Int. J. Appl. Ceram. Technol.

, 10 [6] 887899 (2013)

DOI:10.1111/ijac.12032

Production of Al2O3-Stabilized Tetragonal ZrO2

Nanoparticles for Thermal Barrier Coating
Arumugam Karthik, Palanisamy Manivasakan, Sundaramoorthy Arunmetha,
Rathinam Yuvakkumar, and Venkatachalam Rajendran*
Center for Nano Science and Technology, K. S. Rangasamy College of Technology,
Tiruchengode 637 215, Tamil Nadu, India

Al2O3-stabilized tetragonal ZrO2 nanoparticles were obtained through hot-air spray pyrolysis and characterized after
postsynthesized treatments. The produced nanoparticles were 26 nm in size with surface area of 59 m2/g. A multilayer thermal barrier coating of nanostructured Al2O3-ZrO2-embedded silicate was applied to the mild steel (EN3) specimen using
spin-coating technique and characterized comprehensively employing X-ray diffraction and scanning electron microscope. The
Al2O3-stabilized ZrO2 with silicate matrix facilitates the formation of zirconium silicate nanostructured surface-protective
coating on EN3 specimen. The Al2O3-ZrO2/SiO2 matrix-based hybrid inorganic coating shows effective thermal barrier for
EN3 after firing at a high temperature of 600C.

Introduction
The structural ceramic-based thermal barrier coatings (TBCs) are in great demand for protection of
metallic substrate against harsh environments.1 Nanostructured ceramic coating provides a promising substitute to assist the service durability and reliability of
metallic components by reducing the working temperature of the substrate, over a wide range of high-temper*veerajendran@gmail.com.
2013 The American Ceramic Society

ature applications.24 Zirconia (ZrO2) is a well-known

ideal TBC, due to its remarkable properties.58 However, it loses its phase stability that is accompanied by
volumetric shrinkage when it is exposed to high temperature as in refractory applications9 because of its
high oxygen diffusivity.10 Hence, to improve the phase
stability, a different approach for the incorporation of
ZrO2 in alumina (Al2O3) matrix is eventually required.
The composite materials provide positive and improved
physico-chemical properties as compared to individual
components.11,12 Al2O3-ZrO2 nanocomposites have
demonstrated their utility in industrial applications

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International Journal of Applied Ceramic TechnologyKarthik, et al.

such as thermal barrier and corrosion resistance13 due

to their thermal shock resistance, room temperature
strength, lower thermal conductivity, and thermal diffusivity.14
The ZrO2-based TBCs mainly concentrate on the
stabilization of tetragonal (t)-ZrO2 phase4,15 by the
addition of Al2O3,16 Y2O2, CeO2, CaO, and MgO.17
To prevent the oxidation, delamination, cracking, spallation, and surface deterioration in high-temperature
atmosphere, the multilayer nanostructured coating is
applied to various alloy substrates using Al2O3 and
ZrO2. However, this structural modification is difficult
to achieve through the mono-phase ceramic materials18
as well as by using a single- or double-layer coatings.19
Generally, in multilayer coating, each layer functions as
heat dissipater across the coating. During this process,
thermal conductivity tends to decrease linearly with
increase in the number of structural layers.20 Moreover,
in comparison with only ZrO2, Al2O3-ZrO2 nanocomposite has been used extensively in TBCs. This is
because of the Al2O3 content, as it functions effectively
against the high-temperature oxidation with respect to
high hardness, low porosity, and also the improved performance of composite.21 In addition, Al2O3 enhances
the high-temperature corrosion prevention rate of metal
substrate due to its low oxygen diffusivity.22 Al2O3ZrO2 composite system is used for stabilization of
t-ZrO2 at room temperature, and hence, it is used for
high-temperature applications.23 The strength and
toughness of Al2O3-ZrO2 composite increase due to
the stress-induced transformation of t-ZrO2 to m-ZrO2
around a microcrack.24 It is clear from studies so far
that the volume of m-ZrO2 decreases with the increase
in the Al2O3 content in Al2O3-ZrO2 matrix. In addition, the resultant Al2O3 reduces the size of ZrO2 and
increases the phase volume of t-ZrO2 in the
matrix.25,26
It is evident that the Al2O3-ZrO2 nanocomposite
shows increased toughening behavior than ZrO2.
Highly toughened ZrO2-based ceramics (Al2O3-ZrO2
nanocomposite) are required for industrial coating
applications. Techniques such as suspension plasma
spray,27 atmospheric plasma spray (60:40 wt%),28,29
electron beam physical vapor deposition (85:15 mol%),19
gas tunnel plasma spray (80:20, 50:50, 20:80 wt%),21
and solgel deposition with atomic ratios of 7:93,
10:90, 30:70, and 38:62 are used for the preparation of
Al2O3-ZrO2 composite coating on the metallic substrate.30 Among different compositions, an improved

