Методы исследования адсорбции органических соединений при коррозионных исследованиях. Краткий обзор
https://doi.org/10.61852/2949-3412-2026-4-2-1-16
Аннотация
В статье приведен анализ литературы по методам получения изотерм адсорбции органических соединений на поверхности металлов из коррозионной среды. Рассмотрены подходы, которые предполагают прямую зависимость между эффективностью ингибирования и степенью покрытия поверхности. В некоторых работах из гравиметрических измерений получают степень покрытия поверхности адсорбатом. Эффективность ингибирования определялась также из сравнения анодных плотностей тока без и в присутствии ингибиторов при их постоянной концентрации. Приведены также примеры использования методов спектроскопии электрохимического импеданса, эллипсометрии, пьезокварцевого микробаланса, теоретических расчетов при анализе адсорбции органических соединений.
Ключевые слова
Об авторах
Н. П. АндрееваРоссия
119071, г. Москва, Ленинский проспект, д. 31, корп. 4
Ю. И. Кузнецов
Россия
119071, г. Москва, Ленинский проспект, д. 31, корп. 4
Список литературы
1. A. Döner, R. Solmaz, M. Özcan and G. Kardas, Experimental and theoretical studies of thiazoles as corrosion inhibitors for mild steel in sulphuric acid solution, Corros. Sci., 2011, 53, no. 9, 2902–2913. doi: 10.1016/j.corsci.2011.05.027
2. Ю.И. Кузнецов и Л.П. Подгорнова, Ингибирование коррозии металлов гетероциклическими хелатореагентами, В сб. Итоги науки и техники, серия Коррозия и защита от коррозии, Изд. ВИНИТИ, 1989, 15, 132–177.
3. M.A. Quraishi, M.A. Wajid Khan, A. Ajmal and S. Muralidharan, Influence of substituted benzothiazoles on corrosion in acid solution, J. Appl. Electrochem., 1996, 26, no. 12, 1253–1258.
4. Yu.I. Kuznetsov, Organic Inhibitors of Corrosion of Metals. 1996, Plenum Press, New York, 283 p.
5. M. Finšgar and I. Milošev, Inhibition of copper corrosion by 1,2,3-benzotriazole: A review, Corros. Sci., 2010, 52, 2737–2749. doi: 10.1016/j.corsci.2010.05.002
6. M. Mahdavian and S. Ashhari, Corrosion inhibition performance of 2-mercaptobenzimidazole and 2-mercaptobenzoxazole compounds for protection of mild steel in hydrochloric acid solution, Electrochim. Acta, 2010, 55, no. 5, 1720–1724. doi: 10.1016/j.electacta.2009.10.055
7. G. Quartarone, L. Ronchin, A. Vavasori, C. Tortato and L. Bonaldo, Inhibitive action of gramine towards corrosion of mild steel in deaerated 1.0 M hydrochloric acid solutions, Corros. Sci., 2012, 64, 82–89. doi: 10.1016/j.corsci.2012.07.008
8. Ya.G. Avdeev, Nitrogen-containing five-membered heterocyclic compounds as corrosion inhibitors for metals in solutions of mineral acids – A review, Int. J. Corros. Scale Inhib., 2018, 7, no. 4, 460–497. doi: 10.17675/2305-6894-2018-7-4-1
9. I.A. Arkhipushkin, M.O. Agafonkina, L.P. Kazansky, Yu.I. Kuznetsov and Kh.S. Shikhaliev, Characterization of Adsorption of 5-carboxy-3-amino-1.2.4-Triazole towards Copper Corrosion Prevention in Neutral Media, Electrochim. Acta, 2019, 308, 392–399. doi: 10.1016/j.electacta.2019.04.014
10. Ya.G. Avdeev, Inhibitory protection of metals in acid solutions by pharmaceuticals. A critical review, Int. J. Corros. Scale Inhib., 2024, 13, no. 4, 2543–2569. doi: 10.17675/2305-6894-2024-13-4-35
11. Ya.G. Avdeev, Inhibitory protection of metals in acid solutions by hexamethylenetetramine. A review, Int. J. Corros. Scale Inhib., 2025, 14, no. 3, 1241–1267. doi: 10.17675/2305-6894-2025-14-3-13
