Oxidation of Metals, Vol. 10, No.

4, 1976

The High-Temperature Oxidation Resistance

of Iron-S•con-Aiuminum Alloys
W. E. Boggs*

Received April 5, 1976

Silicon or chromium can be used as an oxygen getter in iron-aluminum

alloys to prevent the internal oxidation of aluminum. This suppresses the
formation of the iron oxide nodules that tend to destroy binary iron-aluminum
alloys during high-temperature oxidation. Alloys of iron containing
aluminum and silicon in varying proportions were heated in flowing air for
50 hr at 1093~ Of the alloys tested, one containing 6 % aluminum and 1%
silicon was the most resistant to oxidation.

KEY WORDS: a l l o y ; i r o n ; a l u m i n u m ; silicon; o x i d a t i o n .

INTRODUCTION
The mechanisms of the high-temperature oxidation resistance and catas-
1
trophic failure of iron-aluminum alloys were discussed in an earlier paper.
Aluminum is preferentially oxidized to form a film of A1203 on the surface of
iron alloys containing at least 0.1% aluminum. While the formation of this
film tends to protect the surface of the alloy from further oxidation, these
aluminum-containing alloys are nevertheless subject to a catastrophic fail-
ure because of the growth of iron oxide nodules. The growth of the
protective A1203 film apparently depletes the subjacent alloy of aluminum,
so that when breaks occur in the protective oxide, the iron-rich substrate is
directly exposed to the atmosphere and an iron oxide nodule begins to form.

* United States Steel Corporation, Research Laboratory, Monroeville, Pennsylvania.

277
9 1976 Plenum Publishing Corporation, 227 West 17th Street, New York, N.Y. 10011. No part of this publication
may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical,
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278 Boggs

Internal oxidation of the aluminum in the alloy substrate ahead of the iron
oxide front prevents or at least delays the rehealing of the protective surface
film of aluminum oxide, so that the iron oxide nodule grows into the alloy at
the normal scaling rate for iron. Water vapor accelerates the initiation and
growth of nodules.
According to Wallwork, 2 the only elements that will form satisfactory
oxidation-resistant scales on iron-, nickel-, or cobalt-based alloys are
aluminum, chromium, and silicon. Chromium provides the well known
oxidation resistance of the stainless steels, but is expensive. Silicon is used in
electrical steels, but the formation of the low-melting iron-silicon-oxygen
phase fayalite (MP 1177 C) during reheating for hot working makes the
silicon steels unpopular among steel producers. Molten fayalite drips off
ingots and slabs and fills up soaking pit and furnace bottoms much faster
than does solid scale. The cost of chromium and the production difficulties
associated with silicon steels periodically revive the interest in using
aluminum for oxidation resistance in spite of the difficulties cited above. 3
Increasing the aluminum concentration to higher levels would tend to
suppress the formation of iron oxide nodules during high-temperature
oxidation, but above about 8% the alloy would not be cold-workable.
Chrysler Corporation 4 solved this problem by aluminizing the surface of an
Fe-6A1 alloy after forming.
Another method for preventing the growth of iron oxide nodules would
be to add a second active element to back up the aluminum. According to
Wagner, 5 the second active element probably acts as a getter for oxygen,
preventing its diffusion into the alloy once a break occurs in the primary
protective film of aluminum oxide. This prevents the internal precipitation
of AlzO3 that precludes the healing of the primary protective film. Wagner
used this mechanistic logic to explain the unusual oxidation resistance of
Cu-Zn-A1 alloys and Fe-Cr-A1 alloys.
At first it would appear that any of the elements, such as V, Ti, Si, or Cr,
that are more reactive to oxygen than iron but less reactive than aluminum
should provide the secondary protection necessary to prevent the formation
of iron oxide nodules. Low melting points, fast diffusion of anions or cations
through the oxides, volatility of the oxides or affinity with H 2 0 and/or CO2
make all possible alloying elements except AI, Si, and Cr unsuitable for
high-temperature oxidation protection. It is not clear that these same
considerations would apply to the mechanism of secondary protection in the
Wagner model. Fast diffusion of anions through the TiOz that should form
under holes in the primary protective A1203 film would probably allow the
internal oxidation of aluminum that the second alloying constituent is
intended to prevent. Vanadium forms a low-melting oxide V205 which is
also relatively volatile. This might preclude vanadium from acting as the
oxygen getter in an iron-aluminum alloy.
The High-Temperature Resistance of Iron-Silicon-Aluminum Alloys 279

