Thin Solid Films 484 (2005) 225 – 231

www.elsevier.com/locate/tsf

Nanostructured zirconia–30 vol.% alumina composite coatings deposited

by atmospheric plasma spraying
Bo Lianga,*, Hanlin Liaob, Chuanxian Dinga, Christian Coddetb
a
Shanghai Institute of Ceramics, Chinese Academic of Sciences, Shanghai 200050, PR China
b
Laboratoire d’Etudes et de Recherches sur les Maériaux, les Procédés et les Surfaces, Université de Technologie de Belfort-Montbéliard,
90010 Belfort Cedex, France

Received 30 June 2004; accepted in revised form 25 February 2005

Available online 12 May 2005

Abstract

Nanostructured zirconia – 30 vol.% alumina composite coatings were deposited by atmospheric plasma spraying using nanosized ZrO2
and Al2O3 powders. The microstructure and phase composition of the coatings were characterized by electron probe X-ray microanalyser
(EPMA), field emission scanning electron microscope (FESEM), X-ray diffraction (XRD), energy dispersive spectroscopy (EDS) and Raman
spectroscopy. Microhardness (HV0.2 kg) and roughness (Ra) were also measured. The as-sprayed coating exhibited a bimodal structure: the
typical lamellar structure comprised of nanosized columnar grains and the nanosized equiaxed grains. Alumina-rich splats were dark grey
colored and non-uniformly embedded in light grey zirconia-rich splats. No monoclinic or cubic zirconia phase and alumina phase were
detected in the as-sprayed coating. Compared to pure zirconia coating, the microhardness of the as-sprayed coating increased from 5.7 GPa to
8.4 GPa, and the roughness increased from 3.74 Am to 6.03 Am with the addition of alumina into feedstock.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Nanostructured; Zirconia – 30 vol.% alumina composite; Atmospheric plasma spraying

