Abstract
Methods of thermomagnetic analysis (TMA) and Mössbauer spectrometry (57Fe) have been used to study the processes of the carburizing of α-Fe under the conditions of mechanical milling in a medium of liquid hydrocarbons. It has been established that, under the chosen conditions of the mechanical synthesis of carbides, the process of carbonization at T < 375 K occurs through the decomposition of the deformation-induced martensite, i.e., the supersaturated bct solid solution α″-Fe(C) with the formation of transitional hcp ε and ε′ phases that precede the formation of cementite. The milling of the metallic iron in the toluene medium substantially enhances the catalytic capability of disperse powders of α-Fe in the process of conversion of cyclic structures of hydrocarbons into other chemical forms. The increase in the dispersity of the iron powder to a nanocrystalline state leads to an increase in the chemical activity of carbon and an increase in the rate of diffusion sufficient for the formation in the Fe-C mixture of both primary cementite (θ′) with an anomalously low Curie temperature T C(θ′)(first stage) and secondary cementite (θ″) at the second stage of mechanosynthesis. The parameters of hyperfine interactions have been calculated for a number of synthesized carbides. It has been shown that the change in the carbon concentration in iron carbides is determined by the following inequality: c C(θ′) > c C(ε) > c C(ε′). The boundary of the temperature stability of cementite has been established. The effect of the decomposition of the θ phase (Fe3C) upon thermal cycling θ ⇔ γ in the temperature range of 300 < T < 1075 K has been revealed. Based on the results obtained, a scheme of the sequence of phase transformations that occur in the Fe-C system under the conditions of low-temperature mechanosynthesis has been derived.
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References
H. H. Podgurski, J. T. Kummer, T. W. Dawitt, and P. H. Emmett, “Preparation, stability and absorptive properties of the carbides of iron,” J. Am. Chem. Soc. 72, 5382–5388 (1950).
E. I. Cohn and L. J. E. Hofer, “Mode of transition from Hägg iron carbide to cementite,” J. Am. Chem. Soc. 72, 4662–4664 (1950).
K. Lohberg, “Zementit als Substitutionsmischkristall des Austenites,” Arch. Eisenhuttenw. 32, 409–412 (1961).
G. Le Caër, J. M. Dubois, and J. P. Senateur, “Etude par spectrometrie Mössbauer des carbures de fer Fe3C et Fe 5C2,” J. Solid State Chem. 19, 19–28 (1976).
G. Le Caër, J. M. Dubois, M. Pijlat, and P. Busslere, “Characterization by Mössbauer spectroscopy of iron carbides formed by Fischer-Tropsch synthesis,” J. Phys. Chem. 86, 4799–4808 (1982).
H. E. Plessis, “The crystal structures of iron carbides,” in Fisher-Tropsh Process Issue, 2008. http://hdl.handle.net/10210/421.
V. A. Barinov, V. A. Tsurin, and V. T. Surikov, “Study of mechanically synthesized carbide Fe7C3,” Phys. Met. Metallogr. 110, 474–484 (2010).
V. A. Barinov, E. P. Elsukov, and L. V. Ovechkin, USSR Inventor’s Certificate No. 1678525. Filing for Application from ΟΦΤΓΦΚΗ 05, 1989.
E. P. Yelsukov, V. A. Barinov, and L. V. Ovetchkin, “Synthesis of disodered Fe3 C alloy by mechanical alloying of iron powders with liquid hydrocarbon (toluene),” J. Mater. Sci. Lett. 11, 662–663 (1992).
E. P. Elsukov, G. A. Dorofeev, V. M. Fomin, G. N. Konygin, A. V. Zagainov, and A. N. Maratkanova, “Mechanically alloyed Fe100-x Cx (x = 5–25 at %) powders: I. Structure, phase composition, and temperature stability,” Phys. Met. Metallogr. 94, 356–366 (2002).
V. S. Rusakov, Mössbauer Spectrometry of Locally Heterogeneous Systems (OPNI IYaF NYaTs RK, Almaty, 2000) [in Russian].
H. E. du Plessis, J. P. R. de Villers, and G. J. Kruger, “Redetermination of the crystal structure of Fe5C2 Hägg carbide,” Z. Kristallogr. 222, 211–217 (2007).
