Effects of Elevated Temperatures

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and Oxidation on Residual
Stresses in (Ti,Al)N Coatings
By Ellen Schffer* and Gnter Kleer

Hard coatings deposited in PVD- or CVD-processes are of

wide interest for the improvement of the wear, corrosion, and Fig. 1. Damages in coating surfaces; a) adhesive failure of a coating by excessive com-
pressive film stresses; b) cohesive failure of a coating by tensile film stresses.
oxidation behavior of tools used in cutting and drilling pro-
cesses, and in the molding of glass and polymer materials. To
rameters were kept constant. The RF magnetron process was
achieve good tool performance under the complex loading
performed with a Nordiko 2050 machine by sputtering a
conditions in service, which include high temperatures and
200 mm diameter target disc in a magnetically enhanced ar-
aggressive environments, the coated tools have to show a
gon/nitrogen discharge driven by a 13.56 MHz RF generator.
high resistance to failure, particularly against microcracking
The total pressure was varied between 0.13 and 1.3 Pa, while
due to high film stresses. Two different examples of such
the other parameters were kept constant. For the deposition
damage occurring by cracking are shown in Figure 1. Fig-
of the coatings in the double ion-beam sputtering process a
ure 1a shows the surface of a TiAlN coating, which was de-
Nordiko ion-beam system 3450 was used. A 150 mm target
posited on silicon and failed directly after deposition due to
disc was sputtered by a high energy argon ion beam. A sec-
high residual compressive stresses. Damage to a TiAlN coat-
ond ion beam, the assist-ion beam, consisting of nitrogen ions
ing by tensile stresses leading to cohesive failure is shown in
was focussed on the substrates while sputtering. The energy
Figure 1b. The damage of the coating in Figure 1b was ob-
of the assist ions UA was varied between UA = 0 and 90 eV. In
served after heating the specimen to 600 C in air. Therefore,
these experiments the ratio of the argon to nitrogen gas flows,
both oxidation effects and effects of thermally induced stress-
the targetsubstrate distance, and the total pressure of 0.05 Pa
es must have contributed to the observed failures. One direc-
were kept constant.
tion in the development of coatings is to reduce the contribu-
The total effective stress, rtot, in a coating is the sum of ex-
tion to stresses occurring during service by intrinsic stresses,
ternal stress, rext, due to the external loading, the thermally
which are dependant on the deposition conditions, particu-
induced stress, rth, due to the difference of the thermal ex-
larly process gas pressures, substrate temperatures, and the
pansion coefficients of substrate and coating materials, and
distance between target and substrate.[110] The aim of the
the intrinsic stress, ri, which depends on the microstructure
present investigation was to study the influence of service
of the coating and therefore on the deposition conditions.
conditions, particularly of high temperatures and aggressive
environment, on the residual film stresses.
rtot = rext + rext + ri (1)
For the investigation TiN and TiAlN coatings were depos-
ited on silica discs (diameter: 22 mm, thickness: 1.2 mm), The main quantity influencing the microstructure and the
which were polished to optical quality. Before sputtering, the intrinsic stress of a coating is the energy of the particles in-
substrates were cleaned in acetone using an ultrasonic bath. volved in the sputtering process. Low energies of these parti-
The coatings were deposited in different sputtering pro- cles result in a porous, open microstructure and intrinsic ten-
cesses: DC triode sputtering, RF magnetron sputtering, and sile stresses. For higher energies the microstructure of
dual ion-beam sputtering. The DC triode sputtering process coatings becomes more and more dense and the intrinsic
was performed in a Balzers 510 device. A 60 mm target was stresses may shift from tensile to compressive stresses. Be-
sputtered in an argon/nitrogen atmosphere at a total pres- sides ionized also neutralized particles, such as neutralized
sure of 0.05 Pa. The machine is equipped with a substrate working gas ions, can contribute to a densification of the mi-
heater, which allows the substrates to be heated additionally crostructure of the coating and thus to an increase or decrease
up to 700 C during the deposition process. The substrate in the intrinsic stress.[6,11,12]
temperature was varied between 500 and 700 C, the other pa- The thermally induced stress, rth, may be estimated by the
following equation.

[*] Dr. E. Schffer, Dr. G. Kleer rth(Tm) = Ec(ac as)(Td Tm) (2)
Fraunhofer-Institut fr Werkstoffmechanik
D-79108 Freiburg (Germany) where Td is the substrate temperature during the deposition
E-mail: gk@iwm.fhg.de process, Tm is the ambient temperature during measurement

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or in service, Ec is the Young's modulus of the coating, ac and
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as are the thermal expansion coefficients of the coating and
the substrate material.
