Improved corrosion resistance of mild steel in acidic solution by hydrazone derivatives: An experimental and computational study

Lgaz, Hassane,Chung, Ill-Min,Albayati, Mustafa R.,Chaouiki, Abdelkarim,Salghi, Rachid,Mohamed, Shaaban K. Elsevier 2020 Arabian journal of chemistry Vol.13 No.1

<P><B>Abstract</B></P> <P>Poor corrosion resistance of mild steel (MS) is a serious concern in many industrial applications. Application of corrosion inhibitors is a possible solution to combat steel corrosion. As yet, there is very little research reported focusing on hydrazone derivatives as corrosion inhibitors, here we present a combined experimental and theoretical study of the adsorption of three newly synthesized hydrazones (HDZs), namely, (E)-N′-(4-(dimethylamino)benzylidene)-2-((2,3-dimethylphenyl)amino)benzohydrazide (HDZ-1), (E)-2-((2,3-dimethylphenyl)amino)-N′-(4-methylbenzylidene)benzohydrazide, (HDZ-2) and (E)-N′-benzylidene-2-((2,3-dimethylphenyl)amino)benzohydrazide (HDZ-3) on the MS surface in 1 M HCl. The interaction of HDZs and the metal surface was investigated using electrochemical techniques, X-ray photoelectron spectroscopy (XPS), DFT and molecular dynamic (MD) simulations. XPS shows that inhibitor molecules form a stable layer on steel surface through chemical and physical interactions. HDZs adsorption onto the steel surface was found to follow Langmuir model. Furthermore, electrochemical measurement results demonstrated that our developed inhibitors act as of mixed-type (anodic and cathodic), with HDZ-1 showing the highest polarization resistance and lowest corrosion current density. Scanning electron microscope (SEM) was used to examine the surface morphology of the steel samples. The new hydrazones showed significantly improved steel corrosion resistance, which provides opportunities to explore the inhibitive activity of structurally similar compounds.</P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Synthesis and evaluation of some new hydrazones as corrosion inhibitors for mild steel in acidic media

Lgaz, Hassane,Chaouiki, Abdelkarim,Albayati, Mustafa R.,Salghi, Rachid,El Aoufir, Yasmina,Ali, Ismat H.,Khan, Mohammad I.,Mohamed, Shaaban K.,Chung, Ill-Min Springer-Verlag 2019 Research on chemical intermediates Vol.45 No.4

3.5 중량% NaCl 매질에서 구리에 대한 새로운 티아졸리딘디온 유도체의 부식 억제 특성

하산르가즈 ( Lgaz¸ Hassane ),이한승 ( Lee¸ Han-seung ) 한국건축시공학회 2021 한국건축시공학회 학술발표대회 논문집 Vol.21 No.2

The search for new corrosion inhibitors for different corrosive mediums is a never-ending task. In the present work, the corrosion inhibition behavior and adsorption mechanism of two novel synthetic thiazolidinedione derivatives noted MTZD and ATZD in 3.5 wt.% NaCl solution on copper were investigated. Electrochemical, scanning electron microscope (SEM), atomic force microscopy (AFM) techniques were used along with first-principles DFT calculations. At maximum inhibitor concentration i.e., 300 ppm corrosion inhibition efficiency reached maximum up to 90% and 96% for MTZD and ATZD, respectively, and thereby followed the order of ATZD > MTZD. The inhibition efficiency increased up to 24 h of immersion, and then decreased after 48h immersion. The potentiodynamic curves suggested that the inhibition action of tested compounds is a mixed type of inhibitor. The first-principles DFT calculations suggested that compounds under investigation formed covalent bonds with Cu(111) surface via reactive sites. SEM and AFM results confirmed the formation of protective barrier that prevent corrosion attack.

탄소강 부식 억제제로서 알칸 티올의 Ab-initio DFT 모델링

핫산라기즈 ( Lgaz Hassane ),이한승 ( Lee Han-seung ) 한국건축시공학회 2021 한국건축시공학회 학술발표대회 논문집 Vol.21 No.1

In the present work, we simulated and explained the bonding of three alkanethiols - hexanethiol (HT), decanethiol (DT), and 11-mercaptoundecanoic acid (MDA) - with Fe(110) surface and Fe2 clusters using Density Functional Theory (DFT) to probe the corrosion inhibition mechanisms. The interaction energies computed from periodic DFT calculations successfully predicted the experimental inhibition performance. We have found strong covalent bond formation between S(thiol) and Fe-atoms in both approaches, further confirmed by the projected density of states and electron density difference. Besides, natural bond orbital (NBO) charge distribution showed that DT had stronger electron-donation and back-donation synergic interactions with Fe-atoms.

