Chinese

Journal of
Aeronautics
Chinese Journal of Aeronautics 23(2010) 370-376 www.elsevier.com/locate/cja

Effect of Rhenium Addition on Isothermal Oxidation Behavior of

Tribaloy T-800 Alloy
Zhang Yuduo, Yang Zhigang*, Zhang Chi, Lan Hao
State Key Laboratory of New Ceramics and Fine Processing, Department of Materials Science and Engineering,
Tsinghua University, Beijing 100084, China

Received 5 May 2009; accepted 17 July 2009

Abstract
The effects of 4 wt% rhenium (Re) addition on isothermal oxidation behavior of Tribaloy T-800 alloy have been studied at
800 °C and 1 000 °C in air. At 800 °C, T-800 shows nonuniform oxidation between dendritic and eutectic areas. Re addition
clearly promotes the nonuniform oxidation, leading to considerably higher mass gains than that of T-800 at this temperature. At
1 000 °C exposure, the thickness of scale on T-800 increases significantly, accompanied by severe scale spallation during cooling
to room temperature. On the contrary, T-800Re shows a marked decrease of oxide growth rate compared to the linear one of
T-800 at 1 000 °C. The scale adhesion is also improved with Re addition at this higher temperature. Therefore, the role of Re
depends on the exposure temperature. Re addition gives high oxidation rate at 800 °C, however, the excellent oxidation resis-
tance is obtained by the addition of Re at a higher temperature of 1 000 °C.

Keywords: rhenium; co-based alloy; Tribaloy T-800; high temperature; oxidation

1. Introduction1 these points did not generally agree in alloy systems

Cobalt-based Tribaloy® (registered trademark of
Deloro Stellite Company) T-800 alloy (Co-Mo-Cr-Si)
is well known for its excellent wear resistance, be-
cause of a large percentage of precipitation of hard
intermetallic phase with exceeded solubility of Mo and
Si[1-2]. It has been widely applied as the anti-wearing
coating served at a temperature as high as 800 °C for
tip shroud of turbine blade[3-6].
Recently, in order to improve the efficiency and
power of gas turbine, turbine inlet temperatures have
been increased rapidly, causing a more severe oxida-
tion attack on the blade coating[7-9]. It was reported that
rhenium (Re) as a reactive element is a useful addition
to improve scale adhesion and long-term oxidation
performance of MCrAlY-type coating materials by
decreasing the extent of β-depletion and increasing the
stability of α-Cr phase[10-12]. It was also reported that
Re addition improved the cyclic oxidation behavior of
β-NiAl+α-Cr alloy by reducing the extent of both
internal oxidation and scale spallation[13]. However,
*Corresponding author. Tel.: +86-10-62795031.
E-mail address: zgyang@tsinghua.edu.cn
1000-9361 © 2010 Elsevier Ltd. Open access under CC BY-NC-ND license.
doi: 10.1016/S1000-9361(09)60229-6
studied, for example, beneficial effect of Re addition
was hardly found on the oxidation behavior of
Cr-Cr2Nb alloy at 950 °C[14].
Up to now, little attention is paid to the effect of Re
addition on the oxidation behavior of the Co-base Tri-
baloy alloy. The present investigation, therefore, is
undertaken to study the effect of Re addition to T-800
on the isothermal oxidation behavior so as to contrib-
ute to improving the oxidation resistance of T-800 and
enhancing the understanding of Re effects in
superalloy systems.
2. Materials and Methods
Standard T-800 and T-800 containing 4 wt% Re
(T-800Re) were prepared by arc-melting process. The
nominal chemical composition of T-800 is
Co-28.5Mo-17.5Cr-3.4Si (in wt%). After melting the
cast samples were subjected to a vacuum anneal for
2 h at 1 120 °C and subsequently 24 h at 850 °C.
Oxidation specimens with dimensions of 10 mm in
diameter and 1 mm in height were mechanically pol-
ished and finished with 0.5 μm diamond paste. The
finished specimens were cleaned in distilled water and
then in acetone with ultrasonic agitation for 2 min
prior to oxidation. Isothermal oxidation tests were
No.3 Zhang Yuduo et al. / Chinese Journal of Aeronautics 23(2010) 370-376 · 371 ·

