Molecular Dynamics, Monte-Carlo Simulations and Atomic Force Microscopy to Study the Interfacial Adsorption Behaviour of Some Triazepine Carboxylate Compounds as Corrosion Inhibitors in Acid Medium

  • K. Alaoui
  • M. Ouakki
  • A. S. Abousalem
  • H. Serrar
  • M. Galai
  • S. Derbali
  • K. Nouneh
  • S. Boukhris
  • M. Ebn Touhami
  • Y. El KacimiEmail author


Molecular dynamic, Monte-Carlo simulation approach and electrochemical methods were used to study the temperature effects on mild steel (MS) corrosion in 1.0 M of HCl in the absence and presence of triazepine carboxylate compounds. The inhibition action of all triazepine carboxylates compound studied was performed via adsorption on MS surface. Comparison between several adsorption isotherms reveals that the adsorption was spontaneous and followed Langmuir isotherm in HCl for all inhibitors and at all studied temperatures. Furthermore, selection is founded on the correlation coefficient is known nearly linear and value close to one. Kinetic and thermodynamic parameters for all inhibitors led to suggest the occurrence of chemical mechanism and also the spontaneity of the adsorption process on mild steel surface. The corrosion inhibition mechanism was discussed with the light of some triazepine carboxylate compounds constituents. The effect of molecular structure on the inhibition efficiency has been explored by quantum chemical computations and obvious correlations were observed. The binding energies of tested triazepine carboxylate compounds on Fe (110) surfaces were calculated using molecular dynamics simulation. Very good agreement was obtained with the experimental data. In addition, Atomic force microscopy (AFM) indicated that Cl–Me–CN molecules contributed to a protective layer formation by their adsorption on the steel surface. AFM parameters, such as root mean square roughness (Rq), average roughness (Ra), and ten-point height (Sz), revealed that a smoother surface of inhibited mild steel was obtained, compared to uninhibited steel surface.


Macromolecular compounds Molecular dynamic simulation Monte-Carlo simulation Atomic force microscopy (AFM) Kinetic-thermodynamic Electrochemical measurement 


