Intermetallics 9 (2001) 697–703

www.elsevier.com/locate/intermet

Effect of nitridation on the oxidation behavior of TiAl-based

intermetallic alloys
Bin Zhao*, Jiansheng Wu, Jian Sun, Bijun Tu, Fei Wang
Key Laboratory of the Ministry of Education for High Temperature Materials and Tests, School of Materials Science and Engineering,
Shanghai Jiao Tong University, Shanghai 200030, PR China

Received 1 December 2000; accepted 29 May 2001

Abstract
In the present work, gas nitridation of the TiAl based alloys in an ammonia atmosphere was carried out at 800, 860 and 940  C
for different time, respectively. The nitride layers were characterized by X-ray diffraction (XRD), electron probe micro-analyzer
(EPMA) and scanning electron microscopy (SEM). The composite of the nitride layers (Ti2AlN as the inner layer and TiN as the
outer layer) and the diffusing layer formed on the surface of the TiAl based alloys. The oxidation behavior of the nitrided alloys in
air was studied between 800 and 1000  C. The scales were characterized by X-ray diffraction (XRD) and scanning electron micro-
scopy (SEM) with energy dispersive X-ray (EDX) analysis. Generally an oxide scale consisting of two layers, an outward- and an
inward-growing layer, formed. The outward-growing part of the scale consisted of mainly of TiO2 (rutile), while the inward-grow-
ing part was composed mainly of a-Al2O3. Due to more a-Al2O3 formed in the outward-growing part, the non-nitrided alloys
showed better oxidation resistance than the nitrided alloys. On the observation of the EDX measurement, the alloys nitrided at
940  C for 50 h grew more a-Al2O3 with fine grains on the outer layer of its scale after 100 h exposure time at 1000  C. Because of
its significant transient oxidation at the initial period, it displayed worse resistance. It is concluded that the high-temperature
nitrided alloys exhibit better oxidation resistance at 1000  C. # 2001 Elsevier Science Ltd. All rights reserved.
Keywords: A. Aluminides, miscellaneous; A. Titanium aluminides, based on TiAl; B. Oxidation; B. Surface properties; C. Coatings, intermetallic and
otherwise

