling behavior of acrylic acid hydrogels prepared by inhibitor of mild steel in normal hydrochloric acid: experimental, spectro-
g-radiation crosslinking of polyacrylic acid in aqueous solution, Eur. Polym. J. scopic and theoretical approach, J. Appl. Electrochem. 51 (2021) 1009e1032.
36 (2000) 2685e2692. [199] V. Dharmalingam, P.A. Sahayaraj, A.J. Amalraj, R. Shobana, R. Mohan, The
[175] G. Li, G. Zhang, R. Sun, C.-P. Wong, Dually pH-responsive polyelectrolyte corrosion inhibition performance of polyacrylic acid with potassium sodium
complex hydrogel composed of polyacrylic acid and poly (2-(dimthylamino) tartrate and Zn2þ for corrosion control of mild steel in aqueous solution, Int.
ethyl methacrylate), Polymer 107 (2016) 332e340. Lett. Chem. Phys. Astron. 61 (2015) 135e146.
[176] H. Ouni, M. Dhahbi, Spectrometric study of crystal violet in presence of [200] V. Dharmalingam, P.A. Sahayaraj, A.J. Amalraj, A.A. Prema, Poly (acrylic acid)
polyacrylic acid and polyethylenimine and its removal by polyelectrolyte and potassium sodium tartrate as effective corrosion inhibitors for mild steel
enhanced ultrafiltration, Separ. Purif. Technol. 72 (2010) 340e346. in aqueous environment, J. Adv. Electrochem. (2016) 37e41.
[177] L. Bromberg, Polyether-modified poly (acrylic acid): synthesis and applica- [201] A. Dwivedi, P. Bharti, S.K. Shukla, Interaction of water soluble polyacrylic acid
tions, Ind. Eng. Chem. Res. 37 (1998) 4267e4274. with mild steel/hydrochloric acid interface, in: IOP Conference Series: Ma-
[178] M. Müller, B. Keßler, J. Fro € hlich, S. Poeschla, B. Torger, Polyelectrolyte com- terials Science and Engineering, vol. 404, IOP Publishing, 2018, 012044.
plex nanoparticles of poly (ethyleneimine) and poly (acrylic acid): prepa- [202] I. Dehri, G. Sigircik, A. Sari, M. Erbil, Inhibition effect of polyacrylic acid and
ration and applications, Polymers 3 (2011) 762e778. its mixture with potassium iodide on mild steel corrosion in acid solution,
[179] T. Grchev, M. Cvetkovska, J. Schultze, The electrochemical testing of poly- Bulg. Chem. Commun. (2018) 60.
acrylic acid and its derivatives as inhibitors of corrosion, Corrosion Sci. 32 [203] X. Gao, W. Li, H. Ma, In situ synthesis of one eco-friendly polyacrylic acid/zinc
(1991) 103e112. colloidal particles doped polyacrylic acid as an efficient corrosion inhibitor
[180] Q. Du, Y. Wang, A. Li, H. Yang, Scale-inhibition and flocculation dual- for iron, Mater. Corros. 71 (2020) 267e279.
functionality of poly (acrylic acid) grafted starch, J. Environ. Manag. 210
(2018) 273e279.
[181] W. Yu, Y. Wang, A. Li, H. Yang, Evaluation of the structural morphology of
Abbreviation
starch-graft-poly (acrylic acid) on its scale-inhibition efficiency, Water Res.
141 (2018) 86e95. %IE: Inhibition efficiency
[182] P. Jitreewas, P. Tansiri, S. Pranee, C. Khemtong, N. Pungwiwat, S. Seeyangnok, BDPs: Biodegradable polymers
Preparation and application of poly (acrylic acid-co-acrylamide) on scale and BDSPs: Biodegradable synthetic polymers
corrosion inhibition, in: Key Engineering Materials vol. 824, Trans Tech Publ, PLA: Poly(lactic acid)
2019, pp. 142e148. PMA: Poly (malic acid)
[183] M. Zhao, M.L. Bruening, Y. Zhou, D.E. Bergbreiter, R.M. Crooks, Effect of pH, PCL: Poly(caprolactone)
fluorination, and number of layers on the inhibition of electrochemical re- PVA: Poly(vinyl alcohol)
actions by grafted, hyperbranched poly (acrylic acid) films, Isr. J. Chem. 37 Cdl: Double layer capacitance
(1997) 277e286. Ch-TH2: Triazine dihydrazide
[184] K. Kamburova, N. Boshkova, N. Boshkov, T. Radeva, Composite coatings with CIs: Corrosion inhibitors
polymeric modified ZnO nanoparticles and nanocontainers with inhibitor for CNTs: Carbon Nanotubes
corrosion protection of low carbon steel, Colloids Surf. A Physicochem. Eng. COC: Cost of corrosion
Asp. 609 (2021), 125741. Ch or CA: Chitosan
[185] T. Shahrabi, B. Ramezanzadeh, G. Bahlakeh, Development of a high- CS: Carbon steel
performance corrosion protective functional nano-film based on poly CV: Cyclic voltammetry
acrylic acid-neodymium nitrate on mild steel surface, J. Taiwan Inst. Chem. DFT: Density functional theory
Eng. 96 (2019) 610e626. Eads: Adsorption energy
[186] X.-J. Ji, Q. Cheng, J. Wang, Y.-B. Zhao, Z.-Z. Han, F. Zhang, et al., Corrosion Ecorr: Corrosion potential
