ISSN 1087-6596, Glass Physics and Chemistry, 2022, Vol. 48, No. 2, pp. 111–116. © Pleiades Publishing, Ltd.

, 2022.
Russian Text © The Author(s), 2022, published in Fizika i Khimiya Stekla.

Effect of Tungsten Oxide on the Crystallization Properties of Glasses

of the B2O3–La2O3–Nb2O5 System
O. A. Bogdanova, b, *, **, D. D. Nesmelovb, and N. O. Tagiltsevab
a Institute of Silicate Chemistry, Russian Academy of Sciences, St. Petersburg, 199034 Russia
b St. Petersburg State Technological Institute (Technical University), St. Petersburg, 190013 Russia
*e-mail: magfer@mail.ru
**e-mail: bogdanov.oa@iscras.ru
Received May 24, 2021; revised October 26, 2021; accepted December 6, 2021

Abstract—The effect of tungsten oxide on the crystallization properties of glasses of the 37.5B2O3 22.5La2O3
(40 – x)Nb2O5 xWO3 (where x = 10, 15, 20, 30, 40 mol %) system when replacing them with niobium pent-
oxide is studied. It is established that during the crystallization of glasses containing niobium and tungsten,
the parallel precipitation of crystalline phases of complex LaxNbyAlzWnOm tungstates and LaNbWAlBO
borates of a variable chemical composition is observed.

Keywords: borate glass, crystallization, SEM, XRF, tungstates, borates

DOI: 10.1134/S108765962202002X

INTRODUCTION [7] and photocatalysts [8], Sc2(WO4)3 has negative

Borate glasses are distinguished by low synthesis
temperatures, good compatibility with rare earth and
transition metals, broad glass formation boundaries,
and optical nonlinearity of the second and third
orders. Boron-lanthanum glasses doped with rare-
earth and transition metals are of interest as materials
for the active medium of solid-state lasers, radiation
scintillators, and other photonic devices. Niobate
boron-lanthanum glasses were originally developed as
optical materials with a very high refractive index
(nD ≥ 1.85). The introduction of niobium pentoxide
inevitably led to an increase in the dispersion of
glasses, and to eliminate this problem, WO3 was intro-
duced into the glasses.
There is not much information about the crystalli-
zation of niobium-containing lanthanum-boron
glasses. These glasses have similar glass transition and
crystallization temperatures and narrow exothermic
peaks on the DSC diagrams [1–3].
Niobium and rare earth elements (REEs) form a
whole class of oxides called orthoniobates (ReNbO4),
which are distinguished by characteristic ferroelastic-
ity and strong luminescence (EuNbO4, ErNbO4). It is
possible to form perovskite-like structures of the
Re0.33NbO3 type [4–6].
Tungstate compounds have been attracting a great
deal of attention due to their unique properties; for
example, ZnWO4 is used as material for scintillators
thermal expansion [9], CaWO4 is used as a low tem-
perature ceramic [10], and KYb(WO4)2 is used as the
active medium of a solid-state laser [11]. Tungstates
doped with Eu3+ can be used as red emitting phos-
phors in white LEDs due to their excellent photolumi-
nescent (PL) properties. For practical applications, it
is important to control the morphology and quality of
tungstate crystals. The crystallization of glass is an
efficient method for manufacturing transparent mate-
rials of the given shape [12–15]. In [16, 17] the glass
crystallization method was applied to synthesize tung-
states containing REEs, and it was found that in
50WO3 25La2O3 25B2O3 glass crystallization of the
single phase LaBWO6 is observed.
Niobium tungstates are used as electrochromic
materials [18, 19].
Thus, the study of the crystallization properties of
glasses 37.5B2O3 22.5La2O3 (40 – x)Nb2O5 xWO3 may
be interesting from the point of view of obtaining,
based on this system, new types of tungstates and nio-
bates containing rare-earth metals, as well as glass-
ceramics.
The aim of this paper is to study the effect of tung-
sten oxide on the crystallization properties of glasses of
the 37.5B2O3 22.5La2O3 (40–x)Nb2O5 xWO3 (where
x = 10, 15, 20, 30, 40 mol %) system when replacing
them with niobium pentoxide and determining the
composition of the precipitated phases.