1. Introduction can be formed on TiAl by direct nitridation with different

The intermetallic compound TiAl has a great poten-
tial as lightweight and high temperature materials for
aerospace and automobile industries [1–4]. In the
development of high performance TiAl, great efforts
have been made to improve room temperature ductility
and oxidation resistance [5–11].
As we known, tribological problems are always
involved in the structural materials, especially in the
case of a turbine engine or a turbocharger rotor. Tita-
nium nitride is a suitable hard material for improving
wear resistance, and coatings of TiN by chemical vapor
deposition (CVD) or physical vapor deposition (PVD)
are often applied to tool steels to improve the service life
of cutting tools in wear application [12,13]. Because TiN
is more thermodynamically stable than AlN, TiN layers
* Corresponding author.
E-mail address: bzhao910@mail1.sjtu.edu.cn (B. Zhao).
0966-9795/01/$ - see front matter # 2001 Elsevier Science Ltd. All rights reserved.
PII: S0966-9795(01)00054-1
atmospheres [14,15], by implantation with N [16] and by
ion nitridation [17]. However, as to its oxidation resis-
tance after nitridation, the systematic study has not
been carried out. The effect of nitrogen on the oxidation
behavior of Ti–Al alloys has been noticed [8–11]. Wu et
al. [11] showed that TiN formation was favored in the
Ti3Al based alloys with Nb after exposure in hot air.
Hanrahan et al. [18] observed that the TiN layer was a
diffusion barrier to oxygen in titanium–tantalum alloys.
However, Choudhury et al. [19] concluded that the fas-
ter oxidation of TiAl in air as compared with that in
oxygen was due to the presence of nitrogen in air. Meier
et al. [20] observed that protective alumina scales
formed on TiAl upon exposure in oxygen up to 1000  C,
while the same exposure in air resulted in the formation
of titannia-rich scale exhibiting faster growth rate.
Meier et al. also suggested that the presence of nitrogen
caused formation of a nitride layer that prevented
the development of a continuous alumina scale. It was
698 B. Zhao et al. / Intermetallics 9 (2001) 697–703
concluded that formation of nitride layer was favored in
Ti3Al based alloys, but for the high Al content alloys,
e.g. TiAl based alloys, it was another story. The oxida-
tion rate of the TiAl based alloys in oxygen was in gen-
eral lower than that in air. However, exceptions had
been observed also [8]. The formation of a nitride layer,
in particular TiN, obviously favored the formation of a
protective Al2O3 layer, because it decreased the Ti and
increased the Al activity of the metal phase. However, it
was only one aspect of the nitrogen effect.
The role of nitride formation on the oxidation kinetics
of TiAl based alloys is not quite clear, especially of these
alloys after nitridation. Compared with the non-nitrided
TiAl based alloys, the following text describes investi-
gations regarding the isothermal oxidation behavior of
nitrided TiAl based alloys in order to get a better
understanding of the role of nitride.
2. Experimental
A conventional tungsten arc melting technique was
employed to prepare titanium aluminide alloy. Experi-
ments were performed with Ti–47Al–2Nb–2Cr–0.2Si
(the compositions are given in at.%) which had been
cast and homogenized at 1050  C for 100 h. Specimens
with dimensions of 10 mm2 mm were cut from the
homogenized ingots followed by surface polishing with
emery paper up to No. 1000 for nitridation and the
oxidation test.
After washed carefully in the acetone and alcohol to
remove grease, all specimens were hung in a high-tem-
perature quartz reaction tube for nitridation. The tube
was evacuated repeatedly and finally filled with argon.
The specimens were heated to the desired temperature
range of 800–940  C with the emphasis at 940  C. The
nitridation time was 10, 30 and 50 h, respectively. And
then argon was replaced with ammonia flowing at the
rate of 5–10 cm3.s 1. When the required period had
been attained, the specimens were cooled down in argon
to room temperature. X-ray diffraction (XRD) using
CuKa radiation, electron probe micro-analyzer (EPMA)
and scanning electron microscopy (SEM) were used to
study the microstructure and morphologies of the nitri-
ded alloys.
Isothermal oxidation was performed in an open air
for 5–100 h at different temperatures from 800–1000  C,
respectively. Oxidation kinetics was measured by an
electrobalance with the precision of 0.1 mg. After oxi-
dation, the phase constitutions of the scales in the sur-
face of the specimens were characterized by X-ray
diffraction (XRD) using CuKa radiation. Scanning
electron microscopy (SEM) and energy dispersive X-ray
spectroscopy (EDX) were employed to investigate both
the surface morphology and the cross-section of the
scale formed on the alloys.
3. Results and discussion
3.1. Nitridation
The nitride layers were detected on the surface of the
TiAl based alloys nitrided at all the temperatures for
different periods. The typical XRD pattern of the
nitride layers is shown in Fig. 1. It has been found that
besides the diffraction peaks of the constituents (TiAl
and Ti3Al) of the alloys, those of the TiN and Ti2AlN
occurred in the XRD pattern, and Ti2AlN is the inner
layer formed under the TiN outer layer [17,21,22]. AlN
and other new Al-rich intermetallics, such as Al2Ti and
Al3Ti in the subscale, were not found at the nitrides/
matrix interface. Fig. 2 shows the cross-section back
scattered electron image and the compositional line scan
of the alloys nitrided at 940  C for 50 h. The enrichment
of Al could be obviously found in the present work (see
Fig. 2b). Al concentration was caused primarily by the
formation of Ti or Ti-rich nitrides. A layer system TiAl
(or Ti3Al)/Ti2AlN/TiN was consistent with the Al–Ti–N
phase diagram according to which Ti2AlN as in equili-
brium with TiN and TiAl [8,23]. The details about
the nitride layers characterization were reported in the
papers [21,22].
3.2. Oxidation kinetics
3.2.1. Oxidation kinetics at 800  C
The results of isothermal exposure at 800  C in air up
to 100 h are summarized in Fig. 3. The overall mass
gain of the nitrided TiAl based alloys at the various
temperatures and time is higher than that of the non-
nitrided. The alloys nitrided at 940  C exhibit a gradu-
ally weakened oxidation resistance with the elongation
of nitridation time. As to the alloys nitrided at 940  C
for 10 h, its mass gain exceeds that of the other two
nitrided alloys after 90 h exposure time (Fig. 3a). The
Fig. 1. The X-ray pattern of TiAl based alloys nitrided at 940  C for
50 h.
 B. Zhao et al. / Intermetallics 9 (2001) 697–703 699

