Surface & Coatings Technology 201 (2007) 6340 – 6344

www.elsevier.com/locate/surfcoat

Influence of thermal shock on insulation effect of nano-multilayer

thermal barrier coatings
Chunxia Zhang, Chungen Zhou, Hui Peng, Shengkai Gong ⁎, Huibin Xu
School of Materials Science and Engineering, Beijing University of Aeronautics and Astronautics, Beijing, 100083, China
Received 15 May 2006; accepted in revised form 29 November 2006
Available online 11 January 2007

Abstract

Thermal barrier coatings (TBCs) with nano-multilayer structure were investigated by thermal shock test. The change of insulation effect during
thermal shock test was studied by in-situ temperature monitor with a thermal couple set into the substrate. Microstructure and electrical properties
of TBCs were characterized by SEM and Impedance Spectroscopy, respectively. Initial increase in insulation effect was observed and related to the
formation and growth of perpendicular microcracks in top coat and transversal microcracks in TGO. With thermal shock, the insulation effect
decreased due to the further growth of microcracks in top coat and TGO which induced the failure of TBCs.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Insulation effect; Thermal barrier coatings; Thermal shock; Nano-multilayer

1. Introduction introduce interfaces into each column structure which are

Increasing attention has been paid to ceramic thermal barrier
coatings (TBCs) for advanced gas turbine engine applications.
Because of its higher strain tolerance and longer liftetime, EB-
PVD (Electron beam physical vapor deposition) TBCs with
columnar microstructure have been widely applied in turbine
blades [1–6]. In order to fully take advantage of the TBC
capability, reduction of the thermal conductivity of TBCs is
essential.
To lower the thermal conductivity of EB-PVD TBCs, Zhu
et al. [7] developed an advanced multi-component, low
conductivity oxide thermal barrier coatings by adding rare
earth oxides such as Nd2O3, Gd2O3, Sm2O3, and Sc2O3. Hass
et al. [8] prepared low thermal conductivity yttria stabilized
zirconia coatings by a low vacuum electron beam directed vapor
deposition process. That top coat has lower thermal conductivity
because of its zig-zag pore microstructure which elongated the
thermal diffusion path. Nicholls and his colleague Rickerby et al.
[1,9] proposed two methods, one is a concept to reduce the
thermal conductivity of EB-PVD TBCs by introducing addi-
tional phonon scattering centers into the coatings, that is to
⁎ Corresponding author. Tel.: +86 10 8231 7117; fax: +86 10 8233 8200.
E-mail address: gongsk@buaa.edu.cn (S. Gong).
0257-8972/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2006.11.042
essentially parallel to the ceramic/bond coat interface, but
without disrupting the columnar structure that provides the EB-
PVD coating with good strain tolerance and erosion resistance.
The other is nano-structure coating because grain boundaries
have a significant effect on thermal conductivity.
In the present work, yttria stabilized zirconia coatings with
nano-multilayer structure are prepared by electron beam
physical vapor deposition. Its insulation effect after thermal
shock (carried out in an infra-red heating instrument) is studied
by in-situ temperature monitoring. The correlation of the
insulation effect with the microstructural evolution and
Impedance Spectroscopy is investigated.
2. Experimental details
The TBCs system used in this study consists of an alumina-
Yttria stabilized zirconia composite top coat with nano-
multilayer structure and NiCoCrAlY bond coat prepared onto
hollow cylindrical superalloy substrate by EB-PVD. Cross-
section morphology of the nano-multilayer ceramic top coat is
shown in Fig. 3(a).
Thermal shock tests were performed in infra-red heating
system (Model1:10K-HR-I, Crystal System Inc., Japan). The
system consists of four high-power lamps whose light can be
 C. Zhang et al. / Surface & Coatings Technology 201 (2007) 6340–6344 6341

Fig. 1. Schematic diagram for temperature measurement.

