Journal of the American Ceramic Society

Deconvoluting interrelationships between low-energy

vibrational modes and elastic properties in CaO - Al2O3
glasses

Journal: Journal of the American Ceramic Society

Manuscript ID JACERS-49233

Manuscript Type: Research Article

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Date Submitted by the
22-Mar-2022
Author:

Complete List of Authors: Nasikas, Nektarios; Hellenic Army Academy Department of Mathematics
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and Engineering, Mathematics and Engineering Sciences

Kalampounias, Angelos; University of Ioannina, Chemistry; Institute of
Chemical Engineering and High-Temperature Processes, University of
Ioannina
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Keywords: Raman spectroscopy, Young-s modulus, calcium aluminate

Author-supplied Keyword: If
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there is one additional

keyword you would like to Boson Peak
include that was not on the
list, please add it below::
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Journal of the American Ceramic Society

Page 1 of 30 Journal of the American Ceramic Society

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5 Deconvoluting interrelationships between low-energy vibrational modes and elastic
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7 properties in CaO – Al2O3 glasses
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12 Nektarios K. Nasikas1,* and Angelos G. Kalampounias2,3,*
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16 1Department of Military Studies, Division of Mathematics and Engineering Sciences, Hellenic Army Academy, GR
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18 16673, Vari, Attica, Greece.
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20 2Department of Chemistry, University of Ioannina, Ioannina, GR-45110, Greece
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3University Research Center of Ioannina (URCI), Institute of Materials Science and Computing, Ioannina, Greece
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Abstract
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31 By employing a non – conventional glass formation technique, namely the aerodynamic levitation
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33 (ADL) combined with CO2 laser melting, we have been able to synthesize a series of glasses in
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the binary system xCaO – (1 – x)Al2O3, (x = 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75 and 0.80).
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38 Utilizing Raman spectroscopy, we have systematically followed the compositionally induced
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40 spectral changes in the low – frequency regime of the spectra, the so-called Boson Peak (BP)
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42 region and unraveled interesting interrelationships between the low energy vibrational modes and
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45 the elastic properties of Calcium Aluminate glasses. It was found that the BP frequency is not only
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47 systematically dependent on altering CaO content by exhibiting a minimum close to the eutectic
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49 composition. Interestingly, the above-mentioned compositional dependence of the BP, which is
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exhibited in the shift of the BP frequency versus the altering CaO content, is also strongly
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54 correlated with its elastic properties and seems to follow similar patterns for the binary Calcium
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56 Aluminate glassy system. The above observations point towards the estimation that the eutectic
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3 point can serve as a strong indicator for various physicochemical phenomena taking place in the
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6 solid – liquid transition and thus provide new insights in an effort to deconvolute the ambiguous
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8 interrelationships occurring in the low vibrational frequency regime of these glasses.
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* Corresponding authors:
14 NKN: Department of Military Studies, Division of Mathematics and Engineering Sciences,
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16 Hellenic Army Academy, GR 16673, Vari, Attica, Greece; email: nasikas@sse.gr
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18 AGK: Department of Chemistry, University of Ioannina, GR-45110, Ioannina, Greece.
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Tel.: +30 26510 08439; e-mail: akalamp@uoi.gr
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Keywords: calcium aluminates glasses; Raman spectroscopy; low frequency vibrations; elastic
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26 properties; Young’s modulus; sound velocities; Boson peak.
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3 1. Introduction
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6 Amorphous and glassy materials are amongst the most intriguing subjects of materials science
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8 and engineering, mostly due to their unique physicochemical and structural characteristics
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10 exhibited in the amorphous state.1 These characteristics have been thoroughly studied in the
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previous decades, with a variety of experimental techniques and theoretical approaches.2-5 In this
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15 context, oxide glasses, have a unique place as they are materials exhibiting a broad spectrum of
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17 scientific interest, stretching from their geological importance6,7 to even their biocompatibility
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applications for health-related issues.8,9
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22 Calcium Aluminate (CA) glasses are amongst those possessing both the above-mentioned
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24 characteristics. They are important geological constituents of the Earth’s mantle and crust10 but
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26 also important ingredients for biomaterials having a variety of applications in dentistry and
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29 elsewhere.11,12 More specifically, CA and CA based glasses have been extensively studied in the
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31 past in an effort to elucidate their structural characteristics with a variety of experimental
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33 techniques, such as Raman spectroscopy, multiple quantum nuclear magnetic resonance (MQ –
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NMR) and XANES (X – ray absorption near edge structure) being the most notable.13-15 The vast
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38 majority of these works have provided valuable insights revealing important structure property
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40 relations.13-17
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Especially Raman spectroscopy has proven a very powerful tool in this effort and has provided
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45 a very detailed and consistent picture regarding the structural characteristics of the existing Ca –
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47 O and Al – O polyhedra in these glasses.15,18,19 The vibrational spectra of these corresponding
