cpomaemКоррозия: защита материалов и методы исследованийTitle in englishИФХЭ РАН10.61852/2949-3412-2024-2-2-122-136cpomaem-60Research ArticleСтатьиО защите меди дикарбоновыми кислотамиAbout the corrosion protection of copper by dicarboxylic acidsКузнецовИ. А.KuznetsovI. A.

Ленинский просп.31, корп. 4, Москва, 119071

Leninsky pr. 31, 119071 Moscow

anarenen@gmail.comВершокД. Б.VershokD. B.

Ленинский просп.31, корп. 4, Москва, 119071

Leninsky pr. 31, 119071 Moscow

Институт физической химии и электрохимии им. А.Н. Фрумкина Российской академии наук (ИФХЭ РАН)РоссияA.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of SciencesRussian Federation20242506202402122136Copyright © Кузнецов И.А., Вершок Д.Б., 20242024Кузнецов И.А., Вершок Д.Б.Kuznetsov I.A., Vershok D.B.This work is licensed under a Creative Commons Attribution 4.0 License.https://www.cpmrm.ru/jour/article/view/60

В качестве ингибиторов коррозии (ИК) меди в нейтральных хлоридсодержащих растворах исследованы дикарбоновые кислоты и их соли. Одна из них, сукцинат натрия, в боратном буферном растворе (рН 7,4), содержащем 10 ммоль NaCl, уменьшает величину тока пассивации iп и увеличивает потенциал локальной депассивации Елд. Натриевые соли смеси алкенилянтарных кислот (НСАЯК) с числом углеродных атомов в алкениле nc=12–15 (КАП-25) являются более гидрофобными и за счет этого показывают лучшие защитные свойства. В том же растворе они при меньших концентрациях Син уменьшают iп и существенно повышают Елд. Другой гидрофобный ИК, тридеканоат натрия с nc=12, показал лучшую эффективность при стабилизации пассивного состояния меди по сравнению с сукцинатом натрия. Показано, что пассивационные свойства известного ИК олеата натрия, также имеющего двойную связь, и НСАЯК близки. Для сравнения эффективности этих ИК проведены ускоренные коррозионные испытания в условиях влажной атмосферы с ежесуточной конденсацией влаги на образцах меди, запассивированной в водных растворах НСАЯК, олеата или тридеканоата натрия. Показано, что в отсутствии хлоридов лучшие защитные свойства показал раствор НСАЯК, но, если после пассивации медных образцов их на 10 секунд погружали в воду, содержащую 1 г/л NaCl, защитные свойства НСАЯК становились слабее, чем у тридеканоата натрия. Для усиления защиты меди анионами НСАЯК в присутствии хлоридов использовали добавки 2-меркаптобензотиазола (2-МБТ), способного образовывать труднорастворимые комплексы с Cu(I). Исследования проводили методом спектроскопии электрохимического импеданса (СЭИ) и с помощью коррозионных испытаний. Показано, что в растворе 3,5% NaCl, содержащем только НСАЯК, полученные годографы описывались эквивалентной электрической схемой Рэндлса-Эршлера, а в присутствии 2-МБТ добавлялась Rс–Cс цепочка, характеризующая свойства слоя сформированного комплекса. Сравнение рассчитанных значений Rс позволило выявить наилучшие композиции ИК. Показано, что малые добавки 2-МБТ значительно усиливают защитное действие НСАЯК, причем наблюдается синергетический эффект: композиция этих ИК может быть эффективнее самого 2-МБТ, который в нейтральных средах малорастворим. Вывод о взаимном усилении защиты меди этими ИК был подтвержден коррозионными испытаниями.

Some salts of dicarboxylic acids were investigated as corrosion inhibitors (CI) for copper in neutral chloride-containing solutions. One of them, sodium succinate, in borate buffer solution (pH 7.4) containing 10 mmol NaCl, decreases the value of passivation current density ip and increases the local depassivation potential Eld. Mixture of alkenylsuccinic acids sodium salts (SAS) with the number of carbon atoms in the alkenyl nC=12–15 (KAP-25) are more hydrophobic than sodium succinate and due to this show better protective properties. In the same solution, they decrease ip at lower concentrations of Cinh and significantly increase Eld. Another hydrophobic CI, sodium tridecanoate with nC=12, showed better efficiency in stabilizing the passive state of copper. The passivation properties of the sodium oleate, well-known CI, also having a double bond, and SAS were shown to be close. In order to compare the efficiency of these CIs, accelerated corrosion tests were carried out in a humid atmosphere with daily condensation of moisture on copper samples passivated in aqueous solutions of SAS, sodium oleate or sodium tridecanoate. It was shown that in the absence of chlorides, the best protective properties were shown by the SAS solution, but if after passivation of copper samples they were immersed for 10 seconds in water containing 1 g/L NaCl, the protective properties of the SAS became weaker than those of sodium tridecanoate. To enhance the protection of copper by AS anions in the presence of chlorides, additives of 2-mercaptobenzothiazole (2-MBT), capable of forming hard-soluble complexes with Cu(I), were used. Studies were carried out by electrochemical impedance spectroscopy (EIS) and by corrosion tests. It was shown that in the 3.5% NaCl solution containing only SAS, the obtained hodographs were described by the equivalent electrical scheme of Randles-Erschler, and in the presence of 2-MBT the Rc–Cc chain characterizing the properties of the formed complex layer was added. Comparison of the calculated Rc values made it possible to identify the best CI compositions. It was shown that small additions of 2-MBT significantly enhance the protective effect of SAS, and a synergistic effect is observed: the composition of these CIs can be more effective than 2-MBT itself, which is little soluble in neutral media. The conclusion about mutual strengthening of copper protection by these CIs was confirmed by corrosion tests.

