Фазовая диаграмма системы Fe-P
К оглавлению: Другие диаграммы (Others phase diargams)
Fe-P (Iron-Phosphorus)
H. Okamoto
The assessed phase diagram for the Fe-P system is based on the experimental
data of [27Hau], [63Wac], [70Hof], [79Ko], and [81Sch]. [79Ko (81Tak)]
calculated the (aFe) solvus including the ferromagnetic effect of aFe, in
which the Gibbs energy functions of related phases were derived considering
the experimental phase boundary data. The assessed solvus is based on this
calculated result. The assessed g loop is based on the thermodynamic
calculation of [62Lor]. The model of [62Lor] was improved by high-temperature
calorimetric data, but the calculated boundaries essentially were unchanged [
81Sch].
The equilibrium phases are: (1) the liquid, L; (2) the fcc terminal solid
solution, (gFe); (3) the bcc terminal solid solution, (aFe); (4) Ni3P-type
tetragonal Fe3P; (5) hexagonal Fe2P; (6) orthorhombic FeP; (7) FeS2-type
orthorhombic FeP2; (8) monoclinic FeP4; and (9) the terminal phase, (P). The P-
rich side of the phase diagram is unknown.
The assessed maximum solubility of P in (gFe) is 0.56 at.% at ~1150 C [62Lor].
The solid solubility of P in (aFe) decreases as the temperature is lowered [
00Ste, 08Ger, 15Ste, 18Hau, 18Ste, 31Kos, 31Vog]. The maximum solubility of P
in (aFe) is about 5 at.% at the L = (aFe) + Fe3P eutectic temperature. The
equilibrium solubility of P in (aFe) at room temperature is essentially
zero.
The metastable solubility limits of P in (gFe) are 1.9, 1.1, and 0.6 at.% at
100, 900, and 800 C, respectively, according to extrapolation from higher-
order systems such as Fe-P-C and Fe-P-Ni [65Kan].
The metastable, orthorhombic preprecipitate Fe4+P forms before Fe3P
precipitates in (aFe) [61Hor]. The formation of Fe3P is suppressed easily by
fast cooling [15Ste, 29Vog].
Amorphous Fe-P alloys are formed at ~20 at.% P [76Tak], corresponding to the
eutectic point of the Fe-P system [83Pal]. [86Miy] measured the magnetic,
dilatometric, and structural changes during the crystallization process of
amorphous Fe-P alloys with 13 to 24 at.% P. No metastable structures were
observed.
FeP2 does not transform to pyrite (FeS2) structure at high pressures [68Don],
but transforms to a Co2Si-type orthorhombic structure at 800 C and 30 kbar [
76Sen]. Orthorhombic FeP4 was synthesized from the elements at 1100 C and 60
kbar [78Sug].
Because the Curie temperature (TC) of pure aFe was not well defined in earlier
works, comparison of measured TC in alloys is ambiguous. The assessed TC of
pure aFe is 770 C [82Swa].
The TC of Fe3P is 440 с 5 [09Lec] or 443 C [62Mey]. Because the TC of Fe2P
and FeP measured by these authors is very much higher than that of more recent
investigators, reinvestigation of TC of Fe3P may be needed.
The TC of Fe2P is 80 [09Lec], -7 [62Mey], -59 [75Wap], -73 [77Fuj], -64 [80Fuj]
, or -68 C [85Kad]. The considerable disagreement in TC may be due to
inhomogeneity or off-stoichiometry of the specimens used by the earlier
investigators. TC decreases rapidly on the P-rich side of the stoichiometry
due to vacancies on the Fe site [75Wap, 78Lun]. At pressures higher than 5
kbar, a metamagnetic phase [81Kad] is observed; the metamagnetic phase shows a
two-step magnetization phenomenon caused by two different types of electron
interactions [85Kad].
Although [62Mey] observed the TC of FeP at -58 C, other investigators found
FeP not to be ferromagnetic. Consistent with the M”ssbauer spectra anomaly
observed by [67Bai], [69Bel] found occurrence of antiferromagnetism at about
120 K (-153 C).
The TC of amorphous Fe-P alloys with 13 to 27 at.% P is nearly constant (~290
C) [85Hul].
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French.
15Ste: J.E. Stead, J. Iron Steel Inst., 91, 140-198 (1915).
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Inst., 97, 413-414 (1918).
18Ste: J.E. Stead, J. Iron Steel Inst., 97, 389-412 (1918).
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in German.
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1963) in French.
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1(1), 82-87 (1969).
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67 (1973).
75Wap: R. Wappling, L. Haggstrom, T. Ericsson, S. Devanarayanan, E. Karlsson,
B. Carlsson, and S. Rundqvist, J. Solid State Chem., 13(3), 258-271 (1975).
76Sen: J.P. Senateur, A. Rouault, R. Fruchart, J.J. Capponi, and M. Perroux,
Mater. Res. Bull., 11(6), 631-635 (1976) in French.
76Tak: S. Takayama, J. Mater. Sci., 11(1), 164-185 (1976).
77Fuj: H. Fujii, T. Kokabe, T. Kamigaichi, and T. Okamoto, J. Phys. Soc. Jpn.,
43(1), 41-46 (1977).
78Jei: W. Jeitschko and D.J. Braun, Acta Crystallogr. B, 34, 3196-3201 (1978).
78Lun: L. Lundgren, G. Tarmohamed, O. Beckman, B. Carlsson, and S. Rundqvist,
Phys. Scr., 17, 39-48 (1978).
78Sug: M. Sugitani, N. Kinomura, and M. Koizumi, J. Solid State Chem., 26(2),
195-201 (1978).
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Japanese.
80Fuj: H. Fujiwara and T. Okamoto, J. Phys. Soc. Jpn., 49(1), 419-420 (1980).
81Kad: H. Kadomatsu, K. Tohma, H. Fujii, T. Okamoto, and H. Fujiwara, Phys.
Lett. A, 84(8), 442-444 (1981).
81Sch: E. Schurmann, H.P. Kaiser, and U. Hensgen, Arch. EisenhЃttenwes., 52(2),
51-55 (1981) in German.
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82Swa: L.J. Swartzendruber, Bull. Alloy Phase Diagrams, 3(2), 161-165 (1982).
83Pal: L.S. Palatnik and I.I. Fal'ko, Dokl. Akad. Nauk SSSR, 270(6), 1380-1384
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85Hul: K. Huller, G. Dietz, R. Hausmann, and K. Kolpin, J. Magn. Magn. Mater.,
53(1-2), 103-110 (1985).
85Kad: H. Kadomatsu, M. Isoda, K. Tohma, H. Fujii, T. Okamoto, and H. Fujiwara,
J. Phys. Soc. Jpn., 54(7), 2690-2699 (1985).
86Miy: T. Miyazaki, X.B. Yang, and M. Takahashi, J. Magn. Magn. Mater., 60(2-3)
, 204-210 (1986).
Published in Bull. Alloy Phase Diagrams, 11(4), Aug 1990. Complete evaluation
contains 3 figures, 3 tables, and 88 references.
Special Points of the Fe-P System