Intermetallics 19 (2011) 744e747

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Intermetallics
journal homepage: www.elsevier.com/locate/intermet

Short communication

Diffusion aluminide coatings for TiAl intermetallic turbine blades

M. Goral a, *, L. Swadzba b, G. Moskal b, G. Jarczyk c, J. Aguilar d
a
Research and Development Laboratory for Aerospace Materials, Rzeszow University of Technology, W. Pola 2, 35-959 Rzeszow, Poland
b
Silesian University of Technology, Department of Materials Science, Krasinskiego 8, 40-019 Katowice, Poland
c
ALD Vacuum Technologies GmbH, AVS-FE Wilh. Rohn Str. 35, 63450 Hanau, Germany
d
Access e.V., Intzestr. 5, D-52072 Aachen, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Alloys based on intermetallic phases of a TieAl system are materials that, thanks to their resistance
Received 5 July 2010 characteristics, can be widely used in automotive and aerospace applications. The main restriction for the
Received in revised form use of TieAl materials is their insufficient oxidation resistance above 850
C. Oxidation parameters might
18 December 2010
be improved by aluminide coatings based on TiAl2 and TiAl3 phases, which could induce the creation of
Accepted 20 December 2010
Available online 20 January 2011
an Al2O3 scale in the oxidation process. This type of aluminide could be deposited on the surface of TiAl
alloys by various methods such as pack cementation, plasma spraying or magnetron sputtering. This
article presents a new method of aluminide coating deposition on TiAl intermetallic alloys: out of pack
Keywords:
A. Titanium aluminides, based on TiAl
technology. The investigated coating was deposited on turbine blades made of a Ti45Al5Nb intermetallic
B. Oxidation alloy. The surface morphology, structure, phase and chemical composition have been investigated using
C. Coatings, intermetallic and otherwise XRD phase analysis, SEM and EDS. The phase analysis showed that TiAl3 and TiAl2 were the main
F. Electron microscopy, scanning components of the deposited coating. An isothermal oxidation test of the TiAl turbine blades was con-
G. Aero-engine components ducted as well. After 1000 h of testing at 950
C, the scale formed on the surface of the uncoated blades
underwent spallation. The scale on the turbine blade with deposited aluminide coatings was very thin
and no spallation was observed.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction existent, especially if the alloy must provide high-temperature

The intermetallic g-TiAl-phase-based alloys are characterized by
many beneficial features, which have enabled their wide interest
for aircraft and automotive industries. The most important features
include: low density (3.8 g/cm3), high specific strength, relatively
high oxidation resistance, high specific modulus of rigidity and high
creep resistance at high temperatures. Research has been focused
on the improvement of mechanical properties, the increase of
oxidation resistance and the reduction of manufacturing costs.
The TiAl-phase-based alloys can be used as an alternative
material for nickel superalloys, especially on the low pressure
turbine blades where the operating temperature was lower (about
900
C). The main restriction for industrial applications of g-TiAl
alloys has been high manufacturing costs and insufficient oxidation
resistance at temperatures above 850
C. Other barriers include low
plasticity and structural instability during prolonged exposure to
high temperatures [1,2]. The technical possibility of accomplishing
an optimal chemical composition of g-TiAl alloys has been non-
* Corresponding author. Tel.: þ48 508 635 222.
E-mail address: m_goral@interia.pl (M. Goral).
oxidation resistance at low manufacturing costs. Despite the
additives, TiAl alloys have been unable to form pure aluminum
oxide scale during oxidation. Consequently, protective coatings
need to be applied.
The main technology to deposit coatings based on high-
aluminum TiAl3 phases on TiAl alloys was the pack cementation
method [3,4]. The coating was formed as a result of diffusion from
the powder in which the samples were placed with a halogenide
activator. The protective coating includes: an outer zone consisting
of the TiAl3 phase; and an inner zone composed of the TiAl2 phase.
Fractures may have appeared during the cooling from the deposi-
tion temperature, due to the brittleness of TiAl3 phase [5]. During
the oxidation tests of aluminide coatings at 800e1000
C, a massive
growth of an intermediate TiAl2 zone took place, at the expense of
the TiAl3 zone [6]. The coatings deposited on the TiAlNb alloys were
characterized by much higher oxidation resistance than those
obtained on the TiAl alloy without Nb additives [7].
The studies by Xiang and Rose proved that silicon and aluminum
can be deposited simultaneously through pack cementation
process [8e11]. The oxidation tests of the coating conducted at
800
C and 850
C confirmed that the process occurred according to
the parabolic curve [11].

