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Mat.-wiss. u. Werkstofftech. 2014, 45, No. 10 DOI 10.1002/mawe.201400248 879

Microstructure behaviour and influence on thermally

grown oxide formation of double-ceramic-layer EB-PVD
thermal barrier coatings annealed at 1,300 °C
under ambient isothermal conditions
Mikrostrukturverhalten und Einfluss des thermisch gewachsenen
Oxids von zweilagigen EB-PVD Wärmedämmschichten nach iso-
thermer Auslagerung bei 1.300 °C unter Atmosphäre

K. Bobzin1, N. Bagcivan1, T. Brögelmann1, B. Yildirim1

To resist high thermal loads in turbines effectively, turbine blades are protected by
thermal barrier coatings in combination with additional air cooling. State-of-the-art
yttria stabilised zirconia top coats do not operate at temperatures higher than
1,200 °C. Promising candidates for alternative top coats are pyrochlores, lanthanum
zirconate and gadolinium zirconate. But lifetime of pyrochlores is short because of
spallation. However, combinations of yttria stabilised zirconia and lanthanum zirco-
nate or gadolinium zirconate as multilayer systems are promising top layers operat-
ing at higher temperatures than yttria stabilised zirconia. Such thermal barrier coat-
ings top coats as double-ceramic-layer systems consisting of 7 wt.% yttria stabilised
zirconia and lanthanum zirconate or gadolinium zirconate were deposited by Elec-
tron Beam-Physical Vapour Deposition. The focus of the work was set on the influ-
ence of the coating design and the microstructure variation generated at different
rotating speeds on the adhesion and thermally grown oxide behaviour after isother-
mal oxidation at 1,300 °C. Phase formation of the thermal barrier coatings top coats
was obtained using X-ray diffraction. After isothermal oxidation tests for 50 h at
1,300 °C, both, microstructure change and the formation of the thermally grown
oxide were investigated. While the pyrochlore single-ceramic-layer are completely
spalled off, microstructure of the double-ceramic-layer reveals only crack initiation.
The thermally grown oxide thickness was determined by means of scanning elec-
tron microscopy. A high aluminum and oxygen content in the thermally grown oxide
is found using X-ray spectroscopy. Existence of α-phase in Al2O3 was proved by X-
ray diffraction. After isothermal testing, no phase transformation can be detected
regarding the double-ceramic-layer coatings.

Keywords: thermal barrier coating / double-ceramic-layer / isothermal oxidation /

multilayer / EB-PVD

Wärmedämmschichten schützen die hochtemperaturbeanspruchten und luftgekühl-

ten Turbinenschaufeln in einer Gasturbine effizient vor erhöhter thermischer Belas-
tung. Die konventionell eingesetzte Wärmedämmschicht bestehend aus Yttriumoxid
stabilisiertem Zirkonoxid besitzt eine Einsatztemperatur bis maximal 1.200 °C. Pyro-
chlormaterialien wie Lanthan- und Gadoliniumzirkonat sind vielversprechende Wär-

Corresponding author: B. Yildirim, Surface Engineering

Institute, RWTH Aachen University, Kackertstraße 15,
1 Surface Engineering Institute, RWTH Aachen Univer- 52072 Aachen, Germany,
sity, Aachen, Germany E-mail: yildirim@iot.rwth-aachen.de

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880 K. Bobzin, N. Bagcivan, T. Brögelmann, B. Yildirim Mat.-wiss. u. Werkstofftech. 2014, 45, No. 10

medämmschichten, die eine ernstzunehmende Alternative zu Yttriumoxid stabilisier-

tem Zirkonoxid darstellen. Nichtsdestrotrotz besitzen Pyrochlormaterialien eine
kurze Lebensdauer, da sie plötzlich abplatzen. Eine Kombination aus Yttriumoxid
stabilisiertem Zirkonoxid und Lanthan- oder Gadoliniumzirkonat als Multilagensys-
tem sind vielversprechende Wärmedämmschichten mit einer Einsatztemperatur
über 1.200 °C. Diese zweilagigen keramischen Wärmedämmschichten, bestehend
aus 7 Gew.-% Yttriumoxid stabilisiertem Zirkonoxid und Lanthan- oder Gadolinium-
zirkonat wurden mittels Electron Beam-Physical Vapour Deposition Technologie ab-
geschieden. Dabei wurde der Einfluss des Schichtdesigns und der Mikrostruktur
Varianten, abhängig von der Rotations-geschwindigkeit während der Abscheidung,
auf die Haftfestigkeit und das Verhalten des thermisch gewachsenen Oxids nach
isothermer Auslagerung bei 1.300 °C untersucht. Die Phasen der Wärme-
dämmschicht wurden mittels Röntgendiffraktometrie analysiert. Sowohl die Mikro-
struktur als auch das thermisch gewachsene Oxid wurden nach isothermer Ausla-
gerung für eine Dauer von 50 h bei 1.300 °C untersucht. Während einlagige
Lanthan- oder Gadoliniumzirkonat-WDS nach der Auslagerung vollständig ab-
platzen, bleiben die zweilagigen Wärmedämmschichten mit geringfügigen Rissen
intakt. Die Schichtdicke des thermisch gewachsenen Oxids wurde mittels Raster-
elektronenmikroskopie bestimmt. Des Weiteren wurde ein hoher Aluminium- und
Sauerstoffgehalt in dem thermisch gewachsenen Oxid mittels energiedispersiver
Röntgenspektroskopie detektiert. Die Röntgendiffraktometrie beweist, dass das
thermisch gewachsene Oxid hauptsächlich aus α-Al2O3 besteht. Die zweilagigen
Wärmedämmschichten zeigen keine Phasentransformation nach der isothermen
Auslagerung bei 1.300 °C.

