Investigation on Barium Zirconate Nanocomposite

for Dielectric Properties

Seenivasan Sivakumar (  seeni95physics@gmail.com )
Selvam college of Technology

Research Article

Keywords: Barium zirconate, chemical oxidation states, dielectric conductivity, impidence stability

Posted Date: July 26th, 2023

DOI: https://doi.org/10.21203/rs.3.rs-3187931/v1

License:   This work is licensed under a Creative Commons Attribution 4.0 International License.
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Abstract
The barium zirconate (BaZrO3) Perovskite is of interest for various fields of applications. It has high
corrosion resistance with respect to molten phases formed during the synthesis of copper-oxide-based
super conducting single crystal. In the present investigation, ZrO2 and BaZrO3 were prepared by co-
precipitation method. The samples were characterized by powder X-ray diffraction, FT-IR spectra and
EDAX-shows the elemental analysis of the specimens. ZrO2 and BaZrO3SEM micrograph of the ZrO2and
BaZrO3 shows the morphological structure of both of the samples it resembles a nano cluster of
spherical particles like a flower. Most of the particles arranged like an agglomerates. The
Photoluminescence spectra indicates the blue emission at zirconate. The red emission region is shifted
of barium. The high ion exchange ability and redox moment must make it useful in many catalystic
processes and also it made the material is useful for the flurosense lamp and flat panel displays. The
dielectric constant and dielectric loss were determined as a function of frequency at 1 MHz. It is found to
be 63.56 forzirconia and 78.24 for barium zirconate. Due to its high dielectric constant value barium
zirconate may be useful in case of ferroelectric applications.

1. Introduction
Barium zirconate is a very promising refractory structural material with a very high melting point (2600°C)
and a low chemical reactivity towards corrosive compounds like high temperature superconductors. Erb
et al. showed that high density barium zirconate could be used as a substrate in the synthesis of high-Tc
superconductors because it does not react with the liquid phases produced at high temperature during
the process.[1]A simple method to synthesis barium zirconate can be the traditional solid state reaction
route in which an appropriate amount of zirconia and barium carbonate are mixed together, ball milled to
both enhance the homogeneity and reduce the particle size, before performing the heat treatment[.2]
However, for such refractory materials, it is necessary to make several cycles of grinding/firing during a
rather long heating time in order to complete the reaction. Perovskite oxides with the formula ABO3 are of
great scientific and technological interest for their ferroelectric, pyroelectric, piezoelectric, dielectric and
catalytic properties.[3–7] Barium zirconate (BaZrO3) (BZ), one of the most investigated Perovskite
materials, presenting a wide range of technological applications.[ 8–10] BZ is a cubic oxide Perovskite
that does not undergo phase transitions in the range 4–1600 K[11] and has a high dielectric permittivity
of about 30 and a reasonably wide band gap of 5.3 eV when compared to other oxides.[12]Several
methods have been employed to prepare metal zirconates such as co-precipitation/calcinations,[12] sol–
gel,[13] polymeric precursor,[14–15] and single-step combustion.[16] However, some of these synthetic
procedures still require a calcination treatment to transform a homogeneous precursor into a crystalline
oxide phase. For BZ, sol–gel oxalate or citrate routes produce powders with very small grain size;
however, many of these methods require organic solvents, which must be recycled.[17–18] Recently, the
possibility of obtaining submicron crystalline BZ by precipitation in an aqueous basic solution below 100
_C has been examined by Boschini et al.,[19 ]while hydrothermal synthesis has been developed over the
last decades in order to obtain nanometric BZ powders[20] using faster and less expensive methods.

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Moreover, powders produced by such a process still keep several drawbacks like a lack of reproducibility,
a large particle size (10mm) and size distribution, a high degree of aggregation and sometimes
inhomogeneities in the chemical composition. To avoid these effects, different synthesis methods have
been developed like the citrate route, the oxalate route.[ 21–22] or the metal -chelate sol-gel route using
ethylene glycol as complexing agent.[23–24]. Recently, barium zirconate has been produced by a co-
precipitation in the presence of sodium chloride in order to precipitate quantitatively barium and to obtain
after calcinations a stoichiometric barium zirconate product.The present work aims to synthesis pure
zirconate and magnesia zirconate by co precipitation method. The synthesized nan powders are
characterized structurally by powder x-ray diffraction, scanning electron microscopy (SEM) with EDAX, FT
– IR and optically by UV- Vis spectrum and photoluminescence ( PL). The dielectric studies have also
carried out for both the nano powders and the results and discussions are presented in this report.