Vol. 10, No. 6, 2013

microstructure performance of the composite is

achieved when Al2O3 and ZrO2 contents are in the
range of 4090% and 1060%, respectively. Particularly, ZrO2 content in the range of 3040% is seen to
be playing a crucial role in arresting the heat transfer of
the substrate by reducing the delamination and cracking of the coating. It was also observed that higher content of ZrO2 (more than 60%) is less suitable for such
uses.31 The processing of solgel coating is one of the
most widely used structural coating that can modify the
surface properties of substrates without altering the nature of materials at low temperature.32 The deposition
of solgel-based Al2O3 stabilized ZrO2 coating offers
hard protection over working mild and stainless steel
specimen in harsh environments.30
Therefore, mass production of Al2O3-ZrO2 binary
nanoparticles is highly required for refractory coating
applications. Different synthesis methods are available
for production of aluminazirconia nanoparticles.25,3335
However, the mass production of Al2O3-ZrO2 binary
nanoparticles from metal nitrate precursors is not well
explored using hot-air spray pyrolysis. The present
work reports on the mass production of high surface
area Al2O3-ZrO2 nanoparticles with free-flowing structure. Further, the prepared nanoparticles can have the
capability of easily fictionalization with silicate and
polymer matrixes. Al2O3-toughened ZrO2 nanoparticles
of the well-explored composition ratio (65:35 wt%)
were produced in large quantity at high temperature
with spherical morphology and high surface area, and
quite reduced grain size. Ceramic-based surface-protective coating is necessary for protection of high-temperature oxidation corrosion of mild steel (EN3) specimen.
Solgel-based spin-coating technique offers structurally
dense and uniform ceramic coating for high-temperature barrier of the EN3 specimen. The nano-Al2O3
ZrO2-embedded silicate sol coating is applied over the
specimen, and the thermal stability of coating through
the firing treatment is evaluated.
Experimental Procedure
Preparation of Metal Nitrate Precursor
Alumina-stabilized zirconia binary nanoparticles
(65 wt% Al2O3-35 wt% ZrO2) were prepared by spray
pyrolysis technique using starting precursors such
as aluminum nitrate (Al (NO3)3.9H2O, 98.5%, Merck,
Mumbai, India) and zirconium oxynitrate (ZrO

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Al2O3-Stabilized t-ZrO2 for Thermal Barrier

(NO3)2.2H2O, Loba Chemie, Mumbai, India). The

metal nitrate precursor solution was prepared by mixing Al (NO3)3 and ZrO (NO3)2 in 500 mL doubledistilled water stirring it vigorously until homogeneous
solution was obtained at an ambient temperature.
H2O2 (25 mL) was added to this homogeneous nitrate
solution to enhance the decomposition rate of metal
nitrates in the reaction chamber. Then, the nitrate precursor was allowed to decompose within the hot air
zone at 400C.
Production of Al2O3ZrO2 Binary Nanoparticles
The spray pyrolysis is a thermal decompositiondependent process that breaks the atomized droplets
(nanosize entities) of nitrate precursor. It can be used
to produce large quantities of Al2O3ZrO2 binary
spherical nanoparticles with high surface area. The
homogeneous solution of mixed metal nitrate precursor
was used as the starting phase, which was fed through a
two-way nozzle into the reaction chamber with the help
of a feed pump (of 23 rpm). Then, the compressed
air was sprayed for atomization of the precursor solution. The hot air was injected into the reaction chamber followed by spraying the precursor in the hot zone
of the reaction chamber. Atomized droplets of the precursor were decomposed at 400C to generate nanoparticles with free-flowing structure. The complete process
of spray pyrolysis is described in our previous study.36
The spray pyrolysis primary experimental setup is
described in Fig. 1. Thermal decomposition reaction of
metal nitrates is given in Eq. (1).
D

2AlNO3 3 :xH2 O ZrONO3 2 :xH2 O !