Schlüsselwörter: Wärmedämmschicht / zweilagig / isotherme Auslagerung /

Multilagen / EB-PVD

1 Introduction Electron Beam-Physical Vapour Deposition top

To reduce the CO2 emission, an increase of the tur-
bine efficiency with higher turbine inlet temperature
is necessary. Such effect demands the protection of
the hot section components. To protect the hot sec-
tion components like turbine vanes and blades in gas
turbines from high temperatures and high tempera-
ture corrosion, thermal barrier coatings consisting of
top coat and bond coat are applied. On the one hand
substrate protection from oxidation and corrosion ef-
fects is maintained by bond coat. On the other hand
substrate lifetime at higher temperatures is increased
by the top coat. Typically, conventional yttria stabi-
lized zirconia resists surface temperature of about
1,220 °C without any degradation [1]. Since the
1980s, yttria stabilized zirconia top coat is used for
thermal insulation of blades and vanes of turbine
first and second stages. Typically, yttria stabilized
zirconia is deposited by means of Atmospheric Plas-
ma Spraying or Electron Beam-Physical Vapour De-
position. Due to better strain tolerance, lifetime of
coats compared to Atmospheric Plasma Spraying
top coats is higher. However, regardless of the de-
position technology, exceeding the surface tempera-
ture of 1,220 °C leads to intensified effect of sinter-
ing and an accelerated phase transformation [2, 3].
Finally, an increase of the elastic modulus results in
a decrease of the strain tolerance. Additionally, ther-
mal conductivity increases because of modified mi-
crostructure of the top coat. Hence, protection of the
blade and vane substrate material no larger exists.
The degradation of yttria stabilized zirconia induces
research activities on alternative materials as top coat
systems in the last decades due to increase of surface
temperature above 1,220 °C. To apply top coat sys-
tems in an aggressive environment at higher tem-
peratures, a lower thermal conductivity of 1.5–
1.8 W/mK [4], a thermal expansion coefficient of
10–11 ∙ 10–6 1/K similar to the bond coat and sub-
strate [5], a minimal sintering tendency and a phase
stability in combination with a high temperature cor-
rosion resistance are absolutely necessary.

