Anda di halaman 1dari 9

ourna, of Non C

sta,,ine So,iris 159 1993 213-221

North-Holland

Structural studies in lead germanate glasses:


EXAFS and vibrational spectroscopy
S.J.L. R i b e i r o a j. D e x p e r t - G h y s b B. Piriou b a n d V.R. M a s t e l a r o c
lnstituto de Quimica - UNESP, CP 355, 14800-900, Araraquara, SP, Brazil
h Laboratoire des Eldments de Transition dans les Solides, CNRS, 1, Pl. A. Briand, 92195, Meudon c~;dex. France
c LURE, Unit,ersit~ Paris Sud, 91405, Orsay, France
Received 9 September 1992
Revised manuscript received 31 December 1992

The Raman, IR absorption and EXAFS spectra at the Ge K-edge and Pb Lm-edge of eight lead germanate glasses, with
general formula x P b O ( 1 - x ) G e O 2 with x = 0.20, 0.25, 0.33, 0.40, 0.50, 0.53, 0.56 and 0.60, have been measured. The
occurrence of [GeO 6] units besides [GeO 4] could not be deduced unambiguously from the data. The vibrational and EXAFS
data agree with a progressive depolymerization of the network. Starting from all Ge atoms linked to four bridging oxygens in
GeO 2 (x = 0), the number of tetrahedral units with one or two non-bridging oxygens increases with x. At low content, Pb ~+
ions act as modifiers in the germanate structure, but to a lesser extent than an equivalent number of alkaline ions.

I. Introduction

Glasses and crystals in the P b O - G e O 2 system


are well known. The phase relations and crystallization of glasses have been established [1]. A
previous investigation by means of europium as a
local probe in glasses of the related system PbF 2G e O 2 has been published [2].
Alkali germanate glasses ( x M 2 0 ( 1 - x ) G e O 2,
M += Li +, Na + or K +) have also been the subject
of many investigations. Most conclude that there
is a partial change of the germanium coordination number from four (Ge TM) in glassy G e O 2 to
six (Ge vI) when x increases. This change would
induce the so-called 'germanate anomaly' observable for several physical properties such as the
refractive indices [3], densities [4], elastic constants and molar volumes [5]. The identification
of Ge w as well as Ge TMhas been corroborated by

Correspondence to: Dr S.J.L. Ribeiro, Instituto de Qulmica UNESP, CP 355, 14800-900, Araraquara, SP, Brazil.Tel: + 55162 322 022. Telefax: + 55-162 227 932. E-mail: uearq@brfapesp.bitnet.

IR absorption [6], Raman scattering [7], X-ray


diffraction [8] and EXAFS [9,10]. From these
measurements it may be concluded that the proportion of Ge w is 20% of the total Ge atoms, at
0.15~<x~<0.20. After that, an excess of alkali
breaks bonds and the local structure is Ge TM, the
number of non-bridging oxygens increasing with
X.

Henderson and Fleet [11] have given another


interpretation of the experimental data, based on
the formation of three-membered Ge TMrings, thus
totally excluding the formation of Ge vl. Itie et al.
[12] obtained XANES and EXAFS data for G e O 2
samples under high pressures and show that pressure-induced Ge TMto Ge vl coordination changes
are reversible. Henderson and Fleet [11] interpreted these data in the sense that sixfold coordination for germanium atoms could not be maintained at room pressure. This reversibility would
also hold for sodium germanate glasses, but this
question is still being investigated [13].
For lead germanate glasses ( x P b O ( 1 - x ) G e O 2) it has been concluded, from the variation
of several properties, that the structural change
Ge w---, Ge vl occurs, but the rate and the total