G. Le Caër and E. Bauer-Grosse, “Aperiodic carbides formed by crystallization of amorphous Fe-C alloys,” Hyperfine Interact. 47, 55–67 (1989).
S. Nagakura and S. Oketani, “Structure of transition metal carbides,” Trans. Inst. Iron Steel Jpn., 8, 265–294 (1968).
V. S. Litvinov, S. D. Karakishev, and V. V. Ovchinnikov, Nuclear Gamma-Resonance Spectroscopy of Alloys (Metallurgiya, Moscow, 1982) [in Russian].
V. S. Rusakov, K. K. Kadyrzhanov, and T. E. Turkebaev, “Mössbauer study of iron surface implanted by carbon atoms,” Poverkhnost, No. 4, 27–33 (2000).
V. M. Nadutov, V. M. Garamus, and J. C. Rawers, “Mössbauer and SANS study of Fe-powder mechanically alloyed with carbon,” Mater. Sci. Forum 343–346, 721–725 (2000).
M. Ron, A. Kidron, H. Schechter, and S. Niedzwiedz, “Structure of Martensite,” J. Appl. Phys. 38, 590–594 (1967).
E. Bauer-Grosse and G. Le Caër, “Structural evolution of sputtered amorphous Fe1-x Cx films for 0.19 ≤ x ≤ 0.49,” Philos. Mag. 56, 485–500 (1987).
G. Kurdjumov, “Röntgenographische Untersuchung der Structur des angelassenen Kohlenstoffstahls,” Z. Phys. 55, 187–198 (1929).
T. V. Panova, V. I. Blinov, and V. S. Kolivchak, Determination of Lattice Parameters of Martensite and Carbon Content in It. Methodical Book (Omsk. Gos. Univ., Omsk, 2004) [in Russian].
K. H. Jack, “Iron-nitrogen, iron-carbon and iron-carbon-nitrogen interstitial alloys: Their occurrence in tempered martensite,” Nature 158, no. 4002, 60–61 (1946).
J. Grangle and W. Sucksmith, “Magnetic analysis of iron-carbon alloys. The tempering of martensite and retained austenite,” J. Iron Steel Inst. 168, 141–151 (1951).
H. Ino, T. Moriya, F. E. Fujita, Y. Maeda, Y. Ono, and Y. Inokuti, “A study of the Mössbauer effect during the tempering of iron-carbon martensite,” J. Phys. Soc. Jpn. 25, 88–99 (1968).
V. I. Izotov and L. M. Utevskii, “On the structure of martensite crystals of high-carbon steel,” Fiz. Met. Metalloved. 25, 98–109 (1968).
E. P. Elsukov, V. M. Fomin, D. A. Vytovtov, G. A. Dorofeev, A. V. Zagainov, N. B. Arsent’eva, and S. F. Lomaeva, “Structural and phase transformations during isothermal annealing of mechanically alloyed iron-amorphous Fe-C phase nanocomposite: Formation of cementite,” Phys. Met. Metallogr. 100, 251–269 (2005).
A. P. Gulyaev, Physical Metallurgy (Metallurgiya, Moscow, 1977) [in Russian].
S. A. Eliason and C. H. Bartholomew, “Reaction and deactivation kinetics for Fischer-Tropsh synthesis on unpromoted iron and potassium-promoted iron catalyst,” Appl. Catal. A: General 186, 229–243 (1999).
V. I. Voronin, I. F. Berger, Yu. N. Gornostyrev, V. N. Urtsev, A. R. Kuznetsov, and A. V. Shmakov, “Composition of cementite in the dependence on the temperature. In situ neutron diffraction study and ab initio calculations,” JETP Lett. 91, 143–146 (2010).
K. P. Bunin and L. A. Dolinskaya, “On the diffusion of carbon in cementite,” Dokl. Akad. Nauk USSR, No. 6, 455–457 (1951).
