Al–Fe–N 309

Aluminium – Iron – Nitrogen

Hermann A. Jehn and Pierre Perrot, up-dated by Pierre Perrot

Literature Data
Al-Fe alloys, in the presence of N, form aluminium nitride which plays an important role in steelmaking
because of grain refining and texture development. Most of the investigations have been directed at the
solubility of N in Al-Fe melts [1960Peh, 1963Mor, 1978Wad, 1979Wad, 1982Ish] and phase boundaries in
the liquid state [1963Mor, 1964Eva, 1968Isa] and in austenite [1951Dar, 1961Isa] represented by the
solubility product of AlN [1984Rag, 1987Rag]. [1961Sta] nitrided four ternary alloys at 600°C for 20 h and
analyzed the resulting phases. A review of the Al-Fe-N system has been presented by [1987Rag] and
updated by [1993Rag]. A Calphad assessment of the Al-Fe-N system has been reported by [1992Hil].
Kinetics of precipitation of AlN in steels has been investigated by [1972Oga, 1988Lan, 1995Big]. Since the
years 1980, no more experimental determinations of the solubilities of nitrogen in Al-Fe alloys are
available. The actual trend is to use the accepted results to calculate the solubility of nitrogen in more
complex alloys, then to check the calculated solubilities with experimental observations.
This evaluation incorporates and continues the critical evaluation made by [1992Jeh] considering new
published data.

Binary Systems
The binaries Al-Fe, Al-N and Fe-N are taken from [2003Pis], [2003Fer] and [2003Per], respectively.
N is practically insoluble in Al(s). The solubility of N in liquid Al under 0.1 MPa is given by [1986Wri]:
log10 (at.% N) = 2.633 - 1157/T
The only stable phase, AlN, melts at 2800 ± 50°C under nitrogen pressure of 10 to 50 MPa. AlN sublimates
congruently, the decomposition pressure being 0.1 MPa at 2435°C. Metastable AlN9 is also reported
[1986Wri].
All Fe modifications dissolve more or less N [1976Kru, 1982Fro, 1987Wri]. The ((Fe) phase is stabilized
to lower temperatures and then decomposes eutectoidally into ("Fe) and ('Fe4N at 590°C and 8.75 at.% N.
(Fe4N, stable up to 670°C transforms into g, hexagonal nitride with a wide homogeneity range. Fe2N
(orthorhombic) is stable up to 500°C [H, 1976Kru]. For the Fe-rich part of the Fe-N phase diagram,
including T-c isobars, see [1976Kru]. A Calphad assessment of the Fe-N diagram has been carried out by
[1987Fri] and an extensive review presented by [1987Wri]. The solubility of nitrogen in pure liquid iron
had been determined between 1580 and 2000°C under 0.1 MPa by [1960Mae, 1960Peh, 1964Eva,
1978Wad, 1982Ish] and [1986Wad].

Solid Phases
No ternary compounds are known. According to [1961Sta], considerable amount of Al is dissolved in the
(' and g iron nitrides (Fig. 1). The lattice parameter of g nitride containing 57 at.% Fe, 19 at.% Al and 24
at.% N (79 mass% Fe, 12.7 mass% Al, 8.3 mass% N) is slightly increased compared to binary iron nitride
of the same N content (see Table 1). The N solubility in austenite containing Al was determined by direct
chemical analysis of alloys equilibrated in gaseous nitrogen [1951Dar]. At low Al content, the N solubility
is independent of the Al content and given by the relation ((%N) in mass%, T in K):
(%N)=0.0404-1.2@10-5T. At higher Al content, the precipitation of AlN is observed. The solubility product
of AlN in (Fe is represented by the equations:
log10((%Al)(%N)) = 1.95 - 7400/T ((%) in mass%, T in K) [1976Kru]
log10(cAlcN) = 2.866 - 7400/T (c in at.%, T in K).
Phase boundaries calculated from the above equations are shown in Fig. 2. Few data exist on the solubility
of N in ("Fe)-Al alloys. They have been obtained when studying the precipitation kinetics of AlN in ferrite
containing 0.19 at.% Al and 0.04 at.% N [1972Oga] or 2 at.% Al and 0.02 at.% N, the maximum amount of

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310 Al–Fe–N

nitrogen dissolved in the ferrite matrix at 575°C [1988Lan]. An appreciable rate of precipitation was found
between 450 and 620°C; the rate was greater in cold-worked samples than in as-quenched ones.

