Applied Physics A

Vibrational and thermal properties of the ternary Tl2O-V2O5-TeO2 glass-forming

system
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Full Title: Vibrational and thermal properties of the ternary Tl2O-V2O5-TeO2 glass-forming
system

Article Type: Regular papers

Corresponding Author: Nektarios K. Nasikas, PhD

Hellenic Army Academy: Stratiotike Schole Euelpidon
GREECE

Corresponding Author Secondary

Information:

Corresponding Author's Institution: Hellenic Army Academy: Stratiotike Schole Euelpidon

Corresponding Author's Secondary

Institution:

First Author: Nektarios K. Nasikas, PhD

First Author Secondary Information:

Order of Authors: Nektarios K. Nasikas, PhD

Pantelis Mpourazanis

Angelos G. Kalampounias

Order of Authors Secondary Information:

Funding Information:

Abstract: In this work, we studied, the vibrational and the thermal properties of the Tl2O-TeO2,
V2O5-TeO2 and Tl2O-V2O5-TeO2 glass-forming systems by means of Fourier
Transform Infrared (FTIR) spectroscopy and Differential Scanning Calorimetry (DSC).
Thermal properties, such as the glass transition temperature (Tg), thermal stability (S),
and thermodynamic fragility (F) were determined and correlated with the structural
characteristics of the glasses. The binary glass-forming system Tl2O-TeO2 exhibits the
transformation of TeO4 trigonal bipyramids into TeO3 trigonal pyramid units due to the
presence of the Tl2O. The decreasing trend of Tg with Tl2O content, along with the
increase of the thermodynamic fragility indicate that the structure becomes less
interconnected and floppier. Concerning the V2O5-TeO2 glass system, we observed
that V2O5 causes structural modifications in the TeO2 sub-network by changing the
coordination number of Te atoms. Furthermore, the glass rigidity reduces as indicated
by the glass transition temperature variation with composition. We also found that the
0.5V2O5-0.5TeO2 glass exhibits the highest resistance to thermal shocks and possess
the most rigid network. Concerning the structure of the ternary glass-forming Tl2O-
TeO2-V2O5 system, the incorporation of the Tl2O into the mixed vanadate-tellurite
glasses decreases the glass transition temperature implying that Tl2O acts as a
network modifier affecting the network’s rigidity. The decreasing trend of the
thermodynamic fragility indicates that the glass network becomes more rigid. Finally,
the significantly high values of thermal stability reveal that the ternary glass-forming
system can be considered as a glass with superior resistance against thermal shocks
making it an ideal candidate for relevant technological applications.

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Vibrational and thermal properties of the ternary Tl2O-V2O5-TeO2 glass-forming system

