Application of polymer corrosion inhibitors in metal corrosion control: a review

doi:10.21203/rs.3.rs-4079905/v1

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Application of polymer corrosion inhibitors in metal corrosion control: a review

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Corrosion can bring serious safety issues, environmental issues, and economic losses. The use of corrosion inhibitors is an important technology for controlling metal corrosion. Compared to small molecule corrosion inhibitors, polymer corrosion inhibitors have better film-forming ability, multifunctionality, viscosity, high temperature resistance, solubility flexibility, and more attachment sites, making them one of the hotspots for the future development of corrosion inhibitors. Here, we review the research progress of natural polymers, polymeric surfactant, polymeric ionic liquids, β-cyolodextrin-based polymers and polymeric nanocomposite as corrosion inhibitors. These types of polymer corrosion inhibitors do not require a high molecular weight to achieve their desired functions and exhibit excellent corrosion inhibition performance. However, from the current application situation, polymer corrosion inhibitors still have some drawbacks. For example, although natural polymer modified polymers do not pollute the environment, their extraction and separation operations are cumbersome, and it is difficult to accurately analyze the active components of polymer corrosion inhibitors; Chemically synthesized polymer corrosion inhibitors still pose a threat to the environment and are not conducive to ecological protection. Here, we review the scientific research of polymer corrosion inhibitors and discuss solutions to make them practical industrial corrosion inhibitors. The major points are the following: 1) Whether substances with good corrosion inhibition performance can be grafted onto the polymer has become a key point in preparing efficient and soluble polymeric corrosion inhibitors; 2) Research and optimization of polymer synthesis processes or extraction and modification methods of natural polymer from the perspectives of material sources, solubility, dosage, and composition; 3) Develop inexpensive, efficient, and environmentally friendly polymer corrosion inhibitors to promote their practical industrial applications. We aim to propose broad application prospects and development potential for polymer corrosion inhibitors in industry.

Metal corrosion control

Polymeric inhibitors

Isothermal adsorption

Synthesis and modification

Corrosion media

Electrochemical evaluation

Carbon steel, its alloys, and other metallic materials are widespread used in industrial production due to their good plasticity, ease of processing, and outstandingly mechanical behavior (Musa et al. 2012). It has been applied widely in water treatment fields such as industrial water circulating control system, hot water boiler, reverse osmosis water-treating system, oil gas field, and seawater desalination plants. Metal corrosion causes accidents due to a decrease in mechanical strength, while also causing huge economic losses. The preparation and cleaning of metal surfaces involve activities such as acid washing, pickling, and descaling (Tiu and Advincula 2015). During the operation, corrosion caused by the acidic media such as hydrochloric acid (HCl) or sulfuric acid (H₂SO₄). In the petroleum industry, metal corrosion is also serious in oilfield production pipelines and storage tanks (Mishra et al. 2016). Seawater is widely used as circulating cooling water for coastal power plants, which can alleviate the shortage of freshwater resources and reduce production costs (Wang et al. 2022). However, it inevitably involves corrosion industrial issues of metal equipment. Adding corrosion inhibitors is one of the most extensive and efficient application ways in various corrosive media (Ganjoo et al. 2023; Verma et al. 2022; Verma et al. 2023; Verma et al. 2022). Corrosion inhibitor is an additive that can reduce the rate of industrial metal corrosion. When present in an appropriate concentration and form in environmental media, it can prevent or slow down metal corrosion. Corrosion inhibitors can significantly alleviate the corrosion of pipelines or equipment in industrial applications.

According to the main chemical substances, they can be divided into inorganic corrosion inhibitors, organic corrosion inhibitors, and polymer corrosion inhibitors (Figure 1) (Dwivedi et al. 2017; Goyal et al. 2018; Verma et al. 2017). Inorganic corrosion inhibitors, such as chromates, molybdates, tungstate salts, nitrates, and nitrites, have been discontinued due to environmental toxicity. Organic corrosion inhibitors mainly adsorb on metal surfaces, isolate water molecules and corrosive media, prevent metal corrosion, and are relatively more effective and environmentally friendly. Inorganic corrosion inhibitors mainly retard both Tafel reactions and are referred to as anodic or cathodic corrosion inhibitors (Noorbakhsh Nezhad et al. 2020; Ma et al. 2021). Meanwhile, organic corrosion inhibitors mostly inhibit the Tafel reaction at the same time and are called hybrid corrosion inhibitors (Verma et al. 2021; Verma et al. 2018a). Organic small molecule corrosion inhibitors can adsorb on metal surfaces to form molecular films to prevent corrosion, but their corrosion protection time is relatively short and their protective effect on high-strength steel pipes is poor (Huang et al. 2022). Polymers are composed of many structural units, and compared to small molecules, their van der Waals forces between molecules exceed their chemical bonding energy, making them difficult to evaporate or decompose. They have good stability and can function in different corrosive environments.