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Mat.-wiss. u. Werkstofftech. 2014, 45, No. 10
Recent research shows promising results since
hexaaluminate, perowskite and pyrochlore fulfill
current requirements for highly-efficient turbines [6,
7]. Hexaaluminates consist of (La, Nd)MAl11O19,
with M representing Cr, Li, Mg, Mn, Sm or Zn.
Hexaaluminates are predestined for use as top coats
in thermal barrier coating systems because of their
low thermal conductivity between 0.8–2.6 W/mK
[8], a thermal expansion coefficient of 7.0–
9.3 ∙ 10–6 1/K [9], a phase stability up to 1,800 °C
and a better sintering resistance compared to yttria
stabilized zirconia. But it is well known that partially
amorphous microstructure areas of hexaaluminates
are generated by means of Atmospheric Plasma
Spraying technology [9, 10]. At a recrystallization
temperature between 800–1,200 °C Atmospheric
Plasma Spraying-sprayed microstructure causes a
volume shrinkage initiating a crack formation and
hence a spallation of the top coat system [6]. Alter-
native deposition technologies as Electron Beam-
Physical Vapour Deposition, low pressure plasma
spraying and high velocity oxy fuel do not provide
success.
Perowskites exhibit the crystalline structure ABO3
(A: e.g. Ba, Ca, Sr and B: as e.g. Ti, Zr). Zr-based
perowskites such as BaZrO3, CaZrO3 and SrZrO3
are mostly examined. Although peroswkites show
favourable thermal conductivity between 2.0–3.4 W/
mK and a high melting point of 2,600 °C, thermal
cycling life behavior is characterized by an early de-
lamination at 1,200 °C [11]. Furthermore, there are
complex forms of perowskites e.g. Ba(Mg1/3Ta2/3)O3,
BaLa2Ti3O10 or La(Al0,25Mg0,5Ta0,25)O3 [6] with
modified thermal properties compared to the ABO3
perowskites. The well examined complex form of
the perowskite Ba(Mg1/3Ta2/3)O3 has a thermal con-
ductivity of 2.1 W/mK, a melting point of 3,100 °C
and a thermal expansion coefficient of 11 ∙ 10–6 1/K
[12]. However, during the thermal cycling testing of
complex forms, spallation occurs due to detrimental
oxidation reactions.
Pyrochlores reveal the crystalline structure
A2B2O7 (A as rare-earth elements, B as elements like
Cs, Hf, Zr). In the last decades, Zr-based pyrochlores
in the form M2Zr2O7 with M representing Eu, Gd,
La, Nd, Sm, Yb were examined especially regarding
thermal barrier coating in turbines [13]. Hence, both,
lanthanum zirconate (La2Zr2O7) and gadolinium zir-
conate (Gd2Zr2O7) become interesting because of
their phase stability up to their melting point and
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Microstructure behaviour and influence on thermally grown oxide formation 881
their lower thermal conductivity compared to yttria
stabilized zirconia [11, 14–19]. Thermal conductiv-
ity of lanthanum zirconate is 1.7 W/mK deposited
by Electron Beam-Physical Vapour Deposition tech-
nology [20]. In contrast thermal conductivity of
Electron Beam-Physical Vapour Deposition gadoli-
nium zirconate is 1.16 W/mK [20–22]. Thermal con-
ductivity of an Electron Beam-Physical Vapour De-
position yttria stabilized zirconia is 2.12 W/mK [18].
Furthermore, lanthanum zirconate phase is stable up
to 2,300 °C with a low sintering tendency. gadoli-
nium zirconate shows no phase transformation up to
1,550 °C [18, 23]. Both pyrochlores have a thermal
expansion coefficient of 10–11 ∙ 10–6 1/K resulting
in thermal expansion mismatch between the bond
coat and substrate. To minimize such mismatch [24]
and to inhibit possible diffusion effects, the idea of a
multilayer system consisting of yttria stabilized zir-
conia and lanthanum zirconate or gadolinium zirco-
nate is pursued.
2 Experimentals
2.1 Coating preparation
To deposit the thermal barrier coating systems, spe-
cimens from an INCONEL® 600 plate (UNS
N06600, Special Metals Corporation, West Virginia,
USA) were cut to rectangular shape of
40 × 20 × 5 mm. Nominal composition and thermal
properties of INCONEL® 600 (IN 600) can be taken
from the data sheet in [25]. Prior to thermal spraying
of MCrAlY (M = NiCo) bond coat, the surface of
the IN 600 specimens was sand-blasted with com-
pressed air at 6 bar to get a maximum mean rough-
ness of about Rz = 12 μm. Afterwards, specimens
were cleaned with isopropanol in an ultrasonic bath.
The powder material NiCoCrAlY with a nominal
composition of Ni–11.9Co–20.8Cr–11.6Al–0.7Y
wt.% (H.C. Starck Co., Germany) and a grain size of
–63 + 22 μm was thermally sprayed by high velocity
oxy fuel (high velocity oxy fuel)-system DJ 2600
(Sulzer Metco, Switzerland). For a bond coat thick-
ness of 150 μm the high velocity oxy fuel parameters
were listed in Table 1.
Prior to deposition of the top coats, the specimens
were annealed at 1,000 °C for 4 h in a high vacuum
furnace PVA MOV 553T, Wettenberg, Germany.
The annealing is for homogenization of the chemical
composition, the reduction of internal stresses and
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882 K. Bobzin, N. Bagcivan, T. Brögelmann, B. Yildirim
Table 1. High velocity oxy fuel parameters for thermal spraying of the NiCoCrAlY bond coat
Tabelle 1. Thermische Spritzparameter für den Haftvermittler NiCoCrAlY mittels Hochgeschwindigkeitsflammspritzen
H/O/N ratio Spray Carrier gas
Distance
[–] [mm] [l/min]
1/0.29/0.44 270 40
porosity, and for an improved adhesion between
bond coat and top coat. After annealing the ther-
mally sprayed specimens were polished to a mean
roughness Ra of 0.2 μm and were cleaned in an ul-
trasonic bath for 15 minutes. The specimens were
positioned above to the crucible. The distance be-
tween crucible and specimen was set to 140 mm.
The single-ceramic-layers and double-ceramic-layers
were deposited by Electron Beam-Physical Vapour
Deposition coating unit CC 500 E of CemeCoat
(now: CemeCon AG), Würselen, Germany, consist-
ing of two electron guns, Fig. 1. Powder was used as
target material.
The substrate was heated up (1,100 ± 25 °C) with-
in 15 minutes by means of gun (1) type KA 6 of
Leybold- Heraeus GmbH, Hanau, Germany. During
the deposition time of 140 min, the substrate tem-
perature was kept at 1,100 ± 25 °C. For evaporating
the powder gun (2) type ESV 14/18 of Leybold-He-
raeus GmbH, Hanau, Germany was used. To elimi-
nate a breakdown of gun (2) caused by splash parti-
cles of the powder material, the high-energy electron
Figure 1. Schematic of the Electron Beam-Physical Vapour
Deposition coating unit CC500 E illustrating the position of
the sample and the gun
Bild 1. Schema der EB-PVD Beschichtungsanlage darge-
stellt mit Position des Probenkörpers und der Elektronen-
strahlkanone
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Mat.-wiss. u. Werkstofftech. 2014, 45, No. 10
Spray velocity Powder feed Stirrer rate Cooling air
rate
[mm/s] [g/min] [%] [bar]
350 30 70 5
beam was deflected by a magnetic field to 270°. The
parameters used for the deposition process of the top
coat by Electron Beam-Physical Vapour Deposition
are listed in Table 2.
Prior to deposition of the top coats, an oxide layer
on the MCrAlY was grown up to improve the adhe-
sion between top coat and MCrAlY. From the feed-
stock material containing of 7 wt.% yttria stabilized
zirconia (7YSZ), lanthanum zirconate (La2Zr2O7)and
gadolinium zirconate (Gd2Zr2O7) each single-cera-
mic-layer was deposited. The double-ceramic-layers
were consisting of 7 wt.% yttria stabilized zirconia as
bottom layer and lanthanum zirconate or gadolinium
zirconate , as top layer. To deposit single-ceramic-
layers and double-ceramic-layers, a single flute cruci-
ble or a two flute crucible was used, respectively. The
filled crucible systems (1–2) are shown in Fig. 2. To
ensure a stoichiometric composition of lanthanum
zirconate and gadolinium zirconate the ratio of the
oxides in the powder was adapted. For stoichiometric
lanthanum zirconate coating lanthanum zirconate and
ZrO2 powder was mixed at the ratio of 40 vol.% to
60 vol.%. In contrast, the gadolinium zirconate coat-
ing was generated at a ratio of 70 vol.% Gd2O3 and
30 vol.% ZrO2 powder taken from the phase diagram.
The deposited top coats were rotated with a velocity
of 2 min–1, 10 min–1 and 20 min–1. After deposition,
the coated specimens were cooled down for 300 min
under vacuum.
Table 2. Process parameters of the Electron Beam-Physi-
cal Vapour Deposition coating unit for the deposition of the
single-ceramic-layers and double-ceramic-layers
Tabelle 2. EB-PVD Prozessparameter für die Abschei-
dung ein- und zweilagiger Wärmedämmschichten
Process parameters Value
cathode power [kW] 2.5–3.0
pressure [mbar] 3 ∙ 10–3
base pressure [mbar] 2 ∙ 10–5
substrate temperature [°C] 1,100 ± 25
deposition time [min] 140
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Mat.-wiss. u. Werkstofftech. 2014, 45, No. 10 Microstructure behaviour and influence on thermally grown oxide formation 883

Figure 2. Filling and sectioning of the crucible for the deposition of single-ceramic-layers (1) and double-ceramic-layers (2) by
Electron Beam-Physical Vapour Deposition technology
Bild 2. Füllung und Aufteilung des Kupfertiegels für die Abscheidung der einlagigen (1) und zweilagigen (2) WDS mittels EB-
PVD Technologie

