Article

Effect of Silicon Nanoparticles on Moisture Absorption and

Fracture Toughness of Polymethyl Methacrylate
Matrix Nanocomposites
Mohammad Ali Golshokouh 1 , Nima Refahati 1, * and Pouyan Roodgar Saffari 2

1 Department of Mechanical Engineering, Damavand Branch, Islamic Azad University,

Damavand P.O. Box 3971878911, Iran
2 Department of Civil Engineering, Faculty of Engineering, Thammasat School of Engineering,
Thammasat University, Pathumthani 12120, Thailand; [email protected]
* Correspondence: [email protected] or [email protected]

Abstract: The effect of silicon nanoparticles with different percentages (2, 5, 7, and 10 wt.%) on
moisture absorption in environments with different pHs (5, 6, 7, 8, 9) as well as fracture toughness of
polymethyl methacrylate is discussed. The samples were prepared using pressure molding. Fracture
strength was tested via the three-point bending method according to the ASTM D5045 standard and
moisture absorption rate according to the absorption test according to the ASTM D570 standard. SEM
images show that up to 7%, the dispersion of silica nanoparticles is acceptable, but the homogeneity
is not acceptable at 10%. The results indicate that the increase in silica nanoparticles has improved
the fracture toughness of the manufactured parts. The highest fracture toughness improvement is
about 57% in the optimal state at 5%. Also, increasing silica nanoparticles increased the moisture
absorption in the produced samples. In addition, as the acidic or base of the liquid moves to neutral,
the reaction between the base polymer molecules and the test liquid decreases and, so, the moisture
absorption also increases.

Keywords: PMMA; silicon nanoparticles; fracture strength; moisture absorption

Citation: Golshokouh, M.A.; Refahati,
N.; Saffari, P.R. Effect of Silicon
Nanoparticles on Moisture
Absorption and Fracture Toughness of
1. Introduction
Polymethyl Methacrylate Matrix
Nanocomposites. J. Compos. Sci. 2024, PMMA (polymethyl methacrylate) is used in medical and dental applications due
8, 69. https://doi.org/10.3390/ to its high mechanical properties. The synthetic process is not difficult to handle and
jcs8020069 less expensive than other polymers. Also, the biocompatibility condition of PMMA is
acceptable [1]. Although PMMA has lower abrasion resistance, hardness, and toughness
Academic Editors: Francesco
than amalgam, due to its low cost, appearance, desirable color, allowable thermal stability,
Tornabene and Thanasis Triantafillou
and high flexibility, it is rapidly replacing amalgam in dental applications [2–4]. Any
Received: 19 December 2023 restorative material or denture must have sufficient mechanical ability to function properly
Revised: 27 January 2024 against the pressures in the oral cavity for a long time [5,6]. Fractures of teeth made of
Accepted: 8 February 2024 PMMA are very common and are a serious problem for their use as dental prostheses [7].
Published: 9 February 2024 Research shows that between 63% and 68% of dentures within a few years of being made
are broken by accidentally falling on a hard surface outside the mouth [8]. Most denture
fractures are due to a weakness in the base polymer. Dental composites are subjected to var-
ious stresses during their operation, including compressive, tensile, and shear stresses [9].
Copyright: © 2024 by the authors.
Therefore, studying the mechanical properties of these materials to use them in clinical
Licensee MDPI, Basel, Switzerland.
contexts is very important [10]. To improve the properties of PMMA, researchers have
This article is an open access article
evaluated the effect of various factors, including fillers, matrices, as well as the interface be-
distributed under the terms and
conditions of the Creative Commons
tween the matrix and the filler, but the results show that their properties have not changed
Attribution (CC BY) license (https://
significantly with changes in the matrix of composites. Therefore, studies have focused on
creativecommons.org/licenses/by/ fillers [11]. The properties of nanofiller-reinforced composites depend on the size, shape,
4.0/). type, and concentration of particles added [12,13].