In recent years, polymer corrosion inhibitors have attracted the attention of researchers due to their low cost, stable performance, and non-toxicity (Fathima Sabirneeza et al. 2015; Saviour A. Umoren and Ubong M. Eduok 2016; Uriondo et al. 2015). It has gradually replaced traditional heterocyclic corrosion inhibitors and become an environmentally friendly corrosion inhibitor. Polymer molecules contain main chain macromolecules with substituent groups (−N=N−, R−NH₂, R−COOH, etc.), which have been used for anti-corrosion coatings or corrosion inhibitors. The adsorption on metal surfaces and their corresponding adhesion properties have an inhibitory effect on corrosion (Finšgar and Jackson 2014). The mechanism of action of polymer inhibitors and heterocyclic inhibitors is similar, generally relying on adsorption on metal substrates to form a covering layer that blocks the corrosive media. The stability and barrier effect of polymer films depend on their solubility in the media, and effective dissolution can ensure the effective adhesion of polymer films. The hydrophilic and hydrophobic properties of polymers ensure that the molecular film formed can prevent corrosion and be stabilized. The appropriate ratio of hydrophilic and hydrophobic parts is crucial for the polymeric corrosion inhibition performance (Verma et al. 2018). Many natural products and chemically synthesized polymers have efficient corrosion inhibition capabilities and have received widespread attention, especially in composite coatings (Umoren and Solomon 2014; Umoren and Solomon 2019). Compared to small molecule organic inhibitors, polymeric inhibitors can introduce more adsorption groups on a single molecule by adjusting the number of repeating units and take advantage of their electron-rich positions to create complexes with metal ions, occupying huge regions, or they can form hybridization/complexes with inorganic corrosion inhibitors to make them effective corrosion inhibitors (Umoren and Eduok 2016; Umoren and Solomon 2014). When considering the design of polymer corrosion inhibitor molecules, on the one hand, the influence of the introduction of heteroatoms on the corrosion inhibition performance of polymer corrosion inhibitors is considered. The heteroatoms O, N, S, and P adsorb with metals and possess both electron donor and acceptor properties. Heteroatoms can generate electrons or π bonds, which can interact with the empty d orbitals of metals to form a metal protective layer (Verma et al. 2018b).

This review presents recent developments and some advances in the design and application of polymers as corrosion inhibitors. In general, natural polymers, polymeric surfactant, polymeric ionic liquids, β-cyolodextrin-based polymers and polymeric nanocomposite as corrosion inhibitors will be summarized, which may be useful for researchers, entrepreneurs and engineers in the field of functional polymers and metal protection.

Natural polysaccharide polymers (Fig. 2), such as chitin (the main component of hard shells in shrimp and beetles), chitosan (deacetylated chitin), starch, as well as lignin and lignin fibers, are key research objects for the application of corrosion inhibitors and have achieved good research results. The corrosion inhibition effect of polysaccharides is directly related to their adsorption effect on metals, which hinders the entry of corrosive active ingredients into the metal surface. They are environmentally friendly macromolecular corrosion inhibitors with chemical stability and biodegradability (Raja et al. 2013). These active ingredients that inhibit metal corrosion are mainly extracted from natural resources and have the characteristics of low cost, renewability, and easy availability (Rahim et al. 2008). There is a lot of interest in naturally occurring compounds because they improve the environmental performance of the product, making it more in line with environmental requirements, have infinitesimal/reduced risk of contamination. Table 1 summarizes the reported literature on natural polymers as metal corrosion inhibitors.

2.1 Starch

Starch is a high molecular weight carbohydrate formed by the polymerization of glucose molecules. It can be regarded as a high polymer of glucose and is also one of the important sugars for humans and animals. It can be composed of branched and straight chains composed of multiple monosaccharide molecules. Starch has extremely stable chemical properties, making it a very durable substance in nature. Natural starches also have anti-corrosion effects on metals. Rosliza et al. (2010) They studied the use of cassava starch as a corrosion inhibitor to improve the corrosion resistance of AA6061 alloy in seawate with the efficiency of 93% at starch concentration of 1000 ppm.

