Corrosion Science, Vol. 33, No. 11, pp. 1677-1690, 1992 0010-938X/92 $5.00 + 0.

00
Printed in Great Britain. © 1992 Pergamon Press Ltd

T H E O X I D A T I O N B E H A V I O U R OF N i A l - - I .
P H A S E T R A N S F O R M A T I O N S IN T H E A L U M I N A SCALE
D U R I N G O X I D A T I O N OF NiA1 A N D NiAI-Cr A L L O Y S

M. W. BRUMM and H. J. GRABKE

Max-Planck-lnstitut ffir Eisenforschung GmbH, Dtisseldorf, Germany

Abstract--The oxide phases formed on NiAI and NiAI-Cr and their oxidation kinetics have been studied
in the temperature range 973-1673 K using TGA, XRD, SEM and TEM. The oxidation rate depends on
the oxide phase formed on the alloy, y-AI203,0-A1203,and a-Al203 have been observed and different kp
values were correlated to their growth. Cr in NiAIaccelerates the O-ct transformation and leads to a higher
kp value. Cr203 formed in the initial stage of oxidation acts as nuclei for the formation of a-Al20 3.

INTRODUCTION
NiAI lS A MATERIALof great interest in high-temperature applications because of its
high melting point and excellent oxidation resistance. This intermetallic phase with
ordered Bz-structure has a wide homogeneity range which varies over 20 at% at
1273 K. 1 As yet NiAI is used mainly as a base material for oxidation resistant
coatings on high temperature alloys. Renewed interest has arisen because of
improvements in mechanical properties 2 and now it is intended to use NiA1 in
structural applications. Therefore, after earlier investigations, >s its oxidation be-
haviour has been reinvestigated in recent years. 6-7 Because of its high aluminium
activity, NiAI forms only the oxide A120 3 upon high temperature oxidation. Since
the diffusivities of cations and oxygen are very low in a - A l 2 0 3, a very slow growing
protective oxide is formed. Most authors assume that the prevailing oxidation
mechanism is growth by inward diffusion of oxygen and outward diffusion of cations
at grain boundaries.
In isothermal oxidation the scale is dense and very adherent in spite of the
formation of voids between A1203 and NiA1. Therefore diffusion-controlled oxi-
dation can be expected to follow a parabolic rate law.
In the oxidation of alumina forming alloys and aluminides, AI203 occurs in
different modifications. At lower temperatures and/or in the early stages of oxi-
dation, the metastable oxides ~-A1203, 6-A1203 and 0-AI203 grow. These contain a
high concentration of cation vacancies. In the early stages of oxidation the cubic
oxides v-A1203 and 6-A120 3 have been observed on Zr-doped NiA1. 6 Later they
transform to the monoclinic 0-A12037"8 and finally, the transformation to a-A1203
takes place. 7-9 The cubic alumina modifications and their transformation to 0-Ai203
were observed at lower temperatures (1073-1223 K). The transformation to a-Al203
was observed at higher temperatures (1273 K and over).
Alloys for high temperature use based on iron or nickel contain chromium (15-

Manuscript received 7 February 1992; in amended form 31 March 1992.

1677
1678 M.W. BRUMMand H. J. GRABKE

25 w t % ) a n d less a l u m i n i u m ( 4 - 8 w t % ) . I n t h e s e a l l o y s o n e p u r p o s e o f t h e c h r o m i u m
a d d i t i o n s is to p r e v e n t i n t e r n a l o x i d a t i o n w h i c h c a n o c c u r at a l o w a l u m i n i u m
c o n t e n t . I n t h e c a s e o f N i A I , c h r o m i u m is a d d e d to e n h a n c e t h e h i g h t e m p e r a t u r e
s t r e n g t h . 2 A c r o s s - s e c t i o n t h r o u g h t h e t e r n a r y p h a s e d i a g r a m o f N i , A I a n d C r at
1273 K is g i v e n in R e f . 10. I n this p r e s e n t s t u d y N i A I a n d N i A 1 w i t h c h r o m i u m
contents of 7-34 at% were examined. The effects of the phase transformations on
oxidation kinetics and the effects of chromium on the phase transformations were
studied.

