Scripta Materialia 51 (2004) 945–948

www.actamat-journals.com

Thermal cycling life and thermal diffusivity of a plasma-sprayed

nanostructured thermal barrier coating
Chungen Zhou *, Na Wang, Zhenbo Wang, Shengkai Gong, Huibin Xu *

Department of Materials Science and Engineering, Beijing University of Aeronautics and Astronautics, No. 37 Xueyuan Road,
Haidan District, Beijing 100083, China

Received 25 March 2004; received in revised form 24 July 2004; accepted 27 July 2004

Abstract

The nanostructured thermal barrier coatings exhibited excellent thermal cyclic resistance and low thermal diffusivity. The thermal
cyclic life of the coating is about 600 h for 1-h cycles at 1050
C. The thermal diffusivity of the coating is 90% of that of conventional
thermal barrier coatings.
 2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Nanostructured thermal barrier coating; Air plasma spraying; Cyclic oxidation; Thermal diffusivity

1. Introduction ficient of thermal expansion and excellent mechanical

Thermal barrier coatings (TBCs) have been widely
used since the 1970s for the protection of hot-section
components used in gas turbine. These coatings reduce
the operating temperature and increase the component
durability. A typical duplex TBC system consists of a
thermally insulating ceramic top coating applied over
an oxidation-resistant metallic bond coating. Zirconia-
based coatings were commonly used as top coating
because of their low thermal conductivity and high coef-
ficient of thermal expansion. MCrAlY (M@Ni, and/or
Co) is used as a bond coat to provide a good thermal
expansion match between the topcoat and substrate
and to inhibit oxidation of the substrate.
Recently, nanostructured coatings have received
widely interest because of their extraordinary properties.
It was reported that yttria stabilized nanostructured zir-
conia coatings have low thermal conductivity, high coef-
*
Corresponding authors. Tel.: +86 108 231 6000; fax: +86 108 231
7116.
E-mail addresses: cgzhou@buaa.edu.cn (C. Zhou), xuhb@buaa.
edu.cn (H. Xu).
properties [1–6]. Therefore, it was expected to improve
the performance of TBCs.
In this paper, an interest has been taken in the ther-
mal cycling life and thermal diffusivity of plasma-
sprayed nanostructured zirconia coatings. There are
many reports on the thermal properties of traditional
thermal barrier coatings [7–9]. However, few reports
on plasma-sprayed nanostructured zirconia coatings
have been published.
The purpose of the present paper was to investigate
the thermal cycling life and thermal diffusivity of the
plasma-sprayed nanostructured zirconia coating.
2. Experimental procedures
The substrates were cut into coupons with a di-
mension of 20 · 15 · 2 mm from a wrought sheet of
nickel-based superalloy with nominal composition
of Ni–10Co–9.0Cr–2.0Mo–7.0W–5.2Al–0.9Ti–3.8Ta–
1.5Hf (DZ125). These coupons were grit-blasted, using
250 lm alumina grit, to obtain a sharply-peaked surface
contour with a roughness average of 4–5 lm, in order to

1359-6462/$ - see front matter  2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.scriptamat.2004.07.024
946 C. Zhou et al. / Scripta Materialia 51 (2004) 945–948