However, molecular starch has low solubility and surface adhesion and therefore has not been widely used. Physical or chemical modification of them can improve their corrosion protection. Deng et al. (2021) have grafted acrylamide (AA) with cassava starch. The results showed that the efficiency was 90.6% of 1.0 g/L CS-AAGC as corrosion inhibition in 1.0 M H₃PO₄ . Table 1 summarizes other corrosion inhibition experiments of starch and its derived polymers. There is a lot of scope for enhancing the corrosion inhibition properties of starch by selecting more effective chemical modification and compounding methods.

2.2 Cellulose

Cellulose is the most abundant natural polymer compound, and its production raw materials come from wood, cotton, wheat straw, reed, mulberry bark and sugarcane bagasse. Natural cellulose has little corrosion inhibiting effect on metals. Due to its limited solubility in polar solvents, cellulose usually needs to be chemically modified by adding functional groups (Rajeswari et al. 2013). Solomon et al. (2010) studied the inhibition properties of carboxymethyl cellulose (CMC) on carbon steel in sulfuric acid medium. The results showed that at 30°C, the corrosion inhibition efficiency of 0.5 g/L CMC was 64.8%. Sobhi et al. (2018) studied the non-toxic green corrosion inhibitor methyl hydroxyethyl cellulose on copper. The corrosion inhibition efficiency reached 90.29% at 4 g/L in 1 M HCl solution. Gan et al. (2018) synthesized boric acid aminated citric acid cellulose (BACC) inhibitor from bagasse cellulose with citric acid, diethanolamine and boric acid. The corrosion inhibition efficiency for A3 steel reached 88.33% at 200 mg L^-1. Al Kiey et al. (2021) synthesized cellulose tetrazolium (CTZ) (Fig. 3.) on carbon steel in 1 M HCl medium and CTZ had the highest efficiency of 94.2% (100 ppm).

Although the corrosion inhibition performance of modified cellulose has been improved, it is still not sufficient to meet the industrial requirements for corrosion inhibitors. Cellulose can synergistically act with halogenated ions and other synergists to improve performance. Arukalam et al. (2014) studied the corrosion inhibition effect of hydroxyethyl cellulose (HEC) with halide additives on mild steel and reached 92.74% with 2 g/L of HEC and 0.5 g/L of KI in 0.5 M H₂SO₄. Thus, cellulose in combination with the synergistic effect is improved over that of a single cellulose corrosion inhibitor.

2.3 Chitosan

Chitosan is a polysaccharide compound obtained by N-deacetylation of chitin. Chitin, chitosan, and cellulose have similar molecular structures in their main chains. Cellulose is a hydroxyl group at the C2 position, while chitosan is an amino substituted group at the C2 position. In addition to its biodegradability, cell affinity, and related biological effects similar to other natural products, chitosan also has its unique properties, especially chitosan containing free amino groups, which is the only alkaline substance in natural polysaccharides. Chitosan can effectively improve the adhesion and corrosion inhibition properties of chitosan derivatives by introducing polar functional groups, making it an environmentally friendly corrosion inhibitor.

Zhang et al. (2023) studied two chitosan derivatives, namely N-phenylthiourea chitosan (CS-PT) and N-phenyl-O-benzylthiourea chitosan (CS-PT-Bn). The experimental results showed that the inhibition rates of CS-PT and CS-PT-Bn at 100mg/L were 98.4% and 98.5%, respectively. Zhang et al. (2023) reported chitosan derivatives with different degrees of substitution on mild steel in 1 M HCl and showed a good inhibition performance with 97.01% at 200 mg/L. The functionalization of chitosan is a powerful way to effectively improve the protective properties of chitosan.

2.4 Pectin

Pectin is usually extracted from citrus and apples. The ability of pectin to reduce metal corrosion is due to the presence of carboxyl (-COOH) and carboxymethyl (-COOCH3), which makes it a green corrosion inhibitor with corrosive properties in different media (Chauhan et al. 2012).