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49 polyhedra are depicted as broad overlapping bands in the medium-to-high frequency spectral
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52 regions. These bands constitute some very distinct vibrational signatures and have been attributed
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3 to various AlOx polyhedra with coordination numbers varying from x = 4, 5 and 6, existing in this
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6 binary CA glassy system.15
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8 On the contrary, very little attention has been given to the low-frequency region, close to the
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10 laser’s excitation line of the Raman spectra acquired from CA glasses, where the so-called Boson
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peak arises. The low-frequency regime (below 150 cm-1) of the Raman spectra acquired from
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15 glassy materials is dominated by the presence of a broad asymmetric band, originating by the
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17 overlapping contributions of two major sources.
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The first source is the vibrational contribution of the so called Boson Peak (BP), whose
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22 intensity generally follows the temperature dependence arising by the Bose factor, namely n(ω,T)
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24 = [exp(ℏω/𝑘𝐵T) – 1]-1. The second source is attributed to the quasi – elastic (QE) factor that is
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generally linked to the presence of a very fast relaxation process with a magnitude of picoseconds.
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29 The BP in general is manifested in most of the cases in the spectral region between 10 and 50
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31 wavenumbers, although some binary oxide glasses, such as Magnesium Silicates, occurring
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33 between the metasilicate and the orthosilicate compositions corresponding to Enstantite (MgSiO3)
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36 and Forsterite (Mg2SiO4) respectively, have demonstrated BP frequency values in the spectral
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38 region between 90 and 100 wavenumbers.20
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40 One of the first works aiming to elucidate the nature of the BP21 proposed that it originates
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43 from light scattering in the low – frequency regime of the Raman spectra and more specifically
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45 from acoustic modes induced by disorder exhibited in the glassy state. Similar efforts proposed a
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47 model aiming to unify the experimental data produced by spectroscopic and diffraction
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experiments of amorphous solids22,23 However, despite systematical efforts to investigate the
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52 origin of the BP, it remains debatable and especially for CA has just started to be systematically
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54 investigated.24
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3 Most studies, so far, that have dealt with the elucidation of structure property relations for
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6 oxide glasses have looked systematically into the compositional dependence of the above-
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8 mentioned linkage. Even less attention has been given to the linkage between the compositional
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10 dependence of the Boson peak and the elastic properties of the corresponding glasses. CA glasses
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are known to possess very interesting elastic properties.25,26
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15 In this work, we have synthesized via aerodynamic levitation combined with CO2 laser
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17 melting, a series of glasses in the binary xCaO – (1-x)Al2O3, (x = 0.45, 0.50, 0.55, 0.60, 0.65, 0.70,
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0.75 and 0.80) system with x denoting the mole fraction. The aerodynamic levitation (ADL)
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22 technique combined with CO2 laser melting has been proven a very versatile and quite reliable
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24 technique that can provide homogeneous glasses, while at the same time expanding the established
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26 glass formation region due to the extremely high cooling rates achieved during synthesis.24,27,28
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29 This expansion in the established glass forming region, is extremely important as the explosion in
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31 the interest shown in glasses and amorphous materials due to their extensive use in technology
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33 related devices and applications, calls for an ever-evolving effort for novel glasses, with novel
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compositions and properties.29,30
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38 Here we report evidence that shed light in the intriguing linkages between the low-frequency
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40 vibrational modes in CA glasses, namely the Boson Peak behavior and how this behavior is
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connected to the elastic properties of CA glasses. The above linkages will be discussed in the
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45 framework of a systematic and very thorough change in the CaO content, of just 0.05 mole, in an
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47 effort to deconvolute a ternary interrelationship between, the Boson Peak, the elastic properties
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49 and composition changes in CA glasses.
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3 2. Experimental
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6 2.1 Previtrification treatment of the starting reagents and glass composition preparations
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8 It is essential, before going into the vitrification process of each of the desired glass
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10 compositions, to perform a series of “previtrification” processes in order to ensure that the prepared
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batches are homogeneous and relieved of any kind of impurities. The first step is to dry the reagent
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15 grade chemicals, namely CaO (Alfa Aesar, 99.95% purity) and Al2O3 (Alfa Aesar, 99.99% purity)
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17 under vacuum at 150 0C for 24 h, removing this way any possible absorbed H2O from the
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atmosphere’s existing moisture.
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22 The second step is to carefully weigh and extensively mix the desired stoichiometric masses
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24 corresponding to CaO and Al2O3 respectively in order to prepare completely homogeneous