0966-9795/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.intermet.2010.12.015
 M. Goral et al. / Intermetallics 19 (2011) 744e747
One of the most widely used methods to investigate the
oxidation resistance of g-TiAl alloys has been ion implantation [12].
Lei et al. [13] proved that Nb, W, Si, Al, Cl, P were the elements that
increased the oxidation resistance of TiAl alloys, whereas the
implantation of Cr, Zr, Mo, Mn, Pt did not influence the oxidation
resistance. Taniguchi et al. [14e17] demonstrated that the ion
implantation of silicon caused formation of intermetallic phases
such as Ti7Al5Si12.
Magnetron sputtering of MCrAlY provided an improvement in
the corrosion resistance of TiAl alloys at temperatures ranging from
800 to 900
C [18]. During the oxidation process diffusion reactions
between the coating elements and the base material occurred.
MeCrAlY coatings may have formed a base material for zirconium-
oxide-based thermal barrier coatings (TBC) [19]. Aluminide coat-
ings or preoxidation process might have been used to form an
interlayer [20]. Recently, the thermal barrier coatings deposited
with electron beam physical vapor deposition (EB-PVD) methods
have been researched [21].
In China [22], efforts were made to form protective coatings on
TiAl alloys by means of immersion in liquid silumin. The result was
a homogenous coating composed mainly of triple phases of
Al12Si3Ti5 and Ti7Al5Si12. In addition, the formation of titanium
silicides was observed.
Excellent properties were achieved in silicon-modified alumi-
nide coatings deposited with the Arc-PVD method (evaporating
silumin targets from AK11 alloy) and subsequent vacuum heat
treatment. The obtained coating was 40 mm thick [23]. Cyclic
oxidation tests, both short and prolonged, were conducted at
950
C and revealed an exceptionally high oxidation resistance of
the deposited coating [24].
The out of pack process operates at temperatures between 900
and 1050
C into Ar atmosphere. The out of pack method has
a number of advantages over pack cementation method (a) faster
cycle time because the parts are not surrounded by pack, (b) better
coating uniformity on each part, (c) less variation in coating
thickness from one place in the retort to another, (d) no coating
defects caused by pack inclusions, (e) lower cost of operation
because less pack material is used [25].
2. Experimental
The turbine blades used in the study were made of a Ti45Al5Nb
alloy, whose chemical composition has been presented in Table 1.
The shell casting of the turbine was performed in a centrifugal
casting device. Oxygen pick-up between 300 and 400 wt. ppm was
expected during melting and super-heating. The key parameters
were: super-heating of the alloy, shell mold temperature, rotation
speed for fast mold filling, high casting pressure, proper shell mold
positioning in order to ensure use of centrifugal and Coriolis forces
and cooling curves. Further processing included knock-off of the
ceramic shell, cutting and polishing of the castings. The knock-off
and polishing were completed with sand blasting; and cutting was
completed with a high pressure water jet. High-temperature
isostatic pressing (HIP) was used to close rest porosities. HIP
parameters were strictly controlled to prevent corrosion, defor-
mation or microstructure modifications.
The cast blades underwent surface preparation processes,
including cleaning and degreasing. The aluminizing process was
done with the out of pack method. The blades were placed in a
Table 1
The chemical composition of the alloy used for turbine blades producing (at.%).
Alloy Al Nb Cr
Ti45Al5Nb 45 5 0.2
745
container between suitably pre-prepared granules containing
aluminum and fluoride activator (AlF3) The container was placed in
the retort furnace. The process was carried out at 1050
C/4 h in a
protective argon atmosphere.
The structural analysis was performed by a high-resolution
scanning electron microscope FEI Inspect F, equipped with a
Schottky Field Emission source and connected to Edax EDS
detector. X-Ray Diffraction Analysis (XRD) was performed with a
JDX-7S Jeol diffractometer.
The oxidation tests were carried out at 950
C in static labora-
tory air. An aluminide-coated blade and an uncoated blade were
used in the investigation. After each 100 h of exposure at high
temperatures, the blades were removed in order to assess the
degree of destruction caused by oxidation and to take photographs.
The testing of all samples ended after 1000 h of exposure. The
individual mass changes of blades were not measured. After the
testing had been completed, the blades underwent surface
morphology and structural examinations, as well as chemical and
phase composition analyses.
3. Results
The TiAlNb turbine blade, presented on Fig. 1a was aluminized
with the out of pack method. The obtained coating completely
covered the turbine blade.
The XRD phase analysis of the sample surface detected the
presence of high-aluminum phases in the TiAl system: TiAl2 and
TiAl3. The cross section of the coated blade is given in Fig. 2a
showed two characteristic layers (Fig. 2a, results of EDS analysis e
Table 2). The outer layer was made up of equiaxed grains containing
approximately 50 at.% Ti and 44 at.% Al (Fig. 2a, point 1). Between
the grains, a high-aluminum area was present (about 69 at.%, point
2, Fig. 2a). The inner zone contained columnar grains with high-
aluminum content (approximately 74 at.%) and niobium (about
10 at.%) (Fig. 2a, point 3). The aluminum content between the grains
amounted to about 67% at.%, whereas the niobium content was
approximately 5 at.% (point 4, Fig. 2a). In the transitional area, the
aluminum content amounted to 50 at.%, and the niobium content
was about 9.5 at.%. (point 5, Fig. 2a).
After the oxidation test, the uncoated blade, presented on
Fig. 1b, was covered with yellow scale that spalled. The largest
damage was revealed in the edge of attack and flow areas of turbine
blade. The XRD phase analysis of the sample surface revealed the
presence of aluminum, titanium and niobium oxides, titanium
nitrides and the TiAl phase. The scale formed on the uncoated
B
Fig. 1. The overview of TiAl turbine blades: (A) after aluminizing, (B) after 1000 h
0.2
oxidation test (without aluminizing) (C) after aluminizing and 1000 h oxidation test.
746 M. Goral et al. / Intermetallics 19 (2011) 744e747

