]OffRNAb OF

ELSEVIER Journal of Non-CrystallineSolids 180 (1994) 51-57

IR spectra and structure of VzO5-GeOe-Bi203 glasses

Vesselin Dimitrov a,,, Yanko Dimitriev a, Angelo Montenero b
a Higher Institute of Chemical Technology, bul. Kl Ohridski 8, Sofia 1756, Bulgaria
b . . . .
DtparUmento dt . Chtmlca Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Universita di Parma, Parma, Italy
Received 23 March 1994

Abstract

This paper reports a study of the structure of V2Os-GeO2-Bi203 glasses by IR spectroscopy to obtain information about
the competitive role of each of V205, GeO2 and Bi203 in the formation of the glass network. The amorphous samples were
obtained by the twin-roller technique. Bi203 leads to transformation of the layered and chain vanadate structure and
depolymerization of the three-dimensional germanate lattice. The bismuthate complexes can be viewed as deformed BiO6
groups. It is established that with a decrease in the V205 content VO4 groups are formed. G e O 4 structural units with
different degrees of polymerization are present in the network in the entire concentration range.

1. Introduction competitive role of each of the three oxides in

GeO 2 is a typical glass-former while V205 and
Bi20 3 are conditional glass-formers [1]. Germanate
glasses are widely known and successfully used in
optics [2,3], Vanadate glasses are amorphous oxide
semiconductors [4-6]. Bismuthate glasses have been
extensively investigated following the pioneering pa-
pers of Dumbaugh [7,8]. Recently, interest in bis-
muthate glasses has increased because of their high
non-linear optical susceptibility [9] and their ability
to synthesize high-temperature ceramic superconduc-
tors [10-12]. Along with their interesting technologi-
cal applications, all three groups of vitreous systems
have been the object of studies related to the elucida-
tion of their structural pecularities [13-15]. From
that point of view it is of interest to study the
* Corresponding author. Tel: +359-2 625 4214. Telefax:
+ 359-2 685 488.
network formation. That problem is of importance
for an explanation of the glass-forming ability of
multicomponent compositions.
The purpose of this paper is to obtain information
on the basic structural polyhedra which form the
glass networks in the V2Os-GeO 2, GeO2-Bi20 3,
VzOs-Bi203 and the V2Os-GeO2-Bi20 3 systems,
with the aid of IR spectroscopy.
2. Experiment
The batches were prepared by melting chemically
pure V205, GeO 2 and BizO 3 for 10-15 min at
900-1000°C in silica crucibles for compositions with
a high V205 concentration and in corundum cru-
cibles for other compositions. Vitrification was at-
tained by the twin-roller technique. Bulk samples
cannot be obtained by this technique, but fragmented
1-3 mm flat pieces, about 50-100 p,m thick are
52 v. Dimitrov et al. /Journal of Non-Crystalline Solids 180 (1994) 51-57

produced. It is assumed that compositions in which V ~ 0 5 2 1 - O e O ~

vitreous pieces form lie in the glass-forming area. If
the volumes of the vitreous and crystalline sections 5
are comparable, they are shown as a mixture of glass 1(]20 830 640
and crystals.
The IR spectra of the glasses and crystal products
'~ ~60 78,0 6
were recorded on a two-beam Specord-M80 spec-
trophotometer (Karl Zeiss, Jena) in the 1300-400
cm-1 range. The samples were prepared as suspen- 550
sions in liquid paraffin. The precision of the absorp-
tion maxima is -t-1.5 cm-~ for the crystalline sam-
870 780 7
ples and + 3 cm- 1 for the glasses. The samples were
confirmed to be amorphous using an X-ray DRON- 4
IM diffractometer (Cu Kot radiation, Ni filter).
870
1020 860780 ~50
3. Results
I I I I I , I J
1200/ 1000 800 6010 400 1200 1000 800 600 400
Fig. 1 shows the location of the compositions in Wavenumber, cm-I
the V2Os-GeO2-Bi203 system. Figs. 2 - 6 give the Fig. 2. IR spectra of glasses in the V 2 0 5 - G e O 2 system: 1 -
IR spectra of glasses in the V2Os-GeO 2, V205- V205; 2 - 80V205•20GeO2;3 - 70V205•30GeO2; 4 - 60V205-
Bi203, GeO2-Bi203 and V2Os-GeO2-Bi203 sys- 40GeO2; 5 - 43V205.57GEO2; 6 - 20V205.80GeO2;7 - GeO2.
tem and also the IR spectra of crystal phases in the
GeO2-Bi203 system. GeO 2 changes the shape of the spectra below 900
cm -~. Three new maxima appear at 870-860, 780
3.1. V 2 0 5 - G e O 2 system and 550 cm -~. The spectrum of vitreous GeO 2 has
two well-defined bands at 870 and 550 cm -~.
The spectrum of pure vitreous V205 is character-
ized by a well-shaped band at 1020 cm -1, a weak 3.2. B i 2 0 3 - G e O 2 system
maximum at 830 cm-1 and a broad absorption band
with a maximum at about 640 cm-1 (Fig. 2). The spectrum of the glass having the highest
The band at 1020 cm -1 is likewise preserved in GeO2 content (90 mol%) is characterized by two
the spectra of binary glasses. The introduction of well-defined bands at 830 and 545 cm-1 (Fig. 3). An
increase of Bi203 to 60 mol% gives a shift of the
Bi 2 03 high-frequency band from 830 to 730 cm-1, while
above 25 mol% of Bi203 a new band appears at 440
cm-~ which gradually increases in intensity. Spectra
of glasses having a high Bi203 content (70 and 80
mol%) possess only two bands at 720 and 475 cm -1.
Comparison of the vitreous Bi2Ge309, BiaGe3012,
Bi2GeO 5 and Bil2GeO20 (Fig. 3) indicates good
coincidence with those of the corresponding crys-
talline phases (Fig. 4).