performed at 800 °C for 60 h and 1 000 °C for 40 h in The oxidation kinetics can be fitted by
still air. Each specimen was oxidized at the appointed
Δm / A = Kt n
temperature for the desired time and the mass gain was
quantified discontinuously by an electronic balance where Δm is the mass change, A the surface area, K the
with a sensitivity of 0.1 mg after cooling to room tem- oxidation rate constant, t the exposure time. n values
perature. are listed in Table 1. Both alloys follow subparabolic
The constituent phases in the oxide scale developed kinetics at 800 °C exposure. It is also found that the Re
on the alloys were identified using X-ray diffraction addition results in a marked increase of mass gain and
(XRD, using Cu Kα radiation). The morphologies and the differences become more pronounced with in-
chemical compositions of top surface and cross-section creasing exposure time at 800 °C. During oxidation at
of the oxide scales were examined by scanning elec- 1 000 °C, n value is 0.94, which indicates that a nearly
tron microscopy (SEM) with energy dispersive spec- linear oxidation kinetics is identified for T-800. How-
troscopy (EDS). ever, the oxidation of T-800Re follows a nearly para-
bolic kinetics at this temperature. It is inferred that the
3. Results oxide growth rate is decreased dramatically by Re ad-
dition at 1 000 °C. Furthermore, after exposure at
3.1. Isothermal oxidation kinetics 1 000 °C, the difference of mass gains between with
and without measuring the spalled oxides is great
Since considerable spallation of oxide scale on (Fig.1(b)), suggesting a considerable extent of oxide
T-800 occurred during cooling to room temperature spallation. However, no spallation is observed for
after exposure at 1 000 °C for 40 h, the specimen of T-800Re. In summary, the role of Re addition to T-800
T-800 was oxidized in a crucible, and then weighed depends on the exposure temperatures.
together with the crucible before and after oxidation.
Fig.1 shows the mass gains per unit surface area of Table 1 n values for oxidation of T-800 and T-800Re at
T-800 and T-800Re oxidized at 800 °C and 1 000 °C, 800 °C and 1 000 °C
respectively. In Fig.1(b), the solid line with filled tri- Correlation
Alloy Temperature/°C n
angle is the mass gain of T-800 including spalled oxide; coefficient
the dashed line with open triangle is from experimental 800 0.39 0.964 50
measurements of T-800 specimen without spalled T-800
1 000 0.94 0.988 00
mass.
800 0.66 0.991 52
T-800Re
1 000 0.50 0.991 00

3.2. Scale morphology and composition

Fig.2 shows the surface morphologies of T-800 and

T-800Re after oxidation at 800 °C for 40 h. It is found
that the oxides formed on T-800 is equaxed, as shown
in Fig.2(a), which is mainly composed of two grained
oxides: coarse-grained oxides and fine-grained oxides.
By EDS analysis, strong Mo, Co and O peaks are de-
tected in coarse oxide regions and strong Co and O
peaks with small Cr peaks in fine oxide regions. Simi-
larly, the fine-grained oxides present around the regions

Fig.1 Oxidation kinetics of T-800 and T-800Re after expo-

sure at 800 oC and 1 000 °C.
· 372 · Zhang Yuduo et al. / Chinese Journal of Aeronautics 23(2010) 370-376 No.3

Fig.2 Surface morphologies of oxide scales on T-800 and Fig.3 Surface morphologies of T-800 and T-800Re after
T-800Re after 40 h of exposure at 800 °C. oxidation at 1 000 °C for 40 h.

