The novel polythiadiazole polymer and its composite with α-Al(OH)3 as inhibitors for steel alloy corrosion in molar H2SO4: Experimental and computational evaluations

https://doi.org/10.1016/j.jiec.2021.09.022Get rights and content

Highlights

  • Novel polythiadiazole and its composite with α-Al(OH)3 were prepared.

  • The protective action of polythiadiazole and α-Al(OH)3@ polyhydrazide on the steel corrosion was evaluated.

  • The inhibition efficiency of ∼97.6% was obtained at 100 ppm of α-Al(OH)3@AMTP composite.

  • The SEM/EDX results indicate that steel surface is protected by α-Al(OH)3@AMTP composite.

  • Computational calculations showed a good agreement with experimental outcomes.

Abstract

Polymer/composite materials have been commonly used as corrosion inhibitors in different fields such as marine, oil field, and engineering industry due to their self-healing and thermal stability features. Herein, novel polythiadiazole, namely poly[(2,6-dicarbonylpyridine)(2,5-dihydrazinyl-1,3,4-thiadiazole)] (AMTP) via the interaction of 2,5-dihydrazinyl-1,3,4-thiadiazole with pyridine-2,6-dicarbonyl dichloride and its composite with α-Al(OH)3-gel were designed in a good yield. The structures of the fabricated materials are characterized by FT-IR, NMR, SEM, and UV–Vis analyses. The protective action of AMTP and α-Al(OH)3@AMTP on the C1018-steel corrosion in molar-sulphuric acid was evaluated by potentiodynamic-polarization (PDP) and electrochemical impedance spectroscopic (EIS) methods. PDP findings presented that the AMTP polymer and α-Al(OH)3@AMTP composite performed as mixed-type inhibitors. The protection capacities of 90.3 and 97.6% were obtained in the presence of optimum dose 100 mg/L of AMTP polymer and α-Al(OH)3@AMTP composite, respectively. The compound's adsorption on C1018-steel follows the Langmuir isotherm model. The SEM/EDX outcomes reveal that the C1018-steel interface is inhibited by AMTP polymer and α-Al(OH)3@AMTP composite. DFT calculations exhibited that the efficiency of the prepared materials correlates well with their electron contributing capability, whereas simulations of Monte Carlo exposed that the favorability and extent of adsorption of additive molecules metal interface establish their corrosion protection routines.

Introduction

Corrosion protection of metals and alloys is a significant subject of practical, ecological, aesthetical, and economical rank. Owing to its cost efficiency and high strength, steel alloys are utilized as a substantial of superior for the structure of manufacturing oil-well processing and pipelines apparatus in the petroleum section. On the other hand, carbon steel is exposed to plain corrosion, particularly in acidic circumstances, and could easily be prone to an acidic medium through acid pickling, cleaning, and descaling, which are renowned industrial processes [1], [2], [3].

Consequently, corrosion inhibition of such steel alloys is of main significance. Amid the various methods of corrosion mitigation, the application of inhibitors is one of the finest choices for impeding the metal's corrosion in several manufacturing procedures [4], [5], [6], [7]. A diversity of carbon-based combinations comprising hetero-atoms (Nitrogen, Oxygen, Sulphur) have free electron lone-pair or heterocyclic inhibitors possess π-electrons and polar groups and result in the transfer of electrons to the metal interface and accordingly are utilized effectively to impede the metal corrosion in the different corrosive environments thru their adsorption on the electrode substrate [8], [9], [10], [11]. These materials interact according to their similarities to be resolutely adsorbed on the metal surface via the functional group's electron density as efficient centers on the bared surface, thus inhibiting the aggressive accomplishment in the acidic solution based on numerous studies [12], [13], [14], [15]. To interact through actives centers or electrons density of the contributor atoms and linked to probable electronic impacts and steric impacts, the inhibitor adsorption relies on the physicochemical characteristics. Furthermore, the adsorption processes as well depend on the metal interface nature, the solution composition, the potential of the electrochemical route at the electrode/electrolyte interface, the pH of the corrosive solution, and the temperature [16], [17], [18]. It is recognized that polymeric materials are adsorbed stronger than their corresponding monomers. Dissimilar to small inhibitor molecules, polymer compounds could cover higher areas on the electrode surface owing to their several adsorption centers for connecting with the electrode interface [19]. Consequently, it is predictable that polymeric materials will be superior corrosion inhibitors to small organic molecules [20]. In this concern, some polymeric materials have been applied as corrosion inhibitors for steel alloys [21], [22], zinc [23], aluminum [24], and other metals and alloys [25], [26].