Fig. 2. The structure of aluminide coating deposited on the TiAl turbine blade (a), structure of scale after oxidation of uncoated blade (b) and turbine blade with aluminide coating (c).

sample surface was characterized by a complex and multi-layer 4. Summary

structure (Fig. 2b, results of EDS analysis e Table 2). In the area near
the surface, titanium and oxygen were dominant elements (point 6, The paper presents the test results of aluminide coating depo-
Fig. 2b). Directly below, the major scale contents were aluminum sition on the blades made of an intermetallic TiAl-type alloy. The
and oxygen (point 7, Fig. 2b). The continuous scale zone, point 8, out of pack technology was widely used in the aero-engine industry
was characterized by 1:2 at.% titaniumeoxygen proportion. The for the aluminizing of nickel alloy blades. The conducted investi-
visibly dark areas (points 9 and 13, Fig. 2b) were rich in aluminum gation proved that it was possible to produce a TiAl3 and TiAl2-
(42 at.%) and contained 54 at.% oxygen. The bright grains, point 10, based coating. The thickness of the deposited coating was relatively
showed high niobium content, which exceeded 35 at.%. The grains small and amounted to approximately 20 mm.
analyzed in point 14 were characterized by a high niobium content The oxidation tests at 950
C for 1000 h confirmed a significant
(about 30 at.%) as well as the presence of oxygen at 15%. The outer increase in the corrosion resistance of the aluminized blades as
zone of the base material contained 10% niobium (point 11, Fig. 2b) compared to the uncoated ones. Thick, complex, multi-layered scale
and only 32 at.% aluminum. In the base material (point 12, Fig. 2b), formed on the surface of the uncoated blade. It was a mixture of
the aluminum content amounted to about 47%, but the niobium aluminum and titanium oxides. This did not provide sufficient
content was the same as in point 11. oxidation resistance, which resulted in the flaking and spalling of the
After testing, the aluminized sample was dark grey (Fig. 1c). The scale on the edge of attack and flow of the blade. On the surface of the
edge of attack included sparse areas of yellow scale. The surface aluminized blade, a continuous dense film of aluminum oxide
morphology analysis of the edge, however, did not reveal any appeared Its formation was due to the preferential oxidation of
fracturing or cracking of the scale. The XRD phase analysis of the aluminum. The performed experiments proved that the out of pack
blade surface revealed the presence of Ti2AlN, TiAl, Al2O3 and TiO2. aluminizing was an effective method for increasing oxidation
The blade structure after 1000 h of testing showed significant resistance in TiAl alloys, which may be applied on an industrial scale.
degradation (Fig. 2c, results of EDS analysis e Table 2). The
formation of continuous uniform scale containing approximately
References
44 at.% aluminum and about 56 at.% of oxygen was confirmed
(point 15, Fig. 2c). The zone underneath (point 16, Fig. 2c) was [1] Loria E. Intermetallics December 2001;9(12):997e1001.
characterized by a lower content of aluminum (about 35%) and [2] Loria E. Intermetallics September 2000;8(9e11):1339e45.