focused on a narrow area (about 20 mm) by four concave

mirrors to implement fast heating and high temperature. Heating
temperature is controlled by operating the heating power of
lamp. A thermocouple on the surface of a reference sample is
used to measure the surface temperature, then a calibration
curve for the heating power of lamp and the surface temperature
of the specimen is figured out. Thermal shock consists of 20 s
heating specimen to the surface temperature be about 1100 °C
and dwelling at that power for 5 min and ramp power from
heating power to zero in 20 s and dwelling at zero for 3 min and
forced air through the hollow during cooling and dwelling at
zero. During thermal shock, a thermocouple set in the substrate
(see Fig. 1) is connected with a computer through a digital volt
gauge to record the temperature in situ. The temperature
difference (the delta T) of the surface and the substrate is
measured by using the surface temperature calibrated according
to the heating power of the lamps and the substrate temperature
measured by thermocouple. In order to evaluate insulation
effect, heating speed of substrate during heating ramp is
calculated as a function of thermal shock.
For impedance measurement, the specimen surface is coated
with platinum gel (5 × 5 mm2) that served as an electrode and
the substrate is polished as another electrode. Impedance
Fig. 3. Morphology of as deposited top coating with nano-multilayer
measurements were carried out at 400 °C using a Solartron SI microstructure, (a) cross-section, and (b) surface.
1260 Impedance/gain-phase analyzer coupled with a Solartron
1296 Dielectric Interface, which is computer controlled. Spectra
analysis was performed using Zview impedance analysis (EDS). Specimen is embedded into the epoxy resin and cut by a
software (Scribner Associates, Inc., Southern Pines, NC). In diamond saw to obtain cross-section and then polished with a
the measurements, alternating current (AC) amplitude of diamond paste and etched with FeSO4, H2SO4, and alcohol
100 mV was employed and the AC frequency was in the solution prior to SEM observation. Surface morphology of
range of 0.01 Hz to 1 × 106 Hz. Microstructure and composition specimen is observed by multiple focus OLYMPUS optical
of specimen is examined by scanning electron microscopy microscope.
(SEM) coupled with energy dispersive X-ray spectroscopy
3. Results

3.1. Insulation effect

Fig. 2 shows the reverse of temperature difference between

surface and substrate as a function of thermal shock number.
Before 220 times, the curves can be divided into three parts,
stage I, II, and III, respectively. For stage I (from 0 to 25 times),
at the initial stage of thermal shock, the value decreases sharply.
With the increase of thermal shock, the curve decreases slowly
as fitted by stage II (from 25 to220 times), and then the value
increases slowly in stage III (above 220).

3.2. Microstructure as a function of thermal shock time

Fig. 2. The reverse of temperature difference between surface and substrate as Fig. 3(a)–(b) show the cross-section SEM image and the
function of thermal shock number. optical photo of surface for as received specimen. Al2O3/YSZ
6342 C. Zhang et al. / Surface & Coatings Technology 201 (2007) 6340–6344

prolonged. After 300 thermal shocks, there are cracks along the
interface of TGO and top layer. The cracks along the columnar
crystals are broadening.

3.3. Impedance Spectroscopy of thermal barrier coatings as a

function of thermal shock number

Fig. 6(a) and (b) show the Impedance Spectroscopy of

thermal barrier coatings as function of thermal shock number
for the low frequency range from 0.01 Hz to 1000 Hz, and for
high frequency range from 1000 Hz to 1,000,000 Hz,
respectively. For the low frequency range (Fig. 6(a)), the
impedance of thermal barrier coatings increases with increasing
thermal shock number, especially for the very low frequency
such as from 0.01 to 1 Hz. But for the system after 150 thermal
shocks, its impedance is even a little larger than system 200
thermal shocks. For system after 300 thermal shocks, its
impedance increases continually.
For the higher frequency range (Fig. 6(b)), the trend of
impedance with the thermal shock shows different results from
the lower frequency. From 0 to 30 thermal shocks, firstly the
impedance increases, then it decreases (from 30 to 150 thermal
shocks), and finally increase again (from 150 to 300 thermal
shocks).

