Materials Chemistry and Physics xxx (2016) 1e6

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Materials Chemistry and Physics

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Physical, thermal and structural properties of Calcium Borotellurite

glass system
E.C. Paz a, b, J.D.M. Dias a, G.H.A. Melo a, c, T.A. Lodi a, J.O. Carvalho a, d, P.F. Façanha Filho a,
M.J. Barboza a, F. Pedrochi a, A. Steimacher a, *
a
CCSST e UFMA, Imperatriz, MA, Brazil
b ^ndia, MA, Brazil
IFMA, Açaila
c
IFMA, Imperatriz, MA, Brazil
d
IFTO, Araguaína, TO, Brazil

h i g h l i g h t s

Glass forming ability on Calcium Borotellurite system was studied.

The glass structure was investigated by XRD, Raman and FTIR.

The glass network structure of the CBTx glasses is formed by BO3, BO4, TeO3, TeO3þ1 and TeO4 units.

The density and thermal stability of the CBTx glass decreases with TeO2 while the Cp and the Tg decreases.

The obtained CBTx glasses are suitable for manufacturing process and rare-earth doping for several optical applications.

a r t i c l e i n f o a b s t r a c t

Article history: In this work the glass forming ability in Calcium Borotellurite (CBTx) glass system was studied. Six glass
Received 16 April 2015 samples were prepared by melt-quenching technique and the obtained samples are transparent, lightly
Received in revised form yellowish, with no visible crystallites. The structural studies were carried out by using XRD, FTIR, Raman
26 October 2015
Spectra, density measurements, and the thermal analysis by using DTA and specific heat. The results are
Accepted 24 April 2016
Available online xxx
discussed in terms of tellurium oxide content and their changes in structural and thermal properties of
glass samples. The addition of TeO2 increased the density and thermal stability values and decreased
glass transition temperature (Tg). Raman and FTIR spectroscopies indicated that the network structure of
Keywords:
Glasses
CBTx glasses is formed by BO3, BO4, TeO3, TeO3þ1 and TeO4 units. CBTx system showed good glass for-
Thermal properties mation ability and good thermal stability, which make CBTx glasses suitable for manufacturing process
Raman spectroscopy and scattering and a candidate for rare-earth doping for several optical applications.
Fourier transform infrared spectroscopy © 2016 Elsevier B.V. All rights reserved.
(FTIR)
Optical materials

1. Introduction good thermal and mechanical stability, good chemical durability,

The physical and structural properties of tellurite, borate and
borotellurite glasses have been widely investigated for their sci-
entific interest and practical applications [1e5]. Borate glasses are
known for having high thermal stability, high chemical durability,
good solubility of rare-earth ion and also for their ease of synthesis
[4,6,7]. Tellurite glasses have lower phonon energy if compared to
phosphates and silicates glasses [5,7], large infrared transparency,
* Corresponding author.
E-mail address: steimacher@hotmail.com (A. Steimacher).
low melting temperature, high refractive index, high dielectric
constant and suitability as host matrix to dopant action
[2e5,8e12]. These features make tellurite glasses promising can-
didates for photonic applications, such as fiber in optical commu-
nication, window materials and up-conversion laser. The addition
of tellurium oxide to another glass former, such as B2O3, can lead to
the production of interesting structural units that affect the phys-
ical properties of the glass network [13,14]. The presence of TeO2 in
alkali borate glasses decreases their hygroscopic nature, reduces
their phonon energy, increases their refraction index and their IR
transmission [14e16]; that makes borotellurite glasses a candidate
for several optical applications. In order to improve those qualities,

http://dx.doi.org/10.1016/j.matchemphys.2016.04.080
0254-0584/© 2016 Elsevier B.V. All rights reserved.