(1022-3093/93/$06.00 1993 - Elsevier Science Publishers B.V. All rights reserved

214

S.J.L. Ribeiro et al. / Lead germanate glasses

amount of change are less than in alkali germanates [14]. Recently, Ruller et al. [15] have
referred to this change in coordination number in
the explanation of some properties of sodiumlead germanate glasses.
Vibrational data (IR absorption and Raman
scattering) have also been interpreted as exhibiting features characteristic of Ge vI [16,17], although Canale et al. [18] have shown that assignments of vibrational frequencies based on [GeO6]
octahedra were very difficult to make since the
broad features observed could obscure characteristic bands.
In this work we describe the investigations by
vibrational spectroscopy (IR absorption and Raman scattering) and EXAFS at the Ge K-edge
and Pb Liii-edge of several lead germanate glasses
with 0.2 4 x 4 0.6. We discuss our results by considering two questions. First, is there any evidence, from our experimental data, supporting
the observation of Ge vI groups in this composition range? Second, to what extent do lead atoms
play the role of modifiers in the germanate network? For this second question we compare our
results with the above-cited works on alkali and
lead germanates, with some Raman data of glasses
containing heavy metal oxides [19], and with results for lead silicate glasses [20] and lead borate
glasses [21]. In the following, the notation Ge TM
and Ge w will refer to germanate entities with
respectively the tetrahedral and octahedral coordination, whereas the different tetrahedral entities containing 4, 3, 2, 1 and 0 bridging oxygens
(and obviously the complement to 4 non-bridging
oxygens) will be labelled Q4 to Q0 as is usual in
N M R notation.

2. Experimental details
Glasses were obtained by melting appropriate
mixtures of the starting oxides (GeO 2 99.999%
and PbO 99.99% Aldrich) in a platinum crucible
at 1000C for one hour followed by quenching on
a steel plate at about 200C (cold water quenching was necessary for the composition x = 0.60).
The amorphous state was measured by X-ray
diffraction and the compositions were deter-

mined by Pb and Ge inductive plasma emission


spectroscopy analysis. Samples were obtained with
the following compositions: x = 0.20, 0.25, 0.33,
0.40, 0.50, 0.53, 0.56 and 0.60. For the last one,
which had very poor optical quality, only IR spectra were obtained.
Crystalline PbGeO 3 was obtained by a solidstate reaction between PbO and GeO 2. Powder
mixtures of the appropriate amounts of the oxides were pelletized and placed in platinum crucibles at 600C for 6 h. The pellets were ground
to powders, and again pelletized and treated for 6
h at 600C. X-ray diffractograms agreed well with
the one given in ref. [22].
The experimental set-up for Raman measurements was an argon ion laser (Spectra-Physics
165), a Coderg P H O double monochromator
spectrometer, a Hammamatsu 1477 photomultiplier and a Keithley 177 multimeter. The output
of the multimeter was linked to a 16-bit BFM 187
computer for storage and processing. Spectra
were obtained at room temperature with the classical 90 geometry between the incident beam
and scattered light. Samples were cut and polished with diamond paste and were investigated
under parallel (VV) and perpendicular (VH) polarizations. The spectral slit widths were routinely
set at 6 cm -1 and the spectrometer was calibrated with the lines of a low-pressure mercury
lamp.
Infrared absorption spectra were obtained with
powders, in KBr pellets with a F T I R Nicolet
730FX (resolution set at 4 cm-1).
Room-temperature transmission EXAFS measurements were obtained at the germanium Kedge and lead Lm-edge. We utilized different
spectrometers (EXAFS I station - Si (331) channel-cut monochromator and EXAFS III station Si (331) double crystal monochromator) with ion
chambers as detectors. The spectra were recorded
using the DCI storage ring at Orsay (France)
which was typically operating at an energy of 1.85
GeV and 250 mA current. The ground samples
(~< 20 p~m in size) were homogeneously layered
on kapton strips.
The EXAFS oscillation curves, x ( k ) , obtained
by a standard procedure [23], were Fourier transformed using k 3 x ( k ) (Ge K-edge) and k 2 x ( k )

215

S.J.L. Ribeiro et al. / Lead germanate glasses

(Pb Lni-edge) weighting. A Kaiser apodization


function was applied over 5 to 11 .~-1 at the Ge
K-edge and over 3.7 to 9 A - 1 at the Pb L nl-edge,
with r = 1.5 in both cases. Using a single scattering theory and the plane-wave approximation, the
normalized oscillatory part of the absorption
spectra is described as

[ f,("rr, k)lN~
x(k)

= - ~_~

kR 2

sin[2kR i +

4hi(k)]

exp( - 2o-i2k 2) e x p ( - 2 R i / A ) .