EDS analysis. After exposure at 1 000 °C for 40 h, the

of coarse-grained oxide for T-800Re, as shown in cross-sectional residual oxide scale on T-800 is shown
Fig.2(b). EDS results show that both coarse-grained by the arrow in Fig.4(a). In contrary, the scale formed
oxide and fine-grained oxide are rich in Co and O. The on T-800Re is adhesive and no spallation is found (see
former contains small amount of Mo but the latter con- Fig.4(b)). This suggests that the oxidation resistance
tains small amount of Cr. With the addition of 4 wt% including mass gain and scale adhesion is improved by
Re, the oxide scale is relatively compact and many Re addition at 1 000 °C exposure.
cracks are observed, as shown by the arrow in
Fig.2(b).
The surface morphologies of T-800 and T-800Re
after oxidation at 1 000 °C for 40 h are shown in Fig.3.
The oxide scale formed on both alloys is rich in Cr, Co
and O according to EDS analysis. Typical morphology
of spinel is observed and presumably it is CoCr2O4.
The extensive oxide spalled area on T-800 oxidized at
1 000 °C for 40 h is shown in Fig.3(c), where the
grooves with loose oxide around Laves phase are ob-
served. The loose oxide is composed of Si and O by

Fig.4 Cross-sectional SEM micrograph of T-800 and

T-800Re after oxidation at 1 000 °C for 40 h.

3.3. Scale microstructure

According to XRD analysis, the oxidation products

are mainly Co3O4, MoO3, Cr2O3, with CoO, SiO2 and a
small amount of complex oxide CoMoO4 and spinel
CoCr2O4 for the two alloys after oxidation in air at
No.3 Zhang Yuduo et al. / Chinese Journal of Aeronautics 23(2010) 370-376 · 373 ·

800 °C for 60 h. In order to understand in detail the

oxidation behavior, the cross-sectional microstructures
of oxide scale were examined. Fig.5 shows cross-
sectional SEM images of the two alloys oxidized at
800 °C for 60 h. The oxide scale formed on T-800
shows two very distinct scales: an external scale with a
columnar microstructure and an internal attack with
protrusion into Laves phases. The thickness of external
scale is not uniform and varies from 2 μm to 4 μm.
The thick parts mainly develop over Laves phases in
the substrate, and the thin parts over the matrix. The
maximal depth of inner protrusion is approximately
8 μm. Fig.6 presents concentration profiles of Co, Mo,
Cr, Si and O measured along A-A line and B-B line in
Fig.5(a) and Fig.5(b), respectively. With the combina-
tion of EDS and XRD results, it suggests the oxidation
products might be divided into five layers. The outer
layer is pure Co oxides (Co3O4). Beneath the Co3O4
layer, complex oxide CoMoO4 and spinel CoCr2O4
form. As the main outer layer, the columnar oxide is
MoO3 with a small amount of CoO, which contributes
to the nonuniformity of external scale. The intermedi-
ate layer is a mixture of Cr2O3, SiO2, MoO3 and CoO.
In internal oxidation region, a discontinuous layer of
Cr2O3 and SiO2 has grown into the Mo and Si-rich
Laves phases including primary Laves dendrite and
I—Co3O4; II—CoMoO4; III—MoO3+CoO;
secondary Laves phases in eutectic. Similar to the case IV— Cr2O3 +SiO2+MoO3+ CoO; V—Cr2O3+SiO2
of T-800, the scale formed on T-800Re presents two
Fig.6 EDS line profiles corresponding to lines in Fig.5.