2. Materials
zirconium oxychloride [ZrOCl2.8H2O] (98%) Barium chloride [BaCl2.2H2O] (99%) were purchased from
Merck in India. All the reagents are used without further purification using deionized (DI) water.

2.1 Synthesis of pure zirconate (ZrO2) Nanoparticles

The ZrO2 NPs were synthesized by co precipitation method using zirconium oxychloride [ZrOCl2 .8H2O]
and sodium hydroxide [NaOH] as starting precursors. Briefly, a 0.4 M aqueous solution of NaOH was
slowly added drop-wise into a 0.6 M[ZrOCl2. 8H2O] aqueous solution of and allowed to vigorous stirring
using Teflon coated magnetic bar for 3 h, yielding a white colored precipitate containing zirconium
hydroxide. The Zr(OH)4 precipitate was washed thoroughly with distilled water and centrifuged 4000 rpm
for 10 min to remove the residuals. The process was repeated several times until the precipitate was free
from any trace impurities. The obtained Zr(OH)4 precipitate was dried in a hot air oven at 110ºC for 1 h
and further calcined at 500º C for2 h resulting in the formation ZrO2 Nanoparticles .

2.2 Synthesis of Barium Zirconate Nanoparticles

0.6M of zirconium oxychloride [ZrOCl2. 8H2O] and 0.4M of Barium chloride [BaCl2 .2H2O] were dissolved
in 100ml of distilled water and allowed to vigorous stirred for 15mins to obtain (A) solution. Then 100ml
of 1M of sodium hydroxide(B)solution was added drop wise into the A solution allowed to vigorous
stirring using Teflon coated magnetic bar for 3 h, yielding a white colored precipitate containing
zirconium hydroxide. The Zr(OH)4 precipitate was washed thoroughly with distilled water and centrifuged
4000 rpm for 10 min to remove the residuals. The process was repeated several times until the precipitate
was free from any trace impurities. The obtain barium zerconate precipitate was dried in a hot air oven at
110ºC for 1h and further calcined at 400º C for2 h resulting in the formation BaZrO3 nanoparticles.

2.3Dielectric Studies

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In the present work, the dielectric, ac conductivity and impedance measurements have been carried out as
a function of composition and frequency (42Hz − 5MHz) using HIOKI-36532-50 HI-TESTER LCR meter.
The SnO2 based DMS material was pelletized using a circular shape dye of 10mm and 12mm diameter.
The thickness of pellets was ~ 1 to 3 mm. For dielectric and ac impedance measurements, silver paste
was coated on the opposite faces of the pellet to make parallel plate capacitor geometry and SnO2 based
DMS material as the dielectric material. For taking dielectric measurements of SnO2 thin films
Au/SnO2/Au sandwich type structure was deposited on quartz substrate to make parallel plate capacitor
geometry and SnO2 thin films. Bauerle was the first to use this technique in 1969 to separate bulk from
interfacial properties in polycrystalline ceramics.[25]. In complex impedance diagrams (Nyquist or Cole–
Cole plot) the imaginary part of the impedance is plotted against the real part of impedance. The
response of an ideal parallel circuit of resistance R and capacitance C is a semicircle centered on the real
axis. R is determined from the diameter of the semicircle, whereas C is calculated from the frequency of
semicircle maximum. Impedance spectroscopy is ideal for investigating the electrical response of
dielectric materials as a function of frequency. It is a powerful technique for unraveling the complexities
of materials, whose properties and applications depend on the close control of structure, composition,
ceramic texture, dopants (or defects) and dopant distribution, which functions by utilizing the different
frequency dependence of constituent components for their separation. The impedance analysis of a
material is based on an idealized circuit model with discrete electrical components. The analysis is
mainly accomplished by fitting the impedance data to an equivalent circuit, which is representative of the
material under investigation. It has been among the most useful investigation techniques since the
impedance of grains can be separated from the other sources of impedance, namely grain boundaries
and electrode effects. When the grain boundary resistance is larger than the resistance of bulk, two
semicircles are often obtained in Cole-Cole plot. Deviations from ideal semicircles have been attributed to
the distribution of relaxation times arising from the micro-structural inhomogeneity or disorder in the
samples [27].