400 C

Al2 O3  ZrO2 8NO2 2O3 xH2 O

The metal nitrate precursors were decomposed into

Al2O3-ZrO2 binary particles during the spray pyrolysis.
Nitric oxide (NO2) gas molecules have been elevated as
by-product that is eliminated as nitric acid using ceramic-based water gas diffusion system through drainage.
The usage of nitrate precursors helps to avoid the corrosion of furnace even at high-temperature decomposition.
The atomized thermal decomposition process was used
to produce the ultrafine Al2O3-ZrO2 binary particles that
were collected from different cyclones using cyclonic process. The obtained aluminazirconia powder was calcinated at different temperatures such as 600, 800, and
1000C for 3 h with a heating rate of 5C/min.

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Powder Characterization Studies

X-ray diffraction: The peak positions and phase
structure of Al2O3-ZrO2 binary particles were determined by X-ray diffractometer (XRD, XPert Pro;
PANalytical, Almelo, The Netherlands) using Cu Ka as
a radiation source (k = 1.54060 
A). The diffractometer
was operated at 40 kV (30 mA) and with an angle (2h)
of 1080 at a scanning rate of 10/s. The crystallite
size was determined by X-ray broadening line of Al2O3
toughened t-ZrO2 using Scherrer formula. The intensity of the binary powder were identified in comparison
with the standard powder diffraction data.
FTIR and XRF spectrometer: The FTIR spectra of
binary particles were identified by an infrared spectrometer (FTIR, Spectrum 100; PerkinElmer, Shelton, CT)
in the range of 4004000/cm using the KBr pellet
method (90 wt% KBr). Al2O3-ZrO2 powder was
ground in an agate mortar for measurement of IR spectra. The purity and stoichiometry of Al2O3-ZrO2 powder were determined using chemical composition
analysis (XRF, XGT-2700; Horiba, Kyoto, Japan).
Particles size and BETSurface area analyser: The
particle size distribution of prepared samples was measured using dynamic light-scattering principle (Nanophox; Sympatec, Clausthal, Germany) in the range of 1
1000 nm with a scattering angle of 90. The threedimensional photon cross-correlation technique was
used for the simultaneous measurement of particle size
and its stability. Surface area of binary nanoparticles
was measured using the surface area analyzer (BET
Autosorb AS-1MP; Quantachrome, Boynton Beach,
FL). Al2O3ZrO2 nanoparticles were degassed at 295C
for 3 h, and then, it was analyzed with N2 adsorption
measurements at liquid N2 temperature. The specific
surface area of Al2O3ZrO2 particulate was measured
using three-point BET correlation techniques.
SEM and TEM: The microstructure and morphology of Al2O3ZrO2 particles were examined using scanning electron microscopy (SEM, JSM-6390LV; JEOL,
Tokyo, Japan). Grain size and microstructures of binary
nanoparticles were examined through transmission electron microscopy (TEM, CM200; Philips, Eindhoven,
The Netherlands) operated at a potential of 120 kV.
Preparation and Studies of Mild Steel (EN3)
Specimen
A 15 9 8 mm size of rectangular mild steel (EN3)
specimen with 1.5 mm thickness was prepared for

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Vol. 10, No. 6, 2013

Fig. 1. Schematic diagram of spray pyrolysis experimental setup.

high-temperature TBC applications. Both surfaces of

the specimen were polished with five different carbide
sheets to obtain a smooth mirror-like surface. Before
start of a coating process, all polished plates were rinsed
with acetone for 10 min under an ultrasonic bath followed by washing with double-distilled water to remove
the polished debris and metallic ions.37 The grade and
elemental compositions of mild steel specimen were
analyzed through the arc/spark optical emission spectroscopy (OES, ARL 4460; Thermo Scientific, East
Grinstead, U.K.). The elemental compositions of EN3
specimen are presented in Table I. The specimen contains iron as major element (99.26 wt% of Fe) that can
easily be indulged for thermal oxidization in hot environment.
Preparation of Nano-Al2O3ZrO2-Embedded Silicate
Sol and Its Fabrications
Silica sol was prepared respectively using 2.5 mL
tetraethyl orthosilicate (TEOS; 99%; Merck), HNO3
(69%), and ethanol. TEOS (2.5 mL, 0.1 M) and ethanol (90 mL) were mixed thoroughly for 10 min, and