1. Introduction the coatings [5]. In addition, the combination of high

ZrO2 – Al2O3 composite coatings deposited by plasma
spraying or electron beam physical vapor deposition (EB-
PVD) have been actively studied in order to improve
properties of zirconia thermal barrier coatings. It was
reported that deposits of ZrO2 and Al2O3 alternating layers
manufactured using plasma spraying or EB-PVD exhibited
the reduction of oxygen diffusion through the deposits.
Plasma sprayed laminated composites showed an increase
in thermal resistance, compared with EB-PVD and single
bulk coatings [1– 3]. Mixing alumina into the zirconia
layers was effective in reducing the residual stresses and the
formation of cracks [4]. The plasma spraying of these
premixed powders also improved mechanical and chemical
properties without compromising the thermal behavior of
* Corresponding author. Tel.: +86 21 52414103; fax: +86 21 52413903.
E-mail address: liangBo@mail.sic.ac.cn (B. Liang).
0040-6090/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2005.02.040
hardness alumina with the low thermal conductivity
zirconia contributed to the development of the thermal
shock resistance, microhardness and wear resistance of the
as-sprayed coatings [6 –9].
Nanostructured coatings are attractive because of their
potential superior mechanical and physical properties [10 –
14]. The plasma spraying of nanostructured powders is one
of the effective means for obtaining nanostructured coat-
ings because of its cost effectiveness [15 – 18]. Although
the microstructure and other properties of the nanostruc-
tured as-sprayed zirconia coatings or alumina coatings
have been discussed in many reports, only limited
researches were published on nanostructured ZrO2 – Al2O3
composite coatings.
In this work, reconstituted nanosized premixed powder
was used as starting powders for manufacturing nano-
structured ZrO2 – 30 vol.% Al2O3 composite coatings by
atmospheric plasma spraying. The powders and coatings
were characterized by X-ray diffraction (XRD), Raman
226 B. Liang et al. / Thin Solid Films 484 (2005) 225 – 231
Fig. 1. (a) TEM image of the ZrO2 – 30 vol.% Al2O3 reconstituted granules. (b) Morphology of the spray-dried ZrO2 – 30 vol.% Al2O3 reconstituted granules.
spectroscopy, energy dispersive spectroscopy (EDS), field
emission scanning electron microscope (FESEM), and
electron probe X-ray microanalyser (EPMA). The objective
of this work was to identify the phase composition and
characterize the microstructure of the ZrO2 –30 vol.% Al2O3
composite coating. The average roughness and microhard-
ness of the as-sprayed coating were also measured.
2. Experimental details
2.1. Preparation of coating
Commercial nanosized powders of yttria stabilized
zirconia (3 mol% Y2O3) with the mean diameter of 50 nm
(Farmeiya Advanced Materials Co. Ltd., Jiujiang) and
alumina powders with the mean diameter of 20 nm (High
Technology Nano Co. Ltd., Nanjing) were used as the
starting particles. The nanosized zirconia and alumina
powders were wet-mixed and milled together for 20 h in a
Fig. 2. The line scanning result of electron probe microanalysis of the
reconstituted granule.
ball mill, then subsequently reconstituted into granules with
the mean diameter of 60 Am by spray drying process. The
microstructure and morphology of the ZrO2 – 30 vol.%
Al2O3 reconstituted granules are shown in Fig. 1. It can
be seen that the spray-dried ZrO2 –30 vol.% Al2O3 granules
are spherical or ellipsoidal, which improve powders feeding
behavior during plasma spraying process. The nanosized
alumina particles were distributed homogeneously within
zirconia particles (Fig. 2).
The coatings were deposited with the help of a Metco A-
2000 atmospheric plasma spraying system (Sulzer Metco
AG, Switzerland).The powder was fed with Twin-System
(Plasma-Technick AG, Switzerland). A mixture of argon
and hydrogen was used as plasma gas. Compressed air was
used as substrate cooling gas during plasma spraying. The
plasma spray parameters are listed in Table 1. Stainless steel
coupons with the dimension of 40 mm
20 mm
2 mm
were used as substrates. Before spraying, the substrates were
degreased ultrasonically in acetone and grit blasted with
white corundum.
2.2. Characterization of coatings
The phase composition of the as-sprayed coating was
examined by XRD using nickel filtered CuKa (k = 1.54056
Å) radiation on a Rigaku D/Max2550 diffractometer and a
LabRam-1B micro-Raman spectrometer (Dilor, France).
The surface and cross-section morphologies of the
coatings were studied using EPMA (EPMA-8705QH22,
Table 1
Plasma spraying parameters for nanostructured ZrO2 – 30 vol.% Al2O3
coating
Parameter Current Voltage Primary Secondary Carrier Spray Feeding
(A) (V) gas (Ar, gas (H2, gas (Ar, distance distance
slpm) slpm) slpm) (mm) (mm)
Value 620 68 40 12 4 100 6
 B. Liang et al. / Thin Solid Films 484 (2005) 225 – 231
Fig. 3. XRD patterns of (a) the as-sprayed coating and (b) starting powders.
Shimadzu, Japan) with EDS detector (IneA Energy, Oxford
Instruments, UK), and FESEM (JSM-6700F, JEOL, Japan).
2.3. The roughness and microhardness
The surface roughness of the as-sprayed coating was
determined using a TK300 HOMMEL WERKE roughness
tester (Wave, Germany) with 0.5 mm/s traverse speed at 4.8
mm length. The results from five measurements were
averaged to determine roughness data. The Vickers micro-
hardness was measured by HX-1000 microhardness tester
(Shanghai, China) at 0.2 kg loads for 15 s on polished cross-
section area of the as-sprayed coatings, and the average
microhardness resulted from 20 measurements.
3. Results and discussion
3.1. Phase composition analysis
Fig. 3 shows the XRD patterns of the reconstituted
powder and the as-sprayed coating. It shows that the
reconstituted powders were composed by a mixture,
Fig. 4. Raman spectrum of (a) the as-sprayed coating and (b) the reconstituted powders.
227
Fig. 5. XRD pattern between 2h = 72- and 76- of the as-sprayed coating.
including the metastable tetragonal zirconia phase, cubic
zirconia phase, monoclinic zirconia phase, gamma alumina
phase and alpha alumina phase. The relative amounts of
monoclinic and tetragonal zirconia phase in the reconsti-
tuted powder were calculated by the following formula [19]:


