applied
sciences
Article
How Ultrasonic Pulse-Echo Techniques and Numerical
Simulations Can Work Together in the Evaluation of the Elastic
Properties of Glasses
Panagiota Siafarika 1 , Nektarios K. Nasikas 2, * and Angelos G. Kalampounias 1,3, *
Citation: Siafarika, P.; Nasikas, N.K.;
Kalampounias, A.G. How Ultrasonic
Pulse-Echo Techniques and
Numerical Simulations Can Work
Together in the Evaluation of the
Elastic Properties of Glasses. Appl.
Sci. 2023, 13, 8240. https://doi.org/
10.3390/app13148240
Academic Editor: Victor Franco
Correia
Received: 13 June 2023
Revised: 11 July 2023
Accepted: 14 July 2023
Published: 16 July 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Appl. Sci. 2023, 13, 8240. https://doi.org/10.3390/app13148240
1 Department of Chemistry, University of Ioannina, GR-45110 Ioannina, Greece
2 Division of Mathematics and Engineering Sciences, Department of Military Studies, Hellenic Army Academy,
16673 Vari, Greece
3 Institute of Materials Science and Computing, University Research Center of Ioannina (URCI),
45110 Ioannina, Greece
* Correspondence: nasikas@sse.gr (N.K.N.); akalamp@uoi.gr (A.G.K.); Tel.: +30-21089-04000 (N.K.N.);
+30-26510-08439 (A.G.K.)
Abstract: This paper presents the numerical simulation of the ultrasonic wave transmittance utiliz-
ing the elastodynamic finite integration technique (EFIT). With this methodology, it is possible to
simulate the propagation of the ultrasound in a medium with a relatively low computational cost.
The capability of this technique for determining the elastic properties of fluorophosphate and the
aluminosilicate glasses is described in detail. The elastic constants of the glasses were calculated
from the theoretically predicted longitudinal and transversal sound velocities and compared with the
corresponding experimental data. Furthermore, the calculated and experimental elastic properties
of the fluorophosphate and aluminosilicate glasses were correlated with the structural peculiarities
of these glasses. This simulation technique is also suitable for unveiling the existence of possible
defects in the glasses by comparing the experimental and simulation data. The EFIT technique
is shown to be a very useful tool in order to provide fast and easy-to-acquire data regarding also
the structural characteristics of various glassy systems. This can be used in conjunction with other
spectroscopic techniques which can prove to be extremely useful for the non-destructive testing of
vitreous materials. The latter can prove very important when vitreous materials used in optical or
optoelectronic applications need continuous monitoring in order to ensure their optimum operation
and functionality with limited intervention. The main contribution of this paper is the treatment
of numerical time-domain modeling of 2D acoustic wave propagation in a viscoelastic medium by
implementing the elastodynamic finite integration technique (EFIT).
Keywords: ultrasonic echography; fluorophosphate glasses; aluminosilicate glasses; wave modeling;
elastic properties; elastodynamic finite integration technique
1. Introduction
Among acoustic techniques, ultrasonic echography stands out as a valuable tool in
various fields for the non-destructive inspection of materials including neat liquids, plastics,
metals, composites, concrete, and cements [1,2] and references therein. Furthermore, ultra-
sonic waves can be used to sono-chemically synthesize materials and for welding purposes.
In terms of ultrasound intensity, the applications are separated into two main groups, namely
the low- and the high-intensity ultrasonic applications. In the low-intensity or equivalent
high-frequency ultrasound group, the low-energy ultrasonic waves propagate through the
medium providing information dynamic analysis, rheology, and process monitoring [3].
Ultrasonic relaxation spectroscopy also utilizes low-power ultrasound waves to deliver in-
formation for the structure of the studied material in the medium- to long-range order. These
studies include proton-transfer reaction [4–6] and association–dissociation mechanisms [7],
https://www.mdpi.com/journal/applsci
Appl. Sci. 2023, 13, 8240 2 of 17

conformations between isomers [8], complexation processes [9–11], backbone segmental

motion and normal mode relaxation mechanisms in polymeric solutions [12,13], and other
processes related to reaction engineering [14]. In the high-intensity or low-frequency ul-
trasound group, the sound waves propagate through the medium inducing locally high
pressures and temperatures. This methodology is utilized in several laboratory and indus-
trial applications involving processes such as emulsification, welding, cleaning, fatigue
testing, chemical reactions, heat generation, and others [15]. In general, ultrasonic measure-
ments are rapid, accurate, non-destructive in the high-frequency region, and can be fully
automated for industrial uses but require experienced operators that master the specific
methodology and be able to precisely interpret the experimental results. The situation in
most of the cases is perplexing since the results are subject to severe disturbances including
beam deviation and/or splitting, mode conversion due to the presence of anisotropic and
heterogeneous domains in the material, etc. These phenomena are reflected in acoustic
spectra as spurious echoes and noise.
On the other hand, the numerical simulation of ultrasonic transmission experiments
is a powerful tool to evaluate the non-destructive inspections of materials performed by
means of acoustic techniques or to progress the optimal design of ultrasonic inspection
systems. The simulation involves the transmission of the acoustic waves into materials and
the subsequent detection and analysis of the reflected or transmitted signal. The relevance
of the simulation data with the experimental results is directly related to the ability of
the numerical approach to handle reflection, dispersions, scattering and mode conversion
phenomena, and the accuracy of the input parameters of the code [16,17].
Fluorophosphate (FP) glasses exhibit improved properties compared with the cor-
responding fluoride and phosphate counterparts. The addition of phosphates into the
fluoride systems enhances its glass-forming ability and the final products are promising ma-
terials for laser and optics applications [18–20]. The short-range structure of FP glasses and
the medium-range order were studied extensively by means of Raman spectroscopy [21,22].
The structure is dominated by PO4 tetrahedra with 2, 3, and 4 non-bridging oxygen atoms
in each tetrahedron corresponding to Q2 , Q1 , and Q0 species, respectively. A recent review
on the structure of FP glasses can be found in [23].
Aluminosilicate glasses doped with lanthanum (LAS) exhibit high glass-transition tem-
perature and refractive indices, high hardness, and are chemically durable [24,25]. Trivalent
rare earth cations, such as La3+ , serve as charge compensators for three neighboring alu-
minum oxide tetrahedra [AlO4 ]5− or for one aluminum oxide octahedron [AlO6 ]9− [26,27].
The structure is dominated by the presence of tetrahedral species, nevertheless aluminum
cations can be found four-, five-, and six-fold coordinated, while the addition of lanthanum
oxide in the aluminosilicate matrix induces the formation of terminal non-bridging oxygen
atoms exhibiting a traditional network modifier behavior [28,29].
The present paper aims to determine the elastic properties of such glasses with the
use of a numerical simulation methodology of ultrasonic transmission of solid materials
performing elastodynamic finite integration techniques (EFIT). The simulation results
were evaluated by means of experimental data available in the literature for two distinct
families of glasses, namely the fluorophosphate and aluminosilicate glasses. The relevant
elastic constants were determined from the longitudinal and transversal sound velocities.
The calculated and the experimental elastic properties were compared and correlated
with the structure of these glasses. To our knowledge, no study has yet compared the
simulation results obtained from the numerical time-domain modeling of 2D acoustic wave
propagation in a viscoelastic medium by implementing the elastodynamic finite integration
technique (EFIT) with the corresponding experimental ultrasonic echography results. The
numerical ultrasonic NDT model presented here can be used effectively for the inspection
of 3D-embedded defects in the material.
Appl. Sci. 2023, 13, 8240 3 of 17

2. Materials and Methods

2.1. Glass Formation
The preparation of the FP glasses was described in detail elsewhere [21,22]. In brief,
the fluoride strontium phosphate-based glasses correspond to xSr(PO3 )2 –(1–x)(0.62MgF2 –
0.38AlF3 ) with x = 0, 0.04, 0.06, 0.1, 0.15, 0.2, 0.3, 0.4, 0.8, 0.9, and 1. The prepared glasses
have a constant ratio of AlF3 /MgF2 . As starting materials we used high purity Sr(PO3 )2 ,
MgF2 , and AlF3 that were used as received. The mole fractions of the fluorophosphate
glasses are presented in Table 1.

