Solid State lonics 70/7 I ( 1994) 380-384

SOLID
North-Holland STATE
IOWICS

New fluoride-conducting glass-ceramics

Goldammer, A. Runge
Department of Chemistry, Friedrich-Schiller-University Jena. Jena. Germany

and

H. Kahnt
Department OfElectronics, FH Jena, Tatzendpromenade lb, 07745 Jena. Germany

Fluoride conducting glass-ceramics were obtained from glasses of the system SiOZ-PbO-PbFZ. Two types of crystallization
behaviour have been established leading to an increase or decrease of conductivity for up to three decades, respectively. Relations
between structure and conductivity of the glass-ceramics are discussed.

1. Introduction ramics are of interest as solid electrolytes for elec-

trochemical applications.
Extensive studies on ionic conductivity in oxide
glasses with cation conduction have been carried out
over many years [ 11. Interest in anion conduction 2. Experimental
in glasses has grown over the last decade, too. Most
of the reports on fast halide conduction in glasses
SiO, p.A., PbO p.A. and PbFz p.A. were used as
have been restricted to fluoride-ion transport in fluo-
starting materials to prepare the glasses. The com-
rozirconate glasses [ 2,3 1. First, Shultz and Missoni
positions of the glasses are given in table 1. Starting
[ 4 ] studied fluoride-ion conduction in oxyhalide
from binary lead silicate glasses of compositions
glasses. Especially the system SiOz-PbO-PbXz
(2O+x)SiO, (80-x)PbO (O<x<30 mol%) up to
(X=F, Cl, Br, I) has been a subject of various in-
35 mol% of the PbO were substituted by PbF2.
vestigations on structure, glass formation, conduc-
Batches of 100 g have been melted in a platinum cru-
tivity and mixed mobile anion effect [ 5-101.
cible covered to reduce vaporisation losses. After
Glasses of this system can be easily transformed
melting for 45 min at 800°C the melt was poured into
into glass-ceramics by heat treatment at tempera-
tures slightly above T,. It is the aim of the present Table 1
paper to give a systematic study on the influence of Composition of the lead fluorosilicate glasses in mol%
crystallization on halide ion conductivity in glasses
of the system SiOz-PbO-PbFz. Covering the whole No. Si02 PbO PbFZ

glass-forming region of the system glasses have been 0 30 70-x x=0,10,15,20,25,35

crystallized under various regimes of heat treatment. 1 25 75-x .x=0,15,25,35
Previous investigations [ 111 revealed that conduc- 2 33,3 66.7-x x=0,15,25,35
3 40 60-x x=0,15,25,35
tivity can be increased up to a factor of 1000 by par-
4 50 50-x x=0,15,25,35
tial crystallization of lead halosilicate glasses under 5 20 80-x x=0,15,25,35
suitable conditions. Fluoride-conducting glass-ce-

0167-2738/94/$07.00 0 1994 Elsevier Science B.V. All rights reserved.

 S. Goldammer et al. /New fluoride-conducting glass-ceramics 381

an iron mould and quenched on air, and annealed

with 5 K/min starting at T,.The glass forming re-
gion is shown in fig. 1. Glasses within this region were
transparent and free of crystals, bubbles and streaks
(circles in fig. 1). Glass transformation temperature
T, and the onset temperature of crystallization T,
were measured by DTA-analysis at a heating rate of
5 K/min. Heat treatment at temperatures between
Tg+ 20 K and T,+ 20 K and a duration from 30 min
to 45 h was applied to form glass-ceramics.
Conductivity measurements were carried out on
polished samples of 2 mm thickness. Aluminium
electrodes were evaporated on both sides of the sam-
ples in a guard ring arrangement. Measurements were
performed with an impedance analyser SI 1260 from
Schlumberger in the frequency range from 1 Hz to
1 MHz at temperatures ranging from room temper-
ature to T,.DC conductivity was determined from
-14,5 ’ , / I I I I
the complex impedance plot as usual.
0 2 4 6 8 10 12
Crystalline phases were determined by means of
X-ray diffraction. In some cases electron microscopy C, (lO"/cm')
was used to get information about the morphology
194
of the glass-ceramics, i.e. arrangement, size and ori- Mel% SiO,

entation of crystalline phases. 0 50 A40 X 33,33 0 30 0 25 l 20

192

3. Results

The conductivity of all glasses is thermally acti-

vated showing an Arrhenius type dependence on
temperature. With increasing F- concentration con-
ductivity is strongly increased (fig. 2a) while the ac-
tivation energy is lowered (fig. 2b). The substitution
of SiOZ by PbO has only a small influence on con-

PbF>

R-4
0 2 4 6 8 10 12 14
c, (10"/cm3)

Fig. 2. Conductivity of glasses in the system Si02-PbO-PbF2 at

100°C as function of fluoride concentration; (b) activation en-
ergy of conductivity as function of fluoride concentration.
AL

L
3’
Pb3Si207
Pb2SnOL

Fig. 1. Glass-forming region in the system SiO*-PbO-PbF,.

