Professional Documents
Culture Documents
North-Holland
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
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.
214
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-
215
[ 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
',U
(1)
it
ljh~li,,,l
. . . . . . . . . . . . .
~0
I000
500
iO00
216
9O
3O
%-
500
1OOO
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)
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)).
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
! ~,2/%~
Fk
' ~2
'
0.20
plCU
bb d
0.25
~.o/
; T ;",
~ ~/\
x
w
q
0.40
o ~
0.50
%fo.~
,~
0.53
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.
218
219
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
(o)
- - exp.
Z
I--
(b )
rr
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