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<article article-type="research-article" dtd-version="1.3" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xml:lang="ru"><front><journal-meta><journal-id journal-id-type="publisher-id">cpomaem</journal-id><journal-title-group><journal-title xml:lang="ru">Коррозия: защита материалов и методы исследований</journal-title><trans-title-group xml:lang="en"><trans-title>Title in english</trans-title></trans-title-group></journal-title-group><publisher><publisher-name>ИФХЭ РАН</publisher-name></publisher></journal-meta><article-meta><article-id pub-id-type="doi">10.61852/2949-3412-2025-3-2-169-177</article-id><article-id custom-type="elpub" pub-id-type="custom">cpomaem-105</article-id><article-categories><subj-group subj-group-type="heading"><subject>Research Article</subject></subj-group><subj-group subj-group-type="section-heading" xml:lang="ru"><subject>Статьи</subject></subj-group></article-categories><title-group><article-title>Защита меди от коррозии супергидрофобизацией ее поверхности</article-title><trans-title-group xml:lang="en"><trans-title>Protection of copper from corrosion by superhydrophobization of its surface</trans-title></trans-title-group></title-group><contrib-group><contrib contrib-type="author" corresp="yes"><name-alternatives><name name-style="eastern" xml:lang="ru"><surname>Кузнецов</surname><given-names>И. А.</given-names></name><name name-style="western" xml:lang="en"><surname>Kuznetsov</surname><given-names>I. A.</given-names></name></name-alternatives><bio xml:lang="ru"><p>119071, Москва, Ленинский проспект, д. 31, корп. 4</p></bio><bio xml:lang="en"><p>Leninsky prospect, 31-4, 119071 Moscow</p></bio><email xlink:type="simple">anarenen@gmail.com</email><xref ref-type="aff" rid="aff-1"/></contrib><contrib contrib-type="author" corresp="yes"><name-alternatives><name name-style="eastern" xml:lang="ru"><surname>Кузнецов</surname><given-names>Ю. И.</given-names></name><name name-style="western" xml:lang="en"><surname>Kuznetsov</surname><given-names>Yu. I.</given-names></name></name-alternatives><bio xml:lang="ru"><p>119071, Москва, Ленинский проспект, д. 31, корп. 4</p></bio><bio xml:lang="en"><p>Leninsky prospect, 31-4, 119071 Moscow</p></bio><xref ref-type="aff" rid="aff-1"/></contrib></contrib-group><aff-alternatives id="aff-1"><aff xml:lang="ru">Федеральное государственное бюджетное учреждение науки Институт физической химии и электрохимии им. А.Н. Фрумкина Российской академии наук<country>Россия</country></aff><aff xml:lang="en">Frumkin Institute of Physical Chemistry and Electrochemistry Russian Academy of Sciences<country>Russian Federation</country></aff></aff-alternatives><pub-date pub-type="collection"><year>2025</year></pub-date><pub-date pub-type="epub"><day>13</day><month>07</month><year>2025</year></pub-date><volume>0</volume><issue>2</issue><fpage>169</fpage><lpage>177</lpage><permissions><copyright-statement>Copyright &amp;#x00A9; Кузнецов И.А., Кузнецов Ю.И., 2025</copyright-statement><copyright-year>2025</copyright-year><copyright-holder xml:lang="ru">Кузнецов И.А., Кузнецов Ю.И.</copyright-holder><copyright-holder xml:lang="en">Kuznetsov I.A., Kuznetsov Y.I.</copyright-holder><license license-type="creative-commons-attribution" xlink:href="https://creativecommons.org/licenses/by/4.0/" xlink:type="simple"><license-p>This work is licensed under a Creative Commons Attribution 4.0 License.