2.2 Analysis of the as-deposited thermal barrier
coatings
For analysis of the as-deposited single-ceramic-layers
and double-ceramic-layers, the specimens were cut to
rectangular shape of 5 × 5 × 5 mm. Firstly, phase ana-
lysis was carried out by X-ray diffractometer 3003 of
General Electric, Connecticut, USA. The phases were
analyzed by the grazing incidence scanning (CuK(α)
(40 kV, 40 mA)) in the range from 25–85° with a step
size of 0.1° and an incidence angle ω of 0,5°. Sec-
ondly, the specimens were embedded in a mixture of
Epo Fix Resin and Epo Fix Hardener under vacuum
conditions. For examination via scanning electron mi-
croscopy, the embedded samples were ground with
Cameo Disks and polished with diamond suspension.
Thirdly, coating thickness, cross section morphology,
layer and interlayer architecture were analyzed by
scanning electron microscopy Zeiss DSM 982 Gemini
at the Central Facility for Electron Microscopy (GfE),
RWTH Aachen University.
2.3 Isothermal oxidation tests at 1,300 °C
The rectangular 5 × 5 × 5 mm specimens were iso-
thermally aged at 1,300 °C for 50 h in a furnace

Figure 3. Phase analysis at the cross-section by (1) X-ray diffractometer XRD 3003 with an incidence angle of 0.5°, (2) Sketch
of the sample in cross-section
Bild 3. Phasenanalyse im Querschnitt mittels (1) Röntgendiffraktometer XRD 3003 mit einem Einfallswinkel von 0,5°, (2) Skizze
der Lage des Probenkörpers während der Messung

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884 K. Bobzin, N. Bagcivan, T. Brögelmann, B. Yildirim Mat.-wiss. u. Werkstofftech. 2014, 45, No. 10

N 100/14 of Nabertherm, Lilienthal, Germany. 3 Results and discussion

Cross-section morphology, thermally grown oxide
(TGO) thickness and chemical composition of the
oxidized samples were examined by means of scan-
ning electron microscopy, Carl Zeiss Microscopy
GmbH, Germany and X-ray spectroscopy measure-
ments, Bruker Nano Analytics, Germany at Welding
and Joining Institute (ISF), RWTH Aachen Univer-
sity. Phase analysis was carried out in cross sections
by means of X-ray diffraction, Fig. 3. X-ray diffrac-
tion in cross-section ensures detection of thermally
grown oxides and possibly mixed oxides or spinels
after isothermal oxidation. Thermally grown oxide
thickness was determined at four different positions
for statistical validation.
3.1 Coating morphology and phase analysis
Scanning electron microscopy micrographs show
the morphology of the as-deposited single-ceramic-
layers consisting of 7 wt.% yttria stabilized zirconia
(1–3), lanthanum zirconate (4–6) and gadolinium
zirconate (7–9), Fig. 4. The top coats are character-
ized by a typical columnar microstructure increasing
the strain tolerance at higher temperatures [26, 27].
Besides different process parameters like deposition
rate, argon and oxygen gasflow and substrate rough-
ness [29], the coating morphology is mainly gener-
ated by the homologous temperature ratio corre-
sponding to the structure zone model of Movchan

Figure 4. Cross-section morphology and a close-up view of the single-ceramic-layers deposited at different rotation speeds;
7 wt.% yttria stabilized zirconia deposited at (1) 2 min–1 (2) 10 min–1 (3) 20 min–1, lanthanum zirconate deposited at (4) 2 min–1
(5) 10 min–1 (6) 20 min–1, gadolinium zirconate deposited at (7) 2 min–1 (8) 10 min–1 (9) 20 min–1
Bild 4. Morphologie und Nahaufnahme der einlagigen Wärmedämmschichten abgeschieden bei unterschiedlichen Rotations-
geschwindigkeiten; 7 Gew.-% Yttriumoxid stabilisiertes Zirkonoxid nach (1) 2 min–1 (2) 10 min–1 (3) 20 min–1, Lanthanzirkonat
nach (4) 2 min–1 (5) 10 min–1 (6) 20 min–1, Gadoliniumzirkonat nach (7) 2 min–1 (8) 10 min–1 (9) 20 min–1

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Mat.-wiss. u. Werkstofftech. 2014, 45, No. 10 Microstructure behaviour and influence on thermally grown oxide formation 885

Figure 5. Cross-section morphology and a close-up of the transition zone of the double-ceramic-layers deposited at different
rotation speeds; 7 wt.% yttria stabilized zirconia + lanthanum zirconate deposited at (1) 2 min–1 (2) 10 min–1 (3) 20 min–1,
7 wt.% yttria stabilized zirconia + gadolinium zirconate deposited at (4) 2 min–1 (5) 10 min–1 (6) 20 min–1
Bild 5. Morphologie und Nahaufnahme der Übergangszone der zweilagigen Wärmedämmschichten abgeschieden bei un-
terschiedlichen Rotationsgeschwindigkeiten; 7 Gew.-% Yttriumoxid stabilisiertes Zirkonoxid + Lanthanzirkonat nach (1) 2 min–1
(2) 10 min–1 (3) 20 min–1, 7 Gew.-% Yttriumoxid stabilisiertes Zirkonoxid + Gadoliniumzirkonat nach (4) 2 min–1 (5) 10 min–1 (6)
20 min–1