then 5 mL of polyethylene glycol was slowly added to

reduce the solvent (ethanol) evaporation. Further,
2.5 mL HNO3 was dropwise added with continuous
stirring for 20 min and was maintained for 1 h. Then,
0.25 g of as-prepared Al2O3-ZrO2 binary nanoparticles
(fired and decomposed at 400C) were used to incorporate silicate sol under sonication for 30 min to get
homogeneous mixture. The prepared homogeneous
nano Al2O3-ZrO2-embedded silicate sol was deposited
on the surface of the mild steel (EN3) specimen using
spin-coating technique (SM 108 BT; Sawatec, Ruggell,
Switzerland). The sol was slowly (drop by drop) loaded
up to 30 s in air, while maintaining the spin speed at
895.518 g32 under vacuum pressure of 0.6 bar. The
coated specimen was allowed to dry to remove its surface hydration at ambient temperature in air for 1 h.
Further, the coated specimen was exposed to heat treatment for 30 min at 400C and then was allowed to
cool to promote the intersplat fine creep that enhances
the densification of coating. To deposit relatively dense
and crack-free coating, the six-layer coating was (layer
by layer) applied individually on both sides of mild
steel (EN3). The deposition of each layer was stabilized

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Al2O3-Stabilized t-ZrO2 for Thermal Barrier

Table I. The elemental compositions of mild steel

(EN3) specimen (wt%)
Elements

Weight %

C
Si
Mn
P
S
Ni
Cr
Mo
V
Cu
W
Ti
Sn
Co
Al
Pb
b
Sb
Nb
Zr
Bi
Ca
Mg
Zn
Ce
La
Fe

0.0640
0.0670
0.2500
0.0320
0.0120
0.0080
0.0140
0.0150
0.0010
0.0110
0.0590
0.0050
0.0040
0.0030
0.0220
0.0170
0.0008
0.0290
0.0020
0.0090
0.0009
0.0020
0.0003
0.0003
0.0070
0.0100
99.2600

through the thermal treatment that improves the quality of coatings.

AluminaZirconia-Embedded Silicate Sol Coating
Characterizations
The particle size distribution of Al2O3-ZrO2-filled
silica sol was measured using dynamic light-scattering
principle. To analyze the thermal stability of Al2O3ZrO2-filled silicate coating on the mild steel (EN3)
specimen, the coated and uncoated specimens were
fired at 600C for 6 h with a heating rate of 5C/min.
The structural phase and composition of uncoated and
coated mild steel specimens were determined by XRD
pattern. The surface feature of specimens and compositions of coating were ensured using SEM and energy

891

dispersive spectrum (EDS; JED-2300; JEOL). After

firing at 600C for 6 h, the density of Al2O3-ZrO2
blended silicate coatings on EN3 mild steel (rectangular
specimen) was measured using conventional method.
To determine the density of Al2O3-ZrO2-enabled silicate hybrid coating, difference between the density of
specimen before and after coating was calculated. The
mass of specimen (before and after coating) was measured using digital balance (CP225D; Sartorius, Goettingen, Germany) with an accuracy of 0.01 mg.
Similarly, the volume was measured using the digimatic
micrometer screw gauge and vernier caliper (Mitutoyo,
Kawasaki, Japan). The density of coating was measured
through the relation as,
Density

Mass
Volume

The volume of the sample is equal to length 9

width 9 height.
The density of coating can be used to explore the
quality of coating at high temperatures. The field emission scanning electron microscopy (FE-SEM; SU6600;
Hitachi) was used to evaluate the surface topography
and coating cross-section.
Results and Discussion
Structural Orientation and Composition Analysis of
Al2O3ZrO2 Binary Particles
The XRD pattern of produced Al2O3-ZrO2 binary
particles calcination at different temperatures for 3 h is
shown in Fig. 2. To understand the structural stability
and crystalline size of binary nanoparticles at high temperature, the produced Al2O3-ZrO2 particles were calcinated at three different temperatures such as 600, 800
and 1000C. The obtained result shows that at 600C,
the powder exhibits an amorphous nature. It shows that
the characteristics of as-prepared Al2O3-ZrO2 amorphous binary particles are similar to the previously
reported data.26,27 However, the powder sintered at
800 and 1000C reveals only the strong crystalline
ZrO2 peaks that are composed of major mono phase of
t-ZrO2 with an average grain size of 6 and 7 nm,
respectively. The existence of controlled grain growth at
high temperature is due to surface enthalpy reduction
of zirconia by influence of alumina.33 The t-ZrO2 stabilized in amorphous Al2O3 reveals broad peaks that
appear at 2h = 30.36, 34.61, 35.31, 50.48, and

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Fig. 2. X-ray diffraction pattern of Al2O3-ZrO2 powder

calcinated for 3 h at (a) 600, (b) 800 and (c)1000C.

