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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.
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.
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
•1\,6o1
correspond mainly to the bending vibrations [20-22].
It was found that the IR spectrum of the vitreous \ / .o
to the bending vibrations of the latter [23]. It was Miyaji et al. [31] in Bi203-CaO-CuO and Bi203-
found that in alkaline-germanate glasses, as well as SrO-CuO glasses. The IR spectra of certain Bi2Ge 3
in other vitreous systems containing GeO 2 [25], the 09, Bi4Ge3012 and Bi12GeO20 phases were ob-
band at 870 cm -1 shifts towards low frequencies tained by Tarasova and Kosov [32] and Firsov et al.
and, at the same time, a new band appears at 720-700 [33]. The two groups of bands at 600-575 and
cm -1 when the GeO 2 content decreases. This is 520-470 cm -1 in the spectrum of the Bi12GeO20
connected with depolymerization of the network of silenite phase were assigned to the vibrations of
vitreous GeO 2 and with the change of Ge coordina- strongly distorted BiO 6 octahedra. A detailed analy-
tion number from four to six in the glasses. As seen sis of the IR spectrum of Bi4Ge3012 was carried out
in the spectra given in Fig. 2, the band discussed by Hirota et al. [34], whose crystal structure was
does not change its location on varying the composi- built up by ring-like Ge30 9 groups and BiO 6 octahe-
tion and also a band at about 700 cm-~ is absent. dra. The bands observed in the spectrum were as-
Therefore no change in the Ge coordination number signed as follows: 900-850 cm -1 (Vas OOeO), 830--
occurs and only GeO 4 polyhedra are present in the 790 cm -1 (v s OGeO), 765-600 cm -1 (Vas GeOGe) and
vitreous network. It is possible that they occupy an 600-500 cm -1 (vs O~O~e)" The bands below 500
position equivalent to the VO 5 groups. A similar cm- 1 are related to stretching vibrations of the Bi-O
situation is shown also for the glasses of the P205 - bonds. It is seen from the spectra of the glasses in
GeO 2, TiO2-GeO 2 and for SiO2-GeO 2 systems the Bi203-GeO 2 binary system (Fig. 3) that the
[26]. introduction of 10 mol% Bi203 results in a shift of
Betsch and White [27] reported detailed data on the band of the double degenerate stretching vibra-
the IR and Raman spectra of ct-Bi203 and bis- tion of Ge-O bonds to 830 cm-1 in relation to the
muthate phases Bi12MO20 having the silenite struc- same band at 870 cm -1 in vitreous GeO 2 (Fig. 2).
ture. In accordance with these investigations, bands As pointed out above, this could be related to the
at 670, 620, 580 and 390 cm -~ in the spectrum of depolymerization of the three-dimensional network
ot-Bi203 and those at 520 and 460 cm -1 in the of GeO 2 with increasing Bi20 3. The decrease in
spectrum of Bi~2GeO20 are interpreted as vibrations frequency of this band continued. In the composition
of Bi-O bonds of different lengths in the distorted having 40 mol% Bi203, corresponding to stoichio-
BiO 6 polyhedra. Bishay and Maghrabi [15] presume metric Bi4Ge3012 , the same band shifts to 750 cm -a.
the existence of BiO 3 polyhedra in fused Bi203 and A comparison of the spectrum of the vitreous
alkaline boron-bismuthate glasses. A precondition BiaGe3012 (Fig. 3) with that of the crystal phase,
for this is the band at 840 cm-1 in the spectra of obtained by Hirota et al. [34] (Fig. 4), shows good
these samples. This band is related to the symmetri- agreement. This suggests that the absorption maxima
cal stretching vibrations of the Bi-O bonds in the of the glasses at 750, 540 and 430 cm-1 could be
BiO 3 groups, having C3~, symmetry. A similar band, related to VasGeOOe, UsGeOGe and uBi_o respectively.
