Novel hybrid halloysite nanotubes (HHNTs) were developed and used as smart carriers for corrosion protection of steel. For this purpose, as-received halloysite nanotubes (HNTs) were loaded with a corrosion inhibitor, imidazole (IM), by vacuum encapsulation. In the next step, a layer by layer technique was employed to intercalate another inhibitor, dodecylamine (DDA), in the polyelectrolyte multilayers of polyethylenimine and sulfonated polyether ether ketone, leading to the formation of HHNTs. During this process, IM (5 wt %) was successfully encapsulated into the lumen of HNTs, while DDA (0.4 wt %) was effectively intercalated into the polyelectrolyte layers. Later, the HHNTs (3 wt %) were thoroughly dispersed into the epoxy matrix to develop smart hybrid self-healing polymeric coatings designated as hybrid coatings. For a precise evaluation, epoxy coatings containing as-received HNTs (3 wt %) without any loading denoted to as reference coatings and modified coatings containing HNTs loaded with IM-loaded HNTs (3 wt %) were also developed. A comparative analysis elucidates that the hybrid coatings demonstrate decent thermal stability, improved mechanical properties, and promising anticorrosion properties compared to the reference and modified coatings. The calculated corrosion inhibition efficiencies of the modified and hybrid coatings are 92 and 99.8%, respectively, when compared to the reference coatings. Noticeably, the superior anticorrosion properties of hybrid coatings can be attributed to the synergetic effect of both the inhibitors loaded into HHNTs and their efficient release in response to the localized pH change of the corrosive medium. Moreover, IM shows an active release in both acidic and basic media, which makes it suitable for the protection of steel at the early stages of damage, while DDA being efficiently released in the acidic medium may contribute to impeding the corrosion activity at the later stages of deterioration. The tempting properties of hybrid coatings demonstrate the beneficial role of the development of novel HHNTs and their use as smart carriers in the polymeric matrix for corrosion protection of steel.

Multifunctional nanocomposite coatings were synthesized by reinforcing a polymeric matrix with halloysite nanotubes (HNTs) loaded with corrosion inhibitor (NaNO3) and urea formaldehyde microcapsules (UFMCs) encapsulated with a self-healing agent (linseed oil (LO)). The developed polymeric nanocomposite coatings were applied on the polished mild steel substrate using the doctor’s blade technique. The structural (FTIR, XPS) and thermogravimetric (TGA) analyses reveal the loading of HNTs with NaNO3 and encapsulation of UFMCs with linseed oil. It was observed that self-release of the inhibitor from HNTs in response to pH change was a time dependent process. Nanocomposite coatings demonstrate decent self-healing effects in response to the external controlled mechanical damage. Electrochemical impedance spectroscopic analysis (EIS) indicates promising anticorrosive performance of novel nanocomposite coatings. Observed corrosion resistance of the developed smart coatings may be attributed to the efficient release of inhibitor and self-healing agent in response to the external stimuli. Polymeric nanocomposite coatings modified with multifunctional species may offer suitable corrosion protection of steel in the oil and gas industry.

Polymeric-based nanocomposite coatings were synthesized by reinforcing epoxy matrix with titanium nanotubes (TNTs) loaded with dodecylamine (DOC). The performance of the developed nanocomposite coatings was investigated in corrosive environments to evaluate their anti-corrosion properties. The SEM/TEM, TGA, and FTIR analysis confirm the loading of the DOC into the TNTs. The UV-Vis spectroscopic analysis confirms the self-release of the inhibitor (DOC) in response to the pH change. The electrochemical impedance spectroscopic (EIS) analysis indicates that the synthesized nanocomposite coatings demonstrate superior anticorrosion properties at pH 2 as compared to pH 5. The improved anticorrosion properties of nanocomposite coatings at pH 2 can be attributed to the more effective release of the DOC from the nanocontainers. The superior performance makes polymeric nanocomposite coatings suitable for many industrial applications.

The utilization of self-healing cerium dioxide nanoparticles (CeO2), modified with organic corrosion inhibitors (dodecylamine (DDA) and n-methylthiourea (NMTU)), in epoxy coating is an efficient strategy for enhancing the protection of the epoxy coating and increasing its lifetime. Fourier transform infrared (FTIR) spectroscopy analysis was used to confirm the loading and presence of inhibitors in the nanoparticles. Thermal gravimetric analysis (TGA) measurement studies revealed the amount of 25% and 29.75% w/w for NMTU and DDA in the nanoparticles, respectively. The pH sensitive and self-release behavior of modified CeO2 nanoparticles is confirmed through UV-vis spectroscopy and Zeta potential. It was observed, through scanning electron microscopy (SEM), that a protective layer had been formed on the defect site separating the steel surface from the external environment and healed the artificially created scratch. This protective film played a vital role in the corrosion inhibition of steel by preventing the aggressiveness of Cl− in the solution. Electrochemical impedance spectroscopy (EIS) measurements exhibited the exceptional corrosion inhibition efficiency, reaching 99.8% and 95.7% for the modified coating with DDA and NMTU, respectively, after five days of immersion time.

Corrosion and heat treatment studies are essential to predict the performance and sustainability of the coatings in harsh environments, such as the oil and gas industries. In this study, nickel phosphorus (NiP)–titanium (Ti) nanocomposite coatings (NiP-Ti nanoparticles (TNPs)), containing various concentrations of Ti nanoparticles (TNPs) were deposited on high strength low alloy (HSLA) steel through electroless deposition processing. The concentrations of 0.25, 0.50 and 1.0 g/L TNPs were dispersed in the electroless bath, to obtain NiP-TNPs nanocomposite coatings comprising different Ti contents. Further, the effect of TNPs on the structural, mechanical, corrosion, and heat treatment performance of NiP coatings was thoroughly studied to illustrate the role of TNPs into the NiP matrix. Field emission scanning electron microscope (FESEM) and energy dispersive spectroscopy (EDX) results confirm the successful incorporation of TNPs into the NiP matrix. A substantial improvement in the mechanical response of the NiP matrix was noticed with an increasing amount of TNPs, which reached to its ultimate values (hardness 675 Hv, modulus of elasticity 18.26 GPa, and stiffness 9.02 kN/m) at NiP-0.5TNPs coatings composition. Likewise, the electrochemical impedance spectroscopy measurements confirmed a tremendous increase in the corrosion inhibition efficiency of the NiP coatings with an increasing amount of TNPs, reaching ~96.4% at a composition of NiP-0.5TNPs. In addition, the NiP-TNPs nanocomposite coatings also unveiled better performance after heat treatment than NiP coatings, due to the presence of TNPs into the NiP matrix and the formation of more stable (heat resistant) phases, such as Ni3P, Ni3Ti, NiO, etc., during the subsequent processing.

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.The cellulose microfibers (CMFs) were synthesized to assist the self-release of loaded product, that provides better corrosion inhibition and self-healing of epoxy coatings.

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