Fig. 3. The FTIR spectrum of Al2O3-ZrO2 binary powder (a)

as-prepared at 400C and calcinated at (b) 600, (c) 800 and
(d) 1000C for 3 h.

60.14. The obtained crystallite size reveals the absence

of abnormal grain growth at high temperature which is
matched with standard diffraction pattern (JCPDS file
no. 80-2155). A similar phase configuration was
reported in ZrO2Y2O3Al2O3 system.38 Thus, the
observed result suggests that the stable t-ZrO2 has been
well stabilized in Al2O3 domain.8
Figure 2 shows clearly that there is no peak detection for Al2O3 content during the crystallization process. It is confirmed that the disorder behavior of Al2O3
is present as fully amorphous state in Al2O3-ZrO2 binary system even during sintered at 1000C.34 These
results lead to conclude that it is possible to retard the
nature of t-ZrO2 crystallite size in the composite matrix
and also to control the migration of ZrO2 phases.39 At
high temperature, the growth of nanophase ZrO2 is faster than that of its counterpart nano-Al2O3.40 Besides,
nano-Al2O3 domain is beneficial to effectively inhibit
the nucleation and crystallite growth of t-ZrO2 at high
temperatures.4042 The Al2O3 matrix-stabilized ZrO2 is
possible due to controlled crystallite size that increases
the stability of t-ZrO2.33 Nanophase of t-ZrO2 is
retained significantly at high temperature as well as at
room temperature primarily due to its fine grain size
and high volume fraction.34,43 The critical size of crystallite t-ZrO2 was easily achieved with Al2O3 matrix
without any other expensive stabilizers such as Y2O2,
CeO2, CaO, and MgO.
The stable nanoscale t-ZrO2 is surrounded by
rigid amorphous-Al2O3 sheath to improve the coating

performance at high temperature.44 In Fig. 2, the

nanograin dispersed in amorphous Al2O3 is identified
by broad diffraction peak of t-ZrO2 phase with grain
size (d) less than 8 nm. The observed results show
that the crystalline growth is restrained at high temperature due to high surface area.45 The thermal stability of Al2O3-ZrO2 binary particles depends on
individual phase elements, temperature and crystallization of amorphous materials. The effect of amorphous
state and stabilization of t-ZrO2 are actively involved
in the thermal stability of the system.33 which may
be due to lack of grain formation in the amorphous
Al2O3 phase within the boundary region and no
direct atmosphere contacts with the sample. In addition, the stress-induced transformation toughening
property of t-ZrO2 is highly stable at high-temperature annealing process.
The FTIR spectra of Al2O3-ZrO2 binary particles at
different temperatures are shown in Fig. 3. The peak
observed at 2069/cm is attributed to stretching and bending vibration of OH group. The hydroxide group is
denoted as a small intense peak and the surface hydration
disappears after high-temperature treatments. Further, the
FTIR spectra show the residual amount of moisture
adsorption in the binary particles even after sintering at
1000C. However, the OH stretching vibration and
bending frequency of ZrO2 molecule also appeared at
1761, 1637, and 1386/cm.46 The formation of OH
groups can be distinguished easily in the form
of H2O molecule due to the bending vibration of a

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Al2O3-Stabilized t-ZrO2 for Thermal Barrier

single band at 1637/cm.47 In addition, peak localized

at 1201/cm is assigned as absorption of Zr ions.48
The characteristic active mode exhibits peak at 597,
827, 950, 1068,49 1107/cm, and 510526 and 532/
cm are assigned to vibration spectra of AlO and Zr
O, respectively.46,50 Obtained result reveal that the
presence of t-ZrO2 peak at 513/cm51 is correlated
with XRD pattern in Figs. 2b,c. The observed crystalline peak is strongly influenced by the intensity of IR
peaks. The comprehensive FTIR result reveals that the
prepared Al2O3-ZrO2 matrix has no intermediate linkage of organic functional groups except OH. The
XRF-spectra of as-prepared Al2O3-ZrO2 binary particles are shown in Fig. 4. The chemical composition of
as-prepared binary particles (at 400C) consists of 65
wt% Al2O3 and 35 wt% ZrO2, which is in close
resemblance to an experiment precursor ratio (70 wt%
Al2O3-30 wt% ZrO2). The observed result reveals that
the produced binary particles have almost maintained
the stoichiometry of experimental compositions of
Al2O3 and ZrO2. The imbalance of stoichiometry
ratio is due to the mixing rate of nitrate precursors.
Moreover, there may be a chance of incomplete
homogeneous mixing of precursor solution. The
obtained 65:35 wt% ratio for Al2O3 and ZrO2 may
be applicable for high-temperature applications to
improve the lifetime expectancy of the materials.31
Size and Surface Morphology of the Al2O3ZrO2
Binary Particles
Figure 5 represents the particle size distribution
(PSD) of as-prepared Al2O3-ZrO2 nanoparticles. It can

Fig. 4. The XRF spectrum of as-prepared Al2O3-ZrO2 binary

particles at 400C.

