Russian Physics Journal, Vol. 46, No.

7, 2003

DIELECTRIC PROPERTIES OF LITHIUM-TITANIUM FERRITE

CERAMICS
A. V. Malyshev, V. V. Peshev, and A. M. Pritulov UDC 541.12.012.4

The temperature dependences of the real and imaginary parts of the complex dielectric permittivities of ceramic Li-
Ti ferrospinel are measured within the frequency range 102–106 Hz. The empirical expressions describing these
dependences are derived and the frequency-independent electrophysical parameters of the material under study
are obtained. The best agreement between the experimental and calculation data is achieved when the time
constant and the static dielectric permittivity are decreasing functions of frequency. A model of relaxational
processes accounting for this result is proposed. A certain role in polarization of the relaxation agents, whose
reorientation is controlled by tunneling electron transitions inside the “two-valence iron ion – three-valence metal
ion”, is assumed. It is stated that under certain conditions, the relaxation agent reorientation is likely to possess a
collective character. The temperature dependences ε' and ε" are derived for a number of dc currents at different
electric field strengths. Sharp variations in the dielectric characteristics of the ceramics are found.

The specific σ and complex dielectric ε* permittivities significantly affect propagation of electromagnetic waves in
ferrite and, therefore, control the performance of devices made thereof. To solve a large number of application problems, in
particular, to predict dielectric characteristics σ, the analytical dependences of the real ε' and imaginary ε" components of
the complex dielectric permittivity ε* on frequency f and temperature T should be made available. Currently, there is a large
number of works on the study of electrophysical properties of ferrite ceramics [1–10]. The dependences of σ and ε* on f
and T are commonly interpreted within the framework of Koops’ model (interlayer polarization) [1] and interlayer
polarization with participation of grain-boundary states [2]. One of the major causes for interlayer polarization is the
process of electric charge transfer; hence the latter affects the characteristics of interlayer polarization. It is accepted that the
electric charge transfer occurs either through motion of a charge carrier through the impurity zone [3, 4] or through hopping
of the carriers over the localized energy levels due to electron-photon interaction [5]. The hopping mechanism of the
electric charge transfer in ferrite ceramics is attributed to the presence of two-valence iron ions and the electron transitions
between the ions of a variable valence, such as: Fe2+ + Me3+ → Fe3+ + Me2+ [6]. It was established that the higher the
concentration of Fe2+, the higher the conductivity, and the higher ε'. Starting from this, it is assumed that it is these
transitions that are responsible for both electric charge transfer and polarization [7–9]. This gives one a chance to omit
Koops’ model, since recharging of the ion pairs Fe2+ + Me3+ ↔ Fe3+ + Me2+ does already provide dipole reorientation in a
variable field. Bearing in mind that the pair components are crystal-forming ions, the high value of ε' may be accounted for
by the high pair concentration. Given the fact that that electron transition in these pairs occurs through tunneling electrons
with participation of photons, one might expect the characteristic time to depend not only on temperature but also on
duration of the polarizing field (for a variable field – on its frequency).
It is well known that at high concentration of electrical dipoles, a spontaneous formation of electric domain may
occur. Since the content of Fe2+ varies in a wide range, the dipole concentration may also be different. We suppose that the
electrical field in certain ferrites may induce formation of electric domains resulting from mutual interaction of such dipoles
as Fe2+ + Me3+, Fe3+ + Me2+ oriented along the field. In fact there are a few works [7, 8] demonstrating that ferrite ceramics
exhibits certain segnetoelectric properties.
The present paper deals with the temperature dependences ε'(T) and ε"(T) for the Li–Ti-ferrite, which were derived
for different frequencies and testing signal amplitudes with an aim:

Tomsk Polytechnic University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 48–
53, July, 2003. Original article submitted October 28, 2002; after revision February 18, 2003.

1064-8887/03/4607-0691$25.00 2003 Plenum Publishing Corporation 691

 а 1'
3
10
1
ε′, rel. units

2 6
10 5
b
2 6

ε″, rel. units

4
10 10 7
3 2
10 8
4
0
10
1
TC
10 10
-2

300 400 500 600 300 400 500 600

T, K

Fig. 1. Temperature dependences ε′ (a) and ε″ (b) obtained at полученные с Utest = 56 mV at different
frequencies (f, Hz: 102 – curves 1′, 1, 5; 103 – curves 2, 6; 104 – curves 3, 7; 106 – curves 4, 8) in the course of
heating (curves 1–8) and cooling (curve 1′); symbols – experiment, solid line – calculation.