and Demchishin [30]. Depending on the rotation

speed of 2, 10 and 20 min–1, thickness and architec-
ture of the columns differ. It is well known that a
modification of the rotation speed determines the
morphology type [31]. Such effect modifies e.g. the
thermal conductivity coefficient or the thermal cy-
cling behaviour. Furthermore, a changing of the
porosity distribution between the columns (interco-
lumnar porosity) and in the columns (intracolumnar
porosity) exists. It can be noticed that especially the
lanthanum zirconate single-ceramic-layers show
changes in their morphology dependent on the rota-
tion speed.
The lanthanum zirconate single-ceramic-layer
morphology without typical feather-arms around the
columns is caused by correlation between the gas
pressure and the composition as shown in [18, 28].
Figure 6. Diffraction patterns of the as-deposited 7 wt.% yttria
Scanning electron microscopy micrographs show the stabilized zirconia, lanthanum zirconate and gadolinium zirco-
morphology of the as-deposited double-ceramic- nate top layers deposited at 2 min–1
layers dependent on the rotation speed, Fig. 5. The Bild 6. Beugungsbild der as-deposited 7 Gew.-% Yttriumoxid
coating design of the double-ceramic-layers is set to stabilisierten Zirkonoxid, Lanthan- und Gadoliniumzirkonat
a coating thickness ratio of 50% 7 wt.% yttria stabi- Wärmedämmschicht abgeschieden bei 2 min–1
lized zirconia and 50% lanthanum zirconate or ga-

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886 K. Bobzin, N. Bagcivan, T. Brögelmann, B. Yildirim Mat.-wiss. u. Werkstofftech. 2014, 45, No. 10

Figure 7. Cross-section morphology and close-up view of the thermally grown oxide of the single-ceramic-layer at different
rotation speeds after isothermal oxidation at 1,300 °C for 50 h; 7YSZ deposited at (1) 2 min–1 (2) 10 min–1 (3) 20 min–1, lantha-
num zirconate deposited at (4) 2 min–1 (5) 10 min–1 (6) 20 min–1, gadolinium zirconate deposited at (7) 2 min–1 (8) 10 min–1m (9)
20 min–1
Bild 7. Morphologie und Nahaufnahme des thermisch gewachsenen Oxids der einlagigen Wärmedämmschichten nach der
isothermen Auslagerung für 50 h bei 1.300 °C; 7 Gew.-% Yttriumoxid stabilisiertes Zirkonoxid abgeschieden bei (1) 2 min–1 (2)
10 min–1 (3) 20 min–1, Lanthanzirkonat abgeschieden bei (4) 2 min–1 (5) 10 min–1 (6) 20 min–1, Gadoliniumzirkonat abgeschie-
den bei (7) 2 min–1 (8) 10 min–1m (9) 20 min–1

dolinium zirconate, respectively. The columnar mi-
crostructure of both layer systems in the double-
ceramic-layer is visible. The intracolumnar porosity
decreases with increasing rotation speed during de-
position process, mainly in the pyrochlore top layer.
Furthermore, a fluent transition zone between bot-
tom and top layer is generated.
The phase analysis of the as-deposited top coat
systems are carried out by means of X-ray diffrac-
tion, Fig. 6. Due to cooling-down phase after the de-
position process, the tetragonal prime (t′)-phase
(JCPDS 01-70-4430) is generated from the cubic
phase. The t′ is a tetragonal phase oversaturated with
yttria (Y2O3) [32, 33]. Hence, 7 wt.% yttria stabi-
lized zirconia remains intact up to 1,220 °C and does
not transform into cubic (c) and monoclinic (m)
phase below 1,200 °C in long-term operation [33,
34]. In contrast, both pyrochlores lanthanum zirco-
nate (JCPDS 01-00-5602) and gadolinium zirconate
(JCPDS 01-78-4085) reveal a cubic phase.
Figure 7 shows the morphology of the single-
ceramic-layers (1–9) and the thermally grown oxide
thickness as a function of the rotation speed at 2, 10
and 20 min–1 after isothermal oxidation at 1,300 °C
for 50 h. Spallation of the 7 wt.% yttria stabilized
zirconia top coat deposited at 10 min–1 is detected.
In the 7 wt.% yttria stabilized zirconia top coats ro-
tated at a velocity of 2 min–1 and 20 min–1 interco-

© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.wiley-vch.de/home/muw


Mat.-wiss. u. Werkstofftech. 2014, 45, No. 10 Microstructure behaviour and influence on thermally grown oxide formation
Table 3. Thermally grown oxide thickness [μm] of the single-ceramic-layers and double-ceramic-layers dependent on
rotation speed of the sample after isothermal oxidation at 1,300 °C for 50 h
Tabelle 3. Schichtdicke des thermisch gewachsenen Oxids [μm] der ein- und zweilagigen Wärmedämmschichten ab-
hängig von der Rotationsgeschwindigkeit, nach einer Auslagerungszeit von 50 h bei 1.300 °C
Top coat
7 wt.% yttria stabilized zirconate
lanthanum zirconate
gadolinium zirconate
7 wt.% yttria stabilized zirconate + lanthanum zirconate
7 wt.% yttria stabilized zirconate + gadolinium zirconate
lumnar macrocracks occur. Nevertheless the coat-
ings are still intact. Furthermore, a horizontal crack
between top coat and thermally grown oxide can be
observed which might lead to an upcoming spalla-
tion. The pyrochlore materials spall almost comple-
tely, but a compact and adherent thermally grown
oxide can be observed. The early spallation of such
pyrochlores is also identified by different research
findings [29, 35].
But it can be assumed that the pyrochlores spall
because of lateral macrocracks at the interface. Pyro-
chlore coating fragments adhere to the thermally
grown oxide. Furthermore, there is a thermal expan-
sion mismatch between lanthanum zirconate or ga-
dolinium zirconate and NiCoCrAlY. Such effect
generates high stresses in the pyrochlore top coat.
Pyrochlores have reveal low toughness initiating the
spallation of the top coat [36]. Additionally, rare-
earth zirconates interact with the thermally grown
oxide. Such effect reduces the thermochemical
resistance of the pyrochlore [29, 37]. Furthermore,
pyrochlore single-ceramic-layers do not achieve the
equivalent lifetime compared to 7 wt.% yttria stabi-
lized zirconia in thermal cycling tests [35, 38].
Due to oxygen permeability of the top coat co-
lumnar microstructure, a thermally grown oxide is
generated on the MCrAlY [39]. An oxidation and
corrosion protection is given by a dense microstruc-
ture of the thermally grown oxide. In addition,
further oxidation is decelerated because of the ther-
mally grown oxide working as a diffusion barrier.
Thermal stress is built up due to phase transforma-
tion, inhomogeneous temperature distribution and
thermal expansion mismatch [40, 41]. But thermally
grown oxide thickness is an influencing factor for
spallation and failure of a top coat system [29]. The
higher the thickness of thermally grown oxide layer,
the higher the maximum stress in the top coat and
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
15214052, 2014, 10, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/mawe.201400248 by University Of Ottawa Library, Wiley Online Library on [04/03/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
887
rounds per minute [–]
2 10 20
7.5 8.0 10.5
9.6 10.1 9.7
10.5 10.6 10.7
9.4 7.8 9.1
10.4 10.9 10.0
the MCrAlY [42]. The critical thermally grown
oxide thickness depends on the thermal load type
e.g. thermal cycling or isothermal oxidation and its
parameters. Furthermore, the failure mechanism of
the top coat depends on thickness and growth rate of
the thermally grown oxide layer [43]. The spallation
of the top coat from the MCrAlY can be found at the
thermally grown oxide or near the thermally grown
oxide. Such spallation mechanism is characteristic
for Electron Beam-Physical Vapour Deposition top
coats [44]. Thermally grown oxide thickness of the
single-ceramic-layers after isothermal test is given in
Table 3. An increase of the thermally grown oxide
thickness of 7 wt.% yttria stabilized zirconia depos-
ited at increased rotation speed can be observed. The
thermally grown oxide layer thicknesses of lantha-
num zirconate (dTGO = 9.6–10.1 μm) and gadolinium
zirconate (dTGO = 10.5–10.7) are about 10 μm. This
might be a critical thermally grown oxide thickness
value for pyrochlore single-ceramic-layer systems.
Although 7 wt.% yttria stabilized zirconia deposited
at 20 min–1 is not spalled off. Due to horizontal ther-
mally grown oxide cracks, spallation occurs.
The lowest thermally grown oxide thickness is
measured at the top coat rotated with a velocity of
2 min–1. Due to lower thickness, the inner thermal
stresses are lesser. But it is well known that the pyro-
chlore single-ceramic-layers spall off from MCrAlY
because of crack formation [35]. The thermally
grown oxide thickness does not represent the main
influence factor on spallation.
The cross-section morphology and the thermally
grown oxide thickness of the double-ceramic-layers
(1–6) after isothermal oxidation at 1,300 °C for 50 h
are shown in Fig. 8. No spallation or crack forma-
tion is observed. Only exception is 7 wt.% yttria sta-
bilized zirconia + lanthanum zirconate double-cera-
mic-layer deposited at 10 min–1 revealing surface de-
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888 K. Bobzin, N. Bagcivan, T. Brögelmann, B. Yildirim Mat.-wiss. u. Werkstofftech. 2014, 45, No. 10

Figure 8. Cross-section morphology and close-up view of the thermally grown oxide of the double-ceramic-layers at different
rotation speeds after isothermal oxidation at 1,300 °C for 50 h; 7 wt.% yttria stabilized zirconia + lanthanum zirconate deposited
at (1) 2 min–1 (2) 10 min–1 (3) 20 min–1 and 7 wt.% yttria stabilized zirconia + gadolinium zirconate deposited at (4) 2 min–1 (5)
10 min–1 (6) 20 min–1
Bild 8. Morphologie und Nahaufnahme des thermisch gewachsenen Oxids der zweilagigen Wärmedämmschichten nach der
isothermen Auslagerung für 50 h bei 1.300 °C; 7 Gew.-% Yttriumoxid stabilisiertes Zirkonoxid + Lanthanzirkonat abgeschieden
bei (1) 2 min–1 (2) 10 min–1 (3) 20 min–1 und 7 Gew.-% Yttriumoxid stabilisiertes Zirkonoxid + Gadoliniumzirkonat abgeschieden
bei (4) 2 min–1 (5) 10 min–1 (6) 20 min–1

fect at the lanthanum zirconate top layer. In compar-
ison to the as-deposited coatings, porosity quantita-
tively decreases in the double-ceramic-layer systems
regardless of the rotation speed. Such effect is found
e.g. in nanostructured zirconia coatings [45]. The
lower the porosity, the higher the thermal cycling re-
sistance [45] because of closed oxygen penetration
paths [46]. Such finding is transferable to isothermal
oxidation resistance because of similar oxidation ki-
netics of both exposure types [47]. Macro- and mi-
crocracks between the columns especially in the bot-
tom layer can be observed which might be initiated
by interfacial thermal stress between bottom layer
and thermally grown oxide during cooling down
from 1,300 °C to room temperature. Microcracks re-
lieve the stress distribution [29, 48].
Small spallation from the lanthanum zirconate top
layer surface of the double-ceramic-layer might be
generated during heating up phase or cooling down
phase. It can be assumed, that sintering first occurs
in the top layer propagating to the 7 wt.% yttria sta-
bilized zirconia bottom layer. Furthermore, surface
defects are generated due to shrinkage during the
sintering. Sintering tendency of the gadolinium zir-
conate top layer columns is visible in the double-
ceramic-layers but not comparable with 7 wt.%
yttria stabilized zirconia bottom layer. Such effect
reduces the ability of strain tolerance. However, the
coating design ensures temperature stability up to
1.300 °C.
Thermally grown oxide thicknesses of the double-
ceramic-layers after isothermal oxidation are listed
in Table 3. Thermally grown oxide thickness of the
7 wt.% yttria stabilized zirconia + lanthanum zirco-
nate double-ceramic-layer is below 10 μm. In con-
trast, thermally grown oxide thickness of the 7 wt.%
yttria stabilized zirconia + gadolinium zirconate dou-
ble-ceramic-layer is above 10 μm.
Although thermally grown oxide thickness
reaches 10 μm, neither spallation between top coat
and NiCoCrAlY and crack initiation nor delamina-
tion of the coating system can be observed. The dur-
ability of the double-ceramic-layers at 1,300 °C after
50 h is proved.
The qualitative trends of aluminum (Al), chro-
mium (Cr), nickel (Ni) and oxygen (O) are shown