3.3. V205-Bi203 system

fie 02 V2 05
Fig. 1. Location of the compositions in the V 2 O s - G e O 2 - B i 2 0 3 An analysis of the spectra in the V2Os-Bi203
system: (3 - glass; ~ - glass + crystal. binary system (Fig. 5) shows that the addition of
 V. Dimitrov et al. /Journal of Non-Crystalline Solids 180 (1994) 51-57 53

Bi203 to V205 causes the disappearance of the

high-frequency band at 1020 cm -1. A new band
appears at 950 cm -1 which shifts slightly to 930
cm -~ for a composition having 40 mol% Bi203.
Simultaneously, along with the band at 820 cm -1 , o
another band is formed at 760 cm-1 which becomes 890 V
determinant with further increases in the Bi20 3 con-
tent to 70 mol%. This is accompanied by the disap-
pearance of the band at 930 cm-1 and the appear-
ance of a shoulder at 620 cm-~ and a new band at
42B
480 c m - 1.

3.4. V205-GeO2-Bi203 system

The IR spectrum of a glass containing 70 mol%

V205 contains a well-shaped band at 930 cm -1 and
,oo I

Bi,',O= - Ge 0 2

~ ~h750
520V/
c 470
L 13
I
1200
I
1000
10
8 0
600 ~00
Wovenumber cm1
Fig. 4. IR spectra of crystal phases in the B i 2 0 3 - G e O 2 system.

three others, having the same intensity at 840, 760

720 ~,75 and 620 cm -1 (Fig. 6). An increase in the Bi203
content instead of GeO 2 and V205 leads to an
alteration of the type of spectra. There is a strong
increase in the intensity in the band at 760-740
cm -1. The IR spectra of glasses with a high Bi203
content (80 and 90 mol%) is defined by two well-
shaped absorption maxima at 730 and 480-475
" \ H;,,o c m - 1.

475 4. Discussion
750
12100 I
1000
t
800
t 1
600 400
I I
1200 1000
I
800
I
600
I
400 The discussion on the bands observed in the
Wovenumber crn-1
spectra of the glasses studied in this paper has been
Fig. 3. IR spectra of glasses in the B i 2 0 3 - G e O 2 system: 8 -
carried out in agreement with the concept about the
1 0 B i 2 0 3 , 9 0 G e O 2 ; 9 - 20Bi2Oa.80GeO2; 10 - 25Bi203-
75GeO 2; 11 - 40Bi203 • 60GeO 2; 12 - 50Bi 203 - 50GeO 2; 13 -
independent vibrations in glasses, discussed by Tarte
6 0 B i 2 0 3 - 4 0 G e O 2 ; 14 - 7 0 B i 2 0 3 . 3 0 G e O 2 ; 15 - 8 0 B i 2 0 3 . [16,17] and Condrate [18]. It is assumed that vibra-
20GEO2; 16 - 8 5 . 7 B i 2 0 3 • 14.3GEO 2. tions of characteristic groups of atoms in the network
54 V. Dimitrov et al. /Journal of Non-Crystalline Solids 180 (1994) 51-57

are independent of vibrations of other groups. This

approach has also been used in the author's earlier
work [14,19]. Such an empirical treatment can pro-
vide significant information on the arrangement of
atoms in glasses.
Infrared spectra of vanadates in the crystalline and g /'~ 992 2 ~ 130
vitreous states have characteristic bands in the 1020-
750 cm-~ range. The IR spectrum of pure crystalline 92
V205 is characterized by an intense band at 1020
cm-1, related to vibrations of isolated V = O vanadyl
groups in VO 5 trigonal bipyramids, a wide absorp-
tion band at 830-820 cm -1, related to vibrations of
V - O - V chains, and bands about 600 cm -~ which

