powderИзвестия вузов. Порошковая металлургия и функциональные покрытияPowder Metallurgy аnd Functional Coatings (Izvestiya Vuzov. Poroshkovaya Metallurgiya i Funktsional'nye Pokrytiya)1997-308X2412-8767НИТУ "МИСИС"10.17073/1997-308X-2025-5-5-16powder-1034Research ArticleТеория и процессы формования и спекания порошковых материаловTheory and Processes of Formation and Sintering of Powder MaterialsСпекание и термокинетическое моделирование эволюции состава термитных смесей в условиях регулируемого нагреваSintering and thermokinetic modeling of the phase evolution in thermite powder mixtures under controlled heatinghttps://orcid.org/0000-0002-9765-7695КнязеваА. Г.KnyazevaА. G.

Анна Георгиевна Князева – гл. науч. сотрудник лаборатории нелинейной механики метаматериалов и многоуровневых систем

Россия, 634055, г. Томск, пр. Академический, 8/2

Anna G. Knyazeva – Chief Researcher, Laboratory of Nonli­near Mechanics of Metamaterials and Multilevel Systems, Institute of Strength Physics and Materials Science

8/2 Akademicheskii Prosp., Tomsk 634055, Russia

anna-knyazeva@mail.ruhttps://orcid.org/0000-0002-4363-3604КоростелеваЕ. Н.KorostelevaЕ. N.

Елена Николаевна Коростелева – ст. науч. сотрудник лаборатории физики консолидации порошковых материалов

Россия, 634055, г. Томск, пр. Академический, 8/2

Elena N. Korosteleva – Senior Researcher, Laboratory of Physics of Powder Materials Consolidation

8/2 Akademicheskii Prosp., Tomsk 634055, Russia

elenak@ispms.ruhttps://orcid.org/0009-0004-7423-5897СафроноваВ. С.SafronovaV. S.

Валерия Сергеевна Сафронова – лаборант-исследователь лаборатории нелинейной механики метаматериалов и много­уровневых систем

Россия, 634055, г. Томск, пр. Академический, 8/2

Valeriya S. Safronova – Research Assistant, Laboratory of Nonlinear Mechanics of Metamaterials and Multilevel Systems

8/2 Akademicheskii Prosp., Tomsk 634055, Russia

l9627826013@yandex.ruИнститут физики прочности и материаловедения Сибирского отделения РАНРоссияInstitute of Strength Physics and Materials Science, Siberian Branch, Russian Academy of SciencesRussian Federation202505112025195516Copyright © Князева А.Г., Коростелева Е.Н., Сафронова В.С., 20252025Князева А.Г., Коростелева Е.Н., Сафронова В.С.Knyazeva А.G., Korosteleva Е.N., Safronova V.S.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://powder.misis.ru/jour/article/view/1034

Проанализировано поведение прессовок из смесей порошков металлов (Al, Ti) и переработанных отходов металло­обработки (Fe + Fe2O3 + C) в условиях вакуумного спекания при регулируемом нагреве для исследования возможности получения in situ металломатричных композиционных материалов с упрочняющими оксидными частицами. В качестве исходных материалов использованы порошки титана и алюминия с фракциями d < 160 мкм и <100 мкм соответственно, а также порошок переработанной стружки из стали размером менее 300 мкм. В результате проведенного эксперимента обнаружен неоднородный фазовый состав образцов, который исследовали с помощью рентгеновского дифрактометра XRD-6000 с CuKα-излучением и оптического микроскопа «Axiovert 200MAT». Продемонстрировано существенное различие в поведении систем на основе алюминия и титана: первая система характеризуется ярко выраженным термическим пиком, а во второй – превращения идут в спокойном режиме. Предложена термокинетическая модель процесса, учитывающая стадийность превращений для обеих систем. Учтены металлотермические реакции и реакции образования интерметаллидов. Дана оценка формально-кинетическим параметрам реакций с помощью полуэмпирического подхода. Полученные параметры корректировались при сравнении с экспериментом. Модель реализована численно с помощью полунеявного метода Эйлера. Проверялись закон сохранения массы и неизменность числа атомов. Начальный состав образцов в расчетах варьировался (за счет учета присутствия кислорода, углерода и соотношения железа и оксида железа в стружке) таким образом, чтобы в результате синтеза получить состав продуктов, максимально приближенный к результатам эксперимента. Получено качественное соответствие теории и эксперимента.