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6 Pantelis Mpourazanis 1,2,§, Nektarios K. Nasikas3,* and Angelos G. Kalampounias1,4,*
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Department of Chemistry, University of Ioannina, Ioannina, GR-45110, Greece
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12 Institute of Experimental Colloidal Physics, Department of Physics, Heinrich-Heine University, Düsseldorf, D-
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14 40225, Germany
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17 Department of Military Sciences, Division of Mathematics and Engineering Sciences, Hellenic Army
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19 Academy, GR 16673, Vari, Attica, Greece.
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University Research Center of Ioannina (URCI), Institute of Materials Science and Computing, Ioannina,
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Greece
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26 §
Current affiliation: Institute of Experimental Colloidal Physics, Department of Physics, Heinrich-Heine
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28 University, Düsseldorf, D-40225, Germany
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31 *Corresponding authors:
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34 Dr. A. G. Kalampounias; E-mail: akalamp@uoi.gr
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Dr. N.K.Nasikas; E-mail: nasikas@sse.gr
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44 Abstract
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47 In this work, we studied, the vibrational and the thermal properties of the Tl2O-TeO2,
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49 V2O5-TeO2 and Tl2O-V2O5-TeO2 glass-forming systems by means of Fourier Transform
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52 Infrared (FTIR) spectroscopy and Differential Scanning Calorimetry (DSC). Thermal
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54 properties, such as the glass transition temperature (Tg), thermal stability (S), and
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57 thermodynamic fragility (F) were determined and correlated with the structural characteristics
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59 of the glasses. The binary glass-forming system Tl2O-TeO2 exhibits the transformation of TeO4
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 trigonal bipyramids into TeO3 trigonal pyramid units due to the presence of the Tl2O. The
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2 decreasing trend of Tg with Tl2O content, along with the increase of the thermodynamic
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5 fragility indicate that the structure becomes less interconnected and floppier. Concerning the
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7 V2O5-TeO2 glass system, we observed that V2O5 causes structural modifications in the TeO2
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10 sub-network by changing the coordination number of Te atoms. Furthermore, the glass rigidity
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12 reduces as indicated by the glass transition temperature variation with composition. We also
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15 found that the 0.5V2O5-0.5TeO2 glass exhibits the highest resistance to thermal shocks and
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17 possess the most rigid network. Concerning the structure of the ternary glass-forming Tl2O-
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TeO2-V2O5 system, the incorporation of the Tl2O into the mixed vanadate-tellurite glasses
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22 decreases the glass transition temperature implying that Tl2O acts as a network modifier
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24 affecting the network’s rigidity. The decreasing trend of the thermodynamic fragility indicates
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27 that the glass network becomes more rigid. Finally, the significantly high values of thermal
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29 stability reveal that the ternary glass-forming system can be considered as a glass with superior
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32 resistance against thermal shocks making it an ideal candidate for relevant technological
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34 applications.
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40 Keywords: Tellurite glasses; Vibrational properties; Thermal properties; Network rigidity;
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43 Thermodynamic fragility; Thermal stability.
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 1. Introduction
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3 Tellurite glasses have attracted great scientific and technological interest due to their
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intriguing physical and chemical properties when compared to other silicate and phosphate
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8 glasses [1]. More specifically, these glasses exhibit high refractive indexes, good infrared and
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10 visible transmittance and non-linear optical properties, which make them suitable materials for
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13 non-linear optical devices, and potential candidates for laser-technology applications [2]. They
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15 also exhibit significant dielectric properties, such as high hyper-polarizability [1], chemical
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18 stability, homogeneity and low absorption coefficients. Pure TeO2 is an intermediate glass-
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20 forming oxide, which is not stable upon devitrification [1]. Due to this characteristic, pure TeO2
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23 presents difficulties in glass-formation and requires rapid cooling techniques. It was recently
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25 reported that TeO2 will form glass by itself, when taken through a suitable thermal cycle [3].
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Furthermore, it is known that the addition of at least one network modifier oxide of the form
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30 AxOy enhances the glass-forming ability, results in a more stable glass structure and affects
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32 significantly their physical and chemical properties [4-11]. Analogous behavior is observed
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35 when a second glass former is added into the tellurite network [12].
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37 Vibrational Raman and infrared (IR) spectroscopies are considered suitable techniques
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40 for the study of the structure of glasses, since they can provide useful information concerning
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42 their structure in the short-range order. In particular, the structure of mixed tellurite glasses has
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been studied extensively in the literature by means of Raman spectroscopy as neat TeO2 is a
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47 natural Raman signal amplifier. The structure of the TeO2 glass consists of TeO4 trigonal
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49 bipyramid units (tbp) and also of TeO3 trigonal pyramids (tp) [3 and references therein]. By
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52 adding network modifying oxides in the structure of the tellurite glasses, the Te-O-Te linkages
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54 start to break and the number of bridging oxygens decreases with a parallel increase of terminal
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57 oxygen atoms [4-11]. Furthermore, TeO3 tp units increase at the expense of the TeO4 tbp units
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59 [4-12]. Analogous behavior exhibit oxyhalide tellurite glasses [13]. These structural alterations
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 affect the physico-chemical properties of tellurite glasses that are of particular interest to the
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2 glass science community.
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5 On the other hand, vanadate glasses are considered semiconducting glasses with special
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7 catalytic properties and potential applications in chemical industry [14]. The semiconducting
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10 properties of vanadate glasses are considered to be due to electron hopping that happens
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12 between V+4 and V+5 site of vanadium ions [15-17], but the nature of this mechanism occurring
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15 in different compositions and temperatures is still under investigation [18, 19]. Moreover,
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17 vanadate glasses find applications in memory switching, switching devices and others [20].
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They present low glass transition temperature (Tg), but they are also characterized by their
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22 tendency to crystallize as well as their low-water absorption resistance. The V2O5 glass
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24 structure is considered in the relevant literature to be consisting out of VO4 tetrahedra and VO5
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27 trigonal bipyramid units [21]. It has also been reported that the amount of VO4 tetrahedral units
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29 in comparison to VO5 octahedral units can affect their electric conductivity [22-24]. Mixed
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32 tellurium-vanadate glasses are also considered semiconducting glasses with high-electric
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34 conductivity. This is due to the fact that the transition metal oxide V2O5, when incorporated
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into TeO2 increases significantly the electric conductivity [25]. A study of the 2TeO2-V2O5
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39 glass by Kjeldsen et. al [26] showed that the glass phase exhibits significantly higher
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41 conductivity compared to its crystalline counterpart. Despite the various mixed vanadate