– to write an expression for Li–Ti-ferrite describing the dependences ε'(Т) and ε"(Т) at different frequencies and
containing frequency-independent electrophysical parameters;
– to identify these parameters using a computer analysis of the experimental dependences ε'(Т) and ε"(Т); and
– to determine a possible mechanism of relaxational polarization.
The objects under investigations were ferrites of the following composition: Li0.649Fe1.598Ti0.5Zn0.2Mn0.051O4 with an
addition of 0.22% Bi2O3, which were synthesized using an industrial ceramic production process and sintered in air at
T = 1280 K for 120 minutes. Upon sintering, the specimens were ground and polished on both sides from an initial
thickness of d = 1 to 0.22 mm. The specimens were shaped as pellets measuring 13 mm in diameter, with silver contacts
deposited onto them in vacuum using thermal vaporization. The measuring contact diameter was 5 mm. The pellets with the
contacts were then subjected to normalizing annealing at T = 570 К for t = 1 hour. The magnetic Curie temperature TC for
this ferrite ceramic material is 575 K. The tests included measurements of capacitance C and conductance G, i.e., the
conductance induced by both the conduction and polarization currents, with the latter being in-phase with the electric field.
The temperature interval of the measurements was 300–600 K. Heating and cooling of the specimens during the runs were
done at a rate of 2 deg/min. The testing signal frequency was f = 100, 103, 104, and 106 Hz. The values of ε' and ε"were
calculated using the well-known formulas ε' = C⋅d/(S⋅ε0), tg δ = G/(ω⋅C), ε" = ε'⋅tg δ, where ε0 is the electrical permittivity
of vacuum and ω is the polarization-field circular frequency.
Figure 1 shows the temperature dependences ε' and ε", measured at the testing signal amplitude Utest = 56 mV. It is
clear from Fig. 1,a that the process of polarization involves at least two stages, and the saturation level (ε'sf) of the value
ε' = F(T) in the low-temperature stage depends on frequency and decreases as the frequency is increased. Further, we will
analyze only the most pronounced low-temperature stage. The absence of relaxational peaks in the dependences ε" = F(T)
(Fig. 1, b) is indicative of the fact that the conduction current by far exceeds the active component of the relaxational
current. The measurements were performed both during cooling and heating. The curves ε" = F(T) coincide both for the
direct and reverse temperature behavior. The dependences ε' = F(T) contains a weak hysteresis at a frequency of 100 Hz,
which decreases as the frequency is increased.
Each of the curves, ε' = F(T) and ε" = F(T), given in Fig. 1 can be well fitted by Debye’s formulas (SGSE system)

ε' = ε∞+(εs – ε∞)/[1 + (ω⋅τ)2] , (1)

ε" = (εs – ε∞)⋅ω⋅τ/[1+(ω⋅τ)2]+4π⋅σa / ω , (2)

692
 TABLE 1. Electrophysical Parameters of Lithium-Titanium Ferrite
Utest, mV Ea, eV A, с1/2 B, с–1/4 Eaσ, eV σ0a, (Ω⋅m)–1 ε∞, rel. units Ud, mV Edσ, eV σ0d, (Ω⋅m)–1
–6
56 0.37 1.77⋅10 5580 0.71 3.26⋅104 20 250 0.67 3.26⋅104
–6 4
2800 0.37 1.71⋅10 5830 0.73 5.93⋅10 20 500 0.67 4.77⋅104
Alternating current, f = 102–106 Hz Direct current

where ε∞ is the dielectric permittivity due to inertia-free polarization processes, εs is the static dielectric permittivity,
τ = τ0⋅exp[Ea /(k⋅T)] is the characteristic relaxational polarization time, Ea is the activation energy of relaxational
polarization, σa = σ0a⋅exp[–Eaσ /(k⋅T)] and Eaσ are the specific conductivity and the activation energy of electric charge
transfer at alternating current, k is Boltzmann’s constant, and τ0 is the pre-exponential factor. The fitting parameters for Ea,
τ0 and εs are, however, different for different frequencies. Therefore, notwithstanding the good agreement between
experimental and calculated dependences, the use of Eqs. (1) and (2) at τ0 and εs = const(f) prevents one from predicting the
values of ε' and ε" for predetermined frequencies and temperatures. We, therefore, introduced a frequency dependence for
τ0 and εs into Eqs. (1) and (2)