In the absence of any external load the sum of rth and ri
can be considered as the temperature-dependent residual
film stress.
rr(T) = rth(T) + ri
In the present investigation rr was determined by measur-
ing the deflection of the plane substrates in an interferometer
before and after deposition and subsequent evaluation of rr
using Stoney's equation.[13]
where Es is the Young's modulus of the substrate, ds the
thickness of the substrate, ms the Poisson ratio of the substrate,
dc the film thickness, and R the radius of the deformed sur-
face due to the film stress. For values of Es and ms refer to the
[9]
literature.
For coatings deposited in the RF magnetron sputtering
process at a high total pressure of 1.3 Pa, tensile stresses of
about 700 MPa were observed whereas at lower total pres-
sure (0.13 Pa) compressive stresses of about 600 MPa were
determined. Also the coatings deposited in the DC sputtering
process showed a transition from tensile to compressive
stresses. For specimens from this process rr at 23 C is plotted
versus the substrate temperatures Td in Figure 2a. For Td =
500 C and 600 C the coatings showed compressive stresses.
At 700 C, however, tensile stresses were observed. In con-
trast to this the stresses of the coatings deposited in the ion-
beam deposition process were all compressive. As Figure 2b
shows, for the coatings deposited in the single ion-beam pro-
cess (UA = 0) compressive stresses of about 5000 MPa were
determined. By increasing the assist-ion energy up to 60 eV,
the compressive residual stress decreases to about 3000 MPa.
Fig. 2. Residual stresses, rr, at 23C of TiAIN-coatings on silica as a function of a) substrate temper-
ature, for coatings deposited in a dc-sputtering process; b) assist ion energy, for coatings deposited in
a dual ion beam sputtering process.
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Schffer, Kleer/Residual Stresses in (Ti,Al)N Coatings
A further increase of the assist-ion energy to UA = 75 and
90 eV then leads again to an increase in the compressive
residual stresses.
In the ion-beam assisted deposition process, as well as the
RF magnetron sputtering process, the coatings were depos-
ited without any additional heating of the substrates. Accord-
ing to measurements performed during the coating process
(3) the substrate temperature was lower than 150 C in these pro-
cesses. For TiAlN coatings on silica this corresponds to a ther-
mally induced tensile stress, rth, at 23 C of about 200 MPa.
For the films sputtered in the ion-beam process these low val-
ues can be neglected compared to the high values of rr, so
that the curve shown in Figure 2b practically represents the
dependence of the intrinsic stresses, ri, on the assist-ion
(4) energy.
The observed change from tensile to compressive stresses
for the coatings deposited in the RF magnetron process, can
be related to results known from the literature where influ-
ences of the total pressure on the residual stresses of transi-
tion-metal coatings[6] and AlN coatings[7] were evaluated. As
the energy of the particles involved in the process is the main
parameter influencing the microstructure, and therefore the
intrinsic stress of a sputtered coating, tensile stresses ob-
served at high pressures can be attributed to losses of energy
through collisions with gas particles during the process. As a
consequence, a porous, open microstructure emerges. If the
pressure of the process gas atmosphere is lower the particles
lose less energy by collision because the mean-free-path is
larger. Compared to the RF magnetron process, in the ion-
beam assisted sputtering process the total pressure is lower
by one order of magnitude, so that the mean-free-path is
raised from a few to some 10 cm. Therefore the energy of the
hit particles is significantly higher and the observed compres-
sive stresses can be directly related to the energies of the as-
sist ions. As described elsewhere,[14] also resputtering pro-
cesses and processes of recombination through thermal
spikes can proceed at sufficiently high energies. Such pro-
cesses seem to be predominant up to assist-ion ener-
gies of UA 60 eV, whereas at further increased en-
ergies a densification of the coating materials and
an increase of the intrinsic compressive stresses oc-
curs.[9]
As the coatings deposited in the DC triode pro-
cess were prepared by application of substrate heat-
ing, the thermally induced stresses can not be ne-
glected. By calculating rth for Td = 500, 600, and
700 C according to Equation 2 and subtracting
these values from rr, ri was calculated for these
specimens. The values obtained were 2800, 2500,
and 1600 MPa for Td = 500, 600, and 700 C, respec-
tively. Thus, the increased temperature leads to de-
creased intrinsic stresses. Similar to the results dis-
cussed previously[15] for AlN coatings, this decrease
in ri could be qualitatively explained by recombina-
tion effects induced by the available high thermal
energies.
