resarПриродные ресурсы Арктики и СубарктикиArctic and Subarctic Natural Resources2618-97122686-9683Академия наук Республики Саха (Якутия)10.31242/2618-9712-2025-30-2-326-336resar-940Research ArticleМатериаловедение и химические технологииMaterials science and chemical technologiesВлияние механохимической активации диоксида церия на структуру и свойства политетрафторэтиленаEffect of mechanochemical activation of cerium dioxide on the structure and properties of polytetrafluoroethylenehttps://orcid.org/0000-0001-7699-533XВасильевА. П.VasilevA. P.

ВАСИЛЬЕВ Андрей Петрович, кандидат технических наук, старший научный сотрудник

ResearcherID: R-8924-2016

г. Якутск

VASILEV, Andrey Petrovich, Cand. Sci. (Eng.), Senior Researcher

ResearcherID: R-8924-2016

Yakutsk

gtvap@mail.ruhttps://orcid.org/0000-0003-0691-7066ОхлопковаА. А.OkhlopkovaA. A.

ОХЛОПКОВА Айталина Алексеевна, доктор технических наук, профессор

ResearcherID: A-6594-2014

г. Якутск

OKHLOPKOVA, Aitalina Alekseevna, Dr. Sci. (Eng.) Professor, Chief Researcher

ResearcherID: A-6594-2014

Yakutsk

okhlopkova@yandex.ruhttps://orcid.org/0000-0002-6469-1491СтручковаТ. С.StruchkovaT. S.

СТРУЧКОВА Татьяна Семеновна, кандидат технических наук, доцент

ResearcherID: E-5047-2014

г. Якутск

STRUCHKOVA, Tatyana Semenovna, Cand. Sci. (Eng.), Associate Professor

ResearcherID: E-5047-2014

Yakutsk

sts_23@mail.ruhttps://orcid.org/0000-0001-5148-2837АлексеевА. Г.AlekseevA. G.

АЛЕКСЕЕВ Алексей Гаврильевич, старший преподаватель

г. Якутск

ALEKSEEV, Alexsey Gavrilievich, Senior Lecturer

Yakutsk

alexalekseev.z@gmail.comСеверо-Восточный федеральный университет имени М.К. АммосоваРоссияAmmosov North-Eastern Federal UniversityRussian Federation202509072025302326336Copyright © Васильев А.П., Охлопкова А.А., Стручкова Т.С., Алексеев А.Г., 20252025Васильев А.П., Охлопкова А.А., Стручкова Т.С., Алексеев А.Г.Vasilev A.P., Okhlopkova A.A., Struchkova T.S., Alekseev A.G.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://resar.elpub.ru/jour/article/view/940

В условиях растущих требований к надежности и долговечности полимерных материалов, используемых в узлах трения и уплотнительных системах, актуальной задачей является разработка композитов с улучшенными триботехническими и механическими свойствами. Политетрафторэтилен (ПТФЭ) широко применяется благодаря своим уникальным антифрикционным характеристикам, однако его низкая износостойкость ограничивает использование в экстремальных условиях. Модификация ПТФЭ наполнителями, такими как диоксид церия (CeO2), позволяет улучшить его эксплуатационные свойства. Цель исследования: изучение влияния механохимической активации оксида церия на свойства и структуру ПТФЭ для улучшения механических и триботехнических характеристик. В работе использовались методы переработки полимерных композиционных материалов (ПКМ) на основе ПТФЭ. Механохимическая активация CeO2 проводилась в планетарной мельнице. Для анализа структуры и свойств применялись рентгеноструктурный анализ, дифференциальная сканирующая калориметрия, ИК-спектроскопия, а также механические и триботехнические испытания. Установлено, что введение 2 мас.% CeO2 в ПТФЭ повышает степень кристалличности и энтальпию плавления ПКМ при использовании механоактивированного наполнителя. Триботехническими испытаниями установлено повышение износостойкости ПКМ с механоактивированным CeO2 в 254 раза при сохранении коэффициента трения на уровне исходного полимера. Исследование поверхностей трения ПКМ методом ИК-спектроскопии выявило образование перфторкарбоксилатных солей в процессе изнашивания, что свидетельствует о протекании трибохимических процессов. Разработанные ПКМ на основе ПТФЭ с механоактивированным CeO2 демонстрируют улучшенные механические и триботехнические свойства, что делает их перспективными материалами для применения в узлах трения и уплотнительных системах.