EXPERIMENTAL METHOD
Samples
NiAI was prepared by induction melting and casting into 1000 ml AI203 crucibles. The resulting
material had some cracks. Alloys of NiAI and chromium with different chromium contents (Table 1) were
hot isostatically pressed and extruded. The materials were cut into specimens (3 x 7 x 10 mm) by spark
erosion and abraded to 1000 grit since it was ascertained that further polishing had no influence on the
oxide growth rate.

Procedure
For thermogravimetric experiments, the specimens were suspended in quartz baskets from the
microbalance (sensitivity 1/~g) into a furnace which was heated up to a maximum temperature of 1373 K.
The furnace could be raised around the specimen which reached the reaction temperature within 15 min of
immersion in the hot zone. Experiments at temperatures between 1373 and 1673 K were conducted in an
immovable furnace which reached temperature within approx. 1 h. The atmosphere was composed of a
He- and O2-flow , establishing 0.13 bar 02.
The mass gain was measured by the microbalance and plotted on a chart recorder. After oxidation, the
oxide layers formed on the specimens were examined by X-ray diffraction (XRD), scanning electron
microscopy and transmission electron microscopy.

Thermogravimetric analysis
During oxidation, the mass of the samples increased monotonically. For evaluation, it was assumed
that oxidation follows parabolic kinetics:

Pieraggi I1 showed that in the formation of transient oxides such as NiO and NiAI204, an error in kp
arises if its value is determined from the slope of (AmlA) 2 vs t, because these oxides do not control the
oxidation rate in the final stage.
On alumina-forming alloys, fast growing transient oxides like y-AI203 and 0-AI203 transform to slow
growing a-Al203 and this a-Al203, formed by transformation, contributes to the rate control in the final
stage additionally to the later grown a-AI203. The occurrence of fast growing metastable aluminas causes
a high oxidation rate in the early stages of oxidation and introduces a deviation to to the time axisII and the
rate law is:

( . ~ ) 2 = kp (t +to)" (2)

TABLE 1. COMPOSITIONiN at% OF mE SAMPLESINVESTIGATED

Ni AI Cr

Nis0Als0 49.7 50.3 --

NiAI-7Cr 47.6 45.6 6.8
NiAI-15Cr 43.4 41.2 15.4
NiAI-34Cr 33.6 31.9 34.3
 Oxidation of N i A I - - I 1679

W h e n equation (2) is differentiated to the time, kpto is omitted and the differential yields the exact value of
kp as a fraction of time:

d(.~-~-~)2/dt=kp. (3)

T h u s , the mass gain curves were squared and differentiated and kp was plotted as a function of time.

TEM preparation
For the examination of oxidized specimens by T E M a technique of Doychak and Rtihle9 was modified:
Two NiA1 rods (0.5 x 1 x 10 m m ) , polished on one side, were oxidized and glued together (MBond 610).
This sandwich was abraded and galvanically e m b e d d e d in nickel after prepolarization (+ 4V) in order to
remove the passive film on NiAI. Cylinders of 3 m m diameter were cut from the sandwich with the axis
parallel to the NiAI rods. Thin slices (400/zm) were cut rectangular to the sample surfaces. The slices were
dimple ground to 40/zm and ion thinned. Screws shadowed the oxide layers from the ion beam parallel to
the specimen surface, otherwise the ion beam would preferentially sputter away the glue layer.
Micrographs and electron diffraction patterns were obtained at 120 keV.