Table 1. Mole fraction of the fluorophosphate glasses used in this study.

xSr(PO3 )2 (1–x)(0.62MgF2 –0.38AlF3 )

0.04 0.96
0.06 0.94
0.1 0.90
0.15 0.85
0.2 0.80
0.3 0.70
0.4 0.60
0.8 0.20
0.9 0.10
1 0

The glass formation was achieved by means of the standard melt-quenching technique.
The materials were melted in crucibles at temperatures above their corresponding melting
points depending on the composition and kept at these temperatures until achieving full
homogenization and then fast quenched on preheated plates near the glass transition
temperature to avoid internal stresses in the resulting glassy materials. Subsequently,
the samples were cooled down to room temperature with a cooling rate of ∼5 K/min.
Annealing was also performed for 1 h near their respective glass transition temperature.
Stable glasses were not obtained in the mole fraction range 0.45 < x < 0.65. The obtained
glasses were fully amorphous and with a low OH content. Before ultrasonic pulse-echo
measurements, the samples were cut into circular disks with ∼10 mm diameter and 3–5 mm
thickness and highly polished to facilitate the ultrasonic wave propagation in the glassy
samples. The non-parallelism between the opposite faces of the studied sample is a key
factor that may affect the accuracy of the sound velocity measurements. Thus, special
attention was paid to the sample during cutting. The parallelism of the opposite faces was
verified by means of a dial gauge.
In this study, we did not prepare the lanthanum aluminosilicate glasses. We only used
the experimental longitudinal and transversal values of sound velocity reported in [30]
to estimate the experimental elastic properties of these glasses and compare these values
with our simulation results. In that work, the authors prepared lanthanum aluminosilicate
glasses corresponding to 15La2 O3 –xAl2 O3 –(85–x)SiO2 and 25La2 O3 –yAl2 O3 –(75–y)SiO2 ,
with x and y = 15, 20, 25, 30, 35 mol%. All the experimental details for the glass formation
can be found in [30]. In the present work, our aim was not to prepare and study the structure
of the FP and LAS glasses, but to evaluate our proposed simulation model by comparing the
experimental and simulated elastic properties for two distinct glass families. Therefore, the
main contribution of this paper is the treatment of the numerical time–domain modeling of
2D acoustic wave propagation in a viscoelastic medium by implementing the elastodynamic
finite integration technique (EFIT). The mole fractions of the lanthanum aluminosilicate
glasses are presented in Table 2.
Appl. Sci. 2023, 13, 8240 4 of 17

Table 2. Mole fraction of the lanthanum aluminosilicate glasses used in this study.

Sample Notation La2 O3 Al2 O3 SiO2

LAS1 0.15 0.15 0.70
LAS2 0.15 0.20 0.65
LAS3 0.15 0.25 0.60
LAS4 0.15 0.30 0.55
LAS5 0.15 0.35 0.50
LAS6 0.25 0.15 0.60
LAS7 0.25 0.20 0.55
LAS8 0.25 0.25 0.50
LAS9 0.25 0.30 0.45
LAS10 0.25 0.35 0.40
SiO2 0 0 1

2.2. Pulse–Echo Measurements

A set of X- and Y-cut wide-band transducers (Olympus Corporation, Tokyo, Japan)
was used to send and receive longitudinal and transversal ultrasonic waves in the glass
samples under isothermal and isobaric conditions in a pulse-echo configuration. The
same piezoelectric element was working both as signal transmitter and receiver of the
echoes. A burst generator (TTi Inc., Munich, Germany) was used to excite the transducers
at a frequency of 10 MHz, which is near the fundamental frequency of the piezoelectric
elements. A second channel of the function generator was utilized to trigger and syn-
chronize a Tektronix digital oscilloscope for accurate measurements of the output signal.
The reference and back wall echo trail monitored in the oscilloscope were averaged over
time and then sent to a computer for further analysis of the signals. A small amount of
couplant, appropriate for common medical applications, was placed in the transducer–glass
interface to ensure the maximum ultrasonic radio frequency (RF) signal transmittance in
the glass sample.
Considering the thickness of the glass sample as d, the longitudinal ul and transversal
us sound velocity can be estimated as:

2d 2d
ul = and us = (1)
tl ts

where tl and ts are the time between two consecutive echoes of the longitudinal and
transversal waves, respectively, that are monitored in the oscilloscope. For a given sample
thickness, the tl and ts time intervals are the main sources of error in the determination
of the ultrasound speed. A mathematical methodology that permits precise estimation of
the time intervals is the cross-correlation technique, which provides an accuracy in sound
velocity better than 0.2% [31].
Considering as r1 (t) and r2 (t) are the two amplitude-normalized signals and τ s the
time-lag between these signals, then the following relation holds:

r2 (t) = r1 (t − τs ) (2)

Subsequently, the cross-correlation function can be estimated as:

ZT
1
R12 (τ ) = r1 (t)r2 (t + τ )dt (3)
2T
0

This function reveals a global maximum at τ s , that is the time interval between
consecutive echoes. The two amplitude-normalized signals r1 (t) and r2 (t), as well as the
cross-correlation function, are presented in Figure 1.
Appl. Sci. 2023, 13, 8240 5 of 17
Appl. Sci. 2023, 13, x FOR PEER REVIEW 5 of 18

The two ultrasonic waves

Figure 1. The
Figure waves r11(t) and rr22(t)
(t) and (t) as
as aa function
function of
of time.
time. Both
Both signals
signals have
have similar
similar
shapes,
shapes, equal
equal intensity
intensity (amplitude-normalized)
(amplitude-normalized) and and are
are only
only shifted
shifted in
in time. The
The time
time series
series are
are
aligned
aligned by a time-lag determined through the cross-correlation function, which exhibits
determined through the cross-correlation function, which exhibits the strongest the strong-
est local
local maximum
maximum at time
at time t = tτs=. τs.

3. Numerical
3. Numerical Simulation
Simulation of of Wave
Wave Propagation
Propagation in in Glasses
Glasses
We implemented
We implemented the elastodynamic
elastodynamic finite integration technique (EFIT) in an an effort
effort to
to
numerically simulate
numerically simulate the
theultrasound
ultrasoundpropagation
propagationinin glasses
glasses taking into
taking account
into accountdispersion,
disper-
scattering,
sion, reflection,
scattering, and mode
reflection, conversion
and mode phenomena
conversion phenomena that that
maymay
overwhelm
overwhelm the desired
the de-
information concerning the structural properties of the material. The
sired information concerning the structural properties of the material. The numericalnumerical simulation
sim-
is performed
ulation in the in
is performed time-domain
the time-domainand and
handles effectively
handles effectively thethe
above
above “defect”
“defect”acoustic
acous-
phenomena
tic phenomena [32–34] and
[32–34] andthethe
papers
paperscited
citedtherein.
therein.The
The first
first step
step is to design
is to design thethe two-
two-
dimensional geometry
dimensional geometry of ofthe
theglass
glasssample
sample or or
“cell”, which
“cell”, which is subjected to the
is subjected toacoustic field;
the acoustic
then, we integrate the corresponding equations over this cell. We utilized
field; then, we integrate the corresponding equations over this cell. We utilized an equiv- an equivalent
formulation
alent of theofKelvin–Voigt
formulation constitutive
the Kelvin–Voigt equations
constitutive by considering
equations the glass
by considering sample
the glass sam-as
a visco-elastic isotropic medium [35,36].
ple as a visco-elastic isotropic medium [35,36].
In the
In the context
context ofof the
the Kelvin–Voigt
Kelvin–Voigt model
model forfor an
an isotropic
isotropic medium,
medium, the the 2D
2D linear
linear
elasto-dynamic equations of momentum conservation in terms of velocity
elasto-dynamic equations of momentum conservation in terms of velocity and stress are: and stress are:
𝜕𝑢 𝜕𝜏 𝜕𝜏
𝜌 ∂u=x ∂τxx+ ∂τ+xy 𝑓 (4a)
ρ𝜕𝑡 =𝜕𝑥 +𝜕𝑦 + fx (4a)
∂t ∂x ∂y
𝜕𝑢 𝜕𝜏 𝜕𝜏
𝜌 = + +𝑓 (4b)
𝜕𝑡∂uy 𝜕𝑥∂τxy 𝜕𝑦∂τyy
ρ = + + fy (4b)
and ∂t ∂x ∂y
𝜕𝜏 𝜕𝑢 𝜕𝑢
and = (𝜆 + 2𝜇) +𝜆 +𝑔 (5a)
𝜕𝑡∂τxx 𝜕𝑥∂u x 𝜕𝑦 ∂uy
= (λ + 2µ) +λ + gxx (5a)
𝜕𝜏 ∂t 𝜕𝑢 ∂x 𝜕𝑢 ∂y
= (𝜆 + 2𝜇) +𝜆 +𝑔 (5b)
𝜕𝑡 𝜕𝑦 𝜕𝑥
∂τyy ∂uy ∂u x
𝜕𝜏 = (λ + 𝜕𝑢2µ) 𝜕𝑢 + λ + gyy (5b)
∂t = 𝜇 + ∂y + 𝑔∂x (5c)
𝜕𝑡 𝜕𝑦 𝜕𝑥
 