Fiori-Bimbi et al. (2015) studied pectin extracted from lemon peel as an environmentally friendly mild steel corrosion inhibitor in hydrochloric acid solution. The results showed that the highest corrosion inhibition efficiency of 94.2% was achieved at a concentration of 2.0 g L^-1. Abou-Elseoud et al. (2021) studied pectin extracted from beet pulp under acidic conditions by enzymatic or acid digestion. At 1.0 g/L, the inhibition efficiencies reached a maximum of 91.5% and 93.9% for acid- and enzyme-extracted pectin, respectively. The corrosion inhibition effects of pectins from different sources and different extraction methods are not the same. Modification of pectin can improve its corrosion inhibition properties.

2.5 Exudate gums

The evolution of natural tree resin as an effective corrosion inhibitor due to its unique chemical composition has attracted much attention in the field of corrosion. Depending on the composition, gum can be dissolved in water or absorb water to form a gel. Barrodi et al. (2023) tudied the corrosion protection performance of xanthan gum (TG) and ceftriaxone (Cef) for mild steel in hydrochloric acid solution. The maximum inhibition efficiency of 98.1% was achieved when the concentration of TG-Cef was 250 ppm. As a non-toxic and non-hazardous polymer corrosion inhibitor with good surface covering ability and retardation efficiency, exudate gum has great potential in the field of corrosion inhibitors.

2.6 Plant polysaccharides

Currently, choosing low-cost and eco-friendly corrosion inhibitors have been combined and formed the main research trend. The polysaccharides contain functional groups with anticorrosive properties. Their electronegativity allows such corrosion inhibitors to isolate the corrosive media by adsorbing on the metal surface to form a barrier layer. Liu et al. (2022) extracted mushroom polysaccharide (LNT) to study the corrosion inhibition properties. When the concentration was 100 mg/L in 1 M HCl, its corrosion inhibition on Q235 steel reached 92.66%. Mobin et al. (2017) studied plantain polysaccharides on carbon steel in 1 M HCl solution and reached to a maximum of 93.54% at 1000 ppm. When selecting plant corrosion inhibitor materials, factors such as plant species, cost and material sources must be considered. At the same time, various plant extraction techniques will produce different chemical active ingredients, which will affect the corrosion inhibition effect. Therefore, choosing low-cost and efficient plant polysaccharide corrosion inhibitors is an important issue.

Surfactants can be categorized on the basis of the chemistry of their polar head (Chowdhury et al. 2019). They can be classified as anionic, cationic, nonionic and amphoteric. The corrosion protection properties of some different types of polymeric surfactant corrosion inhibitors are written in Table 2. Cationic Surfactants have a positive charge on the polar head and may be present only in a certain pH range. Cationic surfactants ionize in aqueous solution and have a positive charge on the surface active portion (Zakharova et al. 2019). Cationic polymer surfactants are stable and widely used. Cationic polymer surfactants form strong adsorption layers and hydrophobicize the surfaces of these materials. Anionic surfactants have hydrophilic groups that are negatively charged at the polar head, such as carboxylates (RCOO^-), sulfonates (RSO^3-) or sulfates (RO-SO^3-) (Hibbs 2006). When these surfactants are dissolved in water, negatively charged particles (anions) are produced. Anionic surfactants, which have different tolerances for different types of salts, are less well documented for applications in the metal corrosion inhibition category. Nonionic surfactants have uncharged polar head groups. In general, nonionic surfactants are not as soluble in water as ionic surfactants. Typical nonionic surfactants are Tween 80, Triton X-100, Brij-35, and alkyl ethers of polyethylene glycol and polypropylene glycol. Amphoteric surfactants contain both positively and negatively charged groups in their molecular structure. The molecular structure has both positive and negative charges.

Polymeric surfactants have many advantages and are gaining popular attention in applications. In terms of synthesis, polymer surfactants offer some flexibility and can be selected according to the characteristics and requirements of the use. While conventional surfactants are challenging to produce on a large scale due to harsh conditions and numerous steps, polymeric surfactants are easily obtainable and have high yields. In addition to this, polymeric surfactants are synthesized using environmentally friendly solvents during the synthesis process and they are usually synthesized at lower reaction temperatures using aqueous or solvent-free techniques (Pirsaheb et al. 2022). Their amphiphilic nature gives them good solubility in both polar and non-polar solutions.

Simultaneously, the large molecular size of polymer surfactants gives them many adsorption sites, which can improve the adsorption capacity and corrosion inhibition capacity on metal surfaces. Their amphiphilic nature gives them good solubility in both polar and non-polar solutions. In terms of solubility, polymer corrosion inhibitors can solve the solubility problem of conventional polymer corrosion inhibitors. Cationic and anionic surfactants, these charged polymer surfactants are not limited by solubility issues.