alloys nitrided at 940  C for 30 h lasts about 35 h at 940  C for 50 h a rapid transient oxidation was
(Fig. 3b), and it takes less than 10 h for the alloys nitri- observed during the initial 5 h of exposure, followed by
ded at 940  C for 50 h to be the severest oxidized a slower oxidation rate than those of all the other alloys
(Fig. 3c). Generally, the non-nitrided alloys exhibited including the non-nitrided alloys. All the alloys exhib-
the best oxidation resistance. Those nitrided at 800  C ited more rapid corrosion rates at 900  C than at 800  C.
did better than the alloys nitrided at 860  C. The nitri- For the alloys nitrided at 800  C, their mean mass
ded alloys displayed the weakened oxidation resistance gains at 900  C were approximately four times as large
by increasing of nitridation time. The largest mass
change of the alloys nitrided at 940  C for 50 h was
almost five times the value as found for the non-nitrided
alloys, which was very low and in the order of 0.3 mg/
cm2. Under the present conditions, no spallation has
happened in all the alloys. And it took about 20 h for all
the alloys to form a protective layer after transient oxi-
dation.

3.2.2. Oxidation kinetics at 900  C

Compared with the results at 800  C, there was a
slight difference among the mass gains of the nitrided
alloys at 900  C for the same exposure time. Fig. 4 is a
typical one which shows the oxidation results of the
alloys nitrided at various temperatures for 50 h. Rela-
tively, the alloys nitrided at 940  C showed the
improved resistance as compared with that at 800  C.
The non-nitrided alloys still exhibited better oxidation
resistance than the nitrided alloys. For the alloys nitrided

Fig. 3. Mass gain–time relationship of various TiAl based alloys in air

Fig. 2. Cross-section back scattered electron image and the composi- at 800  C; (a) nitrided for 10 h, (b) nitrided for 30 h; (c) nitrided for
tional line scan of the TiAl based alloy nitrided at 940  C for 50 h. 50 h.
700 B. Zhao et al. / Intermetallics 9 (2001) 697–703

as those at 800  C. However, alloys nitrided at 860 and substrate from further oxidizing, while the nitrided
940  C acted better and it was about twice. After lost more during the oxidation tests.
exposure at 900  C for 60 h most of the specimens 2. Among the nitrided alloys, it was concluded that
appeared the sign of spallation. It took 15 h for the alloys the high-temperature nitrided alloys displayed a
to form a protective layer to reduce the corrosion rate. sign of better oxidation resistance at more severe
oxidizing conditions. However, more evidences
3.2.3. Oxidation kinetics at 1000  C should provided for a further confirmation. Those
After 100 h exposure time, the alloys nitrided at nitrided at lower temperatures exhibited better
940  C show a clear trend as a rapid transient oxidation
during the initial 5 h, followed by a more slow rate than
all the other alloys. Furthermore, alloys nitrided at
higher temperatures show better oxidation resistance
than those nitrided at the lower temperatures (Fig. 5).
Fig. 5a and c exhibit that alloys nitrided at 940  C make
a slower oxidation rate than the other two nitrided
alloys. It was no doubt that alloys displayed worse
oxidation resistance at 1000  C than at 900  C. But
the ratio of the mass gains between those at 1000  C for
100 h and those at 900  C became smaller. That of the
alloys nitrided at 800 and 860  C was about twice, yet it
was only 1.3 for those nitrided at 940  C.
As a consequence, the oxidation resistance of the
nitride alloys upon 100 h exposure time at 800, 900 and
1000  C displayed the following characteristics:

1. Under the present conditions, non-nitrided alloys

still exhibited the superior oxidation resistance to
the nitrided alloys. Although the formation of a
nitride layer, in particular TiN, obviously favors
the formation of a protective Al2O3 layer because
of the formation of an Al enriched layer [8,21,22].
However, this is only one aspect of the nitridation.
The nitride layers were easily oxidized above
approximately 773 K [24]. It was also considered
that the further nitridation happened during the
oxidation tests, which prevented the continuous
Al2O3 layer forming. As a result, more Al content
on the surface of the non-nitrided alloys acceler-
ated the formation of Al2O3 that protected the

Fig. 5. Mass gain–time relationship of various TiAl based alloys in air

Fig. 4. The typical mass gain–time relationship of nitrided TiAl based at 1000  C: (a) nitrided for 10 h; (b) nitrided for 30 h; and (c) nitrided
alloys in air at 900  C. for 50 h.
 B. Zhao et al. / Intermetallics 9 (2001) 697–703
resistance at 800  C, but at higher temperatures
they were inferior. That was mainly due to the
rapid transient oxidation at the initial stage that
was beneficial to the quick formation for the pro-
tective layers at 1000  C.
3.3. Characterization of the scale
3.3.1. Phase constitution
From X-ray diffraction measurements of scales it
exhibited that the scale was generally composed of TiO2
(rutile) and a-Al2O3, which agreed with data in the lit-
erature [10]. The phase constitutions of the scale on the
alloys, as listed in Table 1, were determined on the sur-
face of the specimens after 100 h exposure time at 800–
1000  C with emphasis on the alloys nitrided at 940  C.
After exposure at 800  C, the intensity of the diffrac-
tion peaks of TiO2 was much higher than that of Al2O3
in the nitrided alloys, which means that the scale formed
on the nitrided alloys consisted of TiO2 as the major
phase and Al2O3 as the minor phase. Additionally, some
peaks from the underlying substrate were determined
(TiAl and Ti3Al). TiN and Ti2AlN were detected on the
surface of all the alloys. As to the non-nitrided alloys,
the phase constitution of the scale was the same as that
of the nitrided alloys. The only difference was that the
intensity of the diffraction peaks of TiO2 was lower and
more Al2O3 formed in the scale, which made it exhibit-
ing better oxidation resistance than the nitrided alloys.
TiO2 was also the major phase and Al2O3 was the
minor phase after exposed at 1000  C for 100 h. How-
ever, the height to height ratio between the peaks from
TiO2 and Al2O3 reduced for alloys nitrided at 940  C for
50 h, compared with the other nitrided alloys. Peaks
related to the nitrided compound Ti2AlN as well as
from the substrate turned weaker and peaks from TiN
disappeared from all the alloys.
On the observation of the XRD measurement, two
conclusions were given as follows:
1. More Al2O3 found on the surface of the non-
nitrided alloys, which offered them better oxida-
tion resistance than the nitrided alloys.
2. The reduced height to height ratio between the
peaks from TiO2 to Al2O3 showed the alloys nitrided
Table 1
Phase constitution of the scale on TiAl based alloys after 100 h exposure time determined by XRD
Alloy Exposed at 800  C
Major phase Minor phase
TiAl Ti2O TiAl,
Nitrided 940  C/10 h Ti2O TiAl,
Nitrided 940  C/30 h Ti2O TiAl,
Nitrided 940  C/50 h Ti2O, TiAl,
701
at 940  C for 50 h displayed better resistance at
1000  C.
3.3.2. Surface morphology
According to SEM investigations, the morphology of
the scale top surface could be divided into two groups:
1. Similar scale morphologies have been found on the
nitrided and the non-nitrided alloys after 100 h of
exposure time at 800–1000  C (see Fig. 6a and b).
They were mainly a mixture of Ti and Al oxide. It
can be found from Fig. 6a and b that the scales
could be divided into two parts, the white was the
outer layer and the black was the inner part. The
non-nitrided alloys formed a more compact outer
layer as compared with that of the nitrided alloys.
According to the compositional analysis of EDX
(see Fig. 6a and b), the outer layer mainly con-
sisted of TiO2 no matter it is the nitrided alloys or
the non-nitrided. But more Al was content in the
outer scales of the non-nitrided alloys (see Fig. 6b),
which explained why the non-nitrided alloys dis-
played a better oxidation resistance.
2. Quite a different morphology of a fine equiaxed
crystals (see Fig. 6c) was formed on the surface of
the alloys nitrided at 940  C for 50 h formed at
1000  C for 100 h. According to EDX (Fig. 6c),
these crystals were mainly composed by Al2O3.
Compared with the non-nitrided alloys, more
Al2O3 formed in the scale of the alloys nitrided at
940  C for 50 h. Just because of the severe tran-
sient oxidation at the initial period, the alloys
nitrided at 940  C 50 h finally demonstrated a
heavy oxidation. A protective layer on the surface
formed after 100 h at 1000  C indicated that the
nitridation could be a beneficial rather than a det-
rimental effect with regard to protective Al2O3
formation, because preferential nitridation of Ti
decreased the Ti and increased the Al activity.
Strong nitridation at 940  C for 50 h leaded to
remarkable Al enrichment in the subsurface zone
and to the formation of a nitride scale/TiAl3/
TiAl2/TiAl layer system [8,21,22]. It was summar-
ized that the nitridation was effective on the
improvement of high temperature oxidation of the
Exposed at 1000  C
Major phase Minor phase
Al2O3, TiN, Ti2AlN, Ti3Al, Ti2O Al2O3, TiAl, Ti3Al
Al2O3, TiN, Ti2AlN, Ti3Al, Ti2O Al2O3, Ti2AlN, Ti3Al, TiAl
Al2O3,Ti2AlN, TiN, Ti3Al, Ti2O Al2O3, Ti2AlN
Al2O3, TiN, Ti2AlN, Ti3Al, Al2O3 Ti2O, Ti2AlN, Ti3Al, TiAl
702 B. Zhao et al. / Intermetallics 9 (2001) 697–703