J. Compos. Sci. 2024, 8, 69. https://doi.org/10.3390/jcs8020069 https://www.mdpi.com/journal/jcs

J. Compos. Sci. 2024, 8, 69 2 of 12

In recent years, several nanoparticles, such as ZrO2 , SiO2 , TiO2 , and diamond nanopar-
ticles, have been used in an attempt to enhance the physical and mechanical properties of
PMMA [14–18].
Silicon dioxide nanoparticles, also known as silica nanoparticles or nano-silica, are
one of the most common mineral fillers [19–22], and due to their molecular stability, low
toxicity, and ability to bond with a wide range of molecules and polymers, as well as
antimicrobial properties [23,24], are the basis of research in the field of biomedicine. Silica
nanocomposites weigh less than conventional composites, and this factor has made them a
suitable alternative to polymers in various applications [25,26].
Silica nanoparticles are used to improve the mechanical properties, adhesion, durabil-
ity, and abrasion resistance of polymers. Silica nanoparticles generally have an amorphous
and hollow structure [27,28]. In some cases, the crystalline structure of nano-silica is avail-
able, which is usually impossible to detect by X-ray tests. The proper shape for suspension
silica nanoparticles is spherical [29]. This spherical shape is available by the synthesis in an
ammonia medium. Most silica nanoparticles are used for industrial applications with one
size (suspension) and two sizes of hydrophobic (oil and water separation).
Due to the presence of hydroxyl groups on the surface of silica nanoparticles, the
agglomeration ability of these particles increases when combined with polymer com-
posites, and this makes it difficult to prepare PMMA composites reinforced with silica
nanoparticles [30]. To overcome the existing problems, many studies have considered the
modification of silica nanoparticles’ surfaces by chemical interaction because it leads to a
much stronger interaction between modifiers and silica nanoparticles. Chemical methods
include modification with modifiers or by bonding polymers. Silane agents, the most fa-
mous of which are gamma-Methacryloxypropyltrimethoxysilane, are capable of hydrolysis
and can reduce hydroxyl groups on the surface of silica nanoparticles [31]. As a result,
it creates a better bond between the filler and the base polymer [32]. This reduces the
accumulation of silica nanoparticles when combined with the base polymer.
Many researchers have studied the mechanical behavior of PMMA and SiO2 mul-
tilayer composites. Zhen et al. [33] and Balso et al. [34] found that with an increase in
silica nanoparticles from 0 to 5 wt.%, the tensile strength and elongation in the fracture
of composites have been improved, and also the flexural strength and elastic modulus
have been significantly increased. Fatalla et al. [35], observed a slight increase in impact
strength, transverse strength, and hardness for 5 wt. % of silica nanoparticles. Siot et al. [36]
believe that, although silica nanoparticles increase the static modulus and yield strength of
composites, the final properties of the composite are strongly influenced by the dispersion
properties of the nanoparticles, and the better performance of the silica filler is related to
its regular dispersion. Mussatto et al. [37], evaluating the mixing effect of modified and
unmodified silica nanoparticles, concluded that with the addition of silica nanoparticles,
the flexural strength of the composite in both modified and unmodified modes was re-
duced by 20 to 27%, and this reduction was not dependent on the amount of filler and the
nanoparticle composition method, Also, nano-silica surface modification did not cause
any major improvement in the mechanical behavior of the composites, but it seemed to
improve the dispersion because the surface roughness was reduced. Salman et al. [38]
showed significant improvements in impact strength, transverse strength, and hardness by
adding silica nanoparticles to PMMA at 3%, 5%, and 7% wt.
Topouzi et al. [39] observed a significant increase in fracture toughness by adding
modified and unmodified silica nanoparticles to PMMA but concluded that increasing
the filler concentration reduces the fracture toughness, and no significant differences were
reported between modified and unmodified fillers. Kundie et al. [40] investigated the
effects of micro- and nano-scale particles on the mechanical properties of dental composites,
concluding that the effects of nanoparticles strongly depend on factors, such as the type
and mechanical properties of mineral nanofillers, uniform dispersion of nanofillers in the
polymer matrix, the volume fraction of filler particles, and the type of silane used.
J. Compos. Sci. 2024, 8, 69 3 of 12

Although many studies have been performed on particle composites and their physical
and mechanical properties, in these studies, some factors such as the percentage of filler
particles and the environment to which the material is exposed have received less attention.
Particularly, in the case of particulate composites used in dentistry (dental composites), little
is known about the relationship between properties and structure, and the acidic or alkaline
environments to which the composite is exposed for use as a denture have not been studied.
According to studies, water absorbed due to the lubricating effect reduces mechanical
properties, such as hardness, transverse strength, and fatigue limit [41]. Water absorption
also causes volumetric expansion of the dental specimen and occlusal changes [42]. Resizing
and exposing dental specimens to internal stresses cause cracks and fractures in dentures [43].
Therefore, it is important to study the environmental impact to which these samples are
exposed. Karabla et al. [44] observed that the amount of water absorbed increases as the
particle size of the fillers decreases. To modify the surface of silica nanoparticles, an acrylate
cylinder modifier, Υ-MPS (gamma-methacryloxy propyl trimethoxy silane), is the most
widely used silane coupling agent in dental composites [45–47] and was prepared from
Sigma Aldrich, Schnelldorf, Germany.
In this research, first, the samples were prepared. In the next step, by simulating the
environment in which this type of material is placed, we aim to have a better understanding
of their behavior. For this purpose, we prepared different solvents with different pHs, then
placed the produced samples in a pH range 5 to 9 (normal pH range of human mouth)
and compared the amount of moisture absorption in the samples. The aim of the current
research is to find the best percentage of nano-silica to obtain better quality.