resistance and antibacterial effects of hydroxyapatite coating induced by EDS or EDX:Energy-dispersive X-ray spectroscopy
polyacrylic acid and gentamicin sulfate on magnesium alloy, Front. Mater. EHOMO: Energy of highest occupied molecular orbital
Sci. 13 (2019) 87e98. Eint: Interaction energy
[187] M.T. Majd, T. Shahrabi, B. Ramezanzadeh, Low carbon steel surface modifi- EIS: Electrochemical impedance spectroscope
cation by an effective corrosion protective nanocomposite film based on ELUMO: Energy of lowest unoccupied molecular orbital
neodymium-polyacrylic acid-benzimidazole, J. Alloys Compd. 783 (2019) EOCP: Electrochemical open circuit potential
952e968. ER: Epoxy resin
[188] C. Li, X. Guo, G.S. Frankel, Corrosion inhibition of AA2024-T3 by a coating FMO: Frontier molecular orbital
containing dual-pH sensitive, corrosion inhibitor loaded microspheres, FTIR: Fourier transform infrared
Corrosion Sci. 192 (2021), 109835. G: Graphene
[189] M.A. Amin, S.S. Abd Ei-Rehim, E.E. El-Sherbini, O.A. Hazzazi, M.N. Abbas, GO: Graphene oxide
Polyacrylic acid as a corrosion inhibitor for aluminium in weakly alkaline HOMO: Highest occupied molecular orbital
solutions. Part I: weight loss, polarization, impedance EFM and EDX studies, Icorr: Corrosion current density
Corrosion Sci. 51 (2009) 658e667. LUMO: Lowest unoccupied molecular orbital
[190] S. Umoren, Y. Li, F. Wang, Synergistic effect of iodide ion and polyacrylic acid MCS: Monte Carlo simulations
on corrosion inhibition of iron in H2SO4 investigated by electrochemical MDS: Molecular dynamic simulations
techniques, Corrosion Sci. 52 (2010) 2422e2429. MS: Mild steel
[191] S. Umoren, Y. Li, F. Wang, Influence of iron microstructure on the perfor- MWCNTs: Multi-wall carbon nanotubes
mance of polyacrylic acid as corrosion inhibitor in sulfuric acid solution, NACE: National association of corrosion engineers
Corrosion Sci. 53 (2011) 1778e1785. NMR: Nuclear magnetic spectroscopy
[192] R. Geethanjali, A. Sabirneeza, S. Subhashini, Water-soluble and biodegrad- OBCIs: oil-based corrosion inhibitors
able pectin-grafted polyacrylamide and pectin-grafted polyacrylic acid: OCP: Open circuit potential
electrochemical investigation of corrosion-inhibition behaviour on mild steel PDP: Potentiodynamic polarization
in 3.5% NaCl media, Ind. J. Mater. Sci. 2014 (2014). PPy: Polypyrrole
[193] J.A. Syed, S. Tang, H. Lu, X. Meng, Water-soluble polyanilineepolyacrylic acid Ra: Average roughness
composites as efficient corrosion inhibitors for 316SS, Ind. Eng. Chem. Res. Rct: Charge transfer resistance
54 (2015) 2950e2959. rGO: Reduced graphene oxide
[194] V. Dharmalingam, P.A. Sahayaraj, A.J. Amalraj, S. Rajendran, Antagonistic Rp: Polarization Resistance
effects of polyacrylic acid with Sodium gluconate and Zn2þ for corrosion Rq: Root mean square roughness
control of mild steel in aqueous solution, Int. J. Nano Corr. Sci. Engg. 2 (2015) SBCIs: Solvent-based corrosion inhibitors
11e24. SCE: Saturated calomel electrode
[195] V. Dharmalingam, P. Sahayaraj, A. Amalraj, A. Prema, C. Pragathiswaran, Poly SECM: Scanning electrochemical microscopy
(acrylic acid) and Sodium gluconate as effective corrosion inhibitors for mild SEM: scanning electron microscopy
steel in chloride environment, Int. J. ChemTech Res. 10 (2017) 630e641. SER: State etch rate
[196] P. Jitreewas, S. Pranee, S. Thepwatee, N. Pungwiwat, S. Seeyangnok, Corro- SWCNTs: Single-wall carbon nanotubes
sion Resistance Properties of Poly (Acrylic Acid-Co-Sodium Styrene Sulfo- TEM: Transmission electron microscope
nate) Inhibitors on Low Carbon Steel AISI 1018 in Recirculating Cooling TGA: Thermogravimetric Analyzer
Water, 2018. TLC: Thin layer chromatography
[197] R. Punitha, S.D. Kirupha, S. Vivek, L. Ravikumar, Synthesis and corrosion UVevis: Ultravioletevisible
inhibition studies of modified polyacrylic acid bearing triazole moieties on WBCIs: Water-based corrosion inhibitors
aluminium in alkaline medium, J. Polym. Res. 26 (2019) 1e12. WPU: Waterborne polyurethane
[198] A. Ouass, M. Galai, M. Ouakki, E. Ech-Chihbi, L. Kadiri, R. Hsissou, et al., Poly XPS: X-ray photoelectron spectroscopy
(sodium acrylate) and Poly (acrylic acid sodium) as an eco-friendly corrosion XRD: X-ray diffraction