(] i\,
/

(
,/'

Ji

b
X = 0.20

Fii
m

3. Results

3.1. Raman scattering


Figure 1 shows Raman scattering spectra for
four samples with x = 0.20, 0.33, 0.50 and 0.56.
These are reduced spectra, corrected for the
thermal population effect, following the relation
I R = Iw[n(~o) + 1] -t. I and I R are the observed
and reduced R a m a n scattering intensity at
wavenumber o) and n(w)= [ e x p ( h w / k T ) - 1] - l
is the Bose population coefficient [24]. Spectra
agree well with those presented by Canale et al.
[18] despite the fact that these authors did not
work with polarization data.
Comparing the general aspects of the spectra
it may be seen that the scattered intensity in the
mid-frequency range (200 to 600 c m - 1) relative to
the one in the high-frequency range (600 to 1100

',U

(1)

In this formula N/ represents the number of


atoms at a distance R i from the absorber, ~ri is a
damping coefficient due to thermal and structural
distributions of distances, A is the mean free path
of the photoelectron and fi(k) and c~i(k) a r e the
amplitude and phase-shift functions, which were
obtained from standard compounds. The energy
threshold was adjusted in all cases. The values for
o- must be taken as relative differences between
the samples and the reference compounds. These
were trigonal G e O 2 ( N = 4, R = 1.739 ,~) and
orthorhombic PbO ( N = 4, R 1 = 2.20 ,~ (2 oxygens) and R 2 = 2.49 A (2 oxygens)). In the analysis we have taken for PbO a mean P b - O distance
of 2.34 A and N = 4.

it

ljh~li,,,l

. . . . . . . . . . . . .

~0

I000

500

iO00

RAMAN SIIWT {cm"tj

Fig. 1. Reduced Raman scattering spectra for the glasses


xPbO(1-x)GeO2: (a) parallel (VV) and (b) perpendicular
(VH) polarizations.

1) decreases when the amount of lead oxide


increases.
A strong polarized band is seen at approximately 450 cm -1 for the samples x = 0.20 and
0.25. It is accompanied by a shoulder near 920
cm 1 in the polarized (VV) spectra and a better
resolved band at about 930 cm i in the depolarized (VH) spectra, both decreasing for higher
PbO content but Still present up to the composition x = 0.40.
A rather narrow band is observed for all polarized spectra, at -- 820 cm i for x = 0.20 shifting
to --790 cm t at x = 0 . 5 6 . A broader line appears in the VH spectra at frequencies ranging
from -~800 cm-1 at x = 0 . 2 0 to ---730 cm-1 at
x = 0.56. Note that for this last sample an intense
component at about 790 cm-1 is observed in the
VH spectrum. This feature is attributed to the
mixing of the VV and V H components. It appears for this composition which lies near the
limits of the glassy state in this system. Some
inhomogeneity at the microscopic scale could have
altered the relative orientation of the incident
and collected lights in a sample of poor optical
quality.
For the composition x = 0.50 and for those
with higher lead contents, we note in VV spectra,
besides the shift of the line at about 800 cm ]
cm

S.J.L. Ribeiro et al. / Lead germanate glasses

216

9O

3O

%-

500

1OOO

RAMAN SHIFT (cr~ll

Fig. 2. Raman scattering spectrum for powdered PbGeO3,


corrected for thermal population effect. Points denote parasitic lines of the argon plasma.

contents is an artifact linked to the mathematical


reduction treatment.
No characteristic feature at 600 or 650 c m could be isolated in the composition range 20 to
30% PbO as was the case in Li, Na, K germanate
glasses [7]. Nevertheless, a shoulder at about 580
c m - 1 occurs in the VV spectra for 0.20 ~<x ~< 0.33.
The R a m a n spectrum for P b G e O 3 is presented in fig. 2. Polarization information is lost as
the sample was a powder. Maxima were observed
in the high-frequency part at 747, 782 and 815
c m - 1.

towards lower wavenumbers, the appearance of a


very weak shoulder at approximately 730 cm-1.
A broad band appears in both orientations for
all samples in the region 520-550 cm -1. At the
same time a band at -- 370 cm-1 is observable in
all spectra and is more intense for V H polarization. Its intensity relative to the one at about 540
cm-1 increases with lead content.
A narrow band is detected at 140 cm-~ for the
compositions x = 0.50, 0.53 and 0.56. The small
feature at 100 cm -~ observed even at low lead

3.2. IR absorption
Figure 3 presents IR absorption spectra (4001500 cm -~) for the glasses studied. They agree
well with those presented in refs. [17] and [18],
and contain a broad and strong band that shifts

x=O

..J
r~
O

,,~
X
Ld

0
W
.3
Z

I--

Z
r"
I--

k(~ -I)
1000

600

WAVENUMBER(cn~1)

Fig. 3. IR absorption spectra for the glasses x P b O ( 1 - x ) GeO 2.

