blackmetИзвестия высших учебных заведений. Черная МеталлургияIzvestiya. Ferrous Metallurgy0368-07972410-2091National University of Science and Technology "MISIS"10.17073/0368-0797-2019-8-639-645blackmet-1699Research ArticleФИЗИКО-ХИМИЧЕСКИЕ ОСНОВЫ МЕТАЛЛУРГИЧЕСКИХ ПРОЦЕССОВPHYSICO-CHEMICAL BASICS OF METALLURGICAL PROCESSESТермодинамическое моделирование изотерм растворимос­ти кислорода в жидком металле системы Fe – Mg – Al – OThermodynamic modeling of isotherms of oxygen solubility in liquid metal of Fe – Mg – Al – O systemМихайловГ. Г.MikhailovG. G.

д.т.н., профессор, заведующий кафедрой материаловедения и физико-химии материалов

Dr. Sci. (Eng.), Professor, Head of the Chair of Materials Science and Physical Chemistry of Materials

mikhailovgg@susu.ruСамойловаО. В.SamoilovaO. V.

к.х.н., старший научный сотрудник кафедры материаловедения и физико-химии материалов

Cand. Sci. (Chem.), Senior Researcher of the Chair of Materials Science and Physical Chemistry of Materials

samoylova_o@mail.ruМакровецЛ. А.MakrovetsL. A.

инженер кафедры материаловедения и физико-химии материалов

Engineer of the Chair of Materials Science and Phy­sical Chemistry of Materials

makrovetcla@susu.ruСмирновЛ. А.SmirnovL. A.

академик РАН, д.т.н., главный научный сотрудник

Academician of Russian Academy of Sciences (RAS), Dr. Sci. (Eng.), Chief Researcher

sekretar@uim-stavan.ruЮжно-Уральский государственный университетРоссияSouth Ural State UniversityRussian FederationИнститут металлургии УрО РАНРоссияInstitute of MetallurgyRussian Federation201912092019628639645Copyright © Михайлов Г.Г., Самойлова О.В., Макровец Л.А., Смирнов Л.А., 20192019Михайлов Г.Г., Самойлова О.В., Макровец Л.А., Смирнов Л.А.Mikhailov G.G., Samoilova O.V., Makrovets L.A., Smirnov L.A.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://fermet.misis.ru/jour/article/view/1699

Изучение взаимодействия растворенных в жидком железе магния и алюминия с кислородом является важной задачей для выбора оптимальных параметров рафинирования и разливки сталей. Актуальность исследования обусловлена определением возможности и условий образования неблагоприятных тугоплавких частиц оксида магния и магнезиальной шпинели в расплаве. Проведено термодинамическое моделирование фазовых равновесий, реализующихся в жидком металле систем Fe – Mg – O, Fe – Al – O и Fe – Mg – Al – O в интервале температур 1550 – 1650 °С. Расчет выполняли с использованием методики построения поверхности растворимости компонентов в металле, которая связывает количественные изменения в составе жидкого металла с изменениями в составе продуктов взаимодействия компонентов металлического расплава. Методика моделирования базировалась не только на использовании констант равновесия реакций, протекающих между компонентами исследуемых систем в выбранном интервале температур, но и на учете значений параметров взаимодействия первого порядка (по Вагнеру) элементов в жидком железе. Для моделирования активностей оксидного расплава, сопряженного с металлическим, использовали приближение теории субрегулярных ионных растворов. Для моделирования активностей твердого раствора оксидов использовали приближение теории регулярных ионных растворов, а для твердого раствора шпинелей – теорию совершенных ионных растворов. Построены изотермы растворимости кислорода в жидком металле систем Fe – Mg – O, Fe – Al – O и Fe – Mg – Al – O и определены области термодинамической стабильности оксидных фаз, сопряженных с металлическим расплавом. В частности, для системы Fe – Mg – Al – O определена область составов жидкого металла, в равновесии с которым будет находиться твердый раствор шпинелей FeAl 2 O 4 , MgAl 2 O 4 | тв.р . Полученные результаты термодинамического моделирования сопоставлены с экспериментальными данными.

