Materials Characterization 159 (2020) 110072

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Materials Characterization
journal homepage: www.elsevier.com/locate/matchar

Interface failure behavior of yttria stabilized zirconia (YSZ), La2Zr2O7, T

Gd2Zr2O7, YSZ/La2Zr2O7 and YSZ/Gd2Zr2O7 thermal barrier coatings (TBCs)
in thermal cyclic exposure
⁎
Abdullah Cahit Karaoglanli , Kadir Mert Doleker, Yasin Ozgurluk
Department of Metallurgical and Materials Engineering, Bartin University, Merkez, 74100 Bartin, Turkey

A R T I C LE I N FO A B S T R A C T

Keywords:
Thermal barrier coatings (TBCs)
Cold gas dynamic spray (CGDS)
Lanthanum zirconate (La2Zr2O7)
Gadolinium zirconate (Gd2Zr2O7)
Interface failure
Gas turbine engines are exposed to severe oxidation and thermal shock under service conditions. Thermal barrier
coatings (TBCs) are used to protect metallic components of gas turbines against such failures. Yttria stabilized
zirconia (YSZ) has been the most common top coating material for TBC systems. However, rare earth zirconates
such as La2Zr2O7 and Gd2Zr2O7 stand out as alternatives to YSZ top coating for TBCs. In this study, Inconel 718
substrates were coated with CoNiCrAlY using cold gas dynamic spray (CGDS) technique, which is a promising
technology for bond coat spraying. All the ceramic top coats were produced by electron beam physical vapor
deposition (EB-PVD) method that provides high strain tolerance under thermal loadings. To predict the lifetime
of TBCs, the samples were subjected to furnace cycling tests at 1150 °C. After the tests, the microstructure of
thermally grown oxide (TGO) layers, crack formations and chemical compatibility between the coating layers
were investigated in detail. Results show that TBCs with double layered rare earth zirconate exhibit longer
lifetime as compared to single layered TBCs.

1. Introduction
Thermal barrier coatings (TBCs) have been widely used on com-
ponents that run at high service temperatures such as gas turbines and
aircraft engines [1,2]. The main intended use of TBCs is to enable high
temperature components to operate with higher efficiencies through
preventing heat transfer to substrate materials [3,4]. MCrAlY-type
coatings have been widely applied to protect nickel based super alloy
substrates of gas turbines from oxidation and hot corrosion. This type of
coatings is generally preferred for TBC systems. In MCrAlY-type coat-
ings, M refers to either nickel or cobalt, or both metals [2,5]. Chromium
and aluminum are added in the composition of metallic bond coat
feedstock to increase oxidation and hot corrosion resistance. Minor
amounts of reactive elements such as yttrium (Y) are also added to
enhance the toughness of the formed oxide and to improve adhesion
[6–8].
Recently, MCrAlY type coatings have been deposited on substrate
surfaces using thermal spray coating processes such as high velocity oxy
fuel (HVOF) and cold gas dynamic spray (CGDS) [9]. Coatings de-
posited with HVOF and CGDS techniques have been preferred over the
conventional thermal spray methods such as atmospheric plasma spray
(APS), detonation gun (D-gun) and arc spray due to their significantly
dense and porosity-free structures [10–12]. CGDS is still being in-
vestigated, and arc spray cannot be used due to severe oxidation of
metallic phases [13]. Another effective approach is low pressure plasma
spray which is more advantageous than APS, HVOF and CGDS. APS and
HVOF can be used for those with short lifetime due to low cost [14].
Except for dense structure with low porosity, diffusion treatment is
critical to improve the oxidation resistance and adhesion strength as
well [14–18].
Oxidation that arises between the bond coat and top coat at high
temperatures significantly impairs the coating structure. During the
oxidation of MCrAlY-type metallic bond coats, a thermally grown oxide
layer (TGO) forms on the coating surface. This TGO layer mainly con-
sists of alpha-alumina (α-Al2O3) and trace amounts of different oxides
[10,19–21].
The design of TBC systems involves deposition of ceramic top
coating layers consisting of Zr and rare earth elements with low por-
osity on the MCrAlY metallic bond coat to provide thermal insulation
[10,22–24]. Such ceramic coatings with significantly high melting
points are generally deposited with two deposition techniques. The first
method is APS as the most commonly known, cost-efficient and ap-
plicable method. The latter is the electron beam physical vapor de-
position (EB-PVD) technique, which is a more expensive and more