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26 mixtures that will be used for glass synthesis. The as prepared batches with stoichiometries within
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29 the compositional range 0.45 ≤ x ≤ 0.80 corresponding to the binary system xCaO – (1-x)Al2O3,
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31 with x denoting the mole fraction, and compositional step of 0.05 mole fraction, can provide a
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33 very detailed picture about the changes induced by altering composition.

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38 2.2 Vitrification process of Calcium Aluminate glasses achieved with aerodynamic levitation
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40 combined with CO2 laser melting
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The vitrification process utilized in order to synthesize the glasses with compositions shown
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45 in Table 1, was through a non – conventional technique, namely the aerodynamic levitation (ADL)
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47 combined with CO2 laser. This technique has proven to be the “technique of choice” when it comes
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49 to vitrify glassy compositions exhibiting either high melting temperatures30,31 or to expand the
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52 glass formation region achieved so far with conventional melt quenching techniques.24,28 The ADL
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54 technique is executed in two distinct steps for the “home made” levitator setup.32,33
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3 Firstly, small amounts, usually a few milligrams (<10 mg) of the glass compositions intended
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6 for vitrification, still in fine grain powder form, are placed on a water-cooled copper hearth for
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8 initial melting. The heating source used to melt the desired glass compositions is the 10.6 μm laser
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10 line of a 240 W, water – cooled, continuous wave CO2 laser (Synrad Evolution series).
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Subsequently, the CO2 laser was turned on and its intensity was gradually increased with a step of
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15 about 10 % of its maximum power per minute. The maximum laser intensity reached at this stage
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17 was limited to 60% of its maximum output. The laser beam was irradiating the desired glass
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composition from above covering the full size of the sample, ensuring this way homogeneity of
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22 the irradiated surface and excluding any unwanted reflections that could create temperature
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24 gradients. As the temperature is carefully increased, ensuring homogeneous melting of the