where λ, µ denote the Lamé constants; ∂τxy ρ is
∂u ∂uy density; and fij, gij with i,j = [x,y] are
xthe mass
=µ + + gxy (5c)
the components of force and stress ∂t sources. ∂y ∂x
where Theλ, first step the
µ denote in the
Laméelastodynamic
constants; ρ finite
is the integration
mass density; technique
and fij , gisij with
to perform space
i,j = [x,y] are
discretization and integration of
the components of force and stress sources. the above equations over the integration cell (glass sam-
ple). In
TheFigure 2, a schematic
first step representation
in the elastodynamic of the
finite velocity and
integration stress components
technique is to performinspace a 2D
grid is presented, where the central point of the integration cell is denoted
discretization and integration of the above equations over the integration cell (glass sample). by i,j. Consid-
ering a tetragonal
In Figure grid or
2, a schematic equivalently of
representation Δxthe = Δy with i and
velocity = [1,n] andcomponents
stress j = [1,n], theinfinite a 2Dinte-
grid
gration provides
is presented, thethe
where following
central discretized
point of theforms for Equations
integration (4) and by
cell is denoted (5):i,j. Considering
Δ𝑡 / / / /
𝑢 ,, =𝑢 ,, + 𝐵 𝜏 , , −𝜏 ,, +𝜏 ,, −𝜏 ,, + Δ𝑡𝐵 𝑓 , , (6a)
Δ𝑥
Appl. Sci. 2023, 13, 8240 6 of 17

a tetragonal grid or equivalently ∆x = ∆y with i = [1,n] and j = [1,n], the finite integration
provides the following discretized forms for Equations (4) and (5):

−1 ∆t  n−1/2 n−1/2 n−1/2 n−1/2


unx,i,j = unx,i,j + Bx τxx,i+1,j − τxx,i,j + τxy,i,j − τxy,i,j −1 + ∆tBx f x,i,j (6a)
∆x

−1 ∆t  n−1/2 n−1/2 n−1/2 n−1/2


uny,i,j = uny,i,j + By τxx,i+1,j − τxx,i,j + τxy,i,j − τxy,i,j + ∆tBy f x,i,j (6b)
∆x − 1

n    
n+1/2 n−1/2 ∆t
τxx,i,j = τxx,i,j + ∆x (λ + 2µ) unx,i,j − unx,i−1,j + λ uny,i,j − uny,i,j−1
    
+(λ0 + 2µ0 ) ∂u x
∂t i,j − ∂u x
∂t i −1,j (7a)
    
+λ0
∂uy ∂uy
∂t − ∂t + ∆tgxx,i,j
i,j i,j−1
n    
n+1/2 n−1/2 ∆t
τyy,i,j = τyy,i,j + ∆x λ unx,i,j − unx,i−1,j + (λ + 2µ) uny,i,j − uny,i,j−1
    
0 0 ∂uy ∂uy
+(λ + 2µ ) ∂t i,j − ∂t i,j−1 (7b)
    
+λ 0 ∂u x
− ∂t ∂u x
+ ∆tgyy,i,j
∂t i,j i −1,j
 
n+1/2 n−1/2 ∆t
τxy,i,j = τxy,i,j +µ xy ∆x unx,i,j+1 − unx,i,j + uny,i+1,j − uny,i,j
     
∆t
+µ0xy ∆x ∂u x ∂u x ∂uy
∂t i,j+1 − ∂t i,j − ∂t i +1,j (7c)
  
∂u
− ∂ty + ∆tgxy,i,j
i,j

where λ’, µ’ are the anelastic parameters; gi,j represent the stress sources; Bi is the effec-
tive buoyancies; and µij , µij0 are the visco-elastic effective rigidity constants, respectively,
given by:
2
Bx = (8)
ρi+1,j + ρi,j
2
By = (9)
ρi,j+1 + ρi,j

4
µij = 1 1 1 1
(10)
µi,j + µi+1,j + µi,j+1 + µi+1,j+1

4
µij0 = 1 1 1 1
(11)
0
µi,j
+ µi0+1,j
+ 0
µi,j
+ µi0+1,j+1
+1

The applied force is:

f ( x, y, t) = [1 − cos(π f 0 t)] cos(2π f 0 t) (12)

where f 0 is the central frequency of the source. Equation (12) has the form of a raised
cosine and is valid for t ≤ 2/ f 0 , while for higher values of t, the applied field is zero.
In Figure 2b, the experimental and simulated ultrasonic signals are presented for direct
comparison. Both signals are attenuated as a function of time in the lossy visco-elastic
material following an exponential profile. Furthermore, the direct comparison between
experimental and simulated ultrasonic signals also provides a direct methodology for the
accurate detection of possible defects in the glasses allowing for the precise determination
of their size and location.
 Appl.Sci.
Appl. Sci.2023,
2023,13,
13,8240
x FOR PEER REVIEW 7 of7 of
1817

Figure
Figure 2. (a) Schematic
2. (a) Schematic representation
representationof
ofthe
thevelocity
velocityand
andstress
stresscomponents
componentsinina a2D
2D grid.
grid. (b)(b) Com-
Com-
parison between experimental
experimental and
and simulated
simulatedpulse-echo
pulse-echosignals.
signals.

Despite
Despite the the fact
fact that
thatseveral
several“defect”
“defect”acoustic
acousticphenomena
phenomenaincluding includingdispersion,
dispersion, scat-
scat-
tering,
tering, reflection, and mode conversion phenomena, have been taken into considerationin
reflection, and mode conversion phenomena, have been taken into consideration
the numerical
in the numerical simulation,
simulation, there areare
there minor
minordifferences
differences between
between thethe
experimental
experimental and andthe
theoretically predicted spectrum. These differences are due to
the theoretically predicted spectrum. These differences are due to the non-perfect paral- the non-perfect parallelism
between the parallel
lelism between phases phases
the parallel of the glass
of thesamples. From the
glass samples. experimental
From point ofpoint
the experimental view,of the
non-parallelism induces a induces
view, the non-parallelism dispersion of the acoustic
a dispersion of thebeam
acousticthatbeam
cannot be cannot
that incorporated
be incor-into
the simulation
porated into theprocedure.
simulation An additional
procedure. An cause of the
additional relative
cause of the intensity
relative differences
intensity differ- is the
shape of the initial pulse. In the numerical simulation, the shape
ences is the shape of the initial pulse. In the numerical simulation, the shape of the pulse of the pulse was raised
cosine,
was raisedwhile the experimental
cosine, waveform iswaveform
while the experimental quite different
is quitesince the probe
different sinceisthenotprobe
ideal.is
In
not ideal.all pulse-echo simulations, we used 5 mm absorbing layers on the left and right side
of theInsample. The piezoelectric elements used to transmit and receive
all pulse-echo simulations, we used 5 mm absorbing layers on the left and right the longitudinal and
shear
side ofultrasonic
the sample. waves had a constant
The piezoelectric diameter
elements usedof 9tomm. The and
transmit frequency
receiveofthe thelongitudi-
ultrasonic
wave
nal and was fixed
shear at 10 MHz
ultrasonic for all
waves had simulations. The shape
a constant diameter ofof9 the
mm.pulse was raisedofcosine
The frequency the
with initial amplitude set to 1 in arbitrary units and the total simulation
ultrasonic wave was fixed at 10 MHz for all simulations. The shape of the pulse was raisedµs time was 25
for all simulations
cosine performed.set
with initial amplitude This
to 1simulation
in arbitrary duration
units and wasthe more
totalthan enoughtime
simulation to receive
was
a25complete
µs for all simulations performed. This simulation duration was more than enough tois
back wall echo train. A schematic representation of the sample modeling
presented in Figureback
receive a complete 3. Inwall
theecho
sametrain.
scheme, the piezoelectric
A schematic representationelements of theand the absorbing
sample model-
layers are also shown. The 2D model used in this work remains
ing is presented in Figure 3. In the same scheme, the piezoelectric elements and the ab- much less computationally
expensive
sorbing layersthanare a full
also3D model.The 2D model used in this work remains much less com-
shown.
The code
putationally for the numerical
expensive than a fullsimulation
3D model. of wave propagation in glasses by EFIT was
developed in Octave programming
The code for the numerical simulation language.ofThe waveOctave syntax isinlargely
propagation glasses compatible
by EFIT was with
MATLAB. The Octave interpreter can be run in GUI mode,
developed in Octave programming language. The Octave syntax is largely compatible as a console, or invoked as part
of a shell script. All calculations were carried out in a Dell
with MATLAB. The Octave interpreter can be run in GUI mode, as a console, or invoked PowerEdge R420 rack server
with
as parttwoofIntel Xeon
a shell E5-2420
script. processors (6-Cores)
All calculations were carried@1.90 outGHz
in aandDellLinux Ubuntu
PowerEdge operating
R420 rack
system. Each processor supports six memory slots. There are
server with two Intel Xeon E5-2420 processors (6-Cores) @1.90 GHz and Linux Ubuntu 12 memory slots in total, with
each processor
operating system.supporting six memory
Each processor modules
supports with maximum
six memory slots. There 384areGB 12of memory
DDR3 memory slots
@1.60 GHz
in total, with supporting
each processortransfer speeds of six
supporting up memory
to 1600 MT/s.
modules Thewith maximum
maximum internal
384 GBstorage
of
was up to 16 TB.
DDR3 memory @1.60 GHz supporting transfer speeds of up to 1600 MT/s. The maximum
internal storage was up to 16 TB.
Appl. Sci. 2023, 13, x FOR PEER REVIEW 8 of 18
Appl. Sci. 2023, 13, 8240 8 of 17