⁎
Corresponding author.
E-mail address: cahitkaraoglanli@gmail.com (A.C. Karaoglanli).

https://doi.org/10.1016/j.matchar.2019.110072
Received 21 August 2019; Received in revised form 3 December 2019; Accepted 11 December 2019
Available online 12 December 2019
1044-5803/ © 2019 Elsevier Inc. All rights reserved.
A.C. Karaoglanli, et al. Materials Characterization 159 (2020) 110072

complex process. Coatings deposited with APS technique feature higher disadvantage, double-layer ceramic coatings are being used. The use of
amounts of oxide (in metallic materials) and porosity content as the YSZ coating as an intermediate layer in dual-layer TBC systems is a
process inherently takes place under atmospheric conditions, hence the factor that increases chemical and thermal stability [54–57]. In order to
name. In addition, the high kinetic energy and high processing tem- increase the thermal expansion coefficient of La2Zr2O7 coatings, CeO2
peratures result in deposition of laminar shaped particles. As an in- addition was provided a higher thermal expansion coefficient and lower
novative technique with an ever-increasing application field, EB-PVD thermal conductivity to La2Zr2O7 [58].
process involves deposition of less porous coatings [25,26]. Moreover, In this research, CoNiCrAlY metallic bond coat was deposited on
in this technique, the deposition process results in a columnar coating Inconel 718 substrate material with CGDS method. Afterwards, YSZ,
microstructure. As a consequence of the expansion tolerance provided La2Zr2O7, Gd2Zr2O7, YSZ/La2Zr2O7 and YSZ/Gd2Zr2O7 rare earth zir-
by EB-PVD process, strains that arise during thermal cyclic oxidation of conates were deposited as the ceramic top coat using EB-PVD tech-
TBCs are tolerated to a greater extent [27–29]. nique. YSZ, La2Zr2O7, Gd2Zr2O7, YSZ/La2Zr2O7 and YSZ/Gd2Zr2O7 TBC
In the hot sections of gas turbine engines, the porosity of fabricated systems were subjected to thermal cyclic tests at 1150 °C to determine
ceramic coatings, sintering speed and the mechanical and thermo-me- their service lives, and the resulting microstructural changes were
chanical characteristics of the applied coatings are the critical para- evaluated via characterization of the tested samples with SEM and
meters for thermal barrier coating systems. The failure mechanisms of mapping analyses.
thermal barrier coatings can be categorized as external and internal
failures. The internal mechanism involves the sintering of the top
2. Experimental
ceramic coating, distortion, and bending of the thermally grown oxide
layer, the porosity of coating layer and residual stresses [30,31]. Me-
2.1. Production and characterization of TBCs
chanical stresses induced by the growth of TGO layer and the particular
effect of thermal coefficient mismatch during cooling are the dom-
TBCs were deposited on nickel-based Inconel 718 superalloy sub-
inating factors in occurrence of failure [31–33]. In addition, formation
strates. The substrate material used was cut into dimensions of 25 mm
of undesired phases in TGO may arise as a result of Al depletion in the
diameter and 5 mm thickness using a wire erosion method. Substrate
bond coat. The rapid growth of the occurring phases in addition to their
surfaces were subjected to sandblasting with Al2O3 abrasive particles
brittle structure results in an expedited damage formation in the further
prior to the deposition of bond coats with a coating thickness of
stages of oxidation [34–36].
100 μm. This process was performed as a means to increase the me-
Zirconia stabilized with 6–8% yttria (YSZ) has proven to be the most
chanical bonding of the bond coat and to remove undesired structures
successful and the most widely used TBC material so far [37–42].
on the bond coat surface. Grit blasting was performed at an angle of 75°
However, as its main drawback, YSZ undergoes phase transformation
under 2.5 bar pressure using Al2O3 abrasive particles about 40 μm in
from semi tetragonal to tetragonal and cubic and, from tetragonal phase
size. Following the sandblasting process, CoNiCrAlY (Sulzer Metco,
to monoclinic during cooling, and it is exposed to sintering effect under
Amdry 9951) metallic bond coat powders with Co-32Ni-21Cr-8Al-0.5Y
long-term usage at high temperatures. Such phase transformations in-
and −37 + 5 μm particle size interval were deposited on substrate
duce spalling and delamination of TBC material. YSZ can be exposed to
surfaces to obtain 100 μm coating thickness. CGDS (PCS-1000, Plasma
distinct phase change period at high temperatures in addition to sin-
Giken, Japan) was preferred as the bond coat fabrication technique. The
tering effect. There is not an exact temperature for phase transforma-
deposition of protective ceramic top coats was performed with EB-PVD
tion, as it is a function of lifetime [43–47]. Increased thrust-to-weight
(UE-202, ICEBT, Ukraine) technique. Yttria-stabilized zirconia (YSZ),
ratios of new-generation engines necessitate higher gas temperatures.
lantanum zirconate (La2Zr2O7), gadolinium zirconate (Gd2Zr2O7) based
The intense interest on rare earth elements in recent decades has led to
materials and YSZ/La2Zr2O7, YSZ/Gd2Zr2O7 double-layer coatings were
the notion that these are likely the ideal ceramic materials for future
used as the coating materials. Single-layer coatings were deposited in
TBC applications [48–51]. Among these materials, La2Zr2O7 and
an approximate thickness of 200 μm, whereas the thickness of each
Gd2Zr2O7 stand out as alternatives to YSZ with their pyrochlore struc-
layer of double-layer coatings was about 100 μm. The parameters used
tures, high phase stability and low thermal conductivity [52,53]. New
in the deposition of bond and ceramic top coatings are shown in
generation TBC systems lanthanum-zirconium-cerium oxide (LaZrCeO)
Table 1. The hardness, porosity and roughness values of the fabricated
has been the focus of recent studies. It has been observed that the
coatings measured are shown in Table 2. To calculate average rough-
thermal cycling behavior of these types of coatings produced by EB-
ness values, five measurements were subjected to the top surface of
PVD methods has a longer service life than those produced by APS
bond and top coat using Mitutoyo SJ-310 (Japan). The hardness of each
method. LaZrCeO has a low thermal conductivity, high melting point
coating was obtained with 25 g load and 15 s duration parameters using
and high phase stability. However, the low thermal durability of
Qness Q10 (Austria). The produced TBCs were subjected to heat
LaZrCeO can lead to high residual stresses during thermal cycles be-
treatment under 10−5 Torr following the deposition process. β-NiAl
tween the bond coating and the top coating. In order to overcome this
phase formations and TGO layers with about 6 μm thickness were