Therefore, it is probable that the only iron-base alloys that will conform
to the Wagner model are Fe-Si-AI, Fe-Cr-Si, and Fe-Cr-A1. As is the case
with the iron-aluminum alloys, the Fe-Si-A1 alloys suffer from the cold-
workability problem in the higher concentrations. The limits of cold worka-
bility for these alloys are given in a recent patent by Regitz 6 (Fig. 1). To be
formable, the concentrations of A1 and Si must be less than the cold-
workability limit shown in Fig. 1. Thus, if the aluminum concentration is
increased, the silicon concentration must be decreased. Another practical
consideration is that the silicon concentration should be low, in order to
minimize the formation of fayalite during reheating for hot working.

MATERIALS A N D EXPERIMENTAL WORK

The compositions of the iron-base alloys included in this study are listed
in Table I. The Series I alloys were used in a preliminary study of the rate of
oxidation by a thermogravimetric technique. These specimens were rolled

Fe
0

8 8
$5. A1

Fig. 1. Cold workability of Fe-Si-A1 alloys.

 Table I. Composition of Alloys, wt.%

Alloy AI Si C Mn P S Cu Ni Cr Mo V Ti Fe

Series I
1 1.80 1.86 0.002 0.15 0.003 0.010 0.052 0.065 0.015 0.012 Bal
2 1.91 1.98 0.016 0.09 0.004 0.010 0.05 0.05 0.04 0.013 Bal
3 3.95 2.00 0.013 0.089 0.004 0.010 0.004 0.005 0.005 0.016 Bal
4 4.94 0.01 0.0015 <0.01 0.002 0.005 0.007 0.006 0.004 Bal
Series II
5 3.33 1.12 0.003 0.01 0.001 0.004 0.011 0.002 0.004 0.007 0.005 Bal
6 3.57 1.13 0.004 0.01 0.001 0.005 0.012 0.002 0.004 0.005 0.005
7 4.79 1.17 0.005 0.01 0.001 0.005 0.015 0.002 0.003 0.005 0.005
8 3.09 2.16 0.005 0.04 0.001 <0.004 0.010 0.002 0.003 0.005 0.005
9 2.06 2.62 0.006 0.03 0.001 <0.004 0.006 0.002 0.002 0.005 0.005
Series III
10 1.94 0.029 0.006 <0.01 0.002 0.004 0.008 0.002 0.005 1.18 <0.005 Bal
11 2.86 0.032 0.007 0.02 0.002 <0.004 0.012 0.002 0.006 1.50 0.005
12 3.50 0.037 0.005 0.03 0.003 <0.004 0.015 0.002 0.007 1.60 0.005
13 4.15 0.044 0.006 0.03 0.003 0.004 0.016 0.002 0.007 1.64 0.005
Series IV
14 3.65 0.020 <0.01 0.004 0.001 0.004 0.011 0.002 0.008 0.85 Be 0.005 <0.005 Bal
Series V
15 4.94 1.75 0.009 0.017 0.001 0.0010 0.012 0.002 0.009 < 0.005 0.005 Bal
16 5.54 1.15 0.006 0.024 0.001 0.0010 0.015 0.002 0.006 <0.005 0.005
17 5.99 1.04 0.006 0.014 0.001 0.0011 0.016 0.004 0.006 < 0.005 0.014
Series VI
18 5.46 0.050 0.014 0.100 0.005 0.018 0.050 0.100 0.050 0.021 Mo Bal
19 8.03 0.010 0.007 <0.01 0.007 0.005 0.010 0.007 0.006 o
The High-Temperature Resistance of Iron-Silicon-Aluminum Alloys 281