m 111̄þ mð111Þ
m ð% Þ ¼

m 111̄þ t ð111Þ þ mð111Þ
where m(111), m(111̄) and t(111) represent the intensity of
the corresponding diffraction peaks in the XRD patterns of
the reconstituted powder. The percentage of monoclinic
phase calculated was at least 35%.
However, in the as-sprayed coating, only the broad
zirconia diffraction peaks at 2h = 30.2-, 35.0-, 50.5-, 59.5-
and 74.2- were observed. The characteristic peaks of
monoclinic zirconia phase at 2h = 28.2-, 31.5- disappeared
after plasma spraying. This result is consistent with the
results of Raman scattering measurements on the same
sample (Fig. 4). Comparing Fig. 4a with Fig. 4b, it can be
seen that only the very broad spectra lines of tetragonal
phase located at 154.7 cm1, 260 cm1, 472.8 cm1 and
639.7 cm1 were observed. The typical characteristic
Raman lines of monoclinic phase at 177.1 cm1, 188.1
228 B. Liang et al. / Thin Solid Films 484 (2005) 225 – 231
cm1, 219.9 cm1 and 379.8 cm1 disappeared. Also, a
new Raman line appeared at 688.6 cm1, which was not
identified in the present work and needs to be further
examined in the future. All the results obtained from XRD
and Raman spectra showed clearly broadening phenomenon
occurring in the as-sprayed coating. This indicated that the
tetragonal structure was seriously distorted. This result was
in agreement with many previous studies [20 –22]. Such
tetragonal zirconia phase with distorted structure was
defined as t¶-phase, resulting from the good melting of
particles and high rate of cooling during plasma spraying
process. The good melting of reconstituted particles resulted
in the transformation of monoclinic to tetragonal or cubic
phase, and subsequently, these high temperature stable
phases were retained at room temperature under the high
cooling conditions.
Although it seemed that there were overlap diffraction
peaks of cubic and tetragonal phase around 2h = 29.8-,
35.0- and 74.2- in XRD pattern of the as-sprayed
coating, no characteristic Raman lines of cubic zirconia
phase were observed in the as-sprayed coating. The
further XRD study between 2h = 72- and 76- was
conducted on the same sample (Fig. 5). The result
showed that the (004) and (400) diffraction peaks of
tetragonal zirconia phase were observed, corresponding to
2h = 73.1- and 74.2-, respectively. The characteristic cubic
phase diffraction peak at 2h = 73.7- was not detected.
Associated with the Raman spectra analysis, it can be
concluded that there was no cubic zirconia phase in the
as-sprayed coating. As the cubic phase in 3 mol% yttria
partially stabilized zirconia is not stable, therefore it
should not appear [23].
Alumina phase exhibited a similar phenomenon as that of
the monoclinic zirconia phase. In the Raman spectra of
starting powder, the Raman line occurring at 978.4 cm1
was clearly observed, which was characteristic of alumina,
and another in the vicinity of 400 cm1 appeared to be
masked by the strong broad lines of zirconia phase with
wave number ranging from 379.8 cm1 to 473.0 cm1.
Fig. 6. EDS analyses of zirconia-rich splats (point A) and alumina-rich splats (point B).
However, none of the two characteristic Raman lines of
alumina was observed in the as-sprayed coating. This was
consistent with result of the XRD analysis. This phenom-
enon could be partially explained in terms of formation of
the metastable Al2O3 – ZrO2 solid solutions with tetragonal
structure.
The solubility of Al2O3 in ZrO2 could be up to 2 mol% at
temperatures 1400 -C, and slightly increases with the
increase of temperature [24 – 26]. In the present work,
nanosized Al2O3 or ZrO2 particles experienced a very high
temperature in plasma jet ranging from 3000 -C to 10,000
-C [27]. Such a high temperature combined with the high
surface energy of nanosized composite particles resulted in
the perfect melting and the formation of solid solution. It
was verified by the EDS results, as shown in Fig. 6. The
results of points A and B revealed that there was a certain
amount of Al element in the ZrO2 splat and some Zr
elements in the Al2O3 splat. The different splat colors
resulted from the different Al2O3 amounts. The dark grey
color indicated the high alumina in the as-sprayed coating.
In addition, it was also observed that the dark grey alumina-
rich splats were non-uniformly embedded in light grey
zirconia-rich splats. The boundaries between the zirconia-
rich and alumina-rich splats were clearly discernable and
relatively free of voids.
3.2. Microstructural analysis
Fig. 7a shows the representative splat morphology of
the ZrO2 – 30 vol.% Al2O3 composite particle on the glass
substrate processed at room temperature (T = 293 K). The
splat morphology was a nearly regular disk-like shape with
limited splashing, indicating a rather good particle flat-
tening [28 – 32] and a strong bonding [33]. These results
conformed to the SEM analyses (Fig. 7b and c). Fig. 7b
revealed that the as-sprayed coating possesses a rather
smooth surface. In fact, the measured average roughness
(Ra) of the as-sprayed coating was about 6.03 Am. Fig. 7c
shows that excellent bonding exists between the substrate
 B. Liang et al. / Thin Solid Films 484 (2005) 225 – 231 229

