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SYNOPSIS OF

STRUCTURAL, MI CROSTRUCTURAL, SPECTROSCOPI C,


MI CROWAVE DI ELECTRI C AND MICROWAVE SI NTERI NG
STUDI ES ON SOME PEROVSKI TE AND I LMENI TE BASED
DI ELECTRI C RESONATORS

A THESIS
to be submitted by
ROOPAS KIRAN SIRUGUDU
for the award of the degree
of

DOCTOR OF PHILOSOPHY



DEPARTMENT OF PHYSICS
INDIN INSTITUTE OF TECHNOLOGY MADRAS
OCTOBER 2011
1

1. INTRODUCTION
Dielectric resonators (DRs) are ceramic materials with high dielectric constant (c
r
>
20), high quality factor (Q >3000 at 10 GHz) and low temperature coefficient of resonant
frequency (t
f
< 10 ppm/
o
C). Application of these dielectric materials in various microwave
components as filters and oscillators shows considerable miniaturization of the
communication devices. The developments in these microwave devices probe the synthesis of
new dielectric resonator materials and invention of new synthesis routes to enhance the
dielectric properties. In contrast, analysis of correlation between the structural parameters
with dielectric properties helps in tailoring the materials for desired applications. Rare earth
based complex perovskites [Ln
2
(B'B)O
6
] receive a lot of attention due to easy attainability
of 1:1 B-site cation ordering and cost effective with the absence of expensive tantalum. The
well studied La(Mg
0.5
Ti
0.5
)O
3
is known to possess high
r
(~28), Q factor (Qxf=114000 GHz)
and higher negative
f
(-81ppm/
o
C) (Seabra et al., 2003a). This negative
f
can be reduced by
the addition of high positive
f
compounds such as CaTiO
3
and SrTiO
3
in a suitable
proportion (Seabra et al., 2003; Avdeev et al., 2002). However, this addition reduces the Q
factor due to disappearance of 1:1 B site cation ordering (Cho et al., 1998). Replacement of
Lanthanum with Neodymium and Samariumwas found to improve
f
without change in
ordering (Cho et al., 1999).
Low temperature co-fired ceramics (LTCC) are the recent advancement in the
technological development for miniaturizing the microwave devices, in which the low
melting point metals such as silver and copper are embedded in ceramic tapes as electrodes
and co-fired. Hence, this ceramic material should possess low dielectric loss and low
sintering temperature (<950
o
C). The dielectric resonators, being the materials with low
dielectric loss, are found to be suitable for LTCC applications. However, the constraint on the
sintering temperature imposes the limitation in selection of dielectric resonators for LTCC
application. Zinc magnesium titanate based materials are well known for their suitability in
the application of dielectric resonators and as LTCC substrates (Kim et al., 1999; Hsieh et al.,
2005). Their sintering temperature can be lowered by addition of sintering aids (Hsieh et al.,
2008).
In order to lower the sintering temperature, microwave sintering of dielectric and
magnetic materials is receiving significant attention by researchers for the last two decades.
The penetration of microwaves into the materials and direct interaction with dipoles causes
uniform and volumetric heat generation inside the material. In addition, this direct interaction
2

reduces the sintering temperature and duration. However, the heat generation predominantly
depends on the dielectric, magnetic and conduction loss of the material. Hence, it is easy to
sinter the materials with high dielectric and magnetic loss. Addition of sintering aids to DRs
can increase the dielectric loss and hence further reduction in sintering temperature can be
achieved with microwave sintering. In contrast, ferrites possess both dielectric and magnetic
loss without addition of any sintering aids itself and hence they are relatively easier to sinter
using microwaves. Various ferrites such as NiZn, MnZn, NiCuZn ferrites are reported to
show enhancement in the magnetic properties with microwave sintering (Tsay et al., 2000;
Penchal Reddy et al., 2011). Ferroelectric materials possess medium dielectric loss.
Microwave sintering of ferroelectrics such as (Ba,Sr)TiO
3
, PZT, NBT also showed increase
in dielectric constant and piezoelectric coefficient over conventional sintered samples
(Thakur et al., 2002; Ramana et al., 2011(a); 2011(b)). But only a few reports are found on
sintering low dielectric loss materials such as dielectric resonators. Sintering dielectric
resonators using microwaves is difficult task due to non-polar nature of the materials.
Vaidhyanathan et al. obtained high dense samples of Ba(Mg
1/3
Ta
2/3
)O
3
using microwave
sintering (Vaidhyanathan et al., 2000) by considering the non-stoichiometric Ta
2
O
5-x
, which
facilitates the increase in dielectric loss with temperature. The use of silicon carbide based
susceptors also increases the dielectric loss of the material with temperature