Table 1
Process parameters for metallic bond and ceramic top coatings.
Bond coat Spray pressure (bar) Gas temperature (°C) Working gas Spray distance (mm) Gun speed
(slpm) (mm/s)

CoNiCrAlY 30 600 Helium (1000) 15 20

Top coat Voltage Temperature Vacuum Rotation speed Deposition rate

(kV) (°C) (Torr) (rpm) (μm/min)

YSZ 20 kV 800 ± 20 °C 5 × 10−5–1 × 10−4 25 4.5

Gd2Zr2O7 20 kV 800 ± 20 °C 5 × 10−5–1 × 10−4 25 3.7
La2Zr2O7 20 kV 800 ± 20 °C 5 × 10−5–1 × 10−4 25 2.5
YSZ/Gd2Zr2O7 20 kV 800 ± 20 °C 5 × 10−5–1 × 10−4 25 3.7/3.9
YSZ/La2Zr2O7 20 kV 800 ± 20 °C 5 × 10−5–1 × 10−4 25 4.1/2.4

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A.C. Karaoglanli, et al.
Table 2
Hardness, porosity and roughness values of TBC systems.
Hardness (GPa)
Inconel 718 substrate 2.7
CoNiCrAlY bond coat 4.2
YSZ top coat 6.5
Gd2Zr2O7 top coat 4.5
La2Zr2O7 top coat 3.45
YSZ/Gd2Zr2O7 top coat
YSZ/La2Zr2O7 top coat
obtained via heat treatment for each fabricated TBC system with a view
of minimizing the effect of initial oxidation which is likely to arise
during thermal cycles.
2.2. Thermal cyclic tests of produced TBCs
The TBC systems produced were subjected to thermal cyclic tests
following their microstructural examination before and after heat
treatment. Each cycle of the thermal cyclic tests involved increasing the
temperature to 1150 °C in 7 min, holding at this temperature for
45 min, and cooling down to 20 °C in 8 min (1 h in total). The thermal
cyclic tests were interrupted when 25% spallation was observed, to
determine the thermal cyclic lives of the samples. XRD (Rigaku, CuKα)
analysis was applied on the as-deposited TBCs to determine the phase
determination of the top coats. Following the tests, images were taken
from the top surfaces of the samples, the damaged samples were cold-
mounted and their cross-sectional images were examined with SEM
(TESCAN, MAIA3).
3. Results and discussion
3.1. Cross-sectional microstructure morphology
The microstructures before the thermal cycling of the TBC systems,
which have YSZ, Gd2Zr2O7, La2Zr2O7, YSZ/Gd2Zr2O7 and YSZ/
La2Zr2O7 top coats and CoNiCrAlY metallic bond coatings, were ana-
lyzed by taking cross-sectional microstructure and top surface SEM
images. The upper surface and cross-sectional microstructure view of
the YSZ sample is given in Fig. 1. In the cross-sectional microstructure
image given in Fig. 1a, the top coating deposited by EB-PVD is clearly
shown. In this image with approximately 3000× magnification, the β-
NiAl and the matrix phases in the CoNiCrAlY bond coating content can
Fig. 1. Cross-sectional and top surface images of YSZ coating sample before thermal cycle test.
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Materials Characterization 159 (2020) 110072
Porosity (%) Roughness (Ra)
– 5.38
1.3 ± 1 7.20
1.7 ± 0.25 8.19
2.0 ± 0.2 8.77
2.33 ± 0.3 7.59
2 ± 0.3/1.8 ± 0.3 5.66
2 ± 0.3/1.85 ± 0.35 8.26
be clearly observed. The image in Fig. 1b was obtained from the upper
surface of the YSZ sample. In some areas of top surface of the YSZ
coating, which has columnar growth, inter-columnar gaps are seen.
Columnar openings appearing in the top coating were caused by the
surface roughness of the bond coating.
Fig. 2 shows a cross-sectional microstructure of the TBC system with
top coating of Gd2Zr2O7. The cross-sectional microstructure image of
the TBC system reveals the characteristic microstructures of columnar
structured top coatings by EB-PVD and quite dense bond coating by
CGDS methods. When Fig. 2b was examined, it was seen that the inter-
columnar voids in the Gd2Zr2O7 top coat are more visible than in the
YSZ one. SEM images of the TBC system with La2Zr2O7 top coating are
given in Fig. 3. Inter-columnar voids are very small in the system, which
has the characteristic feature of EB-PVD method (Fig. 3a). In bond
coating, porosities and oxide structures are observed in some regions.
Fig. 4 shows the SEM images of the YSZ/Gd2Zr2O7 TBC systems. In
the cross-section view given in Fig. 4a, the section shown as the dark
color in the middle section is YSZ, while the light-colored part at the top
shows Gd2Zr2O7 coating. The top surface image of the double-layer
coating is given in Fig. 4b. Inter-columnar voids caused by EB-PVD
method can be easily observed from this image, even with 200×
magnification. Cross-sectional microstructure and top surface images of
YSZ/La2Zr2O7 coating sample before the thermal cycle test are given in
Fig. 5. Cross-sectional microstructure view of the Inconel 718 which is a
superalloy substrate, CoNiCrAlY metallic bond coating, YSZ and
La2Zr2O7 ceramic top coating at 400× magnification are shown in
Fig. 5a. In the production of top coats, there are columnar structures,
which are characteristic of EB-PVD method. Fig. 5b shows the upper
surface SEM image. Inter-columnar voids are also seen in this type of
coating due to the porosity of the bond coat.
In Fig. 6, XRD analysis of as-deposited TBC systems is given. Ac-
cording to the XRD analysis results, single-layered YSZ, La2Zr2O7 and
A.C. Karaoglanli, et al. Materials Characterization 159 (2020) 110072

Fig. 2. Cross-sectional and top surface images of Gd2Zr2O7 coating sample before thermal cycle test.