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44 glasses studied in the literature, their structure is yet to be clarified and still remains an
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46 interesting topic.
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49 In this work, we synthesized and studied for the first time the glass system xTl2O-(1-
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51 x)(66.7TeO2-33.3V2O5) with x=0.1, 0.2, 0.3, 0.4, 0.5, and 0.6 mole fraction by means of
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54 infrared spectroscopy and differential scanning calorimetry. We also synthesized the binary
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56 glass systems xV2O5-(1-x)TeO2, with compositions x=0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 and
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xTl2O-(1-x)TeO2 with x=0.1-0.4 mole fraction. The binary glassy system of xV2O5-(1-x)TeO2
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 was studied in a wide compositional range, despite the significant difficulties to achieve glass-
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2 formation due to its inherent tendency to crystallize. Previous work by means of infrared
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5 spectroscopy and Density Functional Theory (DFT) calculations on vanadate-tellurite glasses
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7 xV2O5-(1-x)TeO2 for x=0.3 and 0.4 has been performed by S. Rada et al [20].
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10 The aim of our research was to study the thermal properties of the above mentioned
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12 mixed glassy systems at various compositions, and to correlate these properties with the
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15 evolution of their structural characteristics obtained by Fourier transform infrared (FTIR)
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17 spectra. In the above framework, we also investigated the role of the Tl2O and its effect on the
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thermal and structural properties of the glasses, when incorporated in the V2O5-TeO2 glass
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22 system. To the best of our knowledge, no experimental studies have been performed so far
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24 concerning the compositional dependence of the thermal and structural properties regarding
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27 the ternary Tl2O-V2O5-TeO2 glass-forming system.
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32 2. Experimental
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35 2.1 Glass preparation
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38 The ternary xTl2O-(1-x)(0.67TeO2-0.33V2O5) glass-forming system with compositions
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40 x=0.1, 0.2, 0.3, 0.4, 0.5 and 0.6 mole fraction was synthesized by mixing the appropriate
41
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43 amounts of Tl2CO3, (Alfa Aesar, 99.955 %), TeO2 (Alfa Aesar, 99.99 %) and V2O5 (Fluka
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45 AG, 99.9 %) as starting materials without any further purification. Moreover, the binary glass
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48 systems xV2O5-(1-x)TeO2 with compositions x=0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 and 0.8 mole
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50 fraction and xTl2O-(1-x)TeO2 with x=0.1, 0.2, 0.3 and 0.4 mole fraction were also synthesized.
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The composition of the glasses prepared in this study are summarized in Table 1. The total
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55 mass of the initial batch was 1 gr. The above-mentioned starting materials were placed into
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57 platinum crucibles and heated in an electric furnace up to 860 oC. During the melting process,
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60 Tl2CO3 decomposes to Tl2O oxide and CO2 gas. All glasses have been prepared using the
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 conventional melt-quenching technique, by dipping rapidly the bottom of the Pt crucible into
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2 cold water. The amorphous nature of all samples was checked by means of XRD. Furthermore,
3
4
5 the FTIR spectra of all glasses exhibit broad vibrational bands characteristic of the amorphous
6
7 phase.
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12 Table 1. Nominal compositions of all glasses prepared. x denotes the mole fraction.
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15 xTl2O - (1-x)TeO2 xV2O5 - (1-x)TeO2 xTl2O - (1-x)(0.67TeO2 – 0.33V2O5)
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17 0.1 0.9 0.1 0.9 0.1 0.9
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20 0.2 0.8 0.2 0.8 0.2 0.8
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22 0.3 0.7 0.3 0.7 0.3 0.7
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25 0.4 0.6 0.4 0.6 0.4 0.6
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27 0.5 0.5 0.5 0.5 0.5 0.5
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0.6 0.4 0.6 0.4
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32 0.7 0.3
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0.8 0.2
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39 2.2 DSC measurements
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The glass transition temperatures (Tg) and crystallization temperatures (Tc) were
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45 determined by differential scanning calorimetry (DSC). The thermographs of all glasses were
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47 recorded using the DSC-50 (SHIMADZU) calorimeter, under dynamic N2 gas atmosphere. The
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50 flow rate of nitrogen gas was set at 40 ml/min. An amount of ~4.5 mg of each glass was placed
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52 into aluminum sample holders appropriate for DSC measurements. From the obtained DSC
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55 thermographs, the glass transition temperature (Tg) was determined as the point of intersection
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57 of the bisector of the angle between the tangents with the measurement curve. Furthermore, the
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60 maxima of the exothermic peaks above glass transition temperatures were considered as the
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 characteristic crystallization temperatures. All DSC measurements were conducted at three
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2 different heating rates of 10, 15 and 20 oC/min, respectively.
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8 2.3 FTIR measurements
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11 Mid infrared spectra of all glass compositions were obtained by using an Alpha
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14 (Bruker) spectrometer in the spectral range of 4000 – 400 cm-1 at ambient temperature
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16 conditions in KBr pellets in transmittance mode. The FTIR spectrometer has sealed and
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18 desiccated optics and utilizes a deuterated triglycine sulfate (DTGS) detector. All powdered
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21 glass samples in the solid form were ground with spectroscopic grade potassium bromide (KBr)
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23 powder with a mixing ratio: 2 mg of sample/200 mg of dry KBr, and afterward pressed into
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26 pellets with a thickness of ~1 mm. The spectral resolution was set at 2 cm-1 for all
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28 measurements. A background spectrum was recorded prior to each FTIR measurement to
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31 account for atmospheric vapor compensation.
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36 3. Results and discussion
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39 3.1 The Tl2O-TeO2 system
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Several studies employing various experimental techniques including Raman, NMR,
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45 and neutron diffraction, have reported that the structure of pure TeO2 glass is composed of
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47 TeO4 trigonal bipyramid and TeO3 trigonal pyramid units [1, 3 and references therein]. In
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50 alkali-tellurite glasses with increasing alkali oxide content [4-11] or Tl2O content [27] the
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52 tellurite glass network is disrupted by the breaking of Te-O-Te linkages and the TeO4 tbp are
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55 transformed to TeO3 tp units with non-bridging oxygens. In this present work, we investigated
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57 the structural characteristics of the xTl2O-(1-x)TeO2 glassy system for x=0.1-0.4 mole fractions
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by recording the FTIR spectra presented in figure 1. A quantification of the existing structural
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 units in this binary glass system was also made and correlated to its thermal properties. The IR
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2 spectra for glasses up to x=0.4 mole fraction exhibit broad bands and correspond to completely
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5 amorphous materials. The terminal glass composition with x=0.5 mole fraction corresponds to
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7 a partially crystalline phase. This crystalline phase is the orthotellurite Tl2TeO3, and consists
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10 of isolated TeO3 trigonal pyramids, which are separated by Tl cations [2]. As shown in figure
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12 1, the bands at ~550-600 cm-1 are assigned to stretching modes of TeO4 tbp units, while the
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15 bands at ~670-720 cm-1 are attributed to stretching modes of the TeO3 tp units. The region at
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17 ~400-500 cm-1 is assigned to bending modes of Te-O-Te linkages present in the glass network.
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23 xTl2O-(1-x)TeO2
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Absorbance