2. Experiments
2.1. Materials
In this experimental study, metamethyl acrylate polymer (MMA) from Taiwan Chemi-
cal Company with a specific gravity of 1.19 gr/cm3 was used as the polymer substrate. This
material is a product of silica nanoparticles made by Acrosun Spain with a size of 20 nm
and a purity of 99.5%, used as reinforcing material. To reduce the viscosity, triethylene
glycol dimethacrylate (TEGDEMA) diluting resin made by the German company Evonic
was used. The molding of the samples was conducted using a two-piece mold made of
aluminum with dimensions of 4 × 50 × 6 mm. Also, to prevent the samples from sticking
inside the mold, TECHNOSIL acrylic separating liquid was used.

2.2. Sample Production

A vacuum mixer was used to achieve a uniform combination of silica and poly-
methyl methacrylate nanoparticles. Studies show that the main problem of using silica
nanoparticles in dental composites is the accumulation of silica nanoparticles together
when combined with polymethyl methacrylate. This leads to the formation of micrometer
particles and reduces the mechanical properties of nanocomposites, so filler particles need
surface modification to reduce the formation of agglomerates and better distribution of
filler particles within the matrix.
In this research, the surface of silica nanoparticles is modified using an acrylate silane
agent, Υ-MPS, and hydrolysis-density method. For this purpose, a solution of water and
alcohol with a weight ratio of 70.30 is used for hydrolysis of Υ-MPS for 30 min. The pH is
regulated by acetic acid at about 3–4. The nanoparticles are then added to this solution and
stored at room temperature for one week. The nanoparticles are washed with alcohol, and
then, in ambient air, the remaining alcohol is evaporated and the nanoparticles are dried.
To produce any desired composition of nanocomposites in all ten samples of each
wt.%, first, the modified silica nanoparticles with a certain weight percentage (2, 5, 7, and
10% wt.) are mixed with monomer methyl methacrylate powder in a mixer. The milling is
carried out for 12 min with a frequency of 20 Hz and a speed of 100 revolutions per minute.
To produce nanocomposite samples, a mixture of methyl methacrylate powder and
milled silica is mixed with diluents to triethylene glycol dimethacrylate (TEGDMA). This is
 milled silica is mixed with diluents to triethylene glycol dimethacrylate (TEGDMA). Thi
is performed mechanically at ambient temperature using a small mixer. The Sample
names and related SiO2 percentage can be seen in Table 1.
J. Compos. Sci. 2024, 8, 69 Figure 1 shows the die in which the samples were produced. The mold4must of 12 be pre
pared to prevent the dough from sticking to the mold. For this purpose, the surface of th
mold is covered with a layer of acrylic separating liquid. After the mold surface is dry (thi
takes about
performed 3 h), enter at
mechanically the paste-shaped
ambient liquid
temperature intoa each
using small part ofThe
mixer. the Samples
mold and then tighten
names
and
the related
two partsSiO2ofpercentage
the moldcan be seen in
together. In Table 1. step, to bake the dough inside the mold
the next
we keep the mold immersed in hot water at a temperature of 80 °C for 50 min, then tak
Table 1. Grouping name of samples based on the percentage of nano-silica.
out the mold and let it stand at room temperature. We then cool and take the sample ou
of the mold. After cooking,
Sample A the samples
B are polished
C with 600
D grains and then
E 1000 grain
withSiOthe help of sandpaper.
2 (%) 0 2 5 7 10
It should be noted that for each weight percentage, 10 samples were produced, and
finally,
Figure5 healthier samples
1 shows the die inwith
which the
thefewest defects
samples were such as fewer
produced. Thebubbles andbesmoothe
mold must
prepared to prevent the dough from sticking to the mold. For this purpose, the surface of silic
surfaces were selected theoretically. Also, ten other samples without a percentage
reinforcement
of were with
the mold is covered produced
a layerto
of compare with theliquid.
acrylic separating reinforced samples,
After the from is
mold surface which w
selected
dry five better
(this takes about samples.
3 h), enter the paste-shaped liquid into each part of the mold and
then tighten the two parts of the mold together. In the next step, to bake the dough inside
the mold,
Table we keep the
1. Grouping mold
name immersed
of samples in hot
based water
on the at a temperature
percentage of 80 ◦ C for 50 min,
of nano-silica.
then take out the mold and let it stand at room temperature. We then cool and take the
sampleSample A cooking, theBsamples are polished
out of the mold. After C D
with 600 grains and then E
SiO2(%)
1000 grains with the help of0sandpaper. 2 5 7 10