improve the adherence of the coating. The powder mate-

rials for spraying were Ni–22Cr–10Al–lY used for the
bond coats and ZrO2–8Y2O3 for the ceramic coats.
The bond coating was sprayed with low pressure plasma
spraying (LPPS) and air plasma spraying (APS) was
used to prepare nanostructured zirconia coating. The
ranges of thickness of bond coats and ceramic coats
were 80–100 lm and 180–220 lm, respectively. The
parameters for plasma spraying have been reported in
our previous study [10]. During the spraying the sample
was rotated.
The phase structure of the as-sprayed coating was
identified with a D/max 2200pc X-ray diffractometer
(Rigaku, Tokyo, Japan). The microstructures of the
nanostructured zirconia coatings were determined with Fig. 1. Surface morphology of the as-sprayed nanostructured zirconia
coating.
an S-3500 scanning electron microscope (Hitachi,
Tokyo, Japan) and an H-800 transmission electron
microscope (Hitachi, Tokyo, Japan).
Cyclic oxidation tests were conducted for evaluation
of thermal cycling life of the coating. The cyclic oxida-
tion tests were performed under atmospheric pressure
at 1050
C in static air. Each cycle consisted of an hour
immersion in the furnace followed by a 10 min cool
down to room temperature. The sample weights were
measured to 0.0001 g at each cycle until the end of their
respective tests. A sample was considered to have failed
when spallation was seen visually.
The samples were machined to disk shape (10.2 mm
in diameter and 1.3 mm in thickness) along the direction
parallel to the coating surface for thermal diffusivity
measurements. The laser-flash diffusivity method was
used to explore the thermal diffusivity in the temperature
from room temperature to 800
C. In order to assure
complete absorption of the laser-flash at the sample sur-
face and measurement of the transient temperature at
the opposite surface, the coating samples were coated
with a carbon film before the measurement.
Fig. 2. Transmission electron micrograph of nanostructured zirconia
coating.