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be seen from PSD analysis that the size distribution of

prepared particles is in the range of 10 (d10) to 55
(d90) nm with the mean diameter of 26 (d50) nm. The
broad and uniform distribution curve (Fig. 5) suggests
that the prepared binary particulate at 400C is well
dispersed without any agglomeration. The obtained
narrow scale particle size distribution confirms that
spray pyrolysis technique is one of the effective ways to
produce the controlled Al2O3-ZrO2 binary nanoparticles. The surface area of Al2O3-ZrO2 as-prepared powder is 59 m2/g; after it is sintered at 1000C for 3 h,
the surface area reduces to 28 m2/g. In case of powder,
the decrease in surface area may be due to the aggregation of nanoparticles with increasing thermal energy at
high temperature.
The microstructure and surface morphology of asprepared Al2O3-ZrO2 binary particles are shown in
Fig. 6. The surface image seems to have spherical morphology and uniformly distributed porous nature. It
can be seen that clusters of particles are closely packed
to form weaker agglomeration. In addition, it reveals
that the free-flowing fine particles are sticking together
to form big particles. TEM micrograph of Al2O3-ZrO2
binary particles are shown in Fig. 7. It shows uniform
distribution of nanoparticles along with weak agglomeration. The presence of agglomeration is due to the fine
nanoparticles having large surface area, high surface
energy, and higher intermolecular interaction force.35
TEM image Fig. 7a represents the as-prepared Al2O3ZrO2 binary nanoparticles. It shows that the obtained
binary nanoparticles reveal an amorphous nature which
is confirmed through an inserted diffraction pattern

Fig. 5. Particle size distribution of as-prepared Al2O3-ZrO2

binary nanopowder at 400C.

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Fig. 6. Scanning electron micrograph of as-prepared Al2O3ZrO2 powder at 400C.

(a)

Fig. 8. Particle size distribution of nano Al2O3-ZrO2-filled

SiO2 sol.

TEM image of the Al2O3-ZrO2 binary nanoparticles

after calcination at 1000C for 3 h. It shows the formation of crystalline t-ZrO2 with amorphous Al2O3
through the hybrid network is evident from the enveloped diffraction pattern as given in Fig. 7b. In addition
to this, even after Al2O3-ZrO2 particles sintered at
1000C, there is no major change in Al2O3-ZrO2
matrix size when compared with the as-prepared binary
particles (Fig. 7a).
(b)

Fig. 7. Transmission electron micrograph of Al2O3-ZrO2

nanocomposite (a) as-prepared at 400C and (b) calcinated at
1000C for 3 h.

image. Moreover, the size of the produced binary particles is 20 nm which is close agreement with mean
diameter of PSD (Fig. 5). However, Fig. 7b shows the

Structural Characterization of Coated and Uncoated

Mild steel (EN3) Specimen
The particle size distribution of Al2O3-ZrO2-filled
SiO2 sol is shown in Fig. 8. The average particle diameter (d50) of 33 nm was obtained with narrow size distribution range of 16 (d10) to 53 (d90) nm. It can be seen
from Figs. 5 and 8 that the mean diameter of as-prepared Al2O3-ZrO2 binary particles is 26 nm, whereas
the diameter for Al2O3-ZrO2-filled SiO2 sol is 33 nm.
It can be inferred that the homogeneous dispersion of
Al2O3-ZrO2 binary particles in silicate sol is formed as
hybrid particles. The formation of silicate hybrid network over the Al2O3-ZrO2 binary particles in turn
increases the mean particle size of homogeneous Al2O3ZrO2 binary particles from 26 to 33 nm. These nanoparticles may be used to laminate the multilayer coating
on the mild steel (EN3) specimen. The hybrid Al2O3ZrO2/SiO2 sol plays a crucial role in enhancing the
reinforcement of coating system at high temperatures.