Figure1.1.Die
Figure Dieused
used
to to produce
produce the the samples
samples (100
(100 × × 80includes
80 mm 4 × Φ64mm).
mm includes × Ф6 mm).

2.3. It
SEMshould be noted that for each weight percentage, 10 samples were produced, and,
Tests
finally, 5 healthier samples with the fewest defects such as fewer bubbles and smoother
After
surfaces wereproducing reinforced Also,
selected theoretically. samples, the first
ten other SEM
samples test isaperformed
without tosilica
percentage of compare th
reinforcement were produced to compare with the reinforced samples, from which wenanopar
quality of reinforced production samples with samples without modified silica
ticles. SEM
selected captures
five better images of different surfaces of the sample transversely to evaluate th
samples.
chemical composition gradient on the surfaces of the samples at a distance of as little as
2.3.
µm,SEM Tests us to obtain a better analysis of the type and distribution of filler particle
allowing
After producing
on the surface of thereinforced samples, the first SEM test is performed to compare the
PMMA matrix.
quality of reinforced production samples with samples without modified silica nanoparti-
cles. SEM captures images of different surfaces of the sample transversely to evaluate the
2.4. Moisture Absorption Test
chemical composition gradient on the surfaces of the samples at a distance of as little as
1 µm, The moisture
allowing us to absorption test
obtain a better is performed
analysis under
of the type andthe ASTM D570
distribution standard.
of filler particlesSince th
pHthe
on range of aofhealthy
surface the PMMA adult’s mouth is between 5 and 9, we performed moisture absorp
matrix.
tion tests in this interval. To increase the contact surface of the samples with the liquid
2.4. Moisture Absorption Test
and also the effect of the environment on the pH of the test liquid, we used closed con
The moisture
tainers, absorption
placing each sampletest
inisaperformed
container under the ASTM D570
and identifying standard.by
the samples Since the
numbering th
pH range of a healthy adult’s mouth is between 5 and 9, we performed moisture absorption
containers.
tests in this interval. To increase the contact surface of the samples with the liquid and also
The recommended duration for the moisture absorption test according to ASTM
the effect of the environment on the pH of the test liquid, we used closed containers, placing
D570 is 24 h.
each sample in The amount
a container ofidentifying
and moisture absorption
the samples is bydetermined
numbering theby containers.
measuring the weigh
of the
Thesamples beforeduration
recommended and after placing
for the them
moisture in the liquid
absorption bath. IttoisASTM
test according worthD570
noting tha
isduring theamount
24 h. The experiments, the absorption
of moisture liquid bath is at a temperature
determined of 20 ±the
by measuring 2 °C is inoftemperatur
weight the
samples before and after placing them in the liquid bath. It is worth noting that during the
experiments, the liquid bath at a temperature of 20 ± 2 ◦ C is in temperature equilibrium
with the environment, and a digital scale with an accuracy of 0.001 g is used to weigh
the samples.
 ant=ʺnormalʺ>M</mi><mn>2</mn><mo>&#x2212;</mo><mi mathvari- (1)
ant=ʺnormalʺ>M</mi><mn>1</mn><mi mathvariant=ʺnor-
malʺ>&#x0020;</mi></mrow><mrow><mi mathvariant=ʺnor-
J. Compos. Sci. 2024, 8, 69 malʺ>M</mi><mn>1</mn><mi mathvariant=ʺnor-
5 of 12
malʺ>&#x0020;</mi></mrow></mfrac></mrow></math>
<!-- MathType@End@5@5@ -->
If M1 is the primary mass of the sample and M2 is the second mass of the sample, then
the amount of moisture absorption is determined using Equation (1).