I0

12

R(~)

Fig. 4. Ge K-edge EXAFS spectra and their Fourier transforms for the glasses x P b O ( 1 - x ) G e O 2 , GeO 2 hexagonal
('quartz-type'-denoted q) and glassy GeO 2. (a) EXAFS spectra (x(k)); (b) Fourier transform modulus (F(R)).

S.J.L. Ribeiro et al. / Lead germanate glasses

from 720 cm -1 for x = 0.60 to 830 cm -~ for


x = 0.20. Besides this shift, components at about
925 and 660 c m - t are resolved for the samples
with x = 0.20, 0.25, 0.33 and 0.40. With increase
in lead content, these shoulders are not resolved.
The main feature observed in the IR spectrum
(not presented here) for crystalline P b G e O 3 is a
strong peak at 753 c m - t, which is about the same
frequency observed for the lead metagermanate
glass (750 cm-~). There are also two other sharp
components at 856 and 908 cm -~.

217

Table 1
Fit results for xPbO(1 - x)GeO 2 glasses (Ge K-edge). Phase
and amplitude from hexagonal GeO 2 (N= 4 and R= 1.739
Sample (x)

N~ o
(+_0.1)

RGe-o(A)
(+0.01)

0
0.20
0.25
0.33
0.40
0.50
0.53

4.0
4.2
4.2
4.3
4.5
4.5
4.8

1.74
1.75
1.75
1.75
1.76
1.77
1.78

A'G,:-O(A)
(0.005)
-- 0 . 0 1 0
0.040
0.028
0.041
0.030
0.041
0.039

3.3. EXAFS spectra


The normalized E X A F s (g(k)) spectra and
the Fourier transforms (modulus) for six lead
germanate glasses at the Ge K-edge are displayed
in figs. 4(a) and (b) respectively. Spectra for glassy
G e O 2 and trigonal quartz-type G e O 2 are also
shown. The spectra are similar for all the samples
investigated.
uR

! ~,2/%~
Fk

' ~2

'

0.20

plCU
bb d

0.25

~.o/

; T ;",
~ ~/\

x
w
q

0.40

o ~

0.50

%fo.~
,~

0.53

One-shell fits were tried and fig. 5 presents the


filtered g(k) E X A F S spectra and the calculated
curves obtained with the parameters shown in
table 1. With respect to the crystalline trigonal
G e O 2 used as reference, we observed a tendency
to an increase in the number of oxygen atoms in
the first coordination shell, N, and an increase in
the average G e - O distances, R, with increase in
lead content. These two features will be discussed
in the following.
Furthermore, one may observe for the Fourier
transforms (fig. 4(b)) the presence of a second
peak which decreases in intensity with increasing
lead content. We attribute this peak to second
neighbour effects, a feature which is rather difficult to observe in glassy systems.
Spectra at the Pb Lm-edge are not presented
here, but some general observations can be made.
A very poor signal-to-noise ratio was observed
mainly due to some intrinsic factors such as the
high absorption cross-section for X-rays presented by lead atoms, the weak scattering power
for oxygen atoms and the large disorder in atomic
distances usually observed in lead compounds.
Nevertheless, one-shell fits were tried giving N =
3 _+ 0.5 and R = 2.35 _+ 0.05 ,~ for all samples.

4. Discussion
6

I0

k(~-I)
Fig. 5. F i r s t - s h e l l f i l t e r e d E X A F S s p e c t r a ( 0 0 o )
and calcul a t e d c u r v e s (---) o b t a i n e d w i t h p a r a m e t e r s f r o m t a b l e 1, f o r
g l a s s e s x P b O ( 1 - x ) G e O 2.