</license-p></license></permissions><self-uri xlink:href="https://www.cpmrm.ru/jour/article/view/105">https://www.cpmrm.ru/jour/article/view/105</self-uri><abstract><p>Медь и её сплавы широко применяются в промышленности благодаря высокой электропроводности, теплопроводности и пластичности. Однако в некоторых нейтральных средах медь подвергается коррозии, что ухудшает её функциональные свойства и сокращает срок службы. Перспективным методом защиты является создание супергидрофобных (СГФ) покрытий, поэтому нами исследовано формирование СГФ-покрытий на меди с использованием алкилмалоновых кислот (АМК) в качестве экологически безопасных гидрофобизаторов. Поверхность меди предварительно структурировали методом лазерной абляции для создания полимодальной шероховатости, после чего модифицировали растворами АМК с длиной алкила C13 и C16. Полученные покрытия демонстрировали СГФ свойства с краевыми углами смачивания (Θc), сопоставимыми с покрытиями на основе стеариновой кислоты (C17). Дополнительная отмывка в изопропаноле с ультразвуковой обработкой увеличивала Θc для АМК, но не влияла на стеариновую кислоту (CK). Испытания в условиях конденсации влаги и в хлоридных растворах подтвердили высокую защитную эффективность покрытий на основе АМК C16, близкую к СК. Установлено, что повышение температуры раствора гидрофобизатора до 60°C или добавление малых концентраций ингибиторов коррозии (например, 0,1 ммоль/л 1,2,3-бензотриазола) увеличивает стабильность СГФ-покрытий. Результаты показывают, что алкилмалоновые кислоты могут служить эффективной и экологичной альтернативой традиционным гидрофобизаторам меди.</p></abstract><trans-abstract xml:lang="en"><p>Copper and its alloys are widely used in industry due to their high electrical conductivity, thermal conductivity, and plasticity. However, in some neutral environments, copper undergoes corrosion, which degrades its functional properties and reduces its service life. Methods of protecting it from corrosion include treatment with inhibitors, but their environmental safety raises concerns. A promising approach is the creation of superhydrophobic (SHP) coatings, which is why we have studied the formation of SHP coatings on copper using alkylmalonic acids (AMAs) as environmentally friendly hydrophobizing agents. The copper surface was preliminarily structured using laser ablation technique to create multimodal roughness, after which it was modified with solutions of AMAs with alkyl chain lengths of C13 and C16. The resulting coatings exhibited superhydrophobic properties with contact angles (Θc) comparable to those of coatings based on stearic acid (C17). Additional rinsing in isopropanol with ultrasonic treatment increased Θc for AMAs but had no effect on stearic acid (SA). Tests under moisture condensation and in chloride-containing solutions confirmed the high protective efficiency of C16 AMA-based coatings, which was close to that of stearic acid. It was found that increasing the temperature of the hydrophobizing solution to 60°C or adding low concentrations of corrosion inhibitors (e.g., 0.1 mmol/ L 1,2,3-benzotriazole) enhanced the stability of the SHP coatings. The results demonstrate that alkylmalonic acids, especially those with long alkyl chains, can serve as an effective and environmentally friendly alternative to traditional hydrophobizing agents for protecting copper against corrosion.