∆w M2 − M1
= (1)
2.5. Fracture Toughness Test W M1
The
2.5. fracture
Fracture toughness
Toughness Test test of nanocomposites was performed according to the
ASTM D5045 standard.
The fracture In this
toughness testtest, a general test was
of nanocomposites device with a speed
performed of 0.1
according mm/min
to the ASTM was
used. The loading of the composite parts made to determine the fracture toughness
D5045 standard. In this test, a general test device with a speed of 0.1 mm/min was used. The is
schematically shown
loading of the in Figure
composite 2, in which
parts made a rectangular
to determine piece
the fracture with anisedge
toughness crack is sub-
schematically
jected to ain
shown three-point
Figure 2, inbending
which aload with a support
rectangular distance
piece with an edgeof crack
s2. is subjected to a
three-point bending load with a support distance of s2.

Figure
Figure 2. Schematic
2. Schematic ofofthe
thetest
testsample.
sample.

Before performing the fracture toughness test to create initial cracks in the samples,
Before performing the fracture toughness test to create initial cracks in the samples,
the rectangular pieces were cut using a thin saw blade to a thickness of 0.25 mm. The tips
theofrectangular pieces were cut using a thin saw blade to a thickness of 0.25 mm. The tips
the created notches were sharpened by pressing a razor blade.
of the created
In this notches
way, thewere groovessharpened
created in bythe
pressing
samples a razor
can beblade.
assumed with acceptable
In this way, the grooves created in the
accuracy as a sharp crack to perform the fracture toughness samples can betest.
assumed withofacceptable
The length the final ac-
curacy
edgeas a sharp
crack crack
created to perform
in the middle ofthe fracture
each specimen toughness
is 3 mm.test.
As aThe length
result, of thelength
the crack final edge
ratio without the a/w dimension in all experiments of this study
crack created in the middle of each specimen is 3 mm. As a result, the crack length is a constant value of ratio
J. Compos. Sci. 2024, 8, x FOR PEER 0.5. Before performing the test, the samples are stored for 24 h in standard
REVIEWthe a/w dimension in all experiments of this study is a constant value of 0.5. Before
without conditions of a 6 of 14
laboratorythe environment (temperature ◦
23 ± 2 for C and 50 ± conditions
performing test, the samples are stored 24 hhumidity
in standard 5%). Then, the
of acracked
laboratory
specimens are placed inside the three-point bending fixture supports (with a support
environment (temperature 23 ± 2 °C and humidity 50 ± 5%). Then, the cracked specimens
distance of 2 s = 40 mm) in the testing machine and loaded monotonically at a constant rate
areofplaced inside
Using
1 mm/min. the theloading
three-point
Thecritical load bending
proportional
continues
fixture supports
to the
until the complete breaking (with
failure ofmoment
a support
the parts of
distance
andeach
of 2 s(FS)
specimen
the growth
= 40ofmm)
thetheKIC in the testing
fracture
crack from the machine
toughness and
tip of theofinitial loaded
dental monotonically
composite
crack, specimens
and, finally, at a constant rate of
was calculatedcurve
the load–displacement 1 mm/min.
fromofEquation
Theeach
loading
(2). sample continues
is obtaineduntil the complete
(Figure 3). failure of the parts and the growth of the crack
from the tip of the initial crack, and, finally, the load–displacement curve of each sample
is obtained (Figure 3).

Figure3.3.Sample
Figure Sample tested
tested in bending
in bending tester.
tester.

<!-- MathType@Translator@5@5@MathML2 (no namespace).tdl@MathML 2.0 (no

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<math><mrow><mi mathvariant=ʺnor-
 J. Compos. Sci. 2024, 8, 69 6 of 12

Using the critical load proportional to the breaking moment of each specimen (FS ), the
KIC fracture toughness of dental composite specimens was calculated from Equation (2).

Fs 1
K IC = f ( a/w) √ MPam 2 (2)
t w

where f (a/w) is a geometric coefficient that depends on the type of part and the load
applied to it. This coefficient is calculated by modeling the finite element method of the
tested part for conditions s/w = 3.3 and a/w = 0.5. Also, t is the thickness (in mm) and w is
the width (in mm).

a 2 3 4
(0.886 + 4.64 wa − 13.32 wa 2 + 14.72 wa 3 − 5.6 wa 4 )


a 2+ w
f = 1
(3)
w (1 − wa ) 2

3. Results and Discussion

3.1. SEM Test
Figure 4 shows SEM data of TESCAN VEGA CZECH taken from the surface of the
sample without filler, while in Figure 5, samples with different weight percentages can be
seen. Figure 4 can be used for evaluation of the volume fraction of the additive, but for
more detailed information about additive roll, XRD can be used. SEM images show that
the higher the filler percentage, the greater the accumulation of filler particles. The highest
number of agglomerates is in samples with 10% wt., where the formation of agglomerates
is due to the presence of hydroxyl groups on the surface of silica nanoparticles, which
prevents proper bonding of the base polymer (PMMA) with silica nanoparticles.
Compos. Sci. 2024, 8, x FOR PEER REVIEWAlthough the surface of silica nanoparticles has been modified, the accumulation of
nanoparticles and the formation of agglomerates can still be seen in some parts of the
composite surface.