Fig. 3. Cross-sectional and top surface images of La2Zr2O7 coating sample before thermal cycle test.

Fig. 4. Cross-sectional and top surface images of YSZ/Gd2Zr2O7 coating sample before thermal cycle test.

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A.C. Karaoglanli, et al. Materials Characterization 159 (2020) 110072

Fig. 5. Cross-sectional and top surface images of YSZ/La2Zr2O7 coating sample before thermal cycle test.

Fig. 6. XRD patterns of as-deposited TBCs.

Table 3 Gd2Zr2O7 TBCs have tetragonal zirconia, cubic defect fluorite lan-
Thermal cycle lifetimes of TBC samples. thanum zirconate and cubic defect fluorite gadolinium zirconate phase.
TBCs Thermal cycle lifetimes YSZ/La2Zr2O7 and YSZ/Gd2Zr2O7 exhibit cubic defect fluorite lan-
thanum zirconate and cubic defect fluorite gadolinium zirconate phase.
YSZ top coat 106 ± 10 cycle
Gd2Zr2O7 top coat 81 ± 7 cycle
La2Zr2O7 top coat 23 ± 4 cycle 3.2. Thermal cycle behaviors of TBC systems
YSZ/Gd2Zr2O7 top coat 139 ± 13 cycle
YSZ/La2Zr2O7 top coat 131 ± 12 cycle
In furnace thermal cycling tests, the bond coat is more oxidized
compared to the burner rig systems, because the sample holding times
in the furnace are longer. Since the TGO layer formed by oxidation of

