Phase Diagram Evaluations: Section II

Al-Fe-Ti (Aluminum-Iron-Titanium)
V. Raghavan

Practical interest in the phase equilibria of this ternary system has focused on the search for ternary phases of high crystal symmetry with acceptable mechanical properties, as compared to the brittle Al-Ti compounds of low crystal symmetry. In addition, the stabilization of the ordered forms of body-centered cubic (bcc) Fe (such as Fe3Al) by the addition of Ti has evoked interest in their possible use for high-temperature applications. The previous review of this system by [1987Rag] presented a liquidus projection, a full isothermal section at 800 C, partial isothermal sections at 1100 and 550 C and a reaction scheme. A vertical section at 5 at.% Ti and a partial isothermal section at 1200 C were presented in the update by [1993Rag]. Several significant new results have been reported recently, which include the work of [1995Pal] and [2000Kai1 and 2000Kai2].

Binary Systems
The Al-Fe phase diagram reviewed by [1993Kat] shows that the face-centered cubic (fcc) solid solution based on Fe

is restricted by a loop. The bcc solid solution ( Fe) exists in the disordered A2 and the ordered B2 and D03 forms. The A2 B2 transition is second-order in nature down to 660 C [1993Kat]; below 660 C, a two-phase field of (A2 + B2) intervenes, indicating a change-over to a first-order transition. The B2 D03 transition is second order and occurs below 550 C. Apart from the hightemperature phase , there are three other intermediate phases in the system with restricted ranges of homogeneity: FeAl2, Fe2Al5, and FeAl3. The Al-Ti system was updated by [1993Oka]. The updated phase diagram was quite different from the version of [Massalski2] and showed that ( Ti) and liquid undergo a peritectic reaction to yield ( Ti) at a high temperature of 1490 C. More recently, [2000Ohn] found additionally that ( Ti) undergoes the A2 B2 transition in the temperature range of 1425-1125 C. This finding was supported by differential scanning calorimetric measurements and by extrapolation of the ternary data on the Al-Fe-Ti and Al-Cr-Ti systems. The ordered B2 phase could not be retained by quenching due to the interven-

Fig. 1 Al-Ti computed binary phase diagram [2000Ohn]

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Fig. 2 Al-Fe-Ti tentative liquidus projection

Fig. 3 Al-Fe-Ti isothermal section at 1000 C [after 1995Pal]

tion of the martensitic transformation of bcc ( Ti) to hexagonal close-packed (hcp) ( Ti) [2000Kai2]. The Al-Ti phase diagram computed by [2000Ohn] is shown in Fig. 1. The intermetallic compounds in this system are Ti3Al (D019 type, hexagonal), TiAl (L10 type, tetragonal), TiAl2 (Ga2Hf

type, tetragonal), Ti2Al5 (tetragonal), and TiAl3 (D022 type, tetragonal). In the Fe-Ti system, there are two intermediate phases: Fe2Ti (C14, hexagonal) and FeTi (B2, cubic). [1998Dum] presented a comparison of the recent Fe-Ti assessments.

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Phase Diagram Evaluations: Section II

Fig. 4 Al-Fe-Ti isothermal section at 800 C [after 1995Pal]

The homogeneity range of Fe2Ti used in this review is from the tentative new assessment of [1998Dum]. The small homogeneity range of FeTi is from [1993Mur]. For more structural details on the binary compounds, see [Pearson3].

Ternary Phases
The three ternary compounds of this system discussed by [1987Rag] are those reported by [1981Sei]. Among these, the existence of the cubic phase AlFe2Ti ( 1) remained doubtful. Recent results of [1995Pal] have established that 1 does not exist. The solidification reactions postulated by [1981Sei] for the formation of 1 could possibly be related to the heat effects associated with the order-disorder reactions in ( Fe) in the ternary region, but no evidence in this regard is available. The 1 phase stands deleted in this update. The second ternary phase Al2FeTi ( 2) has the Mn23Th6 type (D8a) cubic structure. [1995Pal] made a detailed study of the homogeneity range and the lattice parameter variations of this phase. The homogeneity range increases with decreasing temperature. It covers a range of 21-50 at.% Ti at 800 C. At 1000 C, two separate composition islands with Ti ranges of 21-31.5 at.% and 37.5-44 at.% exist. At Ti concentrations above 30 at.%, the structure of 2 at room temperature is the cubic Mn23Th6 type, with the lattice parameter increasing from 1.2038 nm at 31 at.% Ti to 1.2110 nm at 51 at.% Ti. Below 30 at.% Ti, the structure at room temperature is indexed tetragonal, with a 1.1973 nm and c 1.2768 nm at 24 at.% Ti. It