As the demand for reliability and durability in polymer materials used in friction units and sealing systems continues to grow, it is essential to develop composites that exhibit enhanced tribological and mechanical properties. Polytetrafluoroethylene (PTFE) is a popular choice due to its exceptional antifriction qualities; however, its limited wear resistance restricts its application in extreme environments. To address this, we explored the modification of PTFE with cerium dioxide (CeO2) fillers to enhance its performance. The objective of this study was to examine how the mechanochemical activation of cerium oxide influences the properties and structure of PTFE, ultimately aiming to improve its mechanical and tribological characteristics. We employed traditional processing methods for polymer composite materials (PCM) based on PTFE. The mechanochemical activation of CeO2 was conducted using a planetary mill, and we utilized various analytical techniques, including X-ray diffraction analysis, differential scanning calorimetry, and IR spectroscopy, alongside mechanical and tribological testing to evaluate the structure and properties of the composites. Our findings revealed that incorporating 2 wt.% of CeO2 into PTFE significantly increases the degree of crystallinity and the enthalpy of melting of the PCM when using the mechanically activated filler. Notably, tribological tests indicated a remarkable 254-fold increase in wear resistance for the PCM with mechanically activated CeO2, while the friction coefficient remained consistent with that of the initial polymer. Additionally, IR spectroscopy analysis of the friction surfaces of the PCM indicated the formation of perfluorocarboxylate salts during wear, suggesting the occurrence of tribochemical processes. In conclusion, the developed PCM based on PTFE with mechanically activated CeO2 demonstrates enhanced mechanical and tribotechnical properties, positioning them as promising materials for use in friction units and sealing systems.