Liquidus Surface
After early measurements by [1939Ekl], a number of investigations on the solubility of N in liquid Al-Fe
alloys were undertaken in the 1960's. [1960Mae, 1960Peh, 1964Eva] and [1982Ish] report first order
interaction coefficients to be slightly positive indicating that Al increases the activity coefficient of N in the
melt and decreases its solubility at a given N2 pressure. On the contrary, [1963Mor, 1968Isa], confirmed by
more recent work of [1978Wad], found an increase of the N solubility with the Al content of the liquid.
According to [1978Wad], the isobaric N solubility in Al-Fe melts obeys Sieverts' law (cN ~ p(N2)1/2) and
can be represented by the equation:
logcN = 0.5logp(N2)+A+BcAl+Cc2Al
Numerical data for A, B and C are given in Table 2. These results were confirmed by the model of an ideally
associated mixture proposed by [2000Yag]. The solubility product of AlN in Al-Fe melts, is given at
1580°C by [1961Isa], at 1580°C and 1675°C by [1963Mor, 1968Isa] and [1973Mok]. [1978Wad] proposed
the following equation (T in K, (%) in mass%, c in at.%):
log10((% Al)(% N)) = 6.10+5.88@10-2(%Al) - 14000/T
log10(cAl @cN) = 7.016+2.84@10-2cAl - 14000/T
Figure 3 gives the liquidus isotherms under 0.1 MPa N2 and between 1550 and 1700°C according to
[1978Wad]. The solubility of N2 in liquid Al-Fe alloys calculated by [1992Hil] under 0.1 MPa pressure at
1900 K is shown in Fig. 4. A reasonable agreement is observed with experimental solubilities measured by
[1978Wad] in the iron-rich part of the diagram.
The first order interaction parameter of nitrogen for the Al-Fe liquid alloys was experimentally determined
by [1979Wad] between 1600 and 1700 K and may be represented by the following expression:
eN(Al) = d(log10 fN / d(%Al)) = - 0,81+(1426/T) with fN = (%N)pure Fe / (%N)Fe,Al alloy.
(%Al) or (%N) in the above formula represent mass%. In the liquid alloys, eN(Al) < 0, which means that the
solubility of N in liquid alloys increases with the Al content of the alloy. As shown in Fig. 3, once the
solubility product of AlN obtained, the solubility of N in liquid alloy does not increase any more, but
decreases because of the precipitation of AlN. [1982Ish] measures a positive first order interaction
parameter, which implies a decrease of the nitrogen solubility due to aluminium, result which contradicts
the well established experimental observations.

Isothermal Sections
From the phases found by [1961Sta] in four ternary alloys, a partial isothermal section at 600°C is
constructed. It is given in Fig. 1, including the composition of the four alloys and the phases observed.
[1978Tro, 1985Sch] show that the mixture AlN+Fe is thermodynamically stable at 1950°C under a N2
atmosphere, it decomposes above 1750°C under an Ar atmosphere with formation of a FeAl alloy.

Miscellaneous
[1995Big] investigated the kinetics of precipitation of AlN on internal nitriding the Fe-2 at.% Al alloy in
the temperature range 530 - 580°C. The precipitation of AlN is associated with a Gibbs energy barrier for
the formation of a precipitate of critical size and thus is controlled by nucleation and growth.
Multilayered thin films Fe-N/Al-N are currently receiving increasing attention [1991Bar, 2001Liu] due to
their excellent soft magnetic properties with large saturation magnetization of 19 kG and a high relative
permeability of 4300 at high frequency [1991Kub]. These layers are prepared by ion sputtering under a
mixture of Ar and N2 introduced under the sputtering ion source. The layers are generally oversaturated and
the thinnest (less than 12 nm) exhibits an essentially amorphous structure.