12. D.M. Jamil, N. Betti, E.M. Ali, A.H. Kadhum and A. Alamiery, Halogen-substituted thiazole-2-formaldehyde derivatives as corrosion inhibitors for carbon steel in acidic media: a comparative study of adsorption behavior and inhibition efficiency, Int. J. Corros. Scale Inhib., 2025, 14, no. 4, 2312–2333. doi: 10.17675/2305-6894-2025-14-4-32
13. Lj. M. Vracar and D.M. Drazic, Adsorption and corrosion inhibitive properties of some organic molecules on iron electrode in sulfuric acid, Corros. Sci., 2002, 44, 1669–1680. doi: 10.1016/S0010-938X(01)00166-4
14. S. Issaadi, T. Douadi and S. Chafaa, Adsorption and inhibitive properties of a new heterocyclic furan Schiff base on corrosion of copper in 1 M HCl: Experimental and theoretical investigation, Appl. Surf. Sci., 2014, 316, 582–589. doi: 10.1016/j.apsusc.2014.08.050
15. S. Vishwanatham and N. Haldar, Furfuryl alcohol as corrosion inhibitor for N80 steel in hydrochloric acid, Corros. Sci., 2008, 50, 2999–3004. doi: 10.1016/j.corsci.2008.08.005
16. A. Khamis, M.M. Saleh, M.I. Awad and B.E. El-Anadouli, Enhancing the inhibition action of cationic surfactant with sodium halides for mild steel in 0.5 M H2SO4, Corros. Sci., 2013, 74, 83–91. doi: 10.1016/j.corsci.2013.04.026
17. H. Huang, Z. Wang, Y. Gong, F. Gao, Z. Luo, S. Zhang and H. Li, Water soluble corrosion inhibitors for copper in 3.5 wt% sodium chloride solution, Corros. Sci., 2017, 123, 339–350. doi: 10.1016/j.corsci.2017.05.009
18. R. Bostan, S. Varvara, L. Ga˘ina and L.M. Muresan, Evaluation of some phenothiazine derivatives as corrosion inhibitors for bronze in weakly acidic solution, Corros. Sci., 2012, 63, 275–286. doi: 10.1016/j.corsci.2012.06.010
19. P. Song, X.-Y. Guo, Y.-Ch. Pan, S. Shen, Y. Sun, Y. Wen and H.-F. Yang, Insight in cysteamine adsorption behaviors on the copper surface by electrochemistry and Raman spectroscopy, Electrochim. Acta, 2013, 89, 503–509. doi: 10.1016/j.electacta.2012.11.096
20. K. Shalabi, O.A. El-Gammal and Y.M. Abdallah, Adsorption and inhibition effect of tetraaza-tetradentate macrocycle ligand and its Ni (II), Cu (II) complexes on the corrosion of Cu10Ni alloy in 3.5% NaCl solution, Colloids Surf., A, 2020, 5, 125653. doi: 10.1016/j.colsurfa.2020.125653
21. Ya.G. Avdeev, A.Yu. Luchkin, and Yu.I. Kuznetsov, Adsorption of IFKhAN-92 Corrosion Inhibitor on Low Carbon Steel from Hydrochloric Acid Solution, Prot. Met. Phys. Chem. Surf., 2013, 49, no. 7, 865–868. doi: 10.1134/S2070205113070046
22. Ya.G. Avdeev, A.Yu. Luchkin, and Yu.I. Kuznetsov, Adsorption of IFKhAN-92 Inhibitor on Low Carbon Steel from Sulfuric Acid Solution, Prot. Met. Phys. Chem. Surf., 2020, 56, no. 7, 1244–1248. doi: 10.1134/S2070205120070035
23. A. Kokalj, A generalized model of corrosion inhibition efficiency for multilayer adsorption, Corros. Sci., 2026, 261, 113626. doi: 10.1016/j.corsci.2026.113626
24. A. Kokalj, Estimating standard adsorption Gibbs energy from corrosion inhibition efficiencies: A case of multilayer adsorption, Corros. Sci., 2026, 258, 113323. doi: 10.1016/j.corsci.2025.113323
25. A. Kokalj, On the use of the Langmuir and other adsorption isotherms in corrosion inhibition, Corros. Sci., 2023, 217, 111112. doi: 10.1016/j.corsci.2023.111112
26. I. Milosev, P. Taheri, B. Kapun, D.K. Kozlica, A. Mol and A. Kokalj, The effect of molecular structure of imidazole-based compounds on corrosion inhibition of Cu, Zn, and Cu-Zn alloys, Corros. Sci., 2024, 240, 112338. doi: 10.1016/j.corsci.2024.112328
27. Yu.I. Kuznetsov, N.N. Andreev and S.S. Vesely, Why we reject papers with calculations of inhibitor adsorption based on data on protective effects, Int. J. Corros. Scale Inhib., 2015, 4, no. 2, 108–109.