Studying the interaction between oxygen and magnesium and aluminum dissolved in liquid iron is an important task in order to choose optimal parameters for refining and casting of steels. Relevance of this research is caused by determining the possibility and conditions for formation of unfavorable refractory particles of magnesium oxideand magnesian spinel in a metal melt. In the course of this research, thermodynamic modeling of phase equilibria implemented in liquid metal of such systems as Fe – Mg – O, Fe – Al – O and Fe – Mg – Al – O within the temperature range of 1550 – 1650 °С was carried out. Calculation was made using the technique of constructing the solubility surfaces for the metal components which connects quantitative changes in composition of a liquid metal with qualitative changes in composition of products obtained as a result of interaction of a metallic melt’s components. The modeling method was based not only on usin­g equilibrium constants of reactions occurring between components of the systems under research in the selected temperature range, but also on taking into account the values of interaction parameters of the first order (according to Wagner) of elements in liquid iron. In order to simulate activities of the oxide melt conjugated with the metallic one, approximation of the theory of subregular ionic solutions was used. To model activities of oxides solid solution, approximation of the theory of regular ionic solutions was used. And the theory of ideal ionic solutions was used for the solid solution of spinels. In the course of the work, isotherms of oxygen’s solubility in liquid metal of systems Fe – Mg – O, Fe – Al – O and Fe – Mg – Al – O have been constructed, and regions of thermodynamic stability of oxide phases conjugated with the metallic melt have been determined. In particular, compositions area of a liquid metal which is going to be in equilibrium with the solid solution of spinels | FeAl 2 O 4 , MgAl 2 O 4 | solid solution has been determined for Fe – Mg – Al – O system. Results obtained in the course of thermodynamic modeling have been compared to experimental data.