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26 powdered sample, a liquid droplet (due to surface tension) starts to form that is “self-supported”
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29 by its own material. This guarantees the absence of any factor that could possibly contaminate the
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31 sample since there is complete absence of any kind of container. This characteristic is the main
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33 reason why the ADL technique can also be found in the literature as “containerless” technique.34
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After the formation of the droplet, the CO2 laser beam is blocked by the laser’s shutter leading to
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38 rapid cooling of the melt. At this stage the solidified droplet is still opaque and polycrystalline, as
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40 the presence of the powder material in the base of the droplet provides crystallization nucleus
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throughout this procedure.
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45 The second stage, involved in the ADL setup, is as follows. Initially, we exchange the water-
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47 cooled coper hearth with a conical nozzle (CN) through which Ar gas flows. The CN has seven
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49 engraved air flow channels in its body, namely the center one, with the rest laying in a honeycomb
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52 shape around it, creating an “air-cage” that can “trap” and levitate stably the sample. The
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54 polycrystalline, almost spherical, sample is placed in the center of the CN and the Ar gas flow is
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3 gradually increased until stable levitation of the sample is achieved. The Ar gas flow is carefully
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6 monitored through a mass-flow meter with the ability to control the flow in 0.1% intervals. The
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8 next step involves the gradual increase of the CO2 laser’s intensity in order to melt the levitated
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10 sample. This step is very crucial as the increase in temperature, if not properly monitored, might
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lead to temperatures far above the liquidus line and thus inflict compositional alterations due to
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15 evaporation. In order to avoid the above-described situation, the temperature of the levitated and
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17 concomitantly melted sample was carefully monitored through an optical pyrometer.
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When complete melt of the levitated sample occurred, the CO2 laser beam was suddenly
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22 blocked by the laser’s shutter, attaining this way extremely high-cooling rates for the levitated
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24 sample and subsequently causing its vitrification. The synthesized glasses were spherical beads of
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26 a few mm in diameter, completely transparent, colorless and homogeneous.
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31 2.3 Acquisition of the Raman spectra for the corresponding Calcium Aluminate glasses.
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33 For all glasses synthesized via the above-mentioned procedure and had corresponding
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compositions shown in Table 1, we acquired Stokes – side polarized (parallel polarization) and
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38 depolarized (crossed polarization) Raman spectra. The 514.5 nm laser line originating from an Ar+
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40 laser (Spectra Physics. Stabilite 2017) was used as the excitation source and the collection of the
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Raman scattered light was performed in a 900 geometry by a triple monochromator (Jobin – Yvon,
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45 T – 64000) that had the ability to operate in a double subtractive mode, permitting this way the
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47 recording of the Raman spectra very close to the excitation line. In order to receive a very high-
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49 quality Raman spectra, in terms of resolution, we employed holographic gratings of 1800
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52 grooves/mm and their optimized diffraction efficiency was set at 2 cm-1. A two-dimensional
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54 charged coupled device (CCD) camera was used in order to analyze and detect the scattered light,
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3 which had a 1024×256 pixels array and was cooled down to 140 K by filing a proper container
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6 with N2 in order to minimize thermal noise. In order to collect the Raman spectra, every bead was
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8 placed on a proper stage with the ability to move in all three axes. The laser line was carefully
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10 passed along the equatorial plane of each bead in order to minimize any stray light reflections and
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at the same time passing through the full diameter of the bead enhances the collected signal.
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15 In order to ensure that the whole procedure is systematic and reproducible, we performed
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17 periodic calibrations with the aid of CCl4 which was sealed inside a quartz cell. This procedure
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guarantees that the polarization ratio for both scattering geometries (VV and VH) is correct and
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22 accounts for possible shifts of the monochromator’s gratings. The acquisition times for all spectra
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24 were several minutes and were chosen as to acquire a very high signal-to-noise ratio spectra
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26 leading to the acquisition of high-quality Raman spectra.
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29 Similar procedures for acquiring Raman spectra from molten oxides and salts at high
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31 temperatures have been described in detail elsewhere35,36 and can provide a very detailed picture
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38 3. Results and discussion
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40 The reduced low-frequency Stokes-side Raman spectra acquired by all synthesized glasses are
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shown in Figure 1. The reduced low-frequency VV (RLFVV) representation of the Raman spectra,
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45 shows the evolution of the BP with altering CaO content in the binary system xCaO – (1-x)Al2O3,
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47 (x = 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75 and 0.80) with x denoting the mol fraction. We restricted
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0.80
g(ω) C(ω) / ω2

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0.70
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39 0 100 200 300 400
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42 Raman shift [cm-1]
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45 Figure 1. Reduced Raman spectra versus frequency in the Boson peak region for the VV
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respectively.
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3 The BP dominates over low-lying vibrational bending modes the low-frequency regime of the
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6 Raman spectra and its characteristic frequency is strongly depended on altering CaO content.24
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8 If one considers the harmonic approximation for the Stokes-side Raman spectra that is
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10 collected by amorphous materials, it was shown by Shuker and Gammon37 that the Raman intensity
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can be written as follows:
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17 𝐼𝛼𝛽 𝛼𝛽
𝑒𝑥𝑝(𝜔, 𝛵) = 𝐶 (𝜔)𝑔(𝜔)𝜔
―1
[𝑛(𝜔,𝛵) +1] (1)
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22 In the above equation, the 𝐶𝛼𝛽(𝜔) factor denotes the photon – phonon (Raman) coupling
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24 coefficient, which represents the activity of the vibrational density of states (VDoS) and
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26 ―1
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𝑘𝑇 ) ― 1] is the Bose – Einstein factor.37 The superscript αβ denotes the two
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30 different polarization geometries VV and VH. Considering all the above, we have represented the
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32 spectral characteristics exhibited by the BP shown in Figure 1 in the RLFVV form in an effort to
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34 quantitatively follow its behavior. Therefore, the vertical axis is calculated in the g(ω)C(ω)/ω2
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39 elsewhere.37,38
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41 The fitting procedure for the RLFVV spectra shown in Figure 1 involved the use of a log-
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normal function, in order to systematically follow the compositional dependence of the BP for
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46 these glasses. The evolution of the BP frequency versus the altering CaO content can be seen in
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48 Figure 2a. It is readily observed that the BP frequency for both scattering geometries, VV and VH,
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follows almost identical paths exhibiting a monotonical decrease from ~100 cm-1 corresponding
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53 to the x = 0.45 glass to ~80 cm-1 corresponding to the x = 0.65 glass. From that point on, an almost
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55 monotonical increase in the BP frequency is observed reaching almost 85 cm-1 for the x = 0.80
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3 glass. This crossover point is observed at a mole fraction for CaO close to the eutectic points
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6 observed in the CaO – Al2O3 binary phase diagram.39 This composition, namely around the 65
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8 mol% in CaO which lays close to a eutectic point in the binary Calcium Aluminate phase diagram,
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10 seems to play a key role in deconvoluting the interrelationships between the low-frequency
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vibrations, but also for the various physicochemical phenomena occurring in these glasses. A
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15 somewhat similar trend with varying composition is exhibited in the enthalpy of fusion for the
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17 CaO – Al2O3 binary system.39 This observation is quite interesting as it could reveal a missing link
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between these two very important quantities in CA glasses.
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7 100
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[cm-1]
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12 VH
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ΩVV,
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Sound velocities [m/s]

