Materials Science and Engineering A 387–389 (2004) 985–990

Ferritic Fe–Al–Ni–Cr alloys with coherent precipitates for

high-temperature applications
C. Stallybrass∗ , G. Sauthoff
Max-Planck-Institut für Eisenforschung GmbH, D-40074 Düsseldorf, Germany

Received 25 August 2003; received in revised form 25 January 2004

Abstract

Strengthening by a homogeneous distribution of a second phase is a concept that is widely employed in high-temperature materials. It is
shown that suitable microstructures can be obtained in the Fe–Al–Ni–Cr system with ordered (Ni, Fe)Al precipitates in a ferritic matrix. These
precipitates lead to higher levels of yield strength at elevated temperatures than conventional iron-base high-temperature alloys. The results
show that the investigated materials exhibit the highest yield strength after solution heat treatment and lower values after aging, indicating
precipitation of fine particles during air cooling. The decrease of yield strength in the latter case was more pronounced for alloys with a high
precipitate content than for leaner alloys.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Ferritic alloy; B2 precipitates; Microstructure; Mechanical properties

1. Introduction ried out in order to explore the evolution of the microstruc-

ture [4,5] and the mechanical properties [6–9]. Strengthen-
Heat-resistant ferritic steels have superior thermal con- ing steels with low volume fractions of NiAl precipitates has
ductivity and lower thermal expansion than nickel-base su- proven useful and has led to the development of alloys such
peralloys. Both properties are desirable for application in as 17-7 PH or PH 13-8 Mo, among others. However, their
energy conversion systems. However, their high-temperature application is limited to moderate temperatures [10,11].
mechanical properties limit the operational temperature to The present work aims at combining the excellent ox-
about 600 ◦ C. Considerable effort has therefore been made idation resistance of ferritic Fe–Cr–Al alloys with the
to increase the high-temperature strength of ferritic materi- high-temperature strength of Fe–Ni–Al alloys with a high
als in order to achieve higher operational temperatures and volume fraction of the B2 phase. The focus of the study lies
thereby a higher level of efficiency. The approaches that have on mechanical behavior in view of a possible application as
been followed include strengthening by a dispersion of ox- a high-temperature structural material.
ides or precipitates. While the former process has yielded
good results, its feasibility is limited owing to high produc-
tion costs. In this respect, precipitate strengthening is more 2. Experimental
attractive. In the Fe–Ni–Al ternary system there is a mis-
cibility gap between the disordered A2 and the ordered B2 Eight Fe–Al–Ni–Cr alloys were produced by vacuum in-
phases [1–3]. Both phases have very similar lattice param- duction melting with compositions based on the pseudobi-
eters and are coherent and coplanar, a characteristic the al- nary section Fe + 2.5 at.% Al–NiAl + 1.25 at.% Al [1] with
loys with compositions within the miscibility gap share with the aim to obtain two-phase materials consisting of (Ni,
nickel-base superalloys. Therefore, these alloys could be in- Fe)Al precipitates in a ferritic matrix. 10 wt.% of Cr was
teresting for high-temperature applications as an alternative added and substituted for iron and nickel in order to reduce
to nickel-base superalloys, and several studies have been car- the aluminum content necessary to form alumina scales [12].
According to Ref. [13], Cr is mostly distributed in the fer-
∗ Corresponding author. Tel.: +49 211 6972 481; ritic phase. The nominal chemical compositions of the al-
fax: +49 211 6792 537. loys are listed in Table 1. The melts were cast into a copper
E-mail address: [email protected] (C. Stallybrass). mold, yielding rods with a length of approximately 160 mm

0921-5093/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2004.01.108
986 C. Stallybrass, G. Sauthoff / Materials Science and Engineering A 387–389 (2004) 985–990