Polymer surfactants can reduce the amount of corrosion inhibitors and improve corrosion inhibition efficiency through synergistic effects. Wang et al. (2021) studied an environmentally friendly corrosion inhibitor consisting of grape seed proanthocyanidin extract (GSPE) and Tween-80 for mild steel in 1 M HCl. The blended corrosion inhibitor of GSPE and Tween-80 improved the corrosion inhibition performance of mild steel by 96.48% as compared to pre-blended. Zhang et al. (2019) investigated the corrosion inhibition properties of 1-(2,5-dioxoimidazolidin-4-yl)urea (DMU) and Tween-80 on mild steel in 1 M HCl solution. DMU-Tween-80 behaved as a hybrid inhibitor with an optimal inhibition efficiency of 96.35%. Ramji et al. (2008) studied the corrosion inhibition of brass by 2-mercaptobenzothiazole (MBT) and Tween-80 in 0.2 M NaCl. At the optimal concentration, the mixed addition increased the inhibition to 94.0%.

Polymeric surfactants (PS) are another highly water-soluble corrosion inhibitor that has recently emerged with a number of advantages, including ease of synthesis, high solubility, and enhanced metal surface protection. They are characterized by a water-soluble polar head and a water-insoluble polar tail. The adsorption ability of surfactants between oil-water, water-air, and water-metal surfaces enables them to diffuse in aqueous solutions or electrolytes (Tyagi and Tyagi 2009).

Ionic liquid corrosion inhibitors are usually modified on the basis of imidazole, thiazole, pyridine, acrylamide, ammonium, phosphorus and so on. Polymer ionic liquid according to the different molecular structure, usually can also be divided into the following categories, imidazole, acrylamide, ammonium, chitosan and so on. Imidazole derivatives with heteroatoms, such as N, S, π-bonds and aromatic rings, can be widely used in polymeric ionic liquids as active sites. Table 3 summarizes the literature reports on polymeric ionic liquids as corrosion inhibitors. Kamali Ardakani et al. (2020) reported the imidazole-derived polymeric ionic liquid poly[3-butyl-1-vinylimidazolium bromide] (PIL) and studied the corrosion inhibition properties of mild steel specimens immersed in 1.0 M HCl. The experimental results showed that the adsorption of PIL on the mild steel surface conformed to the Frumkin adsorption isotherm model. Based on the results of Tafel plot, PIL is considered as a hybrid corrosion inhibitor with cathodic control advantages. The top and side views of the equilibrium configurations of the corrosion inhibitor molecules adsorbed onto the surface of the mild steel specimen into the 1.0 M HCl establish that the adsorption process occurs by replacing corrosive agents, such as chloride ions, with inhibitor molecules on the metal surface. The adsorption pattern is shown in Fig. 5.

Huang et al. (2019) synthesized bisimidazole monomer-targeted drugs with different backbones through a multi-step copolymerization reaction (Fig.6.), exploiting the self-organizing properties of polypyrrole to form aggregates and without the use of organic solvents in the self-aggregation, and investigated the corrosion inhibition properties on copper in 0.5 M H₂SO₄. The tests showed that the studied PIL aggregates were protected against anodic and cathodic corrosion processes in sulfuric acid solution. XRD and SEM further showed that the investigated PIL aggregates were metal anti-corrosive in acidic solutions.

Acrylamide with the chemical formula CH₂=CHC(O)NH₂and its polymer derivative ionic liquids are also used in the corrosion protection of metallic acid solutions. Atta et al. (2015b) prepared viscous polyionic liquid AMPS/AA-QA by polymerization of, diethylethanolamine with polymerizable monomers such as 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid under solvent-free conditions and evaluated its corrosion inhibition properties as a steel in acidic chloride solutions. The experimental results showed that AMPS/AA-QA is an efficient corrosion inhibitor and the inhibition rate was 93.7% when the concentration of AMPS/AA-QA is 25 ppm. El Tamany et al. (2018) studied three new acrylamide polymer ionic liquids on carbon steel in 1 M HCl. Electrochemical tests showed that the synthesized corrosion inhibitor improved the corrosion protection of the carbon steel surface in acidic corrosive media due to the strong binding of anions and cations in the structure of the ionic liquid.