In ref. [17] Kolesova stated that starting at


x = 0.04 in x P b O ( 1 - x ) G e O 2 glasses, a component at 700 c m - l in I R might be related to Ge v'.
This component should increase continuously

218

S.J.L. Ribeiro et al. / Lead germanate glasses

with increase in lead content but it would be


hidden by a shift of the strongest band occurring
at higher wavenumbers. Canale et al. [18] have
given the interpretation that the shoulders observed for the high-frequency band for x = 0.20
could be due to the convolution of two different
bands related to different glass phases. The I R
absorption spectra presented in fig. 3 also exhibit
a shoulder at around 685 c m - 1 for the two lowest
PbO contents investigated in this work (x = 0.20
and 0.25). We cannot determine whether it is still
present under the main component in the spectra
of samples with higher x.
R a m a n spectra for alkali germanate glasses
( x M 2 0 ( 1 - x ) G e O 2, M = Na or K) have well-resolved bands in the region between 600 and 650
cm -1 for compositions around x = 0.15. These
bands are atributed to Ge w polyhedra and are
supposed to be present also for lithium germanate glasses but as a part of a broader band
[7]. In the compound 2 L i 2 0 9 G e O 2 , where the
germanate skeleton contains chains of Ge TM tetrahedra connected by G e vl octahedra in a network involving only bridging oxygens, the main
bands are at 566 and 595 cm-1 [7].
In R a m a n spectra (fig. 1), no characteristic
band is observed in the 600 to 700 cm-~ region,
which could be unequivocally assigned to Ge w
groups. The shoulder near 600 c m - ~ for x = 0.20,
0.25 and 0.33 may be related to these groups, but
this assignment is speculative. A component at
about 735 cm -~ appears in the high-frequency
R a m a n band for compositions x >/0.50. This
amount of lead oxide is higher than that at which
the discontinuity in physical properties related to
Ge w atoms has been observed (between x = 0.20
and 0.40 from ref. [14]), so that we find no reason
to attribute it to Ge w polyhedra and we rather
interpret it in relation to depolymerization of the
GeW-based skeleton, as discussed below.
The analysis of E X A F S spectra for x N a 2 0 ( 1 - x ) G e O 2 glasses developed in ref. [10] is in
good agreement with the observation of the
' g e r m a n a t e anomaly' in a well-defined range of
compositions. Starting from R = 1.73 A in a Ge TM
network, the average G e - O distance increases
with the increasinog amount of Ge w, up to a
maximum of 1.76 A for x = 0.20 before decreas-

ing again. Also, pressure-induced coordination


changes in crystalline and vitreous G e O 2 have
been confirmed by the observation of increases in
G e - O distances obtained from one-shell fits together with X A N E S measurements [12]. Twoshell fits for the Ge K-edge E X A F S spectra in
x L i 2 0 ( 1 - x ) G e O 2 glasses are presented in ref.
[9]. The conclusion of the authors is that the
number of Ge vI increases markedly between x =
0.05 and x = 0.15, then it is constant to x = 0.25
(the maximum modifier content investigated in
that work).
The results of our E X A F S analysis (fig. 5 and
table 1) show an increase in G e - O distances and
Ge coordination numbers with increase in PbO
content in the whole composition range. Moreover, the results for glassy GeO2, in excellent
agreement with the literature [10], show that the
data treatment was satisfactory.
We may rationalize these results in two ways.
The first interpretation is the appearence of Ge w
groups, in a continuously increasing proportion
up to the limit of the glass domain. If the shoulder at 600 cm 1 in our R a m a n spectra is assigned
to Ge w groups, they occur in a limited range
(0.20 ~ x ~ 0.33) and not above x = 0.33. This
interpretation seems not to be satisfactory.
The second way must involve a decrease of the
disorder with increasing lead content. The Deb y e - W a l l e r disorder parameter, or, and the coordination number, N, are strongly correlated in
the usual least-squares fitting procedures [23]. An
increase in N or a decrease in or may cause the
same effects in the E X A F S amplitudes. Actually,
N is a scale p a r a m e t e r for the whole EXAFS
spectrum while ~r is a damping factor, with its
influence being observed for large values of k
[23]. The spectra obtained could be extended
only up to 11 A - ~ in k-space so that it became
difficult to resolve the contributions from these
two parameters. E X A F S measurements with
higher signal-to-noise ratio on a larger scale in
k-space are necessary to discuss this point accurately.
The variation of the average distance, R, with
x deduced from the E X A F S fits (table 1) can be
reliably related to the increase in G e - O distance
as the depolymerization, or the average number