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7000 longitudinal
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32 3500 transversal
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36 CaO content [mole fraction]
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Figure 2. (a) Composition dependence of the BP frequency for both polarization geometries VV
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43 (red squares) and VH (black circles) (b) Composition dependence of the longitudinal (orange
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45 rhombus) and transversal (blue stars) sound velocities in CA glasses.
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50 The observed non-coincidence for the BP value in the VV and VH representations of the
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52 spectra is quite significant. Analogous results have been observed in other glassy systems, such as
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54 Sr – Mg Fluorophosphates.40 The significant non – coincidence between the polarized and
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3 depolarized values corresponding to the BP frequency is attributed to the different function of C(ω)
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6 corresponding to the VV and VH geometries.
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8 Figure 2b shows the compositional dependence of the longitudinal and transversal sound
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10 velocities in CA glasses reported in the literature.41,42 Both velocities decrease with increasing CaO
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content following similar behavior in their rate of decrease. No abrupt changes are observed but
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15 rather smooth and systematic. It is also readily observed that the transversal sound velocities and
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17 the BP frequency shown in Figure 2 exhibit similar compositional dependence at least up to
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x=0.70. The above finding indicates that the low-frequency vibrations observed in the Raman
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22 spectra acquired from CA glasses originate from transversal phonon vibrations. The above link
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24 has also been shown to hold valid also in the case of fluorophosphate glasses40 and in other systems
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26 both experimentally43 and theoretically.44
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29 It is known that by using the BP frequency, one can derive the Debye temperature, through the
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31 following equation:44
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36 𝜃𝐷 = ħ𝜔𝐷/2𝜋𝑘𝐵 (2)
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40 In the above equation, ħ and 𝑘𝐵 are the Plank’s and Boltzmann’s constants, respectively. Also,
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43 𝜔𝐷 is the Debye frequency corresponding to the depolarized (VH) BP frequency. The Debye
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45 temperature, 𝜃𝐷, calculated through equation (2) and the elastic properties are shown in Figure 3.
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48 For the latter case, namely the derivation of the Debye temperature through the elastic
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50 properties of these glasses, we made use of the following equation:
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ℎ 3𝑃𝑁 1/3
55 𝜃𝐷 = ( (3)
56 𝑘𝐵)( 4𝑉𝜋 ) 𝑢𝑚
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1
2
3
4
5
6 In equation (3), V is the molar volume derived from the ratio between the effective molar
7
8 weight and density. Finally, N is the Avogardo’s number and P is the number of atoms in the
9
10 molecular formula. The rest of the symbols have their usual meanings.
11
12
13
The quantity 𝑢𝑚 in equation (3) is the mean sound velocity, which can be calculated using the
14
15 longitudinal 𝑢𝐿and transversal 𝑢𝑇 velocities, respectively, as shown in equation (4).
16
17
18
19 1
Fo
20 ―3
21
22
𝑢𝑚 = [3 (
1 2
𝑢3𝑇
1
+ 𝑢3 ]
𝐿
) (4)
23
rP