Please cite this article in press as: E.C. Paz, et al., Physical, thermal and structural properties of Calcium Borotellurite glass system, Materials
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2 E.C. Paz et al. / Materials Chemistry and Physics xxx (2016) 1e6
calcium oxide and calcium fluoride were used as glass modifiers
due to their excellent contributions to the glassy formation. Cal-
cium oxide can form promising luminescent host matrix, in which
Ca2þ cation can be replaced by rare earth ions [17]. Furthermore,
CaO addition increases the glass resistance to humidity [18] as well
as the thermal stability of the glass, as it could be observed when
other alkaline earth was added to tellurite glasses [19]. Besides that,
the addition of fluorine compounds, such as CaF2, decreases the
phonon energy of pure oxide glasses and can improve emission and
lifetime of rare earth doped glasses [20,21].
In this work, we present a study of glass-forming ability of
Calcium Borotellurite (CBTx) system, its synthesis with different
concentrations of TeO2, together with the investigation of the
structural and thermal properties. For this aim, six samples were
prepared; they were characterized by determining the volume
mass density, X-ray diffraction (XRD), Raman spectroscopy, Fourier
transform infrared spectroscopy (FTIR) and thermal analysis, which
includes results of Tg, Tx and specific heat. The results of this study
are discussed in terms of the addition of TeO2 and their possible
structural roles in these glasses. We expect that the glass studied in
the CBTx system can be used for optical fiber draw, optical ampli-
fiers or other photonic devices.
2. Experimental procedure
The synthesis of Calcium Borotellurite glasses with composition
10CaF2-(30-0.4x)CaO-(60-0.6x)B2O3-xTeO2, (x ¼ 20, 25, 30, 35, 40
and 50 wt%) (referred as CBTx) was realized by melt quenching
conventional technique. The starting materials, chemical reagents
of analytical grade (purity 98e100%), were melted at ~950  C in
platinum crucibles, under air atmosphere. The melt was poured
into a preheated stainless steel mold at ~500  C and annealed for
4 h to release its inner stress.
A RIGAKU Miniflex II X-ray Diffractometer (Cu Ka,
l ¼ 1.54434 Å), at the rate of 0.02 /second and the variation of 2q
from 10 to 80 , was employed to confirm the amorphous/crys-
talline nature of the samples. Raman spectroscopy was performed
on a triple spectrometer Princeton, Trivista 557, in the range
200e2000 cm1, with spectral resolution of 2 cm1. FTIR spectra
were obtained on a BRUKER FTIR spectrophotometer, model Vertex
70V, in the range between 400 and 4000 cm1, resolution of 4 cm1
and employing the KBr pellet technique with 1% sample.
Density measurements were taken according to the principle of
Archimedes, using distilled water as immersion liquid. Glass tran-
sition (Tg), crystallization start (Tx) and crystallization peak (Tp)
temperatures were determined by differential thermal analysis
(DTA) as described in Ref. [22]. DTA measurements were processed
in equipment TG/DTA Shimadzu, with a heating rate of 10  C min1.
The specific heat was measured at room temperature by using a
thermal relaxation method with a laser beam as the heat source.
The theory and the experimental setup for this method are
described in details in Ref. [23].
3. Results and discussion
Fig. 1 shows the batch of the samples prepared in this work. The
obtained samples, with TeO2 varying from 20 to 50 wt%, present no
visible crystallites or devitrification and good optical quality, under
visual inspection. The pale yellow color of the samples increases
lightly with TeO2 content.
In Fig. 2, the phase diagram (wt%), in which the obtained glass
samples are indicated, is shown.
This diagram shows that all the samples prepared in that system
formed glass free crystalline phase. The confirmation of the sam-
ples glassy nature, which is important to design the phase diagram,
Please cite this article in press as: E.C. Paz, et al., Physical, thermal and structural properties of Calcium Borotellurite glass system, Materials
Chemistry and Physics (2016), http://dx.doi.org/10.1016/j.matchemphys.2016.04.080
is presented as follows.
3.1. XRD
In Fig. 3, the XRD pattern for all the samples is presented. It is
possible to see the presence of two diffuse broad peaks (2q ¼ 30
and 2q ¼ 46 ), which is typical in materials that exhibit long range
structural disorder [24]. No differences were observed on the po-
sition or form of the XRD bands with TeO2 concentration up to
50 wt%. The proof of the amorphous nature of the synthesized
samples reflects the good ability of glass formation in the system
investigated.
3.2. Density
Fig. 4 shows a linear increase of density with TeO2 addition, up
to 50 wt%. The density of the CBTx glass samples increases from
2.97 g cm3 to 3.58 g cm3, which corresponds to an increase of
~21%. That increase occurs mainly due to the substitution of boron
and calcium oxide by tellurium oxide, which has a higher molecular
weight than B2O3 and CaO, resulting in a higher net weight of the
glass structure [15,25].
3.3. Raman analysis
Raman spectra of CBTx glasses (Fig. 5) show the presence of six
main bands: A (z332e338 cm1), B (z486e488 cm1), C
(z686e698 cm1), D (z774e783 cm1), E (z1375e1481 cm1)
and F (z1748e1894 cm1). The center of these bands and the
corresponding peak assignments, for each sample, are shown in
Tables 1 and 2. In Fig. 5(a) it is possible to see an increase in the
bands A, B, C and D with the increase of TeO2, up to 50 wt%. The
band A, around 330 cm1, may be assigned to bending connections
TeeOeTe [26] and CaeO bonds [18]. However, that band increases
with the concentration of TeO2; we believe that this increase occurs
mainly due to TeO2 addition.
The band B corresponds to the stretching of the links and
bendings TeeOeTe [27] and/or stretching BO4 units [28,29]. The
increase of that band with TeO2 suggests an increase of TeeOeTe
bonds and BO4 units in structure.
The band C is attributed to the TeeO bond in TeO4 trigonal
bipyramidal units, which appears in Raman spectra around
630e682 cm1 [30]. The intensity increase of the band D, around of
770 cm1, indicates a change in the number of tetraborate units,
due to TeO2 addition [31]. In agreement with those results, Buerger
et al. [21] show that the tellurium oxide addition, in B2O3eTeO2
system, results in an increase of boron units, tetrahedrally coordi-
nated [32]. This band also can be attributed to TeO3þ1 polyhedral
having one nonbridging oxygen atom (NBO) and TeO3 trigonal
pyramidal units characteristic, Raman spectra around
720e760 cm1 and 770e780 cm1, respectively [30]. Therefore, the
band C in the Raman spectra can indicate an increase of BO4, TeO4,
TeO3þ1 and TeO3 units, which occurs due to the increase of tellu-
rium oxide.
The bands E and F are associated to the stretching vibrations
BeO bonds with non-bridging oxygens (NBO), such as metaborate
and pyroborate groups [30]. These boron groups appear in the re-
gion of 1300e1600 cm1 [33,34]. For CBTx system, there is an ev-
idence of pyroborate (1200e1300 cm1), metaborate chains and
rings (1300e1600 cm1) [35]. Fig. 5 (b), shows the gaussian fit to
Raman spectrum of CTB20, 35 and 50; it is possible to see a
reduction of band E with the increase of TeO2. That fact suggests
that the amount of these borate groups is reduced by increasing the
TeO2 content.
 E.C. Paz et al. / Materials Chemistry and Physics xxx (2016) 1e6 3