29 TeO3
30 TeO3 x=0.5
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x=0.4
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TeO4 x=0.3
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TeO4 x=0.2
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38 x=0.1
39 Te-O-Te
linkages
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42 900 800 700 600 500 400 300
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44 wavenumbers [cm-1]
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49 Figure 1. FTIR absorbance spectra of the binary Tl2O-TeO2 glass system recorded under
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51 ambient conditions.
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Figure 2 shows the results of the analysis of the IR spectra. For the quantification of the
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56 structural units existing in the glass structure of this binary system, a common fitting procedure
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58 involving four Gaussian profiles was performed. Our results are in agreement with previous
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62 8
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 studies based on the Raman spectra acquired from the binary Tl2O-TeO2 glassy system [1] and
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2 reveal an increasing trend of the [TeO3]/[TeO4] absorbance ratio by increasing the Tl2O, which
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5 acts as a network modifier. This is likely caused due to the transformation of TeO4 units into
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7 TeO3 units. Furthermore, the Te-O-Te linkages exhibit a decreasing trend with increasing the
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10 Tl2O content. This affects the rigidity of the glass network and also impacts their thermal
11
12 properties presented in figure 3.
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18 2.5
[TeO3] / [TeO4]

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21 2.0
22 (a)
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24 1.5
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0.10 0.15 0.20 0.25 0.30 0.35 0.40
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30 0.18
31
Te-O-Te

32 0.15
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34 (b)
0.12
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0.09
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39 0.10 0.15 0.20 0.25 0.30 0.35 0.40
40 Tl2O [mole fraction]
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44 Figure 2. Ratio of [TeO3]/[TeO4] absorbances (a) and absorbance of Te-O-Te linkages (b) as
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47 a function of Tl2O content.
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49
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53 It is reasonable to assume that the absorbance of the trigonal pyramid units relative to that of
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55 the trigonal bipyramid species is proportional to the concentration ratio of these structural units
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58 and the conversion of the tbp to the tp species is facilitated by the addition of the Tl2O modifier
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60 into the tellurite glass network.
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 A thermal study was also performed for all synthesized glass compositions and the
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2 results are presented in figures 3 and 4. Figure 3 (a) shows representative DSC thermographs
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5 for the 0.8TeO2-0.2Tl2O glass composition at three different rates of 10, 15 and 20 oC/min. The
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7 endothermic glass transition and the exothermic crystallization process are clearly seen. In
8
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10 figure 3 (b), the glass transition temperature is shown to decrease with increasing Tl2O content.
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12 This trend exhibited by Tg is associated with the weakening of the glass network, which
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15 becomes less interconnected and floppier. Moreover, the thermal stability S and
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17 thermodynamic fragility F were calculated at heating rates of 10 and 20oC/min from the
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19
following equations:
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21
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23 𝑆 = 𝑇𝑐 − 𝑇𝑔 (1)
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25
0.151−𝑥
26 𝐹 = 0.151+𝑥 (2)
27
28
29
30 where 𝑇𝑐 and 𝑇𝑔 are the crystallization and glass transition temperatures, respectively and 𝑥 =
31
32 𝛥𝑇𝑔 ⁄𝑇𝑔 . Figure 4 (a) shows that the thermal stability maximizes at x=0.2 mole fraction in the
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35 xTl2O – (1-x)TeO2 binary system. The trend of the increasing thermodynamic fragility shown
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37 in figure 4(b) implies that the glass network becomes less interconnected and more flexible, as
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40 revealed by the decreasing trend of the glass transition temperature.
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60
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62 10
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 1
2 16

Heat flow [arb. units]

3 14 0.8TeO2-0.2Tl2O (a)
4 exo
12 10oC/min
5 15oC/min
6 10 20oC/min
7 8
8 6
9 4
10
2
11
12 0
100 200 300 400 500
13 T [oC]
14
15 300
16 270 (b)
17 240
18 210
Tg [oC]

19 180
20 150
21 10oC/min
120
22 15oC/min
23 90 20oC/min
24 60
25 0.10 0.15 0.20 0.25 0.30 0.35 0.40
26 Tl2O [mole fraction]
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29
30
31 Figure 3. (a) DSC thermographs of the 0.2Tl2O-0.8TeO2 glass for 10, 15 and 20oC/min heating
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34 rates. (b) Glass transition temperature as a function of Tl2O content for 10, 15 and 20oC/min
35
36 heating rates.
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62 11
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 1
2
3 210
4
5 180

S [oC]
6 (a)
7 150
8 120
9
10oC/min
10 90 20oC/min
11
12 60
13
14 0.3
15
16
0.2
17
F