Ammonium-based ionic liquids are another common type of ionic liquid compounds, the derivatives of which are also used in metal corrosion protection, as ammonium-based il is easy to prepare, cost competitive and less toxic (Bhatt et al. 2015). Udabe et al. (2020) investigated four different ionic liquid monomers and polymer coatings containing hexoxycoumarate anions and different polymerizable countercations and tested their corrosion inhibition properties on the surface of mild steel AS1020. Among the coumalate ionic liquid monomers, the most promising inhibitors were those coupled to ammonium ions with 99.1% inhibition efficiency in solution, followed by imidazole, pyridine and aniline.

Chitosan (CS) ionic liquid polymer has gained attention as a green corrosion inhibitor. Functionalized modification of chitosan can produce new materials. Elsaeed et al. (2018) investigated the corrosion properties of four chitosan-derived polymeric ionic liquids (PILs) on carbon steel in 1 M HCl. The addition of polymeric ionic liquids hindered the rate of hydrogen generation. Experiments showed that CSPTA-lauric could reach 98.6% of slow release efficiency at a concentration of 250 ppm.

Poly ionic liquids (PILs) are a special class of polymer compounds designed with a wide range of monomers to provide unique properties for specific applications (Mecerreyes 2011). PILs have a macromolecular structure consisting not only of a polymer backbone but also of at least ionic liquid (IL) monomers, which together with other polymer species yield other properties of conventional ILs, such as stability in aqueous media, the presence of polymer chains that displace more water molecules from the metal surface, mechanical stability, auto-assembly, and most importantly, the presence of multiple adsorption centers contributes to a slower desorption process and facilitates the formation of coordination complexes with metal surfaces (Fig. 7.) (Abdul Rahiman and Sethumanickam 2017).

Base on β-cyolodextrin (β-CD) compounds are used in the development of corrosion-resistant substances as for their low-cost, good water solubility, and efficient corrosion inhibition. β-CD is a oligomer containing 7 glycosidic unitsto form a large macrocyclic (Challa et al. 2005). It has an inner cavity conical structure with hydrophilicity on the outer surface and hydrophobicity on the inner surface. Has a large spatial interior, π-bonds, and reactive chemical reaction groups (Fig. 8. ). There are heteroatoms (N, O, S, etc.) in the internal structure, whose lone electron pairs provide empty d orbitals to metals (Fe, Al, Cu, Zn, etc.). This is beneficial for development β-CD as a new type of corrosion inhibitor (Chauhan et al. 2021). Table 4 summarizes the reported literature on β-CD-based polymers as metal corrosion inhibitors.

Modification of β-cyclodextrin is an effective method to improve its corrosion inhibition properties, including natural polymer modification, synthetic polymer modification, and supramolecular (host-guest) systems. Natural polymer-modified β-cyclodextrins are of interest because of their low price and non-toxicity. Cao et al. (2021) synthesized a new type of graft polymer based on xanthan gum (XG) and β-CD, and tested its performance on X80 steel in 1 M H₂SO₄. The experiments showed that β-CD-XG had better corrosion inhibition performance compared with XG. Cao et al. (2021) also evaluated the corrosion inhibition effect of β-CD-XG on L80 steel.with 94.74% at 293 K at 200 mg/L. The results showed that β-CD-XG belongs to the hybrid corrosion inhibitor, which mainly inhibits the dissolution of anode metal through dense adsorption film.

Synthetic polymers modified with β-cyclodextrin are also one of the powerful ways to enhance the corrosion inhibition properties because synthetic polymers have large molecular sizes and have more functional active sites that can be better covered on the metal surface for protection. Wang et al. (2021) synthesized β-cyclodextrin grafted polyacrylamide (β-CD-PAM) and investigated its corrosion inhibition performance for pipeline steel (X80 steel). The results showed that the efficiency value was 92.48% at 200 mg /L in 1 M sulfuric acid solution.