Fig. 1. CBTx glasses with different concentrations of TeO2.

TeO2 3.8
0 Glass CBTx glasses
100 3.7
Linear fit
3.6
20 3.5
80
3.4

Density (g cm )
-3
2
F

40 3.3
Ca

60
Te
O+

3.2
O2
Ca

60 3.1
40
3.0

80 2.9
20
2.8
2.7
100 20 25 30 35 40 45 50
0
CaO+CaF2 0 20 40 60 80 100 TeO2 (wt%)
B2O3
B2O3
Fig. 4. Density of CBTx glasses in a function of TeO2 content.

Fig. 2. Phase diagram of the CBTx system (900  C).

stretching mode of TeO4, trigonal bipyramidal with bridging oxy-
gen, and stretching mode of TeO3, trigonal pyramidal with non-
bridging oxygen (NBO), respectively [36,38e40]. Bands at
688 cm1 occur due to the BeOeB bending vibrations [30]. The
band observed in 724 cm1 is attributed to O3BeOeB3O bending
vibrations and TeeO bending vibrations in TeO3 and TeO6 units [37].
The slight increase in band X, due to TeO2 addition, indicates an
increase of these groups in the glass network. Bands around
800e1200 cm1 correspond to stretching vibrations in BO4 units,
such as stretching vibrations in tri-, tetra- and pentaborate groups
(broad band at 1023 cm1) and BeOeB bending vibrations (strong
bands at 944 cm1) [37]. The band around 1200e1600 cm1 is
assigned to asymmetric stretching vibration of the BeO bond of
BO3 units [37,41]. The band Z in the range 1342e1360 cm1 pre-
sents an intensity increase and a small shift of band center, from
1380 to 1342 cm1, with TeO2 addition. These bands indicate the
BeO stretching vibration of BO3 units in varied types of borate
groups with NBOs, such as orthoborate, pyroborate and metaborate
[37]. The band positions (cm1) and its corresponding peak as-
signments of FTIR spectra for CBTx glasses are summarized in
Table 3. The FTIR bands assignment confirms the structural units
Fig. 3. X-ray diffraction patterns of CBTx system with TeO2 content, varying from 20 to
50 wt%.
explored through the Raman spectral analysis, which show that
addition of TeO2, in replacement of B2O3 and CaO, produce a
3.4. FTIR analysis modification in the structural network.