Figure 3. Schematic representation of the model. The two transducers are used to send and receive
Figure 3. Schematic representation of the model. The two transducers are used to send and receive
the ultrasonic signals. Alternatively, only one transducer can be used acting both as emitter and
the ultrasonic signals. Alternatively, only one transducer can be used acting both as emitter and
receiver. The absorbing layers can be used only if it is required for elimination of the reflected sig-
receiver.
nals. The absorbing layers
The implementation of thecan be usedconditions,
boundary only if it is required
where any forstress
elimination of the
is absent, thereflected
vacuumsignals.
con-
The implementation
dition of the
is considered, and bothboundary
elasticityconditions,
moduli Bx where
and By,any
are stress
set to is absent, the vacuum condition is
zero.
considered, and both elasticity moduli Bx and By , are set to zero.
4. Evaluation of the Elastic Properties
4. Evaluation of the Elastic Properties
The elastic properties of a glassy material of mass density 𝜌 can be estimated from
The elastic properties of a glassy material of mass density ρ can be estimated from the
the following simple equations through the longitudinal and transversal sound velocities
following simple equations through the longitudinal and transversal sound velocities [37].
[37].
To describe an isotropic homogeneous material, the longitudinal or constrained modu-
lus,To
L, describe an isotropic
can be used, which ishomogeneous material, thesound
related with longitudinal longitudinal oras:
velocity constrained mod-
ulus, L, can be used, which is related with longitudinal sound velocity as:
= 𝜌𝑢
𝐿L = ρu2L (13)
(13)
The
The resistanceofofa amaterial
resistance materialtotoshear
shearisisevaluated
evaluatedthrough
throughthe
the shear
shear modulus
modulus or
or rigidity,
rigid-
G, which is related with longitudinal sound velocity
ity, G, which is related with longitudinal sound velocity as: as:

𝐺
G== 𝜌𝑢
ρu2S (14)
(14)

The incompressibility
The incompressibilityofof
a material under
a material hydrostatic
under pressure
hydrostatic is is
pressure measured through
measured through
the
the bulk modulus, K that is calculated based on the longitudinal and shear modulus,as:
bulk modulus, K that is calculated based on the longitudinal and shear modulus, as:
4
𝐾=
K = 𝐿L −
− 3 𝐺G
4 (15)
(15)
3
The ratio of the radial to axial strain is evaluated through the Poisson’s Ratio, σ is also
The ratio of the radial to axial strain is evaluated through the Poisson’s Ratio, σ is also
given as a function of the longitudinal and shear modulus:
given as a function of the longitudinal and shear modulus:
(𝐿 − 2𝐺)
𝜎 = ( L − 2G ) (16)
σ = 2(𝐿 − 𝐺) (16)
2( L − G )
The proportionality constant connecting uniaxial stress and strain is the Young’s
Modulus,
TheY,proportionality
calculated by means of the
constant shear modulus
connecting and
uniaxial Poisson’s
stress Ratio as:
and strain is the Young’s
Modulus, Y, calculated by means of the shear modulus and Poisson’s Ratio as:
𝑌 = (1 + 𝜎)2𝐺 (17)
Y = (1 + σ )2G (17)
5. Results and Discussion
5. Results and Discussion
5.1. Fluorophosphate
5.1. FluorophosphateGlasses
Glasses
The
The experimentaland
experimental andthe
thecalculated
calculated longitudinal
longitudinal and transversal ultrasonic
and transversal ultrasonicvelocities
veloci-
ties as well as the elastic properties of the fluorophosphate glasses investigated in the
as well as the elastic properties of the fluorophosphate glasses investigated in the present pre-
sent study
study are are summarized
summarized in Table
in Table 3. The3. first
The row
firstfor
row formole
each each fraction
mole fraction corresponds
corresponds with the
Appl. Sci. 2023, 13, 8240 9 of 17

experimental results, while the second row represents the corresponding calculated value
through the proposed numerical simulation model of the wave propagation in these glasses.

Table 3. Experimental (upper value of each row) and calculated (bottom value of each row) values of
the elastic properties of xSr(PO3 )2 –(1–x)(0.62MgF2 –0.38AlF3 ) glasses.

Sr(PO3 )2 mol
uL (m/s) uS (m/s) L (GPa) G (GPa) K (GPa) σ Y (GPa)
Fraction
5262.6 ± 10.5 1375.0 ± 2.8 95.8 ± 0.4 6.54 ± 0.03 87.1 ± 0.4 0.4634 ± 0.0002 19.15 ± 0.08
0.04
5262.7 ± 10.5 1315.9 ± 2.6 95.8 ± 0.4 5.99 ± 0.02 87.8 ± 0.4 0.4667 ± 0.0002 17.57 ± 0.07
5406.9 ± 10.8 1333.4 ± 2.7 101.6 ± 0.4 6.18 ± 0.02 93.4 ± 0.4 0.4676 ± 0.0002 18.14 ± 0.07
0.06
5406.7 ± 10.8 1351.5 ± 2.7 101.6 ± 0.4 6.35 ± 0.03 93.2 ± 0.4 0.4667 ± 0.0002 18.63 ± 0.07
5420.5 ± 10.8 1394.2 ± 2.8 103.0 ± 0.4 6.81 ± 0.03 93.9 ± 0.4 0.4646 ± 0.0002 19.95 ± 0.08
0.1
5420.6 ± 10.8 1355.4 ± 2.7 103.0 ± 0.4 6.44 ± 0.03 94.4 ± 0.4 0.4667 ± 0.0002 18.88 ± 0.08
5378.1 ± 10.8 1410.2 ± 2.8 102.0 ± 0.4 7.01 ± 0.03 92.7 ± 0.4 0.4631 ± 0.0002 20.53 ± 0.08
0.15
5381.8 ± 10.8 1345.7 ± 2.7 102.2 ± 0.4 6.39 ± 0.03 93.7 ± 0.4 0.4667 ± 0.0002 18.74 ± 0.08
5377.3 ± 10.8 1412.7 ± 2.8 102.3 ± 0.4 7.06 ± 0.03 92.9 ± 0.4 0.4629 ± 0.0002 20.67 ± 0.08
0.2
5381.4 ± 10.8 1345.1 ± 2.7 102.5 ± 0.4 6.40 ± 0.03 94.0 ± 0.4 0.4667 ± 0.0002 18.79 ± 0.08
5427.6 ± 10.9 1359.9 ± 2.7 104.1 ± 0.4 6.53 ± 0.03 95.4 ± 0.4 0.4665 ± 0.0002 19.17 ± 0.08
0.3
5423.9 ± 10.8 1356.2 ± 2.7 103.9 ± 0.4 6.50 ± 0.03 95.3 ± 0.4 0.4667 ± 0.0002 19.06 ± 0.08
5390.2 ± 10.8 1333.4 ± 2.7 101.7 ± 0.4 6.22 ± 0.02 93.4 ± 0.4 0.4674 ± 0.0002 18.26 ± 0.07
0.4
5390.8 ± 10.8 1347.3 ± 2.7 101.7 ± 0.4 6.35 ± 0.03 93.2 ± 0.4 0.4667 ± 0.0002 18.64 ± 0.07
4777.4 ± 9.6 1081.1 ± 2.2 73.6 ± 0.3 3.77 ± 0.02 68.6 ± 0.3 0.4730 ± 0.0002 11.10 ± 0.04
0.8
4779.2 ± 9.6 1195.1 ± 2.4 73.7 ± 0.3 4.61 ± 0.02 67.5 ± 0.3 0.4667 ± 0.0002 13.51 ± 0.05
4770.6 ± 9.5 1052.6 ± 2.1 72.3 ± 0.3 3.52 ± 0.01 67.6 ± 0.3 0.4744 ± 0.0002 10.37 ± 0.04
0.9
4767.2 ± 9.5 1192.3 ± 2.4 72.2 ± 0.3 4.51 ± 0.02 66.1 ± 0.3 0.4666 ± 0.0002 13.24 ± 0.05
4565.9 ± 9.1 1075.3 ± 2.2 65.7 ± 0.3 3.64 ± 0.01 60.8 ± 0.3 0.4706 ± 0.0002 10.71 ± 0.04
1.0
4565.9 ± 9.1 1141.8 ± 2.3 65.7 ± 0.3 4.11 ± 0.02 60.2 ± 0.3 0.4667 ± 0.0002 12.05 ± 0.05