политетрафторэтилендиоксид церияполимерный композиционный материалмеханическая активациятриботехнические свойстваизносостойкостьpolytetrafluoroethylenecerium dioxidepolymer composite materialmechanical activationtribotechnical propertieswear resistanceРабота выполнена в рамках государственного задания Министерства науки и высшего образования РФ (НИР № FSRG-2023-0026).This study was conducted within the project of the Ministry of Science and Higher Education of the Russian Federation (No. FSRG-2023-0026).ReferencesKosenko E.A., Baurova N.I., Zorin V.A. Impact toughness of carbon fiber-reinforced polymers under extremely low arctic temperature conditions: the role of hybrid matrix components. Russian Metallurgy (Metally). 2023;(13):2167–2172. https://doi.org/10.1134/S0036029523700246Kosenko E.A., Baurova N.I., Zorin V.A. Impact toughness of carbon fiber-reinforced polymers under extremely low arctic temperature conditions: the role of hybrid matrix components. Russian Metallurgy (Metally). 2023;(13):2167–2172. https://doi.org/10.1134/S0036029523700246Kosenko E.A., Baurova N.I., Zorin V.A. Investigation of the mechanical properties of polymer composite materials with various types of hybrid matrices in the extreme conditions of the Arctic. IOP Conference Series: Materials Science and Engineering. 2021;1159:012053. https://doi.org/10.1088/1757-899X/1159/1/012053Kosenko E.A., Baurova N.I., Zorin V.A. Investigation of the mechanical properties of polymer composite materials with various types of hybrid matrices in the extreme conditions of the Arctic. IOP Conference Series: Materials Science and Engineering. 2021;1159:012053. https://doi.org/10.1088/1757-899X/1159/1/012053Liu F., Feihua Liu, Jin Y., et al. Improved coefficient thermal expansion and mechanical properties of PTFE composites for high-frequency communication. Composites Science and Technology. 2023;241:110142. https://doi.org/10.1016/j.compscitech.2023.110142Liu F., Feihua Liu, Jin Y., et al. Improved coefficient thermal expansion and mechanical properties of PTFE composites for high-frequency communication. Composites Science and Technology. 2023;241:110142. https://doi.org/10.1016/j.compscitech.2023.110142Mhaske S.T., Mohanty J.D., Chugh K.W. Fluoropolymers: brief history, fundamental chemistry, processing, structure, properties, and applications. In: Deshmukh K., Hussain Ch.M. (eds.) Advanced Fluoropolymer Nanocomposites. Woodhead Publishing; 2023, pp. 1–27. https://doi.org/10.1016/B978-0-323-95335-1.00006-2Mhaske S.T., Mohanty J.D., Chugh K.W. Fluoropolymers: brief history, fundamental chemistry, processing, structure, properties, and applications. In: Deshmukh K., Hussain Ch.M. (eds.) Advanced Fluoropolymer Nanocomposites. Woodhead Publishing; 2023, pp. 1–27. https://doi.org/10.1016/B978-0-323-95335-1.00006-2Пугачев А.К., Росляков О.А. Переработка фторопласта в изделия. Л.: Химия; 1987. 166 с. Pugachev A.K., Roslyakov O.A. Processing of fluoroplastic into products. Leningrad: Khimiya Publ.; 1987. 166 p. (In Russ.)Пугачев А.К., Росляков О.А. Переработка фторопласта в изделия. Л.: Химия; 1987. 166 с. Pugachev A.K., Roslyakov O.A. Processing of fluoroplastic into products. Leningrad: Khimiya Publ.; 1987. 166 p. (In Russ.)Sonawane A., Deshpande A., Chinchanikar S., Munde Y. Dry sliding wear characteristics of carbon filled polytetrafluoroethylene (PTFE) composite against Aluminium 6061 alloy. Materials Today: Proceedings. 2021;44(5):3888–3893. https://doi.org/10.1016/j.matpr.2020.12.929Sonawane A., Deshpande A., Chinchanikar S., Munde Y. Dry sliding wear characteristics of carbon filled polytetrafluoroethylene (PTFE) composite against Aluminium 6061 alloy. Materials Today: Proceedings. 2021;44(5):3888–3893. https://doi.org/10.1016/j.matpr.2020.12.929Rajak D.K., Wagh P.H., Linul E. Manufacturing technologies of carbon/glass fiber-reinforced polymer composites and their properties: a review. Polymers. 2021;13(21):3721. https://doi.org/10.3390/polym13213721Rajak D.K., Wagh P.H., Linul E. Manufacturing technologies of carbon/glass fiber-reinforced polymer composites and their properties: a review. Polymers. 2021;13(21):3721. https://doi.org/10.3390/polym13213721Markova M.A., Petrova P.N. Influence of carbon fibers and composite technologies on the properties of PCM based on polytetrafluoroethylene. Inorganic Materials: Applied Research. 