24
25
26
ee

27 It is readily observed that the Debye temperature derived from the BP frequency is
28
29 monotonically decreasing, while the Debye temperature derived from the elastic properties, seems
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30
31 to be initially decreasing in an almost linear manner, reaching a minimum around 65 mol% in CaO
32
ev

33
34
and then increases slightly in a linear manner again. The latter trend is almost identical to the trend
35
36 exhibited by the BP frequency with altering CaO content (see Figure 2a).
iew

37
38 The compositional dependence of the Debye temperature resembles that of the compositional
39
40
evolution of the corresponding longitudinal and transversal sound velocities as shown in Figure
41
42
43 2b. The latter can also be used as an indicator for the cross-linking density in these glasses since
44
45 Debye temperature is also strongly related to the heat capacity of glasses and thus reflecting their
46
47 cross-linking density.40
48
49
50
51
52
53
54
55
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57
58 15
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1
2
3
4
5
6
7 600
8
9
10 Debye temperature [K]
11
560
12
13
14
15
520
16
17
18 LFR
19 Elastic properties
480
Fo
20
21
22 0.4 0.5 0.6 0.7 0.8
23
rP

24 CaO content [mole fraction]

25
26
ee

27 Figure 3. Composition dependence of the Debye temperature. Orange half circles correspond to
28
29
the Debye temperature derived from the elastic properties, while blue squares correspond to the
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30
31
32 Debye temperature derived from the BP frequency.
ev

33
34
35
36
iew

37
The BP can also be correlated to another very important parameter in these glasses, namely the
38
39 mean atomic volume 𝑉𝑚, through the following equation:45
40
41
42
43 𝑀
44 𝑉𝑚 = 𝜌𝑛 (5)
45
46
47
48
49 where, M, ρ and n are the atomic weight, the density and the number of atoms that are involved in
50
51
52 the stoichiometric formula for a specific glass composition, respectively. The evolution of the BP
53
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1
2
3 maximum frequency for both scattering geometries VV and VH (𝛺𝑉𝑉,𝑉𝐻
𝐵𝑃𝑚𝑎𝑥 ) versus the mean atomic
4
5
6 volume 𝑉𝑚 are shown in Figure 4.
7
8
9
10 102
11
12 100 VV
13 VH
14 98
[cm-1]

15 96
16
17 94
18
VH

92
19
ΒPmax
ΩVV,
Fo
20 90
21
22 88
23
rP

86
24
25 84
26
ee

27 82
28 7.2 7.4 7.6 7.8 8.0 8.2 8.4 8.6 8.8 9.0
29
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30 mean atomic volume Vm [cm3/mol]

31
32
ev

33 Figure 4. Evolution of the BP maximum frequency for both scattering geometries VV (red circles)
34
35
36
and VH (black triangles) versus the mean atomic volume for CA glasses.
iew

37
38
39
40 The results show an astonishing and almost identical dependence of the maximum BP
41
42 frequency for both scattering geometries VV and VH from the mean atomic volume to the
43
44
45 analogous dependence from composition (see Figure 2a).
46
47 Another interesting issue is to investigate the compositional dependence of the bulk and the
48
49 Young’s modulus as this relation can reveal important information about the cross-linking density
50
51
52 in the CA glasses studied here. The above is shown in Figure 5 a and b, respectively.
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54
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58 17
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1
2
3
4
5
6 100
7

Bulk modulus [GPa]

8 96 (a)
9
10
11 92
12
13 88
14
15
16
84
17
18 80
19
Fo
20 0.4 0.5 0.6 0.7 0.8
21
22 140
23
rP
Young's modulus [GPa]

