ISSN 10628738, Bulletin of the Russian Academy of Sciences. Physics, 2014, Vol. 78, No. 8, pp. 719–722.

© Allerton Press, Inc., 2014.

Original Russian Text © N.I. Kadyrova, Y.G. Zainulin, N.V. Mel’nikova, I.S. Ustinova, I.G. Grigorov, 2014, published in Izvestiya Rossiiskoi Akademii Nauk. Seriya Fizicheskaya,
2014, Vol. 78, No. 8, pp. 946–949.

Effect of Thermobaric Treatment on the Structure

and Properties of CaCu3Ti4O12
N. I. Kadyrovaa, Y. G. Zainulina, N. V. Mel’nikovab, I. S. Ustinovab, and I. G. Grigorova
a
Institute for Solid State Chemistry, Ural Branch, Russian Academy of Sciences, Yekaterinburg, 620219 Russia
b
Ural Federal University, Yekaterinburg, 620083 Russia
email: kadyrova@ihim.uran.ru

Abstract—CaCu3Ti4O12 is prepared by means of solidstate sintering. The effect of thermobaric treatment

(P = 8.0 GPa and T = 1100°C) and partial replacement of titanium by vanadium on the microstructure and
dielectric properties of CaCu3Ti4O12 are investigated.

DOI: 10.3103/S1062873814080140

INTRODUCTION con (а = 5.43075(5) Å) was used as our external stan

There is continuing interest in materials possessing dard. The PDF2 Base of Powder Diffraction Stan
high dielectric permeability. With its cubic crystal lat dards (ICDD, United States, 2009) was used to iden
tice and dielectric constant of 104–105 over a wide tify possible impurity phases. Electronic microscopy and
range of temperatures (100–600 K), CaCu3Ti4O12 Xray microanalysis were performed on a JEOLJSM
stands out among materials with high values of dielec 6390 LA apparatus equipped with a JED2300 acces
tric permeability. The reasons for the great dielectric sory. Our universal analyzer of frequency current, a
polarization in these systems have yet to be established Solartron 1260A impedancemeter/dielectric spec
in full. According to [1], the behavior of the high trometer, was used to measure the electric parameters
dielectric constant is determined by local dipole in a temperature interval of 300–573 K and a range of
moments associated with the displacement of Ti ions frequencies of 0.01 Hz–25 MHz. The electric charac
from the center. Other authors associate it with exter teristics can be measured with an accuracy of 0.1% at
nal factors such as the microstructure of the material one point with respect to a group of computationally
(e.g., grain size) [2, 3], treatment conditions (temper
ature and duration of sintering, rate of cooling, etc.)
[4–6], twin formation [7], and the model of an inter I
nal barrier capacitance layer (IBCL) in which the 12500
ceramics consist of ntype semiconducting grains and
nonconducting grains or area boundaries [8–10].
10000
The aim of this work was to study the effect ther
mobaric treatment and the partial replacement of tita
nium by vanadium have on the microstructure and 7500
dielectric properties of CaCu3Ti4O12.
5000 3
EXPERIMENTAL
Pure CaCu3Ti4O12 was prepared by means of solid 2
2500
state sintering. TiO2, CuO, and CaCO3 were used as
the initial components. The thermobaric treatment of 1
the resulting CaCu3Ti4O12 and the synthesis of 0
CaCu3Ti3.5V0.5O12 were performed in highpressure 15 25 35 45 55 65 75
chambers on a DO137A press. The singlephase 2θ
character of the final products of synthesis was moni
tored via Xray diffraction. The diffractograms were Fig. 1. Diffractograms of samples of CaCu3Ti4 – xVxO12:
obtained on a Shimadzu XDR7000 diffractometer (1) CaCu3Ti4O12 (1040°С, 10 h), (2) CaCu3Ti4O12 after
thermobaric treatment (Р = 8.0 GPa, Т = 1100°С, t =
with CuKα radiation and within 2Θ angles ranging 15 min), and (3) CaCu3Ti3.5V0.5O12 (Р = 8.0 GPa,
from 5° to 80° with steps of 0.03°. Polycrystalline sili Т = 1100°С, t = 15 min).

719
720 KADYROVA et al.

Reε, Imε
Imε
109 T = 503 K

105
Reε

5 μm 101
(a) 20 kV ×3.000 10–5 10–1 103 107 f, Hz

Fig. 3. Frequency profiles of the physical and apparent

parts of the dielectric permittivity of CaCu3Ti4O12 synthe
sized in air. The temperature was 503 K.

holder, was placed into the hightemperature furnace

included in the full option set of the spectrometer
using a twoelectrode connection scheme. The system
for stabilizing the temperature included a digital con
troller and sensors to register the temperature of the
sample, allowing integrated monitoring of the progress
of thermal studies.

(b) 20 kV ×3.000
(c) 20 kV ×3.000
Fig. 2. SEM images of (a) CaCu3Ti4O12, (b) CaCu3Ti4O12
after thermobaric treatment, and (c) CaCu3Ti3.5V0.5O12.
selected points, or with an automated scan of the fre
quency, amplitude, and steady component of the exci
tation signal. A ProboStat cell containing a sample,
fastened inside it with a special hightemperature
5 μm
RESULTS AND DISCUSSION
Perovskitelike CaCu3Ti4 – xVxO12 (х = 0, 0.5) com
pounds with a cubic system (sp. gr. Im3, Z = 2) were
obtained. Data on the composition of the feed, syn
thesis conditions, and phase composition of the
obtained compounds are presented in the table. Dif
fractograms of the samples of CaCu3Ti4 – xVxO12
(х = 0; 0.5) are presented in Fig. 1.
Scanning electron microscopy (SEM) images of
the samples of CaCu3Ti4O12, CaCu3Ti4O12 following
treatment with high pressure (9.0 GPa) and tempera
ture (1100°С), and CaCu3Ti3.5V0.5O12 are presented in
Fig. 2. These images reveal a notable microstructural
difference between these samples. The average grain
size grew after the thermobaric treatment of the
CaCu3Ti4O12 sample, but a reduction in grain size was
5 μm observed after the partial replacement of titanium by
vanadium (х = 0.5).
The effect of a change in microstructural charac
teristics on the electric properties of CaCu3Ti4 – xVxO12
(х = 0; 0.5) compounds was studied. The frequency
profiles of the physical and apparent parts of the
dielectric permittivity of CaCu3Ti4O12 synthesized in
air are presented in Fig. 3. It can be seen from Fig. 4
that the values for the physical and apparent parts of
the dielectric permittivity were higher after ther