219

S.J.L. Ribeiro et al. / Lead germanate glasses"

of non-bridging oxygens ( N B O s ) linked to the


germanium, increases. In crystalline P b s G e 3 0 ~ ,
for instance, the structure of which is m a d e of Q~
and Q0, two G e - O distances are e n c o u n t e r e d :
1.75 and 1.79 A [26], while it is 1.739 A. in
crystalline G e O 2 (all Q4). A n o t h e r evidence for
depolymerization is the disappearence of the second-shell p e a k in the Fourier transforms with
increasing lead content. This p e a k is not analyzed
in this work but it must be related to G e - G e
interactions in a polymerized network [10].
T h e G e TM f r a m e w o r k in alkaline g e r m a n a t e
glasses has been investigated by R a m a n scattering [7,27]. T h e description in terms of N B O s used
for silicate networks may be e m p l o y e d as well for
germanates. In vitreous G e O 2 each G e a t o m is
linked to four bridging oxygens (BOs). Alkaline
M + atoms break some of the G e - O - G e links
and create Q3 where G e atoms are s u r r o u n d e d
by three BOs and one N B O . T h e composition
c o r r e s p o n d i n g to all Q3 atoms (in the absence of
disproportionation) is the d i g e r m a n a t e M z G e 2 0 5.
W h e n all G e atoms are Q2 (two BOs and two
NBOs), the composition is M z G e O 3 (metagermanate). O f course, in a glass some dispersion
in coordination numbers, b o n d distances and angles, may exist with respect to this simple description. M o r e o v e r disproportionation equilibria such
as 2 G e ( n ) ~ G e ( n - 1) + G e ( n + 1) must be considered. W e may try to extract information on the
g e r m a n a t e network from the R a m a n scattering
investigations.
T h e spectra may be separated in three ranges.
T h e low-frequency range (0 to 200 c m - ~ ) is due
to lattice m o d e s and P b - O vibrations. T h e mid-

frequency (200 to 600 c m - ~ ) and high-frequency


(600 to 1100 cm - l ) ranges are due to G e - O
vibrations. T h e decreasing scattering intensity in
the mid-frequency range relative to the highfrequency range, with increasing modifier content, is a general observation for g e r m a n a t e s as
well as for silicate glasses [7,27]. It seems obvious
that the increasing scattered intensity between
600 and 1100 c m - ~ is linked to a structural change
from a totally poIymerized network towards a
depolymerized one. Lines et al. [28] established a
quantitative correlation between the ratios of integrated intensities in both ranges and the a m o u n t
of heavy metal oxide (for instance PbO) atributing all scattered intensity in the mid-frequency
range to B O modes. T h e b a n d at - - 3 7 0 cm -1
seems not to have the same decreasing pattern
with increase in P b O concentration. In fact,
Canale et al. [18] have assigned this b a n d to a
P b - O stretching vibration along with deformation m o d e s of the g e r m a n i u m - o x y g e n network.
We have d e c o m p o s e d the high-frequency part
of the spectra, assuming Gaussian b a n d shapes
for the components. V H spectra, which must
contain only depolarized bands, were first decomposed and then VV spectra were similarly decomposed taking into account both polarized and
depolarized bands; for the latter of which the
frequency and line widths were d e t e r m i n e d in the
V H analysis. Figure 6 shows the results for compositions x = 0.25 and 0.53, and table 2 summarizes the decompositions.
T h e depolarized A b a n d may be related to a
completely polymerized Q4 network as its disapp e a r a n c e for higher contents is a c c o m p a n i e d by

Table 2
Parameters for the Gaussian functions utilized in the decompositions of the high-frequency ( > 600 cm t ) part of Raman spectra of
xPbO(1 - x)GeO 2 glasses
x
0.20
0.25
0.33
0.50
0.53

A(dp)
w
920
910
910

B(dp)
y
90
90
90

%
16
11
7

w
830
832
833
835
835

C(P)
y
67
63
65
60
60

%
30
20
18
9
7

o~
824
815
814
802
800

D(dp)
y
50
50
50
50
48

%
26
34
37
42
40

w
770
765
765
765
765

E(P)
y
70
70
70
70
70

%
25
35
37
38
38

dp, depolarized; P, polarized; w, wavenumber (cm-I); y, bandwidth (cm- 1); %(i), a r e a ( i ) / E i areas

3'

720
720

60
62

11
15

220

S.J.L. Ribeiro et al. / Lead germanate glasses

(o)

- - exp.