Fig. 4. Morphology of the specimen after 30 thermal shocks, (a) cross-section,

and (b) surface.

composite ceramic nano-multilayer top coating is prepared by

EB-PVD to improve its thermal resistance. During deposition,
two sources, one is YSZ target, another is Al2O3 target, are
alternately evaporated. As shown in Fig. 3(a), the analysis
results by EDS show that the dark layers are Al2O3 layers and
the grey layers are YSZ layers. Al2O3 layers and YSZ layers are
alternative and continuous, and their thickness is less than
200 nm. From Fig. 3(b), columnar crystal druse and their grain
boundary can be seen from surface morphology of the top
coating, and the surface is smooth and no crack. On the other
hand, due to the roughness of the substrate and relatively fast
deposition speed, the ceramic layers show the fluctuations in
thickness.
Fig. 4(a)–(b) show the cross-section SEM image and optical
photo of surface for specimen after 30 thermal shocks. As
shown in Fig. 4(a) and (b), there are many cracks along the
columnar crystal. There are some holes localized at the bond
coat caused by the etching for SEM observation. And almost all
cracks end before reaching the interface of top coat and bond
coat.
The growth of TGO and cracks during thermal shock is
presented in Fig. 5(a) and (b) for specimens after 200 and 300
thermal shocks, respectively. Obvious TGO can be seen in Fig. 5. Morphology of cross-section for the specimen. (a) After 200 thermal
Fig. 5(a), and the cracks along the columnar crystals are shocks, and (b) after 300 thermal shocks.
 C. Zhang et al. / Surface & Coatings Technology 201 (2007) 6340–6344
4. Discussion
The thermal gradient tested in the experiment depends on the
microstructural features such as microcracks, defects, and micro
composition of the thermal barrier coatings such as TGO
formed during thermal shock. The effect of microcracks (which
are perpendicular to the plane of the film) on the thermal
conductivity of a film system can be expressed as [10],
 