τ0 = A⋅ω–0.5, εs = B⋅ω–0.25, (3)

where the power indices have been selected empirically. Curve 3 (Fig. 1, a, 10 kHz) is computer fit by the “Origin” code.
Using the fitting parameters A, B, and Ea Table 1) obtained in expressions (1) and (3), these dependences were calculated
for other frequencies (Curves 1, 2, and 4).
It is evident that the calculated dependences fairly agree with experiment. By fitting the dependence ε" = F(T)
(Curve 1, b, 7 and 10 kHz) using the already known values of A, B, and Ea, we arrived at Eaσ. A calculation following Eqs.
(2) and (3) (Curves 5, 6, and 8) gave a satisfactory agreement with the experiment.
Thus, the modified Debye’s expressions offer a means to derive frequency-independent parameters (A, B, and Ea)
(using which one can calculate the dielectric characteristics at the temperatures and frequencies within 300 ≤ T ≤ 500 K and
100 Hz ≤ f ≤ 1 MHz, respectively.
Note that the temperature dependences ε' can also be well approximated within the framework of Koops’ model.
However, since one of the reasons for interlayer polarization is the conduction current, the activation energy Ea of the
relaxational process should be equal to that Eaσ of the electric charge transfer. The value of Ea obtained from ε'(T) following
Koops’ model hardly differs from the value resulting from the Debye calculation. The dependences ε"(T) may be, however,
described only with the activation energy E > Ea. In view of the fact that Ea ≠ Eaσ and the conductance temperature
dependences G(T) of the specimens are the same for different frequencies, the experimental dependences ε' and ε" and the
large values of ε' can not be attributed to interlayer polarization.
The data in Fig. 1,a cannot be interpreted within the framework of Debye’s model, since ε'sf depends on frequency.
Recall that in this model, the time constant τ(T) of the relaxational process is independent of the duration of the polarizing
voltage pulse and, hence, the testing signal frequency, therefore, ε'sf is equal to the static dielectric permittivity εs and does
not depend on f, even though there are distributions for Ea and the pre-exponential factor τ0. Thus, when τ(T) = const (f), for
any frequency there is always (theoretically) a temperature range where nearly all of the relaxation agents are involved in
reorientation and ε' attains the same value as εs.
In the case where polarization occurs due to domain reorientation in segnetoelectrics [11] or relaxational agents
whose reorientation is caused by charge-carrier tunneling [5] between the localization centers, then the number of dipoles
involved in the process is limited by the polarizing field duration t. In this case, τ(T, t) and ε'sf (t) are the decreasing
functions, which in fact occurs in Eq. (3) and is evident from Fig. 1,a.
To investigate the effect of the polarizing field strength, we obtained the temperature dependences ε' and ε"
measured at the same frequencies at the testing signal amplitude Utest = 2800 mV (Fig. 2). The electrophysical parameters
derived through fitting Curves 3 and 7 (f = 10 kHz) and used in their calculation at other frequencies, are given in Table 1.
Their values are virtually coinciding with those derived for Utest = 56 mV. It is evident from Fig. 2,a that the dependences

693
 3
10 1'
а
1 2'

2
5
6
10 6
b
ε′, rel. units

2
10 3 7
4
10

ε″, rel. units

8
2
10
4
0
10
TC
1 -2
10 10
300 400 500 600 300 400 500 600
T, K

Fig. 2. Temperature dependences ε' (а) and ε" (b) obtained at Utest = 2800 mV at different frequencies, f, Hz:
102 (curves 1′, 1, and 5), 103 (curves 2′ and 2, 6), 104 (curves 3and 7), and 106 (curves 4and 8) during heating
(curves 1–8) and cooling (curves 1′and 2′); experiment (symbols and dashed lines) and calculation (solid lines).

ε' = F(T) exhibit a pronounced hysteresis at 100 Hz, which is weakened as the frequency is increased. An anomalous
behavior is observed, which consists in a sharp decrease in the values ε' (Curves 1 and 1′) starting from T = 550 K.
The presence of this marked hysteresis in the dependenceε' = F(T) and a sharp drop in the ε' values (Fig. 2,а,
Curves 1 and 1') testify to the fact that ferrite might possess properties somewhat similar to segnetoelectrics. These peculiar
features are, however, observed at large values of Utest (2.8 V) and f (100 Hz) only. When a variable field with high strength
and low frequency is applied, within certain time intervals, it is likely to achieve a sufficiently high concentration of dipoles
oriented in the same direction. Interaction of the latter within these time intervals might give rise to peculiar polarization
behavior associated with collective reorientation of dipoles and, possibly to formation of electric domains. We, therefore,
suppose that the features in the temperature dependences are caused by the collective character of dipole reorientation
within a certain fraction of the variable field half-period. In other words, the electric field periodically induces a dipole
system state similar to the segnetoelectric one.
Based on the above, it is challenging to obtain temperature dependences of dielectric properties at a constant
polarizing voltage Up and variable testing signal Utest = 56 mV < Up applied to the specimen. In this case, the testing signal
exerts no changes on the dipole system state and is a testing signal only, while the concentration of the dipoles oriented by
the constant field is independent of the testing signal frequency. It is expected that at Up , the features in the temperature
dependences of dielectric characteristics would also be present at f > 100 Hz (contrary to the data from Fig. 1, where Utest is
also equal to 56 mV).
Shown in Fig. 3 are the dependences ε' (T) and ε" (T) obtained at a small value of Utest for Up = 0– 0.3 V during
heating and cooling. The temperature step interval in the measurement was 2 degrees. Indeed, these dependences at Up ≠ 0
do exhibit a conspicuous temperature hysteresis. The curves ε' (T) and ε″ (T) obtained during heating at Up ≠ 0, there is a
stepwise increase in ε' and decrease in ε"within the same temperature range 460–530 K. The temperature Tstart, at which
sharp variations of dielectric properties begin to manifest themselves and the temperature Tend, where they terminate, tend to
decrease as Up is increased. There are similar peculiarities in the temperature dependences of dielectric characteristics
obtained at 10 kHz (Fig. 4). As expected, the values of Tstart and Tend at f = 10 kHz are equal to those at f = 1 kHz. That is to
say that Tstart and Tend depend on Up and are independent of f at small values of Utest. The insert shows the peaks in the
dependences ε' (T) measured during cooling.
Figure 5 depicts the temperature dependences of specific conductivity σd = = σ0d⋅exp[–Edσ/(k⋅T)] at direct current
for two values of Ud, 0.25 and 0.5 V. The activation energy Edσ of the electric charge transfer is virtually equal to Eaσ
(Table 1). Thus we may conclude that the activation energy does not depend on frequency within the range 0–1 MHz.