защита медидвухосновные кислотыкарбоновые кислотыСЭИингибиторы коррозии меди2-МБТprotection of copperdicarboxylic acidsEIScorrosion inhibitors2-mercaptobenzothiazoleReferencesYu.I. Kuznetsov and L.P. Kazansky, Physicochemical aspects of metal protection by azoles, Russ. Chem. Rev., 2008, 77, no. 3, 219–232. doi: 10.1070/RC2008v077n03ABEH003753Yu.I. Kuznetsov and L.P. Kazansky, Physicochemical aspects of metal protection by azoles, Russ. Chem. Rev., 2008, 77, no. 3, 219–232. doi: 10.1070/RC2008v077n03ABEH003753N.K. Allam, A.A. Nazeer and E.A. Ashour, A review of the effects of benzotriazole on the corrosion of copper and copper alloys in clean and polluted environments, J. Appl. Electrochem., 2009, 39, 961–969. doi: 10.1007/s10800-009-9779-4N.K. Allam, A.A. Nazeer and E.A. Ashour, A review of the effects of benzotriazole on the corrosion of copper and copper alloys in clean and polluted environments, J. Appl. Electrochem., 2009, 39, 961–969. doi: 10.1007/s10800-009-9779-4M. 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.2010.05.002M. 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.2010.05.002M. Petrović Mihajlović and M.M. Antonijević, Copper Corrosion Inhibitors. Period 2008–2014. A Review, Int. J. Electrochem. Sci., 2015, 10, 1027–1053. doi: 10.1016/S1452-3981(23)05053-8M. Petrović Mihajlović and M.M. Antonijević, Copper Corrosion Inhibitors. Period 2008–2014. A Review, Int. J. Electrochem. Sci., 2015, 10, 1027–1053. doi: 10.1016/S1452-3981(23)05053-8Yu.I. Kuznetsov, Organic corrosion inhibitors: Where are we now? A review. Part II. Passivation and the role of chemical structure of carboxylates, Int. J. Corros. Scale Inhib., 2016, 5, no. 4, 282–318. doi: 10.17675/2305-6894-2016-5-4-1Yu.I. Kuznetsov, Organic corrosion inhibitors: Where are we now? A review. Part II. Passivation and the role of chemical structure of carboxylates, Int. J. Corros. Scale Inhib., 2016, 5, no. 4, 282–318. doi: 10.17675/2305-6894-2016-5-4-1O.A. Goncharova, A.Yu. Luchkin, N.N. Andreev, Yu.I. Kuznetsov, N.P. Andreeva and S.S. Vesely, Protection of copper by treatment with hot vaporous of octadecylamine, 1,2,3-benzotriazole and their mixture, Mater. Corros., 2018, 70, no. 1, 161–168. doi: 10.1002/maco.201810366O.A. Goncharova, A.Yu. Luchkin, N.N. Andreev, Yu.I. Kuznetsov, N.P. Andreeva and S.S. Vesely, Protection of copper by treatment with hot vaporous of octadecylamine, 1,2,3-benzotriazole and their mixture, Mater. Corros., 2018, 70, no. 1, 161–168. doi: 10.1002/maco.201810366Yu.I. Kuznetsov, Triazoles as a class of multifunctional corrosion inhibitors. A review. Part I. 1,2,3-Benzotriazole and its derivatives. Copper, zinc and their alloys, Int. J. Corros. Scale Inhib., 2018, 3, 271–307. doi: 10.17675/2305-6894-2018-7-3-1Yu.I. Kuznetsov, Triazoles as a class of multifunctional corrosion inhibitors. A review. Part I. 1,2,3-Benzotriazole and its derivatives. Copper, zinc and their alloys, Int. J. Corros. Scale Inhib., 2018, 3, 271–307. doi: 10.17675/2305-6894-2018-7-3-1E. Rocca, G. Bertrand, C. Rapin and J.C. Labrune, Inhibition of copper aqueous corrosion by non-toxic linear sodium heptanoate: mechanism and ECAFM study, J. Electroanal. Chem., 2001, 503, no. 1–2, 133–140. doi: 10.1016/S0022-0728(01)00384-9E. Rocca, G. Bertrand, C. Rapin and J.C. Labrune, Inhibition of copper aqueous corrosion by non-toxic linear sodium heptanoate: mechanism and ECAFM study, J. Electroanal. Chem., 2001, 503, no. 1–2, 133–140. doi: 10.1016/S0022-0728(01)00384-9P. Wang, R. Qiua, D. Zhanga, Z. Lina and B. Hou, Fabricated super-hydrophobic film with potentiostatic electrolysis method on copper for corrosion protection. Electrochim. Acta, 2010, 56, 517–522. doi: 10.1016/j.electacta.2010.09.017P. Wang, R. Qiua, D. Zhanga, Z. Lina and B. Hou, Fabricated super-hydrophobic film with potentiostatic electrolysis method on copper for corrosion protection. Electrochim. Acta, 2010, 56, 517–522. doi: 10.1016/j.electacta.2010.09.017Ю.