Моделированиефазовые равновесиятермодинамикадиаграмма состояниймагнийалюминийраскислениеsimulationphase equilibriathermodynamicsphase diagrammagnesiumaluminumdeoxidationReferencesЖучков В.И., Лукин С.В., Шилина И.В. Раскисление стали кальций – магний – кремниевыми ферросплавами // Изв. Вуз. Черная металлургия. 1977. No 12. С. 69 – 71.Zhuchkov V.I., Lukin S.V., Shilina I.V. Deoxidation of steel by calcium-magnesium-silicon ferroalloys. Izvestiya. Ferrous Metallurgy. 1977, no. 12, pp. 69–71. (In Russ.).Жалыбин В.И., Ершов Г.С. О восстановлении магния футеровки при выплавке стали, легированной алюминием // Изв. АН СССР. Металлы. 1966. No 1. С. 49 – 53.Zhalybin V.I., Ershov G.S. On the recovery of magnesium lining at smelting of steel alloyed by aluminum. Izv. AN SSSR. Metally. 1966, no. 1, pp. 49–53. (In Russ.).Xu H., Cao W., Dong H., Li J. Effects of aluminium on the microstructure and mechanical properties in 0,2C – 5Mn steels under different heat treatment conditions // ISIJ Intern. 2015. Vol. 55. No. 3. P. 662 – 669.Xu H., Cao W., Dong H., Li J. Effects of aluminium on the microstructure and mechanical properties in 0.2C–5Mn steels under different heat treatment conditions. ISIJ Intern. 2015, vol. 55, no. 3, pp. 662–669.Hilty D.C., Grafts W. The solubility of oxygen in liquid iron con­taining aluminium // Trans. AIME. 1950. Vol. 188. No. 2. P. 414 – 424.Hilty D.C., Grafts W. The solubility of oxygen in liquid iron containing aluminium. Trans. AIME. 1950, vol. 188, no. 2, pp. 414–424.Gokcen N.A., Chipman J. Aluminium – oxygen equilibrium in liquid iron // Trans. AIME. 1953. Vol. 197. P. 173 – 178.Gokcen N.A., Chipman J. Aluminium – oxygen equilibrium in liquid iron. Trans. AIME. 1953, vol. 197, pp. 173–178.Михайлов Г.Г., Леонович Б.И., Кузнецов Ю.С. Термодинамика металлургических процессов и систем. – М.: Издательский Дом МИСиС, 2009. – 519 с.Mikhailov G.G., Leonovich B.I., Kuznetsov Yu.S. Termodinamika metallurgicheskikh protsessov i sistem [Thermodynamics of metallurgical processes and systems]. Moscow: ID MISiS, 2009, 519 p. (In Russ.).Чернова Л.А., Михайлов Г.Г. Термодинамические характеристики процессов взаимодействия кислорода с металлическими расплавами систем Fe – V – Me – Si – O – C (Me = Cr, Mn) // Журнал физической химии. 2006. Т. 80. No 11. С. 2058 – 2069.Chernova L.A., Mikhailov G.G. Thermodynamic characteristics of the interaction of oxygen with metal melts of Fe–V–Me–Si–O–C (Me = Cr and Mn) systems. Russian Journal of Physical Chemistry A . 2006, vol. 80, no. 11, pp. 1832–1836.Михайлов Г.Г., Чернова Л.А. Термодинамический анализ процессов раскисления стали кальцием и алюминием // Электрометаллургия. 2008. No 3. С. 6 – 8.Mikhailov G.G., Chernova L.A. Thermodynamic analysis of the processes of steel deoxidation by calcium and aluminum. Elektrometallurgiya. 2008, no. 3, pp. 6–8. (In Russ.).Mikhailov G.G., Zherebtsov D.A. On the interaction of calcium and oxygen in liquid iron // Mater. Sci. Forum. 2016. Vol. 843. P. 52 – 61.Mikhailov G.G., Zherebtsov D.A. On the interaction of calcium and oxygen in liquid iron. Mater. Sci. Forum. 2016, vol. 843, pp. 52–61.Jo S.K., Song B., Kim S.H. Thermodynamics on the formation of spinel (MgO·Al 2 O 3 ) inclusion in liquid iron containing chromium // Metall. Mater. Trans. B. 2002. Vol. 33 B. P. 703 – 709.Jo S.K., Song B., Kim S.H. Thermodynamics on the formation of spinel (MgO·Al 2 O 3 ) inclusion in liquid iron containing chromium. Metall. Mater. Trans. B. 2002, vol. 33 B, pp. 703–709.Zhang T., Min Y., Liu C., Jiang M. Effect of Mg addition on the evolution of inclusions in Al – Ca deoxidized melts // ISIJ Intern. 