The behavior of compacted mixtures of metal powders (Al, Ti) and recycled metalworking wastes (Fe + Fe2O3 + C) during vacuum sintering under controlled heating was investigated to assess the possibility of producing in situ metal–matrix composites containing oxide strengthening particles. The starting materials were titanium and aluminum powders (particle size <160 μm and <100 μm, respectively) and a powder produced from recycled steel chips (<300 μm). The resulting samples exhibited a heterogeneous phase composition, which was examined by X-ray diffraction (CuKα radiation, XRD-6000 diffractometer) and optical microscopy (Axiovert 200MAT). A pronounced difference was observed between the aluminum- and titanium-based systems: the former exhi­bited a distinct thermal peak, whereas the latter showed smooth temperature behavior without thermal spikes. A thermokinetic model describing the multi-stage reactions in both systems was developed. The model incorporates metallothermic reduction and intermetallic formation reactions. Formal kinetic parameters were estimated using a semi-empirical approach and refined by comparison with experimental data. The governing equations, including the heat balance equation and the system of kinetic rate equations, were solved numerically using a semi-implicit Euler method, while mass conservation and atomic balance were verified. The initial composition of the samples was varied in the calculations – accounting for oxygen, carbon, and the Fe/Fe2O3 ratio in the steel-chippowder – to reproduce the experimentally observed product compositions. The calculated and experimental results showed qualitative agreement.