EXPERIMENTAL RESULTS
The oxidation of NiA1
Thermogravimetric studies. The plot of the square of mass gain at 973-1123 K vs
time resulted in straight lines (Fig. 1) and the kp values were constant with time (Fig.
2). The plot of these kp values in an Arrhenius diagram gave one line (7 line).
Upon oxidation in the temperature range 1148-1198 K, it was observed that the
oxidation rate increased after some hours. Careful evaluation of kp revealed an
increase of kp by a factor of 2 after about 10 h (Fig. 3). The plot of the initial values in
the Arrhenius diagram gave a line which fits together with the 7 line. The plot of the
values in the final stage (after 60 h) gave another line (0 line) in the Arrhenius
diagram close to the 7 line, but situated somewhat higher (Fig. 4).
Oxidation at 1223-1373 K proceeded according to a non-parabolic rate law: the
plot of the square of mass gain vs time resulted in curves with a higher slope in the
beginning and a lower slope after longer oxidation times. The plot of kp vs time
(equation 3) showed a decrease by a factor of 50 from a high initial value to a lower
one in the final stage. The higher the temperature the more rapid was the decrease of
kp (Fig. 5). The initial kp values at 1223-1323 K gave a common line together with the
later values at 1148-1198 K (0 line) and the final values at 1273-1373 K gave a third

0.001 i i ,

E
u 0.0008 1 73K
O'~
E
0.0006
.c_
D

0.0004
8
E 0.0002

973K
o
= 0 10 20 30 40 50
o-
t i m e [h]
FIG. 1. Square of mass gain of Nis~Mso in the temperature range 973-1123 K.
680 M . W . BRUMM and H. J. GRABKE

i0-13 1 ~ r r
1125K
/
E 1 0 -14
/ 1073K

- 10 -Is
c
(3
t3
0 oo~- 10_10 973K
.t3

t3
t3- 10 -17 d J
0 10 20 50 40 50
time [h]

FIG. 2. Plot of the parabolic rate constants kp of NiAI oxidation in the temperature range
973-1123 K vs time. Error bars result from the uncertainties in the thermogravimetric
measurement which are highest for low mass gain.

10 -12

1198K
E
o
e4 1173K

t-
O . 1148K
o f-
o43 o 10-13

I I I
0 10 20 30 40
time [h]

FIG. 3. Plot of the parabolic rate constants kp of NiAI oxidation in the temperature range
1148-1198 K vs time.

temperature [K]
1675 1475 1275 1173 1075 975
10 -10
,to
E 10-11
o
I0-I ~
10 -13
E
10 -14
o t-
0 O i0-i~
P "~ I0-16
5.5 6 6.5 7 7.5 8 8.5 9 9.5 10 10.5
reciprocal temperature [104/K]

FIG. 4. Arrhenius plot of the parabolic rate constants kp of NiAI oxidation.

 Oxidation of NiAI--I 1681

10-11~ I I I I

.~i.~

1 0 - 1 2 ~ 1375K

~_ "e~:::~.::.i323~
10-13
o o
1273K\,, ,.
10-14 1 I I I I
0 100 200 500 400 500
time [h]
FIG. 5. Plot of the parabolic rate constants kp of NiAI oxidation in the temperature range
1223-1373 K vs time.

line (a line, Fig. 4). The final kp value at 1223 K was obtained after oxidation at 1373
K until a c o n s t a n t kp value had been reached, slow cooling to 1223 K and continued
oxidation.
At 1423-1673 K the oxidation rate was slow and the rate law was parabolic. The
kp values plotted in the Arrhenius diagram were also on the a line. The kp values at
1223 K and the activation energies are entered in Table 2.

TEM electron diffraction and X-ray diffraction results. The oxide films on samples
oxidized for 6 and 16 h (before and after the k p change) at 1173 K were examined by
T E M as described, since the oxide films were too thin for examination by XRD.
After 6 h oxidation y-A120 3 was observed and after 16 h y-AI203 and 0-Ai203. After
oxidation at 1173 K, 0-A1203 and traces of a-A1203 were detected by XRD. After
oxidation for 135 h at 1223 K and 60 h at 1273 K, i.e. when the kp had not yet reached
the a line, the oxide layer consisted of 0-AI20 3 and a-A1203. After 530 h oxidation at
1273 K, only a-Al20 3 was detected. After oxidation at temperatures of 1373 K and
above, the oxide layer contained exclusively a-Al20 3.