The experimental FTIR spectra of CBTx glasses are presented in
Fig. 6, which shows three well defined bands, named X
(440e790 cm1), Y (810e1100 cm1) and Z (1200e1600 cm1). In
Borotellurite glasses, FTIR bands located in the range
447e492 cm1 are due to the bending vibrations of TeeOeTe or
OeTeeO linkages [36]. The band at 613 cm1 is observed while
increasing the content of TeO2 and is due to the TeeOeTe bridges
between four-co-ordinate tellurium atoms (TeO4) [37]. Bands in the
range 610e680 cm1 and 720e780 cm1 may be attributed to the
3.5. Thermal analysis
3.5.1. DTA analysis
The values of glass transition temperature (Tg) and the onset of
crystallization (Tx) for CBTx glasses are shown in Table 4. Fig. 7
presents the values of Tg and Tx for all CBTx glasses, as a function
of TeO2 concentration. A nonlinear decrease in Tg values was
observed due to the replacement of B2O3 and CaO with TeO2. The
replacement of a larger number of strong BeO bonds by the fewer
and weaker TeeO bond is the main responsible for a weakening of

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4 E.C. Paz et al. / Materials Chemistry and Physics xxx (2016) 1e6

D
D CBT50
C

F
Raman intensity (a.u.)

A B
C

Raman intensity (a.u.)

CBT35
D
F
E CBT50 C E F
A B
CBT40
CBT35
CBT20
CBT30
CBT25
D E F
CBT20 C

200 400 600 800 1000 1200 1400 1600 1800 2000 200 400 600 800 1000 1200 1400 1600 1800 2000
-1 -1
Wavenumber (cm ) Wavenumber (cm )

Fig. 5. (a) Raman spectra of CBTx glasses and (b) Raman spectra deconvoluted glasses CBTx.

Table 1 the lattice, that cause a decrease of Tg values [42].

The position of the peaks in the Raman spectra of CBTx glasses. Tg is an important parameter in the study of structural proper-
Sample Code Center bands (cm1) ties and is directly related to network connectivity. However, it
alone does not give any direct information about the glass forming
A B C D E F
tendency, which is connected with the glass chemical composition
CBT20 e e 686 774 1375 1773 [22]. The glass forming tendency is directly proportional to the
CBT25 e e 693 777 1397 1845
CBT30 e e 693 779 1425 1860
thermal stability of the glass, which is the difference between the
CBT35 e e 697 779 1454 1894 glass transition temperatures and crystallization onset [22]. In CBTx
CBT40 338 488 698 781 1481 1894 glass, the increase of tellurium oxide content is responsible for an
CBT50 332 486 698 783 e 1748 increase in the thermal stability of the studied glasses.

Table 2
Band positions (cm1) and its corresponding peak assignments of Raman spectra of CBTx glasses.

Observed bands Reported position (cm1) Assignments

A 330 bending connections TeeOeTe [26]

B 470 stretching of the links and bendings TeeOeTe [27] and/or stretching BO4 units [28,29]
C 630e682 TeeO bond in TeO4 units [30]
D 770 tetraborate units [31]
720e760 TeO3þ1 units [30]
770e780 TeO3 trigonal pyramidal units [30]
EeF 1200e1600 stretching vibrations BeO bonds with non-bridging oxygens (NBO), such as metaborate and pyroborate groups [30]
1200e1300 pyroborate chains and rings [35]
1300e1600 metaborate chains and rings [35]

1,8 The determination of thermal stability of the glass is an

important examination of its potential to manufacturing process of
1,6 optical fiber [46]. In that process the preform is subjected to mul-
tiple cycles of heating above the Tg [46]. Glasses with low thermal
CBT50
1,4 stability are more subject to the crystallization during heating cy-
Transmittance (a.u.)

X Z CBT40 cles. Crystallization in glass, even in small quantities, is the main

Y
1,2 CBT35
responsible for light scattering, which contribute to the attenuation
of the incoming signals. The samples prepared in this work showed
CBT30
1,0 good thermal stability, greater than 100  C, highlighting the CBT50
CBT25
sample due to its higher thermal stability. The values of Tx-Tg ob-
0,8 CBT20 tained for CBTx glasses are greater than fused silica [43] and
phosphate [44] and comparable to germanate glasses [45].
0,6

0,4 3.5.2. Specific heat

The specific heat (Cp) of CBTx glass is presented in Fig 8. It can be
400 800 1200 1600 2000 2400 2800 3200 3600 4000 seen that TeO2 addition causes a linear decrease of Cp values,
Wavenumber (cm )
-1 varying from 0.79 to 0.63 J g1 K1, for CBT20 and CBT50, respec-
tively. That decrease of Cp can be attributed to a reduction in the
Fig. 6. FTIR spectra glasses CBTx system. number of oscillators in the network, from 5 particles (B2O3) to 3

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 E.C. Paz et al. / Materials Chemistry and Physics xxx (2016) 1e6 5

Table 3
Band positions (cm1) and its corresponding peak assignments of FTIR spectra of CBTx glasses.