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 Al–Fe–N 311

References
[1939Ekl] Eklund, L., “The Solubility of Nitrogen in Steel” (in Swedish), Jernkontorets Ann., 123,
545-556 (1939) (Equi. Diagram, Experimental, 13)
[1951Dar] Darken, L.S., Smith, R.P., Filer, E.W., “Solubility of Gaseous Nitrogen in Gamma Iron and
the Effect of Alloying Constituents - Aluminium Nitride Precipitation”, Trans. Metall. Soc.
AIME, 191, 1174-1179 (1951) (Equi. Diagram, Experimental, *, 12)
[1960Mae] Maekawa, S., Nagakawa, Y., “Effect of Titanium, Aluminium and Oxygen on the Solubility
of Nitrogen in Liquid Iron” (in Japanese), Tetsu to Hagane, 46, 1438-1441 (1960) (Equi.
Diagram, Thermodyn., Experimental, 8)
[1960Peh] Pehlke, R.D., Elliott, J.F., “Solubility of Nitrogen in Liquid Iron
Alloys-I-Thermodynamics”, Trans. Metall. Soc. AIME, 218, 1088-1101 (1960) (Equi.
Diagram, Experimental, Thermodyn., *, 32)
[1961Isa] Isaev, V.F., Morozov, A.N., “Conditions of Formation of AlN in Liquid Fe” (in Russian),
Sb. Nauchn.-Tehn. Trud., Nauchno-Issled. Inst. Met. Chelyab. Sovnarkhoz, (4), 12-18
(1961) (Thermodyn., Experimental, 8)
[1961Sta] Stadelmaier, H.H., Yun, T.S., “Alloys of Nitrogen and the Transition Metals Mn, Fe, Co and
Ni with Mg, Al, Zn and Cd”, Z. Metallkd., 52, 477-480 (1961) (Crys. Structure, Equi.
Diagram, Experimental, *, 22)
[1963Mor] Morozov, A.N., Isaev, V.F., Korolev, L.G., “Conditions of Nitride Formation and Solubility
of N in Alloys of Fe with Al, Ti and V” (in Russian), Izv. Akad. Nauk SSSR, Metall. i Gorn.
Delo, (4), 141-144 (1963) (Equi. Diagram, Experimental, 6)
[1964Eva] Evans, D.B., Pehlke, R.D., “The Aluminium Nitrogen Equilibrium in Liquid Iron”, Trans.
Metall. Soc. AIME, 230, 1651-1656 (1964) (Equi. Diagram, Experimental, 12)
[1968Isa] Isaev, V.F., Danilovich, Yu.A., Morozov, A.N., “Solubility of Nitrogen for the Formation
of Nitrides in Molten Alloys Based on Iron and Nickel” (in Russian), Fiz-Khim. Osn. Pro.
Stali. Publ. Nauka, Samarin, A.M. (Ed.), Nauka, Moscow, 296-301 (1968) (Equi. Diagram,
Thermodyn., Experimental, 11)
[1972Oga] Ogawa, R., Fukutsuwa, T., Yagi, Y., “Precipitation of AlN in Cold Worked High Purity
Fe-Al-N Alloys” (in Japanese), Tetsu to Hagane, 58, 872-884 (1972) (Equi. Diagram,
Experimental, 21)
[1973Mok] Mokrov, I.A., Aleshchenko, G.M., Stomakhin, A.Ya., “Thermodynamic Evaluation of
Oxides and Nitrides in Metallic Melts”, (in Russian), Izv. Vyss. Uchebn. Zaved., Chern.
Metall., (7), 63-67 (1973) (Equi. Diagram, Thermodyn., 9)
[1976Kru] Krueger, J., Kunze, H.D., Schuermann, E., “Eisen” (in German), in “Gases and Carbon in
Metals”, Fromm, E., Gebhardt, E, (Eds.), Springer, Berlin, 578-613 (1976) (Equi. Diagram,
Review, *, 241)
[1978Tro] Trontelj, M., Kolar, D., “Reactions of AlN with the Iron Group Elements”, Vestn. Sloven.
Kem. Drus., 25(2), 165-172 (1978) (Thermodyn., Eperimental, 8)
[1978Wad] Wada, H., Pehlke, R.D., “Nitrogen Solubility and Aluminium Nitride Precipitation in
Liquid Fe, Fe-Cr, Fe-Cr-Ni, and Fe-Cr-Ni-Mo Alloys”, Metall. Trans. B, 9B, 441-448
(1978) (Equi. Diagram, Thermodyn., Experimental, *, 12)
[1979Wad] Wada, H., Pehlke, R.D., “Nitrogen Solubility and Aluminium Nitride Precipitation in
Liquid Iron Alloys containing Nickel and Aluminum”, Metall. Trans. B, 10B, 409-412
(1979) (Equi. Diagram, Thermodyn., Experimental, *, 4)
[1982Fro] Fromm, E., Jehn, H., Hehn, W., Speck, H., Hörz, G., “Gases and Carbon in Metals, Pt XV,
Ferrous Metals (3), Iron - Nitrogen”, Phys. Data, Fachinformationszentrum Energie,
Physik, Mathematik, Karlsruhe, 85, 5-17 (1982) (Equi. Diagram, Review, 40)
[1982Ish] Ishii, F., Ban’ya, B., Fuwa, T., “Effect of C, Al, Si, P, Mn and Ni on the Solubility of
Nitrogen in Liquid Iron Alloys” (in Japanese), Tetsu to Hagane, 68, 1551-1559 (1982)
(Equi. Diagram, Experimental, Thermodyn., 43)