металломатричный композитвакуумное спеканиеметаллотермические реакцииинтерметаллидытермокинетическая модельmetal-matrix compositevacuum sinteringmetallothermic reactionsintermetallicsthermokinetic modelРабота выполнена по программе фундаментальных научных исследований ИФПМ СО РАН: проекты FWRW-2022-0003 (теоретическая часть) и FWRW-2021-0005 (экспериментальная часть).This work was carried out within the framework of the Fundamental Research Program of the Institute of Strength Physics and Materials Science, Siberian Branch of the Russian Academy of Sciences (ISPMS SB RAS): Project FWRW-2022-0003 (theoretical part) and Project FWRW-2021-0005 (experimental part).ReferencesYeh C.L., Li R.F. Formation of TiAl–Ti5Si3 and TiAl–Al2O3 in situ composites by combustion synthesis. Intermetallics. 2008;16(1):64–70. https://doi.org/10.1016/j.intermet.2007.07.016Yeh C.L., Li R.F. Formation of TiAl–Ti5Si3 and TiAl–Al2O3 in situ composites by combustion synthesis. Intermetallics. 2008;16(1):64–70. https://doi.org/10.1016/j.intermet.2007.07.016Zhang X., Li X., Wang J., Liu L., Li S., Li B., Hou X., Gao J., Kariya S., Umeda J., Kondoh K., Li S. Synthesis mechanism and interface contribution towards the strengthening effect of in-situ Ti5Si3 reinforced Al mat­rix composites. Materials Science and Engineering: A. 2024; 918:147427. https://doi.org/10.1016/j.msea.2024.147427Zhang X., Li X., Wang J., Liu L., Li S., Li B., Hou X., Gao J., Kariya S., Umeda J., Kondoh K., Li S. Synthesis mechanism and interface contribution towards the strengthening effect of in-situ Ti5Si3 reinforced Al mat­rix composites. Materials Science and Engineering: A. 2024; 918:147427. https://doi.org/10.1016/j.msea.2024.147427Yang Y.F., Mu D.K., Jiang Q.C. A simple route to fabricate TiC–TiB2/Ni composite via thermal explosion reaction assisted with external pressure in air. Materials Chemistry and Physics. 2014;143(2):480–485. https://doi.org/10.1016/j.matchemphys.2013.10.003Yang Y.F., Mu D.K., Jiang Q.C. A simple route to fabricate TiC–TiB2/Ni composite via thermal explosion reaction assisted with external pressure in air. Materials Chemistry and Physics. 2014;143(2):480–485. https://doi.org/10.1016/j.matchemphys.2013.10.003Lemboub S., Boudebane S., Gotor F.J., Haouli S., Mezrag S., Bouhedja S., Hesser G., Chadli H., Chouchane T. Core-rim structure formation in TiC–Ni based cermets fabricated by a combined thermal explosion/hot-pressing process. International Journal of Refractory Metals and Hard Materials. 2018;70:84–92. https://doi.org/10.1016/j.ijrmhm.2017.09.014Lemboub S., Boudebane S., Gotor F.J., Haouli S., Mezrag S., Bouhedja S., Hesser G., Chadli H., Chouchane T. Core-rim structure formation in TiC–Ni based cermets fabricated by a combined thermal explosion/hot-pressing process. International Journal of Refractory Metals and Hard Materials. 2018;70:84–92. https://doi.org/10.1016/j.ijrmhm.2017.09.014Yeh C.L., Ke C.Y. Synthesis of TiB2–Al2O3–FeAl composites via self-sustaining combustion with Fe2O3/TiO2-based thermite mixtures. Ceramics International. 2018;44(13):16030–16034. https://doi.org/10.1016/j.ceramint.2018.06.040Yeh C.L., Ke C.Y. Synthesis of TiB2–Al2O3–FeAl composites via self-sustaining combustion with Fe2O3/TiO2-based thermite mixtures. Ceramics International. 2018;44(13):16030–16034. https://doi.org/10.1016/j.ceramint.2018.06.040Zhang K., Fen W., Zhu J., Wu H. Mechanical properties and microstructure of Al2O3/TiAl in situ composites doped with Cr and V2O5. Science of Sintering. 2012;44(1):73–80. https://doi.org/10.2298/SOS1201073ZZhang K., Fen W., Zhu J., Wu H. Mechanical properties and microstructure of Al2O3/TiAl in situ composites doped with Cr and V2O5. Science of Sintering. 2012;44(1):73–80. https://doi.org/10.2298/SOS1201073ZMotlagh E.B., Nasiri H., Khaki J.V., Sabzevar M.H. Formation of metal matrix composite reinforced with nano sized Al2O3+Ni–Al intermetallics during coating of Al substrate via combustion synthesis. Surface & Coatings Technology. 