Figure
Figure4. SEM of a sample
4. SEM of awithout
sample silica filler.
without silica filler.
J. Compos. Sci. 2024, 8, 69 7 of 12

Figure 4. SEM of a sample without silica filler.

(a) (b)

(c) (d)
Figure
Figure 5. 5.
SEMSEMofofsamples
samplesand
and modified silicafiller
modified silica fillerwith
with different
different percentages:
percentages: (a)by
(a) 2% 2%weight
by weight
of of
filler; (b) 5% by weight of filler; (c) 7% by weight of filler; (d) 10% by weight of
filler; (b) 5% by weight of filler; (c) 7% by weight of filler; (d) 10% by weight of filler.filler.

3.2. Moisture Absorption

Polymer composites filled with hard mineral particles in micro or nano dimensions
show different behaviors with increasing particle percentages. The adsorption of water in
the polymer is the result of the molecular polarity of the polymer, the unsaturated bonds
of the molecules, or the unbalanced intermolecular forces in the polymers. According
to ISO 1567, water absorption for thermal and self-cooking materials should not exceed
32 micrograms per cubic millimeter. The amount of moisture absorption in the samples
(Table 2) shows that with increasing the percentage of nano-silica, the amount of moisture
absorption in the samples decreases. The reason for this may be related to the amorphous
structure of the underlying polymer. The distance between PMMA molecules is greater
in the absence of silica filler particles than in the case in which nanoparticles are added.
Silica nanoparticles fill the gaps between molecules so that as the amount of nano-silica
in the base polymer increases, the distance between the molecules decreases, the polymer
 in the absence of silica filler particles than in the case in which nanoparticles are added.
Silica nanoparticles fill the gaps between molecules so that as the amount of nano-silica in
the base polymer increases, the distance between the molecules decreases, the polymer
J. Compos. Sci. 2024, 8, 69 structure becomes more regular, and, as a result, the amount of moisture absorption 8 of 12 de-
creases. It shows that in 10% by weight of nano-silica, we have the lowest amount of mois-
ture absorption.
structure
On the becomes moreby
other hand, regular, and, asthe
comparing a result,
samplesthethat
amount of moisture
are located absorption
at different pHs, we
decreases. It shows that in 10% by weight of nano-silica, we have the lowest amount
find that the slower the pH of the liquid bath moves to the neutral, the higher the absorp- of
moisture absorption.
tion rate. The maximum amount of moisture absorption for different pHs is pH = 7. The
chemical
Table 2. structure of PMMA
Moisture absorption shows
rate of that the haplomer atoms do not tend to react with
samples.
acidic and alkaline solvents, and, as a result, by being in these media, their adsorption
pH
decreases. On the other hand, silica nanoparticles based on the base polymer do not tend
Sample 5 6 7 8 9
to react with acids and bases. As a result, we see that the more acidic and alkaline the
A
liquid, the lower 0.0174
the absorption 0.0239
(Figure 6). 0.0644 0.0196 0.0177
B 0.0152 0.0195 0.0310 0.0095 0.0075
C 0.0146 0.0189 0.0189 0.0092 0.0070
Table 2. Moisture
D absorption rate of samples.
0.0123 0.0188 0.0167 0.0087 0.0066
E 0.0023 0.0014 0.0059 0.0046 0.0033
pH
Sampl On the other hand,5 6 7 8 9
by comparing the samples that are located at different pHs, we find
thatethe slower the pH of the liquid bath moves to the neutral, the higher the absorption rate.
TheA maximum amount0.0174of moisture0.0239 0.0644 pHs is pH
absorption for different 0.0196 0.0177
= 7. The chemical
structure
B of PMMA shows
0.0152 that the haplomer
0.0195 atoms do not
0.0310 tend to react
0.0095with acidic and
0.0075
alkaline solvents, and, as a result, by being in these media, their adsorption decreases. On
C 0.0146 0.0189 0.0189 0.0092 0.0070
the other hand, silica nanoparticles based on the base polymer do not tend to react with
Dand bases. As
acids 0.0123
a result, we see0.0188 0.0167
that the more acidic and alkaline0.0087 0.0066
the liquid, the lower
E
the absorption 0.0023
(Figure 6). 0.0014 0.0059 0.0046 0.0033

Figure 6. Comparison
Figure 6. Comparisonofofmoisture absorptionforfor
moisture absorption samples
samples at different
at different pHs. pHs.