382 S. Goldammer et al. /New fluoride-conducting glass-ceramics

ductivity. The dependence of conductivity on the ra-

tio of SiOZ to PbO vanishes at higher fluoride
concentration.
Depending on glass composition and heat treat-
ment crystallization of the glasses has a different in-
fluence on conductivity. Systematic variations of
temperature and duration of the thermal treatment
revealed two distinct types of crystallization behav-
ior (type I and type II).
Type I: In glasses with up to 15 mol% PbFz con-
ductivity is increased with the onset of crystalliza-
tion at about 20 K above TK Maximum conductivity
changes observed so far for this type of glasses are
summarized in fig. 3. Two crystalline phases Pb&O, -63 ( - I'hl;z
and PbF, have been established in the glass-ce- 1 I%$3207

ramics. For type I glasses heat treatment slightly - 1 (;hlss - - Glass-ceramic

above 7’, leads to the formation of crystalline /
-7’ D
Pb&O,. The appearance of this crystalline phase is 300 350
accompanied with a strong increase of conductivity temperature [“Cl
(fig. 4). At higher temperature, a second crystalline
Fig. 4. Type 1: influence of heat treatment on crystalline phases
phase PbFz is formed. At the same time conductivity
and conductivity.
decreases. Thus, conductivity passes through a max-
imum value.
Type II: Glasses with more than 15 mol% PbFz be- -5

long to the second type of crystallization behavior.

In contrast to type I, heat treatment at 20 K above
TB leads to the formation of PbFz crystals. At the same -6
time the conductivity decreases (fig. 5). This is ac-
companied with an increase of activation energy (fig.
6, glass with 33.3 mol% SiO, after 45 h at 300°C). -7
S
::
i;
2 -8

300 350 400

temperature [“Cl
Fig. 5. Type II: influence of heat treatment on crystalline phases
and conductivity.

- 1000/l CK-'1 - Further heat treatment at higher temperatures yields

Fig. 3. Conductivity of glasses and glass-ceramics with up to 15 a crystallization of the second phase Pb&O, (fig.
mol% SO2 (type 1) 5). Now, conductivity rises again while the activa-
 S. Goldammer et al. /New fluoride-conducting glass-ceramics 383