Active polyhydrazides with some hydrogen bonds exhibited increasing significantly in stretchable, ultra-tough, and improved post crystallization optical property [27]. Polyhydrazides were synthesized according to oxalyl-hydrazinyl for study ionic conductivity [28]. Polyhydrazides contained thiadiazole moiety was prepared to increase antimicrobial action and thermal stability [29]. This study concentrates on polythiadiazole incorporated with Al(OH)3 nanoparticles. Theoretical calculations are used to examine probable relationships among specific reactivity of a molecular system and molecular quantum chemical descriptors, comprising adsorption route, which converts to corrosion protection [30].

The selection of suitable polymers as an inhibitor for corrosion protection is according to the following concerns: (i) have –NH– group, electronegative sulfur, nitrogen, and oxygen heteroatoms as active sites, (ii) could be simply prepared from comparatively inexpensive raw materials with good yield, and (iii) possess high solubility in the corrosive solution. Polythiadiazole discovers very beneficial applications as corrosion inhibitors. In the current study, we have synthesized a novel poly[(2,6-dicarbonylpyridine)(2,5-dihydrazinyl-1,3,4-thiadiazole)] and incorporated with α-Al(OH)3. The corrosion impeding performance of the prepared materials on C1018-steel corrosion in molar sulphuric acid has been examined using PDP, and EIS methods. The C1018-steel surface morphology was explored using SEM/EDX techniques. DFT calculations and MC simulations were also used to discuss the relationship between the molecule structure of inhibitors and protection efficacy.

Section snippets

Materials and solutions

The materials were obtained from Fluka and Aldrich companies. All materials are used without further purification. We checked the melting points by using Gallen Kamp thermoelectric temperature device. The spectra of 1H and 13C NMR were verified in deuterated-dimethyl-sulfoxide with tetra methyl-silane as an internal average via spectrometer Varian Gemini 300 MHz. Spectra of infrared were investigated via potassium bromide wafer on Pye Unicam and a Fourier transform infrared spectrophotometers.

AMTP polymer and α-Al(OH)3@AMTP composite characterization

In the current paper, poly[(2,6-dicarbonylpyridine)(2,5-dihydrazinyl-1,3,4-thiadiazole)] was produced from the interaction of 2,5-dihydrazinyl-1,3,4-thiadiazole with pyridine-2,6-dicarbonyl dichloride. The reaction can be suggested based on nucleophile substitution reaction of hydrazinyl group with carbonyl of acid chloride via elimination of HCl. As a result to these explanation, we organized poly[(2,6-dicarbonylpyridine)(2,5-dihydrazinyl-1,3,4-thiadiazole)] combined in backbone with

Conclusions

In this report, AMTP polymer-based 2,5-dihydrazinyl-1,3,4-thiadiazole with pyridine-2,6-dicarbonyl dichloride under slight reaction conditions, and its composite with α-Al(OH)3 gel were successively prepared and confirmed. According to the empirical investigation, the resulting conclusions were drawn:

  • 1.

    The AMTP polymer has revealed a good protection act for C1018-steel corrosion in molar H2SO4 medium. As the AMTP dose of the study augmented, the protection capacity increasingly improved, and it

CRediT authorship contribution statement

Hany M. Abd El-Lateef: Conceptualization, Supervision, Investigation, Methodology, Resources, Formal analysis, Data curation, Funding acquisition, Writing - original draft, Writing - review & editing. K. Shalabi: Conceptualization, Investigation, Methodology, Resources, Formal analysis, Data curation, Funding acquisition, Writing - original draft, Writing - review & editing. Abdelwahed R. Sayed: Conceptualization, Supervision, Investigation, Methodology, Resources, Formal analysis, Data

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.

Acknowledgement

The authors acknowledge the Deanship of Scientific Research at King Faisal University, Saudi Arabia for financial support under the research group support track (Grant No.1811008).

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