Observed bands Reported position (cm1) Assignments

X 447e492 Bending vibrations of TeeOeTe or OeTeeO linkages [36]

613 Bridges between co-ordinate tellurium atoms (TeO4) [37]
610e680 Stretching mode of TeO4 with bridging oxygen [36,38e40]
688 BeOeB bending vibrations [30]
720e780 Stretching mode of TeO3 with non-bridging oxygen (NBO), respectively [36,38e40]
724 O3BeOeB3O bending vibrations and TeeO bending vibrations in TeO3 and TeO6 units [37]
Y 800e1200 Stretching vibrations in BO4 units [37]
944 BeOeB bending vibrations in BO4 units [37]
1023 Stretching vibrations in tri-, tetra- and pentaborate groups in BO4 units [37]
Z 1200e1600 Asymmetric stretching relaxation of the BeO bond of BO3 units [37,41]

Table 4
Sample compositions, density (r), glass transition temperature (Tg) crystallization temperature (Tx), peak crystallization temperature (Tp), thermal stability (Tx-Tg) and
specific heat (Cp) of CBTx glasses.

Composition (wt%) r (g cm1) (±0.03) Tg ( C) (±5) Tx ( C) (±5) Tp ( C) (±5) (Tx-Tg) ( C) (±10) Cp (J g1 K1) (±0.02)

Sample code CaF2 CaO B2O3 TeO2

CBT20 10.0 22.0 48.0 20 2.97 602 724 749 122 0.79
CBT25 10.0 20.0 45.0 25 3.04 597 705 744 108 0.74
CBT30 10.0 18.0 42 30 3.14 580 701 747 121 0.73
CBT35 10.0 16 39 35 3.23 569 704 741 135 0.71
CBT40 10.0 14.0 36 40 3.32 556 713 748 157 0.68
CBT50 10.0 10.0 30.0 50 3.58 509 690 701 181 0.63
Fused silicaa 95
Phosphate glassb 96
Germanate glassc 148
a
Ref. [43].
b
Ref. [44].
c
Ref. [45].

800 0.84
Tg 0.82 CBTx glasses
Tx Linear Fit
0.80

0.78
700
Temperature (°C)

0.76
Specific Heat (J/gK)

0.74

0.72
600
0.70

0.68

0.66
500 0.64

0.62

20 25 30 35 40 45 50 0.60

TeO2 (wt%) 20 25 30 35 40 45 50
TeO2 content (wt%)
Fig. 7. Tg and Tx of CBTx glasses as a function of TeO2 content.

Fig. 8. Specific Heat as a function of TeO2 content.

particles (TeO2) [47]. Furthermore, the replacement of strong BeO
bonds by weaker TeeO bonds [42], has formed structural units that
crystallites. The values of the density obtained showed a linear
can vibrate more easily, when heated. The increase of BO3 units
increase with TeO2 content, up to 50 wt%. XRD results confirmed
with NBOs, due TeO2 addition, showed by FTIR, are also responsible
the amorphous nature of all glass synthesized samples. Spectro-
for a weakening of glass network connectivity [48], reducing the
scopic analyses Raman and FTIR indicated that the glass network
specific heat of glass CBTx.
structure of the synthesized samples is formed by BO3, BO4, TeO3,
TeO3þ1 and TeO4 units. The results of Tg show a decrease with the
4. Conclusion addition of TeO2, which occurs due to the substitution of BeO bonds
for TeeO bonds, that causes a decrease in the network connectivity.
The glass forming ability of the CBTx system was investigated in The thermal stability values (Tx-Tg) of CBTx glasses show an in-
this work and the phase diagram was presented. The obtained glass crease with TeO2 content, up to 50 wt%. The values are comparable
samples are transparent, lightly yellowish, with no visible

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6 E.C. Paz et al. / Materials Chemistry and Physics xxx (2016) 1e6
to commercial glasses and present higher values than those found
to fused silica, some germanate and phosphate glasses; that makes
CBTx glasses suitable for manufacturing process.
Acknowledgments
All the authors are thankful to PPGCM and UFMA. We are also
thankful to the Brazilian agencies CNPq, CAPES and FAPEMA for
financial support of this study and the GEFF-UEM for FTIR
measurements.
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