distinct scales, except that external and internal oxida-

Fig.5 Cross-sectional SEM images of T-800 and T-800Re
after oxidation at 800 °C for 60 h.
tions become more severe. The external scale is rela-
tively uniform with a thickness of 11 μm and the in-
ternal attack along Laves phase increases to about
17 μm.
After 40 h of oxidation at 1 000 °C, the external
oxide scale on T-800 is about 3.5 times as thick as that
on T-800Re (see Fig.4). The XRD analysis indicates
the oxidation products are mainly Cr2O3, spinel
CoCr2O4 and a small amount of SiO2 for the two alloys.
Fig.7 and Fig.8 show the cross-sectional SEM images
and the concentration profiles of elements measured
along designated C-C line and D-D line for T-800 and
T-800Re oxidized at 1 000 °C for 20 h. Both scales
have a similar cross-sectional microstructure. Accord-
ing to XRD analysis with combination of cross-sec-
tional examination, it can be seen that a continuous
Cr2O3 layer covered with a thin layer of spinel
CoCr2O4 forms outer scale. After this exposure, the
outer scale thickness of T-800Re is close to that of
T-800, which are about 4.0 μm and 3.3 μm, respec-
tively. Beneath the outer scale, internal voids develop
both at the interface between Lave phase and the ma-
trix, and at the scale/alloy interface together with loose
internal oxide SiO2. Some of the voids are isolated in
cross-section (see Fig.7) but are three-dimensional
continuous, as evidenced by observation of oxide
spalled area (see Fig.3(c)).
· 374 · Zhang Yuduo et al. / Chinese Journal of Aeronautics 23(2010) 370-376
Fig.7 Cross-sectional SEM images of T-800 and T-800Re
after oxidation at 1 000 °C for 20 h.
I—CoCr2O4; II—Cr2O3; III—Voids+SiO2
Fig.8 EDS line profiles corresponding to lines in Fig.7.
No.3
4. Discussion
The variation in effect of Re on oxidation resistance
in the present study should be attributed to the differ-
ent oxidation mechanisms of T-800 at different tem-
peratures. During the exposure at 800 °C, both alloys
exhibit different oxidation behaviors between dendritic
and eutectic regions. Such phenomenon was also ob-
served in other alloy systems, for example, Cu-Ni-
Cr-Fe[15] and Ni3Al alloy[16]. This is associated with the
difference of compositions in individual phases due to
microsegregation during solidification. At 800 °C,
initial oxidation of T-800 is dominated by Co oxides
(Co3O4 and CoO) and MoO3 formation. Over the
Mo-rich laves phase area, thick MoO3 scale forms,
while relatively thin scale forms over the Cr-rich ma-
trix area. Meanwhile, solid-state reactions among ox-
ides may occur, giving rise to the generation of com-
plex oxide CoMoO4 and spinel CoCr2O4. Owing to
rapid transport rate of oxygen in external scale, oxygen
pressure at the scale/substrate interface is high. This,
together with a faster diffusion path for oxygen pro-
vided by cation defection as a result of the outward
diffusion of Mo, causes further selective internal oxi-
dation.
However, the oxidation resistance at 800 °C is wors-
ened dramatically with a larger thickness of scale in
the presence of Re. The oxidation products on
T-800Re are similar to that on T-800 at this tempera-
ture, as indicated in Fig.9(a). Any Re oxide could not
be found in the scale probably due to the formation of
volatile oxide Re2O7, which volatilized as soon as it is
formed. Re enrichment in T-800 is observed in Laves
phase regions and the partitioning of Re between
Laves phase and the matrix is at about a ratio of 2.5:1.
Consequently, the increase of mass gain, on the one
hand, could be deduced that Re addition promotes the
outward diffusion of Mo. As a result, the inward flux