The structure of the pseudo-binary fluorophosphate glasses is analogous to that

reported for multicomponent mixed fluoride-phosphate glassy systems. The study of the
structure of these glasses has been performed and presented in detail in [21,22]. In the
present work, we only used the experimental longitudinal and transversal values of sound
velocity and the experimental elastic properties of these glasses reported in the literature to
compare these values with our simulation results. In an effort to facilitate the validation of
the simulation procedure, we present in Figure 4a,b the experimental and the calculated
values of the longitudinal and transversal sound velocities, respectively, that correspond to
the fluorophosphate glasses at room temperature.
It is widely accepted that the structure of a glass material is completely different
compared with the corresponding crystalline material. Glass only has a short-range order
of atoms, while crystals have a long-range order. When studying the structure of the
specific fluorophosphate glasses [21,22], our aim was to study in detail the structure of
the amorphous phase and this is the reason why we restricted our analysis only in the
glass formation range. Crystalline samples can have altered structural properties and they
may lead to the abnormal propagation of waves compared to the corresponding glasses of
the same composition; thus, causing additional scattering or absorption of the ultrasonic
waves. This comparison of the acoustic wave propagation in crystalline and amorphous
materials could not provide any new information. In terms of elastic properties, it is
proper to examine separately the crystalline and the glassy systems, despite their identical
chemical composition.
The incorporation of metaphosphate units into the fluoride structure results in the
formation of Al(O,F)6 octahedra that link the two sub-networks by bridging the metaphos-
phate and fluoride structural units [21,22] and references therein. In the high metaphos-
phate region, the corresponding phosphate sub-network is dominated by [PO2 (OT )2 ]−
units, the so-called Q2 groups. In the low metaphosphate region, the corresponding net-
work is less polymerized through the formation of pyrophosphate [PO(OT )3 ]2– (Q1 ) and
 isolated orthophosphate [P(OT)4]3– (Q0) structural units [21,22] and references there
transition from the fluoride, which is more ionic in character, to the phosphate n
which is covalent, causes a constant increase in the glass transition temperature
creasing the phosphate content in the glasses. A maximum Tg is detected at ~80 m
Appl. Sci. 2023, 13, 8240 10 of 17
Sr(PO3)2 due to the distinct crosslinking capability of the Al3+ and Sr2+ ions. The Al3
crosslink the short metaphosphate structural units more effectively than the Sr2+
Thus, the
isolated crosslinking
orthophosphate [P(Othrough3– 0Al3+ ions leads to a more rigid glass structure.
T )4 ] (Q ) structural units [21,22] and references therein. This
Thefrom
transition bondthebreaking reduces
fluoride, which the network
is more rigiditytowith
ionic in character, the formation
the phosphate network,of discon
which is covalent, causes a constant increase in the glass transition temperature
in the structure and attenuates the acoustic wave propagation in these glasses, with in- a
creasing the phosphate content in the glasses. A maximum Tg is detected at ~80 mol%
sented in Figure 4. 3+ 2+ 3+
in Sr(PO3 )2 due to the distinct crosslinking capability of the Al and Sr ions. The Al
cations crosslink the short metaphosphate structural units more effectively than the Sr2+
cations. Thus, the crosslinking through Al3+ ions leads to a more rigid glass structure.

6000
(a)
5500
uL [m/s]

5000

4500 exp
calc
4000

2000
(b)
1500
uS [m/s]

1000

500
exp
calc
0
0.0 0.2 0.4 0.6 0.8 1.0
mole fraction
Figure 4. Experimental and calculated longitudinal (a) and transversal (b) sound velocities corre-
sponding to the fluorophosphate glasses at room temperature. Devitrification was observed for
Figure
0.45 < x <4. Experimental
0.65 mole fractions and calculated
of Sr(PO 3 )2 .
longitudinal (a) and transversal (b) sound
velociti
sponding to the fluorophosphate glasses at room temperature. Devitrification was observe
< x <The
0.65bond
molebreaking reduces
fractions the3)network
of Sr(PO 2.
rigidity with the formation of discontinu-
ities in the structure and attenuates the acoustic wave propagation in these glasses, as is
presented in Figure 4.
InInFigure
Figure
5, it5,appears
it appears
that that the experimental
the experimental longitudinal,
longitudinal, shear, andshear, and bulk mo
bulk moduli
strongly
are stronglyaffected
affected by thetransition
by the transition from
from the the fluoride
fluoride (ionic)(ionic) to phosphate
to phosphate (covalent)(covale
with increasing the PO /F ratio in the glasses. The variation in the PO3−−/F− ratio
limit with increasing the PO3−3− /F
− − ratio in the glasses. The variation in the PO3− /F

ratio
atomicleadsvolume
to atomicrise
volume
and rise
bulk and bulk modulus
modulus decrease.
decrease. TheThe behavior of
behavior of the
themoduli
moduli is att
is attributed to the variation in the coordination number with increasing the phosphate
to the variation
content in the glasses.
in the coordination number with increasing the phosphate conten
glasses.
In Figure 6a, the variation in the Poisson’s ratio with the Sr(PO3 )2 mole fraction in
the fluorophosphate glasses is presented. The low values of the Poisson’s ratio imply
a diminished coupling of sound waves from one mode of propagation to another. The
Poisson’s ratio was found experimentally in the range from 0.46 to 0.47. These values
indicate a glass network with low cross-linking density. Both bulk and Young’s moduli
exhibit similar behavior as is observed in Figure 6b.
Appl. Sci. 2023, 13, x FOR PEER REVIEW 11 of 18
Appl. Sci. 2023, 13, 8240 11 of 17

150
120 (a)

L [GPa]
90
60
exp
30 calc
0
12
10 (b)
G [GPa]

8
6
4 exp
2 calc
0
150
(c)
K [GPa]

100

50 exp
calc
0
0.0 0.2 0.4 0.6 0.8 1.0
mole fraction
Appl. Sci. 2023, 13, x FOR PEER REVIEW 12 of 18
Figure
Figure 5. Variation
5. Variation in experimental
in experimental andand calculated
calculated longitudinal
longitudinal (a), shear
(a), shear (b), bulk
(b), and and bulk (c) moduli
(c) moduli
with
with mole
mole fraction
fraction forfor
thethe fluorophosphate
fluorophosphate glasses.
glasses. The The missing
missing points
points in0.45
in the the 0.45
< x <<0.65
x <region
0.65 region
areare
duedue to the
to the observed
observed devitrification.
devitrification.

0.6
In Figure 6a, the variation in the Poisson’s ratio with the Sr(PO3)2 mole fraction in the fluor-
ophosphate glasses is presented. The low values (a)of the Poisson’s ratio imply a diminished
coupling of sound waves from one mode of propagation to another. The Poisson’s ratio
0.5 experimentally in the range from 0.46 to 0.47. These values indicate a glass
was found
network with low cross-linking density. Both bulk and Young’s moduli exhibit similar
σ

behavior as is observed in Figure 6b.

0.4
exp
calc
0.3

30

25 (b)

20
Y [GPa]

15

10
exp
5 calc
0
0.0 0.2 0.4 0.6 0.8 1.0
mole fraction
Figure 6. Variation in experimental and calculated Poisson’s ratio (a) and Young’s modulus (b) with
mole fraction
Figure for the
6. Variation fluorophosphate
in experimental andglasses. ThePoisson’s
calculated missing ratio
points
(a)inand
theYoung’s
0.45 < x modulus
< 0.65 region are due
(b) with
to thefraction
mole observedfor devitrification.
the fluorophosphate glasses. The missing points in the 0.45 < x < 0.65 region are
due to the observed devitrification.

The experimental data available in the literature were compared to the simulated
data. From Figures 4–6, it seems that the direct comparison reveals an adequate agreement
between the experimental and the numerically simulated results demonstrating the ability
Appl. Sci. 2023, 13, 8240 12 of 17

The experimental data available in the literature were compared to the simulated
data. From Figures 4–6, it seems that the direct comparison reveals an adequate agreement
between the experimental and the numerically simulated results demonstrating the ability
of the modelling approach proposed in this work to predict the elastic properties of these
glasses and providing a fine description of the microstructure.

5.2. Aluminosilicate Glasses

The experimental and the calculated longitudinal and transversal ultrasonic velocities
and the elastic properties of the aluminosilicate glasses investigated in [30] are summarized
in Table 4. Also, in this case, the first row for each glass composition corresponds to the
experimental results, while the second row represents the corresponding calculated value
after the simulation procedure.