18 (b)
19 0.1
20 10oC/min
21 20oC/min
22 0.0
23 0.10 0.15 0.20 0.25 0.30 0.35 0.40
24
25 Tl2O [mole fraction]
26
27
28
29
30
31 Figure 4. Thermal stability (a) and thermodynamic fragility (b) as a function of Tl2O content.
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37
3.2 The V2O5-TeO2 system
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40 Several studies have been carried out regarding the structural characteristics and
41
42 electrical properties of vanadium tellurite glasses [28]. Here, we synthesized the binary glassy
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44
45
system xV2O5-(1-x)TeO2 up to x=0.8 mole fraction, in an effort to correlate its structural
46
47 characteristics with its thermal properties for such a wide compositional range for the very first
48
49 time. In V2O5 glass, vanadium ions exhibit four and five-fold coordination numbers, and that
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52 depends on the sample preparation conditions [16, 29]. The structure of tellurite-vanadate
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54 glasses consists of TeO4 tbp, TeO3 tp units, and also of VO4 tetrahedral, and VO5 trigonal
55
56
57 bipyramid units [20]. At low concentrations of V2O5, the VO4 tetrahedra dominate the glass
58
59 structure, while above x=0.2 mole fraction of V2O5, the glass network becomes stronger and
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61
62 12
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64
65
 more interconnected by the formation of VO5 units [21]. In order to quantify the existing
1
2 structural units in the glass structure, we recorded the FTIR spectra of xV2O5-(1-x)TeO2 for all
3
4
5 compositions presented in Table 1. The corresponding FTIR spectra acquired from the prepared
6
7 glasses are shown in figure 5.
8
9
10
11
12
13
14
15 x=0.8
16
17 x=0.7
18
19 x=0.6
20
Absorbance

21
x=0.5
22
23
24 x=0.4
25 x=0.3
26 x=0.2
27
28 x=0.1
29
30
31 xV2O5-(1-x)TeO2
32
33 1000 800 600 400
34
-1
35 wavenumber [cm ]
36
37
38
39
40 Figure 5. FTIR absorbance spectra of the xV2O5-(1-x)TeO2 glasses under ambient conditions.
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42
43
44
45
46 The intense bands at ~ 962-1012 cm-1 are attributed to vibrations of isolated V=O
47
48
49 vanadyl bonds in VO5 units, and the bands observed near 873-877 cm-1 are assigned to VO4
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51 groups. The spectral features observed near 616-639 and 792-818 cm-1, are assigned to the
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53
54 TeO4 tbp and the TeO3 tp units that constitute the tellurite glass network. Furthermore, the
55
56 bands at ~ 400-550 cm-1 are assigned to Te-O-Te and V-O-V linkages. From the fitting
57
58
59
procedure, we are able to quantitatively follow the variation of the absorbance ratios
60
61
62 13
63
64
65
 [TeO3]/[TeO4] and [VO5]/[VO4] as a function of the V2O5 mole fraction. It is interesting to
1
2 note that both ratios, which are proportional to the TeO3/TeO4 and VO5/VO4 species ratios,
3
4
5 demonstrate an increase with V2O5 content as shown in figure 6(a) and 6(b), respectively.
6
7
8 0.88
9
10 0.84
11 [TeO3]/TeO4]
12 0.80
13
14 0.76
15 (a)
16 0.72
17
18 0.68
0.2 0.3 0.4 0.5 0.6 0.7 0.8
19
20 0.88
21
22
0.84
[VO5]/[VO4]

23
24
0.80
25
26
27 0.76
28 (b)
29 0.72
30 0.2 0.3 0.4 0.5 0.6 0.7 0.8
31
32 V2O5 [mole fraction]
33
34
35
36 Figure 6. Absorbance ratio of [TeO3]/[TeO4] (a) and [VO5]/[VO4] (b) species as a function of
37
38 Tl2O content.
39
40
41
42
43
44
45 These structural modifications are caused by V2O5, which acts as a modifier in the
46
47 present system. Specifically, the addition of V2O5 causes the breakage of Te-O-Te linkages and
48
49
50
changes the coordination environment of the Te atoms. As a result, the TeO4 tbp units are
51
52 gradually transformed into TeO3 tp units. Moreover, the VO4 trigonal pyramids are found to
53
54 decrease relative to the VO5 trigonal bipyramids as the content of V2O5 increases. The increase
55
56
57 of V2O5 content also reduces the glass rigidity and affects the thermal properties presented in
58
59
60
61
62 14
63
64
65
 figures 7 and 8, respectively. The reduction of the glass rigidity is also supported by the
1
2 decreasing trend of the glass transition temperature.
3
4
5
6
The DSC thermographs attributed to 10, 15 and 20oC/min heating rates are presented
7
8 in figure 7(a). The intense endothermic glass transition regions are clearly seen, followed by
9
10 the exothermic crystallization peaks. The glass transition temperatures corresponding to 10 and
11
12
13 20oC/min heating rates are shown in figure 7(b) and reveal a decreasing trend with V2O5
14
15 content. This provides evidence of the gradual transformation of a more rigid glass network to
16
17
18 a floppy structure.
19
20 In figure 8 (a) it seems that for x=0.1-0.5 mole fractions of V2O5, the thermal stability
21
22
23 increases and reaches a maximum near x=0.5. This means that the 0.5V2O5-0.5TeO2 glass
24
25 exhibits the highest resistance to thermal shocks and poses the most rigid structural network
26
27
28
compared to other compositions. For higher V2O5 mole fractions, the thermal stability
29
30 decreases and becomes minimum at x=0.8 mole fraction, whereas the thermodynamic fragility
31
32 shown in figure 8(b) presents a decreasing trend up to x=0.5 mole fraction, which means that
33
34
35 the glass network is more rigid, whereas at higher compositions increases and maximizes at
36
37 x=0.8 mole fraction which implies that the glass network becomes floppier. The glass with
38
39
40 composition x=0.5 mole fraction is of particular interest for this glassy system.
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 15
63
64
65
 1
10

Heat flow [arb. units]