3. Results and discussion

3.1 XRD Analysis
Powder X- diffraction (XRD) is a technique used to solve the complex structure, crystalline size (grain
size) and preferred orientation in polycrystalline or powder solid sample. X-ray diffraction measurement
has been performed with a powder X-ray diffraction (Rigaku model, japan) equipped with Cu Kα 1 ( λ =
1,5406 nm) using a generator voltage of 40 kV and 40 mA.Diffraction peaks are used to evaluate
structural order at long range. All powders have characteristic diffraction peaks of a crystalline structure,
suggesting a structural periodic long range order for the BZ phase. The main (111) diffraction plane is
shown in the upper part of Fig. 1 (a) shows the XRD pattern of the pure ZrO2 nano particles this crystal
plane is related to the periodic arrangement of monoclinic (BaZrO3). Figure 1 (B) shows the BaO – ZrO2
(1:1) nanoparticles annealed at 400°C.The XRD pattern revealed only the monoclinic phase of ZrO2 with

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preferred orientation along M (111) plane. The grain size (D) of the nano particles were calculated from
the FWHM of XRD using Scherrer equation [28].

𝐷=𝑘𝜆𝛽𝑐𝑜𝑠𝜃

Where

D = is the grain size,

K = 0.9 a correction factor,

Β = the full width at half maximum (FWHM) of the most intense diffraction

Peak,

λ = the wavelength of X-ray and

θ = the Bragg angle.

summarize the diffraction angle, crystalline phase, d- spacing and miller indices of the crystalline planes
of zirconia and barium Zirconate nanoparticles. The grain sizes of ZrO2 were found to decrease from
59.8 nm to 39.5 nm by the addition of BaO. This is due to the agglomeration of the grains of ZrO2 around
the BaO. Table 3 gives the particle size of the prepared samples.The observed diffraction peaks in the
recorded XRD pattern agrees with the values available in the JCPDS card No 899066. No characteristics
peaks of other impurities were observed in XRD pattern, indicating that phase- pure and high quality
ZrBaO3 nanomaterials are readily obtained.

3.2Fourier Transform Infrared Spectroscopy (FT-IR)

The structural characterization in the analysis of any material is very important to confirm the
synthesized material for its formation. FT = IR spectral analysis is used to identify the functional group
present in the molecule. In the present investigation, FT-IR spectra of synthesized compound where
recorded the range 400-4000nm employing a JASCO FT-IR 460 plus spectrometer. Following the KBr
pellet technique at 300k with scanning speed 2mm/s fig and their vibrational frequencies are tabulated.

The fourier transform infrared spectrum (FT-IR) of BaO – ZrO2shows a strong absorption at 476 cm-1 due
to the Zr – O vibration. The intense bands were observed at 3390and1620 cm-1, it could be due to
hydrated compounds [29].The FT-IR spectrum of BaZrO3 in the (OH) region shows one broad band 3413
cm-1, this band corresponds to –OH stretching vibrations of surface hydroxyl groups. The peak observed
at 715 cm-1 could be due to Ba-O interaction.

3.3Energy Dispersive Analysis by X-ray (EDAX)

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EDAX spectrum of pure ZrO2 and BaZrO3 clearly indicates the presence of Ba Zr metals and oxygen
(Fig. 3). The Percentage composition of various elements presented.

3.4 FE-SEM Analysis

The scanning electron microscopy (SEM) micrograph of prepared nano particle scanned by 20 KV
electron beam at X 10,000, X 55,000 magnification.SEM micrograph of the ZrO2 and BaZrO3 shows the
morphological structure of both of the samples ,it resembles a nanocluster of spherical particles like a
flower. Most of the particles arranged like agglomerates. The forms ZrO2 has formed primarily
agglomerates of average of 59 nm particle size formed its shown as Fig. 4(a) in the case of mixed crystal
BaZrO3with an average of 39.5nm.its shown as Fig. 4 (d-f).