Table 4. Experimental (upper value of each row) and calculated (bottom value of each row) values of
elastic properties of lanthanum aluminosilicate (LAS) and SiO2 glasses.

Glass Name uL (m/s) uS (m/s) L (GPa) G (GPa) K (GPa) σ Y (GPa)

5883 ± 12 3180 ± 6 121.8 ± 0.5 35.60 ± 0.14 74.4 ± 0.5 0.294 ± 0.002 92.1 ± 0.4
LAS1
5888.2 ± 11.8 3062.4 ± 6.1 122.0 ± 0.5 33.01 ± 0.13 78.0 ± 0.5 0.315 ± 0.001 86.8 ± 0.4
6128 ± 12 3329 ± 7 134.1 ± 0.5 39.56 ± 0.16 81.3 ± 0.6 0.291 ± 0.002 102.1 ± 0.4
LAS2
6156.8 ± 12.3 3342.6 ± 6.7 135.3 ± 0.5 39.89 ± 0.16 82.1 ± 0.6 0.291 ± 0.002 103.0 ± 0.4
6144 ± 12 3345 ± 7 132.9 ± 0.5 39.39 ± 0.16 80.4 ± 0.6 0.289 ± 0.002 101.6 ± 0.4
LAS3
6131.3 ± 12.3 3201.7 ± 6.4 132.3 ± 0.5 36.08 ± 0.14 84.2 ± 0.6 0.313 ± 0.001 94.7 ± 0.4
6381 ± 13 3413 ± 7 145.8 ± 0.6 41.70 ± 0.17 90.2 ± 0.6 0.300 ± 0.002 108.4 ± 0.5
LAS4
6368.7 ± 12.7 3294.8 ± 6.6 145.2 ± 0.6 38.86 ± 0.16 93.4 ± 0.6 0.317 ± 0.001 102.4 ± 0.4
6413 ± 13 3449 ± 7 148.1 ± 0.6 42.82 ± 0.17 91.0 ± 0.6 0.297 ± 0.002 111.0 ± 0.5
LAS5
6421.5 ± 12.8 3447.9 ± 6.9 148.4 ± 0.6 42.80 ± 0.17 91.4 ± 0.6 0.297 ± 0.002 111.1 ± 0.5
6015 ± 12 3130 ± 6 154.1 ± 0.6 41.73 ± 0.17 98.5 ± 0.7 0.314 ± 0.001 109.7 ± 0.5
LAS6
6026.1 ± 12.1 3009.7 ± 6.0 154.7 ± 0.6 38.59 ± 0.15 103.2 ± 0.7 0.334 ± 0.001 102.9 ± 0.4
5871 ± 12 3110 ± 6 144.4 ± 0.6 40.53 ± 0.16 90.4 ± 0.6 0.305 ± 0.002 105.8 ± 0.4
LAS7
5895.7 ± 11.8 3116.4 ± 6.2 145.6 ± 0.6 40.69 ± 0.16 91.4 ± 0.6 0.306 ± 0.002 106.3 ± 0.4
6240 ± 12 3339 ± 7 162.8 ± 0.7 46.60 ± 0.19 100.6 ± 0.7 0.300 ± 0.002 121.1 ± 0.5
LAS8
6223.6 ± 12.4 3221.8 ± 6.4 162.0 ± 0.6 43.39 ± 0.17 104.1 ± 0.7 0.317 ± 0.001 114.3 ± 0.5
5923 ± 12 3208 ± 6 145.9 ± 0.6 42.81 ± 0.17 88.9 ± 0.6 0.292 ± 0.002 110.7 ± 0.5
LAS9
5941.1 ± 11.9 3086.4 ± 6.2 146.8 ± 0.6 39.63 ± 0.16 94.0 ± 0.6 0.315 ± 0.001 104.2 ± 0.4
6117 ± 12 3261 ± 7 154.2 ± 0.6 43.81 ± 0.18 95.7 ± 0.7 0.301 ± 0.002 114.0 ± 0.5
LAS10
6126.6 ± 12.3 3157.5 ± 6.3 154.6 ± 0.6 41.08 ± 0.16 99.9 ± 0.7 0.319 ± 0.001 108.4 ± 0.4
5944 ± 12 3748 ± 7 77.7 ± 0.3 30.90 ± 0.12 36.5 ± 0.4 0.170 ± 0.003 72.3 ± 0.3
SiO2
5943.9 ± 11.9 2967.4 ± 5.9 77.7 ± 0.3 19.37 ± 0.07 51.9 ± 0.3 0.334 ± 0.001 51.7 ± 0.2

From Table 4, it is obvious that the longitudinal and transversal elastic constants, the
Young’s modulus, and the bulk modulus are higher in aluminosilicate glasses relative to
that of pure SiO2 glass. This behavior can be explained considering that the structure of the
aluminosilicate glasses is characterized by a high network rigidity. The 15La2 O3 –xAl2 O3 –
(85–x)SiO2 glasses reveal an increase in the elastic moduli with Al2 O3 content. On the
contrary, the elastic moduli of the 25La2 O3 –yAl2 O3 –(75–y)SiO2 glasses exhibit a completely
different behavior with varying the Al2 O3 content. The addition of lanthanum ions in the
structure affects the coordination number of Al3+ , which is evidenced experimentally [30]
and references therein. Indeed, Al3+ ions are five-fold and six-fold coordinated in the
structure of these glasses. These structural characteristics are reflected in the experimental
longitudinal and transversal sound velocities of the aluminosilicate glasses under ambient
conditions presented in Figure 7. In Figure 8, the experimental and calculated longitudinal,
Appl. Sci. 2023, 13, x FOR PEER REVIEW 14 of 18

Appl. Sci. 2023, 13, 8240 13 of 17

Appl. Sci. 2023, 13, x FOR PEER REVIEW 14 of 18

7000and bulk moduli of the LAS and SiO2 glasses are shown. All moduli are found to be
shear,
strongly affected by the Al2 O3 content in(a)
the glasses.
6500
7000

u [m/s]
(a)
6000
6500

uL [m/s] L5500
6000 exp
calc
5000
5500
exp
calc
4200
5000 (b)

3600
4200
u [m/s]

(b)
3000
3600
uS [m/s] S

2400 exp
3000
calc

1 2 exp
3 4 5 6 7 8 9 10SiO2
2400
calc LAS number
1 2 3 4 5 6 7 8 9 10SiO2
LAS number
Figure 7. Experimental and calculated longitudinal (a) and transversal (b) sound velocities corre-
sponding to the aluminosilicate glasses at room temperature. In both panels, the last (eleventh)
Figure 7. Experimental and calculated longitudinal (a) and transversal (b) sound velocities corre-
points correspond to pure SiO2 glass.
Figure 7. to
sponding Experimental and calculated
the aluminosilicate glasses longitudinal (a) and transversal
at room temperature. (b) sound
In both panels, velocities
the last corre-
(eleventh) points
sponding totothe
correspond aluminosilicate
pure SiO2 glass. glasses at room temperature. In both panels, the last (eleventh)
points correspond to pure SiO2 glass.
250
(a)
200
L [GPa]

250
150
(a)
200
100
L [GPa]

150
50 exp
calc
100
0
50 exp
60 calc (b)
0
G [GPa]

40 (b)
60
G [GPa]

20 exp
40
calc
020
exp
calc
150 (c)
0
K [GPa]

100
150 (c)
K [GPa]

50
100 exp
calc
050
1 2 exp
3 4 5 6 7 8 9 10SiO2
calc
0 LAS number
1 2 3 4 5 6 7 8 9 10SiO2
Figure 8. Variation in experimental
LAS number and calculated longitudinal (a), shear (b), and bulk (c) moduli
with mole fraction for the aluminosilicate and pure SiO2 glasses.
Appl.
Appl.Sci.
Sci.2023,
2023,13,
13,x8240
FOR PEER REVIEW 1514
ofof18
17

FigureFigure
8. Variation in experimental
9a,b present and calculated
the variation longitudinal (a),
in the experimental andshear (b), and bulk
calculated (c) moduli
Poisson’s ratio
with mole fraction for the aluminosilicate and pure SiO2 glasses.
and Young’s modulus with mole fraction for the aluminosilicate and for pure SiO2 glasses.
The Poisson’s ratio was found experimentally in the range 0.29 to 0.31. The corresponding
As in the case of fluorophosphate glasses, the experimental data available in the lit-
value for pure SiO2 is 0.16. This difference is explained considering that most of the bonds
erature for the lanthanum
in aluminosilicate glassesaluminosilicate glasses
are ionic compared towere compared
the mainly to simulated
covalent data.
bonds in the Fig-
case
ures 7–9 allow a direct comparison between the experimental and the numerically
of SiO2 . The number of bridging bonds per cation, which is expressed as the cross-link simu-
lated results.
density of theThe agreement
structure, is also adequate
is strongly correlatedin thisthe
with case and further
Poisson’s ratio.validates
When the thecross-link
model-
ling ability
density is to predict
equal to 2,the
1, elastic
and 0,properties
the valuesofofthese glasses providing
the Poisson’s ratio area0.15,
fine description of
0.30, and 0.40.
the microstructure elastic properties. The investigation validates the proposed
Since the Poisson’s ratio in the case of lanthanum aluminosilicate glasses is between 0.29 numerical
simulation procedure
to 0.31, then as a powerful
the cross-link density tool to predict
is equal to 0.15theoretically the elastic
and the structure properties
of the glasses isofa
glasses with completely different structural characteristics.
2D layer structure. For the 25La2 O3 –yAl2 O3 –(75–y)SiO2 glasses, the overall structure is
dominated by four-fold AlO4 tetrahedra and six-fold AlO6 octahedral species [30] and
references therein.