2015. Vol. 55. No. 8. P. 1541 – 1548.Zhang T., Min Y., Liu C., Jiang M. Effect of Mg addition on the evolution of inclusions in Al–Ca deoxidized melts. ISIJ Intern. 2015, vol. 55, no. 8, pp. 1541–1548.Du Y., Zhao J.R., Zhang C., Chen H.L., Zhang L.J. Thermodynamic modeling of the Fe – Mg – Si system // J. Min. Metall. Sect. B. 2007. Vol. 43 B. P. 39 – 56.Du Y., Zhao J.R., Zhang C., Chen H.L., Zhang L.J. Thermodynamic modeling of the Fe–Mg–Si system. J. Min. Metall. Sect. B. 2007, vol. 43 B, pp. 39–56.Zhang X., Han Q., Chen D. Dissolution equilibrium of magnesium vapor in liquid iron // Metall. Trans. B. 1991. Vol. 22 B. P. 918 – 921.Zhang X., Han Q., Chen D. Dissolution equilibrium of magnesium vapor in liquid iron. Metall. Trans. B. 1991, vol. 22 B, pp. 918–921.Stein F., Palm M. Re-determination of transition temperatures in the Fe – Al system by differential thermal analysis // Int. J. Mater. Res. 2007. Vol. 98. No. 7. P. 580 – 588.Stein F., Palm M. Re-determination of transition temperatures in the Fe–Al system by differential thermal analysis. Int. J. Mater. Res. 2007, vol. 98, no. 7, pp. 580–588.Hidayat T., Shishin D., Jak E., Decterov S.A. Thermodynamic re­evaluation of the Fe – O system // Calphad. 2015. Vol. 48. P. 131 – 144.Hidayat T., Shishin D., Jak E., Decterov S.A. Thermodynamic reevaluation of the Fe–O system. Calphad. 2015, vol. 48, pp. 131–144.Wriedt H.A. The Mg – O (magnesium – oxygen) system // Bull. Alloy Phase Diagrams. 1987. Vol. 8. No. 3. P. 227 – 233.Wriedt H.A. The Mg–O (magnesium – oxygen) system. Bull. Alloy Phase Diagrams. 1987, vol. 8, no. 3, pp. 227–233.Wriedt H.A. The Al – O (aluminum – oxygen) system // Bull. Alloy Phase Diagrams. 1985. Vol. 6. No. 6. P. 548 – 553.Wriedt H.A. The Al–O (aluminum – oxygen) system. Bull. Alloy Phase Diagrams. 1985, vol. 6, no. 6, pp. 548–553.Kubaschewski O., Alcock C.B. Metallurgical Thermochemistry. – Oxford: Pergamon Press Ltd Publ., 1979. – 450 p.Kubaschewski O., Alcock C.B. Metallurgical Thermochemistry. Oxford: Pergamon Press Ltd Publ., 1979, 450 p.Darken L.S., Gurry R.W. The system iron–oxygen. II. Equilibrium and thermodynamics of liquid oxide and other phases // J. Am. Chem. Soc. 1946. Vol. 68. P. 798 – 816.Darken L.S., Gurry R.W. The system iron–oxygen. II. Equilibrium and thermodynamics of liquid oxide and other phases. J. Am. Chem. Soc. 1946, vol. 68, pp. 798–816.Wu P., Eriksson G., Pelton A.D., Blander M. Prediction of the thermodynamic properties and phase diagrams of silicate systems – evaluation of the FeO – MgO – SiO 2 system // ISIJ Intern. 1993. Vol. 33. No. 1. P. 26 – 35.Wu P., Eriksson G., Pelton A.D., Blander M. Prediction of the thermodynamic properties and phase diagrams of silicate systems – evaluation of the FeO–MgO–SiO 2 system. ISIJ Intern. 1993, vol. 33, no. 1, pp. 26–35.Slag Atlas. 2 nd Edition. Edited by Verein Deutscher Eisenhüttenleute (VDEh). – Düsseldorf: Verlag Stahleisen GmbH., 1995. P. 40 – 44.Slag Atlas. 