Fig. 5 Al-Fe-Ti isothermal section at 900 C [1998Ohn]

is not known whether the tetragonality exists at high temperatures or occurs at lower temperatures during cooling. Al8FeTi3 ( 3) is cubic L12 type with a 0.3944 nm at 27 at.% Ti. The phase field of 3 is roughly circular with a width of 5 at.% at 800 and 1000 C [1995Pal, 1995Yan], increasing to 7 at.% Fe at 1200 C [1989Maz, 2000Mab]. [1995Pal] found no evidence for the low-symmetry ternary

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Fig. 7 Al-Fe-Ti vertical sections along the Fe3Al-Fe2AlTi and Fe2AlTi-FeAl joins [1998Ohn]

transition line at 1000 C [2000Kai2]. In the Al-Ti compounds, the solubility of Fe is <0.5 at.% in ( Ti), 2.5 at.% in TiAl, and TiAl2 and 1.5 at.% in Ti3Al and TiAl3. The solubility of Ti in Fe-Al compounds is 1.8 at.% in FeAl2, 2.5 at.% in Fe2Al5, and 6.5 at.% in FeAl3 [1995Pal]. In Fe-rich Fe-Al alloys, the addition of Ti strongly stabilizes the B2 (FeAl) and D03 (Fe3Al) structures, increasing the successive order-disorder transition temperatures [1995Ant, 1995Pal, 1997Nis, 1998Ohn, 1999Mek]. For example, the addition of about 11 at.% Ti to Fe3Al increases the D03B2 transition temperature of Fe 64 Ti 11 Al 25 to 1027 C (1300 K) [1997Nis].

The Liquidus Surface

Fig. 6 Al-Fe-Ti partial isothermal sections at (a) 1300 C and (b) 1200 C [2000Kai1]

phase at the composition Al69Fe25Ti6, as already ruled out in [1987Rag]. The binary phases FeTi and Fe2Ti show high solubilities for Al. At 1000 C, most of Fe in FeTi can be replaced by Al. The lattice parameter of FeTi varies linearly according to the equation: a 0.2970 + 0.000507 (50 XFe) nm, where XFe is in at.% [1995Pal]. In Fe2Ti, the maximum Al content is 47.5 at.% at 1000 C and the lattice parameters vary according to the equations: a 0.4770 + 0.000506 (70 0.7783 + 0.001406 (70 XFe) XFe) nm and c [6.78532 106 (70 XFe)2] nm. ( Ti) containing 15 at.% Fe dissolves up to 22 at.% Al at 1000 C. In fact, the large solubility of Al in FeTi and ( Ti) results in a continuous solid solution between them, separated by an order-disorder

The report by [1981Sei] on the solidification reactions of this system needs modifications on the basis of the new results. The nonexistence of the 1 phase requires that the reaction corresponding to its peritectic formation be dropped. In addition, the much wider homogeneity range of 2 and its occurrence as two separate composition islands at high temperatures [1995Pal] imply an additional ternary peritectic reaction for its formation at higher Ti contents. A transition reaction is necessary near Ti2Al5 to eliminate this phase from the liquid equilibrium. With Al present, the ordered form of ( Ti) forms a continuous solid solution with FeTi; this implies that the three-phase equilibrium ( Ti) + FeTi + L must start at a critical point (C2 in Fig. 2) and move down to the binary eutectic reaction on the Fe-Ti side (e5 in Fig. 2). With these modifications, a tentative liquidus surface is drawn in Fig. 2, which retains the other features of the surface of [1981Sei] as reviewed in [1987Rag]. The phases of primary crystallization are marked in Fig. 2.

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Phase Diagram Evaluations: Section II Table 1 A Reaction Scheme for the Al-Fe-Ti System

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Section II: Phase Diagram Evaluations Table 1 A Reaction Scheme for the Al-Fe-Ti System (continued)

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Phase Diagram Evaluations: Section II