The conversion of a glass to a glass-ceramic leads

to a mixture of crystalline and glassy phases. The
-5 - _ Glass
- _ _ Glass-ceramic conductivity of such heterogeneous system depends
not only on the volume fractions and conductivities
of the different compounds. It is also strongly influ-
enced by transport processes along grain boundaries
and by the morphology of the system, i.e. shape, size
and orientation of the compounds and its spatial ar-
rangement. Actually, further research is in progress
-s - to investigate these details in order to get necessary
information for model calculations.
Compositions and morphology of the glass-ce-
2.2 2,L 2.6 2,s 30 3.2 ramics are not identical with the equilibrium state of
- 1000/T tK-' 1 - the systems at the given temperatures of heat treat-
Fig. 6. Conductivity of glasses and glass-ceramics with more than ment. As the heat treatment was interrupted before
15 mol% SiOl (type II). the equilibrium was reached, a transition state of the
system on its way to equilibrium was frozen in. Long
tion energy is lowered, in some cases reaching values time heat treatment leads always to the formation of
(0.25 eV) smaller than for pure PbF2 (0.32 eV). both PbF2 and Pb3Si207, in some cases a small
The glass-ceramics were investigated by means of amount of an unidentified third crystalline phase was
scanning electron microscopy. Glass-ceramics of type observed. However, at short times and at tempera-
I showed spherical agglomerations of Pb&O, (5- tures slightly above T, only a single crystalline
10 pm) distributed within the remaining glass ma- phase-PbF, or PbJSi20+s obtained depending on
trix. PbF2 crystals arising in type II and-at higher the PbF2 content in the glass. Obviously at high PbF2
temperature-in type I glass-ceramics are too small content only slight rearrangement of the glass struc-
to be resolved by scanning electron microscopy ( < 10 ture is required to form PbF2 (type II, > 15 mol%
nm ). Further investigations using replica techniques PbF2). On the other hand at low PbF2 content (type
are in progress to get more detailed information about I, I15 mol%) the formation of Pb$i207 is pre-
the morphology of the glass-ceramics at the initial ferred. In both cases this single crystalline phase arises
state of crystallization. as isolated particles which are enclosed in a glass ma-
trix. Thus, the total conductivity is mainly deter-
mined by the remaining glass matrix. The conduc-
4. Discussion tivity of this glass depends strongly on fluoride
concentration while the network former components
Fluoride conduction in the glasses of the system have only a small influence (fig. 2).
SiOz-PbO-PbF2 shows the same dependence on When Pb3Si20, is formed the F- concentration in
structure and mobile ion concentration as alkali con- the remaining glass increases. That is why the con-
duction in oxide glasses. This similarity is the result ductivity of type-1 glasses increases with the onset of
of the action of PbF2 as a network modifier in the crystallization. In contrast, the glass matrix loses F-
same way as NazO in silicate glasses. This is possible when PbF2 is crystallized. Consequently conductiv-
because in glasses with high lead oxide content the ity of the glass matrix decreases. This is the case when
PbO behaves as a network-former giving rise to heat treatment of type-1 glasses is continued for a
bridging oxygen (Pb-0-Pb) [ 121. When PbO is longer time or at higher temperature.
substituted by PbFZ bridging oxygen is removed while In the high fluoride glasses (type II) the conduc-
fluoride ions are bound to Pb2+. As a consequence tivity decreases with the onset of crystallization be-
glass transformation temperature is lowered and cause the PbF2 crystals are isolated from each other.
conductivity increases exponentially with fluoride However, when heat treatment is continued at higher
concentration up to a saturation at high PbF2 content. temperature and Pb$i20, is crystallized, too, the
384 S. Goldammer et al. /NewJluoride-conducting glass-ceramics

PbFz begins to build a continuous network. Then the References

total conductivity is mainly determined by the con-
ductivity of this network. Interesting to note is that
[ 1 ] H.L. Tuller, D.P. Button and D.R. Uhlmann, J. Non-Cryst.
in some cases the activation energy of conductivity Solids 40 ( 1980) 93.
was found to be lower than for pure PbF2. Possibly [2] D. Leroy and D. Ravaine, C.R. Acad. Sci. (Paris) 287C
this phenomenon can be explained by increasing (1987) 455.
mobility of fluoride ions along the grain boundaries [ 31 G.V. Chandrashekhar and M.W. Shafer, Mat. Res. Bull. I5
(1980) 221.
of lead fluoride crystals. Such effects have been ob-
[4] P.C. Schultz and MS. Mizzoni, J. Am. Ceram. Sot. 56
served in mixtures of ionic conductors with fine dis- (1973) 65.
persed insulating materials [ 13 1. [ 51 J.E. Shelby, J. Am. Ceram. Sot. 68 ( 1985) 55 1.
The present results confirm that it is possible to [6] J.Co0nandJ.E. Shelby,J. Am.Ceram. Sot. 71 (1988) 354.
[7] A. Osaka, Y. Wang, M. Kobayashi, Y. Miura and K.
change the conductivity of fluoride conducting glasses
Takahashi, J. Non-Cryst. Solids 105 ( 1988) 63.
in the system SiOz-PbO-PbF2 in a defined way by [ 81 Y. Wang, M. Kobayashi, .4. Osaka, Y. Miura and K.
means of controlled crystallization. Both increase or Takahashi, J. Am. Ceram. Sot. 71 (1988) 864.
decrease of conductivity can be achieved up to a fac- [9] Y. Wang, A. Osaka and Y. Miura, J. Non-Cryst. Solids 112
tor of three decades. In a further study quantitative (1989) 323.
relations between the content, size and spatial dis- [ lo] H. Kahnt and J.M. Reau, Phys. Status Solidi (a) I21 ( 1990)
73.
tribution of crystalline phases and the conductivity [ 111 Ch. Kaps and H. Kahnt, private communication.
of the glass-ceramics will be established. [ 121 W. Vogel, Glaschemie (VEB Deut. Verlag fur
Grundstoffindustrie, 1975).
[ 131 A.K. Shukla, R. Manoharan and J.B. Goodenough. Solid
State Ionics 26 ( 1988) 5.