694
 a
4
10
1
2
3
ε′, rel. units

3 1',2',3' b
10 4,4'
10
5 5

ε″, rel. units

6
7
2 10
4 8, 5'-8'
10

3
10
400 500 600 400 500 600
T, K

Fig. 3. Temperature dependences ε' (а) and ε" (b) obtained at Utest =56 mV и f = 103 Hz during heating
(curves 1–8) and cooling (curves 1′–8′); Up, V: 0.2 (curves 1, 5, 1′, and 5′), 0.25 (curves 2, b and 2′, b′), 0.3
(curves 3, 7, 3′and 7′), and 0.0 (curves 4, 8, 4′, and 8′).

200
3'
3
10
2' a
100

1'
ε′, rel. units

10
5
5
460 480 1 6
2 2 4 7 b
ε″, rel. units

10 3 10 8, 5'-8'
4, 1'-4'
3
10

2
10
400 500 600 400 500 600
T, K

Fig. 4. Temperature dependences ε' (а) and ε" (b) obtained at Utest =56 mV и f = 104 Hz during heating
(curves 1–8) and cooling (curves 1′–8′); Up, V: 0.2 (curves 1, 5, 1′, and 5′), 0.25 (curves 2, b and 2′, b′), 0.3
(curves 3, 7, 3′and 7′), and 0.0 (curves 4, 8, 4′, and 8′). The insert shows some features of the dependences ε'(T)
measured during cooling (curves 1′–3′). For comparison the figure gives a section from curve 3.

Thus, the empirical dependences providing a satisfactory description for relaxational polarization of lithium-ferrite
ceramics have been obtained for the frequency and temperature ranges under study. The frequency-independent parameters
contained in these expressions have been determined. It has been established that activation energy of relaxational
polarization is not equal to that of charge transfer, and conductivity is independent of frequency, i.e., the contribution from
interlayer polarization into formation of high values of ε' within the frequency and temperature ranges in question is small.
The following extraordinary phenomena have been observed. The dependences ε'(T) demonstrate a temperature hysteresis
that is increased, as the frequency gets smaller and the amplitude of the testing signal increases. At 100 Hz and the testing
signal amplitude 2.8 V, there is a sharp drop in ε' in the vicinity of the magnetic Curie temperature. Large variations in ε'
and ε" have are observed in the temperature dependences of dielectric properties, which were obtained at constant

695
 -2

lg (σd , Ω ⋅ m )
-1
-1
-4

–1
–2
-6

1.6 2.0 2.4 2.8 3.2

3 -1
10 / T, K

Fig. 5. Temperature dependences of specific conductivity σd at Ud = 500 (curve 1) and 250 mV

(curve 2), the solid line shows approximation of the experimental data by linearization.

polarizing voltage Up and variable testing signal Utest < Up applied to the specimens. It has been found out that the
temperature range within which these variations occur depends on constant polarizing field value and is independent of
testing signal frequency. It has been supposed that the peculiar features in the temperature dependences of dielectric
characteristics might be cased by the collective character of dipole reorientation, with the latter likely to be induced by the
electric field.

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5. F. K. Lotgering, J. Phys. Chem. Sol., 25, No. 1, 95 (1964).
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7. Reddy A.V.Ramana, Mohan G.Ranga, D Ravinder., and B.S. Boyanov, Journal of Materials Science, 34, 3169
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Oxford (1977).

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