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Al2O3-Stabilized t-ZrO2 for Thermal Barrier

The XRD patterns of Al2O3-ZrO2-filled silicatecoated and uncoated EN3 specimen are shown in
Fig. 9. The uncoated specimen (Fig. 9a) emerged with
a single phase of iron peaks assigned to the characteristics of the mild steel (EN3) specimen based on the previous report.10,18 However, after heat-treated at 600C
for 6 h, the coated specimen (Fig. 9b) is composed of
distinct complex structural phase of t-zirconium silicate
(ZrSiO4), which is evident from the peaks appearing at
2h = 36.07, 63.52 and 64.73. The diffraction peaks
of coated mild steel (Fig. 9b) are matched with standard diffraction data (JCPDS file no. 75-1564). The
average crystallite size of ZrSiO4 film is observed as
29 nm, which is in close agreement with the mean particles diameter of Al2O3-ZrO2-filled silicate hybrid sol
(Fig. 8).
The formation of ZrSiO4 occurs during the heat-firing phenomena wherein the ZrO2 phase is associated
with silicate (SiO2) network structure. The existence of
ZrSiO4 in coating helps to attain the high-temperature
structural stability of (EN3) specimen. It is noteworthy
that the existence of ZrSiO4 phase is highly suitable for
high-temperature barrier when compared to Al2O3/SiO2
phases.9,52,53 Nanostructured multilayer coating on EN3
specimen consists only of ZrSiO4 phase without the existence of Al2SiO5. The absence of Al2SiO5 phase in coating may be due to the amorphous state of Al2O3 in
silicate matrix. Therefore, Al2O3 retains (Fig. 2) amorphous state in Al2O3-ZrO2 nanocomposites as well as in
Al2O3-ZrO2/SiO2 hybrid nanocomposite coatings. The
amorphous ZrO2 particles in Al2O3-ZrO2 nanocomposite was transformed to t-ZrO2 at high-temperature

Fig. 9. X-ray diffractometer pattern of mild steel (EN3) specimen (a) uncoated and (b) nano Al2O3-ZrO2/SiO2-embedded
six-layer coating heat treated at 600C for 6 h.

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calcinations such as 800 and 1000C (Figs. 2b,c), which

is also retained in the Al2O3-ZrO2/SiO2 hybrid nanocomposites. The structural characterization (Fig. 9b) of
nanostructured multilayer coating emphasizes the formation of a strong protective coating on the mild steel specimen. Thus, the multilayer nanostructured coating
provides a hard surface over the specimen without altering its original surface.
Effect of TBC on the Mild Steel Specimen at
High-Temperature Treatment
The microstructure of TBC is shown in Fig. 10.
The polished mild steel (EN3) specimen (Fig. 10a)
reveals that the surface is a uniform and the parallel feature seen on the specimen that may be due to either
scratches during polishing or the existence of debris.
After treatment at 600C for 6 h, the uncoated specimen
surface (Fig. 10b) is shuttered with an increased roughness as compared with the polished blank specimen. The
thermal damage of EN3 specimen is due to the diffusion
of oxides on the surface, which is caused by either corrosion attack or high-temperature oxidation behaviors.
Figs. 10c and d show six-layer coating of nano Al2O3ZrO2 filled hybrid silicate on EN3 mild steel before and
after heat treatments at 600C for 6 h. The SEM image
(Figs. 10c and d) reveals that the nanostructure coating
is structurally uniform on the specimen. The filling of
Al2O3-ZrO2 nanoparticles in silicate sol features a
smooth surface-nanostructured coating which is covered
with superior adhesion to EN3 base materials. After heat
treatment, the thermal barrier of Al2O3-ZrO2-filled silicate coating (Fig. 10d) indicates the better uniformity
throughout the surface of EN3 specimen as compared
with uncoated specimen (Fig. 10b). The existing nanostructured six-layer (TBCs) Al2O3-ZrO2-filled silicate
results in the simultaneous promotion of cross-linkage
network over the EN3 specimen. Thus, the successive
network layers provide a strong adhesion for the specimen. The superimposed nanostructure coating provides
a better thermal insulating barrier and effectively suppresses the corrosion-oxidizing species on the specimen
at high temperature with minimum surface deterioration.
The degree of surface delamination coating depends on
decomposition and diffusion of elements from substrate.10 The high-temperature retardant behavior of
Al2O3-ZrO2 hybrid silicate coatings are due to the presence of thin films of adherent oxide and critical grain
size that entraps the metallic ions on the EN3 mild steel

896

International Journal of Applied Ceramic TechnologyKarthik, et al.