2011;205(23-24):5515–5520. https://doi.org/10.1016/j.surfcoat.2011.06.026Motlagh E.B., Nasiri H., Khaki J.V., Sabzevar M.H. Formation of metal matrix composite reinforced with nano sized Al2O3+Ni–Al intermetallics during coating of Al substrate via combustion synthesis. Surface & Coatings Technology. 2011;205(23-24):5515–5520. https://doi.org/10.1016/j.surfcoat.2011.06.026Kim J.-W., Lee J.-M., Lee J.-H., Lee J.-C. Role of excess Al on the combustion reaction in the Al–TiO2–C system. Metal­s and Materials International. 2014;20(6): 1151–1156. https://doi.org/10.1007/s12540-014-6020-8Kim J.-W., Lee J.-M., Lee J.-H., Lee J.-C. Role of excess Al on the combustion reaction in the Al–TiO2–C system. Metal­s and Materials International. 2014;20(6): 1151–1156. https://doi.org/10.1007/s12540-014-6020-8Miloserdov P.A., Gorshkov V.A., Andreev D.E., Yukh­vid V.I., Miloserdova O.M., Golosova O.A. Metallothermic SHS of Al2O3–Cr2O3 + TiC ceramic composite material. Ceramics International. 2023;49(14):24071–24076. https://doi.org/10.1016/j.ceramint.2023.04.145Miloserdov P.A., Gorshkov V.A., Andreev D.E., Yukh­vid V.I., Miloserdova O.M., Golosova O.A. Metallothermic SHS of Al2O3–Cr2O3 + TiC ceramic composite material. Ceramics International. 2023;49(14):24071–24076. https://doi.org/10.1016/j.ceramint.2023.04.145Korosteleva E.N., Knyazeva A.G., Nikolaev I.O. Phase formation in reactive sintering with reduction. Physical Mesomechanics. 2023;26(1):39–47. https://doi.org/10.1134/S1029959923010058Korosteleva E.N., Knyazeva A.G., Nikolaev I.O. Phase formation in reactive sintering with reduction. Physical Mesomechanics. 2023;26(1):39–47. https://doi.org/10.1134/S1029959923010058Коростелева Е.Н., Николаев И.О. Эволюция структурно-фазового состояния стальной стружки в процессе ее переработки в порошкообразный продукт. Известия вузов. Порошковая металлургия и функциональные покрытия. 2024;18(4):6–16. https://doi.org/10.17073/1997-308X-2024-4-6-16Korosteleva E.N., Nikolaev I.О. Evolution of the structural-phase state of steel swarf during its processing into a powdered product. Powder Metallurgy and Functional Coatings. 2024;18(4):6–16. https://doi.org/10.17073/1997-308X-2024-4-6-16Коростелева Е.Н., Николаев И.О., Барановский А.В. Синтез и эволюция структурно-фазового состояния порошковых материалов Al–Fe–Fe2O3 в условиях нагрева. В сб.: Материалы XVII Минского международного форума по тепло- и массообмену (20–24 мая 2024 г.). Минск: Институт тепло- и массообмена им. А.В. Лыкова НАН Беларуси, 2024. С. 746–748.Korosteleva E.N., Nikolaev I.О., Baranovsky А.V. Synthesis and evolution of the structural and phase state of powder materials Al–Fe–Fe2O3 under heating conditions. In: Collection of materials of the XVII Minsk International Heat and Mass Transfer Forum (20–24 May 2024). Minsk: Institute of Heat and Mass Transfer n.a. Lykov of the NAS of Belarus, 2024. P. 746–748. (In Russ.).Miedema A.R., de Chȃtel P.F, de Boer F.R., de Chatel P.F. Cohesion in alloys – fundamental of a semi-empirical model. Physica B + C. 1980;100(1):1–28. https://doi.org/10.1016/0378-4363(80)90054-6Miedema A.R., de Chȃtel P.F, de Boer F.R., de Chatel P.F. Cohesion in alloys – fundamental of a semi-empirical model. Physica B + C. 1980;100(1):1–28. https://doi.org/10.1016/0378-4363(80)90054-6Binnewies M., Milke E. Thermochemical data of elements and compounds. Wiley-VCH Verlag GmbH, 2008. 928 p. https://doi.org/10.1002/9783527618347Binnewies M., Milke E. Thermochemical data of elements and compounds. Wiley-VCH Verlag GmbH, 2008. 928 p. https://doi.org/10.1002/9783527618347Safronova V.S., Knyazeva A.G., Korosteleva E.N. A theo­retical and experimental study of phase formation in Ti–CuO powder mixtures under reactive sintering conditions. New Journal of Chemistry. 