along with two others at 600 and 470 cm -1, were Therefore, the main structural groups in the glass are
observed also by Zheng et al. [28] in the spectra of Ge309 ring-like complexes, built up by GeO 4 tetra-
B i - C a - S r - O glasses and the conclusion has been hedra and GeO 6 octahedra. A further increase in
drawn that both BiO 3 and BiO 6 groups exist in the Bi203 content to 85.7 mol%, corresponding to stoi-
glasses. By IR spectral studies, Dimitriev and Mi.. chiometric Bi12GeO20 , leads to a decrease of the
hailova [29] have shown the presence of BiO 6 groups number of bands to two at 720 and 475 cm-1. The
in bismuthate glasses of the Bi203-CuO, BizO3-- correspondence between spectra of vitreous Bil2
PbO, Bi203-SrO-CuO and Bi203-SrO-CaO-CuO GeO20 (Fig. 3) and that of the crystal phase (Fig. 4)
systems and a shift of the band from 480 to 520 is established. On the basis of the crystal structure
cm -1 at low BieO 3 content which is related to the data of Bi12GeO20 [35] and other similar crystalline
change of local symmetry in the polyhedra. New germanates [36], the glass network of Bi12GeO20 is
data of the Bi-O distances were obtained by X-ray built up by BiO 6 octahedra (band at 475 cm -1) and
and neutron diffraction [30]. A strong interaction isolated GeO 4 tetrahedra (band at 720 cm-1).
between the Sr and BiO 6 groups was discussed by 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 a glass with high V205 content (70 mol%) (Fig. 6) is
intensity at 878 and 725 cm-1 depends on the ratio mainly built up by VO 4 groups related to V - O - V
of Bi20 3 to GeO 2. They suggest that germanium bridges (bands at 930 and 840 cm -1). The increase
could be present as GeO 4 and GeO 6 groups simulta- in Bi203 content at the expense of GeO 2 and V205
neously. In this case, BizO 3 modifies this ratio. transforms the structure into a bismuthate one, mainly
Another possibility is that bismuth oxide depolymer- formed by BiO 6 octahedra (band at 480 cm-1). The
izes G e - O chains. More recent EXAFS studies [38] vanadate and germanate ions are incorporated into
on the same system do not report evidence of GeO 6 the glass network as isolated VO 4 and GeO 4 groups.
octahedra. The results obtained in our case are in The well-formed absorption maximum at 740-730
accordance with those in Ref. [38] with respect to the c m - I is evidence for their presence (Fig. 6).
main coordination polyhedra of Ge 4+ and Bi 3+ in Therefore the increase in the Bi20 3 content of the
the glass structure - GeO 4 and BiO 6. glasses leads to transformation of the layered and
As seen from the spectra of glasses in the V205- chain vanadate structure and depolymerization of the
Bi20 3 system, the addition of 20 mol% Bi20 3 leads three-dimensional germanate lattice. VO 4 and GeO 4
to disappearance of the band at 1020 cm -1. In groups are preserved in a broad concentration range.
accordance with the mechanism suggested in Ref. The bismuthate complexes could be viewed as de-
[14], Bi 3÷ cations obviously achieve a direct attack formed BiO 6 groups, since there is no spectral proof
on the V = O bonds as a result of which the polyhe- for formation of BiO 3 polyhedra. This is one of the
dra are transformed into VO 4. The appearance of the reasons for the decreased glass-forming ability the
band at 950 cm -1, which gradually shifts to 930 system.
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. 5. Conclusion
Their bands are in the 840-820 cm-1 region. The
gradual decrease in intensity of that band together It is found on the basis of IR spectral investiga-
with the appearance of a strong band at 760-740 tion of VeOs-GeO2-Bi20 3 glasses that Bi 3+ cations
cm-1 (Fig. 5) after adding 50 mol% of Bi2G 3 could are incorporated in the glass network as deformed
be explained by formation of isolated VO 4 tetrahedra BiO 6 groups. Vanadium and germanium take part in
in the bismuthate network. The band at 760-740 the network of the glasses as VO 5, VO 4 and GeO 4
cm-1 is interpreted as a consequence of triply de- groups.
generate stretching vibrations Vdv_o of isolated VO 4
tetrahedra [19]. Similar behavior was seen in the IR This research work was supported by the Bulgar-
spectrum of the Bi25VO40 phase [39] in whose struc- ian Fundation of Science, Contract X-208, 1993/94.
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 References
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