to foil and prepared in the same way as were the iron-aluminum alloys
discussed in an earlier paper. 1 Specimens of these alloys, suspended from a
recording microbalance in the uniform and constant temperature zone of a
vertical furnace, were oxidized at 800 and 900~ in dry oxygen at 700 Torr,
and at 800~ in oxygen saturated with water vapor to a total pressure of
700 Torr, or in pure water vapor at a pressure of 22 Torr.
The alloys of the other five series were hot rolled to a plate form, ground
to remove scale and surface defects, and then cut into specimens having
dimensions of approximately 5 2 • 25 • mm. After measuring of the
surface area and weighing, the specimens were oxidized at 1093~ for 50 hr

/
/
/
150 /
/
/

m!

4
!
/
/

IOC
i/I /

f//
I
/I

50

Fe-3.95 AI-2.00 Si

1 L
500 I000
TIME , minutes

Fig. 2. Oxidationof Fe-A1-Si alloys at 800~ in oxygen at 700 Torr.

282 Boggs

in flowing ambient air. Similar specimens were oxidized at 1093~ for 50 hr

in flowing air saturated with water vapor. After oxidation, the specimens
were again weighed and the weight gain per unit area was calculated. The
oxidized specimens were inspected for iron oxide nodules. If none was
visible, the specimens were examined by optical and scanning electron
microscopy.

RESULTS A N D DISCUSSION
The microbalance data obtained from the dry oxidation of the first
series at 800~ are presented in Fig. 2. Even the alloy having the lowest

/
/
150 /
/
/

o~/

I
t
I
f
I
I
I00 I
/
II ~"

iI

5O iii II

I 1
500 I000
TIME , minutes

Fig. 3. Oxidation of F e - A I - S i alloys at 900~ in oxygen at 7 0 0 Torr.

The High-Temperature Resistance of Iron-Silicon-Aluminum Alloys 283

concentration of A1 and Si (1.80 AI and 1.86 Si) was more oxidation-

resistant than the Fe-4.94 A1 binary alloy. The alloy containing 3.95 AI and
2.00 Si was the most oxidation-resistant in this series.
The data obtained in the dry oxidation of this first series of Fe-Si-A1
alloys at 900~ are shown in Fig. 3. Again all three of the Fe-Si-A1 alloys
were more oxidation-resistant than was the Fe-4.94 A1 binary alloy. The
alloy containing the greatest amounts of aluminum and silicon was the most
oxidation-resistant by a substantial margin.
The oxidation of these alloys at 800~ in pure water vapor at 22 Tort is
plotted in Fig. 4. Note that the weight-gain scale (ordinate) has been
contracted ten-fold compared with Figs. 2 and 3. The two alloys with the

/I
1500 /

y
V"/ rV

1000 / I
I
I

I
iI
/
/
/
/
/
/
500
/
/
/

//
/
/

AI-2.00 SI
Fe-3.95
H20 AT 22 TORR

I I
500 tO00
TIME , minutes

Fig. 4. Oxidation of Fe-A1-Si alloys at 800~ in pure H20.

284 Boggs

lower aluminum and silicon contents were no better than the binary in
oxidation resistance under these conditions. The higher alloys Fe-2.89 A1-
1.99 Si and Fe-3.95 A1-2.00 Si exhibited substantially superior oxidation
resistance. The weight gain of the latter was only about double its weight
gain in dry oxygen at 900~
The shapes of the oxidation curves for the two lower-alloy-content
steels suggest accelerating nodule growth, whereas the shapes of the oxida-
tion curves for the two higher-alloy-content steels suggest that nodule
growth has been arrested. Dark-field photomicrographs of the oxide formed
in these alloys in water vapor at 800~ are shown in Fig. 5. It is evident that