Morphology. After 6 h oxidation at 1173 K, a relatively smooth and dense oxide

film was formed (Fig. 6). After 16 h oxidation at 1173 K whiskers were observed in
the T E M photograph. After 60 h oxidation at 1223 K, needle-like whiskers were
observed by SEM (Fig. 7). After 130 h oxidation at 1273 K, troughs with less
whiskers had been formed (Fig. 8). After 90 h oxidation at 1373 K, more smooth
troughs were observed with rough ridges between them (Fig. 9).

TABLE 2. VALUES OF kp AT 1223 K AND ACTIVATION ENERGIES OF THE

GROWTH OF THE DIFFERENTOXIDEPHASES

Oxide phase Kp1223k (g2/cm4 s 1) E A (kJ/mol 1)

y-A1203 3.8 X 10 J3 260

0-A1203 6.3 x 10 -13 231
a-A1203 3.5 X 10 15 382
1682 M.W. BRUMMand H. J. GRABKE

Discussion. The plot of the kp values in the Arrhenius diagram shows three lines.
Each line is obviously correlated to the formation of a different oxide phase.
It has been shown by T E M that v-AI20 3 is formed during short time oxidation at
1173 K, while kp is on the ~, line in the Arrhenius diagram. The extensive work of
Doychak 6 has demonstrated that ~,-AI20 3 is the main phase formed upon oxidation
at lower temperatures (about 1073 K). So the V line can be assigned to the formation
of ~,-AIzO 3 and the diffusion in this alumina modification.
The transformation from ~,-AI20 3 to 0-A120 3 takes place after about 10 h at 1173
K. Doychak et al. 8 observed the transformation ~-6-0 on Zr-doped NiA1 single
crystals of different orientations at 1073 K. They detected the spinel NiAI20 4 and
cubic A120 3 phases in the very beginning and 0-A120 3 after I and 10 h. Obviously the
7-0 transformation influences the oxidation kinetics. After the formation of 0-AI203
the kp value is higher. So the diffusion in 0-A1203 may be somewhat more rapid than
in y-Al20 3. However, in the formation of 0-A120 3, whiskers grow on the oxide
surface. Thus the increase of kp may be caused by the defect structure of the oxide
but also by the oxide growth morphology; the gravimetric measurements only yield
integral information on an increase of growth rate. The formation of 0-AI20 3
whiskers is also evident from SEM photographs published in Ref. 8. As in that study,
the whiskers appear needle-like at temperatures up to 1223 K and blade-like at
higher temperatures.
The transformation of 0-A120 3 to a-A120 3 is very slow at 1173 K. Small amounts
of a-Al20 3 are detected after 60 h oxidation at 1173 K. The transformation is faster at
1223 K and above and results in a marked decrease of the kp value from the 0 line.
Once the kp value has reached the a line (after about 300 h at 1273 K, after about
150 h at 1323 K and after 5 h at 1373 K), the oxide layer consists only of a - A l 2 0 3.
Rybicki and Smialek v had also observed a discontinuity in the Arrhenius line
plotting log kp vs l/T, a higher line resulted at lower temperatures and a lower one at
higher temperatures. This behaviour, which was also observed with other alumina-
forming alloys, 12'13 was explained by the formation of fast growing 0-A120 3 at lower
temperatures and slow growing a-A120 3 at higher temperatures. At 1273 K oxi-
dation kinetics with a variable kp was observed with a high kp in the beginning and a
low one after longer oxidation times due to the formation of fast growing 0-Al203
initially with subsequent transformation to slow growing a-AlzO3. 7 In this study it
has been shown that the 0 - a transformation can be observed in the temperature
range 1223-1373 K. The transformation time is very long at 1173 K and becomes too
short to be observed by thermogravimetric means at temperatures over 1373 K.
The phase transformation is reflected by the surface morphology. While 0-Al20 3
is growing, whiskers form on the oxide surface. The nucleation of a-Al20 3 takes
place at the oxide/gas phase boundary. 9 This process results in troughs in the surface
with fewer whiskers where single crystalline a-AI20 3 areas are present. However,
the time taken for the whiskers to disappear is longer than for the transformation of
the bulk oxide. After 530 h at 1273 K, when kp has reached the a line, whiskers are
still visible on the surface. The ridged structure of the final a-Al20 3 scale as described
by Doychak 6 is visible after oxidation at 1373 K (Fig. 9).