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A.C. Karaoglanli, et al.
Fig. 7. Cross-sectional microstructure view of YSZ coating sample after thermal
cycle test.
the bond coat makes this area more sensitive by thickening and con-
taining fast-growing oxides, the damages usually occur from the TGO
layer. In addition, tensile and compressive stresses during heating and
cooling play a role in accelerating damage. The cycle lifetimes of
samples that have been damaged by approximately 25% and above are
given in Table 3.
Fig. 6 shows the cross-sectional microstructure view of the YSZ
sample after a thermal cycling test. Oxygen penetrating from the top
coating resulted in the formation of the TGO layer, which is seen with
dark color in Fig. 7. According to the elemental mapping analysis given
in Fig. 8, it was determined that after the depletion of aluminum in this
Fig. 8. Mapping image of YSZ coating sample after thermal cycle test.
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Materials Characterization 159 (2020) 110072
Fig. 9. Cross-sectional microstructure view of Gd2Zr2O7 coating sample after
thermal cycle test.
region, Cr, Ni and Co elements were also oxidized. Aluminum, which
has the highest affinity with oxygen in the bond coat, started to oxidize
fist and formed an Al2O3 layer. Upon repeated thermal cycling, the
oxidation process continued by affecting other elements. The over-
lapping of Cr, Co and Ni elements and oxygen in upper part of the TGO
layer according to the mapping analysis given in Fig. 8 is proof that
mixed oxides were formed in that region.
The SEM image obtained after the thermal cycling test of Gd2Zr2O7
TBC is given in Fig. 9. Compared to the YSZ sample, the sample of
Gd2Zr2O7 was less resistant to thermal cycling. It is determined from
the dark light gray colors in the TGO layer that the alumina phase was
formed predominantly in the interface and additionally some mixed
and spinel oxide phases were formed. Additionally, it can be seen that
A.C. Karaoglanli, et al.
Fig. 10. Mapping image of Gd2Zr2O7 coating sample after thermal cycle test.
cracks occurred in areas close to the TGO layer. In the mapping analysis
shown in Fig. 10, dark colored region represents the TGO layer, mostly
composed of aluminum oxide. Similar to the other samples, in this TBC
sample, after the depletion of aluminum, the other elements in the bond
coat also reacted with oxygen to form the mixed oxide layer. Fig. 11
shows the SEM image and elemental analysis distribution taken at high
magnification from the TGO layer at the end of the thermal cycle test.
When the elemental distribution was examined, it was seen that the
traces of Gd, Al and O coincide. It was understood that Gd-Al-O phases,
which can be seen in the form of small dots in the area of mixed oxide
traces, had not yet formed sufficiently. As a result of this phase for-
mation, small porosities occurred in Gd2Zr2O7 layer.
The image of a TBC sample having a La2Zr2O7 top coating is given in
Fig. 12. As can be seen from the sample, coating was separated from the
TGO layer as a whole. In the microstructure, light-colored part is the
top coating and area shaped like a thin line is the TGO layer. Low
thermal expansion coefficient and fracture toughness values of
La2Zr2O7 were effective in the early damage in the coating without any
further growth in the TGO layer. While the bond coating was almost
non-oxidized, a certain amount of the top coating remained attached to
the TGO indicating that the damage happened as a result of rapid