In the CDs structure, β-CD molecule has a height of 0.79 ± 0.01 nm and an outer diameter of 1.54 ± 0.04 nm, and is used as the host cavity, suitable for forming supramolecular complexes with the guest part (Loftsson et al. 2019). The host-guest complexes are chemically stable and provide strong protection for metals as corrosion inhibitors. Yang et al. (2019) synthesized a water-soluble host-guest complex containing carboxymethylation (CM), β-CD and aniline trimer (AT) as corrosion inhibition on Q235 carbon steel in 1 M HCl solution. In the presence of AT-CM-β-CD, the inhibition efficiency is significantly improved to 99.2%. Incorporation of an encapsulated corrosion inhibitor in β-CD allows the inhibitor to be released and adsorbed at the corrosion initiation site. Monticelli et al. (2019) investigated the effect of complexes formed by β-CD and 5-mercapto-1-phenyltetrazolium (MPT) on the corrosion protection properties of silane coatings on bronze in normal and concentrated synthetic acid rain. The temporal evolution of the polarization resistance values in concentrated synthetic acid rain for 20 days and the polarization curves recorded at the end of the immersion showed that the coatings containing the β-CD-MPT complex provided higher protection compared to coatings containing only MPT or only β-CD.

β-CD based corrosion inhibitors can cover a large area of the metal surface, forming a dense and strong film. Despite the attention paid to the modification of β-cyclodextrins, problems such as the use of harmful reagents in the synthesis of corrosion inhibitors, incomplete corrosion profiles of various metals, and unclear mechanisms still need to be overcome.

Nanoscale carbon nanoparticles are becoming more and more widely used in corrosion prevention applications. Nanoscale carbon materials with excellent properties can not only functionalize polymers and provide good wear resistance, but also act as corrosion inhibitors to improve the corrosion resistance of polymers. Some types of polymer/nanocomposites are summarized in Fig. 9. Table 5 summarizes the reported literature on polymeric nanocomposites as metal corrosion inhibitors.

Mobin et al. (2022) synthesized a novel ionic liquid, L-proline nitrate with graphene oxide nanohybrids (IL GO) as corrosion inhibition on mild steel in 1 M HCl with the inhibition efficiency of 86.5 at 250 ppm. The adsorption of IL-GO on the surface of mild steel is in accordance with the Langmuir model, which includes the interaction of chemisorption and physisorption.

Metal nanoparticles have small size, large surface area to volume ratio and unique surface structure. There is a wide variety of metal oxide nanoparticles such as TiO₂, Cu₂O, ZnO, etc. with different structures and excellent optical, magnetic, mechanical property and thermal performance. Therefore, the use of NPs in conductive polymer coatings can enhance electrochemical corrosion protection and strong properties such as thermal stability and mechanical strength. Solomon et al. (2017) investigated the corrosion inhibition properties of carboxymethyl cellulose/nanosilver composites on St37 steel in 15% H₂SO₄ medium. It was found that the composites prevented both anodic and cathodic reactions and their adsorption could be explained by the Langmuir adsorption isotherm. The corrosion inhibition of CMC/AgNPs at 60 °C was 96.37% as determined by weight loss method. Gouda et al. (2021) synthesized novel cellulose derivatives containing metal (Cu, Fe, Ni) oxide nanoparticles and investigated their protective properties against c-steel corrosion in hydrochloric acid. The results confirm that the protective capacity increases with increasing inhibitor concentration and the adsorption of the nanocomposites as hybrid inhibitors at the metal interface follows the isothermal Langmuir model. The protective efficiency reaches 88.1, 93.2, 96.1 and 98.6% for PAC/CuO NP, PAC/Fe₃O₄NPs and PAC/NiO NPs at a concentration of 250 ppm, respectively. Meanwhile, El-Lateef et al. (2020) also investigated the corrosion inhibition performance of carboxymethyl cellulose/metal (Fe, Cu and Ni) nanocomposites on carbon steel in hydrochloric acid solution. The PDP data showed that the nanocomposites have good corrosion protection properties and are hybrid corrosion inhibitors. The highest protective powers of CMC and CMC/Fe NP, CMC/Cu NP and CMC/Ni NP composites were 76.6, 94.9, 96.2 and 98.4% at 400 mg L^-1, respectively. While polymer/nanocomposite coatings are receiving attention, the conditions affecting the corrosion performance of the coatings need to be investigated, and most importantly, the dispersion of nanomaterials in the polymer matrix can be solved by using dispersion techniques such as ultrasonication, choosing the appropriate nanomaterials particle size, surface area, and shape, and so on. In addition to this, the application of low-cost, high-performance green nanocomposites is also a new area to be developed.