BULLETIN OF THE RUSSIAN ACADEMY OF SCIENCES. PHYSICS Vol. 78 No. 8 2014

 EFFECT OF THERMOBARIC TREATMENT ON THE STRUCTURE 721

(a) lnσ [S m–1]

Reε, 103
4 1
5 f = 28 kHz

4 2

3
1
2 2
2

0
300 400 500 T, K
0
(b) 1.5 2.5 3.5
Imε, 103
1000/T, K–1
6 f = 28 kHz 2 Fig. 5. Temperature dependences of the specific electric
conductivity of CaCu3Ti3.5V0.5O12 at electric field fre
quencies of (1) 4 kHz and (2) 250 kHz.
4
treatment, could be due to a change in the parameters
1 of polarization associated with changes in the size and
2 thickness of grain boundaries.

0 CONCLUSIONS
300 400 500 600
T, K
Fig. 4. Temperature dependences of the (a) physical and
(b) apparent parts of dielectric permittivity at an alternat
ing electric field frequency of 28 kHz. (1) CaCu3Ti4O12
and (2) CaCu3Ti4O12 after thermobaric treatment.
mobaric treatment, compared to the initial sample.
The rise in dielectric permittivity observed for the
sample with larger grains that formed during thermal
Our analysis of the behavior of the impedance,
admittance, and loss tangent of CaCu3Ti3.5V0.5O12
within the temperature range of 300–550 K showed
that there were no capacitor elements in the equivalent
circuit simulating the cell with the sample; the prob
lem of determining the relative permittivity for this
material requires further investigation. The tempera
ture dependences of the specific electric conductivity,
which were measured at frequencies free from the dis
persion of electric parameters, are presented in Fig. 5.
The electric conductivity within the investigated range
of temperatures revealed an activation dependence

Conditions for the synthesis and treatment of CaCu3 Ti4 – xVxO12 oxide and the phase composition of the reaction products

Treatment conditions
No. Initial materials Obtained product a, Å
P, GPa T, °C τ

1 TiO2 + CuO + CaCO3 – 1040 10 h CaCu3Ti4O12 7.394

2 CaCu3Ti4O12 8.0 1100 15 min CaCu3Ti4O12 7.396

3 CaCu3Ti4O12 + CaCu3V4O12 8.0 1100 15 min CaCu3 Ti4 – xVxO12 + VO2 7.387
→ CaCu3Ti3.5V0.5O12

4 CaCu3Ti4O12 + CaCu3V4O12 9.0 1100 15 min CaCu3Ti3.5V0.5O12 7.383

→ CaCu3Ti3.5V0.5O12

BULLETIN OF THE RUSSIAN ACADEMY OF SCIENCES. PHYSICS Vol. 78 No. 8 2014

722 KADYROVA et al.
with activation energies of 0.1 eV and 0.34 eV within
the temperature ranges of 300 < Т 400 K and 500 < Т <
550 K, respectively.
ACKNOWLEDGMENTS
This work was supported by the Ural Branch, Rus
sian Academy of Sciences, project no. 12U31013; by
the Russian Foundation for Basic Research, grant
no. 120231607; and by the Aid to Young Scientists
section of Ural Federal University’s development
program.
REFERENCES
1. Ke, S.M., Huang, Y.N., and Fan, H.Q., Appl. Phys.
Lett., 2006, vol. 89, no. 9, p. 182904.
2. Li, T., Chen, Z., Chang, F., Hao, J., and Zhang, J.J.,
Mater. Sci., 2009, vol. 44, pp. 6149–6154.
BULLETIN OF THE RUSSIAN ACADEMY OF SCIENCES. PHYSICS
3. Brize, V., Gruener, G., Wolfman, J., et al., Mater. Sci.
Eng. B, 2006, vol. 129, pp. 135–138.
4. Bender, B.A. and Pan, M.J., Mater. Sci. Eng. B, 2005,
vol. 117, pp. 339–347.
5. Kwon, S. and Cann, D.P., J. Electroceram., 2010,
vol. 24, pp. 231–236.
6. Romero, J.J., Leret, P., Marcos, F.R., et al., J. Eur.
Ceram. Soc., 2010, vol. 30, pp. 737–742.
7. Subramanian, M.A., Li, D., Duan, N., et al., J. Solid
State Chem., 2000, vol. 151, no. 2, pp. 323–325.
8. Sinclair, D.C., Adams, T.B., Morrison, F.D., and
West, A.R., Appl. Phys. Lett., 2002, vol. 80, p. 2153.
9. Liu, L., Fan, H., Fang, P., and Chen, X., Mater. Res.
Bull., 2008, vol. 43, pp. 1800–1807.
10. Fang, T.T. and Liu, C.P., Chem. Mater., 2005, vol. 17,
pp. 5167–5171.
Translated by E. Boltukhina
Vol. 78 No. 8 2014