3.5 UV-Visible Absorption Spectroscopy

Absorption spectra of Barium zirconate oxide (BaZrO3) nanoparticles were recorded using UV-Vis
spectrophotometer over the wave length range 200–1100 nm. From this spectrum, it has been inferred
that BaZrO3 nanoparticle has sufficient transmission in the entire visible region as shows in Fig. 5

The band gap energy of the BaZrO3 calculated using the simple equation. The band gap energy is
calculated using the plank’s equation as follows

Eg = hc/λ

Where

h = plank’s constant,

c = Velocity of light,

λ = cut off wavelength,

c = 3 x108 m/s,

λ = 230 x10− 9 nm

λ = 241 x10− 9 nm

Band gap energy (eV) ZrO2 = 5.3967 eV

Band gap energy (eV) BaZrO3 = 5.1504eV

Band gap energy of the BaZrO3 nanoparticles is found to be 5.1504eV. From this it can be concluded that
band gap energy is size dependent. Both the nanomaterials are transparent in the entire visible region
which is suitable for potential optical device fabrications
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3.6 Photoluminescence Spectroscopy
Photoluminescence spectra were recorded for ZrO2 and BaZrO3nanoparticles for a wavelength range of
250- 600nm.To gain a deeper insight into the emission mechanism,luminescent analysis is widely used
as an effective tool. Room temperature PL spectra of the synthesized BZ are shown in Fig. 6. With an
excited wavelength at 537 nm,spectra of all samples shows that the strong broad blue-yellow emission
peak is at 537 nm, and blue emission peak is at 400nm in ZrO2. proposed a mechanism to promote the
formation of defects and/or distortions on the BZ polyhedrons. The emission band profile is a typical
multi phonon process, i.e., a system in which relaxation occurs along several paths and involving the
participation of numerous states within the bandgap of the material. These intermediate levels originate
from a structural disorder at the BZ lattice, the direct electron transition between the valence band and the
conduction band is not allowed in this case. As the PL emissions present the emission center at energies
lower than 5.3 eV, a multi photonic process appears as the main consequence of the existence of excited
degenerated states within the band gap of the material 5.1eV .On the other hand, an analysis of the
recent bibliography on PL behavior of related metal oxide nanostructures, such as ZrO2, allows the
correlation of PL emissions with defect electronic states in the band gap formed by in plane oxygen.

3.7 Dielectric properties

Dielectric properties (dielectric constant, loss) and electrical properties (impedance) have been analyzed
at various frequencies ranging from 100Hz to 1 MHz at room temperature for the pellets of ZrO2 and
BaZrO3 nano particles in the disc form. From the Fig. 7(A). it observed that its dielectric constant
decreases with frequency and attained almost constant for ZrO2 which is the common behaviour of
ceramic oxide. The calculated dielectric constant at 1 MHz frequency for ZrO2 (63.56),which is about 1.2
times higher than BaZrO3 (78.24) (Fig. 7A &B).

The existence of monoclinic and tetragonal phase (mixed phase) in ZrO2 could be the reason for less unit
cell volume, and these leads to the increase in number of polarisable particles per unit cell. Hence the
dielectric constant is higher for ZrO2than other materials.Like dielectric constant, the dielectric loss also
decreased with frequency for both cases. The dielectric loss of ZrO2 is 0.2089 and the BaZrO3 is 9.999.
This may be due to the amount of defects existing in the barium zirconate Fig. 7(D). In order to reduce the
dielectric loss, enhance the densification of the material and it mainly dependson the cubic pervoskite
structure ofBaZrO3,calcinations temperature, duration time etc. Other way to reduce loss is by optimizing
the quality of the sample. The dielectric constant at low frequencies is due to space polarization effect.

Impedance analysis

High dielectric constant at low frequency isdue to the space charge polarization can be easily understood
through impedance analysis as shown in Fig. 8 (A-B). The magnitude of i impedance (Z") value decreases
at very low and increases at mid frequency region and then it remains constant.This indicates the

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presence of space- charge polarization effect at low frequencies. In this relaxation may be due to the
presence of immobile species and defects (or) vacancy clusters as found from photoluminescence
spectrum.