Table 1 low 50 nm. The larger precipitates were formed at the aging
Nominal chemical compositions of investigated alloys temperature and the fraction of small precipitates during air
Fe (wt.%) Ni (wt.%) Al (wt.%) Cr (wt.%) cooling. These hyperfine precipitates are also observed in
Alloy 1 51.63 24.34 14.03 10.00
Ni-base superalloys and are considered undesirable because
Alloy 2 56.04 21.46 12.49 10.00 they lead to high yield stresses and cause ductility prob-
Alloy 3 60.36 18.65 11.00 10.00 lems [14,15]. Alloy 8 did not contain the larger precipitate
Alloy 4 64.57 15.89 9.53 10.00 fraction, indicating that the solubility limits for Ni and Al
Alloy 5 68.69 13.20 8.11 10.00 were not exceeded in this case. The microstructure of the
Alloy 6 72.72 10.55 6.72 10.00
Alloy 7 76.66 7.97 5.37 10.00
alloys 2, 4 and 6 after aging at 900 ◦ C for 100 h is illustrated
Alloy 8 80.52 5.44 4.05 10.00 in Fig. 1. The brighter phase corresponds to the disordered
matrix and the darker phase to the ordered precipitate. It is
apparent that the precipitates are mostly isolated at low vol-
and a diameter of 25 mm. The rods were subsequently cut ume fractions whereas their morphology is maze-like at high
into cylinders with a height of 40 mm by electrodischarge volume fractions. The volume fraction of the larger precipi-
machining (EDM). The cylinders were solution heat treated tate after aging at 900 ◦ C varied linearly between 1.2 vol.%
in air at 1200 ◦ C for 24 h, followed by air cooling and aging for alloy 7 and 44.8 vol.% for alloy 1; the hyperfine pre-
at 900 and 750 ◦ C in air for varying times, again followed by cipitate was ignored. After aging at 750 ◦ C, the investigated
air cooling. Samples of 5 × 5 × 10 mm3 size were cut from alloys contained precipitates that originated from the aging
these cylinders by electrodischarge machining and tested in temperature but no hyperfine precipitate was observed. In
compression at a strain rate of 1 × 10−4 s−1 at tempera- the case of the ternary Fe–Ni–Al system, the solubility of
tures in a range from room temperature to 1000 ◦ C. In ad- the disordered matrix for Ni and Al is significantly lower
dition, a disk was cut from each cylinder perpendicular to at 750 ◦ C than at 900 ◦ C and the atomic mobility is lower.
the axis for scanning electron microscopy purposes. After These factors may account for the absence of the hyperfine
polishing, the disks were not etched in order to get a bet- precipitate. The shape of the precipitates varied with the pre-
ter estimate of the actual precipitate content. The samples cipitate volume fraction. In the alloys with lower volume
were observed using back-scattered electron contrast on a fractions, isolated cubes dominated while, with increasing
JEOL JSM 6500 F high-resolution scanning electron micro- volume content, the precipitates first formed plates and then
scope, also equipped with a TSL EBSD (electron backscat- networks. In all cases, they were aligned along certain crys-
ter diffraction) system. Three pictures were taken from dif- tallographic directions. The volume fractions of the larger
ferent regions of each sample at a magnification appropriate precipitates did not change significantly with aging time.
for the sample, and the precipitate content and particle size The mean string width of the precipitates, denoted by the
distribution were measured using image analysis software. symbols in Fig. 2, is proportional to the cube root of the ag-
The string width of the particles was used as the size crite- ing time. The error bars are a measure of the width of the
rion because the particle shape deviated from cubic geome- observed distribution of string widths. The coarsening rate
try with increasing precipitate content. constants are of the order of 2 × 10−3 ␮m3 /h for 900 ◦ C
and 3 × 10−5 ␮m3 /h for 750 ◦ C. These values compare well
with the values found by Ref. [6] for Fe–Ni–Al ternary al-
3. Results and discussion loys. Comparison of the EBSD patterns of the matrix and
the precipitate revealed that both have the same orientation,
3.1. Microstructure i.e. the two phases are coplanar. Apparently, the precipi-
tates align along the 1 0 0 directions of the matrix. This
After aging at 900 ◦ C for 100 h, all alloys apart from behavior is caused by elastic interactions due to small dif-
alloy 8 contained precipitates with a bimodal size distribu- ferences in the lattice parameters of the matrix and the pre-
tion, with one peak around 600 nm and another peak be- cipitate and was observed in connection with coarsening in

Fig. 1. Microstructures of alloys aged at 900 ◦ C for 100 h.

 C. Stallybrass, G. Sauthoff / Materials Science and Engineering A 387–389 (2004) 985–990 987

1,00 Alloy 6 @ 900˚C

Alloy 4 @ 900˚C
Alloy 2 @ 900˚C
0,80 Alloy 6 @ 750˚C
String width [µm]

Alloy 4 @ 750˚C
Alloy 2 @ 750˚C
0,60

0,40

0,20

0,00
0 50 100 150 200
1/3 1/3
Time [s ]

Fig. 2. String width of the alloys 2, 4 and 6 as a function of the cube root of aging time.