of oxygen in the alloy increases, resulting in higher
oxide growth rate at 800 °C unlike the case of other
reported materials[12,17-18]. This is presumably due to
the various scale-forming elements and the different
presence of Re in the microstructure[17-20]. On the other
hand, it should also be attributed to the increase of the
volume fraction of Laves phase to some extent, which
changes from (61±5)% to (67±4)%.
At 1 000 °C, a continuous external Cr2O3 scale with
an outer thin layer CoCr2O4 is developed on the two
alloys. The voids are generated at the scale/alloy inter-
face and intragranular regions together with loose SiO2
oxide, which demonstrates that the external Cr-rich
oxide scale is less protective. Fig.9(b) schematically
illustrates the cross-sectional microstructure of oxide
scale on T-800Re oxidized at 1 000 °C. As anticipated,
Re addition significantly decreases oxygen gains, re-
duces the oxide growth stresses during 1 000 °C ex-
posure, and thus reduces or prevents the scale detach-
ment and oxide damage on cooling. It is hence sug-
No.3 Zhang Yuduo et al. / Chinese Journal of Aeronautics 23(2010) 370-376
gested that the presence of Re suppressed the outward
diffusion of Cr in the alloy. That may be attributed to
the increase of stability of α-Cr by Re addition[11-12].
In view of the different effects of Re on oxidation
behavior, Re appears to be unfavorable for solely use
in T-800 to improve the oxidation resistance. Therefore
further fine-tuning of alloying elements or co-additions
is needed.
Fig.9 Schematic of cross-sectional microstructure of oxide
scale on T-800Re exposed at 800 °C and 1 000 °C.
5. Conclusions
The influence of Re addition on oxidation resistance
of T-800 depends on the exposure temperature, which
is responsible for different oxidation mechanism. At
800 °C, the oxides grown on T-800 are multi-layer
scales with nonuniform oxidation between dendritic
and eutectic locations. The Re addition promotes the
nonuniform oxidation and results in a marked increase
of oxide growth rate at this temperature. The 1 000 °C
exposure results in a significant increase in mass gain
of T-800 compared to the 800 °C exposure. With the
increase of exposure time, considerable scale spalla-
tion occurrs during cooling to room temperature.
However, Re addition improves oxidation resistance
by reducing oxidation rate and increasing scale adhe-
sion during exposure at 1 000 °C.
· 375 ·
Acknowledgement
The authors gratefully acknowledge the support of
Mitsubishi Heavy Industries (MHI) of Japan.
References
[1] Halstead A, Rawlings R D. Structure and hardness of
Co-Mo-Cr-Si wear resistant alloys (Tribaloys). Metal
Science 1984; 18(10): 491-500.
[2] Bolelli G, Cannillo V, Lusvarghi L, et al. Microstruc-
tural and tribological comparision of HVOF-sprayed
and post-treated M-Mo-Cr-Si (M=Co, Ni) alloy coat-
ings. Wear 2007; 263(7-12): 1397-1416.
[3] Navas C, Cadenas M, Cuetos J M, et al. Microstructure
and properties of Tribaloy T-800 coatings deposited by
laser cladding. Boletin De La Sociedad Espanola De
Ceramica Y Vidrio 2004; 43(2): 319-322.
[4] Navas C, Cadenas M, Cuetos J M, et al. Microstructure
and sliding wear behavior of Tribaloy T-800 coatings
deposited by laser cladding. Wear 2006; 260(7-8):
838-846.
[5] Tobar M J, Amado J M, Alvarez C, et al. Characteris-
tics of Tribaloy T-800 and T-900 coatings on steel sub-
strates by laser cladding. Surface and Coatings Tech-
nology 2008; 202(11): 2297-2301.
[6] Xie Y J, Wang M C, Zhang G, et al. Analysis of super-
alloy turbine blade tip cracking during service. Engi-
neering Failure Analysis 2006; 13(8): 1429-1436.