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Mat.-wiss. u. Werkstofftech. 2014, 45, No. 10 Microstructure behaviour and influence on thermally grown oxide formation 889

Figure 9. Energy dispersive X-ray linescan at the cross-section of the single-ceramic-layers after isothermal oxidation: 7 wt.%
yttria stabilized zirconia deposited at (1) 2 min–1 (2) 10 min–1 (3) 20 min–1, lanthanum zirconate deposited at (4) 2 min–1 (5)
10 min–1 (6) 20 min–1, gadolinium zirconate deposited at (7) 2 min–1 (8) 10 min–1 (9) 20 min–1
Bild 9. Energiedispersiver Röntgenspektroskopie-Linescan am Querschnitt der einlagigen Wärmedämmschichten nach iso-
thermer Auslagerung: 7 Gew.-% Yttriumoxid stabilisiertes Zirkonoxid abgeschieden bei (1) 2 min–1 (2) 10 min–1 (3) 20 min–1,
Lathanzirkonat abgeschieden bei (4) 2 min–1 (5) 10 min–1 (6) 20 min–1, Gadoliniumzirkonat abgeschieden bei (7) 2 min–1 (8)
10 min–1 (9) 20 min–1

by means of X-ray spectroscopy along the cross-sec-
tions of the single-ceramic-layers and double-cera-
mic-layers after isothermal oxidation, Figs. 9 and
10. The chemical composition of the thermally
grown oxide in the single-ceramic-layers and dou-
ble-ceramic-layers is examined.
Due to their columnar microstructure, oxygen
from the hot gas diffuses along the columns to the
surface of the NiCoCrAlY. Al and O peaks indicate
the AlxOy-phase which is formed on the surface of
NiCoCrAlY independent of the material top layer
and the rotation speed. Because of the high chemical
reactivity of Al to O initiated at temperatures above
1,000 °C, formation of Al2O3 is assumed. Such ef-
fect can be explained by the Ellingham and Richard-
son diagram [49]. The thermally grown oxide of the
single-ceramic-layers and double-ceramic-layers is
continuous and dense.
The Al, Cr and Ni peaks belong to the NixAl- and
Cr-rich phases of NiCoCrAlY. Although no spalla-
tion of 7 wt.% yttria stabilized zirconia single-cera-
mic-layer after deposition at rotation speeds of
2 min–1 and 20 min–1 is observed, it can be expected
that time-dependent spallation of 7 wt.% yttria stabi-
lized zirconia top layer will occur. The 7 wt.% yttria
stabilized zirconia single-ceramic-layer does not re-
sist temperatures above 1,220 °C for a long time per-
iod due to phase transformation and existing sinter-
ing effects. Furthermore, Cr peak in the partly adher-
ent parts of the spalled single-ceramic-layers can be

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890 K. Bobzin, N. Bagcivan, T. Brögelmann, B. Yildirim Mat.-wiss. u. Werkstofftech. 2014, 45, No. 10

Figure 10. Energy dispersive X-ray linescan at the cross-section of the double-ceramic-layers after isothermal oxidation: 7 wt.%
yttria stabilized zirconia + lanthanum zirconate deposited at (1) 2 min–1 (2) 10 min–1 (3) 20 min–1, 7 wt.% yttria stabilized zirconia +
gadolinium zirconate deposited at (4) 2 min–1 (5) 10 min–1 (6) 20 min–1
Bild 10. Energiedispersiver Röntgenspektroskopie-Linescan am Querschnitt der zweilagigen Wärmedämmschichten nach iso-
thermer Auslagerung: 7 Gew.-% Yttriumoxid stabilisiertes Zirkonoxid + Lanthanzirkonat abgeschieden bei (1) 2 min–1 (2)
10 min–1 (3) 20 min–1, 7 Gew.-% Yttriumoxid stabilisiertes Zirkonoxid + Gadoliniumzirkonat abgeschieden bei (4) 2 min–1 (5)
10 min–1 (6) 20 min–1

taken as indication of Cr diffusion from
NiCoCrAlY. Nevertheless, such effect occurs after
spallation and therefore can be disregarded. In com-
parison, there is low Cr diffusion between double-
ceramic-layer top coats deposited at 2 min–1 min–1
and NiCoCrAlY at 1,300 °C. The crack formation in
the 7 wt.% yttria stabilized zirconia + lanthanum zir-
conate double-ceramic-layer shows no correlation
with any diffusion effects. The double-ceramic-
layers are still intact up to 1,300 °C for 50 h inde-
pendent from the rotation speed.
The microstructure, the deposition technique and
the ambient temperature influence the formation of a
stable Al2O3 as oxidation and corrosion protective
coating. The growth of a protective α-Al2O3 follows
parabolic growth kinetics [47, 50]. The phase analy-
sis of the top layers and the bond coat was carried
out at the cross-sections of the coatings by means of
X-ray diffraction. The phases were identified using
qualified JCPDS cards. The X-ray diffraction spectra
are illustrated as a function of the rotation speed of
the single-ceramic-layers and double-ceramic-layers,
Figs. 11 and 12. The stable and protective α-Al2O3,
NiCrO3-, NiCrO4- and NiCr2O4-spinels, the interme-
tallic phases NiAl, Ni3Al or NiAl3 of the
NiCoCrAlY coating are detected by X-ray diffraction.
Due to the formation of Al2O3, it can be assumed
that the Al content of the NiAl-phase in the NiCo-
CrAlY reduces with longer oxidation time by out-
ward diffusion. Hence, the Al-rich phase either will
transform into an Al-low phase or will disappear
with time. It can be noticed that spinels are formed
by reaction of NiO with Al2O3 and Cr2O3 [46].
The Al2O3 layer forms in MCrAlY bond coats
slower than spinels [46]. Actually, spinels are mixed
or transient oxides which generate a volume expan-
sion followed by top coat failure [46, 51]. Thermally
grown oxide becomes thermodynamically unstable
due to the formation of mixed oxides like NiO,
Cr2O3 and spinels [43, 52, 53]. But it seems that the
existence of spinels does not influence the durability
of the top coats due to their low thermodynamic sta-
bility. Therefore, it can be assumed that the spinels
do not initiate spallation of the pyrochlore single-
ceramic-layers from the NiCoCrAlY. Spallation of
the pyrochlore single-ceramic-layers is induced by
thermal expansion coefficient mismatch between top
coat and α-Al2O3.