2. OBJ ECTIVES AND SCOPE OF THE WORK
The aim of the present work is to (i) obtain the correlation between the intrinsic and structural
characteristics with microwave dielectric properties of Nd
1-x
Sm
x
(Mg
0.5
Ti
0.5
)O
3
(ii)
understand the phase formation in ZnOTiO
2
system and to synthesize (Zn,Mg)TiO
3

composition for LTCC application (iii) microwave sinter the (Zn,Mg)TiO
3
dielectric
resonators.
In order to achieve these, Nd
1-x
Sm
x
(Mg
0.5
Ti
0.5
)O
3
samples were prepared by solid state
reaction method. Rietveld refinement of the XRD data was done to obtain the B-site cation
ordering (LRO). The A
1g
mode in Raman spectra was fitted to Briet-Wigner-Fano line shape.
ZnO-TiO
2
system with variation in particle size and nature of TiO
2
(anatase and
rutile) was studied to understand the phase formation. (Zn,Mg)TiO
3
samples were ball milled
to understand the effect of Mg substitution and grain size. Ball milled Zn
0.7
Mg
0.3
TiO
3

composition was sintered to achieve the variation in grain size. Single phase (Zn,Mg)TiO
3

compositions were prepared to optimize the composition for LTCC application and finally
various sintering aids were added to reduce the sintering temperature.
3

Single-mode microwave furnace was developed to understand the microwave heating
behavior in materials with different dielectric losses. (Zn,Mg)TiO
3
composition was sintered
in the multimode microwave furnace and compared with conventional sintering.

3. DESCRIPTION OF RESEARCH WORK
3.1 Rare-earth based Dielectric Resonators
Lanthanide based dielectric resonators Ln(B
0.5
B'
0.5
)O
3
(Ln: Nd, Sm; B: Zn, Mg; B':
Ti; Sn) samples were prepared by the conventional solid state reaction method. Calcination
was done in the range of 11501250
o
C. Optimized sintering temperatures of these
compounds exist in the range of 14001600
o
C. Dielectric constant (
r
) was measured by
Hakki-Coleman method (Hakki and Coleman, 1960) and Quality factor (Qf) was obtained
by reflection technique. The temperature coefficient of resonant frequency (
f
) was measured
in the temperature range of 30 70
o
C using an invar cavity. Powder XRD of all the samples
was obtained using PANalytical Xpert Pro. Rietveld refinement Nd
1-x
Sm
x
(Mg
0.5
Ti
0.5
)O
3

(NSMT) was performed to obtain the long range ordering (LRO) in B-site cations. Room
temperature Raman spectra of NSMT samples were obtained using Horiba Jobin Yvon HR
800UV Raman spectrometer (=632.8 nm, 3 mW power at sample) and temperature variation
Raman spectra of Sm(Mg
0.5
Ti
0.5
)O
3
(SMT) was recorded in the range of -196
o
C to 27
o
C using
a custom built Raman spectrometer (=514 nm, 8 mW power at sample). Scanning Electron
Micrographs (SEM) of thermal etched samples are observed by Quanta 200F.
XRD of Ln(B,B')O
3
(Ln: Nd, Sm; B: Zn, Mg; B': Ti; Sn) samples sintered at optimum
temperatures were shown in figure 1.

Figure 1. XRD of (a) Ln(B
0.5
Ti
0.5
)O
3
(b) Ln(B
0.5
Sn
0.5
)O
3
; Ln: Lanthanide (N: Nd; S: Sm), B:
B-site ion (Z: Zn; M: Mg). (Molecular formula represents the nominal composition)
All the titanate based compositions showed perovskite structure, whereas tin based
compositions (figure 1(b)) showed only pyrochlore (Ln
2
Sn
2
O
7
) nature with an exception for
Nd(Mg
0.5
Sn
0.5
)O
3
. This difference in the phase formation for titanium and tin based
(a) (b)
4

compositions can be discussed in terms of tolerance factor, t and electronegativity difference
between A, B site ions and oxygen as follows.
The tolerance factor for a complex perovskite A(B'
0.5
,B"
0.5
)O
3
was defined as
( )
A O
B' B" O
R R
2 0.5R 0.5R R
t
+
=
( + +

,
where R
A
, R
B'
, R
B"
and R
O
are ionic radii of A, B', B" and O ions respectively.
The tolerance factor and the sum of electronegativity differences [(X
A-O
+X
B-O
)/2] of the all
the samples for nominal composition are given in Table 1.
Table 1. Tolerance factor and Sum of electronegativity differences of Ln(B,B')O
3
;
(Ln: Nd, Sm; B: Zn, Mg; B': Ti, Sn)
Compound t (X
A-O
+X
B-O
)/2