Isothermal Sections
There are several new reports of isothermal sections determined for this system. Those published after the review of [1987Rag] are: [1989Maz], a partial section at 1200 C; [1991Nwo], partial sections at 800 and 700 C; [1995Pal], full sections at 1000 and 800 C; [1995Yan], partial section at 800 C; [1998Ohn], partial sections at 900 and 800 C; [1999Gor], full isothermal sections at 1000, 900, and 800 C; [2000Kai1], partial sections at 1300, 1200, and 1000 C; [2000Kai2], partial section at 1000 C; and [2000Mab], partial sections at 1150 and 1000 C. Using starting metals of purity of 99.99% Al, 99.97% Fe and 99.77% Ti, [1995Pal] prepared 59 ternary alloy compositions by levitation melting. Sample were annealed at 1000 and 800 C for 100 and 500 h, respectively, and quenched in brine solution. In addition, diffusion couples were prepared, which were heat treated at 1000 C for 500 h. The phase equilibria were studied by metallography, x-ray powder diffraction, electron probe microanalysis, and energy-dispersive analysis with the scanning electron microscope The isothermal sections determined by [1995Pal] at 1000 and 800 C are redrawn in Fig. 3 and 4 to agree with the accepted binary data. The Ti-rich region at 1000 C (Fig. 3) is drawn according to the results of [2000Kai2], where the ( Ti) phase is divided between A2 and B2 by a second-order transition line and the B2 region becomes continuous with the FeTi field. The FeTi-( Ti) two-phase equilibrium is seen at low Al contents; with increasing Al, ordering occurs in ( Ti). Beyond this point, a miscibility gap is present where two differing compositions of the ordered phase (B2 and B2*) coexist, till the gap closes. The phase relationships in the ( Fe) region indicate a tie-triangle of (B2 + Fe2Ti + D03) [1998Ohn, 1999Gor]. At 800 C (Fig. 4), the continuous B2 region between ( Ti) and FeTi has disappeared, giving rise to a three-phase field of FeTi + ( Ti) + Ti3Al. The phase relationships in the ( Fe) region show that A2, D03, and Fe2Ti are in threephase equilibrium [1998Ohn]. Pending confirmation of the persistence at high temperatures of the tetragonality of the 2 phase, it is represented as one homogeneous region in Fig. 4 [1995Pal]. This region is marked as 2 at higher Ti contents. At lower Ti, where the tetragonal polymorph may be present, it is marked 2*. Because of the absence of the 1 phase and the wider homogeneity range of 2, the phase distribution seen in Fig. 4 is quite different from that given by [1981Sei]. Figure 5 is a partial isothermal section at 900 C for the Fe-rich region from the results of [1998Ohn]. The (A2 + Fe2Ti + D03) three-phase field at 800 C (Fig. 4) is replaced by (B2 + Fe2Ti + D03). A full isothermal section at 900 C [1999Gor] has the same triangulation as that at 800 C. Near the Al-Ti side of the composition triangle, [2000Kai1] investigated the phase equilibria between ( Ti), ( Ti), and TiAl. Using starting metals of purity of 99.99% Al, 99.99% Fe, and 99.7% Ti, [2000Kai1] melted alloy compositions in an arc furnace under Ar atmosphere. The alloys were annealed at 1300 C for 24 h and at 1200 C for 168 h and then quenched in an ice-water mixture. The phase

equilibria were studied by metallography and electron probe microanalysis. The partial isothermal sections determined by them at 1300 and 1200 C are redrawn in Fig. 6(a) and (b). As the temperature decreases, the solubility of Fe in ( Ti) decreases and the three-phase equilibrium in Fig. 6 shifts to higher Ti contents. The strong influence of Ti in raising the order-disorder transition temperatures in bcc Fe is illustrated in Fig. 7 by two vertical sections along the Fe3Al-Fe2AlTi, and Fe2AlTiFeAl joins [1998Ohn].

The Reaction Scheme

With the significant changes in the solidification reactions and in the phase distribution on the isothermal sections as discussed above, the scheme of invariant reactions reviewed by [1987Rag] needs substantial revision. A new reaction scheme is written in Table 1 that is consistent with the tentative liquidus projection in Fig. 2 and the isothermal sections in Fig. 3-6. The course of the reactions between 1000 and 800 C outlined by [1995Pal] is adopted. No distinction is made in the table between 2 and 2*. The postulated reactions are placed in boxes outlined by broken lines. The temperatures shown for the postulated reactions are notional values. They merely indicate the likely sequence. The order-disorder (second-order) transitions in the ( Fe) region are not incorporated in the reaction scheme. Correspondingly, the tie-triangle present in this region involving more than one form of ( Fe) is unaccounted. The temperatures of the binary invariant reactions of the Al-Ti system shown in the reaction table are from [1993Oka]. Underlined three-phase equilibria are expected not to undergo further reactions during cooling. The following are the noteworthy features of the reaction scheme: The independent formation of the 2 phase at higher Ti contents by an additional ternary peritectic reaction P3 at 1230 C; The disappearance of the [L + ( Ti) + 2] and the (L + FeTi + 2) phase fields at the lower critical point C1 (1200 C), as the ( Ti) and FeTi fields are continuous; The start of the three-phase equilibrium [L + FeTi + ( Ti)] at C2 at 1150 C and its termination on the Fe-Ti binary side; The appearance of the three-phase equilibrium [( Ti) + FeTi + Ti3Al] at C3 (950 C), as the ( Ti) and FeTi become separate phases; The disappearance of the two (Fe2Ti + TiAl + 2) fields at C4 (930 C), as the two islands of the 2 phase merge.