2 nd ed. Edited by Verein Deutscher Eisenhüttenleute (VDEh). Düsseldorf: Verlag Stahleisen GmbH., 1995, pp. 40–44.Rankin G.A., Merwin H.E. The ternary system CaO – Al 2 O 3 – MgO // J. Am. Chem. Soc. 1916. Vol. 38. No. 3. P. 568 – 588.Rankin G.A., Merwin H.E. The ternary system CaO–Al 2 O 3 –MgO. J. Am. Chem. Soc. 1916, vol. 38, no. 3, pp. 568–588.Ono A. Fe – Mg partitioning between spinel and olivine // J. Japan Assoc. Min. Petr. Econ. Geol. 1983. Vol. 78. P. 115 – 122.Ono A. Fe–Mg partitioning between spinel and olivine. J. Japan Assoc. Min. Petr. Econ. Geol. 1983, vol. 78, pp. 115–122.Yang J., Kuwabara M., Sakai T., Uchida N., Liu Z., Sano M. Simul taneous desulfurization and deoxidation of molten steel with in situ produced magnesium vapor // ISIJ Intern. 2007. Vol. 47. No. 3. P. 418 – 426.Yang J., Kuwabara M., Sakai T., Uchida N., Liu Z., Sano M. Simultaneous desulfurization and deoxidation of molten steel with in situ produced magnesium vapor. ISIJ Intern. 2007, vol. 47, no. 3, pp. 418–426.Mizukami H., Numata M., Yamanaka A. Generation of heterogeneous nucleus in carbon steel during solidification by magnesium vapor injection // ISIJ Intern. 2016. Vol. 56. No. 8. P. 1420 – 1426.Mizukami H., Numata M., Yamanaka A. Generation of heterogeneous nucleus in carbon steel during solidification by magnesium vapor injection. ISIJ Intern. 2016, vol. 56, no. 8, pp. 1420–1426.Михайлов Г.Г., Макровец Л.А., Смирнов Л.А. Термодинамическое моделирование процессов взаимодействия лантана с компонентами металлических расплавов на основе железа // Изв. Вуз. Черная металлургия. 2015. Т. 58. No 12. С. 877 – 883.Mikhailov G.G., Makrovets L.A., Smirnov L.A. Thermodynamic modeling of lanthanum interaction processes using iron-based metallic melts. Izvestiya. Ferrous Metallurgy. 2015, vol. 58, no. 12, pp. 877–883. (In Russ.).Hasegawa M., Tsukamoto T., Iwase M. Activity of iron oxide in magnesiowüstite in equilibrium with solid metallic iron // Mater. Trans. 2006. Vol. 47. No. 3. P. 854 – 860.Hasegawa M., Tsukamoto T., Iwase M. Activity of iron oxide in magnesiowüstite in equilibrium with solid metallic iron. Mater. Trans. 2006, vol. 47, no. 3, pp. 854–860.Satoh N., Taniguchi T., Mishima S., Oka T., Miki T., Hino M. Prediction of nonmetallic inclusion formation in Fe – 40 mass % Ni – 5 mass % Cr alloy production process // Tetsu-to-Hagané. 2009. Vol. 95. No. 12. P. 827 – 836.Satoh N., Taniguchi T., Mishima S., Oka T., Miki T., Hino M. Prediction of nonmetallic inclusion formation in Fe – 40 mass % Ni – 5 mass % Cr alloy production process. Tetsu-to-Hagané. 2009, vol. 95, no. 12, pp. 827–836.Park J.H., Todoroki H. Control of MgO·Al 2 O 3 spinel inclusions in stainless steels // ISIJ Intern. 2010. Vol. 50. No. 10. P. 1333 – 1346.Park J.H., Todoroki H. Control of MgO·Al 2 O 3 spinel inclusions in stainless steels. ISIJ Intern. 2010, vol. 50, no. 10, pp. 1333–1346.Itoh H., Hino M., Ban-Ya S. Thermodynamics on the formation of non-metallic inclusion of spinel (MgO·Al 2 O 3 ) in liquid steel // Tetsu-to-Hagané. 1998. Vol. 84. No. 2. P. 85 – 90.Itoh H., Hino M., Ban-Ya S. Thermodynamics on the formation of non-metallic inclusion of spinel (MgO·Al 2 O 3 ) in liquid steel. Tetsuto-Hagané. 1998, vol. 84, no. 2, pp. 85–90.Steelmaking Data Sourcebook, Japan Society for the Promotion of Science, The 19 th Committee on Steelmaking. – New York: Gordon and Breach Science Publishers, 1988. P. 288.Steelmaking Data Sourcebook. Japan Society for the Promotion of Science, The 19 th Committee on Steelmaking. New York: Gordon and Breach Science Publishers, 1988, p. 288.Wang L.J., Liu Y.Q., Wang Q., Chou K.C. Evolution mechanisms of MgO·Al 2 O 3 inclusions by cerium in spring steel used in fasteners of high-speed railway // ISIJ Intern. 