Compound t (X
A-O
+X
B-O
)/2
Nd(Mg
0.5
Ti
0.5
)O
3
0.915 2.1575 Nd(Mg
0.5
Sn
0.5
)O
3
0.897 2.0525
Sm(Mg
0.5
Ti
0.5
)O
3
0.905 2.1425 Sm(Mg
0.5
Sn
0.5
)O
3
0.887 2.0375
Nd(Zn
0.5
Ti
0.5
)O
3
0.911 2.0725 Nd(Zn
0.5
Sn
0.5
)O
3
0.893 1.9675
Sm(Zm
0.5
Ti
0.5
)O
3
0.901 2.0575 Sm(Zn
0.5
Sn
0.5
)O
3
0.883 1.9525

The calculated tolerance factor values of all the samples are found to be in the range
corresponding to perovskites (0.81.09). However, it can be observed from the table 1 and
figure 1 that all the compounds with sum of electronegativity values higher than 2 possess
perovskite structure. Although SMS (Sm(Mg
0.5
Sn
0.5
)O
3
) possesses the sum of
electronegativity higher than 2, its lower tolerance factor value may be attributed to
pyrochlore (Sm
2
Sn
2
O
7
) formation after sintering. The microwave dielectric characteristics of
all the titanate based perovskite samples are given in table 2. These microwave dielectric
characteristics can be correlated with intrinsic characteristics such as polarizability, B-site
cation ordering and octahedral tilting. Nd(Mg
0.5
Ti
0.5
)O
3
(NMT) and Sm(Mg
0.5
Ti
0.5
)O
3
are
selected for this purpose due to their higher quality factor.
Table 2. Microwave dielectric characteristics of Ln(B
0.5
Ti
0.5
)O
3
[Ln: Lanthanide (N: Nd,
S:Sm); B: B-site ion (M: Mg, Z: Zn), T: Ti]
Compound
Density
(g/cm
-3
)

r

Qf
(GHz)

f

(ppm/
o
C)
Nd(Mg
0.5
Ti
0.5
)O
3
6.22 26.5 47500 -48
Sm(Mg
0.5
Ti
0.5
)O
3
6.46 24.9 44600 -26
Nd(Zn
0.5
Ti
0.5
)O
3
6.58 30.5 23500 -35
Sm(Zm
0.5
Ti
0.5
)O
3
7.04 30.0 16000 -23
All the composition, Nd
1-x
Sm
x
(Mg
0.5
Ti
0.5
)O
3
(x =0, 0.25, 0.5, 0.75 and 1) (NSMT) were
prepared under same experimental conditions and characterized. The microwave dielectric
characteristics of the NSMT compositions are given in table 3.
5

Table 3. Relative density and microwave dielectric characteristics of Nd
1-x
Sm
x
(Mg
0.5
Ti
0.5
)O
3

Composition,
x
Rel.
Density (%)

r

Qf
(GHz)

f

(ppm/
o
C)
0 97.4 26.5 47500 -48
0.25 96.7 25.7 41700 -42
0.5 96.7 25.3 39800 -35
0.75 97.0 25.3 42200 -31
1 97.1 24.9 44600 -26
The polarizability of Sm (o
Sm
=4.74
3
) is less than that of Nd (o
Nd
=5.01
3
) and
hence the dielectric constant of NSMT is found to decrease with Sm substitution. The quality
factor of NSMT compositions showed a non-monotonic variation. The variation in Qxf is
correlated with the 1:1 B-site cation ordering (LRO), which is obtained by Rietveld
refinement of XRD data. XRD of NSMT samples are given in figure 2.

Figure. 2. XRD of Nd
1-x
Sm
x
(Mg
0.5
Ti
0.5
)O
3
Figure 3. Rietveld refined plot of SMT (x=1)

Presence of (111) reflection in all the compositions indicates 1:1 B-site cation ordering.
Refinement procedure confirmed P2
1
/n symmetry with goodness of fit (_
2
) near to 1.3 and
Rietveld discrepancy parameters R
F
2
and R
wp
are about 8% and 3% respectively. The refined
plot corresponding to SMT is shown in figure 4 and corresponding fractional atomic
coordinates, occupancy and thermal parameters are listed in table 4.
Table 4. Fractional atomic coordinates, occupancy and thermal parameters of SMT
Site x y z Occupancy U
iso.
(
2
)
Sm 4(e) 0.4874(5) 0.5540(1) 0.250(1) 1 0.0046(3)
Mg 2(c) 0 0.5 0 0.93(4) 0.003(1)
Mg 2(d) 0.5 0 0 0.07(4) 0.003(1)
Ti 2(d) 0.5 0 0 0.93(4) 0.003(1)
Ti 2(c) 0 0.5 0 0.07(4) 0.003(1)
O 4(e) 0.298(5) 0.285(6) 0.039(6) 1 0.001
O 4(e) 0.212(6) 0.807(5) 0.053(5) 1 0.001
O 4(e) 0.600(1) -0.032(1) 0.230(3) 1 0.001
6