•1\,6o1
correspond mainly to the bending vibrations [20-22].
It was found that the IR spectrum of the vitreous \ / .o

V205 is similar to that of the crystal [23]. As seen in

g2o\ / ~ 32
Fig. 2 (spectrum 1), the band at 1020 cm -1 is
preserved. This means that isolated V - O bonds are
preserved in the vitreous structure. The band does
not change its location when the GeO 2 content is
increased. This is an indication that in the entire
765
I I I I I [ I I • I
1200 1000 800 600 400 1200 1000 800 600 400
f V2 0 S - Bi 2 0 3 Wovenumber , cn~ 1

Fig. 6. IR spectra o f glasses in the V 2 0 5 - o e O 2 - B i 2 0 3 system:

24 - 7 0 V 2 O s . 1 5 G e O 2 . 1 5 B i 2 0 3 ; 25 - 2 1 V 2 O s . 6 1 G e O 2.
lO2O 830 64o 1 ;o 1 8 B i 2 0 3 ; 26 - 4 0 V 2 O s - 4 0 G e O 2 . 2 0 B i 2 0 3 ; 27 - 6 0 V 2 0 5 .
1 0 G e O 2 - 3 0 B i 2 0 3 ; 28 - 3 2 . 5 V 2 O s . 3 2 . 5 G e O 2 - 3 5 B i 2 0 3 ; 29 -
18V205 . 4 1 G e O 2 . 4 1 B i 2 0 3 ; 30 - 25%1205 • 2 5 G e O 2 . 5 0 B i 2 0 3 ; 31
- 10V205 - 1 0 G e O 2 • 8 0 B i 2 0 3 ; 32 - 5V205 • 5 G e O 2 • 9 0 B i 2 0 3 .