Vol. 10, No. 6, 2013

(a)

(b)

(c)

(d)

Fig. 10. Scanning electron micrographs of mild steel (EN3) specimen: (a) polished surface, (b) uncoated heat-treated for 6 h at 600C,
(c) Al2O3-ZrO2/SiO2-coated and d) Al2O3-ZrO2/SiO2 six-layer coating heat-treated for 6 h at 600C.

substrate. Thus, it is clear from this study (Fig. 10d) that

the high-temperature TBC is not linked with volume
shrinkage and spallation. Moreover, the complex Al2O3ZrO2 filled silica sol matrix is used as thermal barrier in
high-temperature applications.
Figure 11 represents the EDS spectra of multilayer
coated and uncoated mild steel specimen. The EDS
mapping on the uncoated specimen is shown in
Fig. 11a which confirms the chemical compositions of
base materials (includes Fe and C elements). The existence of major element Fe is strongly aligned with
XRD pattern of the mild steel specimen (Fig. 9a).
Figure 11b shows the EDS-spectrum of Al2O3ZrO2-filled silicate-coated EN3 specimen after firing at
600C for 6 h. It is evident from Fig. 11b that the
coating comprises oxides such as Al, Zr, Si, and Fe
with C. Thus, EDS mapping of coated mild steel specimen confirms the presence of thermal barrier coating
on EN3 substrate. The density of Al2O3-ZrO2 enabled
silicate coating layer was measured from before (7.16)
and (7.84) after coating, and is equal to 0.68 g/cm3.
This shows that the nanostructured coating is thermally
stable at elevated temperature.

The cross-sectional and surface topography of the

complex Al2O3-ZrO2-embedded silicate coating is
shown in Fig. 12. The cross-sectional view reveals distinct splat features between the base material (EN3)
and its surface of nanostructured coating after heat
treatment at 600C for 6 h. It reveals that the interface
of six (layer by layer) coating of nano-Al2O3-ZrO2
hybrid silicate and it confirms the deposition of sixlayer coating with thickness of approximately 165 lm.
The existence of parallel surface contour and crack
formation within interface of EN3 specimen is possibly
due to the impact of sectional cutting on the coated
EN3 base material. At interface, the continuation of
each layer is bonded tightly with other layer by the
incorporation of Al2O3ZrO2-filled silicate in the form
of ZrSiO4 at high temperature. Moreover, the lamination of multilayer structural composition is identified
through the XRD (Fig. 9b), which is evident from the
observed EDS mapping (Fig. 11b). Therefore, the
nano-Al2O3-ZrO2-filled silicate coatings provide
required TBC properties which in turn provide strong
adhesion and protection to mild steel (EN3) against
high-temperature resistance.

www.ceramics.org/ACT

Al2O3-Stabilized t-ZrO2 for Thermal Barrier

(a)

(b)

897

precursors. The toughening effect of t-ZrO2 is achieved

at high temperature with critical crystallite size. The
present work identified the novel process for large-scale
production of high surface area (59 m2/g) Al2O3-stabilized t-ZrO2 nanoparticles. Particles produced by this
process have the capability of free-flowing structure
which is used as nanofiller for silicate based inorganicinorganic hybrid coating. The nanostructured Al2O3ZrO2-filled silicate multilayer coating is achieved on
the mild steel (EN3) specimen using spin-coating technique. After high-temperature exposure, the Al2O3ZrO2-embedded silicate coating exhibits better compatibility with improved surface damage resistance as compared with uncoated specimen. The reinforced
nanostructured hybrid TBC is observed as a better
high-temperature barrier by means of their morphological and structural analysis. The present research work
brings out the finding that the nano Al2O3-ZrO2-filled
silicate coating is best suited to obtain the required
TBC properties to protect the mild steel (EN3) specimen against high temperatures.

Acknowledgment
Fig. 11. Energy dispersive spectrum of mild steel (EN3) specimen (a) uncoated and (b) nano Al2O3-ZrO2/SiO2-embedded
six-layer coating heated at 600C for 6 h.

The authors thank the Department of Science and

Technology, New Delhi, India, for providing the spray
pyrolysis instrument to carry out this research work.
References

Fig. 12. Field emission scanning electron microscopy cross-sectional

image of nano Al2O3-ZrO2-filled SiO2 coating on mild steel (EN3).

Conclusions
Al2O3-stabilized t-ZrO2 binary nanoparticles are
produced by hot-air spray pyrolysis using metal nitrate

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