Fig. 6. Scale morphologies and their outer layer EDX analysis of (a) the alloys nitrided at 940  C for 30 h, (b) the non-nitrided alloys and (c) the
alloys nitrided at 940  C for 50 h after they were oxidized in air at 1000  C for 100 h: marks ‘‘A’’ in (a) and (b) point to the outer layers of the
oxidation scales; marks ‘‘B’’ point to the inner layers of the oxidation scales.
 B. Zhao et al. / Intermetallics 9 (2001) 697–703
TiAl based alloys, especially the temperatures
above 1000  C with a longer oxidation time.
4. Conclusions
1. The scales formed on the nitrided alloys in the
range of 800–1000  C was composed mostly of the
phase TiO2 (rutile) and a-Al2O3. It consisted of two
main layers, the outer layer and the inner one. As a
major difference, there were more Al2O3 in the outer
layer of the non-nitrided alloys, which acted as a pro-
tective barrier for the substrate.
2. Alloy nitrided at 800  C for 10 h exhibited better
oxidation resistance at the lower oxidizing temperature
than the other nitrided alloys. But with the increasing of
the temperature, those alloys nitrided at higher tem-
perature for longer nitridation time demonstrated an
improved oxidation resistance, especially the alloys
nitrided at 940  C for 50 h at the oxidation temperature
1000  C for 100 h. A protective layer mainly composed
by Al2O3 formed on the surface of those alloys. It also
indicated that they underwent the slowest oxidation rate
after a rapid transient oxidation among all the alloys
including the non-nitrided alloys.
3. Under the present conditions, the non-nitrided
alloys still displayed the better oxidation resistance than
the nitrided alloys, which was attributed to more Al2O3
formed on the outer layer of their scales. Moreover, that
layer was more compact than that on the nitrided
alloys.
Acknowledgements
This work is sponsored by the Science and Technology
Commission of the Shanghai Municipal Government.
703
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