</p></trans-abstract><kwd-group xml:lang="ru"><kwd>коррозия меди</kwd><kwd>супергидрофобное покрытие</kwd><kwd>алкилмалоновые кислоты</kwd><kwd>лазерная абляция</kwd><kwd>защита от коррозии</kwd><kwd>экологичные ингибиторы</kwd></kwd-group><kwd-group xml:lang="en"><kwd>corrosion of copper</kwd><kwd>superhydrophobic coating</kwd><kwd>alkylmalonic acids</kwd><kwd>laser ablation</kwd><kwd>corrosion protection</kwd><kwd>eco-friendly inhibitors</kwd></kwd-group><funding-group xml:lang="ru"><funding-statement>Работа выполнена в рамках Госзадания при финансовой поддержке Минобрнауки России «Развитие физико-химических основ процессов коррозии металлов и сплавов и методов их защиты» (регистрационный номер 125012200581-1)</funding-statement></funding-group></article-meta></front><back><ref-list><title>References</title><ref id="cit1"><label>1</label><citation-alternatives><mixed-citation xml:lang="ru">A. Igual Munoz, J. Garcia Anton, J.L. Guinon and V. Perez Herranz, Comparison of inorganic inhibitors of copper, nickel and copper–nickels in aqueous lithium bromide solution, Electrochim. Acta, 2004, 50, 957 – 966. doi: 10.1016/j.electacta.2004.07.048</mixed-citation><mixed-citation xml:lang="en">A. Igual Munoz, J. Garcia Anton, J.L. Guinon and V. Perez Herranz, Comparison of inorganic inhibitors of copper, nickel and copper–nickels in aqueous lithium bromide solution, Electrochim. Acta, 2004, 50, 957 – 966. doi: 10.1016/j.electacta.2004.07.048</mixed-citation></citation-alternatives></ref><ref id="cit2"><label>2</label><citation-alternatives><mixed-citation xml:lang="ru">Ю.И. Кузнецов и Л.П. Казанский, Физико-химические аспекты защиты металлов ингибиторами коррозии класса азолов, Успехи химии, 2008, 77, 227 – 241. doi: 10.1070/RC2008v077n03ABEH003753</mixed-citation><mixed-citation xml:lang="en">Ю.И. Кузнецов и Л.П. Казанский, Физико-химические аспекты защиты металлов ингибиторами коррозии класса азолов, Успехи химии, 2008, 77, 227 – 241. doi: 10.1070/RC2008v077n03ABEH003753</mixed-citation></citation-alternatives></ref><ref id="cit3"><label>3</label><citation-alternatives><mixed-citation xml:lang="ru">M. Finšgar and I. Milošev, Inhibition of copper corrosion by 1,2,3-benzotriazole: A review, Corros. Sci., 2010, 52, no. 9, 2737–2749. doi: 10.1016/j.corsci.2010.05.002</mixed-citation><mixed-citation xml:lang="en">M. Finšgar and I. Milošev, Inhibition of copper corrosion by 1,2,3-benzotriazole: A review, Corros. Sci., 2010, 52, no. 9, 2737–2749. doi: 10.1016/j.corsci.2010.05.002</mixed-citation></citation-alternatives></ref><ref id="cit4"><label>4</label><citation-alternatives><mixed-citation xml:lang="ru">M.M. Antonijevic and M.B. Petrovic, Copper Corrosion Inhibitors. A review, Int. J. Electrochem.Sci., 2008, 3, no. 1, 1–28. doi: 10.1016/S1452-3981(23)15441-1</mixed-citation><mixed-citation xml:lang="en">M.M. Antonijevic and M.B. Petrovic, Copper Corrosion Inhibitors. A review, Int. J. Electrochem.Sci., 2008, 3, no. 1, 1–28. doi: 10.1016/S1452-3981(23)15441-1</mixed-citation></citation-alternatives></ref><ref id="cit5"><label>5</label><citation-alternatives><mixed-citation xml:lang="ru">G. Zerjav and I. Milosev, Carboxylic Acids as Corrosion Inhibitors for Cu, Zn and Brasses in Simulated Urban Rain, Int. J. Electrochem.Sci., 2014, 9, no. 5, 2696–2715. doi: 10.1016/S1452-3981(23)07957-9</mixed-citation><mixed-citation xml:lang="en">G. Zerjav and I. Milosev, Carboxylic Acids as Corrosion Inhibitors for Cu, Zn and Brasses in Simulated Urban Rain, Int. J. Electrochem.Sci., 2014, 9, no. 5, 2696–2715. doi: 10.1016/S1452-3981(23)07957-9</mixed-citation></citation-alternatives></ref><ref id="cit6"><label>6</label><citation-alternatives><mixed-citation xml:lang="ru">T. Onda, S. Shibuichi, N. Satoh and K. Tsujii, Super-Water-Repellent Fractal Surfaces, Langmuir, 1996, 12, no. 9, 2125 – 2127. doi: 10.1021/la950418o</mixed-citation><mixed-citation xml:lang="en">T. Onda, S. Shibuichi, N. Satoh and K. Tsujii, Super-Water-Repellent Fractal Surfaces, Langmuir, 1996, 12, no. 9, 2125 – 2127. doi: 