2021;12:551–7. https://doi.org/10.1134/S2075113321020362Markova M.A., Petrova P.N. Influence of carbon fibers and composite technologies on the properties of PCM based on polytetrafluoroethylene. Inorganic Materials: Applied Research. 2021;12:551–7. https://doi.org/10.1134/S2075113321020362Sidebottom M.A., et al. Nanomechanical filler functionality enables ultralow wear polytetrafluoroethylene composites. ACS Applied Materials & Interfaces. 2022;14(48):54293–54303. https://doi.org/10.1021/acsami.2c13644Sidebottom M.A., et al. Nanomechanical filler functionality enables ultralow wear polytetrafluoroethylene composites. ACS Applied Materials & Interfaces. 2022;14(48):54293–54303. https://doi.org/10.1021/acsami.2c13644Van Meter K.E., Babuska T.F., Junk C.P., et al. Ultralow wear behavior of iron–cobalt-filled PTFE composites. Tribology Letters. 2023;71:4. https://doi.org/10.1007/s11249-022-01679-zVan Meter K.E., Babuska T.F., Junk C.P., et al. Ultralow wear behavior of iron–cobalt-filled PTFE composites. Tribology Letters. 2023;71:4. https://doi.org/10.1007/s11249-022-01679-zLi G., Li H., Xu Y., et al. Dual-function hybrid coatings based on polytetrafluoroethylene and Cu2O for anti-biocorrosion and anti-wear applications. Coatings. 2024;14(5):592. https://doi.org/10.3390/coatings14050592Li G., Li H., Xu Y., et al. Dual-function hybrid coatings based on polytetrafluoroethylene and Cu2O for anti-biocorrosion and anti-wear applications. Coatings. 2024;14(5):592. https://doi.org/10.3390/coatings14050592Shiv J.K., Kumar K., Jayapalan S. Recent advances in polymer using metal oxides nanocomposite and its hybrid fillers for tribological application. Advances in Materials and Processing Technologies. 2024;10(4):2720–2731. https://doi.org/10.1080/2374068X.2023.2171673Shiv J.K., Kumar K., Jayapalan S. Recent advances in polymer using metal oxides nanocomposite and its hybrid fillers for tribological application. Advances in Materials and Processing Technologies. 2024;10(4):2720–2731. https://doi.org/10.1080/2374068X.2023.2171673Иванов В.К., Шариков Ф.Ю., Полежаева О.С., Третьяков Ю.Д. Формирование нанокристаллического диоксида церия из водно-спиртовых растворов нитрата церия (III). Доклады Академии наук. 2006;411(4):485–487.Ivanov V.K., Sharikov F.U., Polezhaeva O.S., Tretyakov Yu.D. Formation of nanocrystalline ceria from cerium(III) nitrate solutions in aqueous alcohol. Doklady Chemistry. 2006;411(2):223–225.Аристова Н.М. Термодинамические свойства диоксида церия в конденсированном состоянии. Теплофизика высоких температур. 2022;60(6):824–829. https://doi.org/10.31857/S0040364422040093Aristova N.M. Thermodynamic properties of cerium dioxide in the condensed state. Teplofizika Vysokikh Temperatur. 2022;60(6):824–829. (In Russ.) https://doi.org/10.31857/S0040364422040093.Иванов В.К., Полежаева О.С., Копица Г.П. и др. Особенности высокотемпературного роста наночастиц диоксида церия. Журнал неорганической химии. 2009;54(11):1767–1775.Ivanov V.K., Polezhaeva O.S., Kopitsa G.P., et al. Specifics of high-temperature coarsening of ceria nanoparticles. Russian Journal of Inorganic Chemistry. 2009;54(11):1689–1696.Panda P.K., Dash P., Yang J.M., et al. Development of chitosan, graphene oxide, and cerium oxide composite blended films: structural, physical, and functional properties. Cellulose. 2022;29:2399–2411. https://doi.org/10.1007/s10570-021-04348-xPanda P.K., Dash P., Yang J.M., et al. Development of chitosan, graphene oxide, and cerium oxide composite blended films: structural, physical, and functional properties. Cellulose. 2022;29:2399–2411. https://doi.org/10.1007/s10570-021-04348-xLi H., Wang Z., Song Q., et al. Polyetheretherketone microspheres loaded with cerium dioxide nanoparticles mitigate damage from cellular oxidative stress and promote bone repair. Materials & Design. 2023;225:111426. https://doi.org/10.1016/j.matdes.2022.111426Li H., Wang Z., Song Q., et al. Polyetheretherketone microspheres loaded with cerium dioxide nanoparticles mitigate damage from cellular oxidative stress and promote bone repair. Materials & Design. 