concentration range VO 5 groups, similar to those in

the pure VzO 5 glass, take part in the glass network.
Changes occur in the 900-500 cm -1 range. The
band at 830 cm -1 disappears. This fact provides
grounds to assume that Ge 4+ cations break up V -
O - V chains through formation of bridge bonds,
V - O - G e , without directly attacking isolated V - O
/ \ / BiVO~ k / V bonds at VO 5 groups.
This is a good proof of the mechanism suggested
in Ref. [14]. The band at 780 cm -1 can be assigned
7t.0 to vibrations of this mixed type of V - O - G e bond.
, , I , , I The appearance of the other two new bands in the
12oo 1o'oo ,oo ,2'oo 1ooo spectra of binary glasses correlate well with bands
Wovenumber . c~ I
observed in vitreous GeO 2 (Fig. 2) at 870 and 550
Fig. 5. IR spectra o f glasses in the V 2 O s - B i 2 0 3 system: 1 -
V205; 17 - 8 0 V z O s . 2 0 B i 2 0 3 ; 18 - 7 0 V 2 O s . 3 0 B i 2 0 3 ; 19 -
cm -1. The band at 870 cm -a is referred to the
6 0 V 2 O s . 4 0 B i 2 0 3 ; 20 - 5 0 V 2 O s . 5 0 B i 2 0 3 ; 21 - 4 0 V 2 0 5 . double degenerate stretching vibrations of the G e - O
6 0 B i 2 0 3 ; 22 - 3 0 V 2 0 5 . 7 0 B i 2 0 3 ; 23 - 2 0 V 2 0 5 . 8 0 B i 2 0 3 . bonds of the GeO 4 tetrahedra, and that at 550 cm-1
 V. Dimitrov et al. /Journal of Non-Crystalline Solids 180 (1994) 51-57
to the bending vibrations of the latter [23]. It was
found that in alkaline-germanate glasses, as well as
in other vitreous systems containing GeO 2 [25], the
band at 870 cm -1 shifts towards low frequencies
and, at the same time, a new band appears at 720-700
cm -1 when the GeO 2 content decreases. This is
connected with depolymerization of the network of
vitreous GeO 2 and with the change of Ge coordina-
tion number from four to six in the glasses. As seen
in the spectra given in Fig. 2, the band discussed
does not change its location on varying the composi-
tion and also a band at about 700 cm-~ is absent.
Therefore no change in the Ge coordination number
occurs and only GeO 4 polyhedra are present in the
vitreous network. It is possible that they occupy an
position equivalent to the VO 5 groups. A similar
situation is shown also for the glasses of the P205 -
GeO 2, TiO2-GeO 2 and for SiO2-GeO 2 systems
[26].
Betsch and White [27] reported detailed data on
the IR and Raman spectra of ct-Bi203 and bis-
muthate phases Bi12MO20 having the silenite struc-
ture. In accordance with these investigations, bands
at 670, 620, 580 and 390 cm -~ in the spectrum of
ot-Bi203 and those at 520 and 460 cm -1 in the
spectrum of Bi~2GeO20 are interpreted as vibrations
of Bi-O bonds of different lengths in the distorted
BiO 6 polyhedra. Bishay and Maghrabi [15] presume
the existence of BiO 3 polyhedra in fused Bi203 and
alkaline boron-bismuthate glasses. A precondition
for this is the band at 840 cm-1 in the spectra of
these samples. This band is related to the symmetri-
cal stretching vibrations of the Bi-O bonds in the
BiO 3 groups, having C3~, symmetry. A similar band,
along with two others at 600 and 470 cm -1, were
observed also by Zheng et al. [28] in the spectra of
B i - C a - S r - O glasses and the conclusion has been
drawn that both BiO 3 and BiO 6 groups exist in the
glasses. By IR spectral studies, Dimitriev and Mi..
hailova [29] have shown the presence of BiO 6 groups
in bismuthate glasses of the Bi203-CuO, BizO3--
PbO, Bi203-SrO-CuO and Bi203-SrO-CaO-CuO
systems and a shift of the band from 480 to 520
cm -1 at low BieO 3 content which is related to the
change of local symmetry in the polyhedra. New
data of the Bi-O distances were obtained by X-ray
and neutron diffraction [30]. A strong interaction
between the Sr and BiO 6 groups was discussed by
55
Miyaji et al. [31] in Bi203-CaO-CuO and Bi203-
SrO-CuO glasses. The IR spectra of certain Bi2Ge 3
09, Bi4Ge3012 and Bi12GeO20 phases were ob-
tained by Tarasova and Kosov [32] and Firsov et al.
[33]. The two groups of bands at 600-575 and
520-470 cm -1 in the spectrum of the Bi12GeO20
silenite phase were assigned to the vibrations of
strongly distorted BiO 6 octahedra. A detailed analy-
sis of the IR spectrum of Bi4Ge3012 was carried out
by Hirota et al. [34], whose crystal structure was
built up by ring-like Ge30 9 groups and BiO 6 octahe-
dra. The bands observed in the spectrum were as-
signed as follows: 900-850 cm -1 (Vas OOeO), 830--
790 cm -1 (v s OGeO), 765-600 cm -1 (Vas GeOGe) and
600-500 cm -1 (vs O~O~e)" The bands below 500
cm- 1 are related to stretching vibrations of the Bi-O
bonds. It is seen from the spectra of the glasses in
the Bi203-GeO 2 binary system (Fig. 3) that the
introduction of 10 mol% Bi203 results in a shift of
the band of the double degenerate stretching vibra-
tion of Ge-O bonds to 830 cm-1 in relation to the
same band at 870 cm -1 in vitreous GeO 2 (Fig. 2).
As pointed out above, this could be related to the
depolymerization of the three-dimensional network
of GeO 2 with increasing Bi20 3. The decrease in
frequency of this band continued. In the composition