Z
I--

(b )
rr

660 -60 800 900 I~0 I100


WAVENUMBER (cm I)

Fig. 6. Gaussian decomposition for the high-frequency part of


the VV Raman spectra. (a) x = 0.25; (b) x = 0.53. See text for
assignments of the components.

that of the strongly polarized band at 450 cm-1.


This last band is the feature dominating the Raman spectrum of vitreous G e O 2 (Q4) [25].
The B and D components may be assigned to
the Q3 and Q2 species respectively. The frequencies for alkali and alkaline-earth germanates given
in refs. [7] and [27] are: Q3 (digermanate): 810
(VV), 860 and 780 cm -1 (VH); Q2 (metagermanate): 800 ( v v ) , 800 and 750 c m - 1 (VH).
With the general observation that a higher degree
of depolymerization leads to lower vibration frequencies in this range, our assignment is consistent, consistent as well with the fact that D increases at the expense of B for increasing x.
Surely the situation is more complex. Following
observations on alkali germanate glasses, one expects in fact two resolved partly depolarized bands
for each species in this region, and in lead germanate compounds ( P b G e O 4, P b s G e 3 0 1 0 two or
even three modes characterize one species [29].
In lead germanate glasses we observe a considerable overlap of the components.
We note that the intensities of the C and D
components increase in the same way versus x,
so C may be ascribed to Q2 as well. This assign-

ment is in good agreement with the spectrum of


lead m e t a g e r m a n a t e (fig. 2) where one observes a
band at 815 c m - t and a pair at 782 and 747 cm-1
that correspond to C and D respectively.
The lowest-frequency component, E, could be
due to Q0. A corresponding R a m a n mode occurs
in PbsGe30]] near 710 cm - t [29]. After these
data, the C and D components must also include
the contribution of the species Q1. These assignments for the five components we have isolated
agree with the characteristic frequencies extracted in ref. [29], except for orthogermanate
(Q0) reported at 760 cm-~ on average, instead of
the 720 c m - 1 observed in our glasses.
One may then conclude that lead plays the
role of a modifier of the germanate network, but
to a lesser extent than the alkaline M + ions.
From the data in ref. [7] one observes the presence of Q4 structure for x ~ 0.2 M 2 0 , whereas in
lead germanates evidence for a fully polymerized
network, given by the A mode, is observed for
x ~< 0.4. This observation seems to be a general
trend of lead oxide which to some extent has a
glass network-forming character since it favours
covalent directed P b - O rather than ionic
M + ... O - bonds. This point has been discussed,
for instance, for lead silicate glasses. From the
R a m a n and I R reflectivity data for these systems
obtained by one of us [20], the existence of PbO 4
pyramids in the glass from two peaks at 95 and
138 c m - ] which are also seen in PbO were proposed. Similar conclusions were proposed for lead
borate glasses [21]. The band at 140 cm -1 is
visible in our spectra for compositions x >/0.50
PbO, although it appears with a very weak intensity compared with the characteristic bands of the
germanate. It appears more strongly with respect
to the silicate bands [20]. This difference may be
easily understood if one considers observations
reported in ref. [27] that the intensities of the
R a m a n spectra for germanates are generally much
higher than those for silicates. The same lowfrequency features are observed in lead borate
glasses [21]. As discussed in this last reference,
the highly polarized line at 140 c m - t is due to
the symmetric vibration of the PbO 4 tetragonal
pyramid. Because of the lone electronic pair of
Pb 2+, fourfold or threefold coordinations are en-

S.J.L. Ribeiro et al. / Lead germanate glasses

countered in many oxygenated compounds, crystallized or glasses.


Low coordination of lead in our samples is
verified by the EXAFS analysis at Pb Lm-edge.
The mean values for P b - O distances and coordination numbers (R = 2.35 + 0.05 .& and N = 3 _+
0.5) may be of value in the construction of a
structural model. In lead silicate glasses, for example, different models can be constructed considering the coordination number for lead as 3, 4
or 6 [30].

5. Conclusions
The vibrational and EXAFS studies carried
out for lead germanate glasses xPbO(1 - x ) G e O 2
are satisfactorily interpreted by a structural
change starting from a polymerized germanate
network, with all Ge atoms linked to four bridging o x y g e n s (Q4), to a depolymerized structure
made basically of tetrahedral [GeO 4] units with
one to four non-bridging oxygens ( 0 3 to Q0).
Pb at low content plays the role of modifier in
t h e germanate glass structure, but to a lesser
extent than an equivalent amount of alkaline ions
(M ). Low coordination numbers suggest pyramidal structures for the range of compositions studied.