3.3. Fracture Toughness

The fracture toughness of a material indicates the material’s resistance to crack prop-
agation when subjected to loading and is directly related to the total energy absorbed
to deform the plastic. The cross-sectional areas of the specimen after loading are shown
(Figure 7).
Table 3 shows the results of sample loading. Examination of the test results shows
that increasing the amount of silica filler increased the fracture toughness of the samples,
but when the amount of filler exceeds 5% by weight, not only does the fracture toughness
not improve but it also decreases, so that in the case of 10, the weight percentage of silica
and the fracture toughness of the samples are less than the samples without silica filler. Of
course, fracture toughness in composites is a complex process, and its increase or decrease
cannot be considered only due to the number of fillers. The study of the failure mechanism
 Of course, fracture toughness in composites is a complex process, and its increas
crease cannot be considered only due to the number of fillers. The study of th
mechanism in composites shows that the type of filler, fracture process, protrus
J. Compos. Sci. 2024, 8, 69 thickness of the crack tip, the yield strength of the matrix plastic, the structure 9 of 12 of t
posite, the separation of the joint particle, the matrix, and, especially, the aggreg
filler particles considers other factors, which can affect the fracture toughness tes
in composites shows that the type of filler, fracture process, protrusion and thickness of
of composites. Because polymers have an amorphous and irregular structure, the
the crack tip, the yield strength of the matrix plastic, the structure of the composite, the
in filler particles
separation of the joint reduces
particle, thethe distance
matrix, betweenthe
and, especially, the particles,ofand
aggregation filler this factor red
particles
crack growth
considers rate; the
other factors, which long
can crack growth
affect the fracturepath leads test
toughness to an increase
results in the fractur
of composites.
ness of the composite. Researchers attribute the increase in fracture toughness of
Because polymers have an amorphous and irregular structure, the increase in filler particles
reduces
sites due the to
distance between of
the addition thefiller
particles,
to theandinteraction
this factor reduces
of thethe crack
crack tipgrowth
with rate;
the filler ph
the long crack growth path leads to an increase in the fracture toughness of the composite.
the other hand, increasing the amount of filler, the accumulation of particles incre
Researchers attribute the increase in fracture toughness of composites due to the addition
causes
of filler tothe formationofof
the interaction theagglomerates,
crack tip with thewhich accelerates
filler phase. the hand,
On the other growth of cracks and
increasing
quently,
the amountreduces fracture
of filler, the toughness,
accumulation as can
of particles be seenand
increases in causes
Figurethe 8. formation
Agglomerates of act
agglomerates, which accelerates the growth of cracks and, consequently,
regions in the polymer matrix and collapse in the presence of the applied load reduces fracture
toughness, as can be seen in Figure 8. Agglomerates act as weak regions in the polymer
results in the initial failure of the material and, thus, a reduction in fracture tough
matrix and collapse in the presence of the applied load, which results in the initial failure
addition,
of the materialtheand,
presence
thus, a of agglomerates
reduction in fracture in toughness.
the polymer matrix leads
In addition, to contractio
the presence
contact
of area and
agglomerates thepolymer
in the formation of defects.
matrix This phenomenon
leads to contraction prevents
of the contact area and thethe effective
of the applied
formation load
of defects. from
This the matrix
phenomenon to thethe
prevents filler nanoparticles,
effective transfer of thewhich
applied leads
load to an in
from the matrix to the filler nanoparticles, which
reduction in the fracture toughness of the composite material. leads to an inevitable reduction in the
fracture toughness of the composite material.
Although in this study, we tried to create a uniform distribution of silica na
Although in this study, we tried to create a uniform distribution of silica nanoparti-
clesonon
cles thethe surface
surface of theofbase
thepolymer
base polymer by modifying
by modifying the filler
the filler particles, particles,
at high weight at high
percentages, the accumulation of nanoparticles forms agglomerates.
percentages, the accumulation of nanoparticles forms agglomerates.

Figure
Figure Sample
7. 7. failure
Sample cross-section.
failure cross-section.

Table 3. Results of the three-point bending test.