The oxidation o f NiAI doped with chromium

Thermogravimetric studies. At 1173 K and lower temperatures, parabolic oxi-
dation of all NiAI-Cr alloys was observed during the first hours of oxidation,
Fro. 6. TEM photo of cross section of oxide layers on NisoAls0 after oxidation at 1173 K for
6 h (upper layer), and 16 h (lower layer).
FIG 7. SEM photo of the oxide layer on NisAlst~ after 60 h oxidation at 1223 K, needle-like
whiskers.

1683
FIG. 8. SEM photo of the oxide layer of NisoA15oafter 130 h oxidation at 1273 K, blade-like
whiskers and transformation troughs formed by O-ct transformation.

FIG. 9. SEM photo of the oxide layer on NisoAls0 after 90 h oxidation at 1373 K. Typical
ridge network. 6

1684
FI6. 13. SEM photo of the oxide layer on NiAI-34Cr after 200 h oxidation at 1373 K, fine-
grained convoluted oxide layer.

Fig. 14. SEM photo of the oxide layer on NiAI-34Cr after 20 h oxidation at 1223 K,
fine-grained smooth oxide layer.

1685
 Oxidation of NiAI--I 1687

although after longer times the oxidation rate increased. The plot of kp at 1173 K vs t
(equation 3) shows an approximately constant kp value for ca 10 h, then the kp value
increased markedly. This kp increase is due to the formation of Cr20 3 which occurs at
lower temperatures as will be reported in detail in a forthcoming paper. 14 In the
present study the growth of A120 3 on NiA1-Cr is examined in detail, therefore the kp
values observed before their increase were plotted in the Arrhenius diagram (Fig.
10). These kp values are on the same line as the kp values of the chromium free NiAI
(0 line). Lower initial kp values corresponding to the 7 line were not observed clearly.
The samples of different chromium contents gave similar results.
Oxidation kinetics with a decreasing kp were observed in the temperature range
between 1173 and 1273 K. The kp values determined for the three materials of
different chromium content decreased from the 0 line until a constant kp value was
reached in the final stage (Fig. 11). The kpvalues in the final stage are also plotted in
the Arrhenius diagram. It is obvious that kp is higher the more chromium the sample
contains. Furthermore, the higher the chromium content, the shorter was the
transition time. The transition times from a high kp value to a low constant one are
listed in Table 3.
At temperatures higher than 1273 K after a first increase, the kp values were
nearly constant with time. At 1473 K, a slight decrease of the kp value during 100 h
oxidation was observed for samples with the highest chromium content (Fig. 12).

X-Ray diffraction and TEM examination. Examination by XRD of the oxide

layers formed at 1173-1273 K revealed that the oxide layers contained 0-AI203 and
a-Al203 during the transition stage, while the kp value was not yet constant. As in the
case of chromium-free NiA1, the oxide layer contained only a-Ai203, after a
constant kp value had been reached. So only a-A1203 was detected on NiA1-Cr after
66 h oxidation at 1173 K. At temperatures over 1273 k, small amounts of Cr203 were
formed besides A1203, especially on NiAI-34Cr.
Cross sections of oxide layers formed on NiA1-34Cr after 1 h oxidation at 1273 K
were examined by TEM by Riihle et al.15 Electron diffraction and EDX analysis

temperature [K]
167.5 1475 127.5 117.5 1075 97.5
10 -10 ~ I I I I i i I I i I

~EE 10-"
o
\,
~ 10 -13

"~ 10_14_
._~ "~
-6 o 10-~ - • NiAI-7Cr
~ 10-18 -- NisoAlso
O I I I I I I I I
o_ ~. 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10 10.5
reciprocal femperature [104/K]

FIG. 10. Arrhenius plot of the parabolic rate constants kp OfNiAI and NiAI-Cr oxidation.
1688 M . W . BRUMMand H . J. GRABKE

10 -11 I I I I

E
o 10-12
0

E
0
. . ;:, .... N!AJ-34C~
10 -13
,_0 t-
5
.Q
o
0 N A -15Cr ~" ...............
2
& 2 10-~4 I I [ I
0 20 40 60 80 100
time [h]

FIG. 11. Plot of the parabolic rate constants k] of NiA1 and NiAI-Cr oxidation at 1273 K vs
time.