2
3 0.4TeO2-0.6V2O5 (a)
4 8
5 20oC/min exo
6 6 15oC/min
7 10oC/min
8 4
9
10 2
11
12 0
100 200 300 400 500
13 o
14 temperature [ C]
15
16 300
17 (b)
18 280
19
Tg [oC]

20 260
21
22
240
23 20oC/min
24 10oC/min
25 220
26
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
27
28 V2O5 [mole fraction]
29
30
31
32 Figure 7. (a) Representative DSC thermographs for the 0.4TeO2-0.6V2O5 glass composition.
33
34 (b) Glass transition temperature variation as a function of V2O5 content.
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 16
63
64
65
 1

Thermal stability, S [oC]

2
(a)
3 240
4
5
6 160
7
8 80 20oC/min
9 10oC/min
10
11 0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
12
13
Thermodynamic fragility, F

14
0.6
15
16 20oC/min (b)
17 0.5 10oC/min
18
19 0.4
20
21
22 0.3
23
24 0.2
25 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
26 V2O5 [mole fraction]
27
28
29
30
31 Figure 8. Thermal stability (a) and thermodynamic fragility (b) as a function of V2O5 content.
32
33
34
35
36
37
38 3.3 The Tl2O-V2O5-TeO2 system
39
40
41 The ternary glassy system xTl2O-(1-x)(0.67TeO2-0.33V2O5) with compositions x=0.1,
42
43 0.2, 0.3, 0.4, 0.5 and 0.6 mole fraction, was also synthesized and studied by means of FTIR
44
45
46 spectroscopy and DSC. This system contains two oxides that has been shown to have the ability
47
48 to act as glass formers, namely TeO2 and V2O5. This provides an excellent opportunity to
49
50
51 investigate the role of Tl2O, and its effect on the thermal and structural properties, when
52
53 incorporated into the V2O5-TeO2 glassy system. For this purpose, we systematical collected the
54
55 corresponding FTIR spectra and performed a detailed analysis in order to reveal their structural
56
57
58 characteristics.
59
60
61
62 17
63
64
65
 Furthermore, the thermal properties of this glassy system were investigated and
1
2 correlated to the structural characteristics of each glass synthesized. The corresponding FTIR
3
4
5 spectra of the ternary Tl2O-V2O5-TeO2 glass-forming system at various compositions are
6
7 presented in figure 9.
8
9
10
11
12
13
14 xTl2O-(1-x)(0.667TeO2-0.333V2O5)
15
16
17
18
19
20
Absorbance

21
22
23
24
25
26
27
28 0.6
29 0.5
30 x 0.4
31 0.3
32 0.2
33 0.1
34
35 1000 900 800 700 600 500 400
36
37 wavenumbers [cm-1]
38
39
40
41
42 Figure 9. FTIR absorbance spectra of the ternary glass forming system xTl2O-(1-x)(66.7TeO2-
43
44
45 33.3V2O5) glasses under ambient conditions.
46
47
48
49
50
51 From the acquired FTIR spectra, six (6) broad peaks can be observed as shown in figure
52
53
54
S1 of the supplementary information, using a proper fitting procedure for the 0.5Tl2O –
55
56 0.5(0.67TeO2 – 0.33V2O5) selected glass. The peak observed in the region between 480-490
57
58 cm-1 is assigned to Te-O-Te and V-O-V linkages and their corresponding bending modes. The
59
60
61
62 18
63
64
65
 band centered at ~ 612 cm-1 is attributed to [TeO4] (tbp) units, and the bands centered at about
1
2
690 and 786 cm-1 are attributed to [TeO3] (tp) units. Two more bands, in the region between
3
4
5 880-890 cm-1 , are also appearing in the spectra due to the presence of V2O5, and are assigned
6
7 to [VO4] units, whereas the peak appearing in the region betweed 985-990 cm-1 is attributed to
8
9
10 [VO5] groups. In order to quantify the existing structural units in the glass structure, and to
11
12 determine the role of Tl2O, we performed a systematic fitting procedure. The fitting procedure,
13
14
15 as stated above, involved six (6) Gaussian profiles shown in figure S1 of the supplementary
16
17 information. From the areas of every Gaussian profile employed we were able to quantify the
18
19
20
existence of the above-mentioned structural units and the results are presented in figure 10.
21
22
23 Our findings show that the Te-O-Te and V-O-V linkages are not significantly affected
24
25 by the increasing content of Tl2O, but only exhibit a slight increase. On the contrary, the
26
27
28
[TeO3]/[TeO4] ratio reveals an increasing trend with increasing Tl2O content. This increasing
29
30 [tp]/[tbp] ratio indicates the transformation of the trigonal bipyramid units [TeO4] into the
31
32 trigonal pyramids [TeO3] caused by introducing Tl2O into the system. On the other hand, the
33
34
35 [VO5]/[VO4] ratio is not affected by Tl2O and seems to remain almost constant.
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 19
63
64
65
 1
2 40
3 36

linkages
4 32
5 28
6 (a)
24
7
8 20
9 0.5

[VO5] / [VO4]
10 0.4
11 0.3
12
0.2
13
0.1 (b)
14
15 0.0
16
[TeO3] / [TeO4]