knet ðNslab −1Þð1−aÞbg −1
¼ 1þ : ð1Þ
k 1−ð1−aÞg
Where k is the thermal conductivity of bulk material, knet is
the thermal conductivity of film-microcrack system, Nslab is the
number of slabs divided by microcracks, α is the thermal
conductivity of the cracks, β is the size of cracks, and γ is the
fraction of cross-section of microcracks that they cover.
Therefore, the ratio of the thermal conductivities can be
quantitatively obtained by considering the factors of micro-
cracks such as the number of slabs, the size of the cracks and
the fraction of the cross-sectional area that they cover. For the
top coat of thermal barrier coatings in the case of this paper,
at the initial stage of thermal shock, the factors including the
Fig. 6. Impedance Spectroscopy of thermal barrier coatings as function of
thermal shock number, (a) low frequency range from 0.01 Hz to 1000 Hz, (b)
high frequency range from 1000 Hz to 1,000,000 Hz.
6343
Fig. 7. Changes in reverses of impedance and ΔT for TBCs as function of
thermal shock.
number of slabs divided by microcracks (Nslab), the size of
cracks (β), and the fraction of cross-section of microcracks
that cover (γ) are increasing. That may be the reason that
there is a sharp decline at stage I shown in Fig. 2. And also it
can be confirmed by the cross-section and surface morphol-
ogies of the system after 30 thermal shock shown in Fig. 4(a)
and (b).
After prolonging thermal shock, there is a slow decline as
stage II shown in Fig. 2. This may be due to the slow growth of
perpendicular microcracks and the formation of TGO as shown
in Fig. 5(a). The thermal conductivity of Al2O3 which is the
main composition of TGO is 0.02394 J/cm·s·k, that is larger
than YSZ but less than bond coat. For the number of the
perpendicular microcracks, it should not increase unlimitedly.
Therefore, there is a slow decline of thermal conductivity of
thermal barrier coatings.
After 220 thermal shocks, the parameter 1 / ΔT increases as
stage III shown in Fig. 2. At the same time, cracks with larger
size which are perpendicular to the film plane and along the
interface of top coat/bond coat are observed for system after
300 thermal shock, and some cracks even penetrate through
the top coat layer as shown in Fig. 5(b). In this situation, the
thermal conductivity of system would not follow the micro-
crack model any more. Heat flux would be easy to go through
the top coat layer to reach the substrate, and then the thermal
conductivity of TBCs is increased. On the other hand, the
sintering of the top coat during thermal shock is another
possible mechanism that can lead to an increase in thermal
conductivity.
According to Wiedemann-Franz (WF) law [11], about the
relationship of thermal conductivity (ê) and electrical conduc-
tivity (σ) for bulk materials, there is
j k2 j2B
¼C¼ : ð2Þ
rT 3 e2
Where k is thermal conductivity, σ is electric conductivity, T
is the measurement temperature, Γ is Lorenz number, kB is
Boltzmann's constant, and e is electron charge.
6344 C. Zhang et al. / Surface & Coatings Technology 201 (2007) 6340–6344
According to the assumption proposed by Tien [12],
compared with bulk materials, the thermal conductivity and
electric conductivity for thin film can be expressed as,
jfilm rfilm
¼ : ð3Þ
jbulk rbulk
Where kfilm is thermal conductivity of the film, kbulk is the
thermal conductivity of the bulk material, σfilm is the electric
conductivity of the film, and σbulk is the electric conductivity of
the bulk material. Then, the Eq. (2) can also be applied to the
thin film materials and can be rewritten as,
kfilm
¼ CT C: ð4Þ
rfilm
Therefore, at the temperature for the measurement, the ratio
of the kfilm to the σfilm is a constant. Then measurement results
of electric conductivity can be related with the thermal con-
ductivity of thermal barrier coatings system. Impedance Spec-
troscopy is used in thermal barrier coatings system to evaluate
the failure process and monitor the chemical and physical
variation during service [13–15]. All the research results
showed that the impedance at high frequency part gives the
information about YSZ layer, meanwhile, the low frequency
part gives the information about TGO layer. The impedance
value at low frequency such as 0.01 Hz contained the YSZ and
TGO contributions totally. Therefore, the total impedance
value, |Z| at 0.0 1Hz was used to evaluate the total conductivity
of TGO and YSZ. As shown in Fig. 6(a), the impedance values
at 0.01 Hz for samples after different shock number increase
with the increasing of shock number, and that the trend is
opposite to the 1 / ΔT showed in Fig. 2. The factors including the
perpendicular cracks in ceramic layer and the formation and
growth of TGO that can influence the thermal conductivity also
affect the impedance of TBCs system. The plots of the reverse
impedance at 0.01 Hz and the parameter 1 / ΔT versus the
thermal shock number are shown in Fig. 7. The two plots show
similar trends. Therefore, the variation in thermal conductivity
of thermal barrier coatings system as function of thermal shock
can be characterized in terms of the impedance change to some
degree. Meanwhile, the impedance at higher frequency may
show the crack growth rate for top coat. At initial thermal shock,
the growth of microcracks is very fast, but after that, it gets slow,
and then some macrocracks formed. That may be the reason that
the impedance increases after 30 thermal shocks and then
decreases for system after 150 thermal shocks and then
increases go on.
5. Summary
Thermal conductivity of thermal barrier coatings with nano-
multilayer ceramic top layer is studied in this paper by in-situ
substrate temperature monitor and Impedance Spectroscopy
during thermal shock test. As function of thermal shock, change
of thermal conductivity and impedance is related to the micro-
structural changes such as the formation and growth of per-
pendicular microcracks, TGO growth. A decrease and then an
increase in the thermal conductivity and impedance at low
frequency are observed and discussed in terms of cracks and
relationship of thermal conductivity and electrical conductivity.
The cracks existed in TBCs can be characterized by system
thermal conductivity, and thermal conductivity can be evaluated
by using impedance value.
Acknowledgement
This work is supported by the National Natural Science
Foundation of China under the contact 50546030 and
50420130032.
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