3. Experimental results and discussion

3.1. Microstructure of sprayed coating

Fig. 1 presents surface morphology of the as-sprayed

zirconia coatings. It can be seen that the structure of the
coating is very loose, and the micro-pores between the
nanopowders are in the similar size with the particles,
less than 100 nm. Transmission electron microscopy
image reveals that the coatings are composed of fine
grains with size ranging from 70 to 100 nm, as shown
in Fig. 2. No smaller grains were found in the TEM
image.
Fig. 3 shows the cross-section of the plasma sprayed
NiCrAlY/8wt.%Y2O3–ZrO2. The coating was found to
be continuous, but some pores existed in the zirconia Fig. 3. Cross-sectional morphology of as-sprayed nanostructured
coating. The thickness of the coating was about 300 lm. TBC.
 C. Zhou et al. / Scripta Materialia 51 (2004) 945–948
3.2. Thermal cycling test
Cyclic oxidation test was performed to investigate the
cyclic oxidation kinetics of nanostructured thermal bar-
rier coating. Fig. 4 shows a plot of the weight change per
unit area vs. number of cycles for the test performed at
1050
C in static air. The nanostructured TBC had a
weight gain of approximately 1.2–1.6 mg/cm2 after 300
cycles, indicating a low oxidation rate. Moreover, the
abrupt loss in weight for the nanostructured TBC did
not occur until after approximately 600 cycles. The
result indicates that the thermal cyclic lifetime of the
nanostructured TBC is about 600 h for 1-h cycles at
1050
C. The nanostructured TBC exhibits the promis-
ing thermal cyclic oxidation resistance.
3.3. Thermal diffusivity
Fig. 5 presents the thermal diffusivity of the as-
sprayed nanostructured zirconia coatings and conven-
tional zirconia coating during the temperature from
room temperature to 800
C. It can be seen that the ther-
mal diffusivity of both coatings decreases slightly with
increasing temperatures. The thermal diffusivity of the
as-sprayed nanostructured zirconia coating was in the
range of 2.15–2.75 · 10 3 cm2/s during the tempera-
ture from room temperature to 800
C, while the ther-
mal diffusivity of conventional zirconia coating was
2.35–2.96 · 10 3 cm2/s. The thermal diffusivity of the
plasma-sprayed nanostructured zirconia coating is lower
than that of the conventional zirconia coating. Similar
result has been obtained in previous study [1].
In the present investigation, the nanostructured ther-
mal barrier coating exhibits excellent thermal cycling
resistance. The excellent spallation resistant property
may be attributed to the nanostructure of the coating.
The thermal cycling performance of the coating during
Fig. 4. Kinetics of nanostructured TBC during 1-h cycles at 1050
C.
947
Fig. 5. Thermal diffusivity of the as-sprayed nanostructured zirconia
coating and conventional zirconia coating.
the thermal cycling is related directly to the generation
of thermal fatigue cracks caused by the high residual
stress in the coating [11]. As shown in Fig. 1, there are
micro-pores between the nanopowders, which can ad-
sorb the thermal stress. Also, the nanostructured ther-
mal barrier coating has high bonding strength. Chen
[5] investigated the bonding strength of the sprayed
nanostructured zirconia coatings. The average bonding
strength value is 45 MPa, which is larger than that of
conventional thermal barrier coating. In brief, the rea-
son for the improvement for the thermal cycling resist-
ance for the coating may be attributed to the
adsorbing the residual stress and the increase in cohesive
strength.
The thermal diffusivity of the plasma-sprayed nano-
structured zirconia coating is lower than that of conven-
tional zirconia coating. The decrease in the thermal
diffusivity is attributed to the micro-pores in the nano-
structured zirconia and the decreased grain size of
nanostructured zirconia coatings. At temperature below
1200
C, phonon transport dominates the heat conduc-
tion through zirconia. For conventional materials, the
grain boundary contribution to phonon scattering is
thought to be small [12,13]. However, when the grain
size is of the same order as the mean free path for
phonon scattering, grain boundaries can have a signifi-
cant effect. Kabacoff [13] investigated the influence of
nanograin size on the phonon conductivity of zirco-
nia–7wt.% yttria as a function of temperature. It was
found that the thermal conductivity is drastically re-
duced for fine grained materials, particularly when the
grain size is of nanometer dimensions. As shown in
Fig. 2, grain size of as-sprayed coatings is ranging from
70 to 100 nm. Due to the decrease in grain size, grain
boundary contribution to phonon scattering is in-
creased, resulting in the decrease in thermal diffusivity.
Moreover, as shown in Fig. 1, there existed the micro-
pores between the nanopowders, which have the size less
than 100 nm. The micro-pores may have an effect on
948 C. Zhou et al. / Scripta Materialia 51 (2004) 945–948
phonon scattering, resulting in the decrease in thermal
diffusivity.
4. Conclusion
The nanostructured thermal barrier coatings exhi-
bited excellent thermal cycling resistance. The excellent
thermal cycling resistance for the coating may be
attributed to the increase in cohesive strength, and the
micro-pores between the powders, which can adsorb
the residual stress. The coating had lower thermal
diffusivity compared with traditional thermal barrier
coatings. The lower thermal diffusivity was explained
in terms of micro-pores in the nanostructured zirconia
coating and the decreased grain size of the coating.
Acknowledgments
This work is supported by the National Natural Sci-
ence Foundation of China under the contract 50176005.
References
[1] Chen H, Zhou XM, Ding CX. J Eur Ceram Soc 2003;23:
1449.
[2] Soyez G, Eastman JA, Thompson LJ, DiMelfi RJ, Bai GR, Baldo
PM. Appl Phys Lett 2000;77(8):1155.
[3] Gell M. Mater Sci Eng A 1995;204:246.
[4] Kear BH, Skaudan G. Nanostruct Mater 1997;8:765.
[5] Chen H, Ding CX. Surf Coat Technol 2002;150:31.
[6] Lima RS, Kucuk A, Berndt CC. Surf Coat Technol
2001;135:166.
[7] Kim GM, Yanar NM, Hewitt EN, Pettit FS, Meier GH. Scripta
Mater 2002;46:489.
[8] Gell M, Xie L, Ma X, Jordan EH, Padture NP. Surf Coat Technol
2004;177–178:97.
[9] EI-Turki A, Allen GC, Younes CM, Day JCC. Mater Corros
2004;55:24.
[10] Wang Z, Zhou C, Xu H. Chin J Aeronautics 2004;17:119.
[11] Khor KA, Gu YW. Thin Solid Films 2000;372:104.
[12] Lawson KJ, Nicholls JR, Rickerby DS. The effect of coating
thickness on the thermal conductivity of CVD and PVD coatings.
4th International Conference on Advanced in Surface Engineer-
ing, Newcastle, UK, 1996.
[13] Kabacoff LT. Thermal sprayed nano-structured thermal barrier
coatings. NATO Workshop on Thermal Barrier Coatings, Aaal-
borg, Denmark, AGARD-R-823. 1998, paper 12.