새로운 히드라존에 의한 염화물 오염 합성 콘크리트 공극 솔루션에서 철근의 부식 억제에 대한 통찰력

하산르가즈 ( Lgaz Hassane ),이한승 ( Lee Han-seung ) 한국건축시공학회 2022 한국건축시공학회 학술발표대회 논문집 Vol.22 No.1

A new hydrazone derivatives namely (E)-N'-(4-(dimethylamino)benzylidene)-2-(5-methoxy-2-methyl-1H-indol-3-yl)acetohydrazide (HIND) has been confirmed for mitigating the corrosion of the steel rebar exposed to chloride contaminated synthetic concrete pore solution (ClSCPS). The mitigation of corrosion properties has been characterized by weight loss and electrochemical methods (Electrochemical impedance, Potentiodynamic polarization studies) as well as surface observations. The presence of HIND in the ClSCPS decreased the corrosion of steel rebar by adsorption of HIND molecules on the surface of the steel rebar. The optimal HIND concentration was 0.5 mmol/L, corresponding to an inhibition efficiency of 88.4%. The use of HIND enables the corrosion process to have a higher energy barrier. X-ray photo electron spectroscopy (XPS), atomic force microscopy (AFM), scanning electron microscopyenergy- dispersive spectroscopy (SEM-EDS), and X-ray diffraction (XRD) spectroscopy interpretations confirmed that HIND mitigates the corrosion attack on the surface steel rebar.

합성 콘크리트 공극 솔루션에서 철근에 히드라존 기반 헤테로고리 화합물의 흡착에 대한 실험 및 계산 통찰력

하산르가즈 ( Lgaz Hassane ),카르틱수비아 ( Karthick Subbiah ),이한승 ( Lee Han-seung ) 한국건축시공학회 2022 한국건축시공학회 학술발표대회 논문집 Vol.22 No.2

The corrosion inhibitive effect of a new hydrazone-based heterocyclic compound for steel in simulated concrete pore solution with 3.5 wt.% sodium chloride was investigated by experimental and computational techniques. Electrochemical studies, up to 30 days of immersion, and surface analysis (X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and scanning electron microscope (SEM)) were performed to assess the corrosion protection abilities of investigated compound for steel rebar. Results showed that adding the organic compound to the chloride contaminated concrete pore solution decreased the corrosion rate of the steel rebar thanks to the effective adsorption of inhibitor molecules. After 30 days of immersion of steel rebar in inhibited chloride contaminated synthetic concrete pore solution, the inhibition efficiency exceeded 80% at low concentration of 1 mmol/L. Computational studies by Density Functional based Tight Binding (DFTB) method revealed the formation of covalent bonds between the hydrazone molecule and the iron surface.

염수 환경에서 탄소강의 피리디늄 이온 액체에 대한 부식 억제 평가 연구

하산르가즈 ( Hassane Lgaz ),이한승 ( Lee Han Seung ) 한국건축시공학회 2023 한국건축시공학회 학술발표대회 논문집 Vol.23 No.2

This study investigates the anti-corrosion properties of two eco-friendly pyridinium ionic liquids; 4DMN and 4DMP, in a 3.5% NaCl solution. Utilizing weight loss tests, EIS, PDP, quantum chemical calculations, and molecular dynamics simulations, the study demonstrates concentration-dependent inhibition efficiencies of 94% and 92% for 4DMN and 4DMP, respectively. The compounds modulate both anodic and cathodic reactions without altering the corrosion mechanism. EIS data suggest that a protective layer forms, supported by FE-SEM and AFM surface analyses, which reveal improved morphology and reduced roughness. Computational validations corroborate these empirical findings, highlighting the feasibility of these ionic liquids for effective, sustainable corrosion mitigation.

Fe(110) 표면의 피리딘 옥심 결합 메커니즘 및 전자 구조 해명: 전산 연구

하산르가즈 ( Hassane Lgaz ),이한승 ( Lee Han-seung ) 한국건축시공학회 2023 한국건축시공학회 학술발표대회 논문집 Vol.23 No.1

The development of corrosion inhibitors with outstanding performance is a never-ending and complex process engaged in by researchers, engineers and practitioners. Computational assessment of organic corrosion inhibitors performance is a crucial step towards the design of new task-pecific materials. Herein, electronic features, adsorption characteristics and bonding mechanisms of two pyridine oximes, namely 2-pyridylaldoxime (2POH) and 3-pyridylaldoxime (3POH) with the iron surface were investigated using molecular dynamics (MD), and self-consistent-charge density-unctional tight-binding (SCC-DFTB) simulations. SCC-DFTB simulations revealed that 3POH molecule can form covalent bonds with iron atoms in its neutral and protonated states, while 2POH molecule can only bond with iron through its protonated form, resulting in interaction energies of -2.534, -2.007, -1.897, and -0.007 eV for 3POH, 3POH+, 2POH+, and 2POH, respectively. Projected density of states (PDOSs) analysis of pyridines-Fe(110) interactions indicated that pyridine molecules chemically adsorbed on the iron surface.