having 40 mol% Bi203, corresponding to stoichio-
metric Bi4Ge3012 , the same band shifts to 750 cm -a.
A comparison of the spectrum of the vitreous
BiaGe3012 (Fig. 3) with that of the crystal phase,
obtained by Hirota et al. [34] (Fig. 4), shows good
agreement. This suggests that the absorption maxima
of the glasses at 750, 540 and 430 cm-1 could be
related to VasGeOOe, UsGeOGe and uBi_o respectively.
Therefore, the main structural groups in the glass are
Ge309 ring-like complexes, built up by GeO 4 tetra-
hedra and GeO 6 octahedra. A further increase in
Bi203 content to 85.7 mol%, corresponding to stoi-
chiometric Bi12GeO20 , leads to a decrease of the
number of bands to two at 720 and 475 cm-1. The
correspondence between spectra of vitreous Bil2
GeO20 (Fig. 3) and that of the crystal phase (Fig. 4)
is established. On the basis of the crystal structure
data of Bi12GeO20 [35] and other similar crystalline
germanates [36], the glass network of Bi12GeO20 is
built up by BiO 6 octahedra (band at 475 cm -1) and
isolated GeO 4 tetrahedra (band at 720 cm-1).
In an IR study of bismuth-germanate glasses,
56 v. Dimitrov et al. /Journal of Non-Crystalline Solids 180 (1994) 51-57
Capelletti et al. [37] noticed that the ratio of band
intensity at 878 and 725 cm-1 depends on the ratio
of Bi20 3 to GeO 2. They suggest that germanium
could be present as GeO 4 and GeO 6 groups simulta-
neously. In this case, BizO 3 modifies this ratio.
Another possibility is that bismuth oxide depolymer-
izes G e - O chains. More recent EXAFS studies [38]
on the same system do not report evidence of GeO 6
octahedra. The results obtained in our case are in
accordance with those in Ref. [38] with respect to the
main coordination polyhedra of Ge 4+ and Bi 3+ in
the glass structure - GeO 4 and BiO 6.
As seen from the spectra of glasses in the V205-
Bi20 3 system, the addition of 20 mol% Bi20 3 leads
to disappearance of the band at 1020 cm -1. In
accordance with the mechanism suggested in Ref.
[14], Bi 3÷ cations obviously achieve a direct attack
on the V = O bonds as a result of which the polyhe-
dra are transformed into VO 4. The appearance of the
band at 950 cm -1, which gradually shifts to 930
cm -1 with a 40 mol% Bi20 3 content, can be related
to the vibrations of the free VO 2 groups of the VO,
tetrahedra, forming chains with V - O - V bridges.
Their bands are in the 840-820 cm-1 region. The
gradual decrease in intensity of that band together
with the appearance of a strong band at 760-740
cm-1 (Fig. 5) after adding 50 mol% of Bi2G 3 could
be explained by formation of isolated VO 4 tetrahedra
in the bismuthate network. The band at 760-740
cm-1 is interpreted as a consequence of triply de-
generate stretching vibrations Vdv_o of isolated VO 4
tetrahedra [19]. Similar behavior was seen in the IR
spectrum of the Bi25VO40 phase [39] in whose struc-
ture the VO 4 tetrahedra occupy an isolated position.
Likewise, a tetrahedral coordination of V 5+ was
shown with the aid of electron diffraction and high
resolution microscopy of the superstructures in the
Bi203-V205 system in the range between the pure
Bi203 and the BiVO 4 phase [40]. The band at 480
cm-1 and the shoulder at 620 cm-1 which become
visible in the spectra above 50 mol% Bi20 3 (Fig. 5)
correspond to the B i - O vibrations of the BiO 6
groups. Direct evidence for the affiliation of the band
at 480 cm-1 with B i - O vibrations is the increase in
its intensity with increasing Bi20 3 content.
The structure of glasses in the V2Os-GeO2-Bi203
ternary system could be interpreted on the basis of
IR spectral data for binary systems. The structure of
a glass with high V205 content (70 mol%) (Fig. 6) is
mainly built up by VO 4 groups related to V - O - V
bridges (bands at 930 and 840 cm -1). The increase
in Bi203 content at the expense of GeO 2 and V205
transforms the structure into a bismuthate one, mainly
formed by BiO 6 octahedra (band at 480 cm-1). The
vanadate and germanate ions are incorporated into
the glass network as isolated VO 4 and GeO 4 groups.
The well-formed absorption maximum at 740-730
c m - I is evidence for their presence (Fig. 6).
Therefore the increase in the Bi20 3 content of the
glasses leads to transformation of the layered and
chain vanadate structure and depolymerization of the
three-dimensional germanate lattice. VO 4 and GeO 4
groups are preserved in a broad concentration range.
The bismuthate complexes could be viewed as de-
formed BiO 6 groups, since there is no spectral proof
for formation of BiO 3 polyhedra. This is one of the
reasons for the decreased glass-forming ability the
system.
5. Conclusion
It is found on the basis of IR spectral investiga-
tion of VeOs-GeO2-Bi20 3 glasses that Bi 3+ cations
are incorporated in the glass network as deformed
BiO 6 groups. Vanadium and germanium take part in
the network of the glasses as VO 5, VO 4 and GeO 4
groups.
This research work was supported by the Bulgar-
ian Fundation of Science, Contract X-208, 1993/94.
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