L-cysteine reduced/functionalized graphene oxide application as a smart/control release nanocarrier of sustainable cerium ions for epoxy coating anti-corrosion properties improvement
Graphical abstract
Introduction
Graphene-based nanoparticles are useful reinforcements in the polymeric matrixes due to their high aspect ratio and excellent mechanical properties (Krishnamurthy et al., 2015; Razavi et al., 2017; Javidparvar et al., 2019a). Among different types of graphene-based nanoparticles, graphene oxide (GO) is a popular product due to its facility to synthesize and the possibility of scalable production (Yu et al., 2016; Dimiev and Eigler, 2017). However, due to the presence of the polar functional groups on the surface of GO nanosheets, the low dispersion degree of the nanosheets in the organic coatings (containing nonpolar solvents) is often the main drawback of using the nanosheets in the nanocomposites (Xiang et al., 2017; Chen et al., 2017). Therefore, the reduction of GO can improve the dispersion state of the nanoparticles in the polymeric matrix and so improve the barrier performance of the nanocomposite against the achievement of the corrosive agents to the metal substrate (Li et al., 2016; Ji et al., 2016). In this way, different kinds of chemical reductants can be used to reduce the oxygen functional groups of the GO nanosheets. Although the hydrazine and sodium borohydride are two effective reductants, they are expensive and toxic for the environment and living organisms (Silva et al., 2019). So, the replacement of the compounds with green reductants has been gained increasing interest (De Silva et al., 2017; Ismail, 2019; Aunkor et al., 2016).
Amino acids are widely used as a non-hazardous and relatively inexpensive reductant for reducing the GO-based nanoparticles (Silva et al., 2019; Thakur and Karak, 2015). Wang et al. (2017a) employed alanine, an aliphatic amino acid, as a green reductant for GO nanosheets and found that the one-step reduction process was effective and eco-friendly. l-Cys (HSCH2CH(NH2)CO2H) is another amino acid compound that was used by Wang et al. (2017b) for GO hydrogel reduction. Recently, Liu et al. (2019) investigated the reduction mechanism of a carboplatin Pt(IV) prodrug in human plasma by some small molecules including l-Cys. They concluded that the l-Cys possessed the best results among other used small molecules for the prodrug reduction.
Besides reducing the role of l-Cys, the thiol-amine containing amino acid was used as a potent eco-friendly corrosion inhibitor in the previous works (Ali Fathima Sabirneeza and Subhashini, 2015; Barouni et al., 2010; Stimpfling et al., 2016; Thangakani et al., 2017; Venkatesan and Rajendran, 2014). Wang et al. (2015) investigated the inhibition effect of the l-Cys on the corrosion of bronze coated by a CuCl patina in a simulated acid rain solution and revealed an inhibition efficiency of (IE) = 90%. Thangakani et al. (2017) showed that an excellent corrosion inhibition efficiency (IE = 99%) was obtained in the case of using l-Cys along with the zinc salt for the carbon steel immersed in a corrosive solution. Stimpfling et al. (2016) loaded the l-Cys molecules into different layered double hydroxide (LDH) structures and embedded the pH-sensitive nanocontainer into an epoxy-based coating and applied the nanocomposite on the aluminum alloy 2024 surface. They concluded that the l-Cys released from the carriers in a scratched coating could effectively improve the corrosion inhibition performance of the defected nanocomposite in a saline solution.
In the present study, a new nanocarrier with a high capacity of the cerium ions adsorption/desorption was fabricated through graphene oxide sheets reduction/modification by l-Cys molecules. The cerium modified l-Cys/GO nanosheets were characterized and their corrosion inhibition properties in the saline solution (3.5% NaCl) and the epoxy coating phases were investigated.
Section snippets
Chemicals and materials
In this study, the expandable graphite (purchased from Kropfmuehl Graphite Co. Germany) was used as the initial raw material to produce the graphene oxide sheets. H2O2 (30%), H2SO4 (98%), and KMnO4 were prepared from Aldrich. The l-cysteine, cerium nitrate hexahydrate, sodium nitrate, hydrochloric acid, sodium hydroxide, and N,Ndimethylformamide (DMF) were purchased from Merck. Bisphenol-A epoxy resin (Epiran-01 × 75, EEW 180–230), polyamide hardener (Crayamid 115) and butyl acetate are
Characterization of GO and l-Cys/GO and LCys/GO-Ce
TEM and FE-SEM results of the unloaded GO, unmodified GO loaded by Ce and modified GO loaded by Ce are shown in Fig. 1 and Fig S1 (in Supplamentery part), respectively.
As can be seen in Fig. 1a, the pure GO sheets had a clean surface with the dark regions, indicating that the multi-layers graphene oxide sheets are almost in an agglomerated form. On the other side, the surface of the GO nanosheets modified with cerium is not clean, showing the deposition of fine cerium oxide nanoparticles (Fig. 1
Conclusion
In the present paper, l-Cys was applied for three purposes: (i) GO surface modification and conversion of the non-useful oxygen functional groups (epoxide and hydroxyl) to the useful ones (carboxylic groups), (ii) reduction of GO to improve the dispersion of the nanosheets in the organic coating, and (iii) acting as an organic inhibitor aside the cerium cations as inorganic inhibitor to provide an inhibition synergism. In this way, the synthesized GO nanosheets were modified by l-Cys molecules
CRediT authorship contribution statement
Ali Asghar Javidparvar: Writing - review & editing. Reza Naderi: Writing - review & editing. Bahram Ramezanzadeh: Writing - review & editing.
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.
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