Understanding corrosion inhibition of mild steel in acid medium by new benzonitriles: Insights from experimental and computational studies

Chaouiki, A.,Lgaz, H.,Chung, Ill-Min,Ali, I.H.,Gaonkar, S.L.,Bhat, K.S.,Salghi, R.,Oudda, H.,Khan, M.I. Elsevier 2018 Journal of molecular liquids Vol.266 No.-

<P><B>Abstract</B></P> <P>Two benzonitrile derivatives, namely 4-(isopentylamino)-3-nitrobenzonitrile (PANB) and 3-amino-4-(isopentylamino)benzonitrile(APAB) have been synthesized and evaluated as corrosion inhibitors for mild steel (MS) in 1 M HCl solution at 303 K by gravimetric, potentiodynamic polarization (PDP) curves, and electrochemical impedance spectroscopy (EIS) methods, as well as Density Functional Theory (DFT) and molecular dynamics (MD) simulations. The results suggest that tested compounds are excellent corrosion inhibitors for mild steel with PANB showing superior performance. Polarization measurements revealed that PANB and APAB behaved as mixed type inhibitors. The polarization resistance, according to EIS studies, found to be dependent on the inhibitor's concentration. The adsorption of PANB and APAB on mild steel surface obeyed Langmuir's adsorption isotherm. On the one hand, DFT and MD simulations are being used to explain the effect of the molecular structure on the corrosion inhibition efficiency and on the other hand to simulate the adsorption of benzonitrile derivatives on mild steel surface. The protection of carbon steel in 1 M HCl was confirmed by using scanning electron microscope (SEM) and Atomic Force Microscopy (AFM). Electrochemical, DFT and MD simulations results are in good agreement.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Novel benzonitrile derivatives have been synthesized and characterized. </LI> <LI> Potentiodynamic polarization curves reveal that tested inhibitors act as mixed type. </LI> <LI> The adsorption of two compounds obeys Langmuir adsorption isotherm. </LI> <LI> Surface morphology was examined by SEM and AFM. </LI> <LI> The experimental results were correlated with DFT and MD stimulation results. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Experimental and theoretical investigation of aqueous and methanolic extracts of <i>Prunus dulcis</i> peels as green corrosion inhibitors of mild steel in aggressive chloride media

Pal, Shweta,Lgaz, Hassane,Tiwari, Preeti,Chung, Ill-Min,Ji, Gopal,Prakash, Rajiv Elsevier 2019 Journal of molecular liquids Vol.276 No.-

<P><B>Abstract</B></P> <P> <I>Prunus dulcis</I> (almond) is one of the most commonly ingested dry fruits by peoples in their routine diet plan due to its high nutrition content. However, almond peels are not eaten and thrown as a waste material. The reason is that the peels are not easily digested in human body due to its low solubility in aqueous medium. Also, the peels contain low amount of cyanides. Surprisingly, almond peels also contain various active bio-compounds which have not been explored properly for any industrial purpose. With the idea of utilizing a waste material and checking solution dependability, the aqueous and methanolic extracts of almond peels have been prepared and investigated by experimental techniques and theoretical tools. The protection efficiency of the extracts in reduction of mild steel (MS) dissolution in 0.1 M HCl has been determined by electrochemical methods (impedance analysis and polarization behavior). The results shows that methanolic and aqueous extracts avert 93% and 85% mild steel loss respectively, which portray that methanolic extract is more effective than aqueous extract. This fact is supported by the surface analysis of mild steel samples done by HRSEM and AFM. UV–vis and FTIR spectroscopy analysis reveals the reason that methanol can extract more phytochemcial constituents of almond peels than water. The free energies of adsorption (ΔG°) for both extract's molecules have been determined based on adsorption coefficient (K<SUB>ads</SUB>) obtained from Langmuir isotherm fitting of inhibition data, which suggest that adsorption is neither pure physical nor pure chemical, i.e., mixed type. DFT modeling and Monte carlo simulation techniques are also explored to investigate theoretical adsorption and inhibition characteristics of the molecules, which supports the interpretation of the experimental results.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Almond peels are used for mild steel protection in 0.1 M HCl. </LI> <LI> Methanolic and aqueous extracts of peel provide maximum efficiency of 93% and 85%, respectively. </LI> <LI> UV–vis and FTIR study show that all constituents of peels are present in methanolic extract only. </LI> <LI> Electrochemical investigations suggest a protective barrier formation between steel and HCl. </LI> <LI> Adsorption behaviour of the constituents is also studied by DFT and Monte Carlo simulations. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>