[7] Gurrappa I, Rao A S. Thermal barrier coatings for en-
hanced efficiency of gas turbine engines. Surface and
Coatings Technology 2006; 201(6): 3016-3029.
[8] Pomeroy M J. Coatings for gas turbine materials and
long term stability issues. Materials and Design 2005;
26(3): 223-231.
[9] Wright I G, Gibbons T B. Recent developments in gas
turbine materials and technology and their implications
for syngas firing. International Journal of Hydrogen
Energy 2007; 32(16): 3610-3621.
[10] Czech N, Schmitz F, Stamm W. Improvement of
MCrAlY coatings by addition of rhenium. Surface and
Coatings Technology 1994; 68-69: 17-21.
[11] Czech N, Schmitz F, Stamm W. Microstructural analy-
sis of the role of rhenium in advanced MCrAlY coat-
ings. Surface and Coatings Technology 1995; 76-77
(1-3): 28-33.
[12] Huang L, Sun X F, Guan H R, et al. Improvement of
the oxidation resistance of NiCrAlY coatings by the
addition of rhenium. Surface and Coatings Technology
2006; 201(3-4): 1421-1425.
[13] Pillips M A, Gleeson B. Beneficial effects of rhenium
additions on the cyclic-oxidation resistance of
β-NiAl+α-Cr alloys. Oxidation of Metals 1998; 50(5-6):
399-429.
[14] Liu C T, Tortorelli P F, Horton J A, et al. Effects of
alloy additions on the microstructure and properties of
Cr-Cr2Nb alloys. Materials Science and Engineering: A
1996; 214(1-2): 23-32.
[15] Cao Z Q, Shen Y, Wang C J, et al. Oxidation of a qua-
ternary three-phase Cu-20Ni-20Cr-5Fe alloy at
700-900 °C in 1 atm of pure O2. Corrosion Science
2007; 49(6): 2450-2460.
[16] Lee D Y, Santella M L, Anderson I M, et al. Thermal
aging effects on the microstructure and short-term oxi-
· 376 · Zhang Yuduo et al. / Chinese Journal of Aeronautics 23(2010) 370-376
dation behavior of a cast Ni3Al alloy. Intermetallics
2005; 13(2): 187-196.
[17] Wenderoth M, Völkl R, Vorberg S, et al. Microstruc-
ture, oxidation resistance and high-temperature
strength of γ′ hardened Pt-base alloys. Intermetallics
2007; 15(4): 539-549.
[18] Beele W, Czech N, Quadakkers W J, et al. Long-term
oxidation tests on a Re-containing MCrAlY coating.
Surface and Coatings Technology 1997; 94-95(1-3):
41-45.
[19] Yoon K E, Isheim D, Noebe R D, et al. Nanoscale
studies of the chemistry of a René N6 superalloy. In-
terface Science 2001; 9(3-4): 249-255.
[20] Yoon K E, Noebe R D, Seidman D N. Effects of rhe-
nium addition on the temporal evolution of the nanos-
tructure and chemistry of a model Ni-Cr-Al superalloy.
I: experimental observations. Acta Materialia 2007;
55(4): 1145-1157.
Biographies:
Zhang Yuduo Born in 1978, she received Ph.D. degree
from Tianjin University in 2006, and now is a postdoctoral
researcher in Tsinghua University. Her main research interest
is high-temperature oxidation and hot corrosion of superal-
loy.
E-mail: ydzhang@tsinghua.edu.cn
No.3
Yang Zhigang Born in 1968, he received Ph.D. degree
from Tsinghua University in 1996, and now is a professor
there. His main research interests are high-temperature oxi-
dation and corrosion of superalloy, phase equilibrium and
transformation in steel, etc.
E-mail: zgyang@tsinghua.edu.cn
Zhang Chi Born in 1973, he received Ph.D degree from
Tsinghua University in 2001, and now is an associate pro-
fessor there. His main research interests are phase equilib-
rium and transformation in steel, high temperature oxidation
and corrosion of superalloy, etc.
E-mail: chizhang@tsinghua.edu.cn
Lan Hao Born in 1982, he received Master’s degree from
University of Science & Technology Beijing in 2007, and
now is a Ph.D. candidate in Tsinghua University. His main
research interest is high-temperature oxidation and hot cor-
rosion of superalloy.
E-mail: lanh07@mails.tsinghua.edu.cn