28. M.S. Walczak, P. Morales-Gil and R. Lindsay, Determining Gibbs energies of adsorption from corrosion inhibition efficiencies: Is it a reliable approach?, Corros. Sci., 2019, 258, 182–185. doi: 10.1016/j.corsci.2019.04.040
29. M. Dlouhy and A. Kokalj, Coordination of azole-type corrosion inhibitors with copper ions: A DFT study, Corros. Sci., 2025, 257, 113241. doi: 10.1016/j.corsci. 2025.113241
30. X. Guo, X. Zhang, L. Ma, Y. Li, J. Le, Z. Fu, L. Lu and D. Zhang, Understanding the adsorption of imidazole corrosion inhibitor at the copper/water interface by ab initio molecular dynamics, Corros. Sci., 2024, 236, 112237. doi: 10.1016/j.corsci.2024.112237
31. L.P. Kazansky, I.A. Selyaninov and Yu.I. Kuznetsov, Adsorption of 2-mercaptobenzothiazole on copper surface from phosphate solutions, Appl. Surf. Sci., 2012, 258, 6807–6813. doi: 10.1016/j.apsusc.2012.03.097
32. M. Finšgar and D. Kek Merl, An electrochemical long-term immersion and XPS study of 2-mercaptobenzothiazole as a copper corrosion inhibitor in chloride solution, Corros. Sci., 2014, 83, 164–175. doi: 10.1016/j.corsci.2014.02.016
33. I.E. Salama, B.P. Binks, P.I. Fletcher and D.I. Horsup, Adsorption of benzyldimethyldodecylammonium chloride onto stainless steel using the quartz crystal microbalance and the depletion methods: an optimisation study, Colloids Surf., A, 2014, 447, 155–165. doi: 10.1016/j.colsurfa.2014.01.034
34. Yu.I. Kuznetsov, L.B. Maksaeva, M.A. Petrunin and N.P. Andreeva, Adsorption of sodium phenylanthranylate on gold electrode from aqueous solution, Russ. J. Electrochem., 2009, 45, no. 11, 1240–1244. doi: 10.1134/S1023193509110044
35. M.O. Agafonkina, N.P. Andreeva, Yu.I. Kuznetsov and S.F. Timashev, Substituted Benzotriazoles as Inhibitors of Copper Corrosion in Buffer Borate Solutions, Russ. J. of Phys. Chem. A, 2017, 91, no. 8, 1410–1417. doi: 10.1134/S0036024417080027
36. Ю.И. Кузнецов, Д.Б. Вершок и Н.П. Андреева, Влияние электродного потенциала меди на адсорбцию некоторых триазолов в боратном буфере, Коррозия: материалы, защита, 2018, № 12, 20–25.
37. Yu.I. Kuznetsov, M.O. Agafonkina, N.P. Andreeva and D.B. Vershok, Adsorption of 2-mercaptobenzthiazol on copper and MNZh-5-1 alloy and their protection from corrosion in aqueous solutions, Int. J. Corros. Scale Inhib., 2020, 9, no. 1, 344–361. doi: 10.17675/2305-6894-2020-9-1-23
38. S.L. Cohen, V.A. Brusic, F.B. Kaufman, G.S. Frankel, S. Motakef and B. Rush, X-ray photoelectron spectroscopy and ellipsometry studies of the electrochemically controlled adsorption of benzotriazole on copper surfaces, J. Vac. Sci. Technol., 1990, A 8, 2417–2424. doi: 10.1116/1.576708
39. V. Sirtori, F. Zambon and L. Lombardi, XPS and ellipsometric characterization of zinc-BTA complex, J. Electron. Mater., 2000, 29, 463–467.