2023;225:111426. https://doi.org/10.1016/j.matdes.2022.111426Selvaraj S., Chauhan A., Radhakrishnan A., et al. Cerium oxide nanoparticles and their polymeric composites: advancements in biomedical applications. Journal of Inorganic and Organometallic Polymers and Materials. 2024;34:5691–5717. https://doi.org/10.1007/s10904-024-03263-5Selvaraj S., Chauhan A., Radhakrishnan A., et al. Cerium oxide nanoparticles and their polymeric composites: advancements in biomedical applications. Journal of Inorganic and Organometallic Polymers and Materials. 2024;34:5691–5717. https://doi.org/10.1007/s10904-024-03263-5Oh S., Shim J., Seo D., et al. Organic/inorganic hybrid cerium oxide-based superhydrophobic surface with enhanced weather resistance and self-recovery. Progress in Organic Coatings. 2022;170:106998. https://doi.org/10.1016/j.porgcoat.2022.106998Oh S., Shim J., Seo D., et al. Organic/inorganic hybrid cerium oxide-based superhydrophobic surface with enhanced weather resistance and self-recovery. Progress in Organic Coatings. 2022;170:106998. https://doi.org/10.1016/j.porgcoat.2022.106998Popescu I., Ionita G., Dobrinescu D., et al. Improved characteristics of hydrophobic polytetrafluoroethylene–platinum catalysts for tritium recovery from tritiated water. Fusion Engineering and Design. 2008; 83(10-12):1392–1394. https://doi.org/10.1016/j.fusengdes.2008.05.026Popescu I., Ionita G., Dobrinescu D., et al. Improved characteristics of hydrophobic polytetrafluoroethylene–platinum catalysts for tritium recovery from tritiated water. Fusion Engineering and Design. 2008; 83(10-12):1392–1394. https://doi.org/10.1016/j.fusengdes.2008.05.026Singh H., Sodhi G.P.S., Singh M., et al. Study: wear and superhydrophobic behaviour of PTFE-ceria composite. Surface Engineering. 2019;35(6):550–556. https://doi.org/10.1080/02670844.2018.1499176Singh H., Sodhi G.P.S., Singh M., et al. Study: wear and superhydrophobic behaviour of PTFE-ceria composite. Surface Engineering. 2019;35(6):550–556. https://doi.org/10.1080/02670844.2018.1499176Васильев А.П., Охлопкова А.А., Стручкова Т.С., Алексеев А.Г. Влияние модифицированного серицита на свойства и структуру политетрафторэтилена. Природные ресурсы Арктики и Субарктики. 2020; 25(2):147–1556. https://doi.org/10.31242/2618-9712-2020-25-2-12Vasiliev A.P., Okhlopkova A.A., Struchkova T.S., Alekseev A.G. Influence of modified sericite on the properties and structure of polytetrafluoroethylene. Arctic and Subarctic Natural Resources. 2020;25(2):147–1556. https://doi.org/10.31242/2618-9712-2020-25-2-12 (In Russ.)Стручкова Т.С., Васильев А.П., Охлопкова А.А. и др. Исследование влияния талька и технического углерода на структуру и свойства политетрафторэтилена. Полимерные материалы и технологии. 2021;7(4):39–49.Struchkova T.S., Vasilev A.P., Okhlopkovaet A.A., et al. Study of the effect of talc and indastrial carbon black on the structure and properties of polytetrafluoroethylene. Polimernye materialy i tekhnologii [Polymer Materials and Technologies]. 2021;7(4):39–49. (In Russ.)Кахраманов Н.Т., Гулиев А.Д., Аллахвердиева Х.В. Состояние проблемы получения и исследования структуры и свойств нанокомпозитов на основе полиолефинов и минеральных наполнителей. Пластические массы. 2022;(11-12):46–52. https://10.35164/0554-2901-2021-11-12-46-52Kahramanov N.T., Guliev A.D., Allahverdiyeva H.V. Obtaining and studying the structure and properties of nanocomposites based on polyolefi ns and mineral fi llers: state of the art. Plasticheskie massy. 2022;1(11-12):46–52. (In Russ.) https://10.35164/0554-2901-2021-11-12-46-52Охлопкова А.А., Охлопкова Т.А., Борисова Р.В. Управление процессами структурообразования в полимерных композиционных материалах на основе СВМПЭ. Наука и образование. 2015;78(2):85–90.Okhlopkova A.A., Okhlopkova T.A., Borisova R.V. Control of structure formation processes in polymer composite materials based on UHMWPE. Nauka i Obrazovanie. 2015;78(2):85–90. (In Russ.)Teplov A.A., Belousov S.I., Golovkova E.A., et al. Tribological, physicomechanical, and other properties of composites based on ultra-high molecular-weight polyethylene, polytetrafluoroethylene, and ethylene–tetrafluoroethylene copolymer with quasicrystalline filler Al–Cu–Fe. Crystallography Reports. 