0.48
(a)
0.36
σ

0.24

0.12 exp
calc

0.00

160
(b)
120
Y [GPa]

80

40 exp
calc

0
1 2 3 4 5 6 7 8 9 10SiO2
LAS number
Figure 9. Variation in experimental and calculated Poisson’s ratio (a) and Young’s modulus (b) with
mole fraction for the aluminosilicate and pure SiO2 glasses.
Figure 9. Variation in experimental and calculated Poisson’s ratio (a) and Young’s modulus (b) with
mole fraction for the aluminosilicate and pure SiO2 glasses.
As in the case of fluorophosphate glasses, the experimental data available in the
literature for the lanthanum aluminosilicate glasses were compared to simulated data.
Several solidification phenomena occurring during the fabrication process may lead
Figures 7–9 allow a direct comparison between the experimental and the numerically
to samples with highly anisotropic and heterogeneous structures, both in terms of micro-
simulated results. The agreement is also adequate in this case and further validates the
structure and elastic properties. Because of the internal structure, an ultrasonic beam trav-
modelling ability to predict the elastic properties of these glasses providing a fine description
eling through an anisotropic and heterogeneous structure is subject to severe disturb-
of the microstructure elastic properties. The investigation validates the proposed numerical
ances, such as beam deviation, beam splitting, and mode conversion, resulting in complex
simulation procedure as a powerful tool to predict theoretically the elastic properties of
ultrasonic signals with spurious echoes and structural noise.
glasses with completely different structural characteristics.
Nevertheless, numerical simulations have become an essential tool to demonstrate
Several solidification phenomena occurring during the fabrication process may lead to
the performance
samples with highlyof non-destructive
anisotropic andtesting (NDT). The
heterogeneous relevance
structures, of in
both theterms
numerical results
of microstruc-
isture
directly related with the accuracy of the input data for the simulation. In this context,
and elastic properties. Because of the internal structure, an ultrasonic beam traveling a
complex anisotropic material is commonly represented by a large number of homogenous
through an anisotropic and heterogeneous structure is subject to severe disturbances, such
and anisotropic
as beam domains,
deviation, beam and this method
splitting, and mode hasconversion,
been shownresulting
in the present workultrasonic
in complex to be ef-
fective
signalsaswith
it reproduces the deviation
spurious echoes and splitting
and structural noise. of the acoustic beam and the relevant
mode conversions.
Appl. Sci. 2023, 13, 8240 15 of 17

Nevertheless, numerical simulations have become an essential tool to demonstrate the

performance of non-destructive testing (NDT). The relevance of the numerical results is
directly related with the accuracy of the input data for the simulation. In this context, a
complex anisotropic material is commonly represented by a large number of homogenous
and anisotropic domains, and this method has been shown in the present work to be
effective as it reproduces the deviation and splitting of the acoustic beam and the relevant
mode conversions.
At the ultrasonic frequencies commonly used to inspect a highly anisotropic structure
that are between 0.5 and 10 MHz, the corresponding wavelength ranging from 11 to 0.5 mm
is similar to the grain size. The scattering of the wave by the grain boundaries will thus be
a key factor. Each grain boundary is considered as a discontinuity with specific acoustic
impedance, which finally will scatter the acoustic wave. Under these circumstances, the
structure scatters the acoustic wave, and the ultrasonic energy is diffused away from the
axis of beam propagation. From the probe point of view, the scattering by the microstructure
will induce a decrease in the reflected echo amplitude which depends on the dimension
(depth) of the reflector. The phenomenon is assessed by the use of an attenuation coefficient,
which accounts for the anisotropic dispersion of the ultrasonic power of the beam along its
path. Nevertheless, the variation in the attenuation due to the microstructure scattering,
characteristic of anisotropic structures, is very hard to obtain experimentally. A common
methodology is to utilize samples with various orientations of the elongated grains and
to evaluate their attenuation by transmission or reflection techniques of waves under
normal incidence.
Concerning future applications, by applying the procedure described in this work in
orthotropic, transversely isotropic, or generally anisotropic materials, one can determine
the anisotropic variations of scattering attenuation by describing the microstructure at the
grain-scale based on numerical simulation. The simulation method should combine a 2D
finite element code and a detailed description of the microstructure that will account for the
geometric, elastic, and crystallographic properties of the anisotropic material. This way, the
grain orientation, the grains’ size, and the anisotropy level are the main input parameters
that are implemented for the efficient determination of the acoustic attenuation.

6. Conclusions
In the present work, the transmittance of ultrasonic wave was numerically simulated
by means of elastodynamic finite integration techniques (EFIT). Two distinct families of
glasses, the fluorophosphate and the aluminosilicate glasses, were used as model systems
to evaluate the applicability and effectiveness of the pulse-echo simulation. The relevant
elastic constants were determined from the longitudinal and transversal sound velocities.
The calculated and the experimental elastic properties were compared and correlated with
the structure of these glasses. The comparison between experimental and simulation results
showed low deviations supporting the concept that the numerical simulation of the pulse-
echo ultrasonic inspection signals is effective and applicable for the study of the elastic
properties of amorphous glasses as well as crystalline bulk materials. Elastic properties are
important parameters related to the mechanical behavior of solids and for this reason their
prediction is an important achievement. Their evaluation through computational models
could lead to the reduction in the cost of manufacturing materials while simultaneously
improving their properties. Furthermore, it has been found that using this technique, one
can determine the precise location and size of a possible defect in the studied samples by
comparing the experimental and simulation results.
The latter can prove to be extremely important when one needs to monitor the perfor-
mance of vitreous materials that are used either in optical or optoelectronic applications.
The above can also stretch to defense and space applications where vitreous materials are
commonly used due to their enhanced properties regarding their crystalline counter parts.
Having a fast, non-destructive, and reliable technique can provide significant reductions in
maintenance costs, eliminate failures due to early detection of structural flaws at the atomic
Appl. Sci. 2023, 13, 8240 16 of 17

level and ensure the optimum operation of critical optoelectronic and other components
and infrastructures.

Author Contributions: Conceptualization, A.G.K.; methodology, A.G.K.; validation, A.G.K., N.K.N.