111
112 BOGDANOV et al.
Table 1. Glass composition according to synthesis and analysis
The composition of the synthesis, mol %
B2O3 La2O3 Nb2O5 WO3
37.5 22.5 40 0 53.1
37.5 22.5 30 10
37.5 22.5 20 20
37.5 22.5 10 30
37.5 22.5 0 40
EXPERIMENTAL
H3BO3, La2O3, Nb2O5, and WO3 were used as the
reagents. The glasses were melted in air at a tempera-
ture of 1280°C in a corundum crucible; the cooking
time was 60 min. The mass of glass was 20 g. The glass
mass was produced by casting onto a steel plate with
pressure or into a steel mold. After processing, the
glass was annealed in a muffle furnace at temperatures
close to Tg.
The characteristic temperatures for determining
the temperature-time mode of the glass heat treatment
were determined based on the data obtained from the
analysis of the differential thermal analysis (DTA)
curve. Measurements and mathematical data process-
ing were carried out on a thermomechanical analyzer
of the TMA-60 series (Shimadzu) and the sample
heating rate was 10 K/min. X-ray phase analysis
(XPA) was carried out on a general-purpose X-ray
Rigaku Smartlab III diffractometer using CuKα-radi-
ation and a D/teX Ultra detector. Heat treatment was
carried out in a muffle furnace in the temperature
intervals between the glass transition temperature Tg
and melting point Tmelt. The holding time for glass
crystallization was 6 h. Scanning electron microscopy
was performed using a Tescan Vega 3SBH SEM; and
X-ray microanalysis of the chemical composition was
carried out using an Aztec X-Act X-ray energy-disper-
sive microanalyzer (Oxford Instruments, silicon drift
detector). For the reliability of the calculation of the
energy dispersive analysis data, the area of the spectra
was at least 500 000 pulses.
Elemental analysis. The composition of glasses
according to synthesis and analysis is presented in
Table 1. As can be seen in tungsten oxide glasses, there
is a tendency for the materials of the crucibles to dis-
solve into the glass. It should be noted that with an
increase in the concentration of tungsten oxide, an
GLASS PHYSICS AND CHEMISTRY
The composition of the analysis, mol %
B2O3 La2O3 Nb2O5 WO3 Al2O3
19.9 27.0 0.0 0.0
42.5 17.9 24.4 9.6 5.7
29.6 26.3 21.4 16.4 6.2
45.2 17.0 11.6 13.7 12.5
49.4 15.6 0.0 20.1 14.8
increase in the content of aluminum oxide is also
observed.
Differential thermal analysis. The DTA showed
(Fig. 1) that the introduction of tungsten oxide into
the glass composition leads to a shift in the glass tran-
sition temperature Tg from 620°C, for glass with
10 mol % WO3 to 590°C with the complete replace-
ment of Nb2O5. With an increase in the content of
tungsten, a broadening of the exothermic peaks is
observed up to the formation of a second exothermic
peak for glass with 40 mol WO3. Following the glass
transition temperature, the temperature of the onset of
glass crystallization Tx also decreases.
SEM photographs of glass samples crystallized at
750°C are shown in Figs. 2. As can be seen, as the con-
centration of tungsten oxide increases, the number of
acicular crystals increases.
X-ray fluorescence microanalysis methods estab-
lished (Table 2) that the resulting acicular crystals do
not contain boron. The gray areas represent the
boron-containing residual glass phase or crystallized
solid solutions based on LaBO3. Aluminum has been
found both in boron-containing phases and in acicular
crystals. The concentration of tungsten in the gray
areas is much lower than in acicular crystals.
The results of the X-ray phase analysis are shown in
Fig. 3. Glass with 10 mol % WO3 demonstrates abso-
lute X-ray amorphism (Fig. 3a). As can be seen for
glasses without tungsten (Fig. 3b) during crystalliza-
tion, the formation of a crystalline phase is observed,
whose diffraction peaks can be identified using the
international diffraction base ICDD as the DyBO3
and HoBO3 peaks. Taking into account the fact that
there are no other lanthanides except lanthanum in
the composition of the glasses under consideration, it
can be assumed that the formed phases are
LaNbB6.8O7.8 borate . The formation of niobium lan-
Vol. 48 No. 2 2022
 EFFECT OF TUNGSTEN OXIDE ON THE CRYSTALLIZATION 113

46

44 37.5B2O3–22.5La2O3–0Nb2O5–40WO3

42

40
DTA, μA 37.5B2O3–22.5La2O3–20Nb2O5–20WO3
38

36

34

32 37.5B2O3–22.5La2O3–30Nb2O5–10WO3

30

28

26
0 100 200 300 400 500 600 700 800 900
T, °C

Fig. 1. DTA of glasses with different WO3 content.

4
1

3
2

(a) 5 µm (b) 100 µm

(c) 5 µm (d) 100 µm

Fig. 2. Photographs of the microstructure of crystallized glasses from 10 (a, b) and 20 mol % WO3 (c, d).