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Schffer, Kleer/Residual Stresses in (Ti,Al)N Coatings
Fig. 3. Residual stresses rr as a function of the ambient temperature, Tm, of TiAIN-coatings depos-
ited on silica in different PVD-processes: a) r.f. magnetron sputtering at different total pressures (ptot films under inert conditions (Fig. 3b). Stable bonded
= 0.13 Pa and 1.3 Pa); b) double ion beam sputtering process with different assist ion energies (UA =
30 eV and 90 eV); c) d.c. sputtering process at different substrate temperatures (Td = 500C, 600
and 700C).
For the investigation of the residual stresses as a function
of the ambient temperature, Tm, an interferometer equipped
with a special heater cell was used, which enables in situ ob-
servations of the changes in the deflection of the specimens
up to 500 C. To prevent oxidation of the specimens in the
heater cell a flow of protective nitrogen gas was maintained
during the experiments. After heating the specimens were
cooled down to room temperature. This heating and cooling
cycle was performed several times.
Experimental results for specimens prepared in the RF
magnetron process are shown in Figure 3a, in which rr is
plotted versus Tm. As the figure shows, for coatings depos-
ited at a total pressure of 1.3 Pa, rr decreases after heating up
to 50 C. A further increase of the temperature causes little
change in rr. After cooling the initial value of rr was not
reached again. This occurred by microcracking of the surface,
which is illustrated in the micrograph shown in Figure 3a.
The specimens prepared at the lower deposition pressure
(0.13 Pa), however, showed a nearly linear increase in the re-
sidual compressive stress with increasing the temperature,
ADVANCED ENGINEERING MATERIALS 2000, 2, No. 12
and after cooling the initial rr value was reached.
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Values obtained in further heating and cooling cy-
cles did not differ from the first one. In Figure 3b, rr
is plotted as a function of Tm for specimens depos-
ited in the ion-beam assisted process at UA = 30 and
90 eV. As the figure shows, on first heating the de-
pendence of rr on Tm is not linear as implied by
Equation 2. After cooling from 400 C the compres-
sive residual stresses decrease to lower values than
before heating. In contrast to the first heating cycle,
in the second and further heatings a linear rr(Tm)
dependence could be observed. rr(Tm) curves of the
coatings sputtered in the DC process at different
temperatures Td are shown in Figure 3c. For these
specimens rr(Tm) was linear in the first cycle, and in
the further measurement cycles no deviations from
the first curve occurred.
As the results demonstrate, the contribution of ri
to the total residual stress, rr, may be very high. Ac-
cording to the literature,[6,11,12] ri is related to the
bombardment of the growing film by high-energy
particles: metal atoms sputtered out of the target,
nitrogen and also working gas (argon), which may
be neutralized and reflected at the target. According
to previous work,[16] the energies for the bonding of
argon atoms in a coating are only about 0.03 eV.
Therefore, the exposure of a coating to elevated
temperatures can lead to the desorption of these
weakly bonded argon atoms, which explains the re-
duction of the compressive stresses after heating the
particles, however, remain in the structure and are

responsible for permanent intrinsic stresses.
From the explanation above it also becomes evi-
dent that if higher substrate temperatures are ap-
plied the process of desorption may exceed the incorporation
of argon during the deposition. Consequently, this should
also be the physical reason for the stable linear rr(Tm) curves
in the first cycle for the specimens produced in the DC pro-
cess at Td above 500 C (compare Fig. 3c).
In order to determine the influence of oxidation on the re-
sidual stresses, coated specimens having permanent intrinsic
stresses were exposed to elevated temperatures and oxidative
environments by heating them in a furnace up to 800 C in air
for different exposure times, texp. After cooling the specimens
to room temperature rr was determined as described above.
Results of the measurements of rr as a function of texp are
plotted for the binary material TiN and for TiAlN in Figure 4
and Figure 5, respectively. For TiN specimens having initial
rr values of about 1800 and 3700 MPa, rr is plotted versus
the square root of texp in Figure 4. It is shown that the com-
pressive stress decreases parabolically with increasing texp.
Whereas Coating 1 remains in the range of compressive
stresses, for Coating 2 tensile stresses are reached after the
same exposure times. As Figure 5 shows, the behavior of
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Fig. 4. Residual stresses rr at 23C in dependence of the square root of the exposure
time of different TiN-coatings after several exposure steps at 500C in air.
Fig. 5. Residual stresses rr at 23C of TiAIN-coatings on silica in dependence of the
exposure time at 600C (& ), 650C(*), 700C (D) in air.
TiAlN coatings, however, is quite different in this range of
texp: the compressive stress increases and a constant level
seems to be reached.