observed in the cross-section area. One kind was smaller

pores of less than 5 Am; the other was some large pores of
more than 30 Am. The thickness of the as-sprayed coating
was approximately 450 Am.
Fig. 8a– c presents the high resolution FESEM morphol-
ogies of the surface and fracture surface of the as-sprayed
coating. It shows that the grains visible on the top surface

Fig. 7. SEM morphology of (a) single splat, (b) surface of the coating and
(c) cross-section area of the coating.

and the as-sprayed coating. The bonding strength was

about 40 MPa, tested on American standard of testing
materials C 633-79 [34]. The porosity of the as-sprayed Fig. 8. FESEM micrographs of (a) as-sprayed coating surface morphology,
coating was approximately 6%, measured using SEM (b) fracture surface morphology of lamellar structure, and (c) fracture
image of the cross-section. Two kinds of pores were surface of bimodal structure.
230 B. Liang et al. / Thin Solid Films 484 (2005) 225 – 231
are less than 100 nm (Fig. 8a), and the as-sprayed coating
exhibited the typical lamellar structure with the average
splat thickness of about 1 Am, comprised of columnar grains
with the average diameter size less than 150 nm (Fig. 8b). It
was noted that there was a bimodal structure in the as-
sprayed coating (Fig. 8c). One was the above lamellar
structure, which was invariably aligned parallel to the
substrate and previously deposited material, similar to the
conventional coatings deposited by plasma spraying [35 –
37]; the other was the equiaxed grains with the grain size
less than 100 nm. The former was the main structure in the
as-sprayed coating. The equiaxed grains embedded in the
as-sprayed coating resulted from the high cooling velocity
and very short dwelling time of nanosized particles in
plasma spraying process. Under the above conditions, the
partially melted or unmelted nanosized composite powder
could not grow up and their nanostructure was preserved in
the as-sprayed coating. However, the study about the
nanostructure forming of the as-sprayed coating is still in
progress.
3.3. Microhardness
The average microhardness tested in the present work
was about 8.4 GPa, which was higher than the average value
(å 5.7 GPa) of the nanostructured zirconia coating deposited
by plasma spraying using the same nanostructured zirconia
powder. Corresponding with the improvement of the
microhardness, the average surface roughness value also
increased from 3.74 Am to 6.03 Am. This result indicated
that the microhardness of the coating could be changed by
addition of alumina. This may result in the improvement of
tribology properties of as-sprayed coating.
4. Conclusions
The phase composition of as-sprayed ZrO2 – 30 vol.%
Al2O3 composite coatings deposited by atmospheric
plasma spraying using premixed nanosized Al2O3 and
ZrO2 powders mainly consisted of nontransformable
tetragonal phase of ZrO2; no monoclinic and cubic
zirconia phases of ZrO2 were observed. Alumina phase
was also not observed in XRD pattern or Raman spectra of
the as-sprayed coating. The phenomenon of Al2O3 – ZrO2
solid solution was observed during the plasma spraying
process.
The as-sprayed composite coating exhibited typical
bimodal structures: the lamellar structure comprised of
nanosized columnar grains and equiaxed nanosized grains.
It also showed lower porosity (å 6%), higher bonding
strength and microhardness; particularly, the microhard-
ness of the as-sprayed composite coatings was 8.4 GPa,
which was about 1.5 times that of the nanostructured
zirconia coating deposited using same nanosized zirconia
powder.
Acknowledgement
This work was supported by Chine –France PRA dans
ledomaine des mat é riaux 2002 under grant PRA MX02-
03(C.Coddet and C.Ding). The authors gratefully acknowl-
edge Mrs. Gao Jianhua, Mrs. Qian Weijun for FESEM and
EDS analysis, and Mrs. Zhou Xiaming for preparing the
specimens.
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