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312 Al–Fe–N

[1984Rag] Raghavan, V., “The Al-Fe-N System”, Trans. Indian Inst. Met., 37, 411-415 (1984) (Equi.
Diagram, Review, 16)
[1985Sch] Schuster, J.C., Bauer, J., Nowotny, “Applications to Materials Science of Phase Diagrams
and Crystal Structures in the Ternary Systems Transition Metal-Aluminum-Nitrogen”, Rev.
Chim. Miner., 22(4), 546-554 (1985) (Equi. Diagram, Review, #, 20)
[1986Wad] Wada, H., Lee, S.W., Pehlke, R.D. “Nitrogen Solubility in Liquid Fe and Mn-Fe Alloys”,
Metall. Trans. B, 17B, 238-239 (1986) (Experimental, 17)
[1986Wri] Wriedt, H.A., “The Al-N (Aluminium-Nitrogen) System”, Bull. Alloy Phase Diagrams, 7,
329-333 (1986) (Equi. Diagram, Review, #, 54)
[1987Fri] Frisk, K., “A New Assessment of the Fe-N Phase Diagram”, Calphad, 11, 127-134 (1987)
(Equi. Diagram, Thermodyn., Theory, 34)
[1987Rag] Raghavan, V., “The Al-Fe-N System”, in “Phase Diagrams of Ternary Iron Alloys, Part I”,
ASM International, 1, 145-147 (1987) (Equi. Diagram, Review, 13)
[1987Wri] Wriedt, H.A., Gokcen, N.A., Nafziger, R.H., “The Fe-N (Iron-Nitrogen) System”, Bull.
Alloy Phase Diagrams, 8(4), 355-377 (1987) (Equi. Diagram, Thermodyn., Review, #, 126)
[1988Lan] Lankreijer, L.M., Somers, M.A.J., Mittemeijer, E.T., “Kinetics and Nitride Precipitation in
Fe-Al and Fe-Si Alloys on Nitriding”, Proc. Internat. Conf. High Nitrogen Steels, Lille,
Edited 1989 by the Institute of Metals, London, 108-111 (1988) (Equi. Diagram,
Experimental, 17)
[1991Bar] Barnard, J.A., Tan, M., Waknis, A., Haftek, E., “Magnetic Properties and Structure of Al/
Fe-N Periodic Multilayer Thin Films”, J. Appl. Phys., 69(8), 5298-5300 (1991) (Crys.
Structure, Magn. Prop., 8)
[1991Kub] Kubota, K., Naoe, M., “Magnetic Properties of Fe-N/Al-N Multilayerd Films Pprepared by
Ar Ion-Assist Sputtering”, J. Appl. Phys., 70(10), 6430-6432 (1991) (Crys. Structure, Magn.
Prop., 2)
[1992Jeh] Jehn, H.A., Perrot, P., “Aluminium - Iron - Nitrogen”, MSIT Ternary Evaluation Program,
in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services
GmbH, Stuttgart; Document ID: 10.14876.1.20, (1992) (Crys. Structure, Equi. Diagram,
Assessment, 23)
[1992Hil] Hillert, M., Jonsson, S., “An Assessment of the Al-Fe-N System”, Metall. Trans. A, 23A
(11), 3141-3149 (1992) (Equi. Diagram, Thermodyn., Assessment, #, 27)
[1993Rag] Raghavan V., “Al-Fe-N (Aluminum-Iron-Nitrogen)”, J. Phase Equilib., 14 (5), 617-618
(1993) (Equi. Diagram, Review, 7)
[1995Big] Biglari, M.H., Brakman, C.M., Mittemeijer, E.J., Zwaag, S.V.D., “The Kinetics of the
Internal Nitriding of Fe-2 at.Pct. Al Alloy”, Metall. Mater. Trans. A, 26A, 765-776 (1995)
(Calculation, Experimental, Kinetics, Thermodyn., 41)
[2000Yag] Yaghmaee, M.S., Kaptay, G., Janosfy, G., “Equilibria in the Ternary Fe-Al-N System”,
Mater. Sci. Forum, 329-330, 519-524 (2000) (Equi. Diagram, Theory, 9)
[2001Liu] Liu, Y.-K., Harris, V.G., Kryder, M.H., “Evolutions of Magnetic and Structural Properties
of FeAlN Thin Films via N Doping”, IEEE Trans. Magn., 37(4), 1779-1782 (2001)
(Experimental, Magn. Prop., 8)
[2003Fer] Ferro, R., Bochvar, N., Sheftel, E., Ding, J.J., “Al-N (Aluminum-Nitrogen)”, MSIT
Evaluation Program, in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science
International Services GmbH, Stuttgart; to be published, (2003) (Equi. Diagram, Crys.
Structure, Assessment, 33)
[2003Per] Perrot, P., “Fe-N (Iron-Nitrogen)”, MSIT Binary Evaluation Program, in MSIT Workplace,
Effenberg, G. (Ed.), MSI, Materials Science International Services GmbH, Stuttgart; to be
published, (2003) (Crys. Structure, Equi. Diagram, Assessment, 35)
[2003Pis] Pisch, A., “Al-Fe (Aluminum-Iron)”, MSIT Binary Evaluation Program, in MSIT
Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services GmbH,
Stuttgart; to be published, (2003) (Equi. Diagram, Crys. Structure, Assessment, 58)