From the literature[1720] it is known that by exposure to
hot air, oxide layers are formed on the outer surfaces of the
coatings. According to previous work,[17] TiO2 is formed on
the surface of TiN. As described elsewhere,[1820] in TiAlN
coatings Al and N diffuse towards the surface, where alumi-
num oxidizes, which results[18] in an almost pure aluminum-
oxide scale above a mixed oxynitride interface containing
lower amounts of Al or almost no Al. These layers cover the
remaining initial TiAlN.
In the following discussion it is qualitatively explained
how the differently formed layers can contribute to the resid-
ual stress, rr, of the whole coating: rr can be considered as a
superimposition of the stresses of the different zones formed
during the oxidation. On the outer surface the oxide should
grow under equilibrium-like conditions, so that at the expo-
sure temperature the oxide layer should have no intrinsic
stress. Therefore at texp, rr of the coating is only determined
by the remaining TiN. That means that by increasing thick-
ness of the oxide layer and decreasing thickness of the TiN
810
Schffer, Kleer/Residual Stresses in (Ti,Al)N Coatings
layer the compressive stress (at texp) of the whole coating de-
creases. If the specimen is cooled to 23 C the contribution of
rth to rr of both layers, TiO2 and TiN, has to be considered.
For the explanation of the increase of compressive stresses
observed for the TiAlN coatings additionally the intermediate
zone, occurring during the oxidation, has to be taken into ac-
count. Therefore rr of an oxidized TiAlN coating could be
considered as the superimposition of the stresses of three
layer-zones: the unaffected TiAlN layer, which should remain
under compressive stress, the oxide top-layer, which should
grow without intrinsic stresses in equilibrium-like conditions,
and finally the intermediate layer. Under these assumptions
(i.e., the zero-stress in the oxide layer and the remaining in-
trinsic stress in the TiAlN layer) the only possible explanation
for the increase of the compressive stress of the whole coating
is an increased compressive stress in the intermediate zone.
In the present investigations the influence of elevated tem-
peratures and oxidation on the residual stresses, rr, of TiAlN
and TiN coatings was studied. A linear dependence of rr on
the ambient temperature was found for coatings having per-
manent intrinsic stresses. For several coatings reductions of
compressive and increases of tensile residual stress were ob-
served during heating the specimens in inert gas atmosphere.
This effect was attributed to the desorption of weakly bonded
particles (e.g., working gas particles). Oxidation of TiN coat-
ings at high temperatures led to a reduction in the compres-
sive stresses. This was explained by the superimposition of
the residual stresses of two layers: the unaffected TiN layer
on the substrate, which has compressive stress, and the oxide
layer, which grows in equilibrium-like conditions without in-
trinsic stress on the top of the specimen. For the TiAlN coat-
ings, however, an increase of the compressive residual stress
by heating the specimens in air was observed. For the expla-
nation of this effect it was assumed that rr results from the
superimposition of the stresses of three layers, the unaffected
TiAlN, the oxide layer and an intermediate oxy-nitride layer,
each of having different residual stresses.
Received: August 14, 2000
[1] D. W. Hofmann, J. Vac. Sci. Technol. A 1994, 12, 953.
[2] J. A. Thornton, D. W. Hofmann, J. Vac. Sci. Technol. A
1985, 3, 576.
[3] B. O. Johannson, J.-E. Sundgren, J. E. Greene, A. Rock-
ett, S. A. Barnett, J. Vac. Sci. Technol. A 1985, 3, 303.
[4] H. Oettel, R. Wiedemann, Surf. Coat. Technol. 1995, 76
77, 265.
[5] F. Vz, L. Rebouta, R. M. C. da Silva, M. F. da Silva,
J. C. Soares, Vacuum 1999, 52, 209.
[6] J. A. Thornton, J. Vac. Sci. Technol. A 1986, 4, 3059.
[7] G. Kleer, R. Kassner, E.-M. Meyer, M. G. Schinker, W.
Dll, Surf. Coat. Technol. 1992, 54/55, 167.
[8] L. Cunha, M. Andritschky, Surf. Coat Technol. 1999, 111,
158.
[9] G. Kleer, E. Schffer, M. Bodmann, J. Kraft, Y. Qiang, H.
Haberland, Mat.-wiss. Werkstofftechnik 1998, 29, 545.
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[10] S. J. Bull, Vacuum 1992, 4, 387.
[11] F. M. D'Heurle, J. M. E. Harper, Thin Solid Films 1989,
171, 81.
[12] H. Windischmann, J. Vac. Sci. Technol. A 1984, 9, 2431.
[13] G. G. Stoney, Proc. Roy. Soc. A 1909, 82, 172.
[14] C. A. Davis, Thin Solid Films 1993, 226, 30.
[15] G. Kleer, W. Dll, Mat.-wiss. und Werkstofftechnik 1993,
24, 80.