17 6
18 5
19
20 4
(c)
21 3
22
23 0.1 0.2 0.3 0.4 0.5 0.6
24 Tl2O [mole fraction]
25
26
27
28
29 Figure 10. (a) The Te-O-Te & V-O-V linkages at the studied compositions of Tl2O, (b)
30
31 Quantification of the [VO5]/[VO4] ratio, (c) The increasing ratio [TeO3]/[TeO4] as a function
32
33
34 of Tl2O content. All lines are drawn as guide to the eye.
35
36
37
38
39
40 By using differential scanning calorimetry (DSC) to obtain the glass transition and
41
42 crystallization temperatures, we were also able to calculate some thermochemical properties of
43
44
45 this ternary glass-forming system. Figure 11 (a) presents the DSC thermographs acquired at
46
47 heating rates of 10, 15 and 20oC/min. The glass transition region is clearly seen in all
48
49
50 thermographs as expected before the crystallization peaks. The glass transition temperature Tg
51
52 is shown to be decreasing with increasing Tl2O content as presented in figure 11 (b). This
53
54
55 implies that the Tl2O acts as a modifier in the glass structure, affecting the rigidity of the glassy
56
57 network. The thermal stability exhibited by this system is shown in figure 12 (a) and reveals
58
59
60
an increasing trend with Tl2O content. The experimental values of thermal stability S are
61
62 20
63
64
65
 significantly high, indicating that this ternary glass-forming system is very resistant to thermal
1
2 shocks. In general, glasses showing thermal stability higher than 100 oC are considered of high
3
4
5 quality regarding their optical properties [1, 30, 31]. Finally, the thermodynamic fragility is
6
7 found to be decreasing with increasing Tl2O content as shown in figure 12 (b). This means that
8
9
10 the atomic network in the glass becomes more rigid, which is in agreement with the small
11
12 increase in the presence of V-O-V and Te-O-Te linkages.
13
14
15
16
17
Heat flow [arb. units]

18 0.3Tl2O-0.70(0.67TeO2-0.33V2O5)
19 12
20
21
22 20oC/min
8 exo
23 15oC/min
24 10oC/min
25 4
26 (a)
27
28 0
29 100 200 300 400 500
o
30 temperature [ C]
31
32
270
33
34
35 260
36
Tg [oC]

250
37 (b)
38
39 240
40 20oC/min
41 230 10oC/min
42
43 220
44 0.1 0.2 0.3 0.4 0.5 0.6
45
46
Tl2O content [mole fraction]
47
48
49
50 Figure 11. (a) A representative example of DSC thermographs for a specific glass composition
51
52
53 at various heating rates, (b) Glass transition temperature (Tg) evolution with varying Tl2O
54
55 content in the glass, for two different heating rates.
56
57
58
59
60
61
62 21
63
64
65
 Thermal stability, S [oC]
1
280
2
3 20oC/min
4 260 10oC/min
5
6 240
7
8 (a)
220
9
10
11 200
0.1 0.2 0.3 0.4 0.5 0.6
12
Thermodynamic fragility, F