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Table 1: Crystallographic Data of Solid Phases

Phase/ Pearson Symbol/ Lattice Parameters Comments/References
Temperature Range Space Group/ [pm]
[°C] Prototype
((Fe) cF4 a = 364.67 at 915°C [V-C2, Mas2]
912-1394 Fm3m dissolves 0.1 at.% N at 912°C, 0.1 MPa
Cu
("*Fe) cI2 a = 286.65 at 25°C [Mas2]
# 912 Im3m dissolves up to 54.0 at. % Al at 1102°C
1394-1538 W dissolves 0.0166 at.% N at 912°C,
0.1 MPa
(Al) cF4 a = 404.96 at 25°C, [Mas2]
# 660.452 Fm3m
Cu
(', Fe4N cP5 a = 378.7 [1987Rag]
# 680 Pm3m 19.3 to 20.0 at.% N
Fe4N
g, Fe3N1±x hP3 a = 272.9 ~ 15 to ~ 33 at.%
P63/mmc c = 439.2 23 at.% N
Fe3N1±x
a = 272.9 30 at.% N
c = 440.4

(Fe,Al)3N1±x a = 276 Fe57Al19N24 [1961Sta]

c = 442
Fe2N oP12 a = 551.2 33.7 at.% N, [1984Rag]
# 500 Pbcn b = 482.0
Fe2N c = 441.6
AlN hP4 a = 311.14 at 25°C, [1986Wri]
< 2437.4 P63mc c = 497.92
ZnS- wurtzite

Table 2: Isobaric Nitrogen Solubility in Al-Fe Melts [1978Wad] log10cN=0.5log10pN2+A+BcAl+Cc2Al (cN,

cAl in at.%, PN2 in Pa)
T [°C] A B C
1550 - 3.859 + 1.25@10-2 + 9.8@10-3
1600 - 3.856 + 2.34@10-2 + 8.2@10-3
1650 - 3.852 + 3.37@10-2 + 6.9@10-3
1700 - 3.849 + 4.34@10-2 + 5.7@10-3

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314 Al–Fe–N

N Data / Grid: at.%

Fig. 1: Al-Fe-N. Axes: at.%
Partial isothermal
section at 600°C,
after [1961Sta]
20
80

40
60

AlN

60 ε+AlN
40

γ '+AlN
ε c AlN
pure ε γ'+
γ ',Fe4N ε+
80 γ '+ε
20
γ'
(γ Fe)
(γ Fe)+γ ' γ '+AlN

20 40 60 80
Fe Al

Fig. 2: Al-Fe-N.
Solubility limits in the
((Fe) phase
(Fe)+N2+AlN
after [1951Dar] 0.125

(Fe) + N2 (Fe) + AlN

0.100
N, at.%

0.075
1350
°C

0.050
(Fe) + AlN
120
0°C
0.025 (Fe)+ AlN
(Fe)
1050°C
0
0 0.1 0.2 0.3 0.4

Al, at.%

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Fig. 3: Al-Fe-N. 0.3

Solubility limits in the
liquid phase after
[1978Wad]
L + N2 L +AlN
1700
° C
0.2

L +AlN
N, at.%

1650°
L +AlN C

0.1
1600°C

L 1550°C

0
0 2 4 6

Al, at.%

0.08
Fig. 4: Al-Fe-N.
Solubility of N2 in
Al-Fe liquid alloys at
1627°C under 1 bar
N2 T = 1627°C
0.06
P(N2) = 1 bar
N, mass%

0.04

0.02

0
0 20 40 60 80 100
Fe Al
Al, mass%

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New Series IV/11A2
MSIT®