Figure (8) shows the complex impedance for ZrO2 and BaZrO3.The impedance decreases with low
frequencies and increases at highfrequencies.23 From the figure it can be shown that there are two
regions, one is grain region and another one is grain boundary region For ZrO2 grain region is dominating
factor at high frequencies and grain boundary region is dominating at lower frequency region. This is due
to the nature, segregation of impurities, space charge effects and so on.

From the analysis of impedance data, it can be concluded that the high surface area can easily migrate
the grains but are accumulated at the grain boundaries under the application of an external field. This
process can be produce large polarization and leads high dielectric constant. The small conductivity of
the grain boundary contributes to the high value of the dielectric constant at low frequency region. ZrO2
was used as an insulator in transistor for future nano electronic devices.Dielectric constant is found to be
63.56 for zirconia and 78.24 for barium zirconate. Due to its high dielectric constant barium zirconate
may be useful in the case of ferroelectric applications like super conducting device fabrications.

4. Conclusion
The barium zirconat (BaZrO3) Perovskite is of interest for various fields of applications. It hashigh
corrosion resistance with respect to molten phases formed during the synthesis of copper-oxide-based
super conducting single crystal. In the present investigation, ZrO2 and BaZrO3 were prepared by co-
precipation method. The samples were characterized by powder X-ray diffraction pattern and it was
found that ZrO2 exhibits both tetragonal and monoclinic crystalline phase with particle size of
59nmwhere as the BaZrO3 shows a Perovskite cubic structure with prominent crystallographic planes (
111) & (112).A the particle size was calculated from Scherer’ formula is39.51nm for BaZrO3 and for ZrO2
is 60 nm. FT-IR spectra confirmed that the metal –oxygen absorption of the pervoskite phase at ~ 570cm-
1and ~ 1461cm-1. The particle size depends significantly on the [Ba + Zr] concentration. The particle size
decreases when the concentration of the reactants increases. The band gap energy of ZrO2 and BaZrO3
were determined as_5.396eV_and 5.10 eV Both materials has a wide transparency window ,which is
suitable for the application of optoelectronic device fabrications. EDAX-shows the elemental analysis of
the specimens. ZrO2 and BaZrO3SEM micrograph of the ZrO2and BaZrO3 shows the
morphologicalstructure ofboth of the samples it resembles a nanocluster of spherical particles like a
flower. Most of the particles arranged like an agglomerates. ThePhotoluminescence spectra indicates the
blue emission at 406nm and it also shows visible light emission is in the range of 406–537 nm in the
zirconate. The red emission region is shifted to 557 nm by the addition of barium. The high ion exchange
ability and redox moment must make it useful in many catalystic processes and also it made the material
is useful for the flurosencelampand flat panel displays. The dielectric constant and dielectric loss were
determined as a function of frequency at 1 MHz. It is found to be 63.56 forzirconia and 78.24 for barium
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zirconate. Due to its high dielectric constant value barium zirconate may be useful in case of ferroelectric
applications.

Declarations
Ethical Approval

Ethical Approval is not applicable

Competiting interests

The authors declare that they have no known competiting interest

Authors’ Contribution

S.Seenivasan : Investigation, Data Original Drafting,Conceptualization, Investigation On

Conceptualization

Funding

Funding information is not available.

Availability of Materials and data

The data that has been used confidential.

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Tables
Table 3 is not included with this version

Figures

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Figure 1

(A) X-Ray Diffraction pattern of pure ZrO2 (B) X-Ray Diffraction pattern of BaZrO3

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Figure 2

FT-IR spectra of pure ZrO2 and BaZrO3

Figure 3
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Pure ZrO2 and BaZrO3 EDAX spectrum

Figure 4

(a-c)SEM images of pure ZrO2,(d-f)SEM images of BaZrO3

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Figure 5

UV absorption spectra of (A) ZrO2& (B) BaZrO3

Figure 6
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photoluminescence spectrum of ZrO2 and BaZrO3

Figure 7

(A) Dielectric constant with frequency of ZrO2, (B) Dielectric constant with frequency of BaZrO2(C)
Dielectric loss with frequency of ZrO2(D) Dielectric loss with frequency of BaZrO3

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Figure 8

(A) Z" (Impedance) with frequency of ZrO2(B) Z" (Impedance) with frequency of BaZrO3

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