TABLE 3. T R A N S I T I O N TIMES FROM FAST TO SLOW OXIDATION RATE IN

HOURS

Temperature(K) Nis0 NiA1-7Cr NiAI-15Cr NiA1-34Cr

1373 2-3 0 0 0
1323 40~50 4 0 0
1273 200-300 60 1 0
1223 >1000 -- 100 20
1173 -- -- -- 30

revealed that chromium-containing a - A l 2 0 3 had been formed. The chromium

c o n t e n t i n c r e a s e d f r o m the m e t a l - o x i d e to th e o x i d e - g a s i n t e r f a c e .

Morphology. A f t e r 20 h o x i d a t i o n at 1223 K a s m o o t h w h i s k e r f r e e a - A l 2 0 3 l ay er
was o b s e r v e d . A f t e r 200 h o x i d a t i o n at 1373 K t h e o x i d e layer was fine g r a i n e d an d
c o n v o l u t e d , as s h o w n in Figs 13 and 14.

I I I I

;7
E
Q) 10 -11
,.-------._____ NiAl-54Cr

~D
~ A I s n
Q)
o
./3
,o 2
c"
o
10-12 #
I [ [
0 20 40 60 80 100
time [h]

FIG. 12. Plot of the parabolic rate constants kp of Nis0Als0 and NiAI-34Cr oxidation at
1473 K vs time.
 Oxidation of NiAI--I 1689

Discussion. As in the case of chromium-free NiAl, fast growing metastable

aluminas are formed in the early stages of oxidation, and 0-A1203 was observed by
XRD. The transformation of 0-A1203 to a-A1203 shows in the oxidation kinetics, as
with chromium free NiAI the kp value decreases during the oxidation time, but the
chromium content accelerates the transition time and increases the final kp value.
An explanation for these chromium effects can be given if one considers the
initial stages of oxidation. On the oxide-free metal surface oxides are formed of each
alloying element for which the oxide formation pressure is exceeded. So oxide nuclei
of NiO, Cr203 and A1203 are to be expected on the surface in the initial stage. After a
closed oxide layer has formed, the oxygen partial pressure at the metal-oxide
interface decreases to the formation pressure of A1203 which is the lowest one. At
this phase boundary the other oxides are no longer stable and are undergrown by
AI203. The other oxides are only stable at the oxide-gas interface. NiO reacts with
A1203 to form NiA1203. The hexagonal Cr203 and a-A1203 form a continuous solid
solution over the entire composition range. ~6 Thus the reaction of 0-A1203 or
7-A1203 with Cr203 leads to formation of hexagonal (AI,Cr)203 crystals which can
act as nuclei for the formation of hexagonal a-Al203 (Fig. 15). The more chromium
the alloy contains, the more Cr203 nuclei would form. The more nuclei that are
present, the finer grained is the resulting a-A1203 layer. Since more grain boundaries
are present, more diffusion paths are available for aluminium outward diffusion and
oxygen inward diffusion and higher kp v a l u e s result, as observed.
From the T E M studies of Doychak and R/ihle 9 it is known that the transform-
ation to a-Al203 begins at the oxide-gas interface. The chromium content in the
a-AlaO3 layer detected by Rfihle et al.~5 near the oxide-gas interface also by TEM
studies obviously stems from the Cr203 nuclei.

.m m|o n mmmmm~mm
NiAI NiAI-CF

o e
NiAI NiAI-Cr

NiAI NiAI-Cr

m NiO [~ NiAI204

AI2O3 (AI,Cr)203

] Cr203

FIG. 15. Schematic model of the chromium effect on transformation kinetics.