GLASS PHYSICS AND CHEMISTRY Vol. 48 No. 2 2022

114 BOGDANOV et al.

Table 2. Microanalysis of crystallization products

Spectrum label B, at % O, at % Al, at % Nb, at % La, at % W, at % Total

37.5B2O3 22.5La2O3 25Nb2O5 15WO3

1 30.51 59.11 3.19 3.72 2.79 0.67 100.00

2 18.68 64.70 3.45 6.06 5.63 1.49 100.00

3 24.89 63.12 3.21 4.66 3.37 0.75 100.00

4 28.53 57.22 2.20 5.52 5.14 1.39 100.00

37.5B2O3 22.5La2O3 20Nb2O5 20WO3

5 0.00 75.05 5.63 8.07 8.19 3.06 100.00

6 0.00 71.26 2.33 7.26 13.13 6.02 100.00

Table 3. Stoichiometric composition of glass crystallization products at different concentrations of tungsten oxide

WO3 content Oxide Borate

0WO3 LaNbO8 LaNbB6.83O7.83

10WO3 La0.5Nb0.9Al0.3W0.4O7.2 La0.5Nb0.9Al0.3W0.1B1.9O6.3

20WO3 La1.1Nb0.7Al0.4W0.5O7.2 La0.7Nb0.7Al0.4W0.2B1.4O6.5

30WO3 La1Nb0.5Al0.8W0.4O7.3 La0.6Nb0.3Al0.4W0.3B3.3O5.1

40WO3 Al2O3 La0.6Al0.6W0.5B2.2O6.1

thanum oxide LaNbO8 during crystallization is also
observed in this glass.
For glasses with 10, 15, and 30 mol % WO3, the for-
mation of parallel diffraction peaks characteristic of
solid solutions of LaaNbbBcAleBfOg and LaxNbyAlzWtO3
is observed. The data of the X-ray fluorescence analy-
sis of the crystallization products of all glasses are pre-
sented in Table 3.
As can be seen with the increasing concentration of
WO3, the content of tungsten in the formed borates
increases, while its concentration in oxides remains
constant. As noted above, an increase in the concen-
tration of tungsten leads to an increase in the content
of aluminum in the glass and in the products of its
crystallization. The aluminum content increases with
the increasing tungsten concentration. In borates, the
concentration of aluminum varies slightly to 6 at. %
only with the complete replacement of niobium oxide.
It should be noted that at 40 mol % WO3 corundum
stands out as the oxide phase, which indicates that the
content of Al2O3 in La0.6Al0.6W0.5B2.2O6.1 is the limit.
Based on the results of the X-ray phase and X-ray
fluorescence analysis, it can be argued that the exo-
thermic peaks presented in Fig. 3 are complex. The
formation of the second peak for glass with 40 mol %
WO3 is a consequence of the crystallization of alumi-
num oxide.

GLASS PHYSICS AND CHEMISTRY Vol. 48 No. 2 2022

 EFFECT OF TUNGSTEN OXIDE ON THE CRYSTALLIZATION 115

500 (a)

450

400

Intensity
350

300

250

200

150

100
0 10 15 20 25 30 35 40
2θ, deg
(b)

37.5B2O3–22.5La2O3–0Nb2O5–40WO3
γ γ γ
14 000

12 000 β
β β β 37.5B2O3–22.5La2O3–10Nb2O5–30WO3
β β β β β β
10 000

8000
37.5B2O3–22.5La2O3–20Nb2O5–15WO3

6000
α 37.5B2O3–22.5La2O3–30Nb2O5–10WO3
4000
α α α α α
α
2000
37.5B2O3–22.5La2O3–40Nb2O5–0WO3

0
5 10 15 20 25 30 35 40 45 50 55 60
2θ, deg

Fig. 3. Diffractogram of glass with 10 mol % WO3 before crystallization (a), diffraction patterns of crystallized glasses with differ-
ent contents of tungsten oxide, where α is LaaNbbBcAleBfOg, β is LaxNbyAlzWnOm, γ is Al2O3 (b).

CONCLUSIONS lization of the presented systems can be useful in the

production of complex tungstates containing rare
During the synthesis of glasses of the 37.5B2O3 earth ions and transition metal ions.
22.5La2O3 (40 – x)Nb2O5 xWO3 (where x = 10–
40 mol %) in corundum crucibles with an increase in
the concentration of tungsten, an increase in the vol- FUNDING
ume of soluble aluminum oxide is observed. This study was supported by the Russian Science Foun-
dation (project no. 19-73-10180).
Crystallization of glasses containing tungsten oxide
from 10 to 30 mol % is characterized by the simultane-
ous release of LaxNbyAlzWtO3 oxides, and borates of CONFLICT OF INTEREST
the LaaNbbBcAleBfOg type. This feature of the crystal- The authors declare that they have no conflicts of interest.

GLASS PHYSICS AND CHEMISTRY Vol. 48 No. 2 2022

116 BOGDANOV et al.
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Vol. 48 No. 2 2022