10.1021/la950418o</mixed-citation></citation-alternatives></ref><ref id="cit7"><label>7</label><citation-alternatives><mixed-citation xml:lang="ru">Y. Tian, H. Li, M. Wang, C. Yang, Z. Yang and X. Liu, Insights into the stability of fluorinated super-hydrophobic coating in different corrosive solutions, Prog. Org. Coat., 2021, 151, 106043. doi: 10.1016/j.porgcoat.2020.106043</mixed-citation><mixed-citation xml:lang="en">Y. Tian, H. Li, M. Wang, C. Yang, Z. Yang and X. Liu, Insights into the stability of fluorinated super-hydrophobic coating in different corrosive solutions, Prog. Org. Coat., 2021, 151, 106043. doi: 10.1016/j.porgcoat.2020.106043</mixed-citation></citation-alternatives></ref><ref id="cit8"><label>8</label><citation-alternatives><mixed-citation xml:lang="ru">L.B. Boinovich and A.M. Emelyanenko, Hydrophobic materials and coatings: principles of design, properties and applications, Russ. Chem. Rev., 2008, 77, no. 7, 583–600. doi: 10.1070/RC2008v077n07ABEH003775</mixed-citation><mixed-citation xml:lang="en">L.B. Boinovich and A.M. Emelyanenko, Hydrophobic materials and coatings: principles of design, properties and applications, Russ. Chem. Rev., 2008, 77, no. 7, 583–600. doi: 10.1070/RC2008v077n07ABEH003775</mixed-citation></citation-alternatives></ref><ref id="cit9"><label>9</label><citation-alternatives><mixed-citation xml:lang="ru">D.K. Vairavel, S. Mahadevan and V. Madeshwaren, Enhanced corrosion resistance of copper for agricultural equipment using superhydrophobic stearic acid coatings, Matéria (Rio J.). Laboratório de Hidrogênio, Coppe Universidade Federal do Rio de Janeiro, em cooperação com a Associação Brasileira do Hidrogênio, ABH2, 2025, 30, e20240647. doi: 10.1590/1517-7076-RMAT-2024-0647</mixed-citation><mixed-citation xml:lang="en">D.K. Vairavel, S. Mahadevan and V. Madeshwaren, Enhanced corrosion resistance of copper for agricultural equipment using superhydrophobic stearic acid coatings, Matéria (Rio J.). Laboratório de Hidrogênio, Coppe Universidade Federal do Rio de Janeiro, em cooperação com a Associação Brasileira do Hidrogênio, ABH2, 2025, 30, e20240647. doi: 10.1590/1517-7076-RMAT-2024-0647</mixed-citation></citation-alternatives></ref><ref id="cit10"><label>10</label><citation-alternatives><mixed-citation xml:lang="ru">И.А. Кузнецов и Д.Б. Вершок, О защите меди дикарбоновыми кислотами, Коррозия: защита материалов и методы исследований, 2024, 2, no. 2, 122–136. doi: 10.61852/2949-3412-2024-2-2-122-136</mixed-citation><mixed-citation xml:lang="en">И.А. Кузнецов и Д.Б. Вершок, О защите меди дикарбоновыми кислотами, Коррозия: защита материалов и методы исследований, 2024, 2, no. 2, 122–136. doi: 10.61852/2949-3412-2024-2-2-122-136</mixed-citation></citation-alternatives></ref><ref id="cit11"><label>11</label><citation-alternatives><mixed-citation xml:lang="ru">M.O. Agafonkina, I.A. Kuznetsov, N.P. Andreeva and Yu.I. Kuznetsov, Copper protection with sodium salts of lower dicarboxylic acids in neutral aqueous solution, Int. J. Corros. Scale Inhib., 2020, 9, no. 3, 1000 – 1013. doi: 10.17675/2305-6894-2020-9-3-13</mixed-citation><mixed-citation xml:lang="en">M.O. Agafonkina, I.A. Kuznetsov, N.P. Andreeva and Yu.I. Kuznetsov, Copper protection with sodium salts of lower dicarboxylic acids in neutral aqueous solution, Int. J. Corros. Scale Inhib., 2020, 9, no. 3, 1000 – 1013. doi: 10.17675/2305-6894-2020-9-3-13</mixed-citation></citation-alternatives></ref><ref id="cit12"><label>12</label><citation-alternatives><mixed-citation xml:lang="ru">Z. He, Z. Zhang and J. He, CuO/Cu based superhydrophobic and self-cleaning surfaces, Scr. Mater., 2016, 118, 60–64. doi: 