434
C. Verma, M.A. Quraishi, A. Alfantazi et al. Advanced Industrial and Engineering Polymer Research 6 (2023) 407e435

Chandrabhan Verma works as a researcher at the
Department of Chemical Engineering, Khalifa University of
Science and Technology, P.O. Box 2533, Abu Dhabi, United
Arab Emirates. He did a master of science in organic
chemistry and a PhD in corrosion science and engineering.
He did postdoc studies at the North-West University, South
Africa and King Fahd University of Petroleum and Minerals,
Saudi Arabia. His research mainly focuses on synthesizing
and designing environmentally-friendly corrosion inhibi-
tors useful for several industrial applications. Dr Verma is
the author of several research and reviews articles in
peer-reviewed international journals of ACS, Elsevier,
RSC, Wiley, Springer, etc. He has a total citation of more
than 9500 with an H-index of 55 and an i-10 index of
140. Dr Verma received several awards for his academic achievements. Dr Verma
also edited and authors books for Elsevier, ACS, RSC, Wiley, CRC, Springer, etc. Email:
chandraverma.rs.apc@itbhu.ac.in.
Dr. Rhee, Kyong Yop has been a professor of Mechanical
Engineering at Kyung Hee University (South Korea) since
1999. His main research interests are nanocomposites,
surface treatment, fracture, and composite materials. He
has published 451 scientific papers in the leading inter-
national journals and has led 67 R&D projects. His current
h-index is 63. He earned his BS and MS degrees in me-
chanical engineering from Seoul National University
(South Korea). He earned his PhD in mechanical engi-
neering at the Georgia Institute of Technology followed by
two years Postdoctoral Fellowship at Rutgers University.
Email: rheeky@khu.ac.kr.
NACE International, the Canadian Institute of Mining, Metallurgy and Petroleum, and
the Engineering Institute of Canada. He regularly gives short courses on corrosion/
chemical metallurgy to industry and at international conferences. He has received a
number of awards including the Killam Award for Excellence in Mentoring, the Profes-
sional Engineers and Geoscientists of BC Teaching Award of Excellence, the Materials
Society’s Materials Scientists Distinguished Award, and the Canadian Materials Chem-
istry Award. He was appointed a Chang Jiang Scholar at the China University of Mining
and Technology. Dr. Alfantazi has more than 300 publications including 200 refereed
journal publications. He has also co-edited several books. He has supervised/graduated
more than 22 PhD. students, 25 M.Sc. students and 15 Postdoctoral Fellows. Email:
akram.alfantazi@ku.ac.ae.
Prof. Mumtaz A. Quraishi is a Chair Professor at the
Interdisciplinary Center for Research in Advanced Mate-
rials King Fahd University of Petroleum and Minerals
(KFUPM), Saudi Arabia. He obtained Ph.D. in synthetic
organic chemistry in 1986 from Kurukshetra University
and awarded D.Sc. in 2004 from Aligarh Muslim University
Aligarh in the field of Corrosion Inhibition of Industrial
Metals and Alloys. Before joining KFUPM he was a full
Professor at IIT BHU Varanasi India. He also served as Head
(Chairman) Department of Chemistry IIT BHU. He has
teaching experience of more than 35 years. He received
several national and international awards. Dr. Quraishi is
an Associate editor of Current Material Science Bentham
and a member of Editorial Board of the more than 30 In-
ternational Journals. Dr. Quraishi is a fellow of Royal Society of Chemistry UK and a
member of American Chemical Society. He has published more than 450 Papers in peer
Reviewed Journals having H -index 100 and Citations more than 33000. His Global
status is one in terms of H index in the field of Corrosion Inhibitors. He also authored
and edited a few books at different platforms. Email:maquraishi.apc@itbhu.ac.in.

Akram Alfantazi is currently a Professor of Materials En-

gineering at the Department of Chemical Engineering and
Theme Lead (Materials and Chemistry) in the ENTC. Dr
Alfantazi obtained his PhD in Metallurgical Engineering
from Queen’s University, Canada (1994). In 1996, he joined
Falconbridge Ltd., where he worked as a Project Metal-
lurgist for several years before joining the University of
British Columbia (UBC) in 2001, where he taught and
conducted research in corrosion, electrometallurgy and
electrochemical processes in materials engineering. At
UBC, he was a Professor in the Materials Engineering
Department and Founding Co-Director of the Pipeline
Integrity Institute (PII). From 2006- 2008, he held the
Qatar Petroleum Chair in corrosion. He is a Fellow of

435