I. I. Novikov, Theoretical Principles of Heat Treatment in Metallurgy (Metallurgiya, Moscow, 1978) [In Russian].
G. Le Caër and P. Matteazzi, “Mössbauer study of mechanosynthesized iron carbides,” Hyperfine Interact. 66, 309–318 (1991).
J. M. R. Genin, “The clustering and coarsening of carbon multiplets during aging of martensite from Mössbauer spectroscopy: The precipitation stage of epsilon carbide,” Metall. Trans. A 18, 1371–1388 (1987).
E. J. Fasiska and G. A. Jeffrey, “On the cementite structure,” Acta Crystallogr. 19, 463–471 (1965).
L. J. E. Hofer, E. M. Cohn, and W. C. Peebles, “The modifications of the carbide, Fe2C. Their properties and identification,” J. Am. Chem. Soc. 71, 189–195 (1949).
A. A. Popov, Theoretical Foundations of the Chemical and Thermal Treatment of Steel (Metallurgizdat, Sverdlovsk, 1962) [in Russian].
H. Gleiter, “Hanostructured materials: Basic concepts and microstructure,” Acta Mater. 48, 1–29 (2000).
U. Herr, J. Jing, R. Birringer, U. Gouser, and H. Gleiter, “Investigation of nanocrystalline iron materials by Mössbauer spectroscopy,” Appl. Phys. Lett. 50, 472–474 (1987).
Physical Metallurgy, Ed. by R. W. Cahn and P. Haasen (North-Holland, New York, 1983; Metallurgiya, Moscow, 1987).
J. Horvath, R. Birringer, and H. Gleiter, “Diffusion in nanocrystalline materials,” Solid State Commun. 62, 319–322 (1987).
G. A. Dorofeev, E. P. Elsukov, V. M. Fomin, G. N. Konygin, and A. V. Zagainov, “Solid phase reactions in Fe-C system during metallic welding,” Khim. Interes. Ustoich. Razvit. 10, 53–58 (2002).
K. H. Jack, “Structural transformations in tempering of high-carbon martensitic steels,” J. Iron Steel Inst. 169, 26–36 (1951).
S. Nagakura, “Study of metallic carbides by electron diffraction. Part III. Iron carbides,” J. Phys. Soc. Jpn. 14, 186–195 (1959).
M. Dirand and L. Afqir, “Identification structurale precize des carbures precipites dans aciers faiblement allies aux divers stades du revenu. Mecanismes de precipitation,” Acta Metall. 31, 1089–1107 (1983).
M. J. van Genderin, M. Isac, A. Böttger, and E. J. Mittemeijer, “Aging and tempering behavior of iron-nickel-carbon and iron-carbon martensite,” Metal. Mater. Trans. A 28, 545–561 (1997).
H. Bernas, I. A. Campball, and R. Fruchart, “Electronic exchange and Mössbauer effect in iron-based interstitial compounds,” J. Phys. Chem. Solids 28, 17–24 (1967).
L. J. E. Hoffer, E. M. Cohn, and W. C. Peebles, “Modifications of the carbide Fe2C,” J. Am. Chem. Soc. 71, 189–195 (1949).
R. A. Arents, Yu. V. Maksimov, I. P. Suzdalev, V. K. Imshennik, and Yu. F. Krupyanskii, “Mössbauer study of local magnetic structure of ε-carbide of iron and intermediate carbides obtained during the ε → χ → θ transformations,” Fiz. Met. Metalloved. 36, 277–284 (1973).
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Original Russian Text © V.A. Barinov, V.A.Tsurin, V.A. Kazantsev, V.T. Surikov, 2014, published in Fizika Metallov i Metallovedenie, 2014, Vol. 115, No. 1, pp. 57–73.
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Barinov, V.A., Tsurin, V.A., Kazantsev, V.A. et al. Carbonization of α-Fe upon mechanical alloying. Phys. Metals Metallogr. 115, 53–68 (2014). https://doi.org/10.1134/S0031918X14010025
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DOI: https://doi.org/10.1134/S0031918X14010025