progression of the early cracking occurred in the top coating. EDX maps
taken from the area near the TGO layer are given in Fig. 13. It was
observed that TGO was predominantly composed of alumina and other
oxide formations were very small. Moreover, unlike the Gd2Zr2O7 TBC
system, it was determined that no reaction occurred between TGO and
La2Zr2O7, therefore no LaAlO3 phase was formed. This is due to the fact
that the La2Zr2O7 TBC system was damaged in a very short time period
and was not sufficiently exposed to thermal cycling to form LaAlO3
phase.
SEM image of the YSZ/Gd2Zr2O7 TBC sample is given in Fig. 14. As
seen from the SEM image, the second layer with Gd2Zr2O7 was sepa-
rated by thermal stresses within the structure and only the top layer
with YSZ content is seen. The TBC sample resisted approximately 139
thermal cycling tests was the most durable sample in this study. The
reasons for this can be; less oxidation of the bond coating because the
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Materials Characterization 159 (2020) 110072
double layer conducts less heat to the substrate, minimization of
thermal expansion incompatibility by using YSZ and Gd2Zr2O7 to-
gether, chemical incompatibility in TGO resulting in failure, high sin-
tering resistance provided by Gd2Zr2O7 and oxygen penetration slowing
effect. On the other hand, as in other TBC samples, the growth in the
TGO layer can be seen from the elemental mapping shown in Fig. 15.
The TGO layer was thickened and the mixed oxide amounts were higher
in this TBC sample than in others. The majority of the TGO layer was
composed of aluminum oxide. Furthermore, it was determined that
crack formation occurred in the regions with mixed oxide layers and
these cracks had dominant role in the occurrence of the damage. Fig. 16
shows the SEM image taken from the YSZ/Gd2Zr2O7 TBC system at the
end of the thermal cycle test. It was understood that chemical mismatch
between Gd2Zr2O7 and YSZ occurred in time, during thermal cycling
tests. It was seen that Gd cations diffused into the YSZ layer. As a result
of this diffusion, porosities occurred in Gd2Zr2O7 top coating. This
could be due to the fact that the diffusion coefficient of Gd is higher
than Y. It was seen that the regions above the porous layer were sin-
tered. These newly produced pores may improve thermal barrier re-
sistance due to porosity formation although it may also lead to damage
to cracking due to phase composition change, sintering effect and
porosity formation [59–62]. At the end of thermal cycling tests, it was
thought that this chemical incompatibility had not that much effect on
the damage. The stresses caused by TGO layer were thought to be more
dominant in the damage.
Fig. 17 shows the SEM image after thermal cycling of the TBC
system formed by covering YSZ/La2Zr2O7. The microstructure given in
the cross-sectional microstructure view had withstood approximately
131 cycles in the thermal cycle tests. In contrast to the TBC sample
containing single La2Zr2O7 given in Fig. 12, this coating exhibited
considerable resistance to thermal cycle damages. It was determined
that TGO was formed by alumina and other oxides. As happened in
YSZ/Gd2Zr2O7. TBC system, the cycle life of this TBC system was also
longer compared to single layer TBC systems. Composite coatings with
La2Zr2O7 or Gd2Zr2O7 have a higher thermal resistance than YSZ TBCs
with the same coating thickness. YSZ/La2Zr2O7 and YSZ/Gd2Zr2O7
A.C. Karaoglanli, et al. Materials Characterization 159 (2020) 110072