S.J.L.R. acknowledges CAPES and FUNDUNESP (Brazilian agencies) for financial support, Dr A. Michalowicz for the EXAFS data
treatment software, Dr O.R. Nascimento for the
spectral decomposition software, and Dr J.P. Itie
for the glassy GeO 2 sample. The authors also
acknowledge the referees for helpful suggestions.

References
[1] H. Hasegawa, M. Shimada and M.J. Koizumi, J. Mater.
Sci. 8 (1973) 1725.
[2] S.J.L. Ribeiro, O.L. Malta, G.F. deSS., J. Dexpert-Ghys,

221

B. Piriou, H. Dexpert and V.R. Mastelaro, J. Alloys


Compounds 180 (1992) 117.
[3] A.O. Ivanov and K.S. Evstropiev, Dokl. Akad. Nauk.
USSR 145 (1960) 797.
[4] W.K. Murthy and J. Ip, Nature 18 (1964) 285.
[5] A. Osaka, K. Takahashi and K. Ariyoshi, J. Non-Cryst.
Solids 70 (1985) 243.
[6] M.K. Murthy and E.M. Kirby, Phys. Chem. Glasses 5
(1964) 144.
[7] H. Verweij and J.H. Buster, J. Non-Cryst. Solids 34
(1979) 81.
[8] K, Kamiya and S. Sakka, Phys. Chem. (;lasses 20 (1979)
60.
[9] A.D. Cox and P.W. McMillan, J. Non-Cryst. Solids 44
(1981) 257.
[10] C. Lapeyre, J. Petiau, G. Calas, F. Gauthier and J.
Gombert, Bull. Mineral. 106 (1983) 77.
[11] G.S. Henderson and M.E. Fleet, J. Non-Cryst. Solids 134
(1991) 259.
[12] J.P. Itie, A. Polian, G. Calas, J. Petiau, A. Fontaine and
H. Tolentino, Phys. Rev. Lett. 63 (1989) 398.
[13] J.P. Itie, private communication
[14] J.A. Topping, I.T. Harrower and M.K. Murthy, J. Am.
Ceram. Soc. 57 (1974) 209.
[15] J.A. Ruller, C.M. Shaw and J.E. Shelby, Phys. Chem.
Glasses 33 (1992) 161.
[16] V.N. Morosov, Zh. Prikl. Spectrosc. 8 (1968) 830.
[17] V.A. Kolesova, Fiz. Khim. Stekla 5 (1981)) 325.
[18] J.E. Canale, R.A. Condrate St., K. Nassau and B.C.
Cornilsen, J. Can. Ceram. Soc. 55 (1986) 50.
[19] A.E. Miller, K. Nassau, K.B. Lyons and M.E. Lines, J.
Non-Cryst. Solids 99 (1988) 289.
[20] H. Arashi and B. Piriou, High Temp. Sci. 13 (1980) 299.
[21] A.M. Zahra, C.Y. Zahra and B. Piriou, submitted for
publication.
[22] A.N. Lazarev and V.A. Kolesova, lnorg. Mater. (Englisb
Transl.) 6 (1970) 351.
[23] A. Michalowicz, thesis, Universit~ du Val de Marne,
France (1990).
[24] R. Shuker and P.G. Gammon, Phys. Rev. Lett. 25 (1970)
222.
[25] F.L. Galeener, A.J. Leadbetter and M.W. Stringfellow,
Phys. Rev. B27 (1983) 1052.
[26] R.E. Newnham, R.W. Wolfe and C.N.W. Darlington, J.
Solid State Chem. 6 (1973) 378.
[27] H. Verweij, J. Non-Cryst. Solids 33 (1979) 41; 33 (1979)
55.
[28] M.E. Lines, A.E. Miller, K. Nassau and K.B. Lyons, J.
Non-Cryst. Solids 89 (1987) 163.
[29] G. Burns and B.A. Scott, Phys. Lett. A39 (1973) 177.
[30] H. Hasegawa and M. Imaoka, J. Non-Cryst. Solids 68
(1984) 157.