JOURNAL OF MATERIALS SCIENCE LETTERS 1 (1982) 264--267
Internal friction and electrical conductivity in
iron--vanadium--phosphate glasses
W. CHOMKA, O. GZOWSKI, L. MURAWSKI, D. SAMATOWlCZ
Institute of Physics, Technical University Gdaf}sk-Wrzeszcz, Majakowskiego 11/12, Poland
S. STIZZA, I. DAVOLI, V. PRANTERA
Instituto dl Fisica, Universita di Camerino, Camerino, Italy
It is a well recognized fact that the electrical con-
ductivity in transition metal oxide glasses is due to
the existence of ions in different valency states and
the hopping of the electrons between these ions
[1-3]. In recent years, investigations have been
reported [4-6] on internal friction and electrical
properties of these glasses. The internal friction
peak as well as the dielectric loss peak were
interpreted as the result of dipole re-orientation
under the electric field or mechanical stress.
In the iron-phosphate glasses the jump of the
electron from the bivalent to the trivalent iron ion
produces such a re-orientation of both the elec-
trical and elastic dipoles.
A similar effect can be expected when glass
contains two different transition metal oxides,
e.g. iron and vanadium. In this case, one may
expect, apart from the transition Fe 2÷ ~ Fe 3÷, the
transition V ++ ~ V s+ and also the Fe 2÷ ~ V s+ or
V+++ Fe 3+ transitions. We have briefly reported
the results of electrical conductivity [7] and
internal friction [8] of phosphate glasses con-
taining up to 50mo1% of V+Os and FeO. Since
it is impossible to obtain the redox ratio, C, of
both transition metal elements directly by chemi-
cal analysis, M6ssbauer spectroscopy studies were
conducted in order to determine the valency state
of iron ions [7]. However the valency state of
vanadium ions was still unknown and the full
interpretation of conductivity and internal friction
results was impossible. Recently, we have con-
ducted some experiments using the method of X-ray
absorption near edge structures (XANES) for
determining the local site symmetry of vanadium
ions [9]. These measurements will be fully reported
later, but some results concerning the valency state
of vanadium ions will be used in order to explain
the internal friction and conductivity results.
Glasses of composition 50mo1% P2Os+
(50--x)mol% FeO +xmol% V2Os and 50mo1%
P2Os + (50--x)mol% CaO +xmol% V2Os were
melted in an air atmosphere in alumina crucibles
at 1500K for 3h. They were made from the
reagent-grade materials V2Os, Fe2Oa, CaO and
NH4H~PO4.
The measurements of electrical conductivity of
the button-shaped samples by a three-terminal
method were carried out in vacuum.
The measurements of the internal friction,
Q-', of the fibre samples were performed with a
torsion pendulum in the frequency range 1 to
34 Hz and at temperatures between 150 and 600 K.
Fig. 1 presents a typical set of the electrical
conductivity temperature characteristics for six
glasses of different compositions. The character-
istics in high temperature regions are well described
by the equation o = Oo exp (--E/kT) where E is
the activation energy, k is the Boltzmann constant
and T is the temperature. The minimum of the
conductivity and the maximum of activation
energy is observed for 10 real% of V205.
Fig. 2 presents the set of internal friction
results. Only the low temperature peaks, which are
typical for the electron transition, are shown. For
5 to 10 percent V2Os content, a splitting of the
peak is observable. The arrows indicate the
position of the peak when only iron is present in
the glass matrix [10] and instead ofV2Os, CaO in
the same percentage is added. For the sake of com-
parison, Fig. 3 shows the internal friction results
for vanadium glasses, where instead of iron, the
neutral modifier CaO is introduced.
In iron phosphate or vanadium phosphate
glasses, there exists a mixed valency system of iron
or vanadium ions and the value of the conduc-
tivity depends on the amount of transition metal
264 0261-8028/82/060264-04502.98/0 © 1982 Chapman and Hall Ltd.