24
25 (b)
26 120
ee

27
28
29
rR

30 100
31
32
ev

33
34 80
35
36
iew

37
0.4 0.5 0.6 0.7 0.8
38 CaO content [mole fraction]
39
40
41
42
43 Figure 5. a) Bulk modulus in relation to CaO content in CA glasses (Orange rhombus) b) Young’s
44
45 modulus in relation to CaO content in CA glasses (Black squares).
46
47
48
49
50 It is readily observed that both the bulk and the Young’s modulus follow a similar decreasing
51
52 trend with increasing CaO content. This decrease, especially for the bulk modulus with increasing
53
54 CaO content could be associated with the structural evolution of the various AlOy (y = 4, 5, 6)
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58 18
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1
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3 polyhedra existing in these glasses15 and their contribution towards reducing the rigidity of the
4
5
6 glass network upon addition of CaO, which presumably acts as a glass modifier in this system.
7
8 In this direction, it is also interesting to investigate the relation between the Poisson’s ratio
9
10 and the Debye temperature with composition, namely the CaO content. Figure 6 a and b shows
11
12
13
the above-mentioned dependence for Poisson’s ratio and Debye temperature, respectively.
14
15
16
17
18
19 0.36
Fo
20 (a)
Poisson's ratio

21
22 0.32
23
rP

24
25 0.28
26
ee

27
28
0.24
29
rR

30 0.20
31 0.4 0.5 0.6 0.7 0.8
32
ev

33 620
34
Debye temperature [K]

35 600
36
iew

580 (b)
37
38 560
39
40 540
41
520
42
43 500
44
45 480
46 460
47 0.4 0.5 0.6 0.7 0.8
48
49 CaO content [mole fraction]
50
51
52
53
Figure 6. Poisson’s ratio (a) and Debye temperature (b) in relation to CaO content in CA glasses
54
55
56 (crossed open squares).
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2
3
4
5
6 The Poisson’s ratio seems to be following a somewhat increasing trend with increasing
7
8 CaO content, while the Debye temperature was found to decrease with increasing CaO content. It
9
10 has been shown that the Debye temperature and the Poisson’s ration can be proven very useful
11
12
13
tools in order to estimate the cross-linking density of the glass network.46 Values for the Poisson
14
15 ratio between 0.1 and 0.2 are indicative of high cross-linking, while values between 0.3 and 0.5
16
17 are indicative of the opposite, namely low cross-linking density.46Here, the reported values for the
18
19
CA glasses under investigation show a variation between 0.27 and 0.34. This can be considered as
Fo
20
21
22 indicative of a small cross-linkage transformation occurring in these glasses and thus the
23
rP

24 corresponding glass networks are characterized from low cross-linking density, respectively.
25
26 In previous works regarding binary alkali and alkaline earth silicate glasses, but also
ee

27
28
29 aluminosilicates, the above-mentioned dependence of the 𝛺𝑉𝑉,𝑉𝐻
𝐵𝑃𝑚𝑎𝑥 versus 𝑉𝑚 (see Figure 4) was
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31 found to be linear.47,48 We argue that for CA glasses or for glasses where there is no archetypal
32
ev

33
glass former involved and one of the two components plays the role of the glass former (here nor
34
35
36 CaO nor Al2O3 can from glasses independently, hence are not considered to be archetypal glass
iew

37
38 formers, like SiO2 for example) knowledge of the mean atomic volume can provide a very close
39
40 estimation of how the BP maximum is behaving in these glasses. This will lift significant
41
42
43 experimental difficulties in acquiring a high-quality BP in glasses, as its proximity to the elastic
44
45 scattering hinders its recording.
46
47 It is also worth exploring the dependence of the 𝛺𝑉𝑉,𝑉𝐻
𝐵𝑃𝑚𝑎𝑥 versus the elastic properties of these
48
49
50 glasses and most importantly the shear modulus. The sear modulus or rigidity G, that generally
51
52 shows a system’s resistance to shear can be calculated by equation (6):
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1
2
3 𝐺 = 𝜌𝑢2𝑠 (6)
4
5
6
7
8 The evolution of the 𝛺𝑉𝑉,𝑉𝐻
𝐵𝑃𝑚𝑎𝑥 in relation to G is shown in Figure 7. The relation between these
9
10
11 two quantities is very similar to the one observed in Figure 4, where a characteristic minimum for
12
13 both polarization geometries VV and VH is distinctly observed. This similarity is somewhat
14
15 expected, as both the mean atomic volume 𝑉𝑚 and shear modulus are depended on the anionic
16
17
18 interactions occurring between the structural units existing in these glasses.
19
In this direction, it also interesting to address the intensity of the BP as it is derived from the
Fo
20
21
22 fitting of the Raman spectra shown in Figure 1 and how it is dependent on the inverse shear
23
rP