2025;49(3):893–909. https://doi.org/10.1039/d4nj03751kSafronova V.S., Knyazeva A.G., Korosteleva E.N. A theo­retical and experimental study of phase formation in Ti–CuO powder mixtures under reactive sintering conditions. New Journal of Chemistry. 2025;49(3):893–909. https://doi.org/10.1039/d4nj03751kПодергин В.А. Металлотермические системы. М.: Металлургия, 1992. 272 с.Podergin V.А. Metallothermal systems. Moscow: Metallurgiya, 1992. 272 p. (In Russ.).Корчагин М.А., Подергин В.А. Исследование химических превращений при горении конденсированных систем. Физика горения и взрыва. 1979;(3):48–53.Korchagin M.A., Podergin V.A. Investigation of chemical transformations in the combustion of condensed systems. Combustion, Explosion, and Shock Waves. 1979;15(3):325–329. https://doi.org/10.1007/BF00785065Liu W., Ismail M., Dunstan M.T., Hu W., Zhang Z., Fennell P.S., Scott S.A., Dennis J.S. Inhibiting the interaction between FeO and Al2O3 during chemical looping production of hydrogen. RSC Advances. 2015;5(3):1759–1771. https://doi.org/10.1039/C4RA11891JLiu W., Ismail M., Dunstan M.T., Hu W., Zhang Z., Fennell P.S., Scott S.A., Dennis J.S. Inhibiting the interaction between FeO and Al2O3 during chemical looping production of hydrogen. RSC Advances. 2015;5(3):1759–1771. https://doi.org/10.1039/C4RA11891JLiu Y., Watanabe M., Okugawa M., Hagiwara T., Sato T., Seguchi Y., Adachi Y., Minamino Y., Koizumi Y. Resol­ving the long-standing discrepancy in Fe3Al ordering mobilities: A synergistic experimental and phase-field study. Acta Materialia. 2024;273:119958. https://doi.org/10.1016/j.actamat.2024.119958Liu Y., Watanabe M., Okugawa M., Hagiwara T., Sato T., Seguchi Y., Adachi Y., Minamino Y., Koizumi Y. Resol­ving the long-standing discrepancy in Fe3Al ordering mobilities: A synergistic experimental and phase-field study. Acta Materialia. 2024;273:119958. https://doi.org/10.1016/j.actamat.2024.119958Lin Y.-C., Shteinberg A.S., McGinn P.J., Mukasyan A.S. Kinetics study in Ti–Fe2O3 system by electro-thermal explosion method. International Journal of Thermal Scien­ces. 2014;84:369–378. https://doi.org/10.1016/j.ijthermalsci.2014.06.008Lin Y.-C., Shteinberg A.S., McGinn P.J., Mukasyan A.S. Kinetics study in Ti–Fe2O3 system by electro-thermal explosion method. International Journal of Thermal Scien­ces. 2014;84:369–378. https://doi.org/10.1016/j.ijthermalsci.2014.06.008Mukasyan A.S., Shuck C.E. Kinetics of SHS reactions: A review. International Journal of Self-Propagating High-Temperature Synthesis. 2017;26(3):145–165. https://doi.org/10.3103/S1061386217030049Mukasyan A.S., Shuck C.E. Kinetics of SHS reactions: A review. International Journal of Self-Propagating High-Temperature Synthesis. 2017;26(3):145–165. https://doi.org/10.3103/S1061386217030049Durães L., Costa B.F.O., Santos R., Correia A., Campos J., Portugal A. Fe2O3/aluminum thermite reaction interme­diate and final products characterization. Materials Scien­ce and Engineering: A. 2007;465(1-2):199–210. https://doi.org/10.1016/j.msea.2007.03.063Durães L., Costa B.F.O., Santos R., Correia A., Campos J., Portugal A. Fe2O3/aluminum thermite reaction interme­diate and final products characterization. Materials Scien­ce and Engineering: A. 2007;465(1-2):199–210. https://doi.org/10.1016/j.msea.2007.03.063Bodaghi M., Zolfonoon H., Tahriri M., Karimi M. Synthesis and characterization of nanocrystalline α-Al2O3 usin­g Al and Fe2O3 (hematite) through mechanical alloying. Solid State Sciences. 2009;11(2):496–500. https://doi.org/10.1016/j.solidstatesciences.2008.06.021Bodaghi M., Zolfonoon H., Tahriri M., Karimi M. Synthesis and characterization of nanocrystalline α-Al2O3 usin­g Al and Fe2O3 (hematite) through mechanical alloying. Solid State Sciences. 2009;11(2):496–500. https://doi.org/10.1016/j.solidstatesciences.2008.06.021

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