In recent years, environmentally friendly and green natural nanomaterials have also appeared in the popular consciousness. For example, Wang et al. (2022) investigated the extraction and isolation of GSP, prepared GSP-loaded maize protein-NaCas composite nanoparticles. Corn protein contains sufficient hydrophobic amino acids, which gives it the ability to form spherical nanoparticles, and NaCas can also be used as an emulsifier/stabilizer to increase the efficiency and improve the aggregation of corn protein. The loading of anthocyanins with zein-NaCas can both stabilize the structure of anthocyanins and achieve better practical utility. The experimental results showed that the prepared colloidal particles were stable over a wide range of ionic strengths and pH values, and were able to adapt to changes in seawater environment. Moreover, the electrochemical data showed that the corrosion inhibition efficiency of NPs-GSP on Q235 steel in seawate could reach 96.49% at a concentration of 200 mg/L.

The wide use of nanomaterials in corrosion inhibitors is due to the fact that it not only improves the efficiency of corrosion inhibition of metals in corrosive solutions, but also improves their abrasion resistance against metal substrates. Different nanomaterials have different properties and selectivity, the more common are carbon materials and metal nanoparticles, and in recent years environmentally friendly and non-toxic natural type nanomaterials are also the main direction of research.

The development and application of polymer corrosion inhibitors have played a role in positively affecting the losses caused by metal corrosion, providing feasible solutions to prevent metal corrosion. Polymers are composed of repeating units of monomers, which can form linear, branched, hyperbranched, cross-linked, and branched structures. These materials do not require a high molecular weight to achieve the desired functions. Polymers as corrosion inhibitors have many advantages, such as low dosage, good solubility, high temperature resistance, and having multiple adsorption sites, which have great application prospects in the field of corrosion inhibition. Polymers as corrosion inhibitors also have some drawbacks, such as difficulties in separation, extraction, and characterization of natural polymer modified polymer corrosion inhibitors, as well as difficulty in determining their corrosion inhibiting active components. It is difficult to accurately analyze the corrosion inhibition mechanism of polymer corrosion inhibitors, which also limits further research and development of natural polymer modified polymers. For artificially synthesized polymer corrosion inhibitors, such as polymer surfactants, polymer ionic liquids, cyclodextrin grafted polymers, and polymer nanocomposite corrosion inhibitors, they have varying degrees of toxicity and environmental pollution, which are not conducive to the protection of the ecological environment. Therefore, this review aims to summarize the research methods of polymer corrosion inhibitors and their corrosion inhibition mechanisms that have shown excellent corrosion inhibition performance in recent years, and point out some shortcomings and future development prospects of polymer corrosion inhibitors.

Although polymer corrosion inhibitors have many advantages in metal corrosion inhibition, there is still room for exploration. Research and optimization of polymer synthesis processes or extraction and modification methods for natural polymer materials; Developing efficient and environmentally friendly polymer synthesis processes or improving methods for extracting from natural polymers; Controlling the molecular weight of the polymer while grafting small molecule substances with good corrosion inhibition performance onto the polymer can become a key point in preparing efficient and soluble polymer corrosion inhibitors; The mechanism of action, corrosion process, and structure-activity relationship of polymer corrosion inhibitors need to be fully studied; Especially for composite polymers with uneven composition, design composite materials with responsive release in special environments, analyze their corrosion inhibition mechanism, and expand their application range; Utilize the synergistic corrosion inhibition effect of polymer corrosion inhibitors combined with other treatment agents to achieve multifunctional treatment effects; In future research, develop inexpensive, efficient, biodegradable and environmentally friendly polymer corrosion inhibitors, and promote their industrialization process.

Funding This research was supported by the National Natural Science Foundation of China (22271070), Harbin Institute of Technology “Double First Class” Discipline Construction Fund (2023SYLHY07), and the Project of Improving the Innovation Ability of Medium and Small-Sized Technology Based Enterprises in Shandong Province (2022TSGC1313).

Conflict of interest The authors declare that they have no confict of interest.

Consent for publication All authors have reviewed and approved the final version of the manuscript, and they are aware of and agree to the submission of the manuscript for publication.

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Application of polymer corrosion inhibitors in metal corrosion control: a review

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Abstract

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1. Introduction

2. Natural Polymers for Inhibition of Metal Corrosion

3. Polymeric surfactants for Inhibition of Metal Corrosion

4. Poly ionic liquids for Inhibition of Metal Corrosion

5. β-cyolodextrin-based polymers for Inhibition of Metal Corrosion

6. Polymeric nanocomposites for Inhibition of Metal Corrosion

7. Challenges and prospects

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