niobium (about 4 at.%). In point 17, the Al content increased to [3] Streiff R. Journal de Physiqe IV Colloque C9, supplement au Journal de
Physique 111 d`Ccembre 1993;3:17.
almost 50 at.%, and Nb up to 10 at.%. [4] Smialek JL. Corrosion Science 1993;35:1199e208.
[5] Munoro TC, Gleeson B. Materials Science Forum 1997;251e254:753e60.
Table 2 [6] Xiang ZD, Rose S, Datta PK. Surface and Coatings Technology December 2,
The results of chemical composition microanalysis in points marked on Fig. 2. 2002;161(2e3):286e92.
[7] Jung HG, Kim KY. Oxidation of Metals August 2002;58(1e2):197e216.
Point/area Ti Al Nb O [8] Xiang ZD, Rose SR, Burnell-Gray JS, Datta PK. Journal of Materials Science
January 2003;38(1):19e28.
wt.% at.% wt.% at.% wt.% at.% wt.% at.% [9] Xiang ZD, Rose SR, Datta PK. Journal of Materials Science September 2003;38
1 57.03 49.49 28.62 44.09 14.35 06.42 e e (18):3721e8.
2 40.30 29.01 53.86 68.82 05.85 02.17 e e [10] Xiang ZD, Rose SR, Datta PK. Materials Science and Technology
3 22.13 17.03 53.72 73.39 24.15 09.58 e e 2002;19:1247e52.
[11] Xiang ZD, Rose SR, Datta PK. Journal of Materials Science March 2004;39
4 37.37 28.22 49.82 66.79 12.82 04.99 e e
(6):2099e106.
5 46.39 40.30 32.61 50.30 21.00 09.41 e e
[12] Haanappel VAC, Stroosnijder MF. Surface Engineering 1999;15(2):119e25.
6 60.42 35.32 06.44 06.69 e e 33.14 57.99
[13] Lei MK, Zhu XP, Wang XJ. Oxidation of Metals 2002;58(3/4):361e74.
7 02.30 01.02 57.20 45.11 e e 40.50 53.87 [14] Taniguchi S, Uesaki K, Zhy YC, Matsumoto Y, Shibata T. Materials Science and
8 46.34 30.10 01.98 02.28 20.44 06.85 31.24 60.77 Engineering 1999;266:267e75.
9 06.26 02.83 53.96 43.32 e e 39.77 53.85 [15] Li XY, Taniguchi S. Materials Science and Engineering A May 25, 2005;398
10 25.31 29.74 16.90 35.25 57.79 35.01 e e (1e2):268e74.
11 59.96 57.35 19.01 32.28 21.03 10.37 e e [16] Hornauer U, Richter E, Matz W, Reuther H, Mucklich A, Wieser E, et al. Surface
12 48.18 42.80 29.90 47.15 21.93 10.04 e e and Coatings Technology 2000;128e129:418e22.
13 06.49 02.93 52.98 42.39 e e 40.53 54.69 [17] Li XY, Taniguchi S, Zhu YC, Fujita K, Iwamoto N, Matsunaga Y, et al.
14 25.74 26.98 15.27 28.42 54.09 29.23 04.90 15.37 Intermetallics 2001;9(5):443e9.
15 e e 56.95 43.96 e e 43.05 56.04 [18] Tang Z, Wang F, Wu W. Surface and Coatings Technology November 10,
16 68.99 61.27 21.92 34.56 09.09 04.16 e e 1998;110(1e2):57e61.
17 46.29 40.47 32.07 49.78 21.64 09.75 e e [19] Moskal G. Journal of Achievements in Materials and Manufacturing Engi-
neering June 2007;22(2):31e34,.
 M. Goral et al. / Intermetallics 19 (2011) 744e747 747

[20] Gauthier V, Dettenwanger F, Schütze M. Intermetallics July 2002;10(7):
667e74.
[21] Leyens C, Braun R, Frohlich M, Hovsepian PE. Journal of Materials
2006;58(1):17e21.
[22] Xiong HP, Mao W, Xie YH, Cheng YY, Li XH. Materials Science and Engineering
A January 25, 2005;391(1e2):10e8.
[23] Swadzba L, Maciejny A, Mendala B, Moskal G, Jarczyk G. Surface and Coatings
Technology February 17, 2003;165(3):273e80.
[24] Swadzba L, Moskal G, Hetmanczyk M, Mendala B, Jarczyk G. Surface and
Coatings Technology June 1, 2004;184(1):93e101.
[25] Squillace A, Bonetti R, Archer NJ, Yeatman JA. Surface and Coatings Tech-
nology November 1999;120e121:118e23.