10.1016/j.scriptamat.2016.03.015</mixed-citation><mixed-citation xml:lang="en">Z. He, Z. Zhang and J. He, CuO/Cu based superhydrophobic and self-cleaning surfaces, Scr. Mater., 2016, 118, 60–64. doi: 10.1016/j.scriptamat.2016.03.015</mixed-citation></citation-alternatives></ref><ref id="cit13"><label>13</label><citation-alternatives><mixed-citation xml:lang="ru">F. Xiao, S. Yuan, B. Liang, G. Li, S.O. Pehkonenc and T. Zhang, Superhydrophobic CuO nanoneedle-covered copper surfaces for anticorrosion, J. Mater. Chem. A, 2015, 3, no. 8, 4374–4388. doi: 10.1039/C4TA05730A</mixed-citation><mixed-citation xml:lang="en">F. Xiao, S. Yuan, B. Liang, G. Li, S.O. Pehkonenc and T. Zhang, Superhydrophobic CuO nanoneedle-covered copper surfaces for anticorrosion, J. Mater. Chem. A, 2015, 3, no. 8, 4374–4388. doi: 10.1039/C4TA05730A</mixed-citation></citation-alternatives></ref><ref id="cit14"><label>14</label><citation-alternatives><mixed-citation xml:lang="ru">Q. bao Zhang, D. Xu, T.F. Hung and K. Zhang, Facile synthesis, growth mechanism and reversible superhydrophobic and superhydrophilic properties of non-flaking CuO nanowires grown from porous copper substrates, Nanotechnology, 2013, 24, no. 6, 065602. doi: 10.1088/0957-4484/24/6/065602</mixed-citation><mixed-citation xml:lang="en">Q. bao Zhang, D. Xu, T.F. Hung and K. Zhang, Facile synthesis, growth mechanism and reversible superhydrophobic and superhydrophilic properties of non-flaking CuO nanowires grown from porous copper substrates, Nanotechnology, 2013, 24, no. 6, 065602. doi: 10.1088/0957-4484/24/6/065602</mixed-citation></citation-alternatives></ref><ref id="cit15"><label>15</label><citation-alternatives><mixed-citation xml:lang="ru">А.А. Михайлов, Ю.М. Панченко и Ю.И. Кузнецов, Атмосферная коррозия и защита металлов. Изд-во Першина Р.В., Тамбов, 2016. 555 с.</mixed-citation><mixed-citation xml:lang="en">А.А. Михайлов, Ю.М. Панченко и Ю.И. Кузнецов, Атмосферная коррозия и защита металлов. Изд-во Першина Р.В., Тамбов, 2016. 555 с.</mixed-citation></citation-alternatives></ref><ref id="cit16"><label>16</label><citation-alternatives><mixed-citation xml:lang="ru">K. Popova and T. Prošek, Corrosion Monitoring in Atmospheric Conditions: A Review, Metals, 2022, 12, 171. doi: 10.3390/met12020171</mixed-citation><mixed-citation xml:lang="en">K. Popova and T. Prošek, Corrosion Monitoring in Atmospheric Conditions: A Review, Metals, 2022, 12, 171. doi: 10.3390/met12020171</mixed-citation></citation-alternatives></ref><ref id="cit17"><label>17</label><citation-alternatives><mixed-citation xml:lang="ru">I. Odnevall and C. Leygraf, Atmospheric Corrosion of Copper in a Rural Atmosphere, J. Electrochem. Soc., 1995, 142, 3682. doi: 10.1149/1.2048399</mixed-citation><mixed-citation xml:lang="en">I. Odnevall and C. Leygraf, Atmospheric Corrosion of Copper in a Rural Atmosphere, J. Electrochem. Soc., 1995, 142, 3682. doi: 10.1149/1.2048399</mixed-citation></citation-alternatives></ref><ref id="cit18"><label>18</label><citation-alternatives><mixed-citation xml:lang="ru">S.M.A. Mousavi and R. Pitchumani, A study of corrosion on electrodeposited superhydrophobic copper surfaces, Corros. Sci., 2021, 186, 109420. doi: 10.1016/j.corsci.2021.109420</mixed-citation><mixed-citation xml:lang="en">S.M.A. Mousavi and R. Pitchumani, A study of corrosion on electrodeposited superhydrophobic copper surfaces, Corros. Sci., 2021, 186, 109420. doi: 10.1016/j.corsci.2021.109420</mixed-citation></citation-alternatives></ref></ref-list><fn-group><fn fn-type="conflict"><p>The authors declare that there are no conflicts of interest present.</p></fn></fn-group></back></article>