  1. 1.
    Jiang Z, Wang J, Hu Q et al (1995) The influence of 1-(2-pyridylazo)-2-naphthol (PAN) on the corrosion of titanium in 10 N sulfuric acid solution. Corros Sci 37:1245CrossRefGoogle Scholar
  2. 2.
    El-Rehim SSA, Refaey SAM et al (2001) Corrosion inhibition of mild steel in acidic medium using 2-amino thiophenoland 2-cyanomethyl benzothiazole. J Appl Electrochem 31:429CrossRefGoogle Scholar
  3. 3.
    Popova A, Sokolova E, Raicheva S et al (2003) AC and DC study of the temperature effect on mild steel corrosion in acid media in the presence of benzimidazole derivatives. Corros Sci 45:33CrossRefGoogle Scholar
  4. 4.
    Wang HL, Fan HB, Zheng JS (2003) Corrosion inhibition of mild steel in hydrochloric acid solution by a mercapto-triazole compound. Mater Chem Phys 77:655CrossRefGoogle Scholar
  5. 5.
    Bouklah M, Benchat N, Hammouti B et al (2006) Thermodynamic characterisation of steel corrosion and inhibitor adsorption of pyridazine compounds in 0.5 M H2SO4. Mater Lett 60:1901CrossRefGoogle Scholar
  6. 6.
    Popova A, Christov M, Vasilev A (2007) Inhibitive properties of quaternary ammonium bromides of N-containing heterocycles on acid mild steel corrosion. Part II: EIS results. Corros Sci 49:3290CrossRefGoogle Scholar
  7. 7.
    Alaoui K, Touir R, Galai M et al (2018) Electrochemical and computational studies of some triazepine carboxylate compounds as acid corrosion inhibitors for mild steel. J Bio- Tribo Corros 4:37CrossRefGoogle Scholar
  8. 8.
    El Kacimi Y, Galai M, Alaoui K et al (2018) Surface morphology studies and kinetic-thermodynamic characterization of steels treated in 5.0 M HCl medium: hot-dip galvanizing application. Anti Corros Methods Mater 65(2):176–189CrossRefGoogle Scholar
  9. 9.
    Durnie W, Marco RD, Jefferson A et al (1999) Development of a structure—activity relationship for oil field corrosion inhibitors. J Electrochem Soc 146:1751–1756CrossRefGoogle Scholar
  10. 10.
    Oguzie EE, Okolue BN, Ebenso EE el al (2004) Evaluation of the inhibitory effect of methylene blue dye on the corrosion of aluminum in hydrochloric acid. Mater Chem Phys 87:394–401CrossRefGoogle Scholar
  11. 11.
    Tang L, Lia X, Lia L, Qua Q, Mua G, Liua G (2005) The effect of 1-(2-pyridylazo)-2-naphthol on the corrosion of cold rolled steel in acid media: Part 2: inhibitive action in 0.5 M sulfuric acid. Mater Chem Phys 94:353–359CrossRefGoogle Scholar
  12. 12.
    Tang L, Mu G, Liu G (2003) The effect of neutral red on the corrosion inhibition of cold rolled steel in 1.0 M hydrochloric acid. Corros Sci 45:2251–2262CrossRefGoogle Scholar
  13. 13.
    Serrar H, Marmouzi I, Benzekri Z et al (2017) Synthesis and evaluation of novel pyrido[1,2-b][1,2,4]triazine-2,6-dione and pyrido[1,2-b][1,2,4]triazepine-2,7-dione derivatives as antioxidant agents. Lett Org Chem 14:267–277CrossRefGoogle Scholar
  14. 14.
    Stern M, Geary AL (1957) Electrochemical polarization I. A theoretical analysis of the shape of polarization curves. J Electrochem Soc 104:56–63CrossRefGoogle Scholar
  15. 15.
    Tang Y, Yang X, Yang W, Wan R, Chen Y, Yin X (2010) A preliminary investigation of corrosion inhibition of mild steel in 0.5 M H2SO4 by 2-amino-5-(n-pyridyl)-1, 3, 4-thiadiazole: polarization, EIS and molecular dynamics simulations. Corros Sci 52:1801–1808CrossRefGoogle Scholar
  16. 16.
    Salarvand Z, Amirnasr M, Talebian M, Raeissi K, Meghdadi S (2017) Enhanced corrosion resistance of mild steel in 1 M HCl solution by trace amount of 2-phenyl-benzothiazole derivatives: experimental, quantum chemical calculations and molecular dynamics simulation studies. Corros Sci 114:133–145CrossRefGoogle Scholar
  17. 17.
    Obot IB, Obi-Egbedi NO, Ebenso EE, Afolabi AS, Oguzie EE (2013) Experimental, quantum chemical calculations, and molecular dynamic simulations insight into the corrosion inhibition properties of 2-(6-methylpyridin-2-yl) oxazolo [5, 4-f][1, 10] phenanthroline on mild steel. Res Chem Intermed 39:1927–1948CrossRefGoogle Scholar
  18. 18.
    Fouda AS, Ismail MA, Elewady GY, Abousalem AS (2017) Evaluation of 4-amidinophenyl-2,2′-bithiophene and its aza-analogue as novel corrosion inhibitors for CS in acidic media: experimental and theoretical study. J Mol Liq 240:372–388. CrossRefGoogle Scholar
  19. 19.
    Fouda AS, Ismail MA, Abousalem AS, Elewady GY (2017) Experimental and theoretical studies on corrosion inhibition of 4-amidinophenyl-2,2′-bifuran and its analogues in acidic media. RSC Adv 7:46414–46430. CrossRefGoogle Scholar