13
14 0.48
15 20oC/min
16 0.40 10oC/min
17
18 0.32
19
20 0.24
21 (b)
22 0.16
23
24 0.1 0.2 0.3 0.4 0.5 0.6
25 Tl2O [mole fraction]
26
27
28
29
30
31 Figure 12. Thermal stability, S (a) and thermodynamic fragility, F (b) of the ternary xTl2O-(1-
32
33 x)(66.7TeO2-33.3V2O5) glass-forming system as a function of Tl2O content, for two different
34
35
36 heating rates.
37
38
39
40
41
42 4. Conclusions
43
44
45 In this work we report the synthesis of Tl2O-TeO2, V2O5-TeO2 and Tl2O-V2O5-TeO2
46
47
48
binary and ternary glass-forming systems and the study of their vibrational and thermal
49
50 properties by means of FTIR spectroscopy and differential scanning calorimetry. The aim of
51
52 our work was to study the thermal properties of the above mentioned glassy systems at an
53
54
55 extensive compositional range and to correlate these properties to their structural
56
57 characteristics. We also investigated the role Tl2O plays when incorporated in the V2O5-TeO2
58
59
60 glass system and how it affects the thermal and structural properties of this system.
61
62 22
63
64
65
 Based on our findings regarding the binary system xTl2O-(1-x)TeO2, the ratio
1
2 [TeO3]/[TeO4] increases as the Tl2O content increases, indicating that the Tl2O oxide acts as a
3
4
5 modifier in this system as revealed by the gradual transformation of [TeO4] into [TeO3] units
6
7 with altering Tl2O content. Moreover, the Te-O-Te linkages exhibit a decreasing trend with
8
9
10 Tl2O content as more terminal oxygens are formed. The glass transition temperature Tg
11
12 decreases when increasing the Tl2O content for all different heating rates used, which indicates
13
14
15 that the glass network becomes less interconnected and less rigid. This attribution is also
16
17 supported by the increasing trend of the thermodynamic fragility, for the glasses synthesized
18
19
in this system. Furthermore, the thermal stability of the Tl2O-TeO2 glass system is generally
20
21
22 low, presenting a maximum at x=0.2 mole fraction in Tl2O.
23
24
25 What is reported in the literature is that when mixing V2O5 with TeO2, it forms glass
26
27
28
in the compositional range of 7.5-58 mol% of V2O5 [26]. In this paper we have shown that
29
30 glass formation in this binary system is possible even at 60, 70, and 80 mol% of V2O5. The
31
32 calculated ratio [VO5]/[VO4] shows an increasing trend, similar to the [TeO3]/[TeO4] ratio with
33
34
35 increasing content of V2O5 in the binary V2O5-TeO2 glass system. By increasing the content of
36
37 V2O5, the glass structure is gradually modified due to the transformation of [TeO4] tbp into
38
39
40 [TeO3] tp units. These structural alterations imply that the V2O5 oxide causes structural
41
42 modifications in the TeO2 glass network by changing the coordination environment of Te
43
44
45
atoms. This results to the reduction of the glass rigidity, which is also supported by the
46
47 measured glass transition temperatures, as the Tg exhibits a decreasing trend for all glass
48
49 compositions, in agreement with results previously reported in the literature [27]. For glasses
50
51
52 with x=0.1-0.5 mole fraction of V2O5, the thermal stability increases and reaches a maximum
53
54 at x=0.5 mole fraction. This implies that the glass with composition 0.5V2O5-0.5TeO2 has the
55
56
57 higher resistance to thermal shocks while also having the most rigid network. For glasses with
58
59 x=0.6-0.8 mole fraction of V2O5 the thermal stability decreases and reaches a minimum at
60
61
62 23
63
64
65
 x=0.8 mole fraction. The thermodynamic fragility, F, decreases until reaching the glass
1
2 composition with x=0.5 mole fraction, whereas at higher compositions, F, exhibits an
3
4
5 increasing trend maximizing at x=0.8 mole fraction.
6
7
8 Regarding the ternary glass-forming system xTl2O-(1-x)(66.7TeO2-33.3V2O5) we
9
10 observed that the Te-O-Te and V-O-V linkages are not significantly affected by the increasing
11
12
13 Tl2O content but exhibit only a slight increase. The ratio [TeO3]/[TeO4] shows an increasing
14
15 trend, with increasing Tl2O content due to the transformation of the [TeO4] units into [TeO3]
16
17
18 caused by Tl2O. On the other hand, Tl2O does not seem to affect the [VO5]/[VO4] ratio which
19
20 seems to remain almost constant. The incorporation of Tl2O into vanadate tellurite glasses
21
22
23 resulted in decreasing the glass transition temperature Tg, which means that Tl2O acts as a
24
25 modifier oxide in the glass structure, affecting the network’s rigidity. Furthermore, the thermal
26
27
28
stability, S, seems to increase with increasing Tl2O content. The high values of thermal stability
29
30 indicate that the composed ternary glass-forming system can be considered a high quality glass
31
32 for relevant applications. Finally, the thermodynamic fragility shows a decreasing trend, with
33
34
35 altering glass composition which implies that the atomic network in the glass becomes more
36
37 rigid, in agreement with the small increase of the V-O-V and Te-O-Te linkages in this system.
38
39
40
41
42 Declarations
43
44 Author contributions: All authors contributed to the study conception and design. Material
45
46 preparation and data collection were performed by Pantelis Mpourazanis and Nektarios
47
48 Nasikas. Data analysis was performed by Pantelis Mpourazanis and Angelos Kalampounias.
49
50
All authors contributed equally in writing the final manuscript.
51 Conflict of interest: The authors declare that there is no conflict of interest with others.
52
53 Funding: Pantelis Mpourazanis would like to thank the Research Committee of the University
54
55 of Ioannina for receiving financial support during this study.
56
57
58
59
60
61
62 24
63
64
65
 References
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Supplementary Material

Click here to access/download

Supplementary Material
Supplementary- Tl2O-TeO2-V2O5.docx
Cover Letter Click here to access/download;Cover Letter;Letter to the
Editor_APYA.docx

Hellenic Army Academy

Division of Mathematics and Engineering Sciences,
Hellenic Army Academy, GR 16673, Vari, Attica, Greece.
Assistant Professor, Nektarios Nasikas, PhD
Email: nasikas@sse.gr
Phone: (+30) 698 134 5682

Vari, May 31, 2023

Editor – in – Chief
Applied Physics A

Subject: Original manuscript submission

Dear Editor,

Please consider for publication in the Journal Applied Physics A, the enclosed manuscript
entitled “Vibrational and thermal properties of the ternary Tl2O-V2O5-TeO2 glass-forming
system” by Pantelis Mpourazanis, Nektarios K. Nasikas and Angleos G. Kalampounias. This
manuscript presents an original work that aims to systematically investigate the influence of
altering glass composition on the thermal properties and structural characteristics of ternary
Thallium Vanadate Tellurite glasses.
This is the first attempt to systematically follow compositionally induced structural
changes and subsequently their influence on the thermal properties of these glasses and provide a
more detailed picture about how the above features are interconnected. One additional novelty
presented here is the extension of glass formation in this system, providing important insights for
glasses synthesized for the very first time.
 Our findings can contribute to better understanding of the complex phenomena occurring
in these glasses and possibly shed new light in technologically important applications for such
amorphous materials. Both above-mentioned aspects, namely the vibrational and thermal
properties of these glasses have attracted very little attention so far mainly due to the severe
challenges entailing successful vitrification. Thus, as presented here, a very systematic
investigation of their compositional characteristics and their link to their vibrational and thermal
properties is extremely important.
This manuscript has not been submitted elsewhere, nor has it been previously published,
wholly or in part.
We suggest the following possible reviewers for this manuscript.

1. Professor John C. Mauro

College of Earth and Mineral Sciences
Department of Materials Science and Engineering
Penn State
Email: jcm426@psu.edu

2. Professor Sabyasachi Sen

College of Engineering
Department of Materials Science and Engineering
University of California, Davis
Email: sbsen@ucdavis.edu

3. Professor Lisa C. Klein

School of Engineering
Department of Materials Science and Engineering
Email: licklein@rutgers.edu
Thank you for your consideration.