И. Кузнецов, И.А. Кузнецов и Н.П. Андреева, Формирование адсорбционных слоев на меди из водных растворов лаурата натрия и их защитное действие во влажной атмосфере, Коррозия: материалы, защита, 2017, 4, 26–32.Ю.И. Кузнецов, И.А. Кузнецов и Н.П. Андреева, Формирование адсорбционных слоев на меди из водных растворов лаурата натрия и их защитное действие во влажной атмосфере, Коррозия: материалы, защита, 2017, 4, 26–32.M.O. Agafonkina, Yu.I. Kuznetsov and N.P. Andreeva, Inhibitor Properties of Carboxylates and Their Adsorption on Copper from Aqueous Solutions, Russ. J. Phys. Chem., 2015, 89, no. 6, 1070–1076. doi:10.1134/S0036024415060023M.O. Agafonkina, Yu.I. Kuznetsov and N.P. Andreeva, Inhibitor Properties of Carboxylates and Their Adsorption on Copper from Aqueous Solutions, Russ. J. Phys. Chem., 2015, 89, no. 6, 1070–1076. doi:10.1134/S0036024415060023J.E.O. Mayne, The mechanism of the inhibition of the corrosion of iron in the pH range 5–13, In Proceed. of the 4th Europ. Symp. on Corros. Inhib. Ferrara (Italy), 1975, 1, 1–5.J.E.O. Mayne, The mechanism of the inhibition of the corrosion of iron in the pH range 5–13, In Proceed. of the 4th Europ. Symp. on Corros. Inhib. Ferrara (Italy), 1975, 1, 1–5.A.D. Mercer, The properties of carboxilates as corrosion inhibitors for steel and other metals in neutral aqueous solutions, In Proceed. of the 5th Europ. Symp. on Corros. Inhib. Ferrara (Italy), 1980, 2, 563–581.A.D. Mercer, The properties of carboxilates as corrosion inhibitors for steel and other metals in neutral aqueous solutions, In Proceed. of the 5th Europ. Symp. on Corros. Inhib. Ferrara (Italy), 1980, 2, 563–581.G.T. Hefter, N.A. North and S.H. Tan, Organic corrosion inhibitors in neutral solutions. Part 1. Inhibition of steel, copper and aluminum by straight chain carboxylates, Corrosion, 1997, 53, 657–667. doi: 10.5006/1.3290298G.T. Hefter, N.A. North and S.H. Tan, Organic corrosion inhibitors in neutral solutions. Part 1. Inhibition of steel, copper and aluminum by straight chain carboxylates, Corrosion, 1997, 53, 657–667. doi: 10.5006/1.3290298K. Aramaki and T. Shimura, Self-assembled monolayers of carboxylate ions on passivated iron for preventing passive film breakdown, Corros. Sci., 2004, 46, 313–328. doi: 10.1016/S0010-938X(03)00156-2K. Aramaki and T. Shimura, Self-assembled monolayers of carboxylate ions on passivated iron for preventing passive film breakdown, Corros. Sci., 2004, 46, 313–328. doi: 10.1016/S0010-938X(03)00156-2P. Taheri, J. Wielant, T. Hauffman, J.R. Flores, F. Hannour, J.H.W. Dewit, J.M.C. Mol and H. Terryn, A comparison of the interfacial bonding properties of carboxylic acid functional groups on zinc and iron substrates, Electrochim. Acta, 2011, 56, no. 4, 1904–1911. doi: 10.1016/j.electacta.2010.10.079P. Taheri, J. Wielant, T. Hauffman, J.R. Flores, F. Hannour, J.H.W. Dewit, J.M.C. Mol and H. Terryn, A comparison of the interfacial bonding properties of carboxylic acid functional groups on zinc and iron substrates, Electrochim. Acta, 2011, 56, no. 4, 1904–1911. doi: 10.1016/j.electacta.2010.10.079U. Rammelt, S. Köhler and G. Reinhard, Electrochemical characterization of the ability of dicarboxylic acid salts to the corrosion inhibition of mild steel in