24
25
modulus for both polarization geometries VV and VH. The results are presented in Figure 8.
26
ee

27
28
29
rR

30
31 100 VV
32 VH
ev

33
[cm-1]

34
95
35
36
iew
VH

37
ΒPmax
ΩVV,

38 90
39
40
41
42 85
43
44
45
46 80
25 30 35 40 45 50
47
48 Shear modulus G [GPa]
49
50
51
52
Figure 7. Evolution of the BP maximum frequency for both polarization geometries VV (red
53
54 circles) and VH (black triangles) versus the shear modulus for CA glasses.
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4
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6 In Figure 8, it is directly observed that the BP intensity is linearly correlated with the inverse sear
7
8 modulus (1/G).
9
10
11
12
13 24
14
15 20
[arb. units]

16
16 Pearson's r=0.993
17
18 VV
12
19
VH
Fo
20 8
21 linear fit
VH

22
23
rP
IVV,
ΒP

24 3
25
26
ee

2 Pearson's r=0.995
27
28
29
rR

30 1
0.020 0.025 0.030 0.035 0.040
31
32 1/G [GPa-1]
ev

33
34
35
36
Figure 8. BP intensity in relation to the inverse shear modulus for both polarization geometries
iew

37
38 VV (black squares) and VH (red circles).
39
40
41
42
The strong linear relation between the BP intensity and the inverse shear modulus (1/G) is
43
44
45 reflected in the respective Pearson’s coefficients, which have values equal to 0.993 for the VV and
46
47 0.995 for the VH polarization geometry. It is worth noting that there is a significant difference in
48
49 slopes and intercepts for the lines corresponding to VV and VH polarizations. This is another
50
51
52 indication of the transverse vibrational origin of the BP.
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54
55
56
57
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1
2
3 Tanaka and Shintani,44 proposed a very simple relation between the BP intensity and the
4
5
6 elastic moduli as shown in the following equation:
7
8
9
10 1 1 1
11
𝐼𝐵𝑃~𝐾 + 𝐺 ≈ 𝐺 (7)
12
13
14
15
The quantities K and G in equation (7), represent the bulk and the shear modulus, respectively.
16
17
18 The bulk modulus, K, compared to the shear modulus, G, is larger so the inversed quantity 1/K is
19
Fo
20 very small compared to 1/G. Hence, the BP intensity in equation (7) is considered being only
21
22 proportional to the inverse shear modulus, 1/G. Analogous interrelationships between the BP and
23
rP

24
25 the elastic properties have been shown recently for polymer glasses.49
26
ee

27
28
29 4. Conclusions
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31
32
In this work we have systematically tried to deconvolute the interesting and overlapping
ev

33
34 interrelationships between the low-frequency vibrational modes and the elastic properties of CA
35
36
iew

glasses. For this purpose, we have successfully synthesized a large variety of glasses occurring in
37
38
the binary system xCaO – (1-x)Al2O3, (x = 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75 and 0.80). The
39
40
41 above wide compositional range combined with a very narrow compositional step of just 0.05
42
43 mole provided a very systematic and thorough investigation of the above-mentioned
44
45 interrelationships.
46
47
48 By utilizing Raman spectroscopy, we have been able to systematically follow a well resolved
49
50 BP, which exhibits a strong dependence on altering CaO content. This trend, when taken together
51
52 with the sound velocities in CA glasses, provided strong evidence for the transversal origin of the
53
54
55
BP. The determination of the elastic properties combined with altering CaO provided a very clear
56
57
58 23
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1
2
3 picture about the dependence owed to altering CaO content. The results suggested that the cross-
4
5
6 linking density as depicted in the Poisson’s ratio and the Debye temperature is somewhat low and
7
8 these glasses, who are also characterized by reduced rigidity of the glass network as shown by the
9
10 Young’s and bulk modulus, respectively.
11
12
13
Finally, we argue that the eutectic points are very important points, not only for glass
14
15 formation, but also for elucidating the various physicochemical phenomena occurring in
16
17 amorphous solids and possibly reveal interesting links between the low-frequency vibrations, and
18
19
the elastic properties of glasses.
Fo
20
21
22
23
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24 5. Acknowledgements
25
26 Professor Emeritus G. N. Papatheodorou and Dr. G. A. Voyiatzis are greatly acknowledged
ee

27
28
29 for providing access to experimental facilities.
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iew

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