1690 M.W. BRUMMand H. J. GRABKE

The fine grained structure of the oxide layers is demonstrated in Figs 13 and 14.
Diffusion of both aluminium and oxygen at the grain boundaries leads to formation
of new A l 2 0 3 within the oxide layer. Therefore the oxide layer grows laterally, which
leads to a wrinkled morphology.
U p o n oxidation and diffusion in a fine grained a - A l 2 0 3 layer, the kp value
decreases with time due to grain coarsening and reduction of the diffusion paths. 17
Such behaviour was also observed on NiAl-34Cr (Fig. 12) in this study.
The higher the chromium content and the more a-Al203 nuclei are present, the
shorter is also the transition time until 0-A1203 has been transformed to a-Al203.

SUMMARY
The oxidation kinetics of pure NiAI and N i A I - C r were investigated using T G A ,
X R D , SEM and TEM. The oxidation kinetics of NiA1 shows two phase transform-
ations from ~,-AI203 to 0-AI20 3 and from 0-AI20 3 to a-A1203. The ~,-0-phase
transformation leads to a small increase of kp, the 0-a-phase transformation leads to
a strong decrease of kp over two orders of magnitude. At 1173 K the ~,-0-phase
transformation is immeasurably fast and the 0-a-phase transformation lasts some
hundreds of hours. At 1273 K the 0-a-phase transformation is short, too, and only
a - A l 2 0 3 is observed.
U p o n oxidation of NiA1-Cr alloys it was observed that chromium accelerates the
0-a-phase transformation and leads to higher kp values for the final growth of
a - A I 2 0 3. The chromium effect on the oxidation kinetics was explained by Cr20 3
nuclei formation in the initial stage of oxidation which serve as nucleation sites for
a-A120 3. A high density of nuclei leads to a faster formation a - A l 2 0 3 which is fine
grained with more diffusion paths, causing faster oxide growth.

Acknowledgements Thisstudywas supported by the DFG (Deutsche Forschungsgemeinschaft).Thanks

are due to Prof. M. Riihle and his co-workers. Max-Planck-Institutfiir Metallforschung, Stuttgart, for
performing the TEM preparation and studies of NiAI-34Cr.

REFERENCES
1. T. B. MASSALSKI,Binary Alloy Phase Diagrams Vol. I. American Societyfor Metals, Metals Park,
Ohio (1986).
2. G. SAUTHOFF,Z. Metallkde 81,855 (1990).
3. R. HUTCHINGSand M. H. LORETTO,Metal. Sci. 12, 503 (1978).
4. J. L. SMIALEK,Metall. Trans. A. 9A, 309 (1978).
5. G. C. WOODand F. H. STOTT,Br. Corros J. 6, 247 (1971).
6. J. DOYCHAK,Ph.D. Thesis, Case Western Reserve Univ., Cleveland, OH (1986).
7. G. C. RYBICKIand J. L. SMIALEK,Oxid. Metals 31,275 (1989).
8. J. DOVCHAK,J. L. SMIALEKand T. E. MITCHELL,Metall. Trans. A 20A, 499 (1989).
9. J. DOVCHAKand M. ROHLE,Oxid. Metals 32, 431 (1989).
10. N. C. OFORKAand B. B. ARGENT,J. Less-Common Metals 114, 97 (1985).
11. B. PIERAGGI,Oxid. Metals 27,177 (1987).
12. W. C. HAGEL,General Electric Report, No. 63-rl-3350M(1963).
13. J. L. SMIALEK,J. DOVCHAKand D. J. GAVDOSH.Workshop on Ox. of High Temp. Intermetallics,
Cleveland, OH, 44135-3191, Report No. NASA TM 101402(1988).
14. M. W. BRUMMand H. J. GRABKE,to be published.
15. M. ROHLE,E. SCHUMANNand U. SALZBERGER,unpublished results.
16. E. N. BUNTING,Bur. Standards J. Research 6, 948 (1931).
17. W. J. QUADAKKERS,Werkst. Korros. 41,659 (1990).