aqueous solutions, Corros. Sci., 2011, 53, 3515–3520. doi: 10.1016/j.corsci.2011.06.023U. Rammelt, S. Köhler and G. Reinhard, Electrochemical characterization of the ability of dicarboxylic acid salts to the corrosion inhibition of mild steel in aqueous solutions, Corros. Sci., 2011, 53, 3515–3520. doi: 10.1016/j.corsci.2011.06.023D. Lahem, M. Poelman, F. Atmani and M.G. Olivier, Synergistic improvement of inhibitive activity of dicarboxylates in preventing mild steel corrosion in neutral aqueous solutions, Corros. Eng. Sci. Technol., 2012, 47, 463–471. doi: 10.1179/1743278212Y.0000000030D. Lahem, M. Poelman, F. Atmani and M.G. Olivier, Synergistic improvement of inhibitive activity of dicarboxylates in preventing mild steel corrosion in neutral aqueous solutions, Corros. Eng. Sci. Technol., 2012, 47, 463–471. doi: 10.1179/1743278212Y.0000000030Yu.I. Kuznetsov, Organic corrosion inhibitors: where are we now? A review. Part II. Passivation and the role of chemical structure of carboxylates, Int. J. Corros. Scale Inhib., 2016, 5, 282–318. doi 10.17675/2305-6894-2016-5-4-1Yu.I. Kuznetsov, Organic corrosion inhibitors: where are we now? A review. Part II. Passivation and the role of chemical structure of carboxylates, Int. J. Corros. Scale Inhib., 2016, 5, 282–318. doi 10.17675/2305-6894-2016-5-4-1G. Chan-Rosado and M.A. Pech-Canul, Influence of native oxide film age on the passivation of carbon steel in neutral aqueous solutions with a dicarboxylic acid, Corros. Sci., 2019, 153, 19–31. doi: 10.1016/j.corsci.2019.03.033G. Chan-Rosado and M.A. Pech-Canul, Influence of native oxide film age on the passivation of carbon steel in neutral aqueous solutions with a dicarboxylic acid, Corros. Sci., 2019, 153, 19–31. doi: 10.1016/j.corsci.2019.03.033А.М. Семилетов, Ю.И. Кузнецов и А.А. Колесникова, О защите от атмосферной коррозии алюминиевого сплава АД31 антикоррозионной присадкой КАП-25, Коррозия: материалы, защита, 2019, 12, 17–22.А.М. Семилетов, Ю.И. Кузнецов и А.А. Колесникова, О защите от атмосферной коррозии алюминиевого сплава АД31 антикоррозионной присадкой КАП-25, Коррозия: материалы, защита, 2019, 12, 17–22.R.A. Scherrer and S.M. Howard, Use of distribution coefficients in quantitative structure-activity relationships, J. Med. Chem., 1977, 20, no. 1, 53–58. doi: 10.1021/jm00211a010R.A. Scherrer and S.M. Howard, Use of distribution coefficients in quantitative structure-activity relationships, J. Med. Chem., 1977, 20, no. 1, 53–58. doi: 10.1021/jm00211a010Yu.I. Kuznetsov, I.A. Kuznetsov and N.P. Andreeva, Adsorption of sodium tridecanoate on copper from aqueous solutions and copper protection from atmospheric corrosion, Int. J. Corros. Scale Inhib., 2018, 7, no. 4, 648–656. doi: 10.17675/2305-6894-2018-7-4-11Yu.I. Kuznetsov, I.A. Kuznetsov and N.P. Andreeva, Adsorption of sodium tridecanoate on copper from aqueous solutions and copper protection from atmospheric corrosion, Int. J. Corros. Scale Inhib., 2018, 7, no. 4, 648–656. doi: 10.17675/2305-6894-2018-7-4-11А.А. Чиркунов, Д.О. Чугунов и Ю.И.Кузнецов, Влияние винилтриметоксисилана на эффективность пассивирующих пленок на модифицированной фосфонатами поверхности стали, Коррозия: материалы, защита, 2019, 9, 14–18.А.А. Чиркунов, Д.О. Чугунов и Ю.И.Кузнецов, Влияние винилтриметоксисилана на эффективность пассивирующих пленок на модифицированной фосфонатами поверхности стали, Коррозия: материалы, защита, 2019, 9, 14–18.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.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.

The authors declare that there are no conflicts of interest present.