References
1981Sei: A. Seibold: Phase Equilibria in the Ternary Systems Ti-Fe-O and Ti-Al-Fe, Z. Metallkd., 1981, 77(10), pp. 712-19 (in German). 1987Rag: V. Raghavan: The Al-Fe-Ti (Aluminum-Iron-Titanium) System in Phase Diagrams of Ternary Iron Alloys, ASM International, Materials Park, OH, 1987, pp. 9-21.

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1989Maz: S. Mazdiyasni, D.B. Miracle, D.M. Dimiduk, M.G. Mendiratta, and P.R. Subramanian: High Temperature Phase Equilibria of the L12 Composition in the Al-Ti-Ni, Al-Ti-Fe and Al-Ti-Co Systems, Scr. Metall., 1989, 23(3), pp. 327-31. 1991Nwo: A. Nwobu, T. Maeda, H.M. Flower, and D.R.F. West: The Constitution of Ti-Rich Alloys of the Ti-V-Fe-Al System, Proc. User Aspects of Phase Diagrams, Institute of Metals, London, 1991, pp. 102-11. 1993Kat: U.R. Kattner and B.P. Burton: Al-Fe (AluminumIron) in Phase Diagrams of Binary Iron Alloys, ASM International, Materials Park, OH, 1993, pp. 12-28. 1993Mur: J.L. Murray: Fe-Ti (Iron-Titanium) in Phase Diagrams of Binary Iron Alloys, ASM International, Materials Park, OH, 1993, pp. 414-25. 1993Oka: H. Okamoto: Al-Ti (Aluminum-Titanium), J. Phase Equilib., 1993, 14(1), pp. 120-21. 1993Rag: V. Raghavan: Al-Fe-Ti (Aluminum-Iron-Titanium), J. Phase Equilib., 1993, 14(5), pp. 618-19. 1995Ant: L. Anthony and B. Fultz: Effects of Early Transition Metal Solutes on the D03-B2 Critical Temperature of Fe3Al, Acta Metall. Mater., 1995, 43(10), pp. 3885-891. 1995Pal: M. Palm, G. Inden, and N. Thomas: The Fe-Al-Ti System, J. Phase Equilibria, 1995, 16(3), pp. 209-22. 1995Yan: T.Y. Yang and E. Goo: Phase Stability and Microstructure of Al-Ti-Fe Near Al3Ti, Metall. Mater. Trans. A, 1995, 26A, pp. 1029-033. 1997Nis: Y. Nishino, C. Kumuda, and S. Asano: Phase Stability of Fe3Al with Addition of 3d Transition Elements, Scr. Mater., 1997, 36(4), pp. 461-66. 1998Dum: L.F.S. Dumitrescu, M. Hillert, and N. Saunders: Comparison of Fe-Ti Assessments, J. Phase Equilib., 1998, 19(5), pp. 441-48. 1998Ohn: I. Ohnuma, C.G. Schoen, R. Kainuma, G. Inden, and K. Ishida: Ordering and Phase Separation in the bcc Phase of the Fe-Al-Ti System, Acta Mater., 1998, 46(6), pp. 2083-094. 1999Gor: A. Gorzel, M. Palm, and G. Sauthoff: Constitution Based Alloy Selection for the Screening of Intermetallic Ti-AlFe Alloys, Z. Metallkd., 1999, 90(1), pp. 64-70. 1999Mek: A.O. Mekhrabov and M.V. Akdeniz: Effect of Ternary Alloying Elements Addition on Atomic Ordering Characteristics of Fe-Al Intermetallics, Acta Mater., 1999, 47(7), pp. 2067-075. 2000Kai1: R. Kainuma, Y. Fujita, H. Mitsui, I. Ohnuma, and K. Ishida: Phase Equilibria Among (HCP), (BCC) and (L10) Phases in Ti-Al Base Ternary Alloys, Intermetallics, 2000, 8(8), pp. 855-67. 2000Kai2: R. Kainuma, I. Ohnuma, K. Ishikawa, and K. Ishida: Stability of B2 Ordered Phase in the Ti-Rich Portion of Ti-AlCr and Ti-Al-Fe Ternary Systems, Intermetallics, 2000, 8(8), pp. 869-75. 2000Mab: H. Mabuchi, H. Nagayama, H. Tsuda, T. Matsui, and K. Morii: Formation of Ternary L12 Intermetallic Compound and Phase Relation in the Al-Fe-Ti System, Mater. Trans. JIM, 2000, 41(6), 733-38. 2000Ohn: I. Ohnuma, Y. Fujita, H. Mitsui, K. Ishikawa, R. Kainuma, and K. Ishida: Phase Equilibria in the Ti-Al Binary System, Acta Mater., 2000, 48, pp. 3113-123.

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