1.80 A1 1.86 Si .002C W-8066-IC 1.91 A1 1.98 Si .016 C T - 5 1 0 1

2.89 A1 1.99 Si .013 C T-5102 3.95 A1 2.00 Si .013C T-5103

Fig. 5. Nodular oxide formed on Fe-A1-Si alloysin 1000 min at 800~ in water vapor at
22 Torr. x 83; reduced 35% for reproduction.
The High-Temperature Resistance of Iron-Silicon-AluminumAlloys 285

the size and volume of nodular oxide, if not the actual number of nodes,
decreased as the aluminum concentration in the Fe-A1-Si alloys increased.
Less nodular oxide formed on these alloys than was formed under the same
conditions on the Fe-4.94 A1 binary.* It appears, therefore, that silicon is
definitely beneficial, helping to control nodular oxide growth.
The appearances of specimens of the next three series of alloys,
Fe-Si-A1 (Series II), Fe-V-AI (Series III), and Fe-A1-Be (Series IV) after
50 hr in air at 1093~ are shown in Fig. 6. Of these alloYs, only No. 7 which

* See Fig. 17 in Ref. 1.

Fig. 6. Appearance of specimen of alloys Fe-Si-A1, Fe-V-A1, and Fe-A1-Be after oxidizing
for 50 hr in air at 1093~ (Center specimen not oxidized.)
286 Boggs

contained 4.79% AI and 1.17% Si, resisted nodular oxidation for the
duration of the test. None of the Fe-V-A1 alloys exhibited the desired
oxidation resistance. The alloy that contained 0.85% Be and 3.65% A1 was
better than average for these series (II, III, and IV) but, as is to be expected
from the free energies of formation of the oxides, BeO rather than A1203
formed the primary film under the test conditions. Increasing the Be content
made the material too brittle and therefore higher Be alloys were not
studied.
In view of the oxidation resistance of the highest aluminum-silicon
alloy, No. 7, a series of new alloys was prepared having 5 - 6 % aluminum and
1.00-1.75% silicon (Nos. 15, 16, and 17, Table I). Care was taken to keep
these formulations well within the cold-workable region shown in Fig. 1.
Even so, it was necessary to reanneal (at 950~ the hot-rolled plates before
they could be cold rolled.
The weight gains of these alloys together with those of binary Fe-A1
alloys of similar aluminum contents after 50 hr in flowing air at 1093~ are
given in Table II. The experiments were conducted first in ambient laborat-
ory air and then repeated in air that had been saturated with water at 320C,
because it has been found that water tends to accelerate the formation of
nodular oxide on iron-aluminum alloys. 1 The results of these experiments
indicate that the nominally 6% aluminum steel (No. 18), from an experi-
mental commercial heat, oxidized roughly three times as fast as any of the
three Fe-AI-Si alloys, and that none of these four alloys is particularly
susceptible to increased attack in the presence of water vapor.
Figure 7 is a photograph of samples of the six different alloys after 50 hr
in ambient air at 1093~ Nodular oxide had covered most of the Fe-4.94 A1
binary alloy. Several smaller nodules formed on the Fe-8.03 A1 binary alloy
aswell. One oxide node grew around the suspension hole of the commercial
6% aluminum steel. No nodular oxide is evident on any of the three
Fe-AI-Si alloys.

Table II. Oxidationof Fe-AI-Si Alloysin Air at 1093~ for 50 hr

Weight gain in Weightgain in

ambient air, water-saturated air,
Alloy A1, wt.% Si, wt.% g/cm2 g/cm2

4 4.94 - 234.6 • 1 0 - 3 --
18 5.46 0.050 1.7 • 1 0 - 3 1.7 x 10 -3
19 8.03 - 2.7 x 10.3 -
15 4.94 1.75 0.51 x 10 3 0.32• 10.3
16 5.54 1.15 0.54x 10-3 0.37x 10.3
17 5.99 1.04 0.54 • 1 0 - 3 0.38 • 1 0 - 3
The High-Temperature Resistance of Iron-Silicon-Aluminum Alloys 287