2021;66:883–96. https://doi.org/10.1134/S1063774521060420Teplov A.A., Belousov S.I., Golovkova E.A., et al. Tribological, physicomechanical, and other properties of composites based on ultra-high molecular-weight polyethylene, polytetrafluoroethylene, and ethylene–tetrafluoroethylene copolymer with quasicrystalline filler Al–Cu–Fe. Crystallography Reports. 2021;66:883–96. https://doi.org/10.1134/S1063774521060420Zhang R., Tian J., Wu Y., et al. An investigation on shape memory behaviors of UHMWPE-based nanocomposites reinforced by graphene nanoplatelets. Polymer Testing. 2021;99:107217. https://doi.org/10.1016/j.polymertesting.2021.107217Zhang R., Tian J., Wu Y., et al. An investigation on shape memory behaviors of UHMWPE-based nanocomposites reinforced by graphene nanoplatelets. Polymer Testing. 2021;99:107217. https://doi.org/10.1016/j.polymertesting.2021.107217Sleptsova S.A., Okhlopkova A.A. Study of the thermodynamic parameters of composite materials based on polytetrafluoroethylene and ultrafine fillers. International Polymer Science and Technology. 2001;28(7):44–48. https://doi.org/10.1177/0307174X0102800708Sleptsova S.A., Okhlopkova A.A. Study of the thermodynamic parameters of composite materials based on polytetrafluoroethylene and ultrafine fillers. International Polymer Science and Technology. 2001;28(7):44–48. https://doi.org/10.1177/0307174X0102800708Ning N., Fu S., Zhang W., et al. Realizing the enhancement of interfacial interaction in semicrystalline polymer/filler composites via interfacial crystallization. Progress in Polymer Science. 2012;37(10):1425–55. https://doi.org/10.1016/j.progpolymsci.2011.12.005Ning N., Fu S., Zhang W., et al. Realizing the enhancement of interfacial interaction in semicrystalline polymer/filler composites via interfacial crystallization. Progress in Polymer Science. 2012;37(10):1425–55. https://doi.org/10.1016/j.progpolymsci.2011.12.005Mazur K., Gądek-Moszczak A., Liber-Kneć А., et al. Mechanical behavior and morphological study of polytetrafluoroethylene (PTFE) composites under static and cyclic loading condition. Materials. 2021;14(7):1712. https://doi.org/10.3390/ma14071712Mazur K., Gądek-Moszczak A., Liber-Kneć А., et al. Mechanical behavior and morphological study of polytetrafluoroethylene (PTFE) composites under static and cyclic loading condition. Materials. 2021;14(7):1712. https://doi.org/10.3390/ma14071712Vishal K., Rajkumar K., Sabarinathan P. Effect of recovered silicon filler inclusion on mechanical and tribological properties of polytetrafluoroethylene (PTFE) composite. Silicon. 2022;14:4601–4610. https://doi.org/10.1007/s12633-021-01250-wVishal K., Rajkumar K., Sabarinathan P. Effect of recovered silicon filler inclusion on mechanical and tribological properties of polytetrafluoroethylene (PTFE) composite. Silicon. 2022;14:4601–4610. https://doi.org/10.1007/s12633-021-01250-wAdamov A.A., Keller I.E., Ostrer S.G., et al. Evaluation of the performance of antifriction PTFE composites at a pressure over 60 MPa. I. Comparison of their hardness and deformation properties under free and constrained compression. Mechanics of Composite Materials. 2022;58(5):673–678. https://doi.org/10.1007/s11029-022-10058-7Adamov A.A., Keller I.E., Ostrer S.G., et al. Evaluation of the performance of antifriction PTFE composites at a pressure over 60 MPa. I. Comparison of their hardness and deformation properties under free and constrained compression. Mechanics of Composite Materials. 2022;58(5):673–678. https://doi.org/10.1007/s11029-022-10058-7Адаменко Н.А., Игнатьева Л.Н., Агафонова Г.В. и др. Исследование молекулярной структуры политетрафторэтилена после взрывной обработки. Известия Волгоградского государственного технического университета. 2014;136(9):45–48.Adamenko N.A., Ignatova L.N., Agafonova G.V., et al. Study of the molecular structure of polytetrafluoroethylene after explosive treatment. Izvestiya Volgogradskogo gosudarstvennogo tekhnicheskogo universiteta. 2014;136(9):45–48. (In Russ.)Van Meter K.E., Junk Ch.P., Campbell K.L., et al. Ultralow wear self-mated PTFE composites. Macromolecules. 2022;55(10):3924–3935. https://doi.org/10.1021/acs.macromol.1c02581Van Meter K.E., Junk Ch.P., Campbell K.L., et al. Ultralow wear self-mated PTFE composites. Macromolecules. 2022;55(10):3924–3935. https://doi.org/10.1021/acs.macromol.1c02581

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