√
Sample F (N) Bending Strain KIC (Mpa/ m)
A 140.97 0.06 66.25
B 151.83 0.06 70.97
C 221.97 0.07 104.3
D 175.16 0.06 82.32
E 119.9 0.05 56.35
 Sample F (N) Bending Strain KIC (Mpa/√m)
A 140.97 0.06 66.25
B 151.83 0.06 70.97
C 221.97 0.07 104.3
J. Compos. Sci. 2024, 8, 69 D 175.16 0.06 82.32 10 of 12
E 119.9 0.05 56.35

√
Figure 8.
Figure Fracturetoughness
8. Fracture toughness(Mpa/√m)
(Mpa/ m)forfor samples
samples with
with different
different filler
filler percentages.
percentages.
4. Conclusions
4. Conclusions
In this research, we investigated the effect of adding silica nanoparticles on the mechan-
In this research,
ical properties we investigated
and moisture absorption theofeffect
PMMA-basedof addingdental
silicasamples.
nanoparticles
After on the me-
performing
chanical properties and moisture absorption of PMMA-based
experiments and analyzing the obtained values, it was found that increasing the filler dental samples. After per-
forming
percentage experiments
caused theand analyzing the
accumulation obtained values,
of nano-silica it was
particles andfound that increasing
subsequent agglomerate the
filler percentage caused the accumulation of nano-silica particles
formation, so that the highest number of agglomerates is observed in composites with 10% and subsequent agglom-
erate formation,Also,
wt. nano-silica. so that the highest
increasing numberofofsilica
the amount agglomerates
filler improvesis observed in composites
the fracture toughness,
with 10% wt. nano-silica. Also, increasing the amount of silica
but there is an optimal limit for this increase so that increasing the filler weight filler improves the by
fracture
more
toughness, but there is an optimal limit for this increase so that
than 5% negates the slope of the fracture toughness diagram. And, after the optimal increasing the filler weight
state
by
(5%more
wt. ofthan 5% increasing
filler), negates the theslope
silicaoffiller
the reduces
fracture the toughness
fracture diagram.
toughnessAnd, of theafter the op-
composites.
timal
So, atstate
10% (5%
wt., wt.
notof filler),
only increasing
is the toughness theunimproved
silica filler reduces
but it isthelessfracture
than the toughness
case where of
the composites. So, at 10% wt., not only is the toughness unimproved
PMMA lacks a silicon filler. Increasing the filler reduces moisture absorption. The tested but it is less than
the case where
samples react toPMMA
acidic lacks a siliconenvironments
and alkaline filler. Increasing the filler
so that as thereduces
amountmoisture
of acid or absorp-
liquid
tion.
base The testedneutral,
becomes samplesthe react to acidic of
absorption and alkalineinenvironments
moisture dental samples so that as the amount
increases. Also, in
of acid orless
samples liquid
thanbase
10%becomes
wt., the rateneutral, the absorption
of moisture absorption of in
moisture in dental
acidic media samples
is higher thanin-in
creases.
alkalineAlso,
media, in samples
but at 10% less than
wt., the10%
ratewt., the rate ofabsorption
of moisture moisture absorption
in alkaline in acidic
media is media
higher
is higher
than than in
in acidic alkaline media, but at 10% wt., the rate of moisture absorption in alkaline
media.
media is higher than in acidic media.
Author Contributions: Conceptualization, N.R; methodology, M.A.G. and N.R; Validation, N.R.,
P.R.S. and
Author M.A.G.; Investigation,
Contributions: P.R.S., N.R.N.R;
Conceptualization, and methodology,
M.A.G.; Resources,
M.A.G. P.R.S.;
anddata
N.R;curation, N.R.N.R.
Validation, and
P.R.S.;and
P.R.S. writing—original draft preparation,
M.A.G.; Investigation, P.R.S. N.R.M.A.G. and N.R.;
and M.A.G.; Writing—review
Resources, and
P.R.S.; data editing,N.R.
curation, N.R.and
and
P.R.S.; Visualization,
P.R.S.; N.R. draft
writing—original and M.A.G.; projectM.A.G.
preparation, administration,
and N.R.;N.R. and M.A.G. Alland
Writing—review authors haveN.R.,
editing, read
P.R.S.; Visualization,
and agreed N.R., M.A.G.;
to the published versionproject
of the administration,
manuscript. N.R., M.A.G. All authors have read and
agreed to the published version of the manuscript.
Funding: This research received no external funding.
Funding: This research received no external funding.
Data Availability Statement: Data sharing is applicable to this article by requesting corresponding author.
Data Availability Statement: Data sharing is applicable to this article by requesting corresponding
Conflicts of Interest: The authors declare no conflict of interest.
author.
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