Fig. 11. GdAlO3 phase formation in Gd2Zr2O7 TBC system after thermal cycle test.

coatings presented both longer lifetime and better thermal barrier

Fig. 12. Cross-sectional microstructure view of La2Zr2O7 coating sample after
thermal cycle test.
performance [50,63,64].
YSZ/La2Zr2O7 TBC system at the end of the thermal cycling is given
in Fig. 18. It was seen that the TGO layer consisted alumina pre-
dominantly, but very few other oxides were also formed. Damage was
caused by TGO and there was no separation between YSZ and La2Zr2O7.
SEM and elemental analysis images were taken from intersection of the
two top coatings to view the chemical interaction between YSZ and
La2Zr2O7 (Fig. 19). Diffusion of La to YSZ was not clear in SEM analysis,
so elemental analysis had been performed and it was seen that La ca-
tions diffused in a small amount along column boundaries. In La2Zr2O7
coating layer, there was no porosity formation in contrast to Gd2Zr2O7.
However, it was understood from the SEM analysis that sintering took
place in about 30 μm part in the layer La2Zr2O7. It was thought that
some amount of La was diffused to YSZ because of this concentration. It
was considered that thermal cycle time was not sufficient for porosity
formation. Because, it was determined that sintering effect happened
after the migration of Gd cations between YSZ and Gd2Zr2O7 and ap-
parent porosity occurred in the layer of Gd2Zr2O7 (Fig. 16). These lo-
cally sintered areas were probably the result of fluctuating deposition
during the top coating production. This fluctuating production was
thought to be due to La2O3, Gd2O3 and ZrO2 having different vapor
pressures [6,65,66]. Specifically, the further accumulation of La2O3 and
Gd2O3, which will evaporate more rapidly at the beginning of pro-
duction, may have led to faster sintering of these regions. Moreover, the
fact that La has a higher diffusion coefficient compared to the Y could