Fig. 7. Samples of six alloys after 50 hr in ambient air at 1093~

Polarized light micrographs of the oxide formed on the commercial 6%

aluminum steel and the Fe-A1-Si alloys after 50 hr in wet air at 1093~ are
shown in Fig. 8. Adhering oxide appears dark in the micrographs, and loose
flakes of oxide (some of which are indicated by arrows) are white. The
commercial 6% aluminum steel was'covered with a layer of the loose oxide
(A1203), which tended to flake off in cooling [Fig. 8(A)]. The film formed on
the F e - 4 . 9 4 A l - l . 1 7 5 Si alloy was considerably more adherent during
cooling but still had some tendency to flake [Fig. 8(B)]. The oxide formed on
the Fe-5.54 Al-l.15 Si alloy [Fig. 8(C)], had noticeably less tendency to
flake, whereas that formed on the Fe-5.99 Al-l.04 Si alloy [Fig. 8(D)];
remained tight on cooling. The darker spots appearing in this micrograph
are adherent oxide but have not been identified. X-ray diffraction measure-
ments indicated that the oxide is A1203, and spectrographic analysis did not
show a significant amount of silicon in the oxide film ( < .01% silicon).
On a weight-gain basis, all three Fe-A1-Si alloys performed equally
well. However, it appears that the third alloy, nominally Fe-6AI-ISi, would
be best in a cyclic heating situation because of its resistance to oxide flaking.
288 Boggs

Fig. 8. Oxide formed on Fe-AI-Si steels in wet air for 50 hr at 1093~ Typical loose flakes
are indicated by arrows. • 100; reduced 35% for reproduction.

SUMMARY
Silicon or chromium can be used as an oxygen getter in i r o n -
aluminum alloys to prevent the internal oxidation of aluminum. Silicon was
used as the getter in this investigation because of its lower cost. Preliminary
microbalance experiments with alloys containing 2 - 4 % aluminum and
about 2% silicon showed that the oxidation resistance of these alloys was
superior at 800~ in wet or dry oxygen and in water vapor, and at 900~ in
dry oxygen to that of a nominally 5% aluminum binary alloy.
In view of these results, Fe-Si-A1 alloys were prepared having higher
concentrations of silicon and aluminum. Alloys containing various concen-
trations of F e - V - A 1 and F e - A 1 - B e were also prepared. Coupons of these
The High-Temperature Resistance ot Iron-Silicon-Aluminum Alloys 289

alloys were exposed to flowing air at ambient humidity for 50 hr at 1093~

Only one alloy in this group, No. 7, containing 4.8% aluminum and 1.2%
silicon, resisted the formation of iron oxide nodules throughout this test.
To determine more closely the optimum concentrations of aluminum
and silicon, three more alloys were prepared. These contained 5 - 6 %
aluminum and 1.75% silicon. These were exposed to flowing air at ambient
humidity and to flowing air saturated with water at 32~ for 50 hr at 1093~
All three of these alloys resisted the formation of iron oxide nodules for the
duration of the tests. However, on cooling, the A1203 layers on the two
containing the greater amounts of silicon tended to flake, while the oxide
layer on the 6% aluminum, 1% silicon alloy, No. 17, remained intact. It is
concluded therefore that this alloy would be the best of those tested in
resisting oxidation during cyclic heating.

ACKNOWLEDGMENTS

The author wishes to thank W. A. Linderman, L. E. Barr, and R. T.

Jones for their help with the experiments involved in this work.

REFERENCES

1. W. E. Boggs, J. Electrochem. Soc. 118, 906 (1971).

2. G. R. Wallwork and A. Z. Hed, Oxid. Met. 3, 171 (1971).
3. J. Caule, P. R. Sperry, M. J. Pryor, and J. A. Ford, U.S. Patent No. 3,811,874: Oxidation-
Resistant Iron-Base Alloy, issued May 21, 1974.
4. A. Roy and J. M. Coxwin,Met. Prog. 95, 70 (1969).
5. Carl Wagner, Corros. Sci. 5, 751 (1965).
6. L.J. Regitz, U.S. Patent No. 3,761,253: Steel for ElectricalApplicationsand NovelArticle,
issued September 25, 1973.