[16] G. Franz, Kalte Plasmen, Springer-Verlag, Berlin Heidel-
berg New York, 1990.
[17] M. Wittmer, J. Noser, H. Melchior, J. Appl. Phys. 1981,
52, 6659.
[18] S. Hofmann, H. A. Jehn, Surf. Interf. Anal. 1988, 12, 329.
[19] W.-D. Mnz, Werkst. Korros. 1990, 41, 753.
[20] D. McIntyre, J. E. Greene, G. Hakansson, J.-E. Sund-
gren, W.-D. Mnz, J. Appl. Phys. 1990, 67, 1542.
Ductility of an Aluminide Coating
on a Single-Crystal Nickel-Based
Alloy**
By Ernst Eugen Affeldt*
Aluminide coatings are a typical means of protection
against high-temperature oxidation applied to blades and
vanes in aeroengine or stationary gas turbines. These coatings
enhance oxidation resistance, but they often drastically re-
duce mechanical strength.[15] This behavior is caused by the
well-known brittleness of intermetallics at low temperatures,
because the main constituent of aluminide coatings is the in-
termetallic compound b-NiAl. Turbine blades experience
complex loading cycles during engine operation with typical
strain and temperature histories.[6] If the resultant stress in
the blade at low temperature is high enough to cause fracture,
the coating will crack and thus reduce life under cyclic condi-
tions. To avoid this or, if impossible, to predict it, the ductility
of the coating at different temperatures and the factors influ-
encing it is important information.
Aluminide coatings can be produced by various tech-
niques.[7] These techniques are usually characterized as high'
or low' activity processes. The high-activity process results
in very high concentrations of aluminum at the coating sur-
face and necessitates an additional post-coating heat treat-
ment. The resulting aluminum concentration and the coating
thickness after this treatment are influenced by the applied
[*] Dr. E. E. Affeldt
DaimlerChrysler Aerospace MTU, Dept. TWWS
Dachauerstrae 665, D-80995 Mnchen (Germany)
E-mail: ernst.affeldt@muc.mtu.de
[**] Thanks are given to Joseph Haug, who conducted the experi-
ments.
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temperature and duration. It is well known that higher Al
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contents result in more brittle coatings, but no quantitative re-
sults are reported. The influence of the coating thickness is
deduced from simple fracture mechanics models, showing
that a thick coating stores more elastic energy than a thin one;
energy which gets free by a crack through the coating.[8]
The aim of our work was to study the influence of the
aluminum concentration on the ductility of a typical high-
activity coating (pack cementation). Some specimens with a
low-activity (gas phase) coating were produced too, for com-
parison. It is difficult to produce coatings with different Al
content but similar thickness. The remaining difference in
coating thickness was therefore taken into account with ref-
erence to a fracture mechanics model.[8]
The substrate material was a second-generation single-
crystal nickel-based superalloy. The crystallographic orienta-
tion of the longitudinal axis of the test specimens was within
15 of <001>. Following solution heat treatment of the 25 mm
diameter single crystal blanks, they were machined into
bending specimens (rectangular bars, 5 mm 5 mm
50 mm). The Al concentration of the coating was evaluated
on cross sections by EDX together with the coating thickness.
The results are given in Table 1.
Three-point bending tests were performed to evaluate the
minimum strain necessary to initiate cracks in the aluminide
coating. The specimens were coated on the side that experi-
enced tension under bending loads. Testing was performed
isothermally at different temperatures. Usually the specimens
were loaded to a maximum strain that was 10 % higher than
the strain that corresponds to the yield strength. The strain
that causes cracking of the coating (fracture strain) was evalu-
ated during the test by acoustic emission measurements and
after the test by optical inspection, as follows. The bend test
samples were polished after testing on the surface perpendic-
ular to the coating and to the loading axis. A small bending
apparatus was used to load the specimen to about half of the
yield strength of the substrate to enhance the resolution of the
cracks. Those cracks were evaluated that had the largest dis-
tance to the middle of the specimen and the corresponding
strain at that location was evaluated.
The results of the minimum strain for cracking of the coat-
ing (fracture strain) as a function of temperature are shown in
Figure 1. The results show appreciable scatter, but all show a
slight increase up to 600 C and a very steep increase at high-
er temperature, indicating a brittle-to-ductile transition. Often
the test at that temperature was stopped without cracking of
Table 1. Aluminum concentration and thickness of the coatings investigated.
Process Al concentration Thickness
[wt.-%] [lm]
Pack 24.0 63
Pack 24.8 72
Pack 29.6 67
Pack 31.0 63
Gas phase 34.0 60
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