  20. 20.
    Sun H, Ren P, Fried JR (1998) The COMPASS force field: parameterization and validation for phosphazenes. Comput Theor Polym Sci 8:229–246CrossRefGoogle Scholar
  21. 21.
    El Faydy M, Galai M, Rbaa M, Ouakki M, Lakhrissi B, Touhami ME, Y. El Kacimi (2018) Synthesis and application of new quinoline as hydrochloric acid corrosion inhibitor of carbon steel. Anal Bioanal Electrochem 10(7) 815–839Google Scholar
  22. 22.
    Khamis E (1990) The effect of temperature on the acidic dissolution of steel in the presence of inhibitors. Corrosion 46:476–484CrossRefGoogle Scholar
  23. 23.
    Elayyachy M, El Idrissi A, Hammouti B (2006) New thio-compounds as corrosion inhibitor for steel in 1 M HCl. Corros Sci 48:2470–2479CrossRefGoogle Scholar
  24. 24.
    El Nemr A, Moneer AA, Khaled A, El Sikaily A, El-Sai GF (2014) Modeling of synergistic halide additives’ effect on the corrosion of aluminum in basic solution containing dye. Mater Chem Phys 144:139–154CrossRefGoogle Scholar
  25. 25.
    Dhar HP, Conway BE, Joshi KM (1973) On the form of adsorption isotherms for substitutional adsorption of molecules of different sizes. Electrochim Acta 18:789–798CrossRefGoogle Scholar
  26. 26.
    Avci G (2008) Inhibitor effect of N,N’-methylenediacrylamide on corrosion behavior of mild steel in 0.5 M HCl. Mater Chem Phys 112:234–238CrossRefGoogle Scholar
  27. 27.
    Bayol E, Gurten AA, Dursun M, Kayakırılmaz K (2008) Adsorption behavior and ınhibition corrosion effect of sodium carboxymethyl cellulose on mild steel in acidic medium. Acta Phys Chim Sin 24:2236–2242CrossRefGoogle Scholar
  28. 28.
    El-Sayed M, Sherif (2006) Effects of 2-amino-5-(ethylthio)-1,3,4-thiadiazole on copper corrosion as a corrosion inhibitor in 3%NaCl solutions. Appl Surf Sci 252:8615–8619CrossRefGoogle Scholar
  29. 29.
    Szauer T, Brandt A (1981) On the role of fatty acid in adsorption and corrosion inhibition of iron by amine fatty acid salts in acidic solution. Electrochim Acta 26:1257–1260CrossRefGoogle Scholar
  30. 30.
    Abd E, Rehim SS, Ibrahim MAM, Khalid KF (2001) The inhibition of 4-(2′-amino-5′-methylphenylazo) antipyrine on corrosion of mild steel in HCl solution. Mater Chem Phys 70:268–273CrossRefGoogle Scholar
  31. 31.
    Noor EA, Al-Moubaraki AH (2008) Thermodynamic study of metal corrosion and inhibitor adsorption processes in mild steel/1-methyl-4-styryl pyridinium iodides/hydrochloric acid systems. Mater Chem Phys 110:145–154CrossRefGoogle Scholar
  32. 32.
    Behpour M, Ghoreishi SM, Soltani N, Salavati NM, Hamadanian M, Gandomi A (2008) Electrochemical and theoretical investigation on the corrosion inhibition of mild steel by thiosalicylaldehyde derivatives in hydrochloric acid solution. Corros Sci 50:2172–2181CrossRefGoogle Scholar
  33. 33.
    El Ouali I, Hammouti B, Aouniti A, Ramli Y, Azougagh M, Essassi EM, Bouachrine M (2010) Thermodynamic characterisation of steel corrosion in HCl in the presence of 2-phenylthieno (3, 2-b) quinoxaline. J Mater Environ Sci 1:1–8Google Scholar
  34. 34.
    Singh AK, Quraishi MA (2010) The effect of some bis-thiadiazole derivatives on the corrosion of mild steel in hydrochloric acid. Corros Sci 52:1373–1385CrossRefGoogle Scholar
  35. 35.
    El Belghiti M, Karzazi Y, Dafali A, Hammouti B, Bentiss F, Obot IB, Bahadur I, Ebenso EE (2016) Experimental, quantum chemical and Monte Carlo simulation studies of 3, 5-disubstituted-4-amino-1, 2, 4-triazoles as corrosion inhibitors on mild steel in acidic medium. J Mol Liq 218:281–293CrossRefGoogle Scholar
  36. 36.
    Saha SK, Hens A, Murmu NC, Banerjee P (2016) A comparative density functional theory and molecular dynamics simulation studies of the corrosion inhibitory action of two novel N-heterocyclic organic compounds along with a few others over steel surface. J Mol Liq 215:486–495CrossRefGoogle Scholar

Copyright information

© Springer Nature Switzerland AG 2018

Authors and Affiliations

  1. 1.Laboratory of Materials Engineering and Environment: Modelling and Application, Faculty of ScienceUniversity Ibn TofailKenitraMorocco
  2. 2.Chemistry Department, Faculty of ScienceMansoura UniversityMansouraEgypt
  3. 3.Laboratory of Organic, Organometallic and Theoretical Chemistry, Faculty of ScienceIbn Tofaïl UniversityKenitraMorocco
  4. 4.Laboratory of Physics of Condensed Matter Physics DepartmentIbn Tofail UniversityKenitraMorocco

Personalised recommendations