and P.S.; formal analysis, A.G.K., N.K.N. and P.S.; investigation, P.S. and A.G.K.; resources, A.G.K.;
data curation, P.S., N.K.N. and A.G.K.; writing—original draft preparation, A.G.K.; writing—review
and editing, A.G.K., N.K.N. and P.S.; supervision, A.G.K.; project administration, A.G.K.; funding
acquisition, A.G.K. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data are available upon request from the corresponding author.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Lionetto, F.; Maffezzoli, A. Relaxations during the postcure of unsaturated polyester networks by ultrasonic wave propagation,
dynamic mechanical analysis and dielectric analysis. J. Polym. Sci. Part B Polym. Phys. 2005, 43, 596–602. [CrossRef]
2. Espinoza-Gonzalez, C.; Avila-Orta, C.; Martinez-Colunga, G.; Lionetto, F.; Maffezzoli, A. A measure of CNTs dispersion in
polymers with branched molecular architectures by UDMA. IEEE Trans. Nanotechnol. 2016, 15, 731–737. [CrossRef]
3. Lionetto, F.; Maffezzoli, A.; Ottenhof, M.A.; Farhat, I.A.; Mitchell, J.R. Ultrasonic investigation of wheat starch retrogradation. J.
Food Eng. 2006, 75, 258–266. [CrossRef]
4. Huang, H.; Nishikawa, S.; Dong, S. Kinetic Isotope Effects of Proton Transfer Reaction for Amines by Ultrasonic Relaxation
Methods: Unexpected Evidence from the Results in Ethylamine Solutions. J. Phys. Chem. A 1999, 103, 8799–8802. [CrossRef]
5. Tsigoias, S.; Kouderis, C.; Mylona-Kosmas, A.; Boghosian, S.; Kalampounias, A.G. Proton-transfer in 1,1,3,3 tetramethyl
guanidine by means of ultrasonic relaxation and Raman spectroscopies and molecular orbital calculations. Spectrochim. Acta A
2020, 229, 117958. [CrossRef]
6. Tsigoias, S.; Papanikolaou, M.G.; Kabanos, T.A.; Kalampounias, A.G. Structure and dynamics of aqueous norspermidine solutions:
An in situ ultrasonic relaxation spectroscopic study. J. Phys. Condens. Matter 2021, 33, 495104. [CrossRef]
7. Nishikawa, S.; Haraguchi, H.; Fukuyama, Y. Effect of ether oxygen on proton transfer and aggregation reactions of amines in
water by ultrasonic absorption method. Bull. Chem. Soc. Jpn 1991, 64, 1274–1282. [CrossRef]
8. Stogiannidis, G.; Tsigoias, S.; Kalampounias, A.G. Conformational energy barriers in methyl acetate—Ethanol solutions: A
temperature-dependent ultrasonic relaxation study and molecular orbital calculations. J. Mol. Liq. 2020, 302, 112519. [CrossRef]
9. Siafarika, P.; Papanikolaou, M.G.; Kabanos, T.A.; Kalampounias, A.G. Probing the equilibrium between mono- and di-nuclear
nickel(II)-diamidate {[NiII(DQPD)]x, x = 1,2} complexes in chloroform solutions by combining acoustic and vibrational spectro-
scopies and molecular orbital calculations. Chem. Phys. 2021, 549, 111279. [CrossRef]
10. Meretoudi, A.; Banti, C.N.; Siafarika, P.; Kalampounias, A.G.; Hadjikakou, S.K. TetracyclineWater Soluble Formulations with
Enhanced Antimicrobial Activity. Antibiotics 2020, 9, 845. [CrossRef]
11. Petrucci, S. Ionic Interactions; Academic Press: New York, NY, USA, 1971; Volume 2.
12. Siafarika, P.; Kouderis, C.; Kalampounias, A.G. Non-Debye segmental relaxation of poly-N-vinyl-carbazole in dilute solution.
Mol. Phys. 2021, 119, e1802075. [CrossRef]
13. Kouderis, C.; Siafarika, P.; Kalampounias, A.G. Disentangling proton-transfer and segmental motion relaxations in poly-vinyl-
alcohol aqueous solutions by means of ultrasonic relaxation spectroscopy. Polymer 2021, 217, 123479. [CrossRef]
14. Bernasconi, C.F. Relaxation Kinetics; Academic Press: New York, NY, USA, 1976.
15. Dell’Anna, R.; Lionetto, F.; Montagna, F.; Maffezzoli, A. Lay-Up and Consolidation of a Composite Pipe by In Situ Ultrasonic
Welding of a Thermoplastic Matrix Composite Tape. Materials 2018, 11, 786. [CrossRef]
16. Lhuillier, P.E.; Chassignole, B.; Oudaa, M.; Kerherve, S.O.; Rupin, F.; Fouquet, T. Investigation of the ultrasonic attenuation
in anisotropic weld materials with finite element modeling and grain-scale material description. Ultrasonics 2017, 78, 40–50.
[CrossRef]
17. Seo, H.; Lee, K.; Jhang, K.-Y. In-Line Ultrasonic Monitoring for Sediments Stuck on Inner Wall of a Polyvinyl Chloride Pipe. Sci.
World J. 2014, 2014, 731621. [CrossRef] [PubMed]
18. Ebendorff-Heidepriem, H.; Ehrt, D.; Bettinelli, M.; Speghini, A. Effect of glass composition on Judd–Ofelt parameters and
radiative decay rates of Er3+ in fluoride phosphate and phosphate glasses. J. Non Cryst. Solids 1998, 240, 66–78. [CrossRef]
19. Philipps, J.F.; Topfer, T.; Ebendorff-Heidepriem, H.; Ehrt, D.; Sauerbrey, R. Spectroscopic and lasing properties of Er3+ :Yb3+ -doped
fluoride phosphate glasses. Appl. Phys. B Laser Opt. 2001, 72, 399–405. [CrossRef]
20. Zhang, J.J.; He, D.B.; Duan, Z.C.; Zhang, L.Y.; Dai, S.X.; Hu, L.L. Mechanisms and concentrations dependence of up-conversion
luminescence in Tm3+ /Yb3+ codoped oxyfluoride glass-ceramics. Phys. Lett. 2005, 337, 480–486. [CrossRef]
Appl. Sci. 2023, 13, 8240 17 of 17

21. Mpourazanis, P.; Stogiannidis, G.; Tsigoias, S.; Papatheodorou, G.N.; Kalampounias, A.G. Ionic to covalent glass network
transition: Effects on elastic and vibrational properties according to ultrasonic echography and Raman spectroscopy. J. Phys.
Chem. Solids 2019, 125, 43–50. [CrossRef]
22. Mpourazanis, P.; Stogiannidis, G.; Tsigoias, S.; Kalampounias, A.G. Transverse phonons and intermediate-range order in Sr-Mg
fluorophosphate glasses. Spectrochim. Acta A 2019, 212, 363–370. [CrossRef] [PubMed]
23. Möncke, D.; Eckert, H. Review on the structural analysis of fluoride-phosphate and fluorophosphate glasses. J. Non Cryst. Solids
X 2019, 3, 100026. [CrossRef]
24. Makishima, Y.; Tamura, Y.; Sakaino, T. Elastic Moduli and Refractive Indices of Aluminosilicate Glasses Containing Y2 O3 , La2 O3 ,
and TiO2 . J. Am. Ceram. Soc. 1978, 61, 247–249. [CrossRef]
25. Shelby, J.E.; Minton, S.M.; Lord, C.E.; Tuzzolo, M.R. Formation and properties of yttrium aluminosilicate glasses. Phys. Chem.
Glasses 1992, 33, 93–98.
26. Day, D.E.; Rindone, G.E. Properties of Soda Aluminosilicate Glasses: I, Refractive Index, Density, Molar Refractivity, and Infrared
Absorption Spectra. J. Am. Ceram. Soc. 1962, 45, 489–496. [CrossRef]
27. Kohli, J.T.; Condrate, R.A.; Shelby, J.E. Raman and infrared-spectra of rare earth aluminosilicate glasses. Phys. Chem. Glasses
1993, 34, 81–87.
28. Schaller, T.; Stebbins, J.F. The Structural Role of Lanthanum and Yttrium in Aluminosilicate Glasses: A 27 Al and 17 O MAS NMR
Study. J. Phys. Chem. B 1998, 102, 10690–10697. [CrossRef]
29. Aronne, A.; Esposito, S.; Pernice, P. FTIR and DTA study of lanthanum aluminosilicate glasses. Mater. Chem. Phys. 1997, 51, 163–168.
30. Hwa, L.G.; Leea, T.H.; Szu, S.P. Elastic properties of lanthanum aluminosilicate glasses. Mater. Res. Bull. 2004, 39, 33–40.
[CrossRef]
31. Almond, D.P.; Blairs, S. An apparatus employing the pulse-echo overlap technique for the measurement of sound velocities in
liquid metals. J. Phys. E: Sci. Instrum. 1980, 13, 964–968. [CrossRef]
32. Fellinger, P.; Marklein, R.; Langenberg, K.J.; Klaholz, S. Numerical modelling of elastic wave propagation and scattering with
EFIT elasto-dynamic finite integration technique. Wave Motion 1995, 1, 47–66. [CrossRef]
33. Molero, M.; Medina, L.; Lluveras, D.; Izquierdo, M.A.G.; Anaya, J.J. Numerical simulation of ultrasonic tomography inspections
of highly heterogeeous materials. IOP Conf. Ser. Mater. Sci. Eng. 2012, 42, 012051. [CrossRef]
34. Schubert, F. Numerical time-domain modeling of linear and nonlinear ultrasonic wave propagation using finite integration
techniques –theory and applications. Ultrasonics 2004, 42, 221–229. [CrossRef] [PubMed]
35. Carcione, J. Wave Field in Real Media. In Wave Propagation in Anisotropic, Porous and Electromagnetic Media; Elsevier: Amsterdam,
The Netherlands, 2007.
36. Marklein, R.; Barmann, R.; Langenberg, K. Review of Progress in Quantitative Non-Distractive Evaluation; Thompson, D., Chimenti,
D.E., Eds.; Springer: Manhattan, NY, USA, 1995; Volume 14, pp. 251–255.
37. Hofmann, P. Solid State Physics: An Introduction, 2nd ed.; John Wiley & Sons, Inc.: Hoboken, NJ, USA, 2015.

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