40. S. Jitian, The ellipsometrical study of adsorption-desorption of the corrosion inhibitors on metallic surfaces, Rom. Rep. Phys., 2013, 65, no. 1, 204–212.
41. M. Levin, P. Wiklund and C. Leygraf, Bioorganic compounds as copper corrosion inhibitors in hydrocarbon media, Corros. Sci., 2012, 58, 104–114. doi: 10.1016/j.corsci.2012.01.009
42. M. Levin, P. Wiklund and H. Arwin, Adsorption and film growth of N-methylaminosubstituted triazoles on copper surfaces in hydrocarbon media, Appl. Surf. Sci., 2007, 254, 1528–1533. doi: 10.1016/j.apsusc.2007.07.023
43. R. Longtin, L. Muresan, M. Porus, P. Maroni, S. Rentsch, M. Buri, P. Gane and M. Borkovec, Probing adsorption of sodium poly(acrylate) at the calcite–water interface by ellipsometry, Colloids Surf., A, 2011, 384, 17–22. doi: 10.1016/j.colsurfa.2011.02.041
44. Yu.I. Kuznetsov, Organic corrosion inhibitors: where are we now? A review. Part I. Adsorption, Int. J. Corros. Scale Inhib., 2015, 4, no. 4, 284–310. doi: 10.17675/2305-6894-2015-4-4-1
45. N.P. Andreeva, Yu.I. Kuznetsov and Kh.S. Shikhaliev, The use of ellipsometry for studying adsorption of organic corrosion inhibitors from aqueous solutions on metals. Review. Part 1. Methods for obtaining adsorption isotherms, Int. J. Corros. Scale Inhib., 2022, 11, no. 4, 1716–1733. doi: 10.17675/2305-6894-2022-11-4-20
46. N.P. Andreeva, Yu.I. Kuznetsov and Kh.S. Shikhaliev, The use of ellipsometry for studying adsorption of organic corrosion inhibitors from aqueous solutions on metals. Review. Part 2. Adsorption of salts of organic acids and azoles, Int. J. Corros. Scale Inhib., 2023, 12, no. 2, 560–565. doi: 10.17675/2305-6894-2023-12-2-10
47. Н.П. Андреева и М.О. Агафонкина, Мониторинг эллипсометрических параметров для исследования адсорбции органических соединений на поверхности металлов из водных растворов, Коррозия: защита материалов и методы исследования, 2025, 3, № 4, 1–16. doi: 10.61852/2949-3412-2025-3-4-1-16
48. Ю.И. Кузнецов, Х.С. Шихалиев, М.О. Агафонкина, Н.П. Андреева, А.М. Семилетов, А.А. Чиркунов, А.Ю. Потапов и В.Е. Соловьёв, Формирование пассивующих слоев замещёнными 1,2,4-триазола на меди в водных растворах и защита ими её от атмосферной коррозии, Журнал физической химии, 2017, 91, № 12, 136–144. doi: 10.7868/S0044453717120147
49. М.И. Темкин, Адсорбционное равновесие и кинетика процессов на неоднородных поверхностях и при взаимодействии между адсорбированными молекулами, Журнал физической химии, 1941, XY, no. 3, 296–297.
50. M.O. Agafonkina, N.P. Andreeva, Yu.I. Kuznetsov and Kh.S. Shikhaliev. Inhibition of the corrosion of metals by additions of bicyclic triazolopyrimidine in neutral chloride solutions. Part 3. Enhancement of the protective capacity of a bicyclic triazolopyrimidine by adding polyethylene glycol and triazoles, Int. J. Corros. Scale Inhib., 2026, 15, no. 2, 35–51. doi: 10.17675/2305-6894-2026-15-2-3
Рецензия
Для цитирования:
Андреева Н.П., Кузнецов Ю.И. Методы исследования адсорбции органических соединений при коррозионных исследованиях. Краткий обзор. Коррозия: защита материалов и методы исследований. 2026;(2):1-16. https://doi.org/10.61852/2949-3412-2026-4-2-1-16
For citation:
Andreeva N.P., Kuznetsov Yu.I. Methods for Studying the Adsorption of Organic Compounds in Corrosion Studies. A Brief Review. Title in english. 2026;(2):1-16. (In Russ.) https://doi.org/10.61852/2949-3412-2026-4-2-1-16
JATS XML