The LRO is calculated using LRO =[2(Occupancy)
B
1]100. The calculated LRO
values also showed non-monotonic variation similar to that of Qf. The variation in LRO is
again confirmed with Raman spectra of the NSMT compositions. Raman spectra of these
microwave dielectrics with P2
1
/n space group showed four high intensity modes
(A
1g
+E
g
+2F
2g
). Among these modes, the FWHM of A
1g
mode which is due to the symmetric
stretching of oxygen octahedra occurs at higher wavenumber and represents the details about
the LRO. The A
1g
mode will be more sharp (low FWHM) for samples with higher LRO.
Hence, further analysis was done only on this mode. Raman spectra of NSMT compositions
are shown in figure 5.

Figure 5. Room temperature Raman spectra Figure 6. Temperature variation Raman
of Nd
1-x
Sm
x
(Mg
0.5
Ti
0.5
)O
3
spectra of Sm(Mg
0.5
Ti
0.5
)O
3

The A
1g
mode (at 710cm
-1
) of these compositions are found to possess asymmetric
nature at higher wavenumber side and hence the fitting the mode with a single Lorentzian
peak is not satisfactory. In the present study, the A
1g
mode is assumed to possess Briet-
Wigner-Fano (BWF) peak shape, which is given by
( )
( )
( )
2
0
0 2
0
2
2 1
1
2
1
q
I I
ee (
+
(
I

e =
ee
+
I

where I
0
is a normalization factor for the scattering intensity,
0
is the resonant frequency
corresponding to intensity I, is a measure of the line width and q
-1
is the BWF coupling
coefficient. Further, to ascertain BWF line shape in NSMT, low temperature Raman spectra
up to -196
o
C were performed on SMT. It is well known that low temperature data reduces
thermal broadening resulting in a well resolved Raman spectrum. Figure 6 shows temperature
evolution of Raman modes in the range of 425 to 775 cm
-1
for SMT. The A
1g
mode of SMT
does not show any splitting down to liquid nitrogen temperatures whereas mode at 475 cm
-1

gets resolved up on decreasing the temperature. This reconfirms the need to use a BWF line
7

shape for A
1g
mode of NSMT materials. Figure 7 represents the BWF fit for A
1g
mode of
SMT and the FWHM () of all the NSMT compositions are shown in figure 8 along with
LRO values obtained by Rietveld refinement.

Figure 7. Fit of A
1g
mode to BWF equation Figure 8. LRO and FWHM () of A
1g

corresponding to Sm(Mg
0.5
Ti
0.5
)O
3
mode of Nd
1-x
Sm
x
(Mg
0.5
Ti
0.5
)O
3

The
f
obtained for NMT is -48 ppm/
o
C perovskites and it becomes less negative with
increase in Sm concentration with -26 ppm/
o
C for SMT. In general, the
f
variation is
attributed to the octahedral tilting which increases with decrease in tolerance factor.
However, the measured values of
f
of NSMT in the present study are not in accordance with
octahedral tilting and found to increase with decrease tolerance factor. The similar increase of

f
was observed in the systemof La(Mg
0.5
Ti
0.5
)O
3
Nd(Mg
0.5
Ti
0.5
)O
3
[Seabra et al., 2003b]

3.2 Studies on (Zn,Mg)TiO
3
for LTCC applications
High pure ( 99.9%) ZnO, MgO and TiO
2
(-325 mesh) were used in the present work.
The following experiments were performed in order to observe the dependency of phase
formation in ZnOTiO
2
system on particle size and nature of TiO
2
. ZnO was mixed with a-
TiO
2
(anatase, A) and r-TiO
2
(rutile, R) using agate mortar on one side and high-energy ball
milled on another side. Fritsch P5 Planetary mill with WC jar and balls was used for milling.
Dry milling with ball to powder weight ratio10:1was done for 10 h at a milling speed of
300rpm. Homogeneous mixtures of all the powders were calcined in the temperature range of
700-900
o
C for 4 h. The same processing conditions with which ZnTiO
3
single phase was
observed in ZnOTiO
2
system were employed in the synthesis of Zn
1-x
Mg
x
TiO
3
(x=00.5).
However, the calcined powders were again ball milled for 15 h in this case and then sintered
at different temperatures in the range 10001200
o
C for 2 h. In order to observe the effect of
this ball milling on microwave dielectric properties, all the compositions were prepared with
hand mixing method also. Zn
0.7
Mg
0.3
TiO
3
(x=0.3) is observed to be the optimum composition
8