Ni-base superalloys [16,17] and also with Fe–Ni–Al alloys larger precipitates, or the matrix in these regions was not
[5,6]. saturated with Ni and Al at 900 ◦ C.
The shape of the particle size distributions did not change
significantly with aging time. The experimental particle size 3.2. Compression tests
distributions were broader than the theoretical LSW distri-
bution, which is valid only for highly dilute systems [18,19]. Figs. 4–6 illustrate the 0.2% yield stress of the investigated
From Fig. 3 it is evident that the matrix contains homoge- alloys as a function of temperature after solution treatment,
neously distributed hyperfine precipitates with a size below after aging at 900 ◦ C for 100 h and at 750 ◦ C for 1000 h. The
50 nm. These form during air cooling because the solubil- grey scales in the figures correspond to yield stress levels.
ity of the matrix for Ni and Al decreases with temperature. Generally, the yield strength increased with increasing Ni
These hyperfine precipitates were not present in the vicin- and Al content, i.e. with an increasing volume fraction of
ity of the precipitates formed during aging at 900 ◦ C. Either precipitate. Between room temperature and 1000 ◦ C, most
the hyperfine precipitate directly formed on the neighboring alloys had the highest 0.2% yield strength in the solution

Fig. 3. Microstructure of alloy 6 after aging at 900 ◦ C for 100 h followed by air cooling.
988 C. Stallybrass, G. Sauthoff / Materials Science and Engineering A 387–389 (2004) 985–990

Fig. 4. Yield stress of the investigated alloys after 24 h at 1200 ◦ C.

heat-treated state. The reason for this behavior is that the cases, a plateau in the yield strength was observed between
cooling rate is insufficient to suppress precipitation. These room temperature and 500 to 600 ◦ C before a decrease to
precipitates have a smaller diameter and interparticle spac- lower values.
ing compared to aged alloys and therefore possess a higher After heat treatment at 900 ◦ C for 100 h, a similar behav-
strengthening effect. At room temperature, the values ranged ior was observed, which can also be attributed to the pres-
from 1052 MPa for alloy 1 to 886 MPa for alloy 8. In some ence of hyperfine precipitate but the values were shifted to

Fig. 5. Yield stress of the investigated alloys after 24 h at 1200 ◦ C and 100 h at 900 ◦ C.
 C. Stallybrass, G. Sauthoff / Materials Science and Engineering A 387–389 (2004) 985–990 989

Fig. 6. Yield stress of the investigated alloys after 24 h at 1200 ◦ C and 1000 h at 750 ◦ C.

lower levels. This shift was more pronounced for alloys with cipitate. At a testing temperature between 600 and 700 ◦ C
high volume fractions of precipitates than for leaner alloys. the alloys 4 to 8 showed a strong decrease in yield strength
Alloys 7 and 8, however, had a similar yield strength at low in both the solution-treated state and after aging at 900 ◦ C
testing temperatures after aging at 900 ◦ C compared to the while this decrease was not as pronounced for the alloys
solution heat-treated state, because at the aging temperature with higher Ni and Al content. However, alloys 4 to 6 had a
the alloy compositions are very close to or below the solu- higher yield strength up to 600 ◦ C than alloys 1 to 3, while
bility limit, as mentioned above. Therefore, alloy 7 contains above 600 ◦ C, alloys 1 to 3 had a higher yield strength. At
mostly hyperfine precipitate and alloy 8 only hyperfine pre- a testing temperature of 900 ◦ C, where the precipitates in

Fig. 7. Yield stress of alloy 2 in comparison with conventional heat-resistant steels and nickel–iron superalloys.
990 C. Stallybrass, G. Sauthoff / Materials Science and Engineering A 387–389 (2004) 985–990

alloy 8 have been completely dissolved, the strengthening values found for ternary Fe–Ni–Al alloys, which is impor-
effect of the precipitates can be clearly seen, as the values tant in view of a possible application as high-temperature
after aging at 900 ◦ C for 100 h range from 11 MPa for alloy material. Compression tests showed attractive yield stress
8 to 100 MPa for alloy 1 (Fig. 5) and from 12 to 150 MPa levels at high temperatures.
in the solution-treated state (Fig. 4).
After aging at 750 ◦ C for 1000 h (Fig. 6), there was no
plateau in the yield strength between room temperature Acknowledgements
and 600 ◦ C but a continuous decline. The values up to
a testing temperature of 600 ◦ C were lower than for the The financial support of the Deutsche Forschungsgemein-
solution-treated condition and after aging at 900 ◦ C, al- schaft (DFG) is gratefully acknowledged.
though the size of the precipitates originating from the aging
temperature was below that for 100 h at 900 ◦ C. The ab-
sence of a plateau and the lower values in the yield strength References
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