2015. Vol. 55. No. 5. P. 970 – 975.Wang L.J., Liu Y.Q., Wang Q., Chou K.C. Evolution mechanisms of MgO·Al 2 O 3 inclusions by cerium in spring steel used in fasteners of high-speed railway. ISIJ Intern. 2015, vol. 55, no. 5, pp. 970–975.Prox H., Hino M., Ban-Ya S. Assessment of Al deoxidation equilibrium in liquid iron // Tetsu-to-Hagané. 1997. Vol. 83. No. 12. P. 773 – 778.Prox H., Hino M., Ban-Ya S. Assessment of Al deoxidation equilibrium in liquid iron. Tetsu-to-Hagané. 1997, vol. 83, no. 12, pp. 773–778.Itoh H., Hino M., Ban-Ya S. Thermodynamics on the formation of spinel nonmetallic inclusion in liquid steel // Metall. Mater. Trans. B. 1997. Vol. 28 B. P. 953 – 956.Itoh H., Hino M., Ban-Ya S. Thermodynamics on the formation of spinel nonmetallic inclusion in liquid steel. Metall. Mater. Trans. B. 1997, vol. 28 B, pp. 953–956.Janke D., Fischer W.A. Desoxidationsgleichgewichte von titan, aluminium und zirconium in eisenschmelzen bei 1600 °C // Arch. Eisenhüttenwes. 1976. Vol. 47. No. 4. P. 195 – 198.Janke D., Fischer W.A. Desoxidationsgleichgewichte von Titan, Aluminium und Zirconium in Eisenschmelzen bei 1600 °C. Arch. Eisenhüttenwes. 1976, vol. 47, no. 4, pp. 195–198. (In Germ.).Kang Y., Thunman M., Sichen D., Morohoshi T., Mizukami K., Morita K. Aluminum deoxidation equilibrium of molten iron aluminum alloy with wide aluminum composition range at 1873 K // ISIJ Intern. 2009. Vol. 49. No. 10. P. 1483 – 1489.Kang Y., Thunman M., Sichen D., Morohoshi T., Mizukami K., Morita K. Aluminum deoxidation equilibrium of molten iron – aluminum alloy with wide aluminum composition range at 1873 K. ISIJ Intern. 2009, vol. 49, no. 10, pp. 1483–1489.Paek M.K., Jang J.M., Kang Y.B., Pak J.J. Aluminum deoxidation equilibria in liquid iron: part I. Experimental // Metall. Mater. Trans. B. 2015. Vol. 46. No. 4. P. 1826 – 1836.Paek M.K., Jang J.M., Kang Y.B., Pak J.J. Aluminum deoxidation equilibria in liquid iron: part I. Experimental. Metall. Mater. Trans. B . 2015, vol. 46, no. 4, pp. 1826–1836.Fruehan R.J. Activities in liquid Fe – Al – O and Fe – Ti – O alloys // Metall. Trans. 1970. Vol. 1. No. 12. P. 3403 – 3410.Fruehan R.J. Activities in liquid Fe–Al–O and Fe–Ti–O alloys. Metall. Trans. 1970, vol. 1, no. 12, pp. 3403–3410.Seo J.D., Kim S.H. Thermodynamic assessment of Mg deoxidation reaction of liquid iron and equilibria of [Mg] – [Al] – [O] and [Mg] – [S] – [O] // Steel Res. 2000. Vol. 71. No. 4. P. 101 – 106.Seo J.D., Kim S.H. Thermodynamic assessment of Mg deoxidation reaction of liquid iron and equilibria of [Mg]–[Al]–[O] and [Mg]–[S]–[O]. Steel Res. 2000, vol. 71, no. 4, pp. 101–106.Jung I.H., Decterov S.A., Pelton A.D. Computer applications of thermodynamic databases to inclusion engineering // ISIJ Intern. 2004. Vol. 44. No. 3. P. 527 – 536.Jung I.H., Decterov S.A., Pelton A.D. Computer applications of thermodynamic databases to inclusion engineering. ISIJ Intern. 2004, vol. 44, no. 3, pp. 527–536.Fujii K., Nagasaka T., Hino M. Activities of the constituents in spinel solid solution and free energies of formation of MgO, MgO·Al 2 O 3 // ISIJ Intern. 2000. Vol. 40. No. 11. P. 1059 – 1066.Fujii K., Nagasaka T., Hino M. Activities of the constituents in spinel solid solution and free energies of formation of MgO, MgO·Al 2 O 3 . ISIJ Intern. 2000, vol. 40, no. 11, pp. 1059–1066.

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