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Mat.-wiss. u. Werkstofftech. 2014, 45, No. 10
Figure 11. Diffraction patterns of the single-ceramic-layers
after annealing: (I) 7 wt.% yttria stabilized zirconia, (II) lantha-
num zirconate and (III) gadolinium zirconate deposited at (a)
2 min–1 (b) 10 min–1 min–1 (c) 20 min–1
Bild 11. Beugungsbilder der einlagigen Wärmedämmschich-
ten nach der Auslagerung: (I) 7 Gew.-% Yttriumoxid stabili-
siertes Zirkonoxid, (II) Lanthanzirkonat, (III) Gadoliniumzirko-
nat abgeschieden bei (a) 2 min–1 (b) 10 min–1 (c) 20 min–1
Comparing the diffraction patterns of the single-
ceramic-layers and double-ceramic-layers the X-ray
diffraction spectra are almost similar. No interdiffu-
sion effect can be observed because of the coating
design. The mixed oxides are not harmful to the life-
time of the double-ceramic-layers. Either the inten-
sity of the mixed oxides is still low after 50 h iso-
thermal oxidation or no influence on the stability of
the double-ceramic-layers exists. Furthermore, it can
be observed that chemical composition and phase
stability of the top coats do not change compared to
the as-deposited top coats.
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
15214052, 2014, 10, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/mawe.201400248 by University Of Ottawa Library, Wiley Online Library on [04/03/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Microstructure behaviour and influence on thermally grown oxide formation 891
Figure 12. Diffraction patterns of the double-ceramic-layers
after annealing: (I) 7 wt.% yttria stabilized zirconia + lantha-
num zirconate and (II) 7 wt.% yttria stabilized zirconia + gado-
linium zirconate deposited at (a) 2 min–1 m (b) 10 min–1 (c)
20 min–1
Bild 12. Beugungsbilder der zweilagigen Wärmedämm-
schichten nach der Auslagerung: (I) 7 Gew.-% Yttriumoxid
stabilisiertes Zirkonoxid + Lanthanzirkonat und (II) 7 Gew.-%
Yttriumoxid stabilisiertes Zirkonoxid + Gadoliniumzirkonat ab-
geschieden bei (a) 2 min–1 (b) 10 min–1 (c) 20 min–1
4 Conclusions
Both single-ceramic-layers and double-ceramic-
layers deposited by Electron Beam-Physical Vapour
Deposition technology with different rotation speeds
were examined before and after isothermal oxidation
tests at 1,300 °C for 50 h. The as-deposited top coats
show the typical columnar microstructure with ex-
ception of lanthanum zirconate deposited at 2 min–1.
On the one hand, the as-deposited 7 wt.% yttria sta-
bilized zirconia top coats reveal stable t′-phase. On
the other hand, the as-deposited pyrochlores lantha-
num zirconate and gadolinium zirconate top coats
are in the cubic phase. After isothermal oxidation,
the thermal barrier coatings were analyzed regarding
their cross-section morphology, their chemical and
phase composition and the thickness of the thermally
grown oxide. The results reveal spallation of the
pyrochlore single-ceramic-layers from the thermally
grown oxide independent of the rotation speed. De-
spite thick α-Al2O3 layer in the range of 7.5–
10.6 μm, pyrochlore delamination is initiated by
crack formation and propagation because of low
toughness of pyrochlore materials. The longterm
www.wiley-vch.de/home/muw

892 K. Bobzin, N. Bagcivan, T. Brögelmann, B. Yildirim
durability depends on the influence of the thermal
stress caused additionally by phase transformation or
thermal expansion mismatch. The double-ceramic-
layer systems are still intact with low defects of the
7 wt.% yttria stabilized zirconia + lanthanum zirco-
nate double-ceramic-layers. The formed thermally
grown oxide is an adhesive and homogeneous α-
Al2O3 layer in a thickness range between 7.8–
10.9 μm. Furthermore, detrimental spinels formation
of (Ni,Crx)Ox are identified. Although spinels are
formed, no failure or spallation of the double-cera-
mic-layers is detected. The coating architecture in
double-ceramic-layer compensates the low tough-
ness of the pyrochlore materials. Higher toughness
leads to slower crack propagation. The double-cera-
mic-layers show a thermal oxidation resistance at
1.300 °C for 50 h without any spallation in compar-
ison to the single-ceramic-layers. The coating archi-
tecture consisting of 7 wt.% yttria stabilized zirconia
as bottom layer and lanthanum zirconate or gadoli-
nium zirconate as top layer increases the longterm
durability. For further evaluation, the thermal con-
ductivity and thermal cycling behavior of such coat-
ing design will be analyzed.
Acknowledgements
The research project BO 1979/24-1 “Deposition and
characterization of Electron Beam-Physical Vapour
Deposition multilayered thermal barrier coatings on
basis of pyrochlore materials” this paper is based on
has been financially supported by Deutsche For-
schungsgemeinschaft (DFG). The authors would like
to express their thanks to the DFG for their financial
support.
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Received in final form: July 14th 2014 T 248
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