8
A.C. Karaoglanli, et al.
Fig. 13. Mapping image of La2Zr2O7 coating sample after thermal cycle test.
Fig. 14. Cross-sectional microstructure view of YSZ/Gd2Zr2O7 coating sample
after thermal cycle test.
has a role in this.
The other reasons for the failure of ceramic top coatings of TBCs are
stresses induced by TGO growth, degradation of bond coat during
thermal cycles, and the sintering of TBC. As in the case of the damages
induced by fatigue, initiated cracks start to propagate and combine with
other cracks, thus resulting in the growth of damage [67].
The temperature difference between the superalloy substrate and
the top coating is another factor, which is effective on thermal cycling
lifetime in burner rig and thermal shock tests. Thus, TBC systems ex-
hibit high resistance against thermal cycles to the extent that the top
coat has a low thermal conductivity. Rapid heating and cooling of
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Materials Characterization 159 (2020) 110072
coatings also expedite TGO damage. Temperature gradients arise
during the thermal cycling of TBC systems, which in turn induces
thermal strains in the system. Occurrence of temperature gradients
arises from sudden heating and cooling. Damages occur in the TBC
system when the thermal expansion mismatch between the TGO and
the top coat becomes significantly high. Sudden heating and cooling of
the system induces undesired compressive and tensile stresses within
the system as well, which results in the failure of the coating. Increased
service temperatures lead to reduced coating lifetime as a result of the
microstructural changes induced by sintering in the top coat. The re-
sulting increased stresses further reduces the TBC lifetime under
thermal cyclic loadings [68].
TBCs are subject to damages such as spallation or separation of
coatings during high temperature cycle conditions. In furnace cycling
method, not only the formation of cyclic stresses in TBCs are enabled,
but also the failure of bond coating is ensured through subjecting the
samples to severe oxidation. Bond coat oxidizes through being sub-
jected to high temperatures for long periods. In some of the studies on
thermal cycling of TBCs, different thermal cycling methods were ap-
plied on TBC samples with the same composition and the results in-
dicated that, thermal cycling lifetime of TBCs was highly dependent on
the increase in TGO thickness and the adverse effects of mixed oxide
formations [69,70]. In a similar research, TBC systems with YSZ and
CSZ (ceria-stabilized zirconia) top coats and CoNiCrAlY bond coat were
subjected to furnace cycling at 1150 °C, and the system with CSZ
content was found to outperform the YSZ system in terms of thermal
cycling resistance [71]. Likewise, Yanar et al. examined the thermal
cycling behavior of TBC systems having the same content and produced
with different deposition techniques. They compared APS and EB-PVD
methods and reported that the thermal cycling lifetimes of the samples
varied by the effect of deposition technique on the resulting micro-
structure [67].
The strain tolerance provided by EB-PVD was found to provide good
resistance against the stresses induced by thermal cycling. The thermal
cycling resistance of TBC systems produced with EB-PVD method also
A.C. Karaoglanli, et al.
Fig. 15. Mapping image of YSZ/Gd2Zr2O7 coating sample after thermal cycle test.
Fig. 16. Chemical incompatibility occurred in inter-section of YSZ/Gd2Zr2O7
TBC system.
varies with varying top coating composition. Although the coating
microstructures show similarities, TGO growth behavior of such coat-
ings may vary as a result of thermal expansion mismatch. The lower
coefficients of thermal conductivity of La2Zr2O7 and Gd2Zr2O7 as
compared to YSZ play an inhibiting role in the oxidation of the bond
coat [72]. Moreover, La2Zr2O7 and Gd2Zr2O7 coatings acting as a better
barrier against oxygen diffusion have a limiting effect on oxidation
[23]. However, lower fracture toughness of both La2Zr2O7 and
Gd2Zr2O7 induces early crack initiation during thermal cycles [8].
10
Materials Characterization 159 (2020) 110072
Fig. 17. Cross-sectional microstructure view of YSZ/La2Zr2O7 coating sample
after thermal cycle test.
4. Conclusion
In this study, the thermal cycling resistance of Gd2Zr2O7 and
La2Zr2O7 as the state of the art ceramic top coating materials alternative
to YSZ were compared. Obtained results were mentioned as following;
• The TBC systems that involved a Gd Zr O /YSZ and La Zr O /YSZ
2 2 7 2 2 7
coating, exhibited significantly higher strength than the traditional
YSZ and other TBC systems. As a result of the performed cycling
tests the best performance was exhibited by the YSZ/Gd2Zr2O7
A.C. Karaoglanli, et al. Materials Characterization 159 (2020) 110072

Fig. 18. Mapping image of YSZ/La2Zr2O7 coating sample after thermal cycle test.

Fig. 19. Chemical incompatibility between YSZ and La2Zr2O7 coatings in YSZ/La2Zr2O7 TBC system after thermal cycle test.

coating system whereas La2Zr2O7 TBC system displayed the lowest
performance.
• TGO growth was observed on all samples after a few thermal cycles.
TGO thickness increased with increasing number of thermal cycles,
which resulted in mixed oxide formations.
• After the thermal cycling tests, spallation was observed in all top
coating materials, Evidently, the double layered Gd2Zr2O7 system
(with underlying YSZ) yielded better results in terms of both TGO
growth behavior and spallation. Low thermal conductivity, low
oxygen permeability and low elastic modulus of both Gd2Zr2O7 and
La2Zr2O7 provide an important contribution to YSZ as a double
layer.
• The chemical incompatibilities were detected at the interface of
ceramic layers. However, there is no effective role in the failure of
TBC systems.

11
A.C. Karaoglanli, et al.
In future works, the deposition of the gradient transitional layer will
be designed and the effect of flame shock test facility of the failure will
be also investigated.
Declaration of competing interest
The authors declare no conflict of interest.
Acknowledgments
This investigation was financially supported by The Scientific and
Technological Research Council of Turkey (TUBITAK, 113R049).
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