for further research work and hence the effect of grain size on the microwave dielectric
characteristics of this composition was found in detail by sintering at 1100
o
C for different
durations such as 2, 4, 6, 8, 10 and 20h. Single phase Zn
1-x
Mg
x
TiO
3
(x=0.21) were obtained
by the addition of stoichiometrically excess MgO (4 mol%) to the mixture of the ingredients
and calcination at temperatures in the range of 8501050
o
C for 6 h. The excess MgO was
cleaned by washing with dilute nitric acid. These optimized sintering temperatures of these
compositions in the range of 11001400
o
C were obtained with respect to their quality factor
(Qxf). Various sintering aids such as B
2
O
3
, Bi
2
O
3
, 70ZnO-30B
2
O
3
and V
2
O
5
were used to
reduce the sintering temperature of Zn
0.7
Mg
0.3
TiO
3
down to 900
o
C.
Phase evolution in the ZnOTiO
2
system with variation in particle size (hand mixing
and ball milling) and nature of TiO
2
(anatase and rutile) were given in table 5.
Table 5. Phases evolution in ZnOTiO
2
with variation in particle size and nature of TiO
2

Mixing condition Zn
2
Ti
3
O
8
ZnTiO
3
Zn
2
TiO
4

Micron
Anatase
Rutile
Ball
milling
Anatase
Rutile
All the three phases of ZnOTiO
2
system are observed in compositions synthesized
by hand mixing. The inhomogeneity in the hand mixed powder can cause the formation of
Zn
2
Ti
3
O
8
. This creates the non-stoichiometry (low Ti content) in the mixture and hence
probes the formation of Zn
2
TiO
4
. However, ball milling of ZnOanatase mixture possesses
much higher homogeneity and hence single phase ZnTiO
3
is observed. On the other side,
XRD of hand mixed ZnO-rutile powder showed the presence of Zn
2
TiO
4
along rutile.
However, this rutile after calcination is only due to the dissociation of ZnTiO
3
formed by the
reaction of ZnO with initially considered rutile, which can be inferred from the XRD of
calcined ball milled ZnOrutile mixture and heat treatment of ball milled anatase powder at
600
o
C. Hence, the single phase ZnTiO
3
formation takes place with availability of rutile
during the reaction.
Figure 9(a) and (b) represent the XRD of micron Zn
1-x
Mg
x
TiO
3
samples sintered at
1100
o
C for 4 h for hand mixing (micron) and ball milling (bm) cases respectively. It can be
observed that Mg substitution increases the dissociation temperature in both the cases.
However, it can be seen from these figures that the extent of dissociation could not be
affected by ball milling. The compositions corresponding to x =0 and 0.1 are found to
dissociate completely in to (Zn,Mg)
2
TiO
4
and rutile, whereas x =0. 2 showed only a minimal
dissociation. All the other compositions (x 0.3) are found to possess single phase nature
9

((Zn,Mg)TiO
3
). Dielectric constant and Qxf of all the samples are shown in figure 10 (a) and
(b) respectively for both micron and ball milling cases.

Figure 9. XRD of (a) micron and (b) ball milled compositions of Zn
1-x
Mg
x
TiO
3
(x =0 0.5)
after sintering at 1100
o
C (*: (Zn,Mg)TiO
3
; +: (Zn,Mg)
2
TiO
4
; R: rutile).


Figure 10 (a). Dielectric constant and (b) Quality factor (Qxf) of micron and ball
milled compositions of Zn
1-x
Mg
x
TiO
3
(x =00.5) after sintering at 1100
o
C /4h

The compositions corresponding to x =0 and 0.1 possess high dielectric constant due to the
presence of high dielectric constant rutile phase. The decrease in dielectric constant in other
compositions (x 0.2) is due to the low polarizability of Mg. The quality factor (Qxf) values
are observed to increase with Mg substitution. It can be observed that the compositions x =0
and 0.1 possess lower quality factor values due to the presence of (Zn,Mg)
2
TiO
4
whose
quality factor is much low in comparison with (Zn,Mg)TiO
3
compounds. However, the ball
milled samples showed relatively low quality factor, although their dielectric constant is
almost equal to those of micron samples. This is assumed to be due to the lower grain size in
due to ball milling prior to sintering. The effect of grain size on Qxf is confirmed by sintering
the higher quality factor composition (x =0.3) for different durations. Table 6 represents the
variation in dielectric constant and Qxf with average grain size of Zn
0.7
Mg
0.3
TiO
3
obtained
from SEM images of samples sintered at 1100
o
C for 2, 4, 6, 8, 10 and 20 h.

(b)
(b) bm
(a)
10

Table 6. Variation in dielectric constant and Qxf of Zn
0.7
Mg
0.3
TiO
3
with grain size.
Sintering
duration (h)
Avg. grain
size (m)
Dielectric
constant
Qxf
(GHz)
2 6.7 20.0 32400
4 9.6 20.5 65500
6 11.8 20.6 69000
8 16.6 20.7 78200
10 17.8 20.8 83000
20 19.0 20.9 85600
A remarkable change in the quality factor (Qxf) is observed with sintering duration. The
samples sintered for 2 h shows much less quality factor (32400 GHz) and the rise in sintering
duration to 4 h shows a sudden hike to 65500 GHz and further increase in sintering duration
showed a slow increase up to 85600 GHz with 20 h. The high impact of the balls, during
milling, can produce the defects in the Zn
0.7
Mg
0.3
TiO
3
structure. Heating the ball milled
samples for longer duration reduces the defects in the structure and hence the quality factor is
found to increase rapidly with sintering for 4 h. The increase in grain size with further
increase in sintering duration reduce the grain boundary, which contribute to the additional
loss, and hence increase in quality factor was observed.
The chemical reaction between MgO and TiO
2
indicates that the presence of excess
MgO in the initial mixture avoid the MgTi
2
O
5
phase formation and increase the stability of
(Zn,Mg)TiO
3
phase. XRD of single phase Zn
1-x
Mg
x
TiO
3
compositions obtained by using
excess MgO are shown in figure 11. The dielectric constant and Qxf values of the samples
prepared by using excess MgO are shown in figure 12.

Figure 11. XRD of Zn
1-x
Mg
x
TiO
3
(x=0.21) Figure 12. Dielectric constant and Qxf of
single phase (Zn
1-x
Mg
x
)TiO
3
(x =0.2 1)
It can be observed from figure 12 that the composition x =0.3 possesses higher quality factor
with relatively low sintering temperature. Hence, the effect of various sintering aids such as
B
2
O
3
, Bi
2
O
3
, 70ZnO-30B
2
O
3
and V
2
O
5
was observed by addition 1 mol% of each sintering
11

aid to the single phase Zn
0.7
Mg
0.3
TiO
3
powder and sintering at 900
o
C for 4 h. It is found that
the addition of V
2
O
5
enhanced the shrinkage in the sintered sample among all the sintering
aids. It is also observed that the addition of these sintering aids reduced the quality factor
almost equally (down to 20000 GHz) and hence V
2
O
5
can be used as the suitable sintering aid
for LTCC application.

3.3 Studies on Microwave sintering of Dielectric Resonators
In order to sinter the dielectric resonators, both single-mode and multimode
microwave furnaces were developed. The single-mode microwave consists of 2-port isolator,
3-stub tuner, WR340 waveguide applicator and a precision sliding short obtained from
Gerling Applied Engineering, USA. 2-port isolator was used to protect the source of
microwave (magnetron, 2.45 GHz, 1900 watt) from the reflected waves. 3-stub tuner was
used for impedance matching of the load. The precision sliding short was used to adjust the
antinode position of the standing wave pattern to the sample. The temperature of the sample
was measured by using an IR sensor (Raytek) positioned vertically above the sample. Figure
13 is the photograph of the single-mode microwave furnace used in the present work. The
input power to the magnetron was controlled by the power controller supplied by Enerzi
Microwave Systems Ltd., Bangalore. The water chiller provides the water load to the 2-port
isolator and necessary cooling for the desired components in the system.

Figure 13. Photograph of Single-mode microwave furnace Figure 14. Photograph of
multimode microwave furnace
The photograph of the multimode microwave furnace is shown in figure 14. The
multimode microwave furnace is the microwave oven with a controlled input power to
achieve the set temperature with a desired rate of increase in temperature and was supplied by
12

VB Ceramic Consultants, Chennai. In contrast to the normal microwave oven, the maximum
input power of magnetron source in the present case was 1100 watt. The temperature of the
sample was measured by an R-type thermocouple. Since the energy density of the
microwaves is less in case of multimode furnace, the susceptor configuration was used and
developed in the present work for optimum sintering of samples. Silicon carbide blocks were
used as susceptors in the present work. These susceptors provide additional heating zone
around the sample and hence uniform shrinkage in the sample can be observed. The square
blocks of SiC with a side of 2.5 cm were prepared by compaction of powder and sintering at
1200
o
C for 2 h. A porous alumina block was modified to provide sufficient room for these
silicon carbide (SiC) blocks. This configuration is again immersed in the thermal insulating
box made up of a card board mixed with Al
2
O
3
, SiO
2
and ZrO
2
.
The single-mode microwave furnace is used to study the nature of direct heating in
samples with different dielectric loss such as nickel zinc (NiZn) ferrite, composites (NiZn
ferrite + BaTiO
3
) and dielectric resonators (Zn
0.7
Mg
0.3
TiO
3
). In the present work it is
observed that both the ferrite and composite samples showed heat generation within 5
minutes due to the interaction of dipoles of the samples with microwaves of an input power
of 300 and 430 watt respectively. However, ferroelectric BaTiO
3
could not show any heat
generation even at an input power of 700 watt maintained for 30 minutes. In contrast, the low
dielectric loss samples (dielectric resonators) showed a sudden discharge with an input power
of 300 watt. Figure 15 includes the photographs of these observations.

Figure 15. Photographs of ferrite, composite and dielectric resonator samples in single-mode
microwave furnace.
Although the ferrites samples showed to generate heat energy, the thermal gradient
between sample and surroundings caused non-uniform heating and hence the samples showed
significant cracks after the heat treatment. So, it can be inferred that the provision of
susceptors is needed to obtain the uniform sintering. The single phase Zn
0.7
Mg
0.3
TiO
3
and
MgTiO
3
powders obtained by using excess MgO (described in section 3.2), were sintered in
the multimode furnace at respective optimum sintering temperature (observed with
conventional sintering) for shorter sintering durations. The dielectric constant of these
13

microwave sintered dielectric resonators are much close to those obtained with conventional
sintering. However, the Qxf values are found to be considerably low. The reason for this
reduction of quality factor is again correlated with the grain size variation as described in the
section 3.2. The microstructure of Zn
0.7
Mg
0.3
TiO
3
samples sintered by conventional sintering
at 1150
o
C for 4 h and microwave sintering at 1150
o
C for 30 minutes are shown in figure 16.

Figure 16. SEM of conventional (CS) and microwave (MS) sintered Zn
0.7
Mg
0.3
TiO
3
.
The conventional sintered Zn
0.7
Mg
0.3
TiO
3
sample possesses the quality factor (Qxf) of
109000 GHz. In contrast, the microwave sintering samples showed only 93000 GHz. The
variation in grain size of MgTiO
3
with conventional and microwave sintering are shown in
figure 17. Conventional sintering was done at 1400
o
C for 4 h and microwave sintering at
1400
o
C for 30 minutes. In this case, the quality factor is found to reduce significantly with
microwave sintering. The Qxf value of conventional sintered MgTiO
3
is 165000 GHz
whereas it is 98000GHz for microwave sintered sample.

Figure 17. SEM of conventional (CS) and microwave (MS) sintered MgTiO
3
.

4 CONCLUSIONS
Nd
1-x
Sm
x
(Mg
0.5
Ti
0.5
)O
3
(x=0, 0.25, 0.5, 0.75 and 1) (NSMT) solid solutions exhibit
monoclinic P2
1
/n symmetry and are observed to possess 1:1 B-site cation ordering. The long
range ordering (LRO) of the system showed a non-monotonic variation with increase in Sm
14

concentration. The variation in quality factor (Qxf) is analogous to that of LRO. The
asymmetric A
1g
mode in the Raman spectra of all these compositions is found to possess
BWF line shape and is confirmed with temperature variation Raman spectra of SMT.
ZnTiO
3
phase formation depends on the availability of rutile during the reaction.
Zn
2
Ti
3
O
8
phase occurs in presence of anatase (micron). Both ZnTiO
3
and Zn
2
Ti
3
O
8
phases
dissociate in to Zn
2
TiO
4
and rutile at 950
o
C. However, the dissociation occurs below 950
o
C
with rutile ingredient. The dissociation temperature of ZnTiO
3
increased with Mg
substitution. Qxf of (Zn
1-x
Mg
x
)TiO
3
(x=0, 0.1, 0.2, 0.3, 0.4 and 0.5) samples increased with
increase in Mg concentration. However, ball milling of (Zn
1-x
Mg
x
)TiO
3
samples found to
lower the Qxf values. The lower Qxf values with ball milling are attributed to the lower grain
size. The effect of various sintering aids revealed that V
2
O
5
addition showed higher shrinkage
and better microwave dielectric characteristics.
Single-mode microwave sintering studies on materials with different dielectric loss
showed that high loss samples such as ferrite and composites can generate internal heat due
to the interaction of dipoles with microwaves. However, the heat generation cannot be
achieved in dielectric resonators without susceptor configuration. Multimode microwave
sintered Zn
0.7
Mg
0.3
TiO
3
and MgTiO
3
samples possess low Qxf values with respect to
conventional sintered samples due to the presence of smaller grains.

REFERENCES
Avdeev A., Seabra M.P. and Ferreira M. (2002), Structure evolution in the
La(MgTi)
0.5
O
3
-SrTiO
3
system, Mater. Res. Bull., 37, 1459-1468.
Cho S.Y., Kim I.T. and Hong K.S. (1998), Crystal structure and microwave dielectric
properties of (1-x)La(Zn
1/2
Ti
1/2
)O
3
-xSrTiO
3
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Cho S.Y., Kim C.H., Kim D.W., Hong K.S. and Kim J .H. (1999), Dielectric properties of
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Ti
1/2
)O
3
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c
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(2005), Low-temperature sintering of microwave dielectrics (Zn,Mg)TiO
3
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Phys., 44, 5045-5048.
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Hsieh M.L., Chen L.S., Hsu H.C., Wang S., Houng M.P. and Fu S.L. (2008), Effect of
oxide additives on the low-temperature sintering of dielectric (Zn,Mg)TiO
3
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Bull., 43, 3122-3129.
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3
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Kumar K.V., Murthy V.R.K. and Ramakrishna Reddy R. (2011), Microwave sintering of
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V.R.K. and Murty B.S. (2011a), Investigation and characterization of PZT nanocrystalline
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V.R.K. and Murty B.S. (2011b), Synthesis of lead free sodium bismuth titanate (NBT)
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Seabra M.P., Avdeev M., Ferreira V.M., Pullar R.C. and Alford N.McN. (2003a),
Structure and microwave dielectric propertiesof La(Mg
0.5
Ti
0.5
)O
3
-CaTiO
3
system, J . Eur.
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Seabra M.P., Salak A.N., Avdeev M., Ferreira (2003b), Structure and dielectric
characterization of the La(Mg
1/2
Ti
1/2
)O
3
-Nd(Mg
1/2
Ti
1/2
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3
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Ba
0.95
Sr
0.05
TiO
3
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PROPOSED CONTENTS OF THE THESIS
Chapter 1. Introduction
Chapter 2. Structural and Spectroscopic studies on Nd
1-x
Sm
x
(Mg
0.5
Ti
0.5
)O
3

Chapter 3. Phase formation and Microstructural studies on Zn
1-x
Mg
x
TiO
3

Chapter 4. Microwave sintering studies on Zn
0.7
Mg
0.3
TiO
3
and MgTiO
3
dielectric resonators
Chapter 5. Summary and Conclusions

16

LIST OF PUBLICATIONS BASED ON THE RESEARCH WORK
Publications in Refereed J ournals
1. S. Roopas Kiran, G. Anisha, V.R.K. Murthy, V. Subramanian and B.S. Murty (2011)
Effect on the grain size of single-mode microwave sintered NiCuZn ferrite and zinc
titanate dielectric resonator ceramics, J . Microw Power Electromagn Energy, 45,
128-136.
2. S. Roopas Kiran, G. Sreenivasulu, V.R.K. Murthy, V. Subramanian and B.S. Murty
Effect of grain size on microwave dielectric characteristics of high-energy ball
milled zinc magnesium titanate ceramics J . Am. Cer. Soc. (under revision).
3. S. Roopas Kiran, G. Santosh Babu, Chandrabhas Narayana, V.R.K. Murthy, V.
Subramanian, Correlation of Long range B-site cation ordering, Briet-Wigner-Fano
line shape of A
1g
-like Raman mode and microwave dielectric characteristics of
monoclinic Nd
1-x
Sm
x
(Mg
0.5
Ti
0.5
)O
3
, communicated to J . Phys.: Condens. Matter.
Presentations in Conferences
1. S. Roopas Kiran, V.R.K. Murthy and V. Subramanian, Microwave sintering of some
simple perovskites, National Conference on Ferroics, CVR College of Engineering,
Hyderabad, 30
th
June 1
st
July 2006.
2. S. Roopas Kiran, V.R.K. Murthy and V. Subramanian, Studies on microwave
dielectric properties of Sm(Zn
0.5
Ti
0.5
)O
3
with addition of zinc oxide, 14
th
National
Seminar on Ferroelectrics and Dielectrics, IIT Kharagpur, 1821
st
December 2006.
3. S. Roopas Kiran, V.R.K. Murthy and V. Subramanian, Microwave sintering of
ZnOTiO
2
, DAE Symposium on Solid State Physics, Mysore University, Mysore,
2231
st
December 2007.
4. S. Roopas Kiran, V.R.K. Murthy and V. Subramanian, Microwave assisted
processing of Sm(Zn
0.5
Ti
0.5
)O
3
and ZnOTiO
2
dielectric resonators, Progress in
Electromagnetics Research Symposium (PIERS), Cambridge 26
th
July 2008.
5. S. Roopas Kiran, V.R.K. Murthy and V. Subramanian, Particle size dependence on
the formation of zinc titanate, 15
th
National Seminar on Ferroelectrics and
Dielectrics, Thapar University, Punjab, 68
th
November 2008.
6. S. Roopas Kiran, V.R.K. Murthy and V. Subramanian, Effect of microstructure on
microwave dielectric properties of zinc magnesium titanate, 16
th
National Seminar
